Eleven supramolecular adducts of 5,7-dimethyl-1,8-naphthyridine-2-amine and organic acids assembled by classical hydrogen bonds and other noncovalent intermolecular interactions

Accepted Manuscript Eleven Supramolecular Adducts of 5,7-Dimethyl-1,8-naphthyridine-2-amine and Organic acids Assembled by Classical Hydrogen Bonds and Other Noncovalent Intermolecular Interactions

Yining wang, Lingfeng Dong, Xinxin Xie, Bin Liu, Daqi Wang PII:

S0022-2860(17)30844-X

DOI:

10.1016/j.molstruc.2017.06.063

Reference:

MOLSTR 23949

To appear in:

Journal of Molecular Structure

Received Date:

30 August 2016

Revised Date:

13 June 2017

Accepted Date:

14 June 2017

Please cite this article as: Yining wang, Lingfeng Dong, Xinxin Xie, Bin Liu, Daqi Wang, Eleven Supramolecular Adducts of 5,7-Dimethyl-1,8-naphthyridine-2-amine and Organic acids Assembled by Classical Hydrogen Bonds and Other Noncovalent Intermolecular Interactions, Journal of Molecular Structure (2017), doi: 10.1016/j.molstruc.2017.06.063

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ACCEPTED MANUSCRIPT Eleven Supramolecular Adducts of 5,7-Dimethyl-1,8-naphthyridine-2-amine and Organic acids Assembled by Classical Hydrogen Bonds and Other Noncovalent Intermolecular Interactions

Yining wanga, Lingfeng Donga, Xinxin Xiea, Bin Liua*, and Daqi Wangb aZheJiang

A

&

F

University,

Lin'An

311300,

China.

*E-mail:

[email protected] bDepartment

of Chemical engineering, Liaocheng University, 252059, China.

Abstract: This

article

demonstrates

5,7-dimethyl-1,8-naphthyridine-2-amine

based

supramolecular adducts formation in eleven crystalline solids 1-11, in which the acidic moiety have been integrated. Addition of equivalents of the acid to the solution of

5,7-dimethyl-1,8-naphthyridine-2-amine

generates

the

corresponding

supramolecular assemblies. Except 8, all the compounds crystallize as their organic salts with the acidic proton at the organic acids transferred to the aromatic nitrogen of the

5,7-dimethyl-1,8-naphthyridine-2-amine

moiety.

All

adducts

have

been

characterized through IR, mp, elemental analysis and X-ray single crystal diffraction technique. The major driving force in the adducts 1-11 is attributed to the classical hydrogen-bonds arising from 5,7-dimethyl-1,8-naphthyridine-2-amine and the acids. The other extensive non-covalent interactions also play great functions in space association of the molecular counterparts in relevant crystals. The homo or hetero supramolecular synthons or both were found at these adducts. The common R22(8) graph set has been observed in all of the adducts due to the H-bonds and the noncovalent associations. For the synergistic interactions of the classical H-bonds and the various non-covalent associations, these adducts displayed 2D/3D structures.

Keywords: Structure characterizations; Hydrogen bonding; 5,7-dimethyl-1,8naphthyridine-2-amine; Organic acids; Supramolecular interactions.

ACCEPTED MANUSCRIPT Introduction Noncovalent interactions such as electrostatic forces, hydrogen bonds, CH-π, π-π stacking, cation-π, anion-π, and lone pair-π contacts, as well as other weak forces play significant roles in various fields ranging from molecular recognition, host-guest chemistry,

crystal

engineering,

supramolecular

chemistry,

biochemistry,

pharmaceutical chemistry, to materials science [1-4]. In the past few years, great efforts have been made to elucidate these interactions and their relationship to the final supramolecular architectures [5]. In the case of pharmaceutical ingredients, solid cocrystals/salts with such biopharmaceutical properties as solubility, stability and hygroscopicity have been studied systematically, and these properties are relevant to the non-covalent interactions [6-7]. The organic acid bears the nice donor-acceptor groups for the supramolecular crystal engineering [8], and they aggregate in the solid state as dimer, catemer, and bridged motifs [9]. It is very significative to study the powerful and directional recognition behavior between the organic acids and the basic components such as aromatic amine, aliphatic amine and pyridyl derivatives [10]. In addition to the acidic groups, the CH3, NO2, X (halogen), OH and aromatic moieties are all excellent groups in forming the organic crystalline solids via a wide variety of noncovalent interactions [11], thus we select some organic acids possessing the above mentioned groups. Recently 1,8-naphthyridine derivatives have been documented to produce supramolecular compounds with the assistance of the multiple H-bonds [12]. The derivatives of 1,8-naphthyridine have also been widely utilized as molecular recognition receptors for urea, carboxylic acids, and guanine [13], in which the major driving force is the intermolecular H-bonds. Due to its polytopic potential hydrogen-bonding donor and acceptor N atoms (two ring N, and one NH2), the 5,7-dimethyl-1,8-naphthyridine-2-amine will exhibit distinct non-bonding fashions with acids. In addition to the 1,8-naphthyridine core (N^C^N), there were two more CH3 units which can give rise to more complex nonbonding associations.

ACCEPTED MANUSCRIPT In continuation with our endeavour towards the study of the hydrogen bonding, π-π interaction, and halogen bonding concerning the 1,8-naphthyridine derivatives [14], so we will demonstrate the preparation and structure characterizations of eleven adducts based on 5,7-dimethyl-1,8-naphthyridine-2-amine (L) and organic acids (Scheme 1). The eleven adducts are (5,7-dimethyl-1,8-naphthyridine-2-amine)2 : (2,4,6-trichlorophenol) : H2O (1) [(HL)+ · (L) · (tcp-) · H2O, tcp- = 2,4,6trichlorophenolate], (5,7-dimethyl-1,8-naphthyridine-2-amine) : (trifluoroacetic acid) (2) [(HL)+ · (tfa-), tfa- = trifluoroacetate], (5,7-dimethyl-1,8-naphthyridine-2-amine) : (4-chlorophenoxyacetic acid) (3) [(HL)+ · (4-cpa-), 4-cpa- = 4-chlorophenoxyacetate], (5,7-dimethyl-1,8-naphthyridine-2-amine)2 : ((3,4-dimethoxyphenyl)acetic acid)2 : H2O (4) [(HL)+ · (L) · (dpa-) · (Hdpa) · H2O, Hdpa = (3,4-dimethoxyphenyl)acetic acid, dpa- = (3,4-dimethoxyphenyl)acetate], (5,7-dimethyl-1,8-naphthyridine-2amine)4 : (m-methylbenzoic acid)4 : 3H2O (5) [(HL)2+ · (L)2 · (mba-)2 · (Hmba)2 · 3H2O, Hmba = m-methylbenzoic acid, mba = m-methylbenzoate], (5,7-dimethyl-1,8naphthyridine-2-amine) : (4-tert-butylbenzoic acid) (6) [(HL) · (tba), tba = 4-tertbutylbenzoate], (5,7-dimethyl-1,8-naphthyridine-2-amine) : (3,4,5-trimethoxybenzoic acid) : H2O (7) [(HL) · (tma) · H2O, tma = 3,4,5-trimethoxybenzoate], (5,7-dimethyl1,8-naphthyridine-2-amine) : (3,5-dinitrobenzoic acid) (8) [(L) · (3,5-Hdba), 3,5-Hdba =

3,5-dinitrobenzoic

acid],

(5,7-dimethyl-1,8-naphthyridine-2-amine)

:

(5-

nitroisophthalic acid) (9) [(HL)+ · (5-Hnpa-), 5-Hnpa- = hydrogen 5-nitroisophthalate], (5,7-dimethyl-1,8-naphthyridine-2-amine)2 : (1,4-naphthalene dicarboxylic acid) (10) [(HL)+ · (L) · (Hnapa-), Hnapa- = hydrogen 1,4-naphthalene dicarboxylate], and (5,7dimethyl-1,8-naphthyridine-2-amine)6 : (adipic acid)4 (11) [(HL+)3 · (L)3 · (Hadp-)2 · (H1.5adp)2, Hadp- = hydrogen adipate].

ACCEPTED MANUSCRIPT

Cl H2N

N

N

Cl

HO

OH

F

F F trifluoroacetic acid

Cl 5,7-dimethyl-1,8-naphthyridin-2-amine

2,4,6-trichlorophenol

HO O

O O

Cl

4-chlorophenoxyacetic acid

O

O

O

O

OH

HO m-methylbenzoic acid

(3,4-dimethoxyphenyl)acetic acid O OH

O2N

O

O

HO

OH

O O2N

O

O 4-tert-butylbenzoic acid

3,4,5-trimethoxybenzoic acid

3,5-dinitrobenzoic acid

O OH O

O HO

HO NO2 5-nitroisophthalic acid

O

OH O

1,4-naphthalene dicarboxylic acid

HO

OH O adipic acid

Scheme 1 Molecular structures of the components present in complexes 1-11. Experimental part Materials and Instrumentation The chemicals and solvents utilized in this manuscript are analytical grade commercial products and used without purification. 5,7-Dimethyl-1,8-naphthyridine2-amine was synthesized according to the literature [15]. FT-IR spectra in range 4000-400 cm-1 were recorded on a Mattson Alpha-Centauri spectrometer from KBr discs, and the IR bands were marked as strong (s), medium (m), and weak (w) at the preparation part. The carbon, hydrogen, and nitrogen data were measured microanalytically on a Perkin-Elmer elemental analyzer with Model 2400II, and the melting points of the adducts were performed on an XT-4 thermal instrument without

ACCEPTED MANUSCRIPT correction.

Synthesis of adducts 1-11 Typical preparation procedure Organic acid in methanol or ethanol was added to a methanol solution (5 ml) of 5,7-dimethyl-1,8-naphthyridine-2-amine (34.8 mg, 0.2 mmol). The solution was stirred for a few minutes, then the solution was filtered into a test tube. The solution was left standing at room temperature for several days. Then crystals were isolated after slow evaporation of the solution in air. The crystals were dried in air to give the title compound. The preparation and characterization of the 11 adducts were listed in Table 1 in detail. The elemental analysis of 1 - 11 were shown in Table 2. Table 1. should be inserted here. Table 2. should be inserted here. X-ray Crystallography The single crystals of suitable quality were mounted on a glass fiber on a Bruker SMART 1000 CCD diffractometer operating at 50 kV and 40 mA using graphite monochromatized Mo K radiation (0.71073 Å). Data collection and reduction were carried out through SMART and SAINT softwares [16]. The structures were solved directly, and the non-hydrogen atoms were refined anisotropically via full-matrix least squares on F2 with SHELXL program of the SHELXTL package [17]. Hydrogen atom positions for the eleven structures were located in a difference map and refined independently. The summaries of the key crystallographic information are given in Tables 3, and 4, while selected bond lengths and angles are tabulated in Table 5, and the relevant hydrogen bond parameters in Table 6. Table 3. should be inserted here. Table 4. should be inserted here. Results and Discussion Preparation and General Characterization Similar synthetic procedures were used in the preparation of adducts 1-11. During

ACCEPTED MANUSCRIPT the preparation of 1-11, the acids were mixed directly with 5,7-dimethyl-1,8naphthyridine-2-amine with 1:1 ratio in methanol and/or ethanol solvents, and the crystalline products were formed via evaporating the corresponding solution at ambient conditions. Except the salts 1, 4, 5 and 7, all other compounds crystallized without water molecules accompanied, and neither the compounds are sensitive to the humidity. Except 8, the protons of the OH at the corresponding acids have transferred to the ring N with the NH2 group in the 5,7-dimethyl-1,8-naphthyridine-2-amine molecules. The elemental analysis data and the IR of the eleven adducts fit highly with their chemical components measured by the X-ray diffraction analysis. H atoms bonded to O or N atoms are well found by the difference electron density map. The N-H or O-H stretchings were found at approximately 3714-3338 cm-1 as strong and broad bands in the IR of the eleven compounds. The moderate bands at 1500-1630 cm-1 and 600-750 cm-1 arise from the aromatic and naphthyridinic ring stretching and bending, respectively. IR spectroscopy is also very useful for the diagnosis of organic salts from carboxylic acids [18]. The existence of the deprotonated carboxyl groups in all the compounds except 1 and 8 is elucidated by the presence of strong asymmetrical (1582-1622 cm-1) and symmetrical (1384-1415 cm-1) stretching frequencies for the COO- [19]. Compounds 4, 5, 9, 10, and 11 display the additional bands for the COOH. Table 5. should be inserted here. Table 6. should be inserted here. Molecular and supramolecular structure of (5,7-dimethyl-1,8-naphthyridine-2amine)2 : (2,4,6-trichlorophenol) : H2O [(HL)+ · (L) · (tcp-) · H2O] (1) Fig. 1 should be inserted here. Fig. 2 should be inserted here. Salt 1 with the composition [(HL)+ · (L) · (tcp-) · H2O] was obtained by reacting equal mol of 5,7-dimethyl-1,8-naphthyridine-2-amine with 2,4,6-trichlorophenol, in which 2,4,6-trichlorophenol donated the proton at the OH to the ring N of the naphthyridine. The same as our previously reported results [14a, 14b, 14c], here it is

ACCEPTED MANUSCRIPT also the ring N neighboring to NH2 at the naphthyridine core that has accepted the H. The asymmetric unit of 1 consists of one 5,7-dimethyl-1,8-naphthyridine-2-amine, one

monocation

of

5,7-dimethyl-1,8-naphthyridinium-2-amine,

one

2,4,6-

trichlorophenolate, and one additional water molecule, as shown in Fig. 1. The 2,4,6-trichlorophenol exists in the ionized mode with C-O bond length of 1.295(8) Å, which is significantly shorter than that (1.347(3) Å) at the parent crystal of 2,4,6-trichlorophenol [20], but it is comparable with the corresponding values of 1.282(5)

Å

at

bis(dicyclohexylammonium)

2,4-dichlorophenolate

2,4,6-

trichlorophenolate 2,4-dichlorophenol [21] and 1.306(3) Å at bis(pyridine)bis(2,4,6trichlorophenolato)copper(II) [22]. Unexpectedly, the C(1)-N(1)-C(5) (119.6(6)°) angle is significantly smaller compared with the angle of C(11)-N(4)-C(15) (121.9(5)°). The dihedral angle between the (HL)+ and the L is 4.8º, indicating that both rings are almost coplanar. The aryl ring of the 2,4,6-trichlorophenolate makes dihedral angles of 84.9º, and 87.5º with the (HL)+, and L, respectively, suggesting the perpendicular arrangement of these rings. Two inversion symmetry related naphthyridines produced a supramolecular dimer through the intermolecular N-H···N hydrogen bonds described as the DDAAAD type (D and A represent the donor group NH, and the acceptor unit N, respectively) between HL+ and L, exhibiting two close joint hydrogen-bonded R22(8) rings. The N-N separations at the N-H···N hydrogen bonds were 2.911(8)-3.022(7) Å. The anions were connected to the naphthyridine dimer by the N-H···O hydrogen bond between the NH2 of L and the phenolate with N-O distance of 2.813(7) Å to produce a tri-component adduct. One water molecule associated with the tricomponent adduct by the N-H···O hydrogen bond between the NH2 of HL and the water with N-O distance of 2.948(7) Å to form a tetracomponent aggregate. Two tetracomponent aggregates were held together by the O-H···O hydrogen bond between the water and the phenolate with O-O distance of 2.871(7) Å to form an eight-component assembly. At the eight-component assembly the two tetracomponent aggregates were antiparallelly arranged. The eight-component assemblies were linked together by the

ACCEPTED MANUSCRIPT O-H···O hydrogen bond between the water and the phenolate with O-O distance of 2.914(7) Å, and CH-π association between the phenyl CH of the cation and the phenyl ring of the anion with C-Cg distance of 3.523 Å to form 1D chain running along the b axis. At the chain the water and the phenolate generated the R42(8) ring by the OH···O hydrogen bonds. The 1D chains were connected together by the CH3-Cl contact between the 7-CH3 of L and one o-Cl of the anion with C-Cl distance of 3.873 Å to form 2D sheet extending parallel to the ab plane (Fig. 2). The C-Cl distance of 3.873 Å at the CH3-Cl contact is slightly longer than the known examples [23]. The 2D sheets were further stacked along the c axis to form 3D network.

Molecular and supramolecular structure of (5,7-dimethyl-1,8-naphthyridine-2amine) : (trifluoroacetic acid) [(HL)+ · (tfa-)] (2) Fig. 3 should be inserted here. Fig. 4 should be inserted here. Compound 2 was also prepared by reacting of a methanol solution of trifluoroacetic acid and 5,7-dimethyl-1,8-naphthyridine-2-amine at 1 : 1 ratio, which crystallizes in triclinic P-1 space group. The crystal structure of 2 showing the atomnumbering scheme is depicted in Fig. 3. Compound 2 is classified as a salt in which COOH of the trifluoroacetic acids are absolutely ionized by H transfer to the N (N(1), and N(4)) of the naphthyridines, which is also supported by the O(1)-C(21) (1.236(4) Å), O(2)-C(21) (1.237(4) Å), O(3)-C(23) (1.238(4) Å), and O(4)-C(23) (1.227(3) Å) in the COO- [24]. Here the two C-O bonds in the same carboxylate are of comparable value, indicating that the negative charge is almost equally distributed on both O atoms of the same carboxylate. Similar to 1, in this case the more basic ring N close to NH2 is protonated. The respective C-N-C angles around the protonated N atoms were 123.5(3)° and 123.9(2)°. The deprotonated carboxyl group acts as hydrogen bond acceptor with the NH+ moiety, and the amine group at the naphthyridine simultaneously. The hydrogen bonds involve the N (N(1), and N(4)) atoms on the naphthyridine rings and O (O(1), and O(4)) atoms at the carboxylates in which the naphthyridine-carboxylate moieties are almost coplanar with the torsion angles O(1)-

ACCEPTED MANUSCRIPT C(1)-O(2)-N(1) and O(5)-C(31)-O(4)-N(4) being -1.47º, and -27.08º, respectively. At the two cations there were both bonded a different carboxylate via two NH···O hydrogen bonds between both O of the carboxylate, the NH2, and NH+ to exhibit a cyclic R22(8) ring, which frequently occurred between the carboxylic acid and the aminoheterocycle. The anion was bonded to the cation to form a bicomponent adduct A by the N-H···O hydrogen bonds between the NH+, NH2 and both O of the COO- with N-O distances of 2.770(4) and 2.861(4) Å, respectively. The other anion was bonded to the other cation to form a bicomponent adduct B by the N-H···O hydrogen bonds between the NH+, NH2, and both O of the COO- with N-O distances of 2.761(3)-2.814(3) Å. The bicomponent adducts A and B were connected together by the N-H···O hydrogen bonds between the NH2 and the COO- with N-O distances of 2.860(3)-2.872(3) Å to form 1D chain running along the b axis. The anion and the cation at the same heteroadduct were coplanar, while the planes defined by the adduct A and adduct B were almost perpendicular with each other. The 1D chains were connected together by the CH-O contact between the aromatic CH of the cation and the carboxylate with C-O separation of 3.528 Å to form 2D sheet extending parallel to the ab plane (Fig. 4). Two sheets were joined together by the same face of the sheet by the CH-O contact between the 4-CH of the cation and the COO- with C-O separation of 3.369 Å, and CH-F contact from the 3-CH of the cation and the F of the anion with C-F distance of 3.384 Å to form a double sheet. The CH-F contact was shorter than the documented data [25], but it is similar with the CH-F contact at 3,4dimethoxybenzaldehyde [2,8-bis-(trifluoromethyl)quinolin-4-yl]hydrazone [26]. The CH-O and CH-F contacts generate the R22(8) ring also.

Molecular and supramolecular structure of (5,7-dimethyl-1,8-naphthyridine-2amine) : (4-chlorophenoxyacetic acid) [(HL)+ · (4-cpa-)] (3) Fig. 5 should be inserted here. Fig. 6 should be inserted here. The crystal structure of the compound 3 was found to crystallize in monoclinic P2(1)/c space group as anhydrous salt. X-ray analysis displays that the compound 3

ACCEPTED MANUSCRIPT contains one HL, and one 4-chlorophenoxyacetate (Fig. 5). The result clearly shows that the positive charge coming from the COOH of the 4-chlorophenoxyacetic acid is on the ring N not at the extra-ring NH2. Here it is also the N adjacent to NH2 that accepts the H which is similar to both salts 1 and 2. Phenyl rings of the anions and naphthyridine rings are almost planar, and they intersected at an angle of 16.4° with each other. The carboxylates rotated by 13.6° from the phenyl rings of the anion. The carboxylate made an angle of 3° with the naphthyridine ring. The C-O bonds (C11-O1, 1.259(3) Å; C11-O2, 1.227(3) Å) in the carboxylate O1-C11-O2 are not equal with each other with the Δ = 0.032 Å, which is caused by the different H-bonds the two O atoms were participated in: i.e. the O1 accepts two H-bonds while the O2 accepts only one H-bond. The angle around the protonated N is 123.7(2)° (C(1)-N(1)-C(5)), which is similar to that at 2. One anion was bonded to one cation by the N-H···O H-bonds between the NH+, NH2 and one O of the COO- with N-O distances of 2.636(3)-2.852(3) Å to form a bicomponent adduct. The bicomponent adducts were linked together by the N-H···O hydrogen bond between the NH2 and the other O of the COO- with N-O distance of 2.796(3) Å, N-H···O hydrogen bond between the NH2 and the ether O of the anion with N-O distance of 3.018(3) Å, CH-O association from the 3-CH of the cation and the carboxylate with C-O separation of 3.127 Å, and CH-Cl contact between the 4-CH of the cation and the Cl with C-Cl distance of 3.842 Å to form 1D chain. At the chain the adjacent bicomponent adducts were rotated by ca. 90° from each other. The 1D chains were combined together by the CH3-O contact between the 7-CH3 of the cation and the carboxylate with C-O separation of 3.514 Å, and π-π association between the aromatic rings of the cation with Cg-Cg distance of 3.337 Å to form 2D sheet extending at the direction that made an angle of ca. 60° with the bc plane (Fig. 6). Molecular and supramolecular structure of (5,7-dimethyl-1,8-naphthyridine-2amine)2 : ((3,4-dimethoxyphenyl)acetic acid)2 : H2O [(HL)+ · (L) · (dpa-) · (Hdpa-) · H2O] (4) Fig. 7 should be inserted here.

ACCEPTED MANUSCRIPT Fig. 8 should be inserted here. Salt 4 with the composition [(HL)+ · (L) · (dpa-) · (Hdpa) · H2O] was obtained by reacting

equal

mol

of

5,7-dimethyl-1,8-naphthyridine-2-amine

with

(3,4-

dimethoxyphenyl)acetic acid, in which one (3,4-dimethoxyphenyl)acetic acid donated the H of the COOH to the ring N of the naphthyridine. Here it is also the ring N neighboring to the NH2 that has accepted the H. The asymmetric unit of 4 consists of one 5,7-dimethyl-1,8-naphthyridine-2-amine, one monocation of 5,7-dimethyl-1,8naphthyridinium-2-amine,

one

(3,4-dimethoxyphenyl)acetate,

one

(3,4-

dimethoxyphenyl)acetic acid and one additional water (Fig. 7). One (3,4-dimethoxyphenyl)acetic acid exists in the ionized mode with C-O bond lengths varying from 1.187(12) Å to 1.238(11) Å with the Δ = 0.051 Å. Similar with 1, the C(1)-N(1)-C(5) (118.3(6)°) angle is significantly contracted compared with the angle of C(11)-N(4)-C(15) (121.6(7)°), but it is different from the known examples. The C-O bond lengths at the (3,4-dimethoxyphenyl)acetic acid are 1.318(13) Å (O(2)C(21)), and O(1)-C(21) (1.386(15) Å) with the Δ = 0.068 Å suggesting the unionized COOH, but it is different from those in the crystal of (3,4-dimethoxyphenyl)acetic acid [27]. The endocyclic C-C bonds of the phenyl ring at the (3,4-dimethoxyphenyl)acetate exhibit a bond-length asymmetry: the C34-C35 bond (1.400(12) Å) is elongated, whereas the C(33)-C(34) bond (1.376(12) Å) is shortened. The longest bond is that between C35 and C36 (1.452(12) Å), which have the two methoxy substituents, while the shortest bond is C37-C38 (1.371(11) Å). The C38-C33-C34 angle (119.3(8)°) is less than 120°, whereas the neighboring angles, C33-C34-C35 (121.8(8)°) and C33C38-C37 (120.4(8)°), are increased by 1.8° and 0.4° from 120°, respectively. The endocyclic C-C bonds of the benzene ring at the (3,4-dimethoxyphenyl)acetic acid have a little bond-length asymmetry: the C23-C24 bond (1.389(11) Å) is close to the C24-C25 (1.406(11) Å). The longest bond is that between C24 and C25 (1.406(11) Å), while the shortest bond, C23-C28 (1.350(12) Å) is located orthogonal to the carboxyl substituent. The C28-C23-C24 angle (117.5(8)°) is less than 120°, whereas the neighboring angles, C23-C28-C27 (122.7(9)°) and C23-C24-C25 (121.3(9)°), are

ACCEPTED MANUSCRIPT increased by 2.7° and 1.3° from 120°, respectively. The acetic acid and acetate groups are both twisted out of the corresponding aryl planes they attached [the torsion angles at (3,4-dimethoxyphenyl)acetic acid being C24-C23-C22-C21 = 55.93° and C28-C23-C22-C21 = 58.18°; the torsion angles at (3,4-dimethoxyphenyl)acetate being C34-C33-C32-C31 = 94.59° and C38-C33-C32C31 = -85.32°]. The dihedral angles between the carboxy units and the planes of the phenyl rings they attached were 111.3° (for O1-C21-O2) and 115.9° (for O5-C31O6), which are significantly larger than the corresponding value (54.09(14)°) at the (3,4-dimethoxyphenyl)acetic acid monohydrate [28]. The aryl rings of the anion and (3,4-dimethoxyphenyl)acetic acid intersect at an angle of 64.6° with each other. The two methoxy groups of the (3,4-dimethoxyphenyl)acetic acid and the (3,4dimethoxyphenyl)acetate all lie in the plane of the aryl ring they were attached and point away from each other, as in the reported parent compound [27] [torsion angles C30-O4-C26-C25 = -169.20°, C29-O3-C25-C26 = 166.15° and O3-C25-C26-O4 = 1° for (3,4-dimethoxyphenyl)acetic acid; torsion angles C40-O8-C36-C35 = -176.63°, C39-O7-C35-C36

=

179.29°

and

O7-C35-C36-O8

=

-0.64°

for

(3,4-

dimethoxyphenyl)acetate]. The torsion angles C24-C23-C22-C21 [-124.07°], C23-C22-C21-O2 [97.45°] and C23-C22-C21-O1 [-85.44°] differ from those in the parent compound (3,4dimethoxyphenyl)acetic acid [-100.1(1)°, 86.2(2)° and -90.8(2)°, respectively] [27]. The torsion angles C34-C33-C32-C31 [94.59°], C33-C32-C31-O5 [74.28°] and C33C32-C31-O6 [-107.88°] also differ from those in the parent compound (3,4dimethoxyphenyl)acetic acid [27]. The (HL)+ and (L) formed a dimmer by the DDA-AAD type N-H···N hydrogen bonds with N-N distances of 2.855(9)-3.016(8) Å, forming the hydrogen bonded R22(8) motif. The water connected the anion and the (3,4-dimethoxyphenyl)acetic acid by the O-H···O hydrogen bond, here the water acts as the bis-monodentate donor to form a tricomponent adduct. Here the water also associated with the (3,4dimethoxyphenyl)acetic acid by the CH2-O association between the CH2 spacer and the OW with C-O separation of 2.984 Å. The naphthyridine dimmer and the

ACCEPTED MANUSCRIPT tricomponent adduct were held together by the CH-O association between the 3-CH of the cation and the OH at the COOH with C-O separation of 3.552 Å to form a fivecomponent aggregate. Two five-component aggregates were held together by the CHO association between the 3-CH of the L and the C=O at the COOH with C-O separation of 3.348 Å, and CH3-π association between the 5-CH3 of the L and naphthyridine ring of the cation with C-Cg separation of 3.638 Å to form a 10component assembly. The 10-component assemblies were linked together by the OH···O hydrogen bond between the COOH and the water(acceptor) with O-O distance of 3.106 Å, and CH2-O association between the CH2 spacer and the carboxylate with C-O separation of 3.464 Å to form 1D chain running along the a axis. The 1D chains were connected together by the CH3-O contacts between the 4-CH3O (donor) and the 3-CH3O (acceptor) with C-O distances of 3.380-3.492 Å to form 2D sheet extending at the direction that made an angle of ca. 60° with the ac plane (Fig. 8). The 2D sheets were further stacked along the direction that was perpendicular with its extending direction by the CH3-O contact between the 3-CH3O of the anion and the COO- with C-O distance of 3.175 Å, and CH3-π association between the 7-CH3 of the cation and the aryl ring of the (3,4-dimethoxyphenyl)acetic acid with C-O distance of 3.695 Å to form 3D layer network. Herein the neighboring sheets were slipped some distances from each other along the extending direction.

Molecular and supramolecular structure of (5,7-dimethyl-1,8-naphthyridine-2amine)4 : (m-methylbenzoic acid)4 : 3H2O [(HL)2+ · (L)2 · (mba-)2 · (Hmba)2 · 3H2O] (5) Fig. 9 should be inserted here. Fig. 10 should be inserted here. For 5, the single crystals suitable for X-ray diffraction were obtained by cocrystallization of L and m-methylbenzoic acid in a 1:1 ratio from the solvent of methanol. The compound 5 is an organic salt, in which two m-methylbenzoic acid molecules were fully deprotonated and transferred to the ring N atoms of the L molecules. The asymmetric unit of 5 consisted of two HL, two L, two m-

ACCEPTED MANUSCRIPT methylbenzoate, two m-methylbenzoic acid, and three lattice water (Fig. 9). The C-O bonds of the COOH ranged from 1.283(6) Å (O(3)-C(49)), 1.218(6) Å (O(4)-C(49)), 1.213(7) Å (O(7)-C(65)), to 1.285(7) Å (O(8)-C(65)), where the C-O bonds at the two COOH were comparable. The C-O bonds at the carboxylates were 1.264(9) Å (O(1)-C(41)), 1.217(8) Å (O(2)-C(41)), 1.186(7) Å (O(5)-C(57)), and 1.332(6) Å (O(6)-C(57)). The larger Δ existed in the same COO- at different carboxylates were attributed to the different H-bonds the two O are participated in. Two water molecules generated a water dimmer by the O-H···O hydrogen bonds. Two m-methylbenzoic acids also formed a dimmer. The water dimmer, the mmethylbenzoic acid dimmer, and the m-methylbenzoate were linked into 1D chain A running along the b axis. At the chain A there formed the R66(16) and R44(13) rings. The naphthyridines dimerized by the N-H···N hydrogen bonds with N-N separations of 2.873(5)-3.008(5) Å exhibiting the close joint R22(8) rings. The naphthyridine dimmers were linked together by the CH3-π association between the 5-CH3 of L and the aromatic ring of HL with C-Cg separation of 3.666 Å, and π-π association between the naphthyridine rings of L and HL with Cg-Cg separation of 3.395 Å to form a naphthyridine tetramer. The naphthyridine tetramers were connected together by the CH3-π association between the 5-CH3 of HL and the naphthyridine ring of L with C-Cg separation of 3.566 Å to form 1D naphthyridine chain running also along the b axis. The naphthyridine chain and the chain A alternated and were joined together by the N-H···O hydrogen bonds between the NH2 of HL and the water with N-O distances of 2.974(6)-2.976(6) Å, N-H···O hydrogen bond between the NH2 of L and the carboxylate with N-O distance of 2.752(6) Å, N-H···O hydrogen bond between the NH2 of L and the carboxyl with N-O distance of 2.898(6) Å, CH-O association between the 3-CH of L and the OH at the COOH with C-O distance of 3.427 Å, CH-O association between the 4-CH of L and the COO- with C-O distance of 3.326 Å, and CH-π association between the 4-CH of HL and the aryl ring of the anion with C-Cg separation of 3.688 Å to form 2D sheet A extending parallel to the ab plane (Fig. 10). The other two m-methylbenzoic acids also formed a dimmer B by the O-H···O hydrogen bond. At the anion with C5-O5-O6 there was attached a water

ACCEPTED MANUSCRIPT by the O-H···O hydrogen bond to form the hydrate anion. Two hydrate anions and the dimmer B produced a six-component aggregate. The six-component aggregates were linked together by the CH3-π association between CH3 of the m-methylbenzoic acid and the phenyl ring of the m-methylbenzoic acid with C-Cg separation of 3.748 Å to form 1D chain B running along the a axis. The 1D chain B extending parallelly on the same plane formed a sheet B, but there were no bonding associations between the chain B. The sheets A were sandwiched between two sheets B, but there did not have any associations between the sheet A and sheet B.

Molecular and supramolecular structure of (5,7-dimethyl-1,8-naphthyridine-2amine) : (4-tert-butylbenzoic acid) [(HL) · (tba)] (6) Fig. 11 should be inserted here. Fig. 12 should be inserted here. The asymmetric unit of 6 bears one HL, and one 4-tert-butylbenzoate (Fig. 11). The C-O bonds of the COO- of the 4-tert-butylbenzoate ranged from 1.235(3) Å (C(11)-O(2)) to 1.278(3) Å (C(11)-O(1)), the relative large Δ is resulted from the different H-bonds the O1 and O2 are involved in. Similar with 1-5, herein only the N at the pyridine ring with NH2 has accepted the H. The 4-tert-butyl unit was disordered over two sites with equal occupancy. One cation was bonded to the COO- by the N-H···O hydrogen bond from the NH+, NH2, and both O of the COO- with N-O distances of 2.596(3)-2.835(3) Å to form a heteroadduct displaying the ring with the R22(8) descriptor. The heteroadducts were linked together by the N-H···O hydrogen bond from the NH2, and the COO- with N-O distance of 3.107(3) Å to form 1D chain running along the c axis. Herein the planes of the neighboring heteroadducts were almost vertical with each other. The 1D chains were joined together by the CH3-π association between the CH3 of the tertbutyl and the naphthyridine ring with C-Cg separation of 3.640 Å to form 2D sheet extending parallel to the ac plane (Fig. 12). The 2D sheets were further stacked along the b axis by the CH-π association from the phenyl CH of the anion and the phenyl ring of the anion with C-Cg separation of 3.614 Å, and CH-Cπ contact between the 6-

ACCEPTED MANUSCRIPT CH of the cation and the π-C of the COO- with C-Cπ separation of 3.675 Å to form 3D ABAB layer network. In this case the neighboring sheets were slipped some distance from each other along the extending direction, the first sheet has the same projection on the ac plane as the third sheet, so did the second sheet and the fourth sheet.

Molecular and supramolecular structure of (5,7-dimethyl-1,8-naphthyridine-2amine) : (3,4,5-trimethoxybenzoic acid) : H2O [(HL) · (tma) · H2O] (7) Fig. 13 should be inserted here. Fig. 14 should be inserted here. For 7, the single crystals suitable for X-ray diffraction were obtained by cocrystallization of L and 3,4,5-trimethoxybenzoic acid in a 1:1 ratio from the solvent of methanol. The compound 7 is an organic salt, in which the protons of the 3,4,5trimethoxybenzoic acid were fully deprotonated and transferred to the ring N of the L molecules. The salt 7 has the similar formulation as the benzamidinium 3,4,5trimethoxybenzoate monohydrate [29]. The asymmetric unit of 7 consisted of one HL, one 3,4,5-trimethoxybenzoate, and one lattice water, which is depicted in Fig. 13. In this case the N neighboring to the NH2 at the naphthyridine ring was protonated. The O(1)-C(11) (1.258(5) Å); and O(2)-C(11) (1.245(5) Å) in the carboxylate are close to each other. The valence angles C13-C12-C17 [120.7(3)°] is slightly larger than the standard value of 120°, due to the presence of the CH3O- and COO- moieties. In the anion, the two methoxy groups in meta positions of the carboxylate are coplanar with the phenyl ring and force the remaining methoxy group to be almost orthogonal to the plane of the aromatic fragment [the twist angle between the benzene ring and the methoxy group in the para position is 77.59°]. The carboxylate group is slightly twisted with respect to the plane of the aromatic fragment only by 3.0°. During the salt formation the conformation of the 3,4,5-trimethoxybenzoate was not changed compared with the parent compound of 3,4,5-trimethoxybenzoic acid [30]. One anion was bonded to one cation by the N-H···O hydrogen bonds with N-O distances of 2.702(4)-2.730(4) Å to form a heteroadduct. At the heteroadduct there

ACCEPTED MANUSCRIPT was attached a water by the O-H···O and O-H···N hydrogen bonds to form a tricomponent adduct. The tricomponnet adducts exhibit the close joint R22(8), and R32(8) rings. The tricomponnet adducts were connected together by the CH3-O association between the 4-CH3O of the anion and the carboxylate with C-O separation of 3.470 Å, and C-π contact between the π-C of the carboxylate and the naphthyridine ring with C-C distance of 3.333 Å to form 1D chain. The 1D chains extending parallelly on the ab plane formed a sheet (Fig. 14), however there were no bonding associations between these chains. The 2D sheets were joined together by the NH···O hydrogen bonds between the NH2 and the water with N-O distance of 2.878(5) Å, CH-O association between the 3-CH of the cation and the 4-CH3O with C-O distance of 3.433 Å, and CH3-O association between the CH3O of the anion and the carboxylate with C-O distance of 3.024 Å to form 3D ABAB layer network. In this case the chains at the neighboring sheets made an angle of ca. 120° with each other.

Molecular and supramolecular structure of (5,7-dimethyl-1,8-naphthyridine-2amine) : (3,5-dinitrobenzoic acid) [(L) · (3,5-Hdba)] (8) Fig. 15 should be inserted here. Fig. 16 should be inserted here. Single crystal X-ray diffraction analysis of the isolated 3,5-dinitrobenzoic acid co-crystal

of

5,7-dimethyl-1,8-naphthyridine-2-amine

supramolecular

complex

reveals a 1 : 1 stoichiometry between the two molecules rendering the formulation of 8 to be [(L) · (3,5-Hdba)]. The crystal structure of 8 is occupied by one L, and one 3,5-dinitrobenzoic acid in the asymmetric unit (Fig. 15). Similar to the published organic cocrystal bearing 3,5-Hdba [31], in 8 the COOH of 3,5-dinitrobenzoic acids are not ionized via carboxyl H transfer to the L. The C-O bonds in COOH are 1.244(9) Å (for O(1)-C(11)) and 1.279(9) Å (for O(2)-C(11)), and the difference (Δ = 0.035 Å) between O(1)-C(11) (1.244(9)Å) and O(2)-C(11) (1.279(9) Å) is greatly smaller than the Δ (0.103 Å) in the COOH of the 3,5-dinitrobenzoic acid [32] which may be caused by the different H-bonds the two O are involved in.

ACCEPTED MANUSCRIPT The rings with C12-C17 atoms and N1, and N2 atoms subtended at an angle of 3.4° with each other. In the 3,5-dinitrobenzoic acid, the carboxyl group and the nitro groups all exhibit modest rotations away from the plane of the aryl ring: for the carboxyl group the rotation is 6.1°, for the nitro groups the corresponding ranges are 3.6° (for N4-O3-O4), and 8.1° (for N5-O5-O6). The two nitro groups subtended an angle of 10.6° with each other. For neither group is there any obvious mode to its conformational behaviour: in particular, there is no indication of any important influence of the hydrogen bonding on conformation of 3,5-dinitrobenzoic acid. The L associated with the 3,5-dinitrobenzoic acid by the O-H···N hydrogen bond between the COOH and the ring N with the NH2 unit with O-N distance of 2.776(8) Å, and N-H···O hydrogen bond between the NH2 and the C=O of the COOH with NO distance of 2.776(9) Å to form a bicomponent adduct with R22(8) ring. The bicomponent adducts were linked together by the CH3-O contact between the 5-CH3 of the L and the NO2 with C-O distance of 3.562 Å to form 1D chain. The 1D chains were joined together by C-π contact between the π-C of the COOH and the naphthyridine ring with C-Cg distance of 3.337 Å, O-π contact between the nitro group and the naphthyridine ring with O-Cg distance of 3.197 Å, and π-π associations between the naphthyridine rings with Cg-Cg distances of 3.249-3.339 Å to form 2D sheet extending parallel to the ab plane (Fig. 16). The O-Cg distance is much shorter than the documented data (3.59 Å) [33], but it has similar length as our previously reported values [34]. Two 2D sheets were further stacked along the c axis by the N-H···O hydrogen bond between the NH2 and the C=O of the COOH with N-O distance of 2.845(8) Å, and CH-O associations between the 3-CH of the naphthyridine, the C=O of the COOH and the nitro group with C-O distances of 3.387 Å, and 3.209 Å to form a double sheet. The N-H···O hydrogen bond and one CH-O association produced the R21(6) ring. The double sheets were further stacked along the c axis by the CH3-O association between the 7-CH3 of the L and the nitro group of the 3,5-dinitrobenzoic acid with C-O distance of 3.146 Å to form 3D network.

ACCEPTED MANUSCRIPT Molecular and supramolecular structure of (5,7-dimethyl-1,8-naphthyridine-2amine) : (5-nitroisophthalic acid) [(HL)+ · (5-Hnpa-)] (9) Fig. 17 should be inserted here. Fig. 18 should be inserted here. The dicarboxylic acid in 9 is partially deprotonated, causing a hydrogenphthalate salt with the composition of [(HL+) · (Hnpa-)]. The same as 7, the transferred H was on the ring N with the NH2 at the L. In the asymmetric unit of 9 there existed one HL, and one 5-nitro hydrogenisophthalate (see Fig. 17). Salt 9 belongs to monoclinic centrosymmetric space group P2(1). The angle C(1)-N(1)-C(5) (124.1(7)°) is similar with the corresponding angles at 2 and 3, which also supports our correct assignment of the H to the N of the L. The experimental value [123.8(6)°] of the internal ring angle at the ipso position (C18C17-C16) in (9) agrees well with value of 122.8(2)° for 5-H2npa [35]. The phenyl ring and the carboxyl groups are coplanar. The nitro group is twisted away from the phenyl plane and the average torsion angle around the N4-C17 is 1.7° which is smaller than that at the parent compound (26.1(3)°) [35]. Thus the nitro group in 9 was more coplanar with the attached aryl ring than the nitro group at the parent compound [35]. In the absence of hydrogen bonding and other electronic perturbations, the C-O bond lengths at the COO- should be equal because of resonance. The difference (0.032 Å) between the pair of C-O bonds in the carboxylate was caused by the different hydrogen bond strength that those two O atoms were involved in (Table 6). The average length (1.271 Å) for C-O in the COO- is less than the C-O single bond (1.346(9) Å) and greater than the C=O double bond (1.231(8) Å) in the carboxyl group of the 5-nitro-hydrogenisophthalate. This lends further support to the right assignment of the 5-nitro-hydrogenisophthalate, and the negative charge in the CO2is localized on the O(4). Whereas the corresponding distance for CO2-···HOOC (C(11)-O(1), 1.346(9) Å) supports the existence of the non-ionic acid moieties. The C=O and C-O are longer by about 0.3 Å than the corresponding values found at the 5nitroisophthalic acid hydrate [35].

ACCEPTED MANUSCRIPT The dihedral angle between the cation (HL)+ and phenyl nucleus at the anion is 2.9º, indicating that both rings are almost coplanar. The carboxylates O1-C11-O2, and O3-C12-O4 rotated out of the phenyl plane of the anion by 2.7°, and 6.2°, respectively. The two carboxyl moieties intersected at an angle of 8.6° with each other. The O5-N4-O6 deviated by 3.7° from the phenyl ring. And the O5-N4-O6 inclined at angles of 4.2° and 5.8° with the two carboxyl units. The anion and the cation generated a bicomponent adduct by the N-H···O hydrogen bond to form a R22(8) ring. The bicomponent adducts were linked together by the CH3-O contact between the 5-CH3 of the cation and the nitro unit with C-O distance of 3.358 Å to form 1D chain. The 1D chains were connected together by the C-π contact between the π-C of the carboxylate and the naphthyridine ring with C-Cg distance of 3.347 Å, and π-π association between the naphthyridine rings with Cg-Cg distance of 3.310 Å to form 2D sheet extending parallel to the ab plane (Fig. 18). Two 2D sheets were combined together by the N-H···O hydrogen bond between the NH2 and the COO- with N-O distance of 2.879(8) Å, O-H···O hydrogen bond between the COOH groups with O-O distance of 2.794(8) Å, and CH-O contact between the 3-CH of the cation and the C=O of the COOH with C-O distance of 3.323 Å to form a double sheet with the chains at the different sheet intersected at 60° with each other. The double sheets were further stacked along the c axis by the CH3-O association between the 7-CH3 of the cation and the nitro group with C-O distance of 3.179 Å to form 3D network. Molecular and supramolecular structure of (5,7-dimethyl-1,8-naphthyridine-2amine)2 : (1,4-naphthalene dicarboxylic acid) [(HL)+ · (L) · (Hnapa-)] (10) Fig. 19 should be inserted here. Fig. 20 should be inserted here. Similar to the di-acids in 9, the dicarboxylic acid in 10 is also partially deprotonated, causing a hydrogen 1,4-naphthalene dicarboxylate salt with the composition of [(HL+) · (L) · (Hnapa-)]. The same as 9, the transferred H was on the ring N with the NH2 at the L. In the asymmetric unit of 10 there existed one HL, one

ACCEPTED MANUSCRIPT L, and one hydrogen 1,4-naphthalene dicarboxylate (Fig. 19). Salt 10 belongs to triclinic centrosymmetric space group P-1. The O3 and O4 were both disordered over two positions with equal occupancy. The C(11)-N(4)-C(15) (121.5(2)°) is significantly expanded compared with the angles of C(1)-N(1)-C(5) (118.3(2)°), C(1)-N(2)-C(5) (118.7(2)°), and C(16)-N(5)C(15) (117.12(19)°) which also supports our correct assignment of the (HL)+ and (L), respectively. In the absence of hydrogen bonding and other electronic perturbations, the C-O bond lengths at the COO- should be equal because of resonance. The difference (0.041 Å) between the pair of C-O bonds in the carboxylate was caused by the different H-bond strength that those two O atoms were involved in (Table 6). The average length (1.268 Å) for C-O in the COO- is less than the C-O single bond (1.296(3) Å) and greater than the C=O double bond (1.220(3) Å) in the carboxyl group of the hydrogen 1,4-naphthalene dicarboxylate. This lends further support to the right assignment of the hydrogen 1,4-naphthalene dicarboxylate, and the negative charge in the CO2- is localized on the O(4). Whereas the corresponding distance for CO2-···HOOC (C(21)-O(1), 1.296(3) Å) supports the existence of the non-ionic acid moieties. The unprotonated naphthyridine and the protonated naphthyridine assembled into dimers through N-H···N hydrogen bonds belonging to the type DAA-ADD between NH2 of one naphthyridine and the ring N of another naphthyridine, and between the NH+ of HL and the ring N of the unprotonated naphthyridine, generating two close joint hydrogen-bonded R22(8) motifs. In this case the N-N distances (2.866(3)2.970(3) Å) are similar to that in the compounds 1, 4, and 5. The anion was bonded to the dimmer by the N-H···O hydrogen bond between the NH2 and the carboxylate with N-O distance of 2.866(3) Å, and CH3-O association between the 7-CH3 of the cation and the carboxylate with C-O distance of 3.550 Å to form a tricomponent adduct. The tricomponent adducts were linked together by the O-H···O hydrogen bond between the COOH and COO- with O-O distance of 2.488 Å, and CH3-O association between the 5-CH3 of the L and the carboxylate with C-O distance of 3.562 Å to form 1D chain. The 1D chains were held together by the N-H···O hydrogen bond between the

ACCEPTED MANUSCRIPT NH2 and the C=O of the COOH with N-O distance of 2.950(3) Å, and CH-O association between the 3-CH of the cation and the carboxylate with C-O distance of 3.086 Å to form 2D sheet extending parallel to the ac plane (Fig. 20). The 2D sheets were further stacked along the b axis by the CH-O association between the naphthalene CH of the anion and the carboxylate with C-O distance of 3.203 Å, CH3π association between the CH3 at L and the naphthyridine ring at L with C-Cg distance of 3.609 Å to form a double sheet. The double sheets were further expanded by the π-π association between the naphthalene rings of the anions with Cg-Cg distance of 3.375 Å, and π-π association between the naphthyridine rings of the cations with Cg-Cg distance of 3.346 Å to form 3D layer network.

Molecular and supramolecular structure of (5,7-dimethyl-1,8-naphthyridine-2amine)6 : (adipic acid)4 [(HL+)3 · (L)3 · (Hadp-)2 · (H1.5adp)2] (11) Fig. 21 should be inserted here. Fig. 22 should be inserted here. Compared to the di-acids in 9 and 10, the dicarboxylic acid in 11 is partially deprotonated, causing a hydrogenadipate salt with the composition of [(HL+)3 · (L)3 · (Hadp-)2 · (H1.5adp)2]. The same as the salt 7, the transferred H was on the ring N with the NH2 at the L. In the asymmetric unit of 11 there existed three HL, three L, two Hadp-, and two H1.5adp (see Fig. 21). Salt 11 belongs to triclinic centrosymmetric space group P-1. The H attached to one COOH of the H1.5adp was disordered over two COOH of two H1.5adp moieties with equal occupancies. The anion adopted the extended trans zigzag conformation, the torsion angles around the C-backbone were in the range of 172.80-179.84°. The unprotonated naphthyridine and the protonated naphthyridine assembled into dimers through N-H···N hydrogen bonds belonging to the type DAA-ADD between NH2 of one naphthyridine and the ring N of another naphthyridine, and between the NH+ of HL and the ring N of the unprotonated naphthyridine, generating two close joint hydrogen-bonded R22(8) motifs. In this case the N-N distances (2.843(4)3.012(5) Å) are similar to that in the compounds 1, 4, 5, and 10. The anions were

ACCEPTED MANUSCRIPT connected together by the O-H···O hydrogen bond to form 1D chain running along the b axis. The naphthyridine dimmers were attached to the chains by the N-H···O, and CH-O association to form 2D sheet extending at the direction that made an angle of ca. 60° with the bc plane (Fig. 22). The anionic chain and the cation generated the R21(6), R22(6), and R32(10) rings. The 2D sheets were further stacked along the direction that was perpendicular with its extending direction through the CH-O association between the 4-CH of the cation and the OH at the COOH with C-O distance of 3.394 Å, CH3-O associations between the 5-CH3 of the cation and the OH at the COOH with C-O distances of 3.447-3.571 Å, CH2-C associations between the CH2 of the anion and the π-C of the carboxylate with C-C separations of 3.726-3.795 Å, and CH3-π contact between the 7-CH3 of the L and the naphthyridine ring of the cation with C-Cg distance of 3.708 Å to form 3D network.

Conclusions In summary, a series of eleven 5,7-dimethyl-1,8-naphthyridine-2-amine based adducts have been structurally characterized and the underlying supramolecular chemistry has been elucidated in this article, which make new knowledge to the study into the foundation of acid-5,7-dimethyl-1,8-naphthyridine-2-amine motifs. All adducts show the most common hydrogen-bonded R22(8) rings. Although synthesized with the same common solvent evaporation method, they showed structures as diverse as 2D sheet, 3D network, and 3D ABAB layer network. In all the salts the least basic NH2 groups are never protonated, the most basic N neighboring to the NH2 in the naphthyridine ring of all the salts is protonated. Despite variations in the acids, there all existed strong intermolecular ionic or neutral N-H···O hydrogen bonds. In the naphthyridine salts 1, 4, 5, 10, and 11 there are also one ionic and two neutral N-H···N hydrogen bonds between HL+ and L, leading to the naphthyridine base pairs, so these five molecular salts bear the naphthyridine dimers. Besides the robust classical hydrogen bonds, other different kinds of supramolecular interactions such as CH-O/CH2-O/CH3-O, CH-F, CH-Cl, CH3-Cl, CH-π/CH3-π, C-H···Cπ, CH2···Cπ, C-π, O-π, and π-π are also important in the structure expansion. All

ACCEPTED MANUSCRIPT structures have the 1D substructure (1D chain), from an inspection of the function exhibited by each set of interactions, it seems that the intra- and interchain noncovalent bonding interactions played equal importance in structure propagation. The various of non-covalent bonds accompanied with different geometries and numbers of the acidic units at the acids utilized, has resulted in the construction of higherdimensional structures from the discrete components. On the basis of molecular adducts presented here as well as those reports from the literatures, the results clearly demonstrate that 5,7-dimethyl-1,8-naphthyridine-2amine is a good building block to be incorporated into organic adducts so as to produce diversiform and stable hydrogen-bonded structures. Supplementary Information: Crystallographic data have been registered at the Cambridge Crystallographic data center, CCDC Nos. 1492773 for 1, 1445457 for 2, 959169 for 3, 1447994 for 4, 961368 for 5, 1476466 for 6, 1492774 for 7, 926287 for 8, 1492775 for 9, 1492776 for 10, and 1492778 for 11. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ (UK) with fax +44(1223)336-033 or Email: [email protected].

Acknowledgment This research was supported by Zhejiang Provincial Natural Science Foundation of China under Grant No. LY14B010006, and the Open Fund of Zhejiang Provincial Top Key Discipline of Forestry Engineering under Grant No. 2014LYGCZ017. References [1] (a) M. C. Etter, Acc. Chem. Res. 23 (1990) 120; (b) P. Metrangolo, H. Neukirch, T. Pilati, G. Resnatti, Acc. Chem. Res. 38 (2005) 386; (c) D. A. Britz, A. N. Khlobystov, Chem. Soc. Rev. 35 (2006) 637; (d) B. Moulton, M. J. Zaworotko, Chem. Rev. 101 (2001) 1629. [2] (a) T. Steiner, Angew. Chem. Int. Ed. 41 (2002) 48; (b) K. Kinbara, Y.

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Figure captions

Fig. 1. Molecular structure of 1 showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Fig. 2. 2D sheet structure of 1 formed by the CH3-Cl contact extending parallel to the ab plane.

Fig. 3. The structure of 2, showing the atom-numbering scheme. The water molecules and the methanol molecule are omitted for clarity. Displacement ellipsoids were drawn at the 30% probability level.

ACCEPTED MANUSCRIPT Fig. 4. 2D sheet structure of 2 extending parallel to the ab plane

Fig. 5. Molecular structure of 3 (for the crowdedness of the structure the atomnumbering was not labeled). Displacement ellipsoids were drawn at the 30% probability level. Fig. 6. 2D sheet structure of 3 extending at the direction that made an angle of ca. 60° with the bc plane

Fig. 7. Molecular structure of 4 showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Fig. 8. 2D sheet of 4 formed by the CH3-O contacts extending at the direction that made an angle of ca. 60° with the ac plane

Fig. 9. Molecular structure of 5 showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Fig. 10. 2D sheet A in 5 extending parallel to the ab plane.

Fig. 11. Molecular structure of 6 showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Fig. 12. 2D sheet of 6 produced by the CH3-π association extending parallel to the ac plane.

Fig. 13. Molecular structure of 7 showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Fig. 14. 2D sheet structure of 7 extending parallelly on the ab plane.

Fig. 15. Molecular structure of 8 showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Fig. 16. 2D sheet structure of 8 extending parallel to the ab plane.

ACCEPTED MANUSCRIPT

Fig. 17. Molecular structure of 9 showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Fig. 18. 2D sheet structure of 9 extending parallel to the ab plane.

Fig. 19. Molecular structure of 10 showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Fig. 20. 2D sheet structure of 10 extending parallel to the ac plane.

Fig. 21. Molecular structure of 11 showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Fig. 22. 2D sheet structure of 11 extending at the direction that made an angle of ca. 60° with the bc plane.

Covering information sheet Journal name: JOURNAL OF MOLECULAR STRUCTURE Title: Eleven Supramolecular Adducts of 5,7-Dimethyl-1,8-naphthyridine-2amine and Organic acids Assembled by Classical Hydrogen Bonds and Other Noncovalent Intermolecular Interactions

ACCEPTED MANUSCRIPT Corresponding author: Bin Liu Address: aZheJiang A & F University, Zhuji 311800, P. R. China, Tel & fax: +86575-8776-0141. E-mail: [email protected] Numbers of pages: 28pp Figures: 22 Tables: 6

ACCEPTED MANUSCRIPT Highlights

Eleven adducts have been prepared and characterized. The different H-bonds in the adducts have been analyzed. The classical hydrogen bonds are the primary intermolecular forces in the adducts. The other non-covalent interactions are discussed in detail. Discrete components can be constructed into 2D-3D structures via non-covalent interactions.

ACCEPTED MANUSCRIPT Table 1 The preparation and characterization of the 11 adducts. Sal t

1

2

3

4

5

6

7

8

9

10

Acid

Solvent for acid(volume , ml)

Quan tity (mm ol)

Yield to amine, %

m. °C

2,4,6trichloro phenol trifluoro acetic acid 4chlorop henoxya cetic acid (3,4dimetho xypheny l)acetic acid mmethylb enzoic acid 4-tertbutylben zoic acid 3,4,5trimetho xybenzo ic acid 3,5dinitrob enzoic acid 5nitroiso phthalic acid 1,4naphthal

methanol(12 ml)

0.2 mmo l

80.09

methanol(4 ml)

0.2 mmo l

ethanol(16 ml)

Crystals appearance

Solvent for crystallization

126128

colorless block crystals

methanol

69.62

135136

colorless block

methanol

0.2 mmo l

83.38

164165

colorless block

methanol+ethan ol

ethanol(14 ml)

0.2 mmo l

81.92

142144

colorless block

methanol+ethan ol

ethanol(12 ml)

0.2 mmo l

86.72

139140

colorless block

methanol+ethan ol

methanol(8 ml)

0.2 mmo l

88.21

170172

colorless block

methanol

methanol(10 ml)

0.2 mmo l

76.84

178179

colorless block

methanol

ethanol(18 ml)

0.2

85.96

159161

colorless block

methanol+ethan ol

methanol(2 0.2 0 ml)

78.05

218220

colorless block

methanol

ethanol(18 ml)

85.32

214216

colorless block

methanol+ ethanol

0.2

p.,

ACCEPTED MANUSCRIPT

11

ene dicarbox ylic acid adipic methanol(1 0.2 acid 2 ml)

86.83

143144

colorless block

methanol

ACCEPTED MANUSCRIPT Table 2 Elemental analysis of 1-11 Salt

Formula

1

C26H27Cl3N6O2

2

C12H12F3N3O2

3

C18H18ClN3O3

4

C40H48N6O9

5

C72H82N12O11

6

C21H25N3O2

7

C20H25N3O6

8

C17H15N5O6

9

C18H16N4O6

10

C32H30N6O4

11

C84H106N18O16

Elemental analysis; Calculated: C, 55.53; H, 4.80; N, 14.95 C, 50.13; H, 4.18; N, 14.62 C, 60.03; H, 5.00; N, 11.67 C, 63.42; H, 6.34; N, 11.10 C, 66.90; H, 6.35; N, 13.01 C, 71.70; H, 7.11; N, 11.95 C, 59.49; H, 6.20; N, 10.41 C, 52.94; H, 3.89; N, 18.16 C, 56.20; H, 4.16; N, 14.57 C, 68.25; H, 5.33; N, 14.93 C, 62.07; H, 6.53; N, 15.52

Elemental analysis; Found: C, 55.42; H, 4.68; N, 14.81 C, 50.07; H, 4.13; N, 14.54 C, 59.92; H, 4.88; N, 11.56 C, 63.33; H, 6.25; N, 11.02 C, 66.76; H, 6.22; N, 12.89 C, 71.56; H, 7.02; N, 11.82 C, 59.36; H, 6.12; N, 10.28 C, 52.81; H, 3.76; N, 18.07 C, 56.05; H, 4.04; N, 14.46 C, 68.14; H, 5.22; N, 14.80 C, 61.94; H, 6.40; N, 15.44

ACCEPTED MANUSCRIPT

Formula Fw T, K Wavelength, Å Crystal system space group a, Å b, Å c, Å α, deg. β, deg. γ, deg. V, Å3 Z Dcalcd, Mg/m3 Absorption coefficient, mm-1 F(000) Crystal size, mm3 θ range, deg Limiting indices Reflections collected Reflections independent (Rint) Goodness-offit on F2 R indices [I > 2σI] R indices (all data) Largest diff. peak and hole, e.Å-3

Table 3. Summary of X-ray crystallographic data for complexes 1 - 6. 1 2 3 4 5 C26H27Cl3N6O2 C12H12F3N3O2 C18H18ClN3O3 C40H48N6O9 C72H82N12O11 561.89 287.25 359.80 756.84 1291.50 298(2) 293(2) 298(2) 298(2) 293(2) 0.71073 0.71073 0.71073 0.71073 0.71073

6 C21H25N3O2 351.44 298(2) 0.71073

Triclinic P-1 8.4910(8) 12.5631(11) 13.5634(12) 78.2670(10) 86.002(2) 71.2830(10) 1341.7(2) 2 1.391 0.378

Triclinic P-1 7.1048(7) 12.1152(11) 15.8125(13) 89.369(2) 81.1040(10) 88.390(2) 1344.1(2) 4 1.419 0.126

Monoclinic P2(1)/c 7.8519(5) 14.7443(16) 14.4940(15) 90 93.6010(10) 90 1674.7(3) 4 1.427 0.251

Triclinic P-1 6.9471(6) 12.7714(11) 23.668(2) 101.557(2) 92.4620(10) 97.6970(10) 2033.5(3) 2 1.236 0.089

Triclinic P-1 12.3584(11) 14.1746(14) 21.029(2) 71.1360(10) 74.7790(10) 86.655(2) 3362.2(5) 2 1.276 0.088

Monoclinic P2(1)/c 12.9412(12) 12.7419(12) 12.3692(11) 90 107.789(2) 90 1942.1(3) 4 1.202 0.078

584 0.24 x 0.17 x 0.12 2.53 - 25.02 -10 ≤ h ≤ 6 -14 ≤ k ≤ 13

592 0.45 x 0.20 x 0.17 2.61 - 25.02 -8 ≤ h ≤ 8 -14 ≤ k ≤ 14

752 0.49 x 0.38 x 0.33 2.76 - 25.02 -9 ≤ h ≤ 9 -17 ≤ k ≤ 15

804 0.45 x 0.23 x 0.19 2.64 - 25.02 -8 ≤ h ≤ 8 -15 ≤ k ≤ 15

1372 0.39 x 0.25 x 0.22 2.51 - 25.02 -14 ≤ h ≤ 14 -15 ≤ k ≤ 16

752 0.45 x 0.41 x 0.40 2.35 - 25.02 -15 ≤ h ≤ 15 -15 ≤ k ≤ 13

-16 ≤ l ≤ 16 6788

-18 ≤ l ≤ 18 6899

-11 ≤ l ≤ 17 8219

-21 ≤ l ≤ 28 10061

-25 ≤ l ≤ 24 25070

-14 ≤ l ≤ 14 9497

4591 (0.0899)

4665 (0.0342)

2945 (0.0423)

6991 (0.0736)

11843 (0.0671)

3408 (0.0549)

0.927

0.809

1.071

1.080

1.001

1.051

0.1055, 0.2394

0.0547, 0.1215 0.1307, 0.1456 0.216, -0.187

0.0436,0.1072

0.1400, 0.3587 0.2595, 0.4022 1.502, -0.648

0.0829, 0.2034 0.2084, 0.2914 0.772, -0.275

0.0606, 0.1641 0.1162, 0.2047 0.214, -0.255

0.2189, 0.2905 0.440, -0.395

0.0765,0.1277 0.225, -0.260

ACCEPTED MANUSCRIPT

Formula Fw T, K Wavelength, Å Crystal system space group a, Å b, Å c, Å α, deg. β, deg. γ, deg. V, Å3 Z Dcalcd, Mg/m3 Absorption coefficient, mm-1 F(000) Crystal size, mm3 θ range, deg Limiting indices Reflections collected Reflections independent (Rint) Goodness-offit on F2 R indices [I > 2σI] R indices (all data) Largest diff. peak and hole, e.Å-3

Table 4 Summary of X-ray crystallographic data for complexes 7 - 11. 7 8 9 10 C20H25N3O6 C17H15N5O6 C18H16N4O6 C32H30N6O4 403.43 385.34 384.35 562.62 298(2) 293(2) 298(2) 298(2) 0.71073 0.71073 0.71073 0.71073

11 C84H106N18O16 1623.87 298(2) 0.71073

Monoclinic Cc 10.4500(9) 11.3461(11) 16.9359(14) 90 90.1260(10) 90 2008.0(3) 4 1.334 0.099

Monoclinic P2(1) 7.5015(11) 7.0905(10) 16.175(2) 90 92.9000(10) 90 859.2(2) 2 1.489 0.116

Monoclinic P2(1) 7.6383(8) 7.1941(6) 16.3952(15) 90 91.390(2) 90 900.66(15) 2 1.417 0.109

Triclinic P-1 9.6263(8) 11.6696(9) 12.7238(11) 83.520(2) 82.415(2) 75.2020(10) 1365.15(19) 2 1.369 0.093

Triclinic P-1 10.9070(9) 14.4491(13) 27.490(2) 80.574(2) 79.4500(10) 73.7460(10) 4059.7(6) 2 1.328 0.094

856 0.31 x 0.29 x 0.23 2.41 - 25.02 -12 ≤ h ≤ 11 -13 ≤ k ≤ 11

400 0.40 x 0.11 x 0.06 2.72 - 25.01 -8 ≤ h ≤ 8 -4 ≤ k ≤ 8

400 0.41 x 0.16 x 0.05 2.49 - 25.02 -9 ≤ h ≤ 8 -7 ≤ k ≤ 8

592 0.41 x 0.24 x 0.16 2.33 - 25.02 -11 ≤ h ≤ 6 -13 ≤ k ≤ 11

1728 0.39 x 0.23 x 0.11 2.65 - 25.02 -7 ≤ h ≤ 12 -17 ≤ k ≤ 17

-20 ≤ l ≤ 15 4947

-18 ≤ l ≤ 19 3005

-14 ≤ l ≤ 19 4584

-15 ≤ l ≤ 13 6952

-32 ≤ l ≤ 31 20747

2920 (0.0408)

2160 (0.0667)

3004 (0.0989)

4728 (0.0229)

14116 (0.0580)

1.011

1.042

0.825

0.942

0.799

0.0489, 0.1122

0.0656, 0.0997 0.1509, 0.1540 0.269, -0.244

0.0810, 0.1765 0.1690, 0.2143 0.263, -0.232

0.0495, 0.1241 0.0829, 0.1413 0.202, -0.202

0.0660, 0.1420 0.2054, 0.1956 0.286, -0.322

0.0858, 0.1331 0.238, -0.171

ACCEPTED MANUSCRIPT Table 5 Selected bond lengths [Å] and angles [°] for 1 - 11 1 Cl(1)-C(22) Cl(3)-C(26) N(1)-C(5) N(2)-C(5) N(4)-C(11) N(5)-C(15) N(6)-C(11) C(1)-N(1)-C(5) C(11)-N(4)-C(15) N(1)-C(1)-N(3) N(6)-C(11)-N(4) 2 F(1)-C(22) F(3)-C(22) F(5)-C(24) N(1)-C(1) N(2)-C(6) N(3)-C(1) N(4)-C(15) N(5)-C(16) O(1)-C(21) O(3)-C(23) C(1)-N(1)-C(5) C(11)-N(4)-C(15) N(3)-C(1)-N(1) N(6)-C(11)-N(4) O(1)-C(21)-O(2) 3 Cl(1)-C(16) N(1)-C(5) N(2)-C(6) O(1)-C(11) O(3)-C(13) C(1)-N(1)-C(5) N(3)-C(1)-N(1) O(2)-C(11)-O(1) 4 N(1)-C(5) N(2)-C(6) N(3)-C(1) N(4)-C(15) N(5)-C(16)

1.723(8) 1.726(8) 1.370(8) 1.364(8) 1.359(8) 1.339(7) 1.292(8) 119.6(6) 121.9(5) 120.3(6) 120.1(6)

Cl(2)-C(24) N(1)-C(1) N(2)-C(6) N(3)-C(1) N(4)-C(15) N(5)-C(16) O(1)-C(21) C(6)-N(2)-C(5) C(15)-N(5)-C(16) N(2)-C(5)-N(1) N(5)-C(15)-N(4)

1.750(8) 1.331(8) 1.326(9) 1.338(8) 1.375(7) 1.340(8) 1.295(8) 117.2(6) 119.3(6) 115.8(6) 116.1(6)

1.314(3) 1.326(4) 1.309(5) 1.351(4) 1.338(4) 1.314(4) 1.376(3) 1.341(4) 1.236(4) 1.238(4) 123.5(3) 123.9(2) 119.1(4) 119.9(3) 129.5(4)

F(2)-C(22) F(4)-C(24) F(6)-C(24) N(1)-C(5) N(2)-C(5) N(4)-C(11) N(5)-C(15) N(6)-C(11) O(2)-C(21) O(4)-C(23) C(6)-N(2)-C(5) C(15)-N(5)-C(16) N(2)-C(5)-N(1) N(5)-C(15)-N(4) O(4)-C(23)-O(3)

1.310(4) 1.329(5) 1.297(4) 1.365(4) 1.345(4) 1.344(3) 1.334(3) 1.318(4) 1.237(4) 1.227(3) 116.2(3) 115.9(3) 114.6(3) 114.7(2) 128.5(3)

1.744(3) 1.379(3) 1.337(3) 1.259(3) 1.368(3) 123.7(2) 119.6(2) 125.5(3)

N(1)-C(1) N(2)-C(5) N(3)-C(1) O(2)-C(11) O(3)-C(12) C(5)-N(2)-C(6) N(2)-C(5)-N(1)

1.343(3) 1.337(3) 1.307(3) 1.227(3) 1.419(3) 115.9(2) 115.2(2)

1.349(9) 1.335(9) 1.342(9) 1.425(9) 1.380(11)

N(1)-C(1) N(2)-C(5) N(4)-C(11) N(5)-C(15) N(6)-C(11)

1.362(8) 1.368(9) 1.336(9) 1.316(9) 1.299(10)

ACCEPTED MANUSCRIPT O(1)-C(21) O(3)-C(25) O(4)-C(26) O(5)-C(31) O(7)-C(35) O(8)-C(36) C(5)-N(1)-C(1) C(11)-N(4)-C(15) N(3)-C(1)-N(1) N(6)-C(11)-N(4) O(2)-C(21)-O(1) 5 N(1)-C(1) N(2)-C(6) N(3)-C(1) N(4)-C(15) N(5)-C(15) N(7)-C(21) N(8)-C(26) N(9)-C(21) N(10)-C(35) N(11)-C(36) O(1)-C(41) O(3)-C(49) O(5)-C(57) O(7)-C(65) C(1)-N(1)-C(5) C(11)-N(4)-C(15) C(21)-N(7)-C(25) C(31)-N(10)-C(35) N(3)-C(1)-N(1) N(4)-C(11)-N(6) N(9)-C(21)-N(7) N(12)-C(31)-N(10) O(2)-C(41)-O(1) O(5)-C(57)-O(6) 6 N(1)-C(1) N(2)-C(6) N(3)-C(1) O(2)-C(11) C(6)-N(2)-C(5) N(2)-C(5)-N(1) 7

1.386(15) 1.378(9) 1.377(10) 1.238(11) 1.357(10) 1.360(9) 118.3(6) 121.6(7) 119.1(7) 117.8(7) 117.8(11)

O(2)-C(21) O(3)-C(29) O(4)-C(30) O(6)-C(31) O(7)-C(39) O(8)-C(40) C(6)-N(2)-C(5) C(15)-N(5)-C(16) N(1)-C(5)-N(2) N(5)-C(15)-N(4) O(6)-C(31)-O(5)

1.318(13) 1.446(11) 1.403(12) 1.187(12) 1.420(11) 1.422(11) 118.7(6) 114.7(7) 115.7(6) 113.9(7) 120.3(10)

1.339(5) 1.337(6) 1.309(6) 1.369(5) 1.353(5) 1.338(6) 1.324(6) 1.330(6) 1.388(6) 1.344(6) 1.264(9) 1.283(6) 1.186(7) 1.213(7) 120.3(4) 118.4(4) 120.0(4) 121.4(4) 118.8(4) 117.6(4) 118.9(4) 119.4(4) 126.9(7) 121.4(7)

N(1)-C(5) N(2)-C(5) N(4)-C(11) N(5)-C(16) N(6)-C(11) N(7)-C(25) N(8)-C(25) N(10)-C(31) N(11)-C(35) N(12)-C(31) O(2)-C(41) O(4)-C(49) O(6)-C(57) O(8)-C(65) C(6)-N(2)-C(5) C(16)-N(5)-C(15) C(26)-N(8)-C(25) C(35)-N(11)-C(36) N(2)-C(5)-N(1) N(5)-C(15)-N(4) N(8)-C(25)-N(7) N(11)-C(35)-N(10) O(4)-C(49)-O(3) O(7)-C(65)-O(8)

1.386(6) 1.339(5) 1.327(5) 1.338(6) 1.341(6) 1.371(6) 1.348(6) 1.356(6) 1.329(5) 1.303(6) 1.217(8) 1.218(6) 1.332(6) 1.285(7) 118.0(4) 116.7(4) 117.3(4) 117.4(4) 115.5(4) 115.2(4) 115.5(4) 114.5(4) 123.8(6) 123.9(5)

1.323(3) 1.336(3) 1.321(3) 1.235(3) 116.7(2) 115.5(2)

N(1)-C(5) N(2)-C(5) O(1)-C(11) C(1)-N(1)-C(5) N(3)-C(1)-N(1) O(2)-C(11)-O(1)

1.372(3) 1.344(3) 1.278(3) 122.2(2) 119.3(2) 123.6(3)

ACCEPTED MANUSCRIPT N(1)-C(1) N(2)-C(6) N(3)-C(1) O(2)-C(11) O(3)-C(18) O(4)-C(19) O(5)-C(20) C(6)-N(2)-C(5) N(2)-C(5)-N(1) 8 N(1)-C(1) N(2)-C(5) N(3)-C(1) N(4)-O(4) N(5)-O(6) N(5)-C(16) O(2)-C(11) C(5)-N(2)-C(6) N(2)-C(5)-N(1) 9 N(1)-C(1) N(2)-C(6) N(3)-C(1) N(4)-O(5) O(1)-C(11) O(3)-C(12) C(1)-N(1)-C(5) N(3)-C(1)-N(1) O(2)-C(11)-O(1) 10 N(1)-C(1) N(2)-C(6) N(3)-C(1) N(4)-C(15) N(5)-C(15) O(1)-C(21) O(3)-C(22) O(3')-C(22) C(1)-N(1)-C(5) C(11)-N(4)-C(15) N(3)-C(1)-N(1) N(6)-C(11)-N(4) O(2)-C(21)-O(1) O(3')-C(22)-O(3)

1.333(5) 1.329(5) 1.315(5) 1.245(5) 1.403(6) 1.413(5) 1.403(5) 116.9(3) 116.8(3)

N(1)-C(5) N(2)-C(5) O(1)-C(11) O(3)-C(14) O(4)-C(15) O(5)-C(16) C(1)-N(1)-C(5) N(3)-C(1)-N(1) O(2)-C(11)-O(1)

1.374(5) 1.332(5) 1.258(5) 1.361(5) 1.382(5) 1.370(5) 123.1(3) 120.0(3) 124.4(4)

1.337(9) 1.335(10) 1.311(10) 1.220(10) 1.227(9) 1.475(10) 1.279(9) 115.8(7) 114.8(7)

N(1)-C(5) N(2)-C(6) N(4)-O(3) N(4)-C(14) N(5)-O(5) O(1)-C(11) C(1)-N(1)-C(5) N(3)-C(1)-N(1) O(1)-C(11)-O(2)

1.379(9) 1.342(10) 1.208(9) 1.475(9) 1.243(9) 1.244(9) 122.7(7) 121.6(8) 126.2(8)

1.349(9) 1.335(10) 1.335(10) 1.228(8) 1.346(9) 1.255(9) 124.1(7) 121.1(8) 123.3(7)

N(1)-C(5) N(2)-C(5) N(4)-O(6) N(4)-C(17) O(2)-C(11) O(4)-C(12) C(6)-N(2)-C(5) N(2)-C(5)-N(1) O(3)-C(12)-O(4)

1.422(9) 1.361(9) 1.224(9) 1.501(9) 1.231(8) 1.287(8) 115.5(7) 115.6(7) 126.1(8)

1.336(3) 1.333(3) 1.334(3) 1.382(3) 1.346(3) 1.296(3) 1.247(7) 1.15(2) 118.3(2) 121.5(2) 118.3(2) 119.9(2) 124.0(2) 20.7(8)

N(1)-C(5) N(2)-C(5) N(4)-C(11) N(5)-C(16) N(6)-C(11) O(2)-C(21) O(4)-C(22) O(4')-C(22) C(6)-N(2)-C(5) C(16)-N(5)-C(15) N(2)-C(5)-N(1) N(5)-C(15)-N(4) O(3')-C(22)-O(4') O(4')-C(22)-O(3)

1.378(3) 1.350(3) 1.342(3) 1.337(3) 1.317(3) 1.220(3) 1.288(7) 1.198(19) 118.7(2) 117.12(19) 114.9(2) 115.72(19) 118.1(14) 114.8(9)

ACCEPTED MANUSCRIPT O(3')-C(22)-O(4) O(3)-C(22)-O(4) 11 N(1)-C(1) N(2)-C(6) N(3)-C(1) N(4)-C(15) N(5)-C(15) N(7)-C(21) N(8)-C(26) N(9)-C(21) N(10)-C(35)

119.7(11) 126.6(5)

O(4')-C(22)-O(4)

25.9(9)

1.342(5) 1.334(5) 1.327(5) 1.362(5) 1.368(5) 1.355(5) 1.334(5) 1.311(5) 1.377(5)

N(1)-C(5) N(2)-C(5) N(4)-C(11) N(5)-C(16) N(6)-C(11) N(7)-C(25) N(8)-C(25) N(10)-C(31) N(11)-C(36)

1.360(5) 1.362(5) 1.335(5) 1.336(5) 1.326(5) 1.406(5) 1.341(5) 1.358(5) 1.343(5)

N(11)-C(35) N(13)-C(41) N(14)-C(46) N(15)-C(41) N(16)-C(55) N(17)-C(55) O(1)-C(61) O(3)-C(66) O(5)-C(67) O(7)-C(72) O(9)-C(73) O(11)-C(78) O(13)-C(79) O(15)-C(84) C(1)-N(1)-C(5) C(11)-N(4)-C(15) C(21)-N(7)-C(25) C(31)-N(10)-C(35) C(41)-N(13)-C(45) C(51)-N(16)-C(55) N(3)-C(1)-N(1) N(6)-C(11)-N(4) N(9)-C(21)-N(7) N(12)-C(31)-N(10) N(15)-C(41)-N(13) N(16)-C(51)-N(18) O(1)-C(61)-O(2) O(5)-C(67)-O(6) O(9)-C(73)-O(10) O(14)-C(79)-O(13)

1.347(5) 1.350(5) 1.334(5) 1.316(5) 1.371(5) 1.364(5) 1.219(5) 1.259(4) 1.207(4) 1.275(4) 1.212(4) 1.287(4) 1.298(5) 1.226(5) 120.1(4) 120.2(3) 120.5(3) 119.6(3) 121.6(4) 118.1(4) 119.9(4) 120.6(4) 119.4(4) 118.7(4) 119.1(4) 119.4(4) 124.1(4) 123.4(4) 124.5(4) 124.0(4)

N(12)-C(31) N(13)-C(45) N(14)-C(45) N(16)-C(51) N(17)-C(56) N(18)-C(51) O(2)-C(61) O(4)-C(66) O(6)-C(67) O(8)-C(72) O(10)-C(73) O(12)-C(78) O(14)-C(79) O(16)-C(84) C(6)-N(2)-C(5) C(16)-N(5)-C(15) C(26)-N(8)-C(25) C(36)-N(11)-C(35) C(46)-N(14)-C(45) C(56)-N(17)-C(55) N(1)-C(5)-N(2) N(4)-C(15)-N(5) N(8)-C(25)-N(7) N(11)-C(35)-N(10) N(14)-C(45)-N(13) N(17)-C(55)-N(16) O(3)-C(66)-O(4) O(8)-C(72)-O(7) O(12)-C(78)-O(11) O(15)-C(84)-O(16)

1.325(5) 1.385(5) 1.351(5) 1.329(5) 1.334(5) 1.334(5) 1.289(5) 1.261(5) 1.281(4) 1.209(5) 1.275(4) 1.210(4) 1.210(5) 1.301(5) 117.8(3) 118.0(4) 116.9(4) 118.2(4) 116.8(4) 118.0(4) 115.7(4) 115.2(4) 114.5(4) 115.2(3) 115.2(4) 115.0(4) 122.8(4) 125.7(4) 124.4(4) 122.5(4)

ACCEPTED MANUSCRIPT Table 6 Hydrogen bond distances and angles in studied structures 1 - 11 D-H···A

d(D-H) [Å]

O(2)-H(2D) ···O(1)#1 O(2)-H(2C) ···Cl(3) O(2)-H(2C) ···O(1) N(6)-H(6B) ···O(1)#2 N(6)-H(6A) ···N(2) N(3)-H(3B) ···O(2) N(3)-H(3A) ···N(5) N(1)-H(1) ···N(4)

0.85 0.85 0.85 0.86 0.86 0.86 0.86 0.86

N(6)-H(6B) ···O(1)#1 N(6)-H(6A) ···O(4)#2 N(4)-H(4) ···O(3)#2 N(3)-H(3B) ···O(3)#2 N(3)-H(3A) ···O(2)#2 N(1)-H(1) ···O(1)#2

0.86 0.86 0.86 0.86 0.86 0.86

N(3)-H(3B)···O(3) N(3)-H(3B)···O(2) N(3)-H(3A)···O(1)#1 N(1)-H(1)···O(1)#1

0.86 0.86 0.86 0.86

O(9)-H(9G)···O(2)#1 O(9)-H(9F)···O(5) O(1)-H(1A)···O(9) N(6)-H(6A)···N(2)#2 N(3)-H(3A)···N(5)#3 N(1)-H(1)···N(4)#3

0.85 0.85 0.82 0.86 0.86 0.86

O(10)-H(10G) ···O(9) O(10)-H(10F) ···O(2) O(9)-H(9I)···O(4)#1 O(9)-H(9H)···O(1)#2 O(8)-H(8)···O(8)#3 O(6)-H(6)···O(11)#4 O(3)-H(3)···O(3)#1 N(12)-H(12B)···O(2) N(12)-H(12A)···N(5) N(9)-H(9B)···O(10) N(9)-H(9A)···N(2)#5 N(7)-H(7)···N(1)#5

0.85 0.85 0.85 0.85 0.82 0.82 0.82 0.86 0.86 0.86 0.86 0.86

d(H···A) [Å] 1 2.03 2.97 2.07 1.96 2.05 2.13 2.11 2.16 2 2.01 1.96 1.90 2.00 2.00 1.91 3 2.40 1.98 2.14 1.84 4 1.70 1.85 2.25 2.00 2.13 2.16 5 1.92 2.02 1.98 1.85 1.68 1.81 1.68 1.89 2.02 2.15 2.06 2.13

d(D···A) [Å] <(DHA)[°]

2.871(7) 3.481(6) 2.914(7) 2.813(7) 2.911(8) 2.948(7) 2.967(8) 3.022(7)

168.8 120.8 168.9 171.9 175.0 159.6 175.7 179.5

2.872(3) 2.814(3) 2.761(3) 2.860(3) 2.861(4) 2.770(4)

179.0 169.4 173.3 173.7 176.1 176.1

3.018(3) 2.796(3) 2.852(3) 2.636(3)

128.7 157.2 139.9 153.6

2.446(11) 2.521(11) 3.034(15) 2.855(9) 2.990(10) 3.016(8)

145.6 134.5 160.3 173.8 176.7 177.5

2.762(6) 2.863(8) 2.828(6) 2.695(7) 2.482(7) 2.621(6) 2.481(7) 2.752(6) 2.873(5) 2.976(6) 2.918(6) 2.986(5)

173.8 174.6 174.1 174.0 165.4 171.5 163.6 175.7 174.7 160.4 178.1 177.6

ACCEPTED MANUSCRIPT N(6)-H(6B)···O(9)#5 N(6)-H(6A)···N(11) N(4)-H(4)···N(10) N(3)-H(3B)···O(4)#1 N(3)-H(3A)···N(8)#6

0.86 0.86 0.86 0.86 0.86

2.974(6) 2.948(5) 3.008(5) 2.898(6) 2.874(5)

161.3 177.1 179.1 158.3 174.7

3.107(3) 2.835(3) 2.596(3)

143.1 172.4 166.3

2.995(4) 2.757(4) 2.878(5) 2.702(4) 2.730(4)

157.4 156.8 171.4 176.4 177.7

2.776(8) 2.845(8) 2.776(9)

161.7 168.2 174.2

2.794(8) 2.879(8) 2.821(9) 2.819(8)

155.9 168.9 175.2 172.9

2.950(3) 2.866(3) 2.970(3) 2.949(3)

150.3 163.9 169.2 161.7

0.82

2.15 2.09 2.15 2.08 2.02 6 2.38 1.98 1.75 7 2.19 1.95 2.03 1.84 1.87 8 1.99 2.00 1.92 9 2.03 2.03 1.96 1.96 10 2.17 2.03 2.12 2.12 11 1.82

N(3)-H(3B) ···O(1)#1 N(3)-H(3A) ···O(2)#2 N(1)-H(1) ···O(1)#2

0.86 0.86 0.86

O(6)-H(6D) ···N(2)#1 O(6)-H(6C) ···O(1)#2 N(3)-H(3B) ···O(6) N(3)-H(3A) ···O(2)#3 N(1)-H(1) ···O(1)#3

0.85 0.85 0.86 0.86 0.86

O(2)-H(2)···N(1)#1 N(3)-H(3B)···O(1)#2 N(3)-H(3A)···O(1)#3

0.82 0.86 0.86

O(1)-H(20) ···O(2)#1 N(3)-H(3B) ···O(4)#2 N(3)-H(3A) ···O(4)#3 N(1)-H(1) ···O(3)#3

0.82 0.86 0.86 0.86

N(6)-H(6B) ···O(2)#1 N(6)-H(6A) ···N(2)#1 N(4)-H(4) ···N(1)#1 N(3)-H(3A) ···N(5)#2

0.86 0.86 0.86 0.86

O(16)H(16A)···O(15)#1 O(11)-H(11)···O(11)#2 O(10)-H(10)···O(13)#3 O(7)-H(7)···O(2)#4 O(6)-H(6)···O(6)#5 O(3)-H(3)···O(4)#6 N(18)H(18B)···O(14)#7 N(18)-H(18A)···N(14) N(15)-H(15B)···O(8)#6 N(15)-H(15A)···N(17) N(13)-H(13)···N(16) N(12)-H(12B)···O(12)

2.641(4)

173.6

0.82 0.82 0.82 0.82 0.82 0.86

1.62 1.68 1.63 1.67 1.85 2.02

2.431(5) 2.480(4) 2.433(4) 2.487(5) 2.649(4) 2.866(5)

170.5 165.3 167.0 171.1 164.7 167.9

0.86 0.86 0.86 0.86 0.86

2.12 1.97 2.01 2.15 2.07

2.976(5) 2.829(5) 2.869(5) 3.012(5) 2.894(4)

178.4 172.2 175.5 176.9 160.9

ACCEPTED MANUSCRIPT N(12)-H(12A)···N(2) N(9)-H(9B)···O(9)#8 N(9)-H(9A)···N(5) N(6)-H(6B)···O(1) N(6)-H(6A)···N(8) N(4)-H(4)···N(7) N(3)-H(3B)···O(5) N(3)-H(3A)···N(11) N(1)-H(1)···N(10)

0.86 0.86 0.86 0.86 0.86 0.86 0.86 0.86 0.86

2.02 1.96 1.99 2.06 2.12 2.14 1.99 2.05 2.12

2.883(4) 2.781(4) 2.843(4) 2.887(4) 2.976(5) 2.997(4) 2.805(5) 2.910(5) 2.976(4)

176.7 159.6 174.6 162.2 179.2 177.3 158.7 176.7 178.2

Symmetry transformations used to generate equivalent atoms for 1: #1 -x+1, -y, -z+1; #2 x, y+1, z. Symmetry transformations used to generate equivalent atoms for 2: #1 x1, y+1, z; #2 x-1, y, z. Symmetry transformations used to generate equivalent atoms for 3: #1 -x+1, y+1/2, -z+1/2. Symmetry transformations used to generate equivalent atoms for 4: #1 x-1, y, z; #2 x, y, z+1; #3 x, y, z-1. Symmetry transformations used to generate equivalent atoms for 5: #1 -x+1, -y+1, -z+1; #2 -x+1, -y, -z+1; #3 -x, -y+2, z; #4 -x+1, -y+1, -z; #5 x-1, y, z; #6 x+1, y, z. Symmetry transformations used to generate equivalent atoms for 6: #1 x+1, -y+3/2, z+1/2; #2 x+1, y, z. Symmetry transformations used to generate equivalent atoms for 7: #1 x, -y+1, z+1/2; #2 x-1, y, z; #3 x-1, -y+1, z-1/2. Symmetry transformations used to generate equivalent atoms for 8:

#1 x+1, y+1, z; #2 -x+1, y-1/2, -z+1; #3 x-1, y-1, z. Symmetry

transformations used to generate equivalent atoms for 9: #1 -x+2, y+1/2, -z; #2 -x+1, y+1/2, -z; #3 x, y+1, z. Symmetry transformations used to generate equivalent atoms for 10: #1 x-1, y, z; #2 x+1, y, z. Symmetry transformations used to generate equivalent atoms for 11: #1 -x+2, -y, -z+1; #2 -x+1, -y+1, -z+1; #3 x, y-1, z; #4 x, y+1, z; #5 -x+2, -y+1, -z; #6 -x+1, -y+2, -z ; #7 x-1, y, z; #8 -x+1, -y, -z+1.