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Interplay between tetrel bonding and hydrogen bonding interactions in complexes involving F2XO (X = C and Si) and HCN
Accepted Manuscript Interplay between tetrel bonding and hydrogen bonding interactions in complexes involving F2XO (X = C and Si) and HCN Qingjie Tang, Qingzhong Li PII: DOI: Reference:
S2210-271X(14)00473-3 http://dx.doi.org/10.1016/j.comptc.2014.10.025 COMPTC 1649
To appear in:
Computational & Theoretical Chemistry
Received Date: Revised Date: Accepted Date:
11 September 2014 20 October 2014 20 October 2014
Please cite this article as: Q. Tang, Q. Li, Interplay between tetrel bonding and hydrogen bonding interactions in complexes involving F2XO (X = C and Si) and HCN, Computational & Theoretical Chemistry (2014), doi: http:// dx.doi.org/10.1016/j.comptc.2014.10.025
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Interplay between tetrel bonding and hydrogen bonding interactions in complexes involving F2XO (X = C and Si) and HCN Qingjie Tang,a Qingzhong Li*,b a
College of Material Science and Engineering, Henan Polytechnic University, Jiaozuo
454000, People’s Republic of China b
The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and
Chemical Engineering, Yantai University, Yantai 264005, People’s Republic of China Corresponding authors: Qingzhong Li The Laboratory of Theoretical and Computational Chemistry School of Chemistry and Chemical Engineering Yantai University Yantai 264005 People’s Republic of China Tel. (+086) 535 6902063 Fax. (+086) 535 6902063 E-mail:[email protected]
1
Abstract The complexes F2XO···NCH···NCH and F2XO···HCN···HCN (X = C and Si) have been studied by quantum chemical calculations at the MP2/aug-cc-pVTZ level. These four trimers show similar stability except F2SiO···HCN···HCN. The C–H···N hydrogen bond is enhanced by the presence of tetrel bond in F2XO···NCH···NCH. Interestingly, the stronger tetrel bond in F2SiO···NCH···NCH
exhibits
a
greater
enhancement
than
the
weaker
one
in
F2CO···NCH···NCH. The positive cooperativity is mainly attributed to the polarization and dispersion energies in the former but to the polarization energy in the latter. The tetrel bond and C–H···O hydrogen bond are also strengthened each other in HCN···F2XO···HCN. The tetrel bonds are weakened in HCN···F2XO···NCH, where the weakening is caused mainly by electrostatic energy for HCN···F2CO···NCH and by electrostatic and polarization energies for HCN···F2SiO···NCH. The C–H···N and C–H···O hydrogen bonds show a positive cooperative effect in F2XO···HCN···HCN due to the polarization interaction. Keywords: Cooperativity; Interplay; Tetrel bond; Hydrogen bond; F2XO
2
1. Introduction Hydrogen cyanide (HCN) is a common interstellar molecule [1], produced in the reactions of ammonia and methane [2], and is also of great importance in atmospheric chemistry as a result of its release by biomass burning [3], thus the structures and the vibrational spectra of small, hydrogen-bonded clusters of HCN in the gas phase have been the subject of extensive investigations, both experimentally and theoretically [4-6]. The polymers of HCN turned out to be of particular interest [6-12] due to the existence of cooperativity in these clusters, which has a significant contribution to the applications of hydrogen bonds in catalytic reactions, molecular materials, molecular recognition, and biological systems. It has proved that the HCN polymer in the gas phase exists in both a linear and a cyclic form [11] but in the solid state arranges in extended, perfectly linear chains [12]. Two different mechanisms for the cooperativity of C–H···N hydrogen bond in the clusters of HCN were proposed. King and Weinhold [9] thought that the cooperativity in the HCN polymer mainly arises from the donor–acceptor orbital interaction of LPN→BD*C-H in the C–H···N hydrogen bond, whereas Stone and Buckingham ascribed the cooperativity to induction effects [10]. Parallel to the just-mentioned polymers of HCN, numerous quantum chemical calculations have been performed on the mixed trimers involving HCN [13-20]. It was demonstrated that these mixed trimers display greater cooperativity than the HCN polymers do. The C–H···N hydrogen bond in HCN···HCN dimer is strengthened by the presence of another type of interaction in these mixed trimers. Furthermore, the stronger second interaction results in the larger increase of the strength of C–H···N hydrogen bond. For instance, at the MP2/6-311++G(2d,2p) level, the interaction energy varies from –4.42 kcal/mol in HCN···HCN dimer to –7.12 kcal/mol in HLi···HCN···HCN trimer, increased by 3
~61% in the presence of a strong lithium bond [15]. Very recently, a new intermolecular interaction, named tetrel bonding [21], was suggested to serve as a new possible molecular linker [21] and a preliminary stage of the SN2 reaction [22]. Its formation is attributed to a positive electrostatic potential on the group IV atomic surface [23]. On the other hand, the experimental evidence for its existence was given with charge density analysis for a large number of known crystal structures [24]. The importance of tetrel-bonding in cyclobutane rings was demonstrated by combining high level theoretical calculations and the Cambridge Structural Database (CSD) analysis, showing that tetrel-bonding interactions are quite common in nitro-substituted cubanes [25]. By means of the above methods, Bauzá and coworkers suggested that the strength of interaction between the sp3 C-atom in para-substituted ArCF3 and electron rich atoms is comparable to that of CH···πinteractions [26], and the strong complexes are formed between the derivatives of small cycloalkane rings containing four cyano groups in the 1,1’,2,2’ positions and electron rich entities [27]. It was theoretically demonstrated that the carbon atom in a methyl group is able to form a tetrel bond when it is adjoined with electron-withdrawing substituents [28], and also the weak attractive interactions were found between the two methyl groups in the complexes of XCH3···CH3BH2 (X = F, CN, NO2, HCO, and SOCH3) [29], where the former methyl group acts as a Lewis acid and the latter one is a Lewis base. Similar to the cases of other types of interactions, the Lewis base in tetrel bonds arise from radicals [30] and metal hydrides [31], besides lone pairs and anion. When calix[4]pyrrole was decorated with four SiF3 groups, its anion binding ability was enhanced due to the additional contribution of tetrel bonding, along with hydrogen bonding [32]. Hence, it is interesting to study the influence of tetrel bond on the strength of hydrogen bond. 4
In this paper, we studied the interplay between the tetrel bond and hydrogen bond in the complexes composed of one F2XO (X = C and Si) and two HCN molecules. Carbonyl fluoride (F2CO), a chamber-cleaning agent, can replace the traditional perfluorocarbons used in the plasma semiconductor industry [33], and has some effects on the photochemistry of the Earth’s upper atmosphere [34]. Hence, this study can provide some important information for the interactions between both interstellar molecules. Also interesting would be to unveil the enhancing mechanism of tetrel bond on the hydrogen bond. In addition, we paid our attention to the interplay between both tetrel bonds as well as that between both hydrogen bonds. 2. Theoretical methods All structures were optimized at the MP2/aug-cc-pVTZ level. Frequency calculations were performed at the same level to confirm that all structures are local minima on the potential energy surfaces. The interaction energy was calculated with supermolecular method and corrected for basis set superposition error (BSSE) using the counterpoise procedure of Boys and Bernardi [35]. All calculations were carried out via the Gaussian 09 program [36]. Molecular electrostatic potentials (MEPs) at the 0.001 electrons Bohr-3 isodensity surfaces of F2XO were calculated with the Wave Function Analysis-Surface Analysis Suite (WFA-SAS) program [37] at the MP2/aug-cc-pVTZ level. The wavefunction obtained at the MP2/aug-cc-pVTZ level was used to calculate the electron density at the critical point and plot the molecular graph using AIM2000 software [38]. The orbital interactions and natural population analysis (NPA) charges were calculated with natural bond orbital (NBO) theory [39] using NBO version 3.1 implemented in Gaussian 09. To gain an insight into the nature of the investigated intermolecular interactions, the energy decomposition analysis (EDA) was performed by the GAMESS program [40] with the localized molecular orbital EDA method 5
[41] at the MP2/aug-cc-pVTZ level. 3. Results and discussion It was known that HCN is able to act as both the Lewis acid with the H atom and the Lewis base with the N atom in the formation of hydrogen bonds. On the other hand, F2CO also has dual roles of both Lewis acid and base with the C and O atoms, respectively, characterized by the positive MEP on the C atom and the negative one on the O atom (Fig. 1). Consequently, both molecules have two interaction modes: a hydrogen bond between the H atom of HCN and the O atom of F2CO as well as a tetrel bond between the N atom of HCN and the C atom of F2CO. More importantly, both dimers also exhibit dual roles of Lewis acid and base. As a consequence, they can bind with the second HCN through a hydrogen bond or a tetrel bond. Namely, four types of mixed trimers involving one F2XO and two HCN molecules were obtained for F2CO and F2SiO, respectively. Their equilibrium geometries are shown in Fig. 2, marked as T1-T8 in turn for easy illustration. F2CO···NCH···NCH (T1) and F2SiO···NCH···NCH (T2) are stabilized by a tetrel bond and a C-H···N hydrogen bond, where the angle of O–X···N is a litter larger than that in the corresponding dimer. HCN···F2CO···HCN (T3) and HCN···F2SiO···HCN (T4) are cyclic structures involving with a tetrel bond, a C-H···O hydrogen bond, and a C···N interaction. The angle of O–X···N in T3 and T4 decreases due to the cyclic structure. The π-hole of F2XO, as a double Lewis acid, interacts with two HCN molecules in HCN···F2CO···NCH (T5) and HCN···F2SiO···NCH (T6), in which two same tetrel bonds are present. The angle of O–X···N becomes smaller in T5 and T6 relative to the respective dimers, and a prominent decrease is found in T6, indicating a weakening of the tetrel bond in both trimers. Two different types of hydrogen bonds (C–H···N and C–H···O) coexist in F2CO···HCN···HCN (T7) and F2SiO···HCN···HCN (T8). Four types of 6
structures are comparable each other for the F2CO trimers with the total interaction energy in the range of –23.2 ~ –37.5 kJ/mol (Table 1), while the three trimers of F2SiO (T2, T4, and T6) containing a tetrel bond are far more stable than T8 due to the strong tetrel bond. These trimers are more stable in the order of T5 < T7 < T1 < T3 and T8 < T6 < T2 < T4, showing a main dependence on the strength of tetrel bond. The most positive MEP on the X atom is 1.835 eV for carbon and 3.447 eV for silicon, resulting in the formation of a strong tetrel bond for F2SiO. Four types of systems are discussed separately in the following sections. 3.1. Influence of tetrel bond on hydrogen bond The interaction energy of C–H···N hydrogen bond is calculated to be –19.7 kJ/mol in HCN···HCN (Table 1), showing a similar strength with the O–H···O one in water dimer [41]. Here we want to strengthen the C–H···N hydrogen bond by the tetrel bond in T1 and T2. It is found from Table 1 that the interaction energy of C–H···N hydrogen bond becomes more negative with the presence of the tetrel bond. Furthermore, the stronger tetrel bond has a greater enhancing effect on the strength of C–H···N hydrogen bond in T2. It was demonstrated that the LPN→BD*C–H orbital interaction has a great contribution to the formation of C–H···N hydrogen bond in HCN···HCN, thus the strengthening of C–H···N hydrogen bond can be understood with the variation of this orbital interaction in the trimers (Table 2). The perturbation energy is 25.6 kJ/mol for the LPN→BD*C–H (LPN is the lone pair orbital on the N atom of HCN and BD*C–H denotes the C–H anti-bonding orbital of another HCN) orbital interaction in HCN···HCN, and it increases in T1 and T2 due to the presence of tetrel bond, particularly showing the larger increase in T2 with a stronger tetrel bond. The interaction energy of C–H···N hydrogen bond increases by 7.6% and 74.6% in T1 and T2, respectively, and in the latter trimer this percentage is larger than that in HLi···HCN···HCN, where the 7
interaction energy of lithium bond is –62.2 kJ/mol at the MP2/6-311++G(2d,2p) level [15], smaller than that of tetrel bond in T2. Accompanied with the enhancement of C–H···N hydrogen bond in T1 and T2, the H···N distance is shorter relative to the HCN dimer (Table 3). Especially, the shorting of H···N distance is prominent in T2 (–0.206 Å), consistent with the great increase of C–H···N interaction energy. Also, the AIM analysis (Fig. 3) shows the existence of a Si···N BCP in F2SiO···NCH, with an electron density almost four times larger than that associated with the C–H···N hydrogen bond in HCN···HCN, where the electron density has a larger increase in T2 than in T1. On the other hand, the hydrogen bond also has an enhancing effect on the tetrel bond. It is interesting to find that the stronger tetrel bond in F2SiO···NCH is greatly strengthened with the presence of C–H···N hydrogen bond in T2. The Si···N distance (1.957 Å) in F2SiO···NCH is much smaller than the sum of the corresponding ver der Waals radii (3.6 Å) and is close to the length of Si–N bond (1.75 Å), indicating that the Si···N interaction has a partially covalent nature with the big interaction energy of –95.5 kJ/mol. Consequently, there are two strong orbital interactions for the tetrel bond in F2SiO···NCH: LPN→RY*Si and LPN→BD*Si–F, where RY*Si is 1-center Rydberg orbital of Si and BD*Si–F is the anti-bonding orbital of Si–F bond. The presence of C–H···N hydrogen bond makes E(2)LPN→RY*Si in T2 increased larger than E(2)LPN→BD*C=O in T1, consistent with the change of interaction energy for the tetrel bond in both trimers. The change of X···N interaction energy is larger in T2 than that in T1, but the shortening of X···N distance is almost the same in both trimers. Consistently, the electron density at the X···N BCP is much higher in T2 than in T1. Consequently both hydrogen bond and tetrel bond are enhanced, indicating a positive 8
cooperativity. The interplay between hydrogen bond and tetrel bond can be estimated with cooperative energy (Ecoop) using the formula of Ecoop = ΔEtotal – (ΔEAB + ΔEBC + ΔEAC), where ΔEtotal is the total interaction energy of the trimer, ΔEAB and ΔEBC are the interaction energies of the optimized dimers, and ΔEAC is the interaction energy between A and C in the trimer geometry. It is obvious in Table 1 that Ecoop is negative in both trimers and T2 shows a more negative Ecoop, amounting to ~11% of the total interaction energy. As expected, the stronger hydrogen bond has a greater effect on the weaker tetrel bond in T1, while the stronger tetrel bond has a greater effect on the weaker hydrogen bond in T2. One can see from Fig. 3 that the sum of the variation of the electron density at the BCP from the dimer to the trimer is 0.0021 au and 0.0146 au in T1 and T2, respectively. Clearly, this sum exhibits a consistent change with the cooperative energy in the trimer (Table 1), which is -1.4 kJ/mol and -14.6 kJ/mol in T1 and T2, respectively. The cooperative effect between the hydrogen bond and tetrel bond can also be analyzed with the change of C–H bond length and the shift of C–H stretch frequency (Table 4). The elongation of the associated C–H bond in T1 and T2 is larger than the sum of that in F2XO···NCH and HCN···HCN. Correspondingly, the red shift of C–H stretch vibration in the trimer is greater than the sum of the red shift in the respective dimers. To unveil the enhancing mechanism between the hydrogen and tetrel bonds in T1 and T2, their interaction energies were decomposed into five components: electrostatic energy (Eele), exchange energy (Eex), repulsion energy (Erep), polarization energy (Epol), and dispersion energy (Edisp), and the results are collected in Table 5. The Erep term is very large for the tetrel bond in T2, due to the strong orbital overlap between F2SiO and HCN. As expected, the C–H···N hydrogen bond is mainly dominated by electrostatic energy. Similarly, the main 9
contribution to the stability of F2CO···NCH is from electrostatic energy. However, for the tetrel bond in F2SiO···NCH, the polarization contribution is comparable to the electrostatic one. The relatively large Epol suggests the orbitals undergo significant change in their shapes, characterized by the geometric deformation of F2SiO in the complex. This provides a further evidence for the nature of partially covalent interaction in F2SiO···NCH. All terms become larger in the trimers, among the three attractive terms Eele, Epol, and Edisp of the hydrogen bond in T1, the increase of the first term is larger than that of the second one, and the final term is almost unchanged, indicating that the enhancement of C–H···N hydrogen bond in T1 is mainly attributed to the increase of electrostatic energy. The positive charge (0.252e) on the H atom of the terminal HCN and the negative one (–0.408e) on the N atom of the middle HCN become larger in T1 than those in HCN–0.403e···0.247eHCN, thus the electrostatic interaction between two atoms are stronger. The reason for the enhancement of tetrel bond in T1 is similar to that of C–H···N hydrogen bond in T1. For the C–H···N hydrogen bond in T2, the increase of Epol is 12.1 kJ/mol, almost half the value of Eele, indicating that both electrostatic and polarization energies are responsible for its strengthening. Similarly, the enhancement of tetrel bond in T2 arises from the increase of both terms. In Table 6, we performed a many-body analysis for T1 and T2 with the LMOEDA method to explore the origin of the cooperativity between the hydrogen bond and tetrel bond. As expected, the sums of the pairwise electrostatic and exchange energies in the three dimers are, respectively, the same as the total electrostatic and exchange energies in the trimers. The sum of the pairwise dimer repulsion energies is the same as that in T1 and is 0.46 kJ/mol less repulsive than that for T2. So, the repulsion energy is roughly additive for the hydrogen and tetrel bonds in T1 and T2. The sums of the dimer polarization and dispersion energies are 1.9 10
and 3.3 kJ/mol less attractive than that for T1, respectively, thus the cooperative energy between the hydrogen and tetrel bonds in T1 results from the polarization and dispersion energies. The polarization energy is also not additive in T2: the sum of the dimer polarization energy is 23.2 kJ/mol less attractive than that in the trimer, which is more prominent than the dispersion energy. Clearly, the cooperative energy in T2 is mainly attributed to the polarization energy. 3.2. Many-body analysis for cyclic trimers The cyclic structures of T3 and T4 are confirmed by the presence of a ring critical point (RCP) (Fig. 3). This cyclic structure makes it difficult to compare the interaction energy of each type of interaction in the same way with that in T1 and T2. This problem can be overcome with many-body analysis, which had been described previously [42]. In T3, the interaction energy of tetrel bond is almost as much as that in the respective dimer, although the structure has a prominent change, while it has a prominent increase in T4. The interaction energy of C–H···O hydrogen bond has a small decrease in T3 but an obvious decrease in T4. However, it should be cautious about comparing the two-body energy in the trimer and the interaction energy in the respective dimer because the charge density of the dimer used for obtaining the two-body energy is different from that in the trimer. This can be verified by analyzing the change of the electron densities at the intermolecular BCPs in the trimers. Clearly, the electron densities at the X···N and O···H BCPs in the trimers are larger than those in the respective dimers. They are consistent with the change of interaction energy of tetrel bond but inconsistent with that of C–H···O hydrogen bond in T3 and T4. More importantly, the orbital interactions involving the C–H···O hydrogen bond and tetrel bond become stronger in the trimers (Table 2). As a result, the C–H···O hydrogen bond and tetrel bond are 11
strengthened each other in T3 and T4. The C···N interaction between the two HCN molecules in T3 and T4 can be evidenced with the presence of a C···N BCP, and its electron density indicates that this interaction is stronger in T4 than that in T3. However, the two-body energies between the two HCN molecules in the trimers are less negative in T4 than that in T3. This further shows the uncertainty of many-body analysis for the interaction energy. The change of electron density at the C···N BCP is consistent with the C···N distance in both trimers, while the change of two-body energy between the two HCN molecules is inconsistent with the C···N distance. The binding distances of the C–H···O hydrogen bond and tetrel bond become shorter in T3 and T4 than those in the respective dimers except for the H···O distance in T3. The possible reason is that the interaction direction is different in both T3 and F2CO···HCN, together with the weak interaction of C–H···O hydrogen bond. As expected, the three-body energy is negative in T3 and T4. Furthermore, due to the strong tetrel bond, the latter trimer shows a very large three-body energy value of –35.3 kJ/mol, amounting to 23.0% of the total interaction energy. The C–H bond is elongated and the corresponding bond stretch vibration exhibits a red shift for the tetrel bond of F2XO···NCH (X = C and Si), and both of them become larger in T3 and T4. The similar changes are also found for the hydrogen bond in F2XO···HCN (X = C and Si). In T3 and T4, the Eele and
Eex
terms are additive, while the Epol one is non-additive at all.
The Erep and Edisp terms are also non-additive, but their additivity is small than that of Epol. Thus the three-body energy in T3 and T4 mainly results from the polarization energy. 3.3. Negative cooperativity of tetrel bonds In T5 and T6, the interaction energies of tetrel bonds are smaller in magnitude than those in the respective dimers, therefore, the two tetrel bonds exhibit negative cooperativity with a 12
positive cooperative energy (Table 1). This is attributed to the role of double Lewis base for F2XO (X = C and Si) in T5 and T6. Furthermore, the interaction energy of tetrel bond decreases by 2.3 kJ/mol in T5, while it is decreased by ~50% in T6. Clearly, the stronger tetrel bond has a prominent weakening; even so, the tetrel bond is still much stronger than the C–H···N hydrogen bond. The weakening of tetrel bond is characterized with the weak orbital interactions, the small electron density at the X···N BCP, the long binding distance, the small elongation of C–H bond as well as the small red shift of the C–H stretch vibration. In T5, all energy components are decreased in magnitude, in which the decrease of electrostatic energy is the largest and the dispersion energy is almost not changed. This indicates that the weakening of tetrel bond in T5 is mainly attributed to the electrostatic energy. In T6, the decrease of electrostatic energy is comparable to that of polarization energy; both terms have a more prominent change than the dispersion energy, indicating that the electrostatic and polarization energies give rise to the weakening of tetrel bond in T6. It is found from Table 6 that the negative cooperative energy in T5 and T6 is caused by polarization energy. 3.4. Interplay between C–H···O and C–H···N hydrogen bonds In T7 and T8, the middle molecule HCN acts as the dual roles of Lewis acid in the C–H···O hydrogen bond and Lewis base in the C–H···N one, as a result, both types of hydrogen bonds are strengthened, characterized with the more negative interaction energy, the negative cooperative energy, the shorter binding distance, the larger elongation of C–H bond, and the bigger red shift of C–H stretch vibration. The interaction energy of C–H···O hydrogen bond has a greater increase than that of C–H···N one in T7, that is, the effect of C–H···N hydrogen bond on the C–H···O one is prominent than the effect of C–H···O hydrogen bond on 13
the C–H···N one. Interestingly, the similar conclusion is obtained in T8, although the C–H···O hydrogen bond is stronger than the C–H···N one in T8. For the two types of hydrogen bonds in T7 and T8, the increase of electrostatic energy is larger than that of polarization energy, indicating that the strengthening of both types of hydrogen bonds are mainly attributed to the electrostatic energy. However, the cooperative energy in both trimers is mainly from the polarization interaction. 4. Conclusions Mixed trimers composed of one F2XO (X = C and Si) and two HCN molecules have been investigated on the basis of ab initio results, and other tools such as the NBO method, AIM theory, as well as the LMOEDA approach. Four types of trimers were obtained for F2XO, in which the trimers of F2CO are comparable in energy, while those of F2SiO have a difference in energy. In F2XO···NCH···NCH, the tetrel bond and C–H···N hydrogen bond are strengthened each other. The interaction energy of C–H···N hydrogen bond is increased to be –34.4 kJ/mol in F2SiO···NCH···NCH by the stronger tetrel bond. Interestingly, the strong tetrel bond has a greater enhancement in F2SiO···NCH···NCH than that in F2CO···NCH···NCH. The strengthening of both types of interactions in F2CO···NCH···NCH is mainly attributed to the electrostatic energy, while that in F2SiO···NCH···NCH is from the electrostatic and polarization energies. The positive cooperative energy arises from the polarization and dispersion energies in F2CO···NCH···NCH but the polarization energy in F2SiO···NCH···NCH. The cyclic trimers of HCN···F2XO··· HCN are the most stable among all the trimers. Both tetrel bond and C–H···O hydrogen bond become stronger in the trimer relative to the respective dimer. The three-body energy is mainly attributed to the polarization energy. 14
The tetrel bond is weakened in HCN···F2XO··· NCH with a positive cooperative energy. The weakening of tetrel bond is mainly caused by the decrease of electrostatic and polarization energies, but only the polarization energy is responsible for the positive cooperative energy. Both C–H···O and C–H···N hydrogen bonds are enhanced in F2XO···HCN···HCN, where the enhancement of C–H···N hydrogen bond is smaller than that in F2XO···NCH···NCH. Surprisingly, the stronger C–H···O hydrogen bond has a greater strengthening than the weaker C–H···N hydrogen bond in F2XO···HCN···HCN. The enhancement of both types of hydrogen bonds is mainly attributed to the electrostatic energy, while the negative cooperative energy is mainly caused by the polarization energy. Acknowledgements This work was supported by the Outstanding Youth Natural Science Foundation of Shandong Province (JQ201006) and the Program for New Century Excellent Talents in University (NCET-2010-0923). References [1].
E. Herbst, E.F. van Dishoeck, Complex organic interstellar molecules, Annu. Rev. Astron. Astrophys. 47(2009) 427-480.
[2].
C.N. Matthews, R.D. Minard, Hydrogen cyanide polymers, comets and the origin of life, Faraday Discuss. 133(2006) 393-401.
[3].
Q.B. Li, D.J. Jacob, R.M. Yantosca, C.L. Heald, H.B. Singh, M. Koike, Y. Zhao, G.W. Sachse, D.G. Streets, A global three-dimensional model analysis of the atmospheric budgets of HCN and CH3CN: Constraints from aircraft and ground measurements, J. Geophys. Res: Atmos. 108(2003) 48/1-48/11. 15
[4].
R.D. Brown, P.D. Godfrey, D.A. Winkler, The microwave spectrum of HCN dimer, J. Mol. Spectrosc. 89 (1981) 352-355.
[5].
M. Sanchez, P.F. Provasi, G.A. Aucar, I. Alkorta, J. Elguero, Theoretical study of HCN and HNC neutral and charged clusters, J. Phys. Chem. B 109(2005) 18189-18194.
[6].
A. Karpfen, Linear and cyclic clusters of hydrogen cyanide and cyanoacetylene:
A
comparative ab Initio and density functional study on cooperative hydrogen bonding, J. Phys. Chem. 100(1996) 13474-13486. [7].
R. Rivelino, P. Chaudhuri, S. Canutoc, Quantifying multiple-body interaction terms in H-bonded HCN chains with many-body perturbation/coupled-cluster theories, J. Chem. Phys. 118 (2003) 10593-10601.
[8].
B.F. King, T.C. Farrar, F. Weinhold, Structure and spectroscopy of (HCN)n clusters: Cooperative and electronic delocalization effects in C–H···N hydrogen bonding, J. Chem. Phys. 103 (1995) 333-347.
[9].
B.F. King, T.C. Farrar, F. Weinhold, Quadrupole coupling constants in linear (HCN)n clusters: Theoretical and experimental evidence for cooperativity effects in C–H···N hydrogen bonding, J. Chem. Phys. 103 (1995) 348-352.
[10].
A.J. Stone, A.D. Buckingham, Comment on “Structure and spectroscopy of (HCN)n clusters: Cooperative and electronic delocalization effects in C–H⋯N hydrogen bonding” [J. Chem. Phys. 103, 333 (1995)], J. Chem. Phys. 107 (1997) 1030-1031.
[11].
R.S. Ruoff, T. Emilsson, T.D. Klots, C. Chuang, H.S. Gutowsky, Rotational spectrum and structure of the linear HCN trimer, J. Chem. Phys. 89(1988) 138-148.
[12].
W.J. Dulmage, W.N. Lipscomb, The crystal structures of hydrogen cyanide, HCN, Acta Crystallogr. 4 (1951) 330-334. 16
[13].
Q.Z. Li, X.L. An, F. Luan, W.Z. Li, B.A. Gong, J.B. Cheng, J.Z. Sun, Cooperativity between two types of hydrogen bond in H3C–HCN–HCN and H3C–HNC–HNC complexes, J. Chem. Phys. 128(2008) 154102.
[14].
Q.Z. Li, T. Hu, X.L. An, B.A. Gong, J.B. Cheng, Cooperativity between the dihydrogen bond and the N···HC hydrogen bond in LiH–(HCN)n complexes, ChemPhysChem 9(2008) 1942-1946.
[15].
Q.Z. Li, T. Hu, X.L. An, W.Z. Li, J.B. Cheng, B.A. Gong, J.Z. Sun, Theoretical study of the interplay between lithium bond and hydrogen bond in complexes involved with HLi and HCN, ChemPhysChem 10 (2009) 3310-3315.
[16].
R.S. Ruoff, T. Emilsson, C. Chuang, T.D. Klots, H.S. Gutowsky, Rotational spectra and structures of small clusters containing the HCN dimer: X–(HCN)2 with X=CO, N2, NH3, and H2O, J. Chem. Phys. 93(1990) 6363-6370.
[17].
M. Solimannejad, M. Malekani, Cooperative and diminutive interplay between the hydrogen bonding and halogen bonding in ternary complexes of HCCX (X = Cl, Br) with HCN and HNC, Comput. Theo. Chem. 998(2012) 34-38.
[18].
Sean A.C. McDowell, J.A. Joseph, Cooperative effects of noncovalent bonds to the Br atom of halogen-bonded H3N···BrZ and HCN···BrZ (Z = F, Br) complexes, J. Chem. Phys. 137(2012) 074310.
[19].
B.G. Oliveira, T.F. Costa, R.C.M.U. Araújo, A new theoretical analysis of the cooperative effect in T-shaped hydrogen complexes of CnHm···HCN···HW with n = 2, m = 2 or 4, and W = F or CN, J. Mol. Model. 19(2013) 3551-3568.
[20].
R. Rivelino, S. Canuto, Theoretical study of mixed hydrogen-bonded complexes: H2O···HCN···H2O and H2O···HCN···HCN···H2O, J. Phys. Chem. A 105(2001) 17
11260-11265. [21].
A. Bauza, T.J. Mooibroek, A. Frontera, Tetrel-bonding interaction: Rediscovered supramolecular force? Angew. Chem. Int. Ed. 52(2013) 12317-12321.
[22].
S.J. Grabowski, Tetrel bond–σ-hole bond as a preliminary stage of the SN2 reaction, Phys. Chem. Chem. Phys. 16(2014) 1824-1834.
[23].
J.S. Murray, P. Lane, P. Politzer, Expansion of the σ-hole concept, J. Mol. Model. 15(2009) 723-729.
[24].
S.P. Thomas, M.S. Pavan, T.N.G. Row, Experimental evidence for ‘carbon bonding’ in the solid state from charge density analysis, Chem. Commun. 50(2014) 49-51.
[25].
A. Bauzá, T.J. Mooibroek, A. Frontera, Influence of ring size on the strength of carbon bonding complexes between anions and perfluorocycloalkanes, Phys. Chem. Chem. Phys. 16(2014) 19192-19197.
[26].
A. Bauzá, T.J. Mooibroek, A. Frontera, Non-covalent sp3 carbon bonding with ArCF3 is analogous to CH–πinteractions, Chem. Commun. 50(2014) 12626-12629.
[27].
A. Bauzá, T.J. Mooibroek, A. Frontera, Small cycloalkane (CN)2C-C(CN)2 structures are highly directional non-covalent carbon-bond donors, Chem. Eur. J. 20(2014 10245-10248.
[28].
D. Mani, E. Arunan, The X–C···Y (X = O/F, Y = O/S/F/Cl/Br/N/P) ‘carbon bond’ and hydrophobic interactions, Phys. Chem. Chem. Phys. 15(2013) 14377-14383.
[29].
H.Y. Zhuo, L.X. Jiang, Q.Z. Li, W.Z. Li, J.B. Cheng, Is there an attractive interaction between two methyl groups? Chem. Phys. Lett. 608(2014) 90-94.
[30].
Q.Z. Li, X. Guo, X. Yang, W.Z. Li, J.B. Cheng, H.B. Li, A σ-hole interaction with radical species as electron donors: does single-electron tetrel bonding exist? Phys. Chem. Chem. 18
Phys. 16(2014) 11617-11625. [31].
Q.Z. Li, H.Y. Zhuo, H.B. Li, Z.B. Liu, W.Z. Li, J.B. Cheng, Tetrel−hydride interaction between XH3F (X = C, Si, Ge, Sn) and HM (M = Li, Na, BeH, MgH), J. Phys. Chem. A (2014) dx.doi.org/10.1021/jp503735u
[32].
A. Bauzá, R. Ramis, A. Frontera, Computational study of anion recognition based on tetrel and hydrogen bonding interaction by calix[4]pyrrole derivatives, Comput. Theor. Chem. 1038(2014) 67-70.
[33].
Y. Mitsui, Y. Ohira, T. Yonemura, T. Takaichi, A. Sekiya, T. Beppu, The possibility of carbonyl fluoride as a new CVD chamber cleaning gas, J. Electrochem. Soc. 151(2004) G297-G301.
[34].
C.P. Rinsland, R. Zander, L.R. Brown, C.B. Farmer, J.H. Park, R.H. Norton, J.M. III Russell, O.F. Raper, Detection of carbonyl fluoride in the stratosphere, Geophys. Res. Lett. 13(1986) 769-772.
[35].
S.F. Boys, F. Bernardi, The calculation of small molecular interactions by the difference of separate total energies. Some procedures with reduced errors, Mol. Phys. 19(1970) 553-558.
[36].
M.J. Frisch, et al., GAUSSIAN 09, Revision A.02, Gaussian Inc., Wallingford, CT, 2009.
[37].
F.A. Bulat, A. Toro-Labbé, T. Brinck, J.S. Murray, P. Politzer, Quantitative analysis of molecular surfaces: areas, volumes, electrostatic potentials and average local ionization energies, J. Mol. Model. 16(2010) 1679-1691.
[38].
R.F.W. Bader, AIM2000 Program, Version 2.0, McMaster University, Hamilton, Canada, 2000.
[39].
A.E. Reed, L.A. Curtiss, F. Weinhold, Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint, Chem. Rev. 88(1988) 899-926. 19
[40].
M.W. Schmidt, K.K. Baldridge, J.A. Boalz, S.T. Elbert, M.S. Gorden, J.H. Jensen, S. Koseki, N. Matsunaga, K.A. Nguyen, S.J. Su, T.L. Windus, M. Dupuis, J.A. Montgomery, General atomic and molecular electronic structure system, J. Comput. Chem. 14(1993) 1347-1363.
[41].
P.F. Su, H. Li, Energy Decomposition analysis of covalent bonds and intermolecular interactions, J. Chem. Phys. 131(2009) 014102.
[42].
X.X. Santheas, Ab initio studies of cyclic water clusters (H2O)n, n=l-6. II. Analysis of many-body interactions, J. Chem. Phys. 100(19944) 7523-7534.
20
Table 1 Total interaction energy (ΔEtotal), interaction energy between the molecular pairs (ΔE), and cooperative energy (Ecoop) in the trimers. All are in kJ/mol.a ΔEtotal
ΔEAB
ΔEBC
ΔEAC
Ecoop/Ethree-dody
T1
–35.9
–15.8(–14.3)
–21.2(–19.7)
–0.6
–1.4[3.9%]
T2
–133.3
–110.6(–95.5)
–34.4(–19.7)
–3.5
–14.6[11.0]
–37.5
–14.5(–14.3)
–12.0
–9.6(–10.8)
–1.4[3.7%]
T4b
–153.5
–123.5(–95.5)
–10.1
–18.6(–24.1)
–35.3[23.0%]
T5
–23.2
–12.0(–14.3)
2.7
–12.0(–14.3)
2.1[–8.6%]
T6
–114.6
–47.7(–95.5)
5.5
–47.7(–95.5)
70.9[–61.9%]
T7
–31.6
–11.9(–10.8)
–20.5(–19.7)
–0.9
–1.8[5.8%]
T8
–53.3
–29.6(–24.1)
–23.3(–19.7)
–1.9
–7.6[14.3%]
T3
a
b
Data in parentheses are the interaction energies in the respective dimers and those in
brackets are the percentage of Ecoop(Ethree-dody) to ΔEtotal. b
Two-body energy (ΔEAB, ΔEBC, and ΔEAC) and three-body energy (Ethree-dody) in T3 and T4 were
calculated with many-body analysis method.
21
Table 2 Second-order perturbation energy (E(2), kJ/mol) in the trimers at the HF/aug-cc-pVTZ level E(2)1
E(2)2
E(2)3
T1
12.9(8.2)
40.2(25.6)
---
T2
592.5(535.9)
64.3(25.6)
70.9(65.9)
T3
8.9(8.2)
10.3(14.0)
---
T4
638.4(535.9)
68.1(34.7)
60.0(65.9)
T5
6.6(8.2)
---
---
T6
310.3(535.9)
---
53.1(65.9)
T7
17.1(14.0)
28.8(25.6)
---
T8
42.9(34.7)
33.1(25.6)
---
Note: Data in parentheses are the perturbation energies in the respective dimers. E(2)1 corresponds to the orbital interaction of LPN→BD*C=O in T1, T3, T5, LPN→RY*Si in T2, T4, T6, and LPO→BD*C–H in T7, T8. E(2)2 corresponds to the orbital interaction of LPN→BD*C–H in T1, T2, T7, T8 and LPO→BD*C–H in T3, T4. E(2)3 corresponds to the LPN→BD*Si–F orbital interaction.
22
Table 3 Binding distances (R, Å) in the trimers and their differences (ΔR, Å) relative to the respective dimers at the MP2/aug-cc-pVTZ level R1
R2
ΔR1
ΔR2
T1
2.742(2.767)
2.158(2.188)
–0.025
–0.030
T2
1.932(1.957)
1.982(2.188)
–0.025
–0.206
T3
2.739(2.767)
2.186(2.174)
–0.028
0.012
T4
1.923(1.957)
1.853(1.971)
–0.037
–0.118
T5
2.839(2.767)
2.839(2.767)
0.072
0.072
T6
2.130(1.957)
2.129(1.957)
0.173
0.173
T7
2.128(2.174)
2.164(2.188)
–0.046
–0.024
T8
1.920(1.971)
2.135(2.188)
–0.051
–0.053
Note: Data in parentheses are the binding distance in the respective dimers.
23
Table 4 Change of C–H bond length (Δr, Å) and shift of C–H stretch frequency (Δv, cm-1) in the trimers at the MP2/aug-cc-pVTZ level Δr1
Δr2
Δv1
Δv2
T1
0.008
0.001
–150
–15
T2
0.018
0.002
–245
–21
T3
0.002
0.004
–18
–40
T4
0.005
0.024
–38
–324
T5
0.001
0.001
–8
–8
T6
0.001
0001
–9
–9
T7
0.004
0.007
–46
–99
T8
0.012
0.009
–170
–117
Note: The C–H bond is elongated by 0.002 Å, 0.009 Å, 0.001 Å, 0.003 Å, and 0.006(0.001) Å in F2CO···HCN, F2SiO···HCN, F2CO···NCH, F2SiO···NCH, and HCN···HCN dimers, respectively. The shift of C–H stretch frequency is –18 cm-1, –120 cm-1, –8 cm-1, –20 cm-1, and –85(–12) cm-1 in F2CO···HCN, F2SiO···HCN, F2CO···NCH, F2SiO···NCH, and HCN···HCN dimers, respectively.
24
Table 5 Energy components (E, kJ/mol) and interaction energy (Eint, kJ/mol) of tetrel bond (TB) and hydrogen bond (HB) in the triads at the MP2/aug-cc-pVTZ level Eele
Eex
Erep
Epol
Edisp
Eint
TBT1
–26.7(–22.8)
–29.2(–25.9)
52.4(46.4)
–5.8(–4.8)
–7.5(–7.6) –16.8
HBT1
–30.6(–27.7)
–24.2(–22.3)
44.3(40.6)
–8.4(–7.3)
–3.0(–3.1) –21.9
TBT2
–276.8(–240.7) –316.8(–292.8) 657.4(606.5) –224.3(–202.5) 12.0(6.9)
HBT2
–52.2(–27.7)
–38.5(–22.3)
73.4(40.6)
–19.4(–7.3)
–2.1(–3.1) –38.8
TBT5
–15.4(–22.8)
–21.5(–25.9)
37.9(46.4)
–3.3(–4.8)
–7.5(–7.6) –9.8
TBT6
–156.2(–240.7) –234.2(–292.8) 461.0(606.5) –109.3(–202.5) –10.5(6.9) –49.2
–148.6
HBT7(O···H) –19.6(–16.2)
–14.0(–12.2)
25.7(22.2)
–5.4(–4.1)
–0.3(–0.8) –13.6
HBT7(N···H) –31.7(–27.7)
–24.8(–22.3)
44.9(40.6)
–8.4(–7.3)
–2.6(–3.1) –22.3
HBT8(O···H) –50.0(–41.4)
–37.2(–32.4)
68.6(58.9)
–15.5(–12.1)
3.9(2.5)
HBT8(N···H) –36.7(–27.7)
–28.0(–22.3)
50.8(40.6)
–9.8(–7.3)
–1.9(–3.1) –25.5
Note: Data in parentheses are the energy components in the respective dimer.
25
–30.2
Table 6 Energy components (E, kJ/mol) of each molecule pair frozen in the trimers as well as their sum (Esum, kJ/mol) in the trimers, and energy components for the trimers as a whole (EABC, kJ/mol) at the MP2/aug-cc-pVTZ level T1
T2
T3
T4
T5
T6
T7
T8
EeleAB
–24.0
–254.4
–23.2
–258.7
–19.7
–164.1
–17.4
–44.6
EeleBC
–28.8
–37.2
–19.1
–28.1
3.2
6.3
–28.6
–29.7
EeleAC
–0.6
–4.3
–16.2
–58.4
–19.7
–164.1
–1.1
–2.7
–53.4
–295.9
–58.5
–345.2
–36.2
–321.9
–47.1
–77.0
–53.4
–295.9
–58.5
–345.2
–36.1
–321.9
–47.1
–77.0
AB
–28.0
–308.8
–28.6
–321.4
–20.9
–219.5
–14.6
–38.6
BC
–24.7
–44.7
–20.4
–43.9
0.0
–0.2
–24.2
–26.7
AC
0.0
0.0
–15.5
–71.9
–20.9
–219.5
0.0
0.0
sum
–52.7
–353.5
–64.4
–437.2
–41.8
–439.2
–38.8
–65.3
ABC
–52.7
–353.5
–64.4
–437.2
–41.7
–439.3
–38.8
–65.3
AB
50.4
643.8
51.2
670.5
37.1
435.7
26.7
70.6
BC
45.1
83.1
35.1
77.3
0.0
0.3
44.1
48.7
AC
0.0
0.0
28.1
133.1
37.1
435.7
0.0
0.0
sum
95.5
726.9
114.4
880.9
74.2
871.7
70.8
119.3
ABC
95.5
726.3
113.9
874.2
74.4
874.9
70.7
119.3
AB
–5.1
–216.8
–5.2
–225.9
–3.8
–116.5
–4.6
–14.1
EpolBC
–7.9
–13.4
–3.1
–5.6
–0.1
–0.3
–7.8
–8.5
AC
0.0
–0.1
–4.2
–21.7
–3.8
–116.5
0.0
–0.0
sum
–13.0
–230.3
–12.5
–253.2
–7.7
–233.3
–12.4
–22.6
ABC
–15.1
–253.5
–16.5
–288.1
–6.0
–217.0
–14.6
–27.4
EdispAB
–7.9
8.9
–8.6
8.7
–7.0
–7.8
–1.0
2.3
disp
–3.3
–5.2
–5.0
–9.9
–0.5
–1.2
–3.3
–3.5
0.0
0.8
–1.8
0.3
–7.0
–7.8
0.3
0.7
–11.2
4.5
–15.4
–0.9
–14.5
–16.8
–4.0
–0.5
EdispABC –14.5
6.8
–14.3
5.8
–14.5
–18.5
–3.6
0.4
E
ele sum
EeleABC E
ex
E
ex
E
ex
E
ex
E
ex
E
rep
E
rep
E
rep
E
rep
E
rep
E
pol
E
pol
E
pol
E
pol
E
BC
EdispAC E
disp
sum
26
Figure captions Fig. 1 MEP maps of F2XO (X = C and Si). Color ranges are: red, greater than 2.18; yellow, between 2.18 and 1.09; green, between 0 and 1.09; blue, less than 0. All are in eV. Fig. 2 Structures of trimers formed of one F2XO (X = C and Si) and two HCN. Fig. 3 Molecular graphs of trimers. Yellow and red dots indicate the locations of ring and bond critical points, respectively. Electron densities at the RCPs and BCPs are listed for the trimers and the respective dimers (in parentheses) with a unit of au.
27
Fig. 1
28
Fig. 2
29
Fig. 3
30
Graphical abstract
Highlights
There is positive cooperativity between the tetrel bond and hydrogen bond;
It is attributed to the polarization and dispersion energies in F2CO···NCH···NCH;
It arises from the polarization energy in F2SiO···NCH···NCH.
31
S2210-271X(14)00473-3 http://dx.doi.org/10.1016/j.comptc.2014.10.025 COMPTC 1649
To appear in:
Computational & Theoretical Chemistry
Received Date: Revised Date: Accepted Date:
11 September 2014 20 October 2014 20 October 2014
Please cite this article as: Q. Tang, Q. Li, Interplay between tetrel bonding and hydrogen bonding interactions in complexes involving F2XO (X = C and Si) and HCN, Computational & Theoretical Chemistry (2014), doi: http:// dx.doi.org/10.1016/j.comptc.2014.10.025
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Interplay between tetrel bonding and hydrogen bonding interactions in complexes involving F2XO (X = C and Si) and HCN Qingjie Tang,a Qingzhong Li*,b a
College of Material Science and Engineering, Henan Polytechnic University, Jiaozuo
454000, People’s Republic of China b
The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and
Chemical Engineering, Yantai University, Yantai 264005, People’s Republic of China Corresponding authors: Qingzhong Li The Laboratory of Theoretical and Computational Chemistry School of Chemistry and Chemical Engineering Yantai University Yantai 264005 People’s Republic of China Tel. (+086) 535 6902063 Fax. (+086) 535 6902063 E-mail:[email protected]
1
Abstract The complexes F2XO···NCH···NCH and F2XO···HCN···HCN (X = C and Si) have been studied by quantum chemical calculations at the MP2/aug-cc-pVTZ level. These four trimers show similar stability except F2SiO···HCN···HCN. The C–H···N hydrogen bond is enhanced by the presence of tetrel bond in F2XO···NCH···NCH. Interestingly, the stronger tetrel bond in F2SiO···NCH···NCH
exhibits
a
greater
enhancement
than
the
weaker
one
in
F2CO···NCH···NCH. The positive cooperativity is mainly attributed to the polarization and dispersion energies in the former but to the polarization energy in the latter. The tetrel bond and C–H···O hydrogen bond are also strengthened each other in HCN···F2XO···HCN. The tetrel bonds are weakened in HCN···F2XO···NCH, where the weakening is caused mainly by electrostatic energy for HCN···F2CO···NCH and by electrostatic and polarization energies for HCN···F2SiO···NCH. The C–H···N and C–H···O hydrogen bonds show a positive cooperative effect in F2XO···HCN···HCN due to the polarization interaction. Keywords: Cooperativity; Interplay; Tetrel bond; Hydrogen bond; F2XO
2
1. Introduction Hydrogen cyanide (HCN) is a common interstellar molecule [1], produced in the reactions of ammonia and methane [2], and is also of great importance in atmospheric chemistry as a result of its release by biomass burning [3], thus the structures and the vibrational spectra of small, hydrogen-bonded clusters of HCN in the gas phase have been the subject of extensive investigations, both experimentally and theoretically [4-6]. The polymers of HCN turned out to be of particular interest [6-12] due to the existence of cooperativity in these clusters, which has a significant contribution to the applications of hydrogen bonds in catalytic reactions, molecular materials, molecular recognition, and biological systems. It has proved that the HCN polymer in the gas phase exists in both a linear and a cyclic form [11] but in the solid state arranges in extended, perfectly linear chains [12]. Two different mechanisms for the cooperativity of C–H···N hydrogen bond in the clusters of HCN were proposed. King and Weinhold [9] thought that the cooperativity in the HCN polymer mainly arises from the donor–acceptor orbital interaction of LPN→BD*C-H in the C–H···N hydrogen bond, whereas Stone and Buckingham ascribed the cooperativity to induction effects [10]. Parallel to the just-mentioned polymers of HCN, numerous quantum chemical calculations have been performed on the mixed trimers involving HCN [13-20]. It was demonstrated that these mixed trimers display greater cooperativity than the HCN polymers do. The C–H···N hydrogen bond in HCN···HCN dimer is strengthened by the presence of another type of interaction in these mixed trimers. Furthermore, the stronger second interaction results in the larger increase of the strength of C–H···N hydrogen bond. For instance, at the MP2/6-311++G(2d,2p) level, the interaction energy varies from –4.42 kcal/mol in HCN···HCN dimer to –7.12 kcal/mol in HLi···HCN···HCN trimer, increased by 3
~61% in the presence of a strong lithium bond [15]. Very recently, a new intermolecular interaction, named tetrel bonding [21], was suggested to serve as a new possible molecular linker [21] and a preliminary stage of the SN2 reaction [22]. Its formation is attributed to a positive electrostatic potential on the group IV atomic surface [23]. On the other hand, the experimental evidence for its existence was given with charge density analysis for a large number of known crystal structures [24]. The importance of tetrel-bonding in cyclobutane rings was demonstrated by combining high level theoretical calculations and the Cambridge Structural Database (CSD) analysis, showing that tetrel-bonding interactions are quite common in nitro-substituted cubanes [25]. By means of the above methods, Bauzá and coworkers suggested that the strength of interaction between the sp3 C-atom in para-substituted ArCF3 and electron rich atoms is comparable to that of CH···πinteractions [26], and the strong complexes are formed between the derivatives of small cycloalkane rings containing four cyano groups in the 1,1’,2,2’ positions and electron rich entities [27]. It was theoretically demonstrated that the carbon atom in a methyl group is able to form a tetrel bond when it is adjoined with electron-withdrawing substituents [28], and also the weak attractive interactions were found between the two methyl groups in the complexes of XCH3···CH3BH2 (X = F, CN, NO2, HCO, and SOCH3) [29], where the former methyl group acts as a Lewis acid and the latter one is a Lewis base. Similar to the cases of other types of interactions, the Lewis base in tetrel bonds arise from radicals [30] and metal hydrides [31], besides lone pairs and anion. When calix[4]pyrrole was decorated with four SiF3 groups, its anion binding ability was enhanced due to the additional contribution of tetrel bonding, along with hydrogen bonding [32]. Hence, it is interesting to study the influence of tetrel bond on the strength of hydrogen bond. 4
In this paper, we studied the interplay between the tetrel bond and hydrogen bond in the complexes composed of one F2XO (X = C and Si) and two HCN molecules. Carbonyl fluoride (F2CO), a chamber-cleaning agent, can replace the traditional perfluorocarbons used in the plasma semiconductor industry [33], and has some effects on the photochemistry of the Earth’s upper atmosphere [34]. Hence, this study can provide some important information for the interactions between both interstellar molecules. Also interesting would be to unveil the enhancing mechanism of tetrel bond on the hydrogen bond. In addition, we paid our attention to the interplay between both tetrel bonds as well as that between both hydrogen bonds. 2. Theoretical methods All structures were optimized at the MP2/aug-cc-pVTZ level. Frequency calculations were performed at the same level to confirm that all structures are local minima on the potential energy surfaces. The interaction energy was calculated with supermolecular method and corrected for basis set superposition error (BSSE) using the counterpoise procedure of Boys and Bernardi [35]. All calculations were carried out via the Gaussian 09 program [36]. Molecular electrostatic potentials (MEPs) at the 0.001 electrons Bohr-3 isodensity surfaces of F2XO were calculated with the Wave Function Analysis-Surface Analysis Suite (WFA-SAS) program [37] at the MP2/aug-cc-pVTZ level. The wavefunction obtained at the MP2/aug-cc-pVTZ level was used to calculate the electron density at the critical point and plot the molecular graph using AIM2000 software [38]. The orbital interactions and natural population analysis (NPA) charges were calculated with natural bond orbital (NBO) theory [39] using NBO version 3.1 implemented in Gaussian 09. To gain an insight into the nature of the investigated intermolecular interactions, the energy decomposition analysis (EDA) was performed by the GAMESS program [40] with the localized molecular orbital EDA method 5
[41] at the MP2/aug-cc-pVTZ level. 3. Results and discussion It was known that HCN is able to act as both the Lewis acid with the H atom and the Lewis base with the N atom in the formation of hydrogen bonds. On the other hand, F2CO also has dual roles of both Lewis acid and base with the C and O atoms, respectively, characterized by the positive MEP on the C atom and the negative one on the O atom (Fig. 1). Consequently, both molecules have two interaction modes: a hydrogen bond between the H atom of HCN and the O atom of F2CO as well as a tetrel bond between the N atom of HCN and the C atom of F2CO. More importantly, both dimers also exhibit dual roles of Lewis acid and base. As a consequence, they can bind with the second HCN through a hydrogen bond or a tetrel bond. Namely, four types of mixed trimers involving one F2XO and two HCN molecules were obtained for F2CO and F2SiO, respectively. Their equilibrium geometries are shown in Fig. 2, marked as T1-T8 in turn for easy illustration. F2CO···NCH···NCH (T1) and F2SiO···NCH···NCH (T2) are stabilized by a tetrel bond and a C-H···N hydrogen bond, where the angle of O–X···N is a litter larger than that in the corresponding dimer. HCN···F2CO···HCN (T3) and HCN···F2SiO···HCN (T4) are cyclic structures involving with a tetrel bond, a C-H···O hydrogen bond, and a C···N interaction. The angle of O–X···N in T3 and T4 decreases due to the cyclic structure. The π-hole of F2XO, as a double Lewis acid, interacts with two HCN molecules in HCN···F2CO···NCH (T5) and HCN···F2SiO···NCH (T6), in which two same tetrel bonds are present. The angle of O–X···N becomes smaller in T5 and T6 relative to the respective dimers, and a prominent decrease is found in T6, indicating a weakening of the tetrel bond in both trimers. Two different types of hydrogen bonds (C–H···N and C–H···O) coexist in F2CO···HCN···HCN (T7) and F2SiO···HCN···HCN (T8). Four types of 6
structures are comparable each other for the F2CO trimers with the total interaction energy in the range of –23.2 ~ –37.5 kJ/mol (Table 1), while the three trimers of F2SiO (T2, T4, and T6) containing a tetrel bond are far more stable than T8 due to the strong tetrel bond. These trimers are more stable in the order of T5 < T7 < T1 < T3 and T8 < T6 < T2 < T4, showing a main dependence on the strength of tetrel bond. The most positive MEP on the X atom is 1.835 eV for carbon and 3.447 eV for silicon, resulting in the formation of a strong tetrel bond for F2SiO. Four types of systems are discussed separately in the following sections. 3.1. Influence of tetrel bond on hydrogen bond The interaction energy of C–H···N hydrogen bond is calculated to be –19.7 kJ/mol in HCN···HCN (Table 1), showing a similar strength with the O–H···O one in water dimer [41]. Here we want to strengthen the C–H···N hydrogen bond by the tetrel bond in T1 and T2. It is found from Table 1 that the interaction energy of C–H···N hydrogen bond becomes more negative with the presence of the tetrel bond. Furthermore, the stronger tetrel bond has a greater enhancing effect on the strength of C–H···N hydrogen bond in T2. It was demonstrated that the LPN→BD*C–H orbital interaction has a great contribution to the formation of C–H···N hydrogen bond in HCN···HCN, thus the strengthening of C–H···N hydrogen bond can be understood with the variation of this orbital interaction in the trimers (Table 2). The perturbation energy is 25.6 kJ/mol for the LPN→BD*C–H (LPN is the lone pair orbital on the N atom of HCN and BD*C–H denotes the C–H anti-bonding orbital of another HCN) orbital interaction in HCN···HCN, and it increases in T1 and T2 due to the presence of tetrel bond, particularly showing the larger increase in T2 with a stronger tetrel bond. The interaction energy of C–H···N hydrogen bond increases by 7.6% and 74.6% in T1 and T2, respectively, and in the latter trimer this percentage is larger than that in HLi···HCN···HCN, where the 7
interaction energy of lithium bond is –62.2 kJ/mol at the MP2/6-311++G(2d,2p) level [15], smaller than that of tetrel bond in T2. Accompanied with the enhancement of C–H···N hydrogen bond in T1 and T2, the H···N distance is shorter relative to the HCN dimer (Table 3). Especially, the shorting of H···N distance is prominent in T2 (–0.206 Å), consistent with the great increase of C–H···N interaction energy. Also, the AIM analysis (Fig. 3) shows the existence of a Si···N BCP in F2SiO···NCH, with an electron density almost four times larger than that associated with the C–H···N hydrogen bond in HCN···HCN, where the electron density has a larger increase in T2 than in T1. On the other hand, the hydrogen bond also has an enhancing effect on the tetrel bond. It is interesting to find that the stronger tetrel bond in F2SiO···NCH is greatly strengthened with the presence of C–H···N hydrogen bond in T2. The Si···N distance (1.957 Å) in F2SiO···NCH is much smaller than the sum of the corresponding ver der Waals radii (3.6 Å) and is close to the length of Si–N bond (1.75 Å), indicating that the Si···N interaction has a partially covalent nature with the big interaction energy of –95.5 kJ/mol. Consequently, there are two strong orbital interactions for the tetrel bond in F2SiO···NCH: LPN→RY*Si and LPN→BD*Si–F, where RY*Si is 1-center Rydberg orbital of Si and BD*Si–F is the anti-bonding orbital of Si–F bond. The presence of C–H···N hydrogen bond makes E(2)LPN→RY*Si in T2 increased larger than E(2)LPN→BD*C=O in T1, consistent with the change of interaction energy for the tetrel bond in both trimers. The change of X···N interaction energy is larger in T2 than that in T1, but the shortening of X···N distance is almost the same in both trimers. Consistently, the electron density at the X···N BCP is much higher in T2 than in T1. Consequently both hydrogen bond and tetrel bond are enhanced, indicating a positive 8
cooperativity. The interplay between hydrogen bond and tetrel bond can be estimated with cooperative energy (Ecoop) using the formula of Ecoop = ΔEtotal – (ΔEAB + ΔEBC + ΔEAC), where ΔEtotal is the total interaction energy of the trimer, ΔEAB and ΔEBC are the interaction energies of the optimized dimers, and ΔEAC is the interaction energy between A and C in the trimer geometry. It is obvious in Table 1 that Ecoop is negative in both trimers and T2 shows a more negative Ecoop, amounting to ~11% of the total interaction energy. As expected, the stronger hydrogen bond has a greater effect on the weaker tetrel bond in T1, while the stronger tetrel bond has a greater effect on the weaker hydrogen bond in T2. One can see from Fig. 3 that the sum of the variation of the electron density at the BCP from the dimer to the trimer is 0.0021 au and 0.0146 au in T1 and T2, respectively. Clearly, this sum exhibits a consistent change with the cooperative energy in the trimer (Table 1), which is -1.4 kJ/mol and -14.6 kJ/mol in T1 and T2, respectively. The cooperative effect between the hydrogen bond and tetrel bond can also be analyzed with the change of C–H bond length and the shift of C–H stretch frequency (Table 4). The elongation of the associated C–H bond in T1 and T2 is larger than the sum of that in F2XO···NCH and HCN···HCN. Correspondingly, the red shift of C–H stretch vibration in the trimer is greater than the sum of the red shift in the respective dimers. To unveil the enhancing mechanism between the hydrogen and tetrel bonds in T1 and T2, their interaction energies were decomposed into five components: electrostatic energy (Eele), exchange energy (Eex), repulsion energy (Erep), polarization energy (Epol), and dispersion energy (Edisp), and the results are collected in Table 5. The Erep term is very large for the tetrel bond in T2, due to the strong orbital overlap between F2SiO and HCN. As expected, the C–H···N hydrogen bond is mainly dominated by electrostatic energy. Similarly, the main 9
contribution to the stability of F2CO···NCH is from electrostatic energy. However, for the tetrel bond in F2SiO···NCH, the polarization contribution is comparable to the electrostatic one. The relatively large Epol suggests the orbitals undergo significant change in their shapes, characterized by the geometric deformation of F2SiO in the complex. This provides a further evidence for the nature of partially covalent interaction in F2SiO···NCH. All terms become larger in the trimers, among the three attractive terms Eele, Epol, and Edisp of the hydrogen bond in T1, the increase of the first term is larger than that of the second one, and the final term is almost unchanged, indicating that the enhancement of C–H···N hydrogen bond in T1 is mainly attributed to the increase of electrostatic energy. The positive charge (0.252e) on the H atom of the terminal HCN and the negative one (–0.408e) on the N atom of the middle HCN become larger in T1 than those in HCN–0.403e···0.247eHCN, thus the electrostatic interaction between two atoms are stronger. The reason for the enhancement of tetrel bond in T1 is similar to that of C–H···N hydrogen bond in T1. For the C–H···N hydrogen bond in T2, the increase of Epol is 12.1 kJ/mol, almost half the value of Eele, indicating that both electrostatic and polarization energies are responsible for its strengthening. Similarly, the enhancement of tetrel bond in T2 arises from the increase of both terms. In Table 6, we performed a many-body analysis for T1 and T2 with the LMOEDA method to explore the origin of the cooperativity between the hydrogen bond and tetrel bond. As expected, the sums of the pairwise electrostatic and exchange energies in the three dimers are, respectively, the same as the total electrostatic and exchange energies in the trimers. The sum of the pairwise dimer repulsion energies is the same as that in T1 and is 0.46 kJ/mol less repulsive than that for T2. So, the repulsion energy is roughly additive for the hydrogen and tetrel bonds in T1 and T2. The sums of the dimer polarization and dispersion energies are 1.9 10
and 3.3 kJ/mol less attractive than that for T1, respectively, thus the cooperative energy between the hydrogen and tetrel bonds in T1 results from the polarization and dispersion energies. The polarization energy is also not additive in T2: the sum of the dimer polarization energy is 23.2 kJ/mol less attractive than that in the trimer, which is more prominent than the dispersion energy. Clearly, the cooperative energy in T2 is mainly attributed to the polarization energy. 3.2. Many-body analysis for cyclic trimers The cyclic structures of T3 and T4 are confirmed by the presence of a ring critical point (RCP) (Fig. 3). This cyclic structure makes it difficult to compare the interaction energy of each type of interaction in the same way with that in T1 and T2. This problem can be overcome with many-body analysis, which had been described previously [42]. In T3, the interaction energy of tetrel bond is almost as much as that in the respective dimer, although the structure has a prominent change, while it has a prominent increase in T4. The interaction energy of C–H···O hydrogen bond has a small decrease in T3 but an obvious decrease in T4. However, it should be cautious about comparing the two-body energy in the trimer and the interaction energy in the respective dimer because the charge density of the dimer used for obtaining the two-body energy is different from that in the trimer. This can be verified by analyzing the change of the electron densities at the intermolecular BCPs in the trimers. Clearly, the electron densities at the X···N and O···H BCPs in the trimers are larger than those in the respective dimers. They are consistent with the change of interaction energy of tetrel bond but inconsistent with that of C–H···O hydrogen bond in T3 and T4. More importantly, the orbital interactions involving the C–H···O hydrogen bond and tetrel bond become stronger in the trimers (Table 2). As a result, the C–H···O hydrogen bond and tetrel bond are 11
strengthened each other in T3 and T4. The C···N interaction between the two HCN molecules in T3 and T4 can be evidenced with the presence of a C···N BCP, and its electron density indicates that this interaction is stronger in T4 than that in T3. However, the two-body energies between the two HCN molecules in the trimers are less negative in T4 than that in T3. This further shows the uncertainty of many-body analysis for the interaction energy. The change of electron density at the C···N BCP is consistent with the C···N distance in both trimers, while the change of two-body energy between the two HCN molecules is inconsistent with the C···N distance. The binding distances of the C–H···O hydrogen bond and tetrel bond become shorter in T3 and T4 than those in the respective dimers except for the H···O distance in T3. The possible reason is that the interaction direction is different in both T3 and F2CO···HCN, together with the weak interaction of C–H···O hydrogen bond. As expected, the three-body energy is negative in T3 and T4. Furthermore, due to the strong tetrel bond, the latter trimer shows a very large three-body energy value of –35.3 kJ/mol, amounting to 23.0% of the total interaction energy. The C–H bond is elongated and the corresponding bond stretch vibration exhibits a red shift for the tetrel bond of F2XO···NCH (X = C and Si), and both of them become larger in T3 and T4. The similar changes are also found for the hydrogen bond in F2XO···HCN (X = C and Si). In T3 and T4, the Eele and
Eex
terms are additive, while the Epol one is non-additive at all.
The Erep and Edisp terms are also non-additive, but their additivity is small than that of Epol. Thus the three-body energy in T3 and T4 mainly results from the polarization energy. 3.3. Negative cooperativity of tetrel bonds In T5 and T6, the interaction energies of tetrel bonds are smaller in magnitude than those in the respective dimers, therefore, the two tetrel bonds exhibit negative cooperativity with a 12
positive cooperative energy (Table 1). This is attributed to the role of double Lewis base for F2XO (X = C and Si) in T5 and T6. Furthermore, the interaction energy of tetrel bond decreases by 2.3 kJ/mol in T5, while it is decreased by ~50% in T6. Clearly, the stronger tetrel bond has a prominent weakening; even so, the tetrel bond is still much stronger than the C–H···N hydrogen bond. The weakening of tetrel bond is characterized with the weak orbital interactions, the small electron density at the X···N BCP, the long binding distance, the small elongation of C–H bond as well as the small red shift of the C–H stretch vibration. In T5, all energy components are decreased in magnitude, in which the decrease of electrostatic energy is the largest and the dispersion energy is almost not changed. This indicates that the weakening of tetrel bond in T5 is mainly attributed to the electrostatic energy. In T6, the decrease of electrostatic energy is comparable to that of polarization energy; both terms have a more prominent change than the dispersion energy, indicating that the electrostatic and polarization energies give rise to the weakening of tetrel bond in T6. It is found from Table 6 that the negative cooperative energy in T5 and T6 is caused by polarization energy. 3.4. Interplay between C–H···O and C–H···N hydrogen bonds In T7 and T8, the middle molecule HCN acts as the dual roles of Lewis acid in the C–H···O hydrogen bond and Lewis base in the C–H···N one, as a result, both types of hydrogen bonds are strengthened, characterized with the more negative interaction energy, the negative cooperative energy, the shorter binding distance, the larger elongation of C–H bond, and the bigger red shift of C–H stretch vibration. The interaction energy of C–H···O hydrogen bond has a greater increase than that of C–H···N one in T7, that is, the effect of C–H···N hydrogen bond on the C–H···O one is prominent than the effect of C–H···O hydrogen bond on 13
the C–H···N one. Interestingly, the similar conclusion is obtained in T8, although the C–H···O hydrogen bond is stronger than the C–H···N one in T8. For the two types of hydrogen bonds in T7 and T8, the increase of electrostatic energy is larger than that of polarization energy, indicating that the strengthening of both types of hydrogen bonds are mainly attributed to the electrostatic energy. However, the cooperative energy in both trimers is mainly from the polarization interaction. 4. Conclusions Mixed trimers composed of one F2XO (X = C and Si) and two HCN molecules have been investigated on the basis of ab initio results, and other tools such as the NBO method, AIM theory, as well as the LMOEDA approach. Four types of trimers were obtained for F2XO, in which the trimers of F2CO are comparable in energy, while those of F2SiO have a difference in energy. In F2XO···NCH···NCH, the tetrel bond and C–H···N hydrogen bond are strengthened each other. The interaction energy of C–H···N hydrogen bond is increased to be –34.4 kJ/mol in F2SiO···NCH···NCH by the stronger tetrel bond. Interestingly, the strong tetrel bond has a greater enhancement in F2SiO···NCH···NCH than that in F2CO···NCH···NCH. The strengthening of both types of interactions in F2CO···NCH···NCH is mainly attributed to the electrostatic energy, while that in F2SiO···NCH···NCH is from the electrostatic and polarization energies. The positive cooperative energy arises from the polarization and dispersion energies in F2CO···NCH···NCH but the polarization energy in F2SiO···NCH···NCH. The cyclic trimers of HCN···F2XO··· HCN are the most stable among all the trimers. Both tetrel bond and C–H···O hydrogen bond become stronger in the trimer relative to the respective dimer. The three-body energy is mainly attributed to the polarization energy. 14
The tetrel bond is weakened in HCN···F2XO··· NCH with a positive cooperative energy. The weakening of tetrel bond is mainly caused by the decrease of electrostatic and polarization energies, but only the polarization energy is responsible for the positive cooperative energy. Both C–H···O and C–H···N hydrogen bonds are enhanced in F2XO···HCN···HCN, where the enhancement of C–H···N hydrogen bond is smaller than that in F2XO···NCH···NCH. Surprisingly, the stronger C–H···O hydrogen bond has a greater strengthening than the weaker C–H···N hydrogen bond in F2XO···HCN···HCN. The enhancement of both types of hydrogen bonds is mainly attributed to the electrostatic energy, while the negative cooperative energy is mainly caused by the polarization energy. Acknowledgements This work was supported by the Outstanding Youth Natural Science Foundation of Shandong Province (JQ201006) and the Program for New Century Excellent Talents in University (NCET-2010-0923). References [1].
E. Herbst, E.F. van Dishoeck, Complex organic interstellar molecules, Annu. Rev. Astron. Astrophys. 47(2009) 427-480.
[2].
C.N. Matthews, R.D. Minard, Hydrogen cyanide polymers, comets and the origin of life, Faraday Discuss. 133(2006) 393-401.
[3].
Q.B. Li, D.J. Jacob, R.M. Yantosca, C.L. Heald, H.B. Singh, M. Koike, Y. Zhao, G.W. Sachse, D.G. Streets, A global three-dimensional model analysis of the atmospheric budgets of HCN and CH3CN: Constraints from aircraft and ground measurements, J. Geophys. Res: Atmos. 108(2003) 48/1-48/11. 15
[4].
R.D. Brown, P.D. Godfrey, D.A. Winkler, The microwave spectrum of HCN dimer, J. Mol. Spectrosc. 89 (1981) 352-355.
[5].
M. Sanchez, P.F. Provasi, G.A. Aucar, I. Alkorta, J. Elguero, Theoretical study of HCN and HNC neutral and charged clusters, J. Phys. Chem. B 109(2005) 18189-18194.
[6].
A. Karpfen, Linear and cyclic clusters of hydrogen cyanide and cyanoacetylene:
A
comparative ab Initio and density functional study on cooperative hydrogen bonding, J. Phys. Chem. 100(1996) 13474-13486. [7].
R. Rivelino, P. Chaudhuri, S. Canutoc, Quantifying multiple-body interaction terms in H-bonded HCN chains with many-body perturbation/coupled-cluster theories, J. Chem. Phys. 118 (2003) 10593-10601.
[8].
B.F. King, T.C. Farrar, F. Weinhold, Structure and spectroscopy of (HCN)n clusters: Cooperative and electronic delocalization effects in C–H···N hydrogen bonding, J. Chem. Phys. 103 (1995) 333-347.
[9].
B.F. King, T.C. Farrar, F. Weinhold, Quadrupole coupling constants in linear (HCN)n clusters: Theoretical and experimental evidence for cooperativity effects in C–H···N hydrogen bonding, J. Chem. Phys. 103 (1995) 348-352.
[10].
A.J. Stone, A.D. Buckingham, Comment on “Structure and spectroscopy of (HCN)n clusters: Cooperative and electronic delocalization effects in C–H⋯N hydrogen bonding” [J. Chem. Phys. 103, 333 (1995)], J. Chem. Phys. 107 (1997) 1030-1031.
[11].
R.S. Ruoff, T. Emilsson, T.D. Klots, C. Chuang, H.S. Gutowsky, Rotational spectrum and structure of the linear HCN trimer, J. Chem. Phys. 89(1988) 138-148.
[12].
W.J. Dulmage, W.N. Lipscomb, The crystal structures of hydrogen cyanide, HCN, Acta Crystallogr. 4 (1951) 330-334. 16
[13].
Q.Z. Li, X.L. An, F. Luan, W.Z. Li, B.A. Gong, J.B. Cheng, J.Z. Sun, Cooperativity between two types of hydrogen bond in H3C–HCN–HCN and H3C–HNC–HNC complexes, J. Chem. Phys. 128(2008) 154102.
[14].
Q.Z. Li, T. Hu, X.L. An, B.A. Gong, J.B. Cheng, Cooperativity between the dihydrogen bond and the N···HC hydrogen bond in LiH–(HCN)n complexes, ChemPhysChem 9(2008) 1942-1946.
[15].
Q.Z. Li, T. Hu, X.L. An, W.Z. Li, J.B. Cheng, B.A. Gong, J.Z. Sun, Theoretical study of the interplay between lithium bond and hydrogen bond in complexes involved with HLi and HCN, ChemPhysChem 10 (2009) 3310-3315.
[16].
R.S. Ruoff, T. Emilsson, C. Chuang, T.D. Klots, H.S. Gutowsky, Rotational spectra and structures of small clusters containing the HCN dimer: X–(HCN)2 with X=CO, N2, NH3, and H2O, J. Chem. Phys. 93(1990) 6363-6370.
[17].
M. Solimannejad, M. Malekani, Cooperative and diminutive interplay between the hydrogen bonding and halogen bonding in ternary complexes of HCCX (X = Cl, Br) with HCN and HNC, Comput. Theo. Chem. 998(2012) 34-38.
[18].
Sean A.C. McDowell, J.A. Joseph, Cooperative effects of noncovalent bonds to the Br atom of halogen-bonded H3N···BrZ and HCN···BrZ (Z = F, Br) complexes, J. Chem. Phys. 137(2012) 074310.
[19].
B.G. Oliveira, T.F. Costa, R.C.M.U. Araújo, A new theoretical analysis of the cooperative effect in T-shaped hydrogen complexes of CnHm···HCN···HW with n = 2, m = 2 or 4, and W = F or CN, J. Mol. Model. 19(2013) 3551-3568.
[20].
R. Rivelino, S. Canuto, Theoretical study of mixed hydrogen-bonded complexes: H2O···HCN···H2O and H2O···HCN···HCN···H2O, J. Phys. Chem. A 105(2001) 17
11260-11265. [21].
A. Bauza, T.J. Mooibroek, A. Frontera, Tetrel-bonding interaction: Rediscovered supramolecular force? Angew. Chem. Int. Ed. 52(2013) 12317-12321.
[22].
S.J. Grabowski, Tetrel bond–σ-hole bond as a preliminary stage of the SN2 reaction, Phys. Chem. Chem. Phys. 16(2014) 1824-1834.
[23].
J.S. Murray, P. Lane, P. Politzer, Expansion of the σ-hole concept, J. Mol. Model. 15(2009) 723-729.
[24].
S.P. Thomas, M.S. Pavan, T.N.G. Row, Experimental evidence for ‘carbon bonding’ in the solid state from charge density analysis, Chem. Commun. 50(2014) 49-51.
[25].
A. Bauzá, T.J. Mooibroek, A. Frontera, Influence of ring size on the strength of carbon bonding complexes between anions and perfluorocycloalkanes, Phys. Chem. Chem. Phys. 16(2014) 19192-19197.
[26].
A. Bauzá, T.J. Mooibroek, A. Frontera, Non-covalent sp3 carbon bonding with ArCF3 is analogous to CH–πinteractions, Chem. Commun. 50(2014) 12626-12629.
[27].
A. Bauzá, T.J. Mooibroek, A. Frontera, Small cycloalkane (CN)2C-C(CN)2 structures are highly directional non-covalent carbon-bond donors, Chem. Eur. J. 20(2014 10245-10248.
[28].
D. Mani, E. Arunan, The X–C···Y (X = O/F, Y = O/S/F/Cl/Br/N/P) ‘carbon bond’ and hydrophobic interactions, Phys. Chem. Chem. Phys. 15(2013) 14377-14383.
[29].
H.Y. Zhuo, L.X. Jiang, Q.Z. Li, W.Z. Li, J.B. Cheng, Is there an attractive interaction between two methyl groups? Chem. Phys. Lett. 608(2014) 90-94.
[30].
Q.Z. Li, X. Guo, X. Yang, W.Z. Li, J.B. Cheng, H.B. Li, A σ-hole interaction with radical species as electron donors: does single-electron tetrel bonding exist? Phys. Chem. Chem. 18
Phys. 16(2014) 11617-11625. [31].
Q.Z. Li, H.Y. Zhuo, H.B. Li, Z.B. Liu, W.Z. Li, J.B. Cheng, Tetrel−hydride interaction between XH3F (X = C, Si, Ge, Sn) and HM (M = Li, Na, BeH, MgH), J. Phys. Chem. A (2014) dx.doi.org/10.1021/jp503735u
[32].
A. Bauzá, R. Ramis, A. Frontera, Computational study of anion recognition based on tetrel and hydrogen bonding interaction by calix[4]pyrrole derivatives, Comput. Theor. Chem. 1038(2014) 67-70.
[33].
Y. Mitsui, Y. Ohira, T. Yonemura, T. Takaichi, A. Sekiya, T. Beppu, The possibility of carbonyl fluoride as a new CVD chamber cleaning gas, J. Electrochem. Soc. 151(2004) G297-G301.
[34].
C.P. Rinsland, R. Zander, L.R. Brown, C.B. Farmer, J.H. Park, R.H. Norton, J.M. III Russell, O.F. Raper, Detection of carbonyl fluoride in the stratosphere, Geophys. Res. Lett. 13(1986) 769-772.
[35].
S.F. Boys, F. Bernardi, The calculation of small molecular interactions by the difference of separate total energies. Some procedures with reduced errors, Mol. Phys. 19(1970) 553-558.
[36].
M.J. Frisch, et al., GAUSSIAN 09, Revision A.02, Gaussian Inc., Wallingford, CT, 2009.
[37].
F.A. Bulat, A. Toro-Labbé, T. Brinck, J.S. Murray, P. Politzer, Quantitative analysis of molecular surfaces: areas, volumes, electrostatic potentials and average local ionization energies, J. Mol. Model. 16(2010) 1679-1691.
[38].
R.F.W. Bader, AIM2000 Program, Version 2.0, McMaster University, Hamilton, Canada, 2000.
[39].
A.E. Reed, L.A. Curtiss, F. Weinhold, Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint, Chem. Rev. 88(1988) 899-926. 19
[40].
M.W. Schmidt, K.K. Baldridge, J.A. Boalz, S.T. Elbert, M.S. Gorden, J.H. Jensen, S. Koseki, N. Matsunaga, K.A. Nguyen, S.J. Su, T.L. Windus, M. Dupuis, J.A. Montgomery, General atomic and molecular electronic structure system, J. Comput. Chem. 14(1993) 1347-1363.
[41].
P.F. Su, H. Li, Energy Decomposition analysis of covalent bonds and intermolecular interactions, J. Chem. Phys. 131(2009) 014102.
[42].
X.X. Santheas, Ab initio studies of cyclic water clusters (H2O)n, n=l-6. II. Analysis of many-body interactions, J. Chem. Phys. 100(19944) 7523-7534.
20
Table 1 Total interaction energy (ΔEtotal), interaction energy between the molecular pairs (ΔE), and cooperative energy (Ecoop) in the trimers. All are in kJ/mol.a ΔEtotal
ΔEAB
ΔEBC
ΔEAC
Ecoop/Ethree-dody
T1
–35.9
–15.8(–14.3)
–21.2(–19.7)
–0.6
–1.4[3.9%]
T2
–133.3
–110.6(–95.5)
–34.4(–19.7)
–3.5
–14.6[11.0]
–37.5
–14.5(–14.3)
–12.0
–9.6(–10.8)
–1.4[3.7%]
T4b
–153.5
–123.5(–95.5)
–10.1
–18.6(–24.1)
–35.3[23.0%]
T5
–23.2
–12.0(–14.3)
2.7
–12.0(–14.3)
2.1[–8.6%]
T6
–114.6
–47.7(–95.5)
5.5
–47.7(–95.5)
70.9[–61.9%]
T7
–31.6
–11.9(–10.8)
–20.5(–19.7)
–0.9
–1.8[5.8%]
T8
–53.3
–29.6(–24.1)
–23.3(–19.7)
–1.9
–7.6[14.3%]
T3
a
b
Data in parentheses are the interaction energies in the respective dimers and those in
brackets are the percentage of Ecoop(Ethree-dody) to ΔEtotal. b
Two-body energy (ΔEAB, ΔEBC, and ΔEAC) and three-body energy (Ethree-dody) in T3 and T4 were
calculated with many-body analysis method.
21
Table 2 Second-order perturbation energy (E(2), kJ/mol) in the trimers at the HF/aug-cc-pVTZ level E(2)1
E(2)2
E(2)3
T1
12.9(8.2)
40.2(25.6)
---
T2
592.5(535.9)
64.3(25.6)
70.9(65.9)
T3
8.9(8.2)
10.3(14.0)
---
T4
638.4(535.9)
68.1(34.7)
60.0(65.9)
T5
6.6(8.2)
---
---
T6
310.3(535.9)
---
53.1(65.9)
T7
17.1(14.0)
28.8(25.6)
---
T8
42.9(34.7)
33.1(25.6)
---
Note: Data in parentheses are the perturbation energies in the respective dimers. E(2)1 corresponds to the orbital interaction of LPN→BD*C=O in T1, T3, T5, LPN→RY*Si in T2, T4, T6, and LPO→BD*C–H in T7, T8. E(2)2 corresponds to the orbital interaction of LPN→BD*C–H in T1, T2, T7, T8 and LPO→BD*C–H in T3, T4. E(2)3 corresponds to the LPN→BD*Si–F orbital interaction.
22
Table 3 Binding distances (R, Å) in the trimers and their differences (ΔR, Å) relative to the respective dimers at the MP2/aug-cc-pVTZ level R1
R2
ΔR1
ΔR2
T1
2.742(2.767)
2.158(2.188)
–0.025
–0.030
T2
1.932(1.957)
1.982(2.188)
–0.025
–0.206
T3
2.739(2.767)
2.186(2.174)
–0.028
0.012
T4
1.923(1.957)
1.853(1.971)
–0.037
–0.118
T5
2.839(2.767)
2.839(2.767)
0.072
0.072
T6
2.130(1.957)
2.129(1.957)
0.173
0.173
T7
2.128(2.174)
2.164(2.188)
–0.046
–0.024
T8
1.920(1.971)
2.135(2.188)
–0.051
–0.053
Note: Data in parentheses are the binding distance in the respective dimers.
23
Table 4 Change of C–H bond length (Δr, Å) and shift of C–H stretch frequency (Δv, cm-1) in the trimers at the MP2/aug-cc-pVTZ level Δr1
Δr2
Δv1
Δv2
T1
0.008
0.001
–150
–15
T2
0.018
0.002
–245
–21
T3
0.002
0.004
–18
–40
T4
0.005
0.024
–38
–324
T5
0.001
0.001
–8
–8
T6
0.001
0001
–9
–9
T7
0.004
0.007
–46
–99
T8
0.012
0.009
–170
–117
Note: The C–H bond is elongated by 0.002 Å, 0.009 Å, 0.001 Å, 0.003 Å, and 0.006(0.001) Å in F2CO···HCN, F2SiO···HCN, F2CO···NCH, F2SiO···NCH, and HCN···HCN dimers, respectively. The shift of C–H stretch frequency is –18 cm-1, –120 cm-1, –8 cm-1, –20 cm-1, and –85(–12) cm-1 in F2CO···HCN, F2SiO···HCN, F2CO···NCH, F2SiO···NCH, and HCN···HCN dimers, respectively.
24
Table 5 Energy components (E, kJ/mol) and interaction energy (Eint, kJ/mol) of tetrel bond (TB) and hydrogen bond (HB) in the triads at the MP2/aug-cc-pVTZ level Eele
Eex
Erep
Epol
Edisp
Eint
TBT1
–26.7(–22.8)
–29.2(–25.9)
52.4(46.4)
–5.8(–4.8)
–7.5(–7.6) –16.8
HBT1
–30.6(–27.7)
–24.2(–22.3)
44.3(40.6)
–8.4(–7.3)
–3.0(–3.1) –21.9
TBT2
–276.8(–240.7) –316.8(–292.8) 657.4(606.5) –224.3(–202.5) 12.0(6.9)
HBT2
–52.2(–27.7)
–38.5(–22.3)
73.4(40.6)
–19.4(–7.3)
–2.1(–3.1) –38.8
TBT5
–15.4(–22.8)
–21.5(–25.9)
37.9(46.4)
–3.3(–4.8)
–7.5(–7.6) –9.8
TBT6
–156.2(–240.7) –234.2(–292.8) 461.0(606.5) –109.3(–202.5) –10.5(6.9) –49.2
–148.6
HBT7(O···H) –19.6(–16.2)
–14.0(–12.2)
25.7(22.2)
–5.4(–4.1)
–0.3(–0.8) –13.6
HBT7(N···H) –31.7(–27.7)
–24.8(–22.3)
44.9(40.6)
–8.4(–7.3)
–2.6(–3.1) –22.3
HBT8(O···H) –50.0(–41.4)
–37.2(–32.4)
68.6(58.9)
–15.5(–12.1)
3.9(2.5)
HBT8(N···H) –36.7(–27.7)
–28.0(–22.3)
50.8(40.6)
–9.8(–7.3)
–1.9(–3.1) –25.5
Note: Data in parentheses are the energy components in the respective dimer.
25
–30.2
Table 6 Energy components (E, kJ/mol) of each molecule pair frozen in the trimers as well as their sum (Esum, kJ/mol) in the trimers, and energy components for the trimers as a whole (EABC, kJ/mol) at the MP2/aug-cc-pVTZ level T1
T2
T3
T4
T5
T6
T7
T8
EeleAB
–24.0
–254.4
–23.2
–258.7
–19.7
–164.1
–17.4
–44.6
EeleBC
–28.8
–37.2
–19.1
–28.1
3.2
6.3
–28.6
–29.7
EeleAC
–0.6
–4.3
–16.2
–58.4
–19.7
–164.1
–1.1
–2.7
–53.4
–295.9
–58.5
–345.2
–36.2
–321.9
–47.1
–77.0
–53.4
–295.9
–58.5
–345.2
–36.1
–321.9
–47.1
–77.0
AB
–28.0
–308.8
–28.6
–321.4
–20.9
–219.5
–14.6
–38.6
BC
–24.7
–44.7
–20.4
–43.9
0.0
–0.2
–24.2
–26.7
AC
0.0
0.0
–15.5
–71.9
–20.9
–219.5
0.0
0.0
sum
–52.7
–353.5
–64.4
–437.2
–41.8
–439.2
–38.8
–65.3
ABC
–52.7
–353.5
–64.4
–437.2
–41.7
–439.3
–38.8
–65.3
AB
50.4
643.8
51.2
670.5
37.1
435.7
26.7
70.6
BC
45.1
83.1
35.1
77.3
0.0
0.3
44.1
48.7
AC
0.0
0.0
28.1
133.1
37.1
435.7
0.0
0.0
sum
95.5
726.9
114.4
880.9
74.2
871.7
70.8
119.3
ABC
95.5
726.3
113.9
874.2
74.4
874.9
70.7
119.3
AB
–5.1
–216.8
–5.2
–225.9
–3.8
–116.5
–4.6
–14.1
EpolBC
–7.9
–13.4
–3.1
–5.6
–0.1
–0.3
–7.8
–8.5
AC
0.0
–0.1
–4.2
–21.7
–3.8
–116.5
0.0
–0.0
sum
–13.0
–230.3
–12.5
–253.2
–7.7
–233.3
–12.4
–22.6
ABC
–15.1
–253.5
–16.5
–288.1
–6.0
–217.0
–14.6
–27.4
EdispAB
–7.9
8.9
–8.6
8.7
–7.0
–7.8
–1.0
2.3
disp
–3.3
–5.2
–5.0
–9.9
–0.5
–1.2
–3.3
–3.5
0.0
0.8
–1.8
0.3
–7.0
–7.8
0.3
0.7
–11.2
4.5
–15.4
–0.9
–14.5
–16.8
–4.0
–0.5
EdispABC –14.5
6.8
–14.3
5.8
–14.5
–18.5
–3.6
0.4
E
ele sum
EeleABC E
ex
E
ex
E
ex
E
ex
E
ex
E
rep
E
rep
E
rep
E
rep
E
rep
E
pol
E
pol
E
pol
E
pol
E
BC
EdispAC E
disp
sum
26
Figure captions Fig. 1 MEP maps of F2XO (X = C and Si). Color ranges are: red, greater than 2.18; yellow, between 2.18 and 1.09; green, between 0 and 1.09; blue, less than 0. All are in eV. Fig. 2 Structures of trimers formed of one F2XO (X = C and Si) and two HCN. Fig. 3 Molecular graphs of trimers. Yellow and red dots indicate the locations of ring and bond critical points, respectively. Electron densities at the RCPs and BCPs are listed for the trimers and the respective dimers (in parentheses) with a unit of au.
27
Fig. 1
28
Fig. 2
29
Fig. 3
30
Graphical abstract
Highlights
There is positive cooperativity between the tetrel bond and hydrogen bond;
It is attributed to the polarization and dispersion energies in F2CO···NCH···NCH;
It arises from the polarization energy in F2SiO···NCH···NCH.
31