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1.
Specific short contacts are important in crystal engineering. Hydrogen bonds have been particularly successful and together with halogen bonds can be useful for assembling small molecules or ions into crystals. The ionic constituents in the isomorphous 3,5‐dichloropyridinium (3,5‐diClPy) tetrahalometallates 3,5‐dichloropyridinium tetrachloridozincate(II), (C5H4Cl2N)2[ZnCl4] or (3,5‐diClPy)2ZnCl4, 3,5‐dichloropyridinium tetrabromidozincate(II), (C5H4Cl2N)2[ZnBr4] or (3,5‐diClPy)2ZnBr4, and 3,5‐dichloropyridinium tetrabromidocobaltate(II), (C5H4Cl2N)2[CoBr4] or (3,5‐diClPy)2CoBr4, arrange according to favourable electrostatic interactions. Cations are preferably surrounded by anions and vice versa ; rare cation–cation contacts are associated with an antiparallel dipole orientation. N—H…X (X = Cl and Br) hydrogen bonds and X X halogen bonds compete as closest contacts between neighbouring residues. The former dominate in the title compounds; the four symmetrically independent pyridinium N—H groups in each compound act as donors in charge‐assisted hydrogen bonds, with halogen ligands and the tetrahedral metallate anions as acceptors. The M X coordinative bonds in the latter are significantly longer if the halide ligand is engaged in a classical X …H—N hydrogen bond. In all three solids, triangular halogen‐bond interactions are observed. They might contribute to the stabilization of the structures, but even the shortest interhalogen contacts are only slightly shorter than the sum of the van der Waals radii.  相似文献   

2.
An unpredicted fourfold screw N—H…O hydrogen bond C(4) motif in a primary dicarboxamide (trans‐cyclohexane‐1,4‐dicarboxamide, C8H14N2O2) was investigated by single‐crystal X‐ray diffraction and IR and Raman spectroscopies. Electron‐density topology and intermolecular energy analyses determined from ab initio calculations were employed to examine the influence of weak C—H…O hydrogen‐bond interactions on the peculiar arrangement of molecules in the tetragonal P43212 space group. In addition, the way in which the co‐operative effects of those weak bonds might modify their relative influence on molecular packing was estimated from cluster calculations. Based on the results, a structural model is proposed which helps to rationalize the unusual fourfold screw molecular arrangement.  相似文献   

3.
Weak interactions between organic molecules are important in solid‐state structures where the sum of the weaker interactions support the overall three‐dimensional crystal structure. The sp‐C—H…N hydrogen‐bonding interaction is strong enough to promote the deliberate cocrystallization of a series of diynes with a series of dipyridines. It is also possible that a similar series of cocrystals could be formed between molecules containing a terminal alkyne and molecules which contain carbonyl O atoms as the potential hydrogen‐bond acceptor. I now report the crystal structure of two cocrystals that support this hypothesis. The 1:1 cocrystal of 1,4‐diethynylbenzene with 1,3‐diacetylbenzene, C10H6·C10H10O2, (1), and the 1:1 cocrystal of 1,4‐diethynylbenzene with benzene‐1,4‐dicarbaldehyde, C10H6·C8H6O2, (2), are presented. In both cocrystals, a strong nonconventional ethynyl–carbonyl sp‐C—H…O hydrogen bond is observed between the components. In cocrystal (1), the C—H…O hydrogen‐bond angle is 171.8 (16)° and the H…O and C…O hydrogen‐bond distances are 2.200 (19) and 3.139 (2) Å, respectively. In cocrystal (2), the C—H…O hydrogen‐bond angle is 172.5 (16)° and the H…O and C…O hydrogen‐bond distances are 2.25 (2) and 3.203 (2) Å, respectively.  相似文献   

4.
The asymmetric unit of O,O′‐dimethyl [(2,3,4,5,6‐pentafluorophenyl)hydrazinyl]phosphonate, C8H8F5N2O3P, is composed of two symmetry‐independent molecules with significant differences in the orientations of the C6F5 and OMe groups. In the crystal structure, a one‐dimensional assembly is mediated from classical N—H…O hydrogen bonds, which includes R22(8), D(2) and some higher‐order graph‐set motifs. By also considering weak C—H…O=P and C—H…O—C intermolecular interactions, a two‐dimensional network extends along the ab plane. The strengths of the hydrogen bonds were evaluated using quantum chemical calculations with the GAUSSIAN09 software package at the B3LYP/6‐311G(d,p) level of theory. The LP(O) to σ*(NH) and σ*(CH) charge‐transfer interactions were examined according to second‐order perturbation theory in natural bond orbital (NBO) methodology. The hydrogen‐bonded clusters of molecules, including N—H…O and C—H…O interactions, were constructed as input files for the calculations and the strengths of the hydrogen bonds are as follows: N—H…O [R22(8)] > N—H…O [D(2)] > C—H…O. The decomposed fingerprint plots show that the contribution portions of the F…H/H…F contacts in both molecules are the largest.  相似文献   

5.
In the title compound, C29H35ClN4O2, the bond lengths provide evidence for aromatic delocalization in the pyrazole ring but bond fixation in the fused imidazole ring, and the octyl chain is folded, rather than adopting an all‐trans chain‐extended conformation. A combination of N—H...N, C—H...N and C—H...O hydrogen bonds links the molecules into sheets, in which the hydrogen bonds occupy the central layer with the tert‐butyl and octyl groups arranged on either side, such that the closest contacts between adjacent sheets involve only the octyl groups. Comparisons are made with the supramolecular assembly in some simpler analogues.  相似文献   

6.
In the title compound, C16H11Cl3N6S·C3H7NO, the seven‐membered ring adopts a conformation which is close to the twist‐boat form. The molecular components are linked into sheets by a combination of two N—H...N hydrogen bonds and two C—H...O hydrogen bonds. Comparisons are made with other aminopyrimidine derivatives.  相似文献   

7.
Oxazolidin‐2‐ones are widely used as protective groups for 1,2‐amino alcohols and chiral derivatives are employed as chiral auxiliaries. The crystal structures of four differently substituted oxazolidinecarbohydrazides, namely N′‐[(E)‐benzylidene]‐N‐methyl‐2‐oxo‐1,3‐oxazolidine‐4‐carbohydrazide, C12H12N3O3, (I), N′‐[(E)‐2‐chlorobenzylidene]‐N‐methyl‐2‐oxo‐1,3‐oxazolidine‐4‐carbohydrazide, C12H12ClN3O3, (II), (4S)‐N′‐[(E)‐4‐chlorobenzylidene]‐N‐methyl‐2‐oxo‐1,3‐oxazolidine‐4‐carbohydrazide, C12H12ClN3O3, (III), and (4S)‐N′‐[(E)‐2,6‐dichlorobenzylidene]‐N,3‐dimethyl‐2‐oxo‐1,3‐oxazolidine‐4‐carbohydrazide, C13H13Cl2N3O3, (IV), show that an unexpected mild‐condition racemization from the chiral starting materials has occurred in (I) and (II). In the extended structures, the centrosymmetric phases, which each crystallize with two molecules (A and B) in the asymmetric unit, form A+B dimers linked by pairs of N—H...O hydrogen bonds, albeit with different O‐atom acceptors. One dimer is composed of one molecule with an S configuration for its stereogenic centre and the other with an R configuration, and possesses approximate local inversion symmetry. The other dimer consists of either R,R or S,S pairs and possesses approximate local twofold symmetry. In the chiral structure, N—H...O hydrogen bonds link the molecules into C(5) chains, with adjacent molecules related by a 21 screw axis. A wide variety of weak interactions, including C—H...O, C—H...Cl, C—H...π and π–π stacking interactions, occur in these structures, but there is little conformity between them.  相似文献   

8.
9.
Two inclusion compounds of dithiobiurea and tetrapropylammonium and tetrabutylammonium are characterized and reported, namely tetrapropylammonium carbamothioyl(carbamothioylamino)azanide, C12H28N+·C2H5N4S2, (1), and tetrabutylammonium carbamothioyl(carbamothioylamino)azanide, C16H36N+·C2H5N4S2, (2). The results show that in (1), the dithiobiurea anion forms a dimer via N—H...N hydrogen bonds and the dimers are connected into wide hydrogen‐bonded ribbons. The guest tetrapropylammonium cation changes its character to become the host molecule, generating pseudo‐channels containing the aforementioned ribbons by C—H...S contacts, yielding the three‐dimensional network structure. In comparison, in (2), the dithiobiurea anions are linked via N—H...S interactions, producing one‐dimensional chains which pack to generate two‐dimensional hydrogen‐bonded layers. These layers accommodate the guest tetrabutylammonium cations, resulting in a sandwich‐like layer structure with host–guest C—H...S contacts.  相似文献   

10.
In the title salt, C14H18N22+·2C9H5N4O, the 1,1′‐diethyl‐4,4′‐bipyridine‐1,1′‐diium dication lies across a centre of inversion in the space group P21/c. In the 1,1,3,3‐tetracyano‐2‐ethoxypropenide anion, the two independent –C(CN)2 units are rotated, in conrotatory fashion, out of the plane of the central propenide unit, making dihedral angles with the central unit of 16.0 (2) and 23.0 (2)°. The ionic components are linked by C—H...N hydrogen bonds to form a complex sheet structure, within which each cation acts as a sixfold donor of hydrogen bonds and each anion acts as a threefold acceptor of hydrogen bonds.  相似文献   

11.
Molecules of 1,2‐bis(4‐bromophenyl)‐1H‐benzimidazole, C19H12Br2N2, (I), and 2‐(4‐bromophenyl)‐1‐(4‐nitrophenyl)‐1H‐benzimidazole, C19H12BrN3O2, (II), are arranged in dimeric units through C—H...N and parallel‐displaced π‐stacking interactions favoured by the appropriate disposition of N‐ and C‐bonded phenyl rings with respect to the mean benzimidazole plane. The molecular packing of the dimers of (I) and (II) arises by the concurrence of a diverse set of weak intermolecular C—X...D (X = H, NO2; D = O, π) interactions.  相似文献   

12.
The structures of ammonium 3,5‐dinitrobenzoate, NH4+·C7H3N2O6, (I), ammonium 4‐nitrobenzoate dihydrate, NH4+·C7H4NO4·2H2O, (II), and ammonium 2,4‐dichlorobenzoate hemihydrate, NH4+·C7H3Cl2O2·0.5H2O, (III), have been determined and their hydrogen‐bonded structures are described. All three salts form hydrogen‐bonded polymeric structures, viz. three‐dimensional in (I) and two‐dimensional in (II) and (III). With (I), a primary cation–anion cyclic association is formed [graph set R43(10)] through N—H...O hydrogen bonds, involving a carboxylate group with both O atoms contributing to the hydrogen bonds (denoted O,O′‐carboxylate) on one side and a carboxylate group with one O atom involved in two hydrogen bonds (denoted O‐carboxylate) on the other. Structure extension involves N—H...O hydrogen bonds to both carboxylate and nitro O‐atom acceptors. With structure (II), the primary inter‐species interactions and structure extension into layers lying parallel to (001) are through conjoined cyclic hydrogen‐bonding motifs, viz.R43(10) (one cation, an O,O′‐carboxylate group and two water molecules) and centrosymmetric R42(8) (two cations and two water molecules). The structure of (III) also has conjoined R43(10) and centrosymmetric R42(8) motifs in the layered structure but these differ in that the first motif involves one cation, an O,O′‐carboxylate group, an O‐carboxylate group and one water molecule, and the second motif involves two cations and two O‐carboxylate groups. The layers lie parallel to (100). The structures of salt hydrates (II) and (III), displaying two‐dimensional layered arrays through conjoined hydrogen‐bonded nets, provide further illustration of a previously indicated trend among ammonium salts of carboxylic acids, but the anhydrous three‐dimensional structure of (I) is inconsistent with that trend.  相似文献   

13.
It has been observed that when electron‐rich naphthyl rings are present in chalcones they can participate in π–π stacking interactions, and this can play an important role in orientating inhibitors within the active sites of enzymes, while chalcones containing heterocyclic substituents additionally exhibit fungistatic and fungicidal properties. With these considerations in mind, three new chalcones containing 2‐naphthyl substituents were prepared. 3‐(4‐Fluorophenyl)‐1‐(naphthalen‐2‐yl)prop‐2‐en‐1‐one, C19H13FO, (I), crystallizes with Z ′ = 2 in the space group P and the four molecules in the unit cell adopt an arrangement which resembles that in the space group P 21/a . Although 3‐(4‐bromophenyl)‐1‐(naphthalen‐2‐yl)prop‐2‐en‐1‐one, C19H13BrO, (II), with Z ′ = 1, is not isostructural with (I), the molecules of (I) and (II) adopt very similar conformations. In 1‐(naphthalen‐2‐yl)‐3‐(thiophen‐2‐yl)prop‐2‐en‐1‐one, C17H12OS, (III), the thiophene unit is disordered over two sets of atomic sites, with occupancies of 0.780 (3) and 0.220 (3), which are related by a near 180° rotation of the thiophene unit about its exocyclic C—C bond. The molecules of compound (I) are linked by three independent C—H…π(arene) hydrogen bonds to form centrosymmetric octamolecular aggregates, whereas the molecules of compound (II) are linked into molecular ladders by a combination of C—H…π(arene) and C—Br…π(arene) interactions, and those of compound (III) are linked into centrosymmetric dimers by C—H…π(thiophene) interactions.  相似文献   

14.
The adsorption behaviour of the CdII–MOF {[Cd(L)2(ClO4)2]·H2O ( 1 ), where L is 4‐amino‐3,5‐bis[3‐(pyridin‐4‐yl)phenyl]‐1,2,4‐triazole, for butan‐2‐one was investigated in a single‐crystal‐to‐single‐crystal (SCSC) fashion. A new host–guest system that encapsulated butan‐2‐one molecules, namely poly[[bis{μ3‐4‐amino‐3,5‐bis[3‐(pyridin‐4‐yl)phenyl]‐1,2,4‐triazole}cadmium(II)] bis(perchlorate) butanone sesquisolvate], {[Cd(C24H18N6)2](ClO4)2·1.5C4H8O}n, denoted C4H8O@Cd‐MOF ( 2 ), was obtained via an SCSC transformation. MOF 2 crystallizes in the tetragonal space group P43212. The specific binding sites for butan‐2‐one in the host were determined by single‐crystal X‐ray diffraction studies. N—H…O and C—H…O hydrogen‐bonding interactions and C—H…π interactions between the framework, ClO4? anions and guest molecules co‐operatively bind 1.5 butan‐2‐one molecules within the channels. The adsorption behaviour was further evidenced by 1H NMR, IR, TGA and powder X‐ray diffraction experiments, which are consistent with the single‐crystal X‐ray analysis. A 1H NMR experiment demonstrates that the supramolecular interactions between the framework, ClO4? anions and guest molecules in MOF 2 lead to a high butan‐2‐one uptake in the channel.  相似文献   

15.
The title compound, C23H17N3O4S, crystallizes with Z′ = 3 in the space group P. Two of the three independent molecules are broadly similar in terms of both their molecular conformations and their participation in hydrogen bonds, but the third molecule differs from the other two in both of these respects. The molecules are linked by a combination of N—H...O, N—H...N, C—H...O, C—H...N and C—H...π(arene) hydrogen bonds to form a continuous three‐dimensional framework structure within which a centrosymmetric six‐molecule aggregate can be identified as a key structural element.  相似文献   

16.
The antibiotic trimethoprim [5‐(3,4,5‐trimethoxybenzyl)pyrimidine‐2,4‐diamine] was cocrystallized with glutarimide (piperidine‐2,6‐dione) and its 3,3‐dimethyl derivative (4,4‐dimethylpiperidine‐2,6‐dione). The cocrystals, viz. trimethoprim–glutarimide (1/1), C14H18N4O3·C5H7NO2, (I), and trimethoprim–3,3‐dimethylglutarimide (1/1), C14H18N4O3·C7H11NO2, (II), are held together by three neighbouring hydrogen bonds (one central N—H...N and two N—H...O) between the pyrimidine ring of trimethoprim and the imide group of glutarimide, with an ADA/DAD pattern (A = acceptor and D = donor). These heterodimers resemble two known cocrystals of trimethoprim with barbituric acid and its 5,5‐diethyl derivative. Trimethoprim shows a conformation in which the planes of the pyrimidine and benzene rings are approximately perpendicular to one another. In its glutarimide coformer, five of the six ring atoms lie in a common plane; the C atom opposite the N atom deviates by about 0.6 Å. The crystal packing of each of the two cocrystals is characterized by an extended network of hydrogen bonds and contains centrosymmetrically related trimethoprim homodimers formed by a pair of N—H...N hydrogen bonds. This structural motif occurs in five of the nine published crystal structures in which neutral trimethoprim is present.  相似文献   

17.
Four 2,2′‐bisindolylmethanes (BIMs), a useful class of polyindolyl species joined to a central carbon, were synthesized using salicylaldehyde derivatives and simple acid catalysis; these are 2‐[bis(3‐methyl‐1H‐indol‐2‐yl)methyl]‐6‐methylphenol, (IIa), 2‐[bis(3‐methyl‐1H‐indol‐2‐yl)methyl]‐4,6‐dichlorophenol, (IIb), 2‐[bis(3‐methyl‐1H‐indol‐2‐yl)methyl]‐4‐nitrophenol, (IIc), and 2‐[bis(3‐methyl‐1H‐indol‐2‐yl)methyl]‐4,6‐di‐tert‐butylphenol, (IId). BIMs (IIa) and (IIb) were characterized crystallographically as the dimethyl sulfoxide (DMSO) disolvates, i.e. C26H24N2O·2C2H6OS and C25H20Cl2N2O·2C2H6OS, respectively. Both form strikingly similar one‐dimensional hydrogen‐bonding chain motifs with the DMSO solvent molecules. BIM (IIa) packs into double layers of chains whose orientations alternate every double layer, while (IIb) forms more simply packed chains along the a axis. BIM (IIa) has a remarkably long c axis.  相似文献   

18.
In recent years, N‐heterocyclic carboxylate ligands have attracted much interest in the preparation of new coordination polymers since they contain N‐atom donors, as well as O‐atom donors, and have a rich variety of coordination modes which can lead to polymers with intriguing structures and interesting properties. A new two‐dimensional coordination polymer, namely poly[[μ3‐2,2′‐(1,2‐phenylene)bis(4‐carboxy‐1H‐imidazole‐5‐carboxylato)‐κ6O4,N3,N3′,O4′:O5:O5′]manganese(II)], [Mn(C16H8N4O8)]n or [Mn(H4Phbidc)]n, has been synthesized by the reaction of Mn(OAc)2·4H2O (OAc is acetate) with 2,2′‐(1,2‐phenylene)bis(1H‐imidazole‐4,5‐dicarboxylic acid) (H6Phbidc) under solvothermal conditions. In the polymer, each MnII ion is six‐coordinated by two N atoms from one H4Phbidc2− ligand and by four O atoms from three H4Phbidc2− ligands, forming a significantly distorted octahedral MnN2O4 coordination geometry. The MnII ions are linked by hexadentate H4Phbidc2− ligands, leading to a two‐dimensional structure parallel to the ac plane. In the crystal, adjacent layers are further connected by N—H…O hydrogen bonds, forming a three‐dimensional structure in the solid state.  相似文献   

19.
<!?tlsb=‐0.2pt>Nitrogen‐based polydentate ligands are of interest owing to their flexible complexation to transition metal atoms. For the title compound, [Ni(C15H17N2)2], a transition metal complex formed by the coordination of two identical N,N′‐bidentate mono(imino)pyrrolyl ligands to an NiII centre, an X‐ray crystal diffraction study indicates that the two ligands show an inverted arrangement with respect to one another around the NiII centre, which is located on a crystallographic inversion centre. The planes of the aromatic substituents at the imine N atoms of the ligands show dihedral angles of 85.91 (5)° with respect to the NiN4 plane. The Ni—N bond lengths are in the range 1.9072 (15)–1.9330 (15) Å and the Nimino—Ni—Npyrrole bite angles are 83.18 (6)°. The Ni—Npyrrole bond is substantially shorter than the Ni—Nimino bond. Molecules are linked into an extensive network by means of intermolecular C—H...π(arene) hydrogen bonds in which every molecule acts both as hydrogen‐bond donor and acceptor. The supramolecular assembly takes the form of an infinite two‐dimensional sheet.  相似文献   

20.
4‐Antipyrine [4‐amino‐1,5‐dimethyl‐2‐phenyl‐1H‐pyrazol‐3(2H)‐one] and its derivatives exhibit a range of biological activities, including analgesic, antibacterial and anti‐inflammatory, and new examples are always of potential interest and value. 2‐(4‐Chlorophenyl)‐N‐(1,5‐dimethyl‐3‐oxo‐2‐phenyl‐2,3‐dihydro‐1H‐pyrazol‐4‐yl)acetamide, C19H18ClN3O2, (I), crystallizes with Z′ = 2 in the space group P, whereas its positional isomer 2‐(2‐chlorophenyl)‐N‐(1,5‐dimethyl‐3‐oxo‐2‐phenyl‐2,3‐dihydro‐1H‐pyrazol‐4‐yl)acetamide, (II), crystallizes with Z′ = 1 in the space group C2/c; the molecules of (II) are disordered over two sets of atomic sites having occupancies of 0.6020 (18) and 0.3980 (18). The two independent molecules of (I) adopt different molecular conformations, as do the two disorder components in (II), where the 2‐chlorophenyl substituents adopt different orientations. The molecules of (I) are linked by a combination of N—H…O and C—H…O hydrogen bonds to form centrosymmetric four‐molecule aggregates, while those of (II) are linked by the same types of hydrogen bonds forming sheets. The related compound N‐(1,5‐dimethyl‐3‐oxo‐2‐phenyl‐2,3‐dihydro‐1H‐pyrazol‐4‐yl)‐2‐(3‐methoxyphenyl)acetamide, C20H21N3O3, (III), is isomorphous with (I) but not strictly isostructural; again the two independent molecules adopt different molecular conformations, and the molecules are linked by N—H…O and C—H…O hydrogen bonds to form ribbons. Comparisons are made with some related structures, indicating that a hydrogen‐bonded R22(10) ring is the common structural motif.  相似文献   

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