- Email: [email protected]
Synthesis and characterization of a new cyclohexaphosphate, (C6H7ClN)6P6O18·0.5(H2O)
Accepted Manuscript Synthesis and Characterization of a New Cyclohexaphosphate, (C6H7ClN)6P6O18.0.5(H2O) L. Khediri, E. Jeanneau, F. Lefebvre, M. Rzaigui, C. Ben Nasr PII:
S0022-2860(15)30308-2
DOI:
10.1016/j.molstruc.2015.10.007
Reference:
MOLSTR 21852
To appear in:
Journal of Molecular Structure
Received Date: 8 July 2015 Revised Date:
29 August 2015
Accepted Date: 13 October 2015
Please cite this article as: L. Khediri, E. Jeanneau, F. Lefebvre, M. Rzaigui, C. Ben Nasr, Synthesis and Characterization of a New Cyclohexaphosphate, (C6H7ClN)6P6O18.0.5(H2O), Journal of Molecular Structure (2015), doi: 10.1016/j.molstruc.2015.10.007. 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.
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Synthesis and Characterization of a New Cyclohexaphosphate, (C6H7ClN)6P6O18.0.5(H2O) L. Khediria, E. Jeanneaub, F. Lefebvrec, M. Rzaiguia, C. Ben Nasra Laboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna,
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a
Université de Carthage, Tunisie. b
Centre de Diffractométrie Henri Longchambon, Université Claude Bernard Lyon 1,
c
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Villeurbanne, France.
Laboratoire de Chimie Organométallique de Surface (LCOMS), Ecole Supérieure de Chimie
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Physique Electronique, 69622 Villeurbanne Cedex, France. Corresponding email: [email protected]
Abstract
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A new cyclohexaphosphate with the composition (C6H7ClN)6P6O18.0.5(H2O) has been synthesized at room temperature in the presence of 4-chloroaniline as organic template and investigated by various physicochemical techniques. Its unit cell is triclinic P-1 with
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parameters a = 9.0054(8), b = 10.1053(9), c = 16.4454(14)Å, α = 100.476(7), β = 93.485(7),
γ = 115.407(9) °, Z = 2 and V = 1313.0(2)Å3. The structure involves a network of inorganic
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ି parallel layers built up by P Oଵ଼ ring anions, NH3 groups and water molecules. Charge
balance is achieved by the protonated amine which is trapped in the interlayer space and interacts with the organic framework through strong hydrogen bonding. The 13C, 15N and 31P CP-MAS NMR spectra are in agreement with the X-ray structure. The vibrational absorption bands were identified by infrared spectroscopy. DFT calculations allowed the attribution of the NMR peaks. Keywords: Cyclohexaphosphate; X-ray diffraction; CP-MASNMR, DFT calculations.
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ACCEPTED MANUSCRIPT 1. Introduction Since the preparation and identification of Li6P6O18.6H2O [1], this salt has been used as starting material to prepare other cyclohexaphosphates. Organic phosphate materials have attracted considerable interest in recent years because of their structural diversity, stability and
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potential uses in various fields. Indeed, depending on the cation associated with the phosphate anion, such compounds could have interesting structures and properties potentially useful in nonlinear optics [2], heterogeneous catalysis [3], photochemical and photopysical processes
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[4], molecular sieves [5], and other areas that include electronic materials [6] and ceramic precursors [7].
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In the present work, the results of X-ray structure analysis of a new cyclohexaphosphate, (C6H7ClN)6P6O18.0.5(H2O), prepared by an ion-exchange resin, are discussed with respect to the geometry and flexibility of the cyclohexaphosphate ring system and H-bonding interactions between the inorganic acceptor, the solvent H2O, and the organic
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donor molecules. This hybrid material was also characterized by solid-state NMR and infrared
2. Experimental
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spectroscopy.
2.1. Chemical Preparation
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An acidic aqueous solution of H6P6O18 (10 mL, 3.5 mmol) is immediately neutralized by the stoichiometric amount of 4-chloro-aniline (21 mmol in 20 mL of ethanol) under continuous stirring until the solution exhibits a light yellowish aspect. Schematically the reaction can be written:
H6P6O18 + 6 (C6H6ClN)
H2O
(C6H7ClN)6P6O18. 0.5 H2O
The entire molecular structure of the obtained cyclohexaphosphate is:
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The resulting solution is then slowly evaporated at room temperature for several days
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to give large rectangular prisms of the title compound which are stable for months in normal conditions of temperature and humidity. The cyclohexaphosphoric acid used in this reaction was produced from an aqueous solution of Li6P6O18 [1] passed through an ion exchange resin (Amberlite IR120).
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2.2. X-Ray Single Crystal Structural Analysis
A Suitable crystal was selected and mounted on a Gemini kappa-geometry diffractometer (Agilent Technologies UK Ltd) equipped with an Atlas CCD detector and
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using the Mo radiation ( λ= 0.71073 Å).
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Intensities were collected at 100 K by means of the CrysalisPro software [8]. Reflection indexing, unit-cell parameters refinement, Lorentz-polarization correction, peak integration and background determination were carried out with the CrysalisPro software [8]. An analytical absorption correction was applied using the modeled faces of the crystal [9]. The resulting set of hkl was used for structure solution and refinement. The structure was solved by direct methods with SIR97 [10] and the least-square refinement on F2was achieved with the CRYSTALS software [11].
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ACCEPTED MANUSCRIPT All non-hydrogen atoms were refined anisotropically. The hydrogen atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C-H in the range 0.93-0.98 and N-H in the range 0.86-
positions were refined with riding constraints.
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0.89 Å) and Uiso(H) (in the range 1.2-1.5 times Ueq of the parent atom),after which the
The drawings were made with Diamond [12]. The details of data collection,
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2.3. NMR and IR measurements
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refinement and crystallographic data are summarized in Table 1.
The NMR spectra were recorded on a solid-state high-resolution Bruker DSX-300 spectrometer operating at 75.49 MHz for
13
C, 30.30 MHz for
15
N and 121.51 MHz for
31
P
with a classical 4 mm probehead allowing spinning rates up to 10 kHz. 13C, 15N and 31P NMR
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chemical shifts are given relative to tetramethylsilane, neat nitromethane and 85 wt. % phosphoric acid, respectively (precision 0.5 ppm). For 13C and 15N, the spectra were recorded by use of cross polarization (CP) from protons (contact time 2ms). Before recording the
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spectrum it was checked that there was a sufficient delay between the scans allowing a full relaxation of the protons. For 31P, the isotropic chemical shift values (δiso) of the three NMR
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components were determined from the position of the side band that did not change in the spectra taken with different spinning rates. The analysis of the31P MAS-NMR spectrum was carried out by using the Bruker program WINFIT [13]. The intensities of the side bands were computed by the method of Herzfeld and Berger [14]. Chemical shift anisotropy (∆δCS) and the asymmetric parameter (η) of NMR components were then determined (Table 6). The IR spectra were recorded in the range 4000-400 cm-1 with a ‘‘Perkin–Elmer FTIR’’
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3. Results and Discussion
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3.1. Structure description
The X-ray diffraction study of the title compound leads to the determination of its chemical formula. Configurations of the different organic and inorganic speciesincluding the
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atom’s labelling and their vibrational ellipsoids at 50% probability are depicted in the Fig. 1.
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The atomic arrangement can be described by layers of inorganic entities, made up from P6O18 rings, NH3 groups and water molecules, developed in the (a, b) planes. The complete atomic arrangement, projected along the a direction, is shown in Fig. 2, whereas Fig. 3 exhibits how the different components of a layer are linked through H-bonds involving the hydrogen atoms of the –NH3 entities, water molecules and some external oxygen atoms of the P6O18 groups.
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The N(O)...O(E,W) distances vary between 2.204(6) and 2.967(6) Å and H...O(E,W)
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distances range between 1.45 and 2.17 Å (Table 4).
Inside such a layer, the phosphoric ring is formed by six corner-sharing PO4tetrahedra.
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ି The P Oଵ଼ anion is located around the inversion center (1/2, 1/2, 0) and is built up by three
independent PO4tetrahedra. Examination of the main geometrical features (P-O and P-P distances as well as P-O-P or O-P-O angles) (Table 2) shows that they correspond to what iscommonly observed in cyclic or linear condensed phosphoric anions. The cyclohexaphosphate ring is distorted, the P-P-P angles vary between 95.84(4) and 117.37(4)°. These angles, with an average of 104.47(4)°, show very large deviations from the ideal value of 120°, compared to the other types of phosphoric rings such as cyclotri- and cyclotetraphosphates, in which the P-P-P angles never depart significantly from their ideal 5
ACCEPTED MANUSCRIPT values of 60 ± 2° for cyclotriphosphates and 90 ± 4° for cyclotetraphosphates. Cyclotri- and cyclotetraphosphates are much less flexible than the described cyclohexaphosphates in which the “ideal” configuration has a certain void in the center. According to the flexibility of the PO4 tetrahedra, an equilibrium between repulsion of the oxygen atoms and the attraction to
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hydrogen bonding donor groups of the organic parts and the water molecules can destroy the ideal geometry of the six P-atoms. This can also be demonstrated by comparing the distances of the symmetry related P-atoms (P1-P1i = 5.621, P2-P2i = 4.721, and P3-P3i = 5.838(Å);
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(i): −x+1, −y+1, −z) which exhibit a deviation varying between 0.217 and 1.117 Å. The presence of strong hydrogen bonding such as O(N)-H...O (1.45, 1.75, 1.80 and 1.81 Å) (Table
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4) in the studied compound is certainly one of the most important distortion factors. Nevertheless, this distortion is comparatively less important than that observed in Cs6P6O18.6H2O, which shows the greatest distortion for the same angles ranging between 93.2 and 145.5° [15].
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The calculated average values of the distortion indices [16] corresponding to the different angles and distances in the PO4 tetrahedra, DI(PO) = 0.038, DI(OPO) = 0.040 and DI(OO) = 0.014 show an above distortion of the O-O distances compared to P-O ones. The
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PO4 tetrahedron is then described by regular oxygen atoms arrangement with the phosphorus atom slightly shifted from the center of gravity (δP1 = 0.151, δP2 = 0.128, δP3 = 0.141)
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In this structure, three independent [C6H7ClN]+ cationic groups coexist, compensating
ି the negative charge of the P Oଵ଼ ring anions and performing the electric neutrality of the total
complex. These organic groups are anchored onto successive layersby establishing weak CH...O(E,W) interactions with the C...O(E,W) distances of 2.952(6)-3.254(6) Å (Table 4). All these hydrogen bonds, van der Waals, and electrostatic interactions between organic cations and cyclohexaphosphate anions increase the structure stability in the title compound.
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ACCEPTED MANUSCRIPT The mean value of the C-C bond lengths [1.382 Å] (Table 3) which is between a single
bond
and
a
double
bond,
agrees
with
that
in
4-chloroanilinium
dihydrogenmonoarsenate [1.377Å] [17]. Furthermore, the mean value of the C-N distances [1.457 Å], clearly indicates a single bond. The bond lengths of C4-Cl1, C10-Cl2 and C16-Cl3
cyclohexaphosphate dehydrate [18]. A
comparison
of
the
title
compound
(I)
to
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[1.736(4), 1.740(4) and 1.737(5)] also agree with the data of 3-chloro-2-methylanilinium
Hexakis(p-ethoxyanilinium
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cyclohexaphosphate octahydrate (II) [19] shows that they differ essentially by the nature of the substituents at the para-position on the phenyl ring. However, some similarities can be
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observed between these structures. In each of the two cases, the structure has a layer organization, which contains the P6O18 rings NH3, groups and water molecules in the same P1 space group of the triclinic system. In these structures, the anionic networks contain centrosymmetric cyclohexaphophates entities where each P6O18 is acceptor of hydrogen bond
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and adopts chair conformation. In addition, the geometrical parameters of anilinium groups have comparable values in the two compounds and are similar to those observed in other complexes containing anilinium cation. Similarly as in (I), the asymmetric unit of (II) consists
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of the organic cations water molecules and the cyclohexaphosphate anion, joined by medium and strong N–H…O hydrogen bonds. As shown in the schematic diagrams, the organic cation
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has different substituents which are placed in opposite ends of the aromatic ring. The nature of different substituents affects weakly the strength of the intermolecular hydrogen bonds and the atomic arrangement.
Recently a similar structure for the Tetrakis(2-amino-5-chloropyridinium) dihydrogen cyclohexaphosphate (C5H6ClN2)H2P6O18 (III) has been published [20]. This latter and the title compound present several differences which affect the atomic arrangement, hydrogen bond network and the unit-cell parameters. Thus, the structure (III) contains the dihydrogen 7
ACCEPTED MANUSCRIPT cyclohexaphosphate anions [H2P6O18]4- interconnected by strong O–H…O hydrogen bonds which form infinite ribbons extending along the a-axis direction. These ribbons are linked to the organic cations via N-H…O and C-H…O hydrogen bonds into a three-dimensional
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network. In spite of these differences, the anionic ring shows its standard geometry. 2.2. NMR spectroscopy The
13
C CP–MAS NMR spectrum of (C6H7ClN)6P6O18.0.5(H2O) is shown on Fig. 4.
Nine peaks with different intensities and linewidhs are resolved, which correspond to the
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can be attributed to the overlapping resonance signals.
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eighteen crystallographically independent carbon atoms. The failure to resolve all the peaks
The 15N CP-MAS NMR spectrum of the title compound (Fig. 5) is in good agreement with the X-ray structure. Indeed, it exhibits three well-defined resonances at -353.2, -354.0 and -356.2 ppm corresponding to the three crystallographically independent nitrogen atoms,
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in agreement with three organic cations in the unit cell.
Cyclohexaphosphates are formed by tetrahedra sharing two corners with neighboring tetrahedra (Q2units in Lipmaa’snotation) [21], and two other ones interacting with cations. 31
P isotropic chemical shift value δiso are higher thanthose
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According to this, the
corresponding to monophosphates (between -10 and +5 ppm) or diphosphates (between -10
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and -20 ppm) of alkali and alkaline-earth cations [22-26]. Chemical shift valuesof cyclohexaphosphates are similar to those obtained previously in polyphosphates, indicating that δiso values are mainly defined by tetrahedral condensation of phosphates. The solid state
31
P spectrum of the sample is formed by three components with their
corresponding satellite spinning bands spaced at equal intervals (Fig. 6). As the chemical environments of all P-atoms are similar in the cyclohexaphosphate, resolved components must correspond to different crystallographically sites occupied by P-atoms. On the other
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ACCEPTED MANUSCRIPT hand, distortions of the polyhedra are responsible for the observed chemical shift anisotropies and for the detection of the spinning side band patterns covering important regions of the 31PNMR spectra. Spectral regions occupied by these bands are proportional to tetrahedral distortions. Hence, NMR patterns could be used to minor distortions. To analyze this point,
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experimental envelopes were deconvoluted, determining for each component δiso, ∆δCS and η (Table 6).
The cyclohexaphosphate group has a center of gravity that coincides with a
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cristallographic center of symmetry. This is deduced from the NMR analysis of the
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asymmetric parameter η, which average value is 0.38 (Table 6), indicating that the local symmetry of the tetrahedra is lower. This agrees with the results obtained with other cyclohexaphosphates [27].
Theoretical calculations were undertaken in order to assign the NMR resonances to the 31
P-atoms of the unit cell. Two different
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different crystallographically inequivalent
calculations were made on the cyclohexaphosphate anion and in all cases the theoretical chemical shifts were subtracted from those of the reference (phosphoric acid) calculated at the
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same level of theory:
(1) Calculation of the NMR chemical shifts (B3LYP/6-311++G** method) by using the
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positions of atoms obtained by X-ray diffraction; (2) Otimization of the oxygen atoms only and calculation of NMR chemical shifts. The results are listed on Tables 7 and 8. Clearly, there is a very good agreement
between the experimental and the theoretical values, allowing unambiguously the attribution of the different NMR signals, even if the calculated values for the isotropic chemical shifts are far away from the experimental ones. This behavior is probably related to a bad choice of the molecule for the calculations of the reference (one isolated PO43- tetrahedron while experimentally the liquid used is 85 wt. % H3PO4). 9
ACCEPTED MANUSCRIPT 3.3. IR spectroscopy To gain information on the crystal structure, we have carried out a vibrational study using
infrared
absorption.
The
infrared
spectrum
of
the
title
compound
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(C6H7ClN)6P6O18.0.5(H2O) recorded at room temperature is shown in Fig. 7. Based on some studies carried out for previous works and reported on similar cyclohexaphosphates compounds [28], we propose an attempt of assignment of the observed bands. In the highfrequency region, between 3600 and 2300 cm-1, the observed bands correspond to the
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stretching vibrations of the N-H, C-H and O-H groups [29]. Hydrogen bonding interactions
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are able to affect the frequency as well as the intensity and width of these vibrations. The two bands at 1639and 1592 cm-1 correspond to δ(O-H) and δ(N-H) deformation vibrations, respectively. The two bands at 1558 and 1500 cm-1 are assigned to ν(C=C)Ar stretching vibrations [30, 31]. The strong bands observed in the ranges 1260-1220, 1110-1070, 1015900, and 830-700 cm-1 can be assigned to stretching vibrations νas(OPO), νs(OPO), νas(POP),
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and νs(POP), respectively [32, 33]. We note that the supplementary frequency in the νs(OPO) domain can be assigned to the stretching ν(C-C) and ν(C-N), δ(C-H) and γ(C-H) vibrations
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P6O18 ring anion.
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[34]. Frequencies below 660 cm-1 can be assigned to bending, translation and rotation of the
Conclusion
A new cyclohexaphosphate, (C6H7ClN)6P6O18.0.5(H2O), has been prepared at room
temperature and characterized by physicochemical methods. In the atomic arrangement, the cyclohexaphosphate anions are linked to the NH3 groups and water molecules forming inorganic layers parallel to the (a, b) plane. The organic cations are anchored between these layers and connect them via hydrogen bonds to form an infinite three-dimensional network. The structure cohesion is ensured by N-H…O, C-H…O and O-H…O hydrogen bonds. The 10
ACCEPTED MANUSCRIPT number of 13C 15N and 31PCP–MAS NMR lines is in full agreement with the crystallographic data. DFT calculations allow the attribution of the experimental
31
P NMR lines. The
vibrational absorption bands were identified by infrared spectroscopy. Supplementary data
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Crystallographic data for the structural analysis have been deposited at the Cambridge Crystallographic Data Centre, CCDC No 1409242. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the CCDC, 12 Union Road,
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Cambridge, CB2 1EZ, UK: fax: (+44) 01223-336-033; e-mail: [email protected].
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ACCEPTED MANUSCRIPT Figure captions Fig. 1 ORTEP view of (C6H7ClN)6P6O18.0.5(H2O)with the atom-labeling. Displacement ellipsoids are drawn at 50% probability. H-atoms are represented withsmall arbitrary radii. Symmetry
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code: (i) −x+1, −y+1, −z. Fig. 2
Fig. 3
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Three-dimensional network of (C6H7ClN)6P6O18.0.5(H2O), projected along the a-axis.
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Projection along the c-axis, of an inorganiclayer in (C6H7ClN)6P6O18.0.5(H2O). Organic cations are reduced to NH3 groups for figure clarity. Fig. 4
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Simulated and experimental 13C CP-MAS NMR spectra of (C6H7ClN)6P6O18.0.5(H2O). Fig. 5
N CP-MAS NMR spectrum of (C6H7ClN)6P6O18.0.5(H2O).
31
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Fig. 6
P MAS NMR spectrum of (C6H7ClN)6P6O18.0.5(H2O). Fig.7
Infrared absorption spectrum of(C6H7ClN)6P6O18.0.5(H2O).
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Fig. 7
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ACCEPTED MANUSCRIPT Table 1.Crystal data and experimental parameters used for the intensity data collection. Procedure and final results of the structure determination. C36H43Cl6N6O18.5P6
Formula weight [g mol-1]
627.16
Crystal colour, habit
yellow, block
Crystal temperature [K]
100
3
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Empirical formula
0.304 × 0.506 × 0.663
Radiation, wavelength [Å]
MoKα, 0.71073
Crystal system
triclinic
Space group
P-1
Unit-cell dimensions:
9.0054(8), 10.1053(9),16.4454(14)
Reflections for cell determination
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a, b, c [Å]
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Crystal size [mm ]
θrange for cell determination [°]
8-10
Absorption coefficient µ [mm-1]
0.586
F(000)
641
α, β, γ [°]
100.476(7), 93.485(7), 115.407(9)
Volume [Å3]
1313.0(2)
Z
2
Density calc.[g cm-3]
1.586
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25
Limiting indices
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θ-Range for data collection [°]
3.011 to 29.538 -12 ≤ h ≤ 12, -13 ≤ k ≤ 13, -19 ≤ l ≤ 22
Reflections collected/unique
23373/6523 (Rint = 0.041) Full-matrix least-squares on F2
Data, restrains, parameters (I > 2 σ)
5235, 0, 335
Goodness-of-fit on F2
0.9805
R indices (all data, on F2)
R= 0.0758, wR = 0.1125
∆ρ(min, max)[e Å-3]
-1.62 and1.50
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Refinement method
22
ACCEPTED MANUSCRIPT Table 2. Main interatomic distances (Å) and bond angles (°) in the title compound. P(1)O4 tetrahedron O1
O2
O3
O4
O1
1.483(3)
2.599(2)
2.486(2)
2.474(2)
O2
122.20(18)
1.486(3)
2.469(2)
2.562(2)
O3
107.09(13)
105.88(17)
1.606(2)
2.495(2)
O4
106.23(17)
111.72(16)
101.78(13)
1.609(3)
O3
O5
O6
O7
O3
1.590(2)
2.541(2)
2.518(2)
2.450(2)
O5
110.88(12)
1.494(2)
2.555(2)
2.447(2)
O6
109.88(13)
118.17(13)
1.484(2)
2.530(2)
O7
100.77(11)
104.94(12)
110.70(12)
1.590(2)
O7
O8
O9
2.464(2)
2.497(2)
2.509(2)
1.611(2)
2.519(2)
2.497(2)
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P2
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P(2)O4 tetrahedron
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P1
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P(3)O4 tetrahedron O4
O4
1.595(2)
O7
100.42(12)
O8
108.18(16)
108.78(12)
1.486(3)
2.549(2)
O9
110.05(14)
108.36(13)
119.38(14)
1.467(2)
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P3
P1-P2 2.861(10)
P2-O3-P1
127.02(14)
P1-P2-P3
117.37(4)
P2-P3 2.900(8)
P1-O4-P3
132.74(17)
P2-P3-P1
95.84(4)
P3-P1 2.935(22)
P3-O7-P2
129.83(14)
P3-P1-P2
100.20(4)
23
ACCEPTED MANUSCRIPT Table 3.Selected bond lengths (Å) and bond angles (°) in the organic groups of (C6H7ClN)6P6O18. 0.5(H2O)
120.3(3) 118.2(3) 121.4(3) 119.6(3) 118.7(4) 119.7(3) 118.6(3) 121.6(3) 119.4(3) 119.3(3)
N2—C7—C8 N2—C7—C12 C8—C7—C12 C7—C8—C9 C8—C9—C10 C9—C10—C11 C9—C10—Cl2 C11—C10—Cl2 C10—C11—C12 C11—C12—C7
118.9(3) 119.8(3) 121.3(3) 119.3(3) 119.3(4) 121.5(4) 119.6(3) 118.9(3) 119.2(3) 119.4(3)
N3—C13—C14 N3—C13—C18 C14—C13—C18 C13—C14—C15 C14—C15—C16 C15—C16—C17 C15—C16—Cl3 C17—C16—Cl3 C16—C17—C18 C17—C18—C13
118.1(3) 119.8(3) 122.1(4) 119.7(3) 117.8(4) 122.5(4) 117.8(4) 119.8(4) 119.3(4) 118.7(4)
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EP
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[C6H7ClN(2)]+group N2—C7 1.459(4) C7—C8 1.377(5) C7—C12 1.387(4) C8—C9 1.383(5) C9—C10 1.384(5) C10—C11 1.376(5) C11—C12 1.383(5) Cl2—C10 1.740(4)
[C6H7ClN(3)]+group N3—C13 1.454(4) C13—C14 1.385(5) C13—C18 1.371(5) C14—C15 1.391(5) C15—C16 1.382(6) C16—C17 1.380(8) C17—C18 1.389(7) Cl3—C16 1.737(5)
N1—C1—C2 N1—C1—C6 C2—C1—C6 C1—C2—C3 C2—C3—C4 C3—C4—Cl1 C5—C4—Cl1 C3—C4—C5 C4—C5—C6 C5—C6—C1
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[C6H7ClN(1)]+group N1—C1 1.458(4) C1—C2 1.372(5) C1—C6 1.381(4) C2—C3 1.389(5) C3—C4 1.386(5) C4—C5 1.372(5) C5—C6 1.382(5) Cl1—C4 1.736(4)
24
ACCEPTED MANUSCRIPT Table 4.Hydrogen-bond geometry (Å, º). D—H
H···A
D···A
D—H···A
N2—H9···O6
0.89
1.89
2.733 (6)
158
N2—H10···O8ii
0.91
1.86
2.734 (6)
162 (1)
N2—H8···O1iii
0.91
1.75
2.647 (6)
172 (1)
N1—H3···O9
0.89
1.80
2.689 (6)
175
N1—H2···O6ii
0.89
2.02
2.823 (6)
149 (1)
iv
0.90
1.88
2.772 (6)
169 (1)
C6—H4···O6ii
0.93
2.54
3.254 (6)
134 (1)
N3—H16···O5v
0.90
1.81
2.697 (6)
167 (1)
N3—H17···O8ii
0.90
1.87
N3—H15···O2ii
0.90
2.15
0.90
2.17
0.94 0.82
C18—H18···O10 O10—H23···O2
2.735 (6)
161 (1)
2.925 (6)
145 (1)
2.967 (6)
149 (1)
2.13
2.952 (6)
145 (1)
1.45
2.204 (6)
151 (1)
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N3—H15···O10v
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N1—H1···O5
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D—H···A
v
i
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y−1, z.
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Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y, −z; (iii) −x+1, −y, −z; (iv) x−1, y, z; (v) x−1,
25
ACCEPTED MANUSCRIPT Table 5.Interatomic PO distances (Å), OPO angles (degrees) tetrahedral distortion indexes ID(PO), ID(OPO) and ID(OO) of the cyclohexaphosphate(C6H7ClN)6P6O18. 0.5(H2O).
P-Om
ID (P-O)
(O-P-O)m
ID (OPO)
P1(O4)
1.546
0.040
109.15
0.048
2.514
0.018
P2(O4)
1.540
0.033
109.22
0.039
2.507
0.015
P3(O4)
1.540
0.041
109.20
0.034
2.506
0.008
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O-Om
ID (O-O)
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Tetrahedron
ACCEPTED MANUSCRIPT Table 6.Isotropic chemical shift (δiso), Linewidh, Amplitude, Chemical shift anisotropy (∆δCS) and assymetry (η) parameters of 31P MAS-NMR components in the title cyclohexaphosphate. Linewidh [ppm]
Amplitude
∆δCS [ppm]
η
-16.47
0.54
1625.78
-123.24
0.49
-23.16
0.79
508.20
-155.18
0.35
-26.62
0.67
653.05
-143.40
0.30
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δiso [ppm]
27
ACCEPTED MANUSCRIPT Table 7. Comparison of calculated and experimental chemical shift values of the phosphorus atoms in the title cyclohexaphostate. Atoms
X-Rays
Optimisation of
Experimental
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oxygens P1
-81.7
-61.3
-23.2
P2
-78.8
-64.9
P3
-84.9
-61.5
P4
-81.7
-61.3
-23.2
P5
-78.8
-64.9
-16.5
P6
-84.9
-16.5
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-26.6
AC C
EP
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-61.5
28
-26.6
ACCEPTED MANUSCRIPT Table 8.Comparison of calculated and experimental Chemical shift anisotropy (∆δCS) and assymetry (η) parameters of 31P MAS-NMR components in the title cyclohexaphosphate. Calculated
Experimental η
∆δ
η
P1
155.1
0.44
-155.18
P2
144.1
0.47
-123.24
P3
161.5
0.36
-143.40
P4
155.2
0.44
P5
144.0
0.47
P6
161.4
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∆δ
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Atoms
29
0.49 0.30
-155.18
0.35
-123.24
0.49
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EP
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0.36
0.35
-143.40
0.30
ACCEPTED MANUSCRIPT
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• •
A new cyclohexaphosphate (C6H7ClN)6P6O18.0.5(H2O) was synthesized. ି The structure involves a network of inorganic parallel layers built up by P Oଵ଼ ring anions, NH3 groups and water molecules. The crystal packing is also stabilized hydrogen bonds. The 13C, 15N and 31P CP-MAS NMR spectra are in agreement with the X-ray structure.
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• •
S0022-2860(15)30308-2
DOI:
10.1016/j.molstruc.2015.10.007
Reference:
MOLSTR 21852
To appear in:
Journal of Molecular Structure
Received Date: 8 July 2015 Revised Date:
29 August 2015
Accepted Date: 13 October 2015
Please cite this article as: L. Khediri, E. Jeanneau, F. Lefebvre, M. Rzaigui, C. Ben Nasr, Synthesis and Characterization of a New Cyclohexaphosphate, (C6H7ClN)6P6O18.0.5(H2O), Journal of Molecular Structure (2015), doi: 10.1016/j.molstruc.2015.10.007. 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.
ACCEPTED MANUSCRIPT
Synthesis and Characterization of a New Cyclohexaphosphate, (C6H7ClN)6P6O18.0.5(H2O) L. Khediria, E. Jeanneaub, F. Lefebvrec, M. Rzaiguia, C. Ben Nasra Laboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna,
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a
Université de Carthage, Tunisie. b
Centre de Diffractométrie Henri Longchambon, Université Claude Bernard Lyon 1,
c
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Villeurbanne, France.
Laboratoire de Chimie Organométallique de Surface (LCOMS), Ecole Supérieure de Chimie
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Physique Electronique, 69622 Villeurbanne Cedex, France. Corresponding email: [email protected]
Abstract
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A new cyclohexaphosphate with the composition (C6H7ClN)6P6O18.0.5(H2O) has been synthesized at room temperature in the presence of 4-chloroaniline as organic template and investigated by various physicochemical techniques. Its unit cell is triclinic P-1 with
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parameters a = 9.0054(8), b = 10.1053(9), c = 16.4454(14)Å, α = 100.476(7), β = 93.485(7),
γ = 115.407(9) °, Z = 2 and V = 1313.0(2)Å3. The structure involves a network of inorganic
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ି parallel layers built up by P Oଵ଼ ring anions, NH3 groups and water molecules. Charge
balance is achieved by the protonated amine which is trapped in the interlayer space and interacts with the organic framework through strong hydrogen bonding. The 13C, 15N and 31P CP-MAS NMR spectra are in agreement with the X-ray structure. The vibrational absorption bands were identified by infrared spectroscopy. DFT calculations allowed the attribution of the NMR peaks. Keywords: Cyclohexaphosphate; X-ray diffraction; CP-MASNMR, DFT calculations.
1
ACCEPTED MANUSCRIPT 1. Introduction Since the preparation and identification of Li6P6O18.6H2O [1], this salt has been used as starting material to prepare other cyclohexaphosphates. Organic phosphate materials have attracted considerable interest in recent years because of their structural diversity, stability and
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potential uses in various fields. Indeed, depending on the cation associated with the phosphate anion, such compounds could have interesting structures and properties potentially useful in nonlinear optics [2], heterogeneous catalysis [3], photochemical and photopysical processes
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[4], molecular sieves [5], and other areas that include electronic materials [6] and ceramic precursors [7].
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In the present work, the results of X-ray structure analysis of a new cyclohexaphosphate, (C6H7ClN)6P6O18.0.5(H2O), prepared by an ion-exchange resin, are discussed with respect to the geometry and flexibility of the cyclohexaphosphate ring system and H-bonding interactions between the inorganic acceptor, the solvent H2O, and the organic
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donor molecules. This hybrid material was also characterized by solid-state NMR and infrared
2. Experimental
EP
spectroscopy.
2.1. Chemical Preparation
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An acidic aqueous solution of H6P6O18 (10 mL, 3.5 mmol) is immediately neutralized by the stoichiometric amount of 4-chloro-aniline (21 mmol in 20 mL of ethanol) under continuous stirring until the solution exhibits a light yellowish aspect. Schematically the reaction can be written:
H6P6O18 + 6 (C6H6ClN)
H2O
(C6H7ClN)6P6O18. 0.5 H2O
The entire molecular structure of the obtained cyclohexaphosphate is:
2
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ACCEPTED MANUSCRIPT
The resulting solution is then slowly evaporated at room temperature for several days
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to give large rectangular prisms of the title compound which are stable for months in normal conditions of temperature and humidity. The cyclohexaphosphoric acid used in this reaction was produced from an aqueous solution of Li6P6O18 [1] passed through an ion exchange resin (Amberlite IR120).
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2.2. X-Ray Single Crystal Structural Analysis
A Suitable crystal was selected and mounted on a Gemini kappa-geometry diffractometer (Agilent Technologies UK Ltd) equipped with an Atlas CCD detector and
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using the Mo radiation ( λ= 0.71073 Å).
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Intensities were collected at 100 K by means of the CrysalisPro software [8]. Reflection indexing, unit-cell parameters refinement, Lorentz-polarization correction, peak integration and background determination were carried out with the CrysalisPro software [8]. An analytical absorption correction was applied using the modeled faces of the crystal [9]. The resulting set of hkl was used for structure solution and refinement. The structure was solved by direct methods with SIR97 [10] and the least-square refinement on F2was achieved with the CRYSTALS software [11].
3
ACCEPTED MANUSCRIPT All non-hydrogen atoms were refined anisotropically. The hydrogen atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C-H in the range 0.93-0.98 and N-H in the range 0.86-
positions were refined with riding constraints.
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0.89 Å) and Uiso(H) (in the range 1.2-1.5 times Ueq of the parent atom),after which the
The drawings were made with Diamond [12]. The details of data collection,
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2.3. NMR and IR measurements
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refinement and crystallographic data are summarized in Table 1.
The NMR spectra were recorded on a solid-state high-resolution Bruker DSX-300 spectrometer operating at 75.49 MHz for
13
C, 30.30 MHz for
15
N and 121.51 MHz for
31
P
with a classical 4 mm probehead allowing spinning rates up to 10 kHz. 13C, 15N and 31P NMR
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chemical shifts are given relative to tetramethylsilane, neat nitromethane and 85 wt. % phosphoric acid, respectively (precision 0.5 ppm). For 13C and 15N, the spectra were recorded by use of cross polarization (CP) from protons (contact time 2ms). Before recording the
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spectrum it was checked that there was a sufficient delay between the scans allowing a full relaxation of the protons. For 31P, the isotropic chemical shift values (δiso) of the three NMR
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components were determined from the position of the side band that did not change in the spectra taken with different spinning rates. The analysis of the31P MAS-NMR spectrum was carried out by using the Bruker program WINFIT [13]. The intensities of the side bands were computed by the method of Herzfeld and Berger [14]. Chemical shift anisotropy (∆δCS) and the asymmetric parameter (η) of NMR components were then determined (Table 6). The IR spectra were recorded in the range 4000-400 cm-1 with a ‘‘Perkin–Elmer FTIR’’
4
ACCEPTED MANUSCRIPT spectrophotometer1000 using samples dispersed in spectroscopically pure KBr pressed into a pellet.
3. Results and Discussion
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3.1. Structure description
The X-ray diffraction study of the title compound leads to the determination of its chemical formula. Configurations of the different organic and inorganic speciesincluding the
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atom’s labelling and their vibrational ellipsoids at 50% probability are depicted in the Fig. 1.
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The atomic arrangement can be described by layers of inorganic entities, made up from P6O18 rings, NH3 groups and water molecules, developed in the (a, b) planes. The complete atomic arrangement, projected along the a direction, is shown in Fig. 2, whereas Fig. 3 exhibits how the different components of a layer are linked through H-bonds involving the hydrogen atoms of the –NH3 entities, water molecules and some external oxygen atoms of the P6O18 groups.
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The N(O)...O(E,W) distances vary between 2.204(6) and 2.967(6) Å and H...O(E,W)
EP
distances range between 1.45 and 2.17 Å (Table 4).
Inside such a layer, the phosphoric ring is formed by six corner-sharing PO4tetrahedra.
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ି The P Oଵ଼ anion is located around the inversion center (1/2, 1/2, 0) and is built up by three
independent PO4tetrahedra. Examination of the main geometrical features (P-O and P-P distances as well as P-O-P or O-P-O angles) (Table 2) shows that they correspond to what iscommonly observed in cyclic or linear condensed phosphoric anions. The cyclohexaphosphate ring is distorted, the P-P-P angles vary between 95.84(4) and 117.37(4)°. These angles, with an average of 104.47(4)°, show very large deviations from the ideal value of 120°, compared to the other types of phosphoric rings such as cyclotri- and cyclotetraphosphates, in which the P-P-P angles never depart significantly from their ideal 5
ACCEPTED MANUSCRIPT values of 60 ± 2° for cyclotriphosphates and 90 ± 4° for cyclotetraphosphates. Cyclotri- and cyclotetraphosphates are much less flexible than the described cyclohexaphosphates in which the “ideal” configuration has a certain void in the center. According to the flexibility of the PO4 tetrahedra, an equilibrium between repulsion of the oxygen atoms and the attraction to
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hydrogen bonding donor groups of the organic parts and the water molecules can destroy the ideal geometry of the six P-atoms. This can also be demonstrated by comparing the distances of the symmetry related P-atoms (P1-P1i = 5.621, P2-P2i = 4.721, and P3-P3i = 5.838(Å);
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(i): −x+1, −y+1, −z) which exhibit a deviation varying between 0.217 and 1.117 Å. The presence of strong hydrogen bonding such as O(N)-H...O (1.45, 1.75, 1.80 and 1.81 Å) (Table
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4) in the studied compound is certainly one of the most important distortion factors. Nevertheless, this distortion is comparatively less important than that observed in Cs6P6O18.6H2O, which shows the greatest distortion for the same angles ranging between 93.2 and 145.5° [15].
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The calculated average values of the distortion indices [16] corresponding to the different angles and distances in the PO4 tetrahedra, DI(PO) = 0.038, DI(OPO) = 0.040 and DI(OO) = 0.014 show an above distortion of the O-O distances compared to P-O ones. The
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PO4 tetrahedron is then described by regular oxygen atoms arrangement with the phosphorus atom slightly shifted from the center of gravity (δP1 = 0.151, δP2 = 0.128, δP3 = 0.141)
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In this structure, three independent [C6H7ClN]+ cationic groups coexist, compensating
ି the negative charge of the P Oଵ଼ ring anions and performing the electric neutrality of the total
complex. These organic groups are anchored onto successive layersby establishing weak CH...O(E,W) interactions with the C...O(E,W) distances of 2.952(6)-3.254(6) Å (Table 4). All these hydrogen bonds, van der Waals, and electrostatic interactions between organic cations and cyclohexaphosphate anions increase the structure stability in the title compound.
6
ACCEPTED MANUSCRIPT The mean value of the C-C bond lengths [1.382 Å] (Table 3) which is between a single
bond
and
a
double
bond,
agrees
with
that
in
4-chloroanilinium
dihydrogenmonoarsenate [1.377Å] [17]. Furthermore, the mean value of the C-N distances [1.457 Å], clearly indicates a single bond. The bond lengths of C4-Cl1, C10-Cl2 and C16-Cl3
cyclohexaphosphate dehydrate [18]. A
comparison
of
the
title
compound
(I)
to
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[1.736(4), 1.740(4) and 1.737(5)] also agree with the data of 3-chloro-2-methylanilinium
Hexakis(p-ethoxyanilinium
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cyclohexaphosphate octahydrate (II) [19] shows that they differ essentially by the nature of the substituents at the para-position on the phenyl ring. However, some similarities can be
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observed between these structures. In each of the two cases, the structure has a layer organization, which contains the P6O18 rings NH3, groups and water molecules in the same P1 space group of the triclinic system. In these structures, the anionic networks contain centrosymmetric cyclohexaphophates entities where each P6O18 is acceptor of hydrogen bond
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and adopts chair conformation. In addition, the geometrical parameters of anilinium groups have comparable values in the two compounds and are similar to those observed in other complexes containing anilinium cation. Similarly as in (I), the asymmetric unit of (II) consists
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of the organic cations water molecules and the cyclohexaphosphate anion, joined by medium and strong N–H…O hydrogen bonds. As shown in the schematic diagrams, the organic cation
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has different substituents which are placed in opposite ends of the aromatic ring. The nature of different substituents affects weakly the strength of the intermolecular hydrogen bonds and the atomic arrangement.
Recently a similar structure for the Tetrakis(2-amino-5-chloropyridinium) dihydrogen cyclohexaphosphate (C5H6ClN2)H2P6O18 (III) has been published [20]. This latter and the title compound present several differences which affect the atomic arrangement, hydrogen bond network and the unit-cell parameters. Thus, the structure (III) contains the dihydrogen 7
ACCEPTED MANUSCRIPT cyclohexaphosphate anions [H2P6O18]4- interconnected by strong O–H…O hydrogen bonds which form infinite ribbons extending along the a-axis direction. These ribbons are linked to the organic cations via N-H…O and C-H…O hydrogen bonds into a three-dimensional
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network. In spite of these differences, the anionic ring shows its standard geometry. 2.2. NMR spectroscopy The
13
C CP–MAS NMR spectrum of (C6H7ClN)6P6O18.0.5(H2O) is shown on Fig. 4.
Nine peaks with different intensities and linewidhs are resolved, which correspond to the
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can be attributed to the overlapping resonance signals.
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eighteen crystallographically independent carbon atoms. The failure to resolve all the peaks
The 15N CP-MAS NMR spectrum of the title compound (Fig. 5) is in good agreement with the X-ray structure. Indeed, it exhibits three well-defined resonances at -353.2, -354.0 and -356.2 ppm corresponding to the three crystallographically independent nitrogen atoms,
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in agreement with three organic cations in the unit cell.
Cyclohexaphosphates are formed by tetrahedra sharing two corners with neighboring tetrahedra (Q2units in Lipmaa’snotation) [21], and two other ones interacting with cations. 31
P isotropic chemical shift value δiso are higher thanthose
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According to this, the
corresponding to monophosphates (between -10 and +5 ppm) or diphosphates (between -10
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and -20 ppm) of alkali and alkaline-earth cations [22-26]. Chemical shift valuesof cyclohexaphosphates are similar to those obtained previously in polyphosphates, indicating that δiso values are mainly defined by tetrahedral condensation of phosphates. The solid state
31
P spectrum of the sample is formed by three components with their
corresponding satellite spinning bands spaced at equal intervals (Fig. 6). As the chemical environments of all P-atoms are similar in the cyclohexaphosphate, resolved components must correspond to different crystallographically sites occupied by P-atoms. On the other
8
ACCEPTED MANUSCRIPT hand, distortions of the polyhedra are responsible for the observed chemical shift anisotropies and for the detection of the spinning side band patterns covering important regions of the 31PNMR spectra. Spectral regions occupied by these bands are proportional to tetrahedral distortions. Hence, NMR patterns could be used to minor distortions. To analyze this point,
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experimental envelopes were deconvoluted, determining for each component δiso, ∆δCS and η (Table 6).
The cyclohexaphosphate group has a center of gravity that coincides with a
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cristallographic center of symmetry. This is deduced from the NMR analysis of the
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asymmetric parameter η, which average value is 0.38 (Table 6), indicating that the local symmetry of the tetrahedra is lower. This agrees with the results obtained with other cyclohexaphosphates [27].
Theoretical calculations were undertaken in order to assign the NMR resonances to the 31
P-atoms of the unit cell. Two different
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different crystallographically inequivalent
calculations were made on the cyclohexaphosphate anion and in all cases the theoretical chemical shifts were subtracted from those of the reference (phosphoric acid) calculated at the
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same level of theory:
(1) Calculation of the NMR chemical shifts (B3LYP/6-311++G** method) by using the
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positions of atoms obtained by X-ray diffraction; (2) Otimization of the oxygen atoms only and calculation of NMR chemical shifts. The results are listed on Tables 7 and 8. Clearly, there is a very good agreement
between the experimental and the theoretical values, allowing unambiguously the attribution of the different NMR signals, even if the calculated values for the isotropic chemical shifts are far away from the experimental ones. This behavior is probably related to a bad choice of the molecule for the calculations of the reference (one isolated PO43- tetrahedron while experimentally the liquid used is 85 wt. % H3PO4). 9
ACCEPTED MANUSCRIPT 3.3. IR spectroscopy To gain information on the crystal structure, we have carried out a vibrational study using
infrared
absorption.
The
infrared
spectrum
of
the
title
compound
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(C6H7ClN)6P6O18.0.5(H2O) recorded at room temperature is shown in Fig. 7. Based on some studies carried out for previous works and reported on similar cyclohexaphosphates compounds [28], we propose an attempt of assignment of the observed bands. In the highfrequency region, between 3600 and 2300 cm-1, the observed bands correspond to the
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stretching vibrations of the N-H, C-H and O-H groups [29]. Hydrogen bonding interactions
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are able to affect the frequency as well as the intensity and width of these vibrations. The two bands at 1639and 1592 cm-1 correspond to δ(O-H) and δ(N-H) deformation vibrations, respectively. The two bands at 1558 and 1500 cm-1 are assigned to ν(C=C)Ar stretching vibrations [30, 31]. The strong bands observed in the ranges 1260-1220, 1110-1070, 1015900, and 830-700 cm-1 can be assigned to stretching vibrations νas(OPO), νs(OPO), νas(POP),
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and νs(POP), respectively [32, 33]. We note that the supplementary frequency in the νs(OPO) domain can be assigned to the stretching ν(C-C) and ν(C-N), δ(C-H) and γ(C-H) vibrations
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P6O18 ring anion.
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[34]. Frequencies below 660 cm-1 can be assigned to bending, translation and rotation of the
Conclusion
A new cyclohexaphosphate, (C6H7ClN)6P6O18.0.5(H2O), has been prepared at room
temperature and characterized by physicochemical methods. In the atomic arrangement, the cyclohexaphosphate anions are linked to the NH3 groups and water molecules forming inorganic layers parallel to the (a, b) plane. The organic cations are anchored between these layers and connect them via hydrogen bonds to form an infinite three-dimensional network. The structure cohesion is ensured by N-H…O, C-H…O and O-H…O hydrogen bonds. The 10
ACCEPTED MANUSCRIPT number of 13C 15N and 31PCP–MAS NMR lines is in full agreement with the crystallographic data. DFT calculations allow the attribution of the experimental
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P NMR lines. The
vibrational absorption bands were identified by infrared spectroscopy. Supplementary data
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Crystallographic data for the structural analysis have been deposited at the Cambridge Crystallographic Data Centre, CCDC No 1409242. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the CCDC, 12 Union Road,
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Cambridge, CB2 1EZ, UK: fax: (+44) 01223-336-033; e-mail: [email protected].
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U. Schülke, R. Kayser, Z. Anorg. Allg. Chem. 531 (1985) 167-175.
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P. W. Betteridge, J. R. Carruthers, R. I. Cooper, K. Prout, D. J. Watkin. Version 12 CRYSTALS: Software for Guided Crystal Structure Analysis. J. Appl. Cryst. 36 (2003) 1487. K. Brandenburg, (1998). Diamond Version 2.0 Impact GbR. Bonn, Germany.
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H. Marouani, M. Rzaiguia S. S. Al-Deyab, Phosphorus, Sulfur, and Silicon, 186
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S. Long, M. Siegler, T. Li, Acta Cryst. E63 (2007) o3080.
[29]
W. Clegg, D. G. Watson, Acta Cryst. E63 (2007) o929-o931.
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S. Soudani, J.-X. Mi, F. Lefebvre, C. Jelsch, C. Ben Nasr, J. Mol. Struct. 1084 (2015)
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46-54.
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A. Oueslati, C. Ben Nasr, A. Durif, F. Lefebvre, Mater. Res. Bull. 40 (2005) 970-980.
[34]
C. Ben Nasr, Solid State Sci. 2 (2000) 501-506.
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[33]
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ACCEPTED MANUSCRIPT Figure captions Fig. 1 ORTEP view of (C6H7ClN)6P6O18.0.5(H2O)with the atom-labeling. Displacement ellipsoids are drawn at 50% probability. H-atoms are represented withsmall arbitrary radii. Symmetry
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code: (i) −x+1, −y+1, −z. Fig. 2
Fig. 3
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Three-dimensional network of (C6H7ClN)6P6O18.0.5(H2O), projected along the a-axis.
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Projection along the c-axis, of an inorganiclayer in (C6H7ClN)6P6O18.0.5(H2O). Organic cations are reduced to NH3 groups for figure clarity. Fig. 4
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Simulated and experimental 13C CP-MAS NMR spectra of (C6H7ClN)6P6O18.0.5(H2O). Fig. 5
N CP-MAS NMR spectrum of (C6H7ClN)6P6O18.0.5(H2O).
31
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Fig. 6
P MAS NMR spectrum of (C6H7ClN)6P6O18.0.5(H2O). Fig.7
Infrared absorption spectrum of(C6H7ClN)6P6O18.0.5(H2O).
14
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Fig. 1
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Fig. 2
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Fig. 3
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Fig. 4
18
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Fig. 5
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Fig. 6
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Fig. 7
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ACCEPTED MANUSCRIPT Table 1.Crystal data and experimental parameters used for the intensity data collection. Procedure and final results of the structure determination. C36H43Cl6N6O18.5P6
Formula weight [g mol-1]
627.16
Crystal colour, habit
yellow, block
Crystal temperature [K]
100
3
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Empirical formula
0.304 × 0.506 × 0.663
Radiation, wavelength [Å]
MoKα, 0.71073
Crystal system
triclinic
Space group
P-1
Unit-cell dimensions:
9.0054(8), 10.1053(9),16.4454(14)
Reflections for cell determination
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a, b, c [Å]
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Crystal size [mm ]
θrange for cell determination [°]
8-10
Absorption coefficient µ [mm-1]
0.586
F(000)
641
α, β, γ [°]
100.476(7), 93.485(7), 115.407(9)
Volume [Å3]
1313.0(2)
Z
2
Density calc.[g cm-3]
1.586
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Limiting indices
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θ-Range for data collection [°]
3.011 to 29.538 -12 ≤ h ≤ 12, -13 ≤ k ≤ 13, -19 ≤ l ≤ 22
Reflections collected/unique
23373/6523 (Rint = 0.041) Full-matrix least-squares on F2
Data, restrains, parameters (I > 2 σ)
5235, 0, 335
Goodness-of-fit on F2
0.9805
R indices (all data, on F2)
R= 0.0758, wR = 0.1125
∆ρ(min, max)[e Å-3]
-1.62 and1.50
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Refinement method
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ACCEPTED MANUSCRIPT Table 2. Main interatomic distances (Å) and bond angles (°) in the title compound. P(1)O4 tetrahedron O1
O2
O3
O4
O1
1.483(3)
2.599(2)
2.486(2)
2.474(2)
O2
122.20(18)
1.486(3)
2.469(2)
2.562(2)
O3
107.09(13)
105.88(17)
1.606(2)
2.495(2)
O4
106.23(17)
111.72(16)
101.78(13)
1.609(3)
O3
O5
O6
O7
O3
1.590(2)
2.541(2)
2.518(2)
2.450(2)
O5
110.88(12)
1.494(2)
2.555(2)
2.447(2)
O6
109.88(13)
118.17(13)
1.484(2)
2.530(2)
O7
100.77(11)
104.94(12)
110.70(12)
1.590(2)
O7
O8
O9
2.464(2)
2.497(2)
2.509(2)
1.611(2)
2.519(2)
2.497(2)
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P(2)O4 tetrahedron
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P1
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P(3)O4 tetrahedron O4
O4
1.595(2)
O7
100.42(12)
O8
108.18(16)
108.78(12)
1.486(3)
2.549(2)
O9
110.05(14)
108.36(13)
119.38(14)
1.467(2)
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P3
P1-P2 2.861(10)
P2-O3-P1
127.02(14)
P1-P2-P3
117.37(4)
P2-P3 2.900(8)
P1-O4-P3
132.74(17)
P2-P3-P1
95.84(4)
P3-P1 2.935(22)
P3-O7-P2
129.83(14)
P3-P1-P2
100.20(4)
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ACCEPTED MANUSCRIPT Table 3.Selected bond lengths (Å) and bond angles (°) in the organic groups of (C6H7ClN)6P6O18. 0.5(H2O)
120.3(3) 118.2(3) 121.4(3) 119.6(3) 118.7(4) 119.7(3) 118.6(3) 121.6(3) 119.4(3) 119.3(3)
N2—C7—C8 N2—C7—C12 C8—C7—C12 C7—C8—C9 C8—C9—C10 C9—C10—C11 C9—C10—Cl2 C11—C10—Cl2 C10—C11—C12 C11—C12—C7
118.9(3) 119.8(3) 121.3(3) 119.3(3) 119.3(4) 121.5(4) 119.6(3) 118.9(3) 119.2(3) 119.4(3)
N3—C13—C14 N3—C13—C18 C14—C13—C18 C13—C14—C15 C14—C15—C16 C15—C16—C17 C15—C16—Cl3 C17—C16—Cl3 C16—C17—C18 C17—C18—C13
118.1(3) 119.8(3) 122.1(4) 119.7(3) 117.8(4) 122.5(4) 117.8(4) 119.8(4) 119.3(4) 118.7(4)
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[C6H7ClN(2)]+group N2—C7 1.459(4) C7—C8 1.377(5) C7—C12 1.387(4) C8—C9 1.383(5) C9—C10 1.384(5) C10—C11 1.376(5) C11—C12 1.383(5) Cl2—C10 1.740(4)
[C6H7ClN(3)]+group N3—C13 1.454(4) C13—C14 1.385(5) C13—C18 1.371(5) C14—C15 1.391(5) C15—C16 1.382(6) C16—C17 1.380(8) C17—C18 1.389(7) Cl3—C16 1.737(5)
N1—C1—C2 N1—C1—C6 C2—C1—C6 C1—C2—C3 C2—C3—C4 C3—C4—Cl1 C5—C4—Cl1 C3—C4—C5 C4—C5—C6 C5—C6—C1
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[C6H7ClN(1)]+group N1—C1 1.458(4) C1—C2 1.372(5) C1—C6 1.381(4) C2—C3 1.389(5) C3—C4 1.386(5) C4—C5 1.372(5) C5—C6 1.382(5) Cl1—C4 1.736(4)
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ACCEPTED MANUSCRIPT Table 4.Hydrogen-bond geometry (Å, º). D—H
H···A
D···A
D—H···A
N2—H9···O6
0.89
1.89
2.733 (6)
158
N2—H10···O8ii
0.91
1.86
2.734 (6)
162 (1)
N2—H8···O1iii
0.91
1.75
2.647 (6)
172 (1)
N1—H3···O9
0.89
1.80
2.689 (6)
175
N1—H2···O6ii
0.89
2.02
2.823 (6)
149 (1)
iv
0.90
1.88
2.772 (6)
169 (1)
C6—H4···O6ii
0.93
2.54
3.254 (6)
134 (1)
N3—H16···O5v
0.90
1.81
2.697 (6)
167 (1)
N3—H17···O8ii
0.90
1.87
N3—H15···O2ii
0.90
2.15
0.90
2.17
0.94 0.82
C18—H18···O10 O10—H23···O2
2.735 (6)
161 (1)
2.925 (6)
145 (1)
2.967 (6)
149 (1)
2.13
2.952 (6)
145 (1)
1.45
2.204 (6)
151 (1)
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N3—H15···O10v
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N1—H1···O5
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D—H···A
v
i
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y−1, z.
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Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y, −z; (iii) −x+1, −y, −z; (iv) x−1, y, z; (v) x−1,
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ACCEPTED MANUSCRIPT Table 5.Interatomic PO distances (Å), OPO angles (degrees) tetrahedral distortion indexes ID(PO), ID(OPO) and ID(OO) of the cyclohexaphosphate(C6H7ClN)6P6O18. 0.5(H2O).
P-Om
ID (P-O)
(O-P-O)m
ID (OPO)
P1(O4)
1.546
0.040
109.15
0.048
2.514
0.018
P2(O4)
1.540
0.033
109.22
0.039
2.507
0.015
P3(O4)
1.540
0.041
109.20
0.034
2.506
0.008
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O-Om
ID (O-O)
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Tetrahedron
ACCEPTED MANUSCRIPT Table 6.Isotropic chemical shift (δiso), Linewidh, Amplitude, Chemical shift anisotropy (∆δCS) and assymetry (η) parameters of 31P MAS-NMR components in the title cyclohexaphosphate. Linewidh [ppm]
Amplitude
∆δCS [ppm]
η
-16.47
0.54
1625.78
-123.24
0.49
-23.16
0.79
508.20
-155.18
0.35
-26.62
0.67
653.05
-143.40
0.30
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δiso [ppm]
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ACCEPTED MANUSCRIPT Table 7. Comparison of calculated and experimental chemical shift values of the phosphorus atoms in the title cyclohexaphostate. Atoms
X-Rays
Optimisation of
Experimental
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oxygens P1
-81.7
-61.3
-23.2
P2
-78.8
-64.9
P3
-84.9
-61.5
P4
-81.7
-61.3
-23.2
P5
-78.8
-64.9
-16.5
P6
-84.9
-16.5
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-26.6
ACCEPTED MANUSCRIPT Table 8.Comparison of calculated and experimental Chemical shift anisotropy (∆δCS) and assymetry (η) parameters of 31P MAS-NMR components in the title cyclohexaphosphate. Calculated
Experimental η
∆δ
η
P1
155.1
0.44
-155.18
P2
144.1
0.47
-123.24
P3
161.5
0.36
-143.40
P4
155.2
0.44
P5
144.0
0.47
P6
161.4
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∆δ
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0.49 0.30
-155.18
0.35
-123.24
0.49
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0.35
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• •
A new cyclohexaphosphate (C6H7ClN)6P6O18.0.5(H2O) was synthesized. ି The structure involves a network of inorganic parallel layers built up by P Oଵ଼ ring anions, NH3 groups and water molecules. The crystal packing is also stabilized hydrogen bonds. The 13C, 15N and 31P CP-MAS NMR spectra are in agreement with the X-ray structure.
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