More insight into the crystal structure of [Co(H 2 O) 4 (4-nba) 2 ]·2H 2 O (4-nba=para-nitrobenzoate): an unprecedented hydrogen bonded Supramolecular network (original) (raw)
Crystal and molecular structure of di(para-nitrobenzoato)diaquolead
Journal of Structural Chemistry, 1990
In previous work [1], we synthesized a complex of lead p-aminobenzoate. The results of a structural analysis showed that p-aminobenzoic acid reacts with lead to form a coordination polymer. The effect of the substituent at the para position relative to the carboxyl group of the benzoate anion is very significant. The nitro group is more "flexible" in comparison with the amino group. It was of interest to study the dependence of the structure formation on the nature of the substituent in the benzoate anion. For this purpose, we studied the structure of di(para-nitrobenzoata)diaquolead. Lead nitrobenzoate, [Pb(p-NO2C6H4CO2)2.2H20] was synthesized by the reaction of aqueous solutions of Pb(NO3) 2 and sodium para-nitrobenzoate in 1:2 stoichiometric ratio. The mixture of these solutions was stirred for 20 min on a steam bath, cooled, and filtered. Colorless platelets precipitated upon standing for several days at room temperature. The x-ray diffraction structural analysis was carried out on a Syntex P21 automatic diffractometer with 6/20 scanning, 2ema x = 60 ~ The unit cell parameters of the triclinic crystals are as follows: a =__7.22(1), b = I 1.60(2), c = 6.98(3) A, a = 114.48(1), fl = 111.69(1), 7 = 65.06(1)*, V-463.78/k z, Z = 1, space group P1. A total of 1199 independent reflections were measured. A total of 1188 reflections with F 2 ~ 2a were used in the structural calculations. Absorption was not taken into account. All the calculations were carried out on an ES-1022 computer using the SHELX-76 program [2]. The structure was solved by the heavy atom method. The coordinates of the lead atom were determined from the three-dimensional Patterson map. The R value was 0.15 after anisotropic refinement cycles. The three-dimensional electron density difference map revealed the positions of all the nonhydrogen atoms of the complex. Three refinement cycles (anisotropic approximation for Pb, isotropic approximation for oxygen and carbon atoms) reduced R to 0.10. The basis atoms are given in Table 1. The projection of the structure of [Pb(p-NO2C6H4CO2)2.2H20] on the (100) plane is shown in Fig. 1. The bond lengths and bond angles are given in Table 2. The crystal structure of this complex is insular. The lead atom is in a special position. The lead atom has octahedral coordination. The apices of the octahedron are occupied by four carboxyl group oxygen atoms and two water molecules. The centrosymmetric carboxyl groups form a chelate with the metal atom (Pb-O(I), 2.48(6); Pb-O(2), 2.71(3) A). The Pb-O bond lengths in the structure are greater than the analogous values for the para-aminobenzoate complex (Pb-O(3), 2.39(3); Pb-O(4), 2.51(3) A) [1]. The Pb-O w bond length involving the centrosymmetric water molecule is 2.55(7) A. This value is in accord with the corresponding lengths 2.33-2.55 A in PbC204.3H20 [3]. According to the literature data, the Pb-OH 2 bond lengths lie in the range from 2.38 to 3.30 A. The analogous bond lengths found in the present structure approach the lower limit of this range. Thus, the coordination number of lead is expanded to six. Table 2 shows that the coordination polyhedron of lead is highly distorted. The distortions of the coordination polyhedron may be explained by the formation of a chelate ring of the R-CO2-groups. The sum of the intracyclic angles in the PbO(I)C(I)O(2) chelate ring (359.8 ~ differs only slightly from the ideal value of 360*. This indicates a planar structure of the chelate ring. The lengths of the CO bonds in the coordinated nitrobenzoate anion are 1.26(3) and 1.29(3) A and are identical to the CO bond lengths in Pb(p-HOC6H4CO2)2-H20 [4] (1.26(7) and 1.29(4) A) although the dentation of the carboxyl groups differs (a-4s-a). A marked increase is noted for the O-CO bond angle (136.0(5)~ Such increases and decreases in O-C-Obond angles are encountered in all aromatic lead carboxylates studied in our laboratory [1, 4-6]. The mean CC bond length in the benzene ring is 1.39(1) A, while the mean bond angle is 118.5". These values coincide with the corresponding values in analogous complexes and indicate a planar structure of the benzene ring.
2020
Dissolution of a fine powder obtained by mechanochemical grinding of cobaltous carbonate with 4-nitrobenzoic acid (4-nbaH) in hot dimethylsulfoxide (DMSO) followed by slow evaporation of the solvent resulted in the formation of cis-diaquabis(dimethylsulfoxide)4-nitrobenzoatocobalt(II) 4-nitrobenzoate 1 in good yield. The title compound [Co(H2O)2(DMSO)2(4-nba)]4-nba 1 crystallizes in the centrosymmetric monoclinic P21/c space group. The structure of 1 consists of two crystallographically independent Co(II) ions. Each unique cobalt exhibits octahedral geometry and is bonded to a pair of terminal aqua ligands situated cis to each other and a bidentate 4-nba ligand which form the square base of the octahedron. A pair of DMSO ligands disposed trans to each other complete the hexa coordination around the central metal. The [Co(H2O)2(DMSO)2 (4-nba)] cations and the 4-nba anions are interlinked with the aid of several weak H-bonding interactions. A comparative study of several 4-nitrobenzoa...
Crystal structure of 4-formyl-2-nitrophenyl 4-chloro-2-nitrobenzoate
Acta Crystallographica Section E Crystallographic Communications, 2015
In the title compound, C14H7ClN2O7, the central ester moiety is essentially planar, with an r.m.s. deviation of 0.0113 Å. The ester group is twisted away from the chloro- and formyl-substituted rings by 84.60 (9) and 88.55 (9)°, respectively. The crystal packing shows intermolecular C—H...O interactions. These interactions generateR22(20) andR44(22) edge-fused rings parallel to (20-2).
Acta crystallographica. Section C, Crystal structure communications, 2005
Anilinium 2-carboxy-4-nitrobenzoate, C6H8N+.C8H4NO6-, (I), 4-chloroanilinium 2-carboxy-4-nitrobenzoate, C6H7ClN+.C8H4NO6-, (II), 4-bromoanilinium 2-carboxy-4-nitrobenzoate, C6H7BrN+.C8H4NO6-, (III), and 4-iodoanilinium 2-carboxy-4-nitrobenzoate, C6H7IN+.C8H4NO6-, (IV), are approximately isostructural. In each compound, the ions are linked into complex sheets by a combination of O-H...O and N-H...O hydrogen bonds. Within the sheets, two distinct one-dimensional substructures can be identified, viz. a chain of edge-fused R(3)3(13) rings and a double helix of simple C(2)2(9) chains. In (I) and (IV), the sheets are linked by a C-H...O(nitro) hydrogen bond and a two-centre C-I...O(nitro) interaction, respectively, but the corresponding C-Cl...O and C-Br...O contact distances in (II) and (III) are not significantly shorter than the sum of the van der Waals radii.
Hydrogen-bonding network in the organic salts of 4-nitrobenzoic acid
Central European Journal of Chemistry, 2006
The crystal structures of six novel salts of 4-nitrobenzoic acid — namely, 2-hydroxyethylammonium 4-nitrobenzoate (I), 2-hydroxypropylammonium 4-nitrobenzoate (II), 1-(hydroxymethyl)propylammonium 4-nitrobenzoate (III), 3-hydroxypropylammonium 4-nitrobenzoate (IV), bis-(2-hydroxyethylammonium) 4-nitrobenzoate (V), morpholinium 4-nitrobenzoate (VI) — containing the same anion but different cations have been studied. The ionic forms of I-VI serve as building blocks of the supramolecular architecture, and in crystals they are held together via ionic N-H···O and O-H···O hydrogen bonds. In the crystal packing the building blocks of I-III are self-assembled via N-H...O, O-H···O and C-H...O hydrogen bonds to form the chains which are further consolidated into two-dimensional layers by the same type of interactions. In IV-VI the chain-like structures have been generated by building blocks.
First alkaline earth 2-carbamoyl-4-nitrobenzoate: Synthesis and supramolecular structure
2009
2-Carbamoyl-4-nitrobenzoic acid (2-ca-4nbaH) has been prepared by alkaline hydrolysis of 4-nitrophthalimide. Aqueous reaction of MgCO 3 with 2-ca-4nbaH results in the formation of [Mg(H 2 O) 6 ](2-ca-4nba) 2 , which crystallizes in the centrosymmetric monoclinic space group P2 1 /c with Mg(II) situated on an inversion center. The crystal structure consists of a distorted octahedral hexaaquamagnesium(II) cation and a free uncoordinated 2-ca-4nba anion. The cation and anion are involved in three varieties of H-bonding interactions, resulting in a supramolecular bilayer of 2-ca-4nba anions sandwiched between layers of [Mg(H 2 O) 6 ] 2+ cations.
The crystal structure of 4-(pyren-1-yl)butyl-4-nitrobenzoate, C27H21NO4
Zeitschrift für Kristallographie - New Crystal Structures
C27H21NO4, triclinic, P 1 ‾ Poverline1P\overline{1}Poverline1 (no. 2), a = 7.3476(2) Å, b = 7.4894(2) Å, c = 20.5137(5) Å, α = 89.33000(10)°, β = 79.7070(10)°, γ = 67.5220(10)°, V = 1024.31(5) Å3, Z = 2, R gt (F) = 0.0536, wR ref (F 2) = 0.1792, T = 296.15 K.
Acta Crystallographica Section E Crystallographic Communications
The asymmetric unit of the title co-crystal, C12H9N5O·C7H6O3, contains one molecule ofN6-benzoyladenine (BA) and one molecule of 4-hydroxybenzoic acid (HBA). TheN6-benzoyladenine (BA) has an N(7)—H tautomeric form with nonprotonated N-1 and N-3 atoms. This tautomeric form is stabilized by a typical intramolecular N—H...O hydrogen bond between the carbonyl (C=O) group and the N(7)—H hydrogen on the Hoogsteen face of the purine ring, forming a graph-setS(7) ring motif. The primary robustR22(8) ring motif is formed in the Watson–Crick faceviaN—H...O and O—H...N hydrogen bonds (involving N1, N6—H and the carboxyl group of HBA). Weak interactions, such as, C—H...π and π–π are also observed in this crystal structure.
Acta Crystallographica Section E Crystallographic Communications
The crystal and molecular structures of the title molecular salts, C4H12NO+·C7H5N2O4 −, (I), C6H16NO+·C7H5N2O4 −, (II), and C4H12NO3 +·C7H5N2O4 −, (III), are described. The common feature of these salts is the presence of the 2-amino-4-nitrobenzoate anion, which exhibit non-chemically significant variations in the conformational relationships between the carboxylate and nitro groups, and between these and the benzene rings they are connected to. The number of ammonium-N—H H atoms in the cations increases from one to three in (I) to (III), respectively, and this variation significantly influences the supramolecular aggregation patterns in the respective crystals. Thus, a linear supramolecular chain along [100] sustained by charge-assisted tertiary-ammonium-N—H...O(carboxylate), hydroxy-O—H...O(carboxylate) and amino-N—H...O(carboxylate) hydrogen-bonds is apparent in the crystal of (I). Chains are connected into a three-dimensional architecture by methyl-C—H...O(hydroxy) and π–π inter...
Supramolecular 2D structure of Co(2-Me-Pyz)2(H2O)42
Russian Journal of Coordination Chemistry, 2009
The complex [ Co (2-Me -Pyz ) 2 ( H 2 O ) 4 ]( NO 3 ) 2 is synthesized and its structure is determined. The crystals are monoclinic: space group P 2 1 / n , a = 10.685(2) Å, b = 6.837(1), c = 12.515(3) Å , β = 91.84(3)°, V = 913.8(3) Å 3 , ρ calcd = 1.042 g/cm 3 , Z = 2. The Co 2+ ion (in the inversion center) is coordinated at the vertices of the distorted octahedron by two nitrogen atoms of methylpyrazine and four oxygen atoms of the water molecules (Co(1)-N(1) 2.180(3), average Co(1)-O( w ) 2.079(3) Å, angles at the Co atom 87.9(1)-92.1(1)° ). Supramolecular pseudometallocycles are formed in the structure through the O( w )-H ···N (1) hydrogen bonds between the coordinated H 2 O molecules and the terminal nitrogen atoms of the 2-methylpyrazine molecules. Their interaction results in the formation of supramolecular layers joined by the N O 3 groups into a three-dimensional framework.
Acta Crystallographica Section E Crystallographic Communications, 2016
The title 2:1 co-crystal, 2C7H5NO4·C14H14N4O2, in which the complete diamide molecule is generated by crystallographic inversion symmetry, features a three-molecule aggregate sustained by hydroxyl-O—H...N(pyridyl) hydrogen bonds. Thep-nitrobenzoic acid molecule is non-planar, exhibiting twists of both the carboxylic acid and nitro groups, which form dihedral angles of 10.16 (9) and 4.24 (4)°, respectively, with the benzene ring. The diamide molecule has a conformation approximating to a Z shape, with the pyridyl rings lying to either side of the central, almost planar diamide residue (r.m.s. deviation of the eight atoms being 0.025 Å), and forming dihedral angles of 77.22 (6)° with it. In the crystal, three-molecule aggregates are linked into a linear supramolecular ladder sustained by amide-N—H...O(nitro) hydrogen bonds and orientated along [10-4]. The ladders are connected into a double layerviapyridyl- and benzene-C—H...O(amide) interactions, which, in turn, are connected into a ...
Zeitschrift für Kristallographie - Crystalline Materials, 2018
Crystallography reveals two polymorphs for the salt [4-(4-acetylphenyl)piperazin-1-ium][2-amino-4-nitrobenzoate], a monoclinic form (2; modelled as P21/n with Z′=4) formed directly from the reaction mixture, and a triclinic form (1; Z′=1) isolated from recrystallisation. Relatively minor differences are noted in the conformations of the anions and of the cations, mainly relating to the twist of, respectively, the carboxylate groups and piperazin-1-ium rings with respect to the phenyl rings they are connected to. The key feature of the packing of both forms is the formation of charge-assisted ammonium-N–H···O (carboxylate) hydrogen bonds which lead to cyclic 12-membered {···HNH ···OCO}2 synthons in the case of 1 but, supramolecular chains in 2. The three-dimensional architecture in the crystal of 1 is further stabilised by amine-N–H···O (nitro) and amine-N–H···O (acetyl) hydrogen bonds, leading to double-layers in the bc-plane, which are linked along the a-axis by methylene-C–H···O (...
Crystal structure and Hirshfeld surface analysis of 2-(4-nitrophenyl)-2-oxoethyl 2-chlorobenzoate
Acta Crystallographica Section E Crystallographic Communications, 2019
The title compound, C15H10ClNO5, is relatively planar with the two aromatic rings being inclined to each other by 3.56 (11)°. The central —C(=O)—C–O—C(=O)— bridge is slightly twisted, with a C—C—O—C torsion angle of 164.95 (16)°. In the crystal, molecules are linked by C—H...O and C—H...Cl hydrogen bonds, forming layers parallel to the (101) plane. The layers are linked by a further C—H...O hydrogen bond, forming a three-dimensional supramolecular structure. There are a number of offset π–π interactions present between the layers [intercentroid distances vary from 3.8264 (15) to 3.9775 (14) Å]. Hirshfeld surface analyses, the d norm surfaces, electrostatic potential and two-dimensional fingerprint plots were examined to verify the contributions of the different intermolecular contacts within the supramolecular structure. The shape-index surface shows that two sides of the molecule are involved in the same contacts with neighbouring molecules, and the curvedness plot shows flat surfa...
Low-temperature 4-thiacyclohexylm-nitrobenzoate
Acta Crystallographica Section E Structure Reports Online, 2003
The crystal structure of the title compound, C 12 H 13 NO 4 S, reveals that the molecule exists with the ester group in the axial conformation, which differs from that observed in solution. The CÐO bond distance from the cyclohexyl group to the ester O atom is 1.471 (2) A Ê. The structure was determined at 130 K. Comment As part of our studies on the factors in¯uencing CÐOR (R = hydroxy, ester or ether) bond distances (White & Robertson, 1992; Green et al., 2000; Pool et al., 2000), we have determined the structure of 4-thiacyclohexyl m-nitrobenzoate, (1). CÐO bond distances are sensitive to the effects of electron donation into the CÐO antibonding orbital (Amos et al., 1992). We were interested in establishing whether a through-bond interaction between the sulfur lone pair of electrons and the CÐO bond in the ester (1) (Fig. 1) would result in any signi®cant lengthening of the CÐO(ester) bond.