Dimethyl-formamide Solvent Mol-ecules Research Articles

Poly[bis-(μ2-N,N-di-methyl-formamide-κ2 O:O)bis-(μ4-thio-phene-2,5-di-carboxyl-ato-κ4 O:O':O'':O''')dicobalt(II)

The asymmetric unit of the title three-dimensional metal-organic hybrid compound, [Co2(C6H2O4S)2(C3H7NO)2] n , comprises two cobalt(II) cations, one residing on a twofold axis and the other on a centre of inversion, one thio-phene-2,5-di-carboxyl-ate (tdc2-) ligand and one coordinating di-methyl-formamide (DMF) solvent mol-ecule. Both of the cobalt(II) cations exhibit an octa-hedral coordination environment from the four carboxyl O atoms of the tdc2- anions in a μ 4-κ 1:κ 1:κ 1:κ 1 fashion and two O atoms from DMF. A pair of carboxyl O atoms and one DMF molecule connect the adjacent cobalt(II) cations into an infinite chain, leading to a rod-spacer framework with rhombus-window channels, yet no residual solvent-accessible voids are present because the coordinating DMF molecules are oriented into the potential channels.

Crystal structure and Hirshfeld surface analysis of 2-(4-amino-6-phenyl-1,2,5,6-tetra-hydro-1,3,5-triazin-2-yl-idene)malono-nitrile di-methyl-formamide hemisolvate.

The title compound, 2C12H10N6·C3H7NO, crystallizes as a racemate in the monoclinic P21/c space group with two independent mol-ecules (I and II) and one di-methyl-formamide solvent mol-ecule in the asymmetric unit. Both mol-ecules (I and II) have chiral centers at the carbon atoms where the triazine rings of mol-ecules I and II are attached to the phenyl ring. In the crystal, mol-ecules I and II are linked by inter-molecular N-H⋯N, N-H⋯O and C-H⋯N hydrogen bonds through the solvent di-methyl-formamide mol-ecule into layers parallel to (001). In addition, C-H⋯π inter-actions also connect adjacent mol-ecules into layers parallel to (001). The stability of the mol-ecular packing is ensured by van der Waals inter-actions between the layers. The Hirshfeld surface analysis indicates that N⋯H/H⋯N (38.3% for I; 35.0% for II), H⋯H (28.2% for I; 27.0% for II) and C⋯H/H⋯C (23.4% for I; 26.3% for II) inter-actions are the most significant contributors to the crystal packing.

Mol-ecular and crystal structure of 5,9-dimethyl-5H-pyrano[3,2-c:5,6-c']bis-[2,1-benzo-thia-zin]-7(9H)-one 6,6,8,8-tetroxide di-methyl-formamide monosolvate.

The title mol-ecule crystallizes as a di-methyl-formamide monosolvate, C19H14N2O6S2·C3H7NO. The mol-ecule was expected to adopt mirror symmetry but slightly different conformational characteristics of the condensed benzo-thia-zine ring lead to point group symmetry 1. In the crystal, mol-ecules form two types of stacking dimers with distances of 3.464 (2) Å and 3.528 (2) Å between π-systems. As a result, columns extending parallel to [100] are formed, which are connected to inter-mediate di-methyl-formamide solvent mol-ecules by C-H⋯O inter-actions.

N′-[5-Acetyl-3-(4-chlorophenyl)-2,3-dihydro-1,3,4-thiadiazol-2-ylidene]-5-(1H-indol-3-yl)-1-phenyl-1H-pyrazole-3-carbohydrazide dimethylformamide monosolvate

In the title solvate, C28H20ClN7O2S·C3H7NO, the main molecule consists of chlorophenyl (A), thiadiazolyl (B), pyrazolyl (C), phenyl (D) and indolyl (E) rings, with twist angles between neighbouring rings A/B, B/C, C/D and D/E of 32.6 (1), 14.8 (1), 60.8 (1) and 20.1 (1)°, respectively. The dimethylformamide solvent molecule accepts an N—H...O hydrogen bond from the indole group. In the extended structure, molecules related by 21 screw axes are stacked in the [001] direction to form columns linked by weak C—H...O interactions.

Two- and three-dimensional coordination polymers based on zinc(II) and furan-2,5-dicarboxylic acid: structure variation due to metal-to-linker ratio.

Two ZnII-based coordination polymers (CPs) were synthesized by the hydrothermal method, using Zn(NO3)2·6H2O and furan-2,5-dicarboxylic acid (FDCA) in dimethylformamide (DMF) solvent, at 95 °C. Poly[tetrakis(dimethylazanium) [tetrakis(μ2-furan-2,5-dicarboxylato-κ2O2:O5)dizinc(II)]], {(C2H8N)4[Zn2(C6H2O5)4]}n or {[DMA]4[ZnII2(FDC)4]}n (DMA = dimethylazanium and FDC= furan-2,5-dicarboxylate), (1), was obtained with a 1:1 molar ratio of ZnII and FDCA. It crystallized in the monoclinic space group C2/c. Coordinated by ZnII ions, FDC2- ligands form 21 double-stranded helices propagating along the b axis. The helices are interconnected and extend laterally in the a direction, forming a two-dimensional (2D) sheet-like network. The 2D sheets are stacked along the c direction without interconnections. DMA cations are cocrystallized in (1) and are hydrogen bonded with carboxylate O atoms of the FDC2- ligands. The hydrogen-bonding pattern consists of R22(4) and R22(10) motifs alternating in a chain. Poly[bis(dimethylazanium) [bis(μ4-furan-2,5-dicarboxylato-κO2:κO2':κO5:κO5)bis(μ3-furan-2,5-dicarboxylato-κO2:κO2':κO5)dizinc(II)] dimethylformamide 3.08-solvate], {(C2H8N)2[Zn2(C6H2O5)4]·3.08C3H7NO}n or {[DMA]2[ZnII3(FDC)4]·3.08DMF}n, (2), was obtained with a 1:2 molar ratio of ZnII and FDCA. It crystallized in the monoclinic space group P21/c, forming a three-dimensional network. The pores are filled with DMA cations and DMF solvent molecules.

5-[(4-Bromophenyl)diazenyl]-2-{2-[1-(1H-indol-3-yl)ethylidene]hydrazinyl}-4-methylthiazole dimethylformamide hemisolvate

The asymmetric unit of the title compound, 2C20H17BrN6S·C3H7NO, comprises two molecules of the thiazole derivative and one molecule of dimethylformamide (DMF) solvent. The twist angles between the planes through the bromophenyl, methylthiazolyl and indolyl groups are 10.1 (1) and 44.2 (1)°, respectively, for one molecule and 11.3 (1) and 1.6 (1)° for the other. In the crystal, N—H...N hydrogen bonds link four of the main molecules into tetramers. N—H...O bonds involving the DMF solvent molecule also occur.

Incorporating the Thiazolo[5,4-d]thiazole Unit into a Coordination Polymer with Interdigitated Structure

The linker 2,5-di(4-pyridyl)thiazolo[5,4-d]thiazole (Dptztz), whose synthesis and structure is described here, was utilized together with benzene-1,3-dicarboxylate (isophthalate, 1,3-BDC2−) for the preparation of the two-dimensional coordination network [Zn(1,3-BDC)Dptztz]·DMF (DMF = dimethylformamide) via a solvothermal reaction. Compound [Zn(1,3-BDC)Dptztz]·DMF belongs to the class of coordination polymers with interdigitated structure (CIDs). The incorporated DMF solvent molecules can be removed through solvent exchange and evacuation such that the supramolecular 3D packing of the 2D networks retains porosity for CO2 adsorption in activated [Zn(1,3-BDC)Dptztz]. The first sorption study of a tztz-functionalized porous metal-organic framework material yields a BET surface of 417 m2/g calculated from the CO2 adsorption data. The heat of adsorption for CO2 exhibits a relative maximum with 27.7 kJ/mol at an adsorbed CO2 amount of about 4 cm3/g STP, which is interpreted as a gate-opening effect.

ПРЯМИЙ СИНТЕЗ ТА КРИСТАЛІЧНА БУДОВА ДИМЕТИЛФОРМАМІДНОГО СОЛЬВАТУ БІС(БРОМІДО-БІС(1,10-ФЕНАНТРОЛІНО)-КУПРУМУ(II)) НІТРОПРУСИДУ

The title compound, [Cu(C12H8N2)2Br]2[Fe(CN)5(NO)]·C3H7NO, was prepared by the self-assembly of nitroprusside anion and Cu cation containing a bidentate amine in the reaction of copper powder and sodium nitroprusside with NH4Br and 1,10-phenanthroline (phen) in dimethylformamide (DMF). The complex is formed of discrete [Cu(phen)2Br]+ cations, nitroprusside [Fe(CN)5(NO)]2– anions and DMF molecules of crystallization. The cation has no crystallographically imposed symmetry; the metal atom coordinates two nitrogen atoms of two phen molecules and bromide ion. The copper coordination geometry is intermediate between a square pyramid and a trigonal bipyramid. The [Fe(CN)5(NO)]2– anion is located on an inversion centre with the nitrosyl group modelled as disordered with one of the CN groups. The DMF solvent molecule was found to be disordered about the crystallographic inversion centre; geometries were restrained to ideal values. In the solid state, alternating layers of cations and of anions plus DMF molecules are stacked along the b axis.

Crystal structure of a Zn complex with tereph-thalate and 1,6-bis-(1,2,4-triazol-1-yl)hexa-ne.

A new zinc coordination polymer with rigid benzene-1,4-di-carboxyl-ate (bdc) and flexible 1,6-bis-(1,2,4-triazol-1-yl)hexane (btrh), namely poly[[(μ2-benzene-1,4-di-carboxyl-ato)[μ2-1,6-bis-(1,2,4-triazol-1-yl)hexa-ne]zinc] di-methyl-form-amide monosolvate], [Zn(C8H4O4)(C10H16N6)]·C3H7NO, was synthesized. According to the single-crystal XRD analysis, the product crystallizes in the P-1 space group and has a layered structure. Analysis of the layered structure reveals {Zn(bdc)} chains which are connected by pairs of btrh ligands. The layers are packed tightly perpendicular to the [1-22] direction, separated by one non-disordered di-methyl-formamide solvent mol-ecule per formula unit. According to thermogravimetric analysis, the product completely loses this solvent at 453 K; the desolvated compound is stable up to 503 K. As a result of the lack of hydrogen-donor groups, hydrogen bonds are not observed in the structure of the complex; however, an inter-molecular C-H⋯π contact of 3.07 Å occurs.

Crystal structures and supra-molecular features of 9,9-dimethyl-3,7-di-aza-bicyclo-[3.3.1]nonane-2,4,6,8-tetra-one, 3,7-di-aza-spiro-[bi-cyclo-[3.3.1]nonane-9,1'-cyclo-penta-ne]-2,4,6,8-tetra-one and 9-methyl-9-phenyl-3,7-di-aza-bicyclo-[3.3.1]nonane-2,4,6,8-tetra-one di-methyl-formamide monosolvate.

Compounds (I), C9H10N2O4, (II), C11H12N2O4, and (III), C14H12N2O4·C3H7NO represent 9,9-disubstituted-3,7-di-aza-bicyclo-[3.3.1]nonane-2,4,6,8-tetra-one deriv-atives with very similar mol-ecular geometries for the bicyclic framework: the dihedral angle between the planes of the imide groups is 74.87 (6), 73.86 (3) and 74.83 (6)° in (I)-(III), respectively. The dimethyl derivative (I) is positioned on a crystallographic twofold axis and its overall geometry deviates only slightly from idealized C2v symmetry. The spiro-cyclo-pentane derivative (II) and the phen-yl/methyl analog (III) retain only inter-nal Cs symmetry, which in the case of (II) coincides with crystallographic mirror symmetry. The cyclo-pentane moiety in (II) adopts an envelope conformation, with the spiro C atom deviating from the mean plane of the rest of the ring by 0.548 (2) Å. In compound (III), an N-H⋯O hydrogen bond is formed with the di-methyl-formamide solvent mol-ecule. In the crystal, both (I) and (II) form similar zigzag hydrogen-bonded ribbons through double inter-molecular N-H⋯O hydrogen bonds. However, whereas in (I) the ribbons are formed by two trans-arranged O=C-N-H amide fragments, the amide fragments are cis-positioned in (II). The formation of ribbons in (III) is apparently disrupted by participation of one of its N-H groups in hydrogen bonding with the solvent mol-ecule. As a result, the mol-ecules of (III) form zigzag chains rather than the ribbons through inter-molecular N-H⋯O hydrogen bonds. The crystal of (I) was a pseudo-merohedral twin.

A new example of intra-molecular C-H⋯Ni anagostic inter-actions: synthesis, crystal structure and Hirshfeld analysis of cis-bis-[4-methyl-2-(1,2,3,4-tetra-hydro-naphthalen-1-yl-idene)hydrazinecarbo-thio-amidato-κ2N1,S]nickel(II) di-methyl-formamide monosolvate.

The reaction of NiII acetate tetra-hydrate with 4-methyl-2-(1,2,3,4-tetra-hydro-naphthalen-1-yl-idene)hydrazinecarbo-thio-amide in a 2:1 molar ratio and recrystallization from di-methyl-formamide yielded the title compound, [Ni(C12H14N3S)2]·C3H7NO. The ligands act as monoanionic κ2N1,S-donors, forming five-membered metallarings. The NiII ion is fourfold coordinated in a distorted square-planar cis-configuration, which is rather uncommon for mono-thio-semicarbazone complexes. Intra-molecular H⋯Ni trans-inter-actions are observed [H⋯Ni distances are 2.50 and 2.57 Å] and thus anagostic inter-actions can be suggested. The Hirshfeld surface analysis indicates that the major contributions for the crystal packing are H⋯H (66.6%), H⋯S (12.3%) and H⋯C (10.9%) inter-actions. In the crystal, the complex mol-ecules are linked by di-methyl-formamide solvent mol-ecules through N-H⋯O inter-actions into one-dimensional hydrogen-bonded polymers along [010].

A new one-dimensional Cd(II) coordination polymer with a two-dimensional layered structure incorporating 2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole and benzene-1,2-dicarboxylate ligands.

The N-heterocyclic ligand 2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole (imb) has a rich variety of coordination modes and can lead to polymers with intriguing structures and interesting properties. In the coordination polymer catena-poly[[cadmium(II)-bis[μ-benzene-1,2-dicarboxylato-κ(4)O(1),O(1'):O(2),O(2')]-cadmium(II)-bis{μ-2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole}-κ(2)N(2):N(3);κ(2)N(3):N(2)] dimethylformamide disolvate], {[Cd(C8H4O4)(C11H10N4)]·C3H7NO}n, (I), each Cd(II) ion exhibits an irregular octahedral CdO4N2 coordination geometry and is coordinated by four O atoms from two symmetry-related benzene-1,2-dicarboxylate (1,2-bdic(2-)) ligands and two N atoms from two symmetry-related imb ligands. Two Cd(II) ions are connected by two benzene-1,2-dicarboxylate ligands to generate a binuclear [Cd2(1,2-bdic)2] unit. The binuclear units are further connected into a one-dimensional chain by pairs of bridging imb ligands. These one-dimensional chains are further connected through N-H...O hydrogen bonds and π-π interactions, leading to a two-dimensional layered structure. The dimethylformamide solvent molecules are organized in dimeric pairs via weak interactions. In addition, the title polymer exhibits good fluorescence properties in the solid state at room temperature.

Crystal structure of (E,E)-2',4'-di-hydroxy-aceto-phenone azine di-methyl-formamide disolvate.

In the title compound {systematic name: 4,4'-[1,1'-(hydrazinediyl-idene)bis-(ethan-1-yl-1-yl-idene)]bis-(benzene-1,3-diol)}, C16H16N2O4·2C3H7NO, the (E,E)-2',4'-di-hydroxy-aceto-phenone azine mol-ecule is centrosymmetric, the mid-point of the N-N bond being located on an inversion centre. All the non-H atoms of the azine mol-ecule are approximately coplanar, the maximum deviation being 0.017 (2) Å. An intra-molecular O-H⋯N hydrogen bond occurs between the azine N atom and the hy-droxy group. In the crystal, azine and di-methyl-formamide solvent mol-ecules are linked by O-H⋯O hydrogen bonds.

Crystal structure of N'-[(E)-3,5-di-chloro-2-hy-droxy-benzyl-idene]-4-nitro-benzo-hydrazide di-methyl-formamide monosolvate.

In the title compound, C14H9Cl2N3O4·C3H7NO, the hydrazone mol­ecule adopts an E conformation with respect to azomethine bond, and the dihedral angle between the two aromatic rings [8.96 (11)°] shows that the rings are almost co-planar. The planar conformation of the mol­ecule is stabilized by the intra­molecular O—H⋯N hydrogen bond involving the OH group and azomethine N atom. The azomethine and keto bond distances [1.269 (2) and 1.210 (2) Å, respectively] are very close to the formal C=N and C=O bond lengths. The di­methyl­formamide solvent mol­ecule is connected to the hydrazone NH group via an N—H⋯O hydrogen bond. In the crystal, non-classical C—H⋯O and C—H⋯Cl hydrogen bonds link the mol­ecules into chains along [322]. A supra­molecular three-dimensional architecture is created by weak C—Cl⋯π [4.163 (3) Å, 83.26 (9)°] and π–π [centroid–centroid distance = 4.0395 (14) Å] inter­actions.

Crystal structure of poly[[[μ4-5-(9H-carbazol-9-yl)isophthalato][μ3-5-(9H-carbazol-9-yl)isophthalato]bis-(di-methyl-formamide)(methanol)dizinc] di-methyl-formamide monosolvate

The structure of the polymeric title compound, {[Zn2(C20H11NO4)2(C3H7NO)2(CH3OH)]·C3H7NO}n, comprises carbazolylisophthalate moieties connecting dimetallic tetra­carboxyl­ate zinc secondary building units (SBUs) parallel to [100] and [010], leading to a layer-like arrangement parallel to (001). Each SBU consists of two Zn atoms in slightly distorted tetra­hedral and octa­hedral coordination environments [Zn⋯Zn = 3.5953 (6) Å]. Three carboxyl­ate groups bridge the two Zn atoms in a μ2-O:O′ mode, whereas the fourth coordinates through a single carboxyl­ate O atom (μ1-O). The O atoms of two di­methyl­formamide (DMF) and one methanol mol­ecule complete the Zn coordination spheres. The methanol ligand inter­acts with the noncoordinating DMF mol­ecule via an O—H⋯O hydrogen bond of medium strength. Carbazoles between the layers inter­digitate through weak C—H⋯.π inter­actions to form a laminar solid stacked along [010]. Two kinds of C—H⋯π inter­actions are present, both with a distance of 2.64 Å, between the H atoms and the centroids, and a third C—H⋯π inter­action, where the aromatic H atom is located above the carbazole N-atom lone pair (H⋯N = 2.89 Å). Several C—H⋯O inter­actions occur between the coordinating DMF mol­ecule, the DMF solvent mol­ecule, and ligating carboxyl­ate O atoms.

Crystal structure of aqua-[(E)-N'-(5-bromo-2-oxido-benzyl-idene-κO)benzohydrazidato-κ(2) O,N']dioxidomolybdenum(VI) di-methyl-formamide monosolvate.

The title compound, [Mo(C14H9BrN2O2)O2(H2O)]·C3H7NO, has a distorted octa-hedral geometry around the Mo atom, with the two terminal oxide groups lying cis to each other. The two aromatic rings present in the mol-ecule are almost coplanar, forming a dihedral angle of 1.4 (2)°. The five-membered ring involving the metal atom is puckered, with an amplitude Q = 0.358 (2) Å and ϕ = 204.1 (6)°. In the crystal, pairs of inversion-related mol-ecules are linked by O-H⋯N hydrogen bonds. An O-H⋯O hydrogen bond connects the water ligand to the di-methyl-formamide solvent mol-ecule. The crystal packing also features π-π [centroid-centroid distance of 3.688 (2) Å] and C-H⋯O inter-actions.

Crystal structure of [2-({4-[2,6-bis(pyri-din-2-yl)pyri-din-4-yl]phenyl}(methyl)amino)-ethanol-κ(3) N,N',N'']bis-(thio-cyan-ato-κN)zinc N,N-di-methyl-formamide monosolvate.

In the title compound, [Zn(NCS)2(C24H22N4O)]·C3H7NO, the ZnII cation is N,N′,N′′-chelated by one 2-({4-[2,6-bis­(pyridin-2-yl)pyridin-4-yl]phen­yl}(meth­yl)amino)­ethanol ligand and coordinated by two thio­cyanate anions in a distorted N5 trigonal–bipyramidal geometry. In the mol­ecule, the three pyridine rings are approximately coplanar [maximum deviation = 0.026 (5) Å], and the mean plane of the three pyridine rings is twisted to the benzene ring with a small dihedral angle of 5.9 (2)°. In the crystal, complex mol­ecules are linked by weak C—H⋯O hydrogen bonds into supra­molecular chains propagated along [110]; π–π stacking is observed between adjacent chains [centroid–centroid distance = 3.678 (4) Å]. The di­methyl­formamide solvent mol­ecules are linked with the complex chains via weak C—H⋯O hydrogen bonds.

Crystal structure of bis-(2-{[(pyridin-2-yl)methyl-idene]amino}-benzoato-κ(3) N,N',O)cobalt(II) N,N-di-methyl-formamide sesquisolvate.

The title compound, [Co(C13H9N2O2)2]·1.5C3H7NO, is formed as a neutral Co(II) complex with di-methyl-formamide (DMF) solvent mol-ecules. The Co(II) atom has a distorted O2N4 octa-hedral coordination sphere defined by two tridentate anionic Schiff base ligands with the O atoms being cis. The coordination sphere around the Co(II) atom is geometrically different from that reported for the co-crystal [Co(C13H9N2O2)2]·AA·H2O (AA is anthranilic acid). One of the DMF solvent mol-ecules was modelled as being disordered about a crystallographic inversion centre with half-occupancy. The crystal structure is made up from alternating layers of complex mol-ecules and DMF mol-ecules parallel to (010). C-H⋯O hydrogen-bonding inter-actions between the complex mol-ecules and the solvent mol-ecules consolidate the crystal packing.

(R,S)-2'-Amino-6'-methyl-2,5',5'-trioxo-6'H-spiro-[indoline-3,4'-pyrano[3,2-c][2,1]benzo-thia-zine]-3'-carbo-nitrile di-methyl-formamide monosolvate.

The title solvate, C20H14N4O4S·C3H7NO, comprises a stereogenic centre but the centrosymmetric space group causes the presence of the racemate in the crystal. The spiro-joined fragments are almost orthogonal, with a dihedral angle of 86.8 (2)° between the mean planes of the pyrane ring and the dihydroindolone ring system. The atoms of the indolinone bicycle are coplanar, with an r.m.s. deviation of 0.005 Å. In the crystal, pairs of N—H⋯O hydrogen bonds link the mol­ecules into centrosymmetric dimers which are linked to the di­methyl­formamide solvent mol­ecules by further N—H⋯O hydrogen bonds. N—H⋯N hydrogen bonds link neighbouring dimers into [010] chains.

Ethyl 2-[2-(2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9-ylidene)hydrazin-1-yl]-4-methyl-1,3-thiazole-5-carboxylate dimethylformamide monosolvate

In the title mol­ecule, C27H30N4O2S·C3H7NO, the fused piperidine and cyclo­hexane rings adopt a twin chair conformation and the phenyl groups occupy equatorial sites. The phenyl rings make a dihedral angle of 40.74 (2)°. In the crystal, the di­methyl­formamide solvent mol­ecule is connected to the main mol­ecule by an N—H⋯O hydrogen bond. An additional N—H⋯O hydrogen bond connects mol­ecules into chains along [100]. Pairs of weak C—H⋯O hydrogen bonds connect inversion-related chains. The ethyl group was refined as disordered over two sets of sites with an occupancy ratio of 0.660 (17):0.340 (17).