Crystal structure, thermal analysis, and IR spectrometric investigation of bis(tert-butylammonium) sulfate

Chemical preparation, X-ray single crystal, thermal analysis, and IR spectrometric investigation of (C₄H₁₂N)₂SO₄, denoted tBAS, are described. The compound crystallizes in the monoclinic system with C2/c space group. Its unit cell dimensions are a = 11.1585(5) Å, b = 6.2148(4) Å, c = 20.070(1) Å, = 102.004(4)°, V = 1361.4(1) ų, and Z = 4. The crystal structure of tBAS can be described as a typical thick layered organization built by all the components of the structure and centered by planes z = 1/4 and 3/4. Connection in these layers are established by N—H···O hydrogen bonds. Thermal analysis shows a reversible weak phase transition.     

Influence of the spectator cation on the structure of anionic pyridine-2,6-dicarboxylato complexes of cobalt(II), nickel(II), and copper(II)

The structures of anionic pyridine-2,6-dicarboxylato (pdc^2–) complexes of cobalt, nickel, and copper have been studied. The stoichiometries and structures are very much dependent on whether KOH, Et₄NOH, or NaOH is used in the synthesis to deprotonate the H₂pdc ligand. Crystallographic results are: (1) K₂[Co(pdc)₂] · 7H₂O, orthorhombic, Pnna, Z = 4, a = 20.637(2)Å, b = 13.480(1)Å, c = 8.200(1)Å (2) K₂[Ni(pdc)₂] · 7H₂O, orthorhombic, Pnna, Z = 4, a = 20.648(1)Å, b = 13.375(1)Å, c = 8.2393(8)Å (3) [Co₂(H₂O)₅(pdc)₂] · 2H₂O, monoclinic, P2₁/c, Z = 4, a = 8.3880(6)Å, b = 27.384(2)Å, c = 9.6110(8)Å, = 98.271(6)° (4) [Ni(Hpdc)₂] · 3H₂O, monoclinic, P2₁/c, Z = 4, a = 13.679(1)Å, b = 10.0450(9)Å, c = 13.767(2)Å, = 115.184(7)° (5) Na₆[Co(H₂O)₆][Co(pdc)₂]₄ · 28H₂O, monoclinic, P2₁/n, Z = 2, a = 13.363(1)Å, b = 8.437(1)Å, c = 40.689(3)Å, = 91.288(5)° (6) Na[Ni(Hpdc)(pdc)] · 11.5H₂O, monoclinic, C2/m, Z = 4, a = 15.200(2)Å, b = 22.299(2)Å, c = 8.3596(7)Å, = 118.894(7)° (7) Na[Cu(Hpdc)(pdc)] · 3H₂O, monoclinic, P2₁/n, Z = 4, a = 9.516(4)Å, b = 14.917(6)Å, c = 12.247(5)Å, = 92.00(5)°. The potassium and sodium complexes have extensive K⁺—H₂O and Na⁺—H₂O networks. The fact the Et₄N⁺ ion does not appear in any of the complexes is likely due to the fact that it is incapable of forming the intricate cation—water and hydrogen-bonding networks observed in all of the other structures.     

Crystal structure of 2-{(R)-1-hydroxy-1-[(2S)-1-tritylaziridin-2-yl] methyl}acrylate and spectroscopic properties of the (R,S) and (S,S) stereoisomers

The crystal and molecular structure of 2-{(R)-1-Hydroxy-1-[(2S)-1-tritylaziridin-2-y1] methy1}acrylate is described. Crystal data: C₂₆H₂₅NO₃, orthorhombic, space group P2₁2₁2₁, a = 9.6954(5), b = 13.1458(5), c = 16.7885(7) Å, V = 2139.8(2) ų, Z = 4. The (R,S) diastereomer shows an intramolecular hydrogen bonding N···H—O under formation of a five-membered ring with N···O distance of 2.664 Å. IR, ¹H NMR and ¹³C NMR data are discussed. The ¹H NMR of the (R,S) diastereomer shows a singlet- whereas the (S,S) diastereomer exhibits a doublet-pattern for the hydroxyl proton.     

Synthesis and crystal structure of indium arsenate and phosphate dihydrates with variscite and metavariscite structure types

The hydrothermal synthesis, crystal structure analysis, and spectroscopic studies of InPO₄·2H₂O (1) and InAsO₄·2H₂O (2) are reported. Compound 1 is isomorphic with metavariscite: monoclinic P2₁/n (No. 14), a = 5.4551(3) Å, b = 10.2293(4) Å, c = 8.8861(3) Å, = 91.489(4)°, Z = 4, and compound 2 is isomorphic with variscite: orthorhombic Pbca (No. 61), a = 10.478(1) Å, b = 9.0998(8) Å, c = 10.345(1) Å, Z = 8. Their three-dimensional frameworks are built of corner sharing InO₄(H₂O)₂ octahedra and MO₄ (M = P⁵⁺ or As⁵⁺) tetrahedra. The water molecules in both compounds have different environments and are involved in different types of hydrogen bonding. Infrared spectroscopy indicates that water molecules are true H₂O species.     

Synthesis and X-ray structure of 11-N-benzylamido-9,10-dihydro-9,10-ethenoanthracene

As a part of studies on MDR reversing agents, the structure of a benzylamido-9,10-dihydro-9,10-ethenoanthracene is reported: C₂₄ H₁₉ N O; orthorhombic; space group: Pca2₁; a = 9.214(2), b = 18.624(4), c = 10.170(2) Å; 1745.2(6) ų; Z = 4. The three nonplanar rings from the 9,10-dihydro-9,10-ethenoanthracene skeleton of the molecule adopt a boat conformation. The benzamide side-chain is extended (conformation, trans-trans-gauche). The molecules in the crystal are joined by infinite chains of H-bonds N14–H14···O13.     

Crystal structure and thermal analysis of 1,5-diammonium-2-methyl pentane sulfate monohydrate

Chemical preparation, x-ray single crystal, and thermal analysis of C₆H₁₈N₂SO₄·H₂O (denoted DMPS) are described. The compound crystallizes in the triclinic system with P space group. Its unit cell dimensions are a = 5.826(1) Å, b = 10.014(1) Å, c = 11.221(1) Å, = 66.716(1)°, = 84.395(1)°, = 83.759(1)°, V = 596.7(1) ų, and Z = 2. The DMPS structure is built up from inorganic chains parallel to the a axis and linked via O(W)-H···O hydrogen bonds. These chains are interconnected by organic groups. Thermal analysis reveals the presence of one water molecule in the structure and shows a reversible weak phase transition.     

Crystal structure of a one-dimensional ladder-shape CoII complex through hydrogen bonds with an amino-acid-like ligand 1,5-diazacyclooctane-N,N′-diacetate acid

The crystal structure of a one-dimensional ladder-shape complex [CoL(H₂O)]·2H₂O, (L being 1,5-diazacyclooctane-N,N-diacetate acid), has been determined by X-ray diffraction analysis: monoclinic, space group P2₁/c with a = 14.406(4) Å, b = 7.380(2) Å, c = 14.594(5) Å, = 112.685(2)°, M _r = 341.23, V = 1431.5(8) ų, Z = 4. The Co^II center is penta-coordinated by two O atoms of the carboxylic pendant arms, two nitrogen donors of the 1,5-diazacyclooctane (DACO) moiety, and a water molecule. The coordination geometry of Co^II could be described as a distorted square pyramid and the DACO backbone adopts a normal boat/chair conformation. The complex forms a one-dimensional ladder-shape structure through inter- and intra-molecular O—H···O hydrogen bonds.     

Synthesis and crystal structure of [Y(NO3)3(OH2)3]·(Me2-16-crown-5)·H2O

The complex [Y(NO₃)₃(OH₂)₃]·(Me₂-16-crown-5)·H₂O has been prepared and its crystal and molecular structure determined using single crystal X-ray diffraction. The colorless crystals belong to the monoclinic space group P2₁/n with Z = 4. Lattice parameters are a = 10.420(1), b = 17.257(3), c = 14.646(2) Å, = 96.79(1)°, V = 2615.1(6) ų. The yttrium(III) ion is nine-coordinate, bonded to three bidentate nitrate groups and three water molecules. The average Y–O(nitrate) and Y–O(water) distances are 2.42(3) and 2.33(1) Å, respectively. The average HO–H···O hydrogen bonded separation is 2.767Å.     

Di-hydroxy malonic acid as a building block of hydrogen-bonded 3-dimensional architectures

An examination of the crystal structures of di-hydroxy malonic acid 1 (P2₁/na = 5.384(2), b = 6.268(2), c = 14.354(8) Å, = 103.57(3)°) and N-ethylbenzylammonium di-hydroxy hydrogenmalonate 2 (P2₁2₁2₁ a = 13.373(2), b = 15.342(4), c = 18.741(4) Å,) has highlighted the influence of directional O–H···O interactions in the assembly of hydroxy-substituted dicarboxylic acids. The complementarity of carboxylic and hydroxy groups in 1 creates a very dense 3-D structure (D _c = 1.919 g cm^–3) through four O–H···O hydrogen bonds. In 2, the anions form infinite, spiraling chains created by head-to-tail O–H···O hydrogen bonds. Neighbouring chains are crosslinked into a complex 3-D anionic network with channels parallel to a and b. The cations are positioned within these channels and held in place via two N–H···O interactions.     

First example of cocrystals of polymorphic maleic hydrazide

The first cocrystals of polymorphic maleic hydrazide with 3-methyluracil have been studied by X-ray diffraction methods. They crystallize in the orthorhombic system, space group Pmcn, a = 6.440 (1) Å, b = 6.974 (1) Å, c = 22.829 (11) Å, V = 1025.3 (5) ų, Z = 4. The asymmetric unit contains one molecule of each compound. Planar ribbons of the (1:1) molecular complex are obtained through the formation of O–H···O and O–H···N intermolecular hydrogen bonds, just forming a well-known R² ₂(8) supramolecular synthon. Supramolecular assemblies are then formed by weak C–H···O and C–H···N hydrogen bonds through adjacent antiparallel ribbons.     

Dalspinin, an isoflavone from Dalbergia spinosa roots

The X-ray crystal structure of the plant isoflavone dalspinin from Dalbergia spinosa is determined. The compound, C₁₇H₁₂O₇, is monoclinic in P2₁/n with a = 3.970(1), b = 23.607(5), c = 14.633(3) Å, = 94.46(3)°, V = 1367.2(5) ų, D _calc = 1.595 g cm^–1 and Z = 4. The molecular structure is characterized by a short intramolecular O–H···O=C hydrogen bond, and a large tilt angle of the two rigid ring systems with respect to each other. The intermolecular interactions in the crystal are discussed.     

Helical chirality of 1-phenacyl-1,10-phenanthrolinium bromides

Evidence for non-coplanarity of the pyridine and pyridinium rings in a series of 1-phenacyl-1,10-phenanthrolinium bromides was gleaned from ¹H-NMR data recorded in DMSO-d ₆ solution. The X-ray structure of 1-(4-chlorophenacyl)-1,10-phenanthrolinium bromide, as representative of this series, was determined in order to establish whether such a molecular distortion occurs in the solid state. The title compound crystallizes in the space group C2/c as a sesquihydrate of formula C₂₀H₁₄BrClN₂O·1.5H₂O with a = 35.7348(3) Å, b = 5.3468(1) Å, c = 21.7312(2) Å, = 116.4076(4)° and Z = 8. In the crystal, the helical chirality is manifested as a pronounced twist in the phenanthrolinium moiety, with the pyridine and pyridinium rings inclined at 6.8(2)°. This distortion is attributed to intramolecular hydrogen bonding of type C–H···N involving the methylene group and the uncharged nitrogen atom of the phenanthrolinium moiety. In the crystal, the cations surround an intricate array of water molecules and bromide ions held together by O–H···Br^– hydrogen bonds and comprising infinite chains ···Br^–···H–O–H···Br^–···, cross-linked by water molecules.     

Spectroscopic,thermal, and X-ray diffraction studies of tetrakis(thiourea) palladium chloride bis (5,7-dimethyl[1,2,4]triazolo[1,5-a]pyrimidine dihydrate

The crystal and molecular structure of the title compound, ·[Pd(S=C(NH₂)₂)₄]Cl₂·2dmtp·2H₂O. has been determined and refined to a finalR=0.034. The cation is centrosymmetric with the Pd atom existing in a square planar geometry with two disparate Pd–S bond distances of 2.3129(9) and 2.292(1)Å. Interatomic parameters are reported for the first non-coordinated dmtp molecule; these suggest the predominance of a particular canonical form in the solid state. The lattice is stabilized via a series H-bonding contacts involving the thiourea. Cl^– and dmtp species. Crystals of [Pd(S=C(NH₂)₂)₄]Cl₂ · 2dmtp · 2H₂O are monoclinic with space groupP2₁/c, and unit cell dimensionsa=15.129(1),b=8.512(1),c=12.663(1) Å, =104.05(1)°.     

Crystal structure of [Mn2(III)(salpa)2Cl2(H2O)2] (H2salpa = 1-(salicylaldeneamino)-3-hydroxypropane)

The manganese complex, (Mn₂(III)(salpa)₂Cl₂(H₂O)₂], has been prepared and its structure determined using x-ray crystallography. The dimer is a di-₂-alkoxo complex which is a six-coordinate manganese dimer with unsupported alkoxide bridges and a rare example of a chloride- and water-containing manganese dimer. The complex crystallizes in the monoclinic space group P2₁/c with a = 9.315(5), b = 11.130(4), c = 11.637(5) Å, = 104.33(3)°, V = 1169.0(9) ų, and Z = 2. The structure comprises discrete binuclear clusters in which the metal atoms are bridged by two alkoxo oxygens of the salpa^2– ligands. The Mn—O and Mn—N distances are in good agreement with those found for other manganese(III) Schiff base complexes. The Mn—Cl and Mn—O3 distances are 2.585(2) and 2.371(2) Å, respectively, and the Mn ··· Mn distance is 3.001(1) Å. In the crystal, there are two types of hydrogen bonding between the H₂O molecule and the Cl atom with Cl ··· H(H₂O) distance of 2.33(6) (intramolecule: –1 + x, y, –1 + z) and 2.68(6) Å (intermolecule: –1 + x, 0.5–y, –0.5 + z).     

The crystal structures of p-iodo-N-(p-cyanobenzylidene)aniline and p-cyano-N-(p-iodobenzylidene)aniline

The crystal structures of the isomers NC–C₆H₄–CH=N–C₆H₄–I (CN/I) and I–C₆H₄–CH=N–C₆H₄–CN (I/CN) have been determined. CN/I is triclinic, space group P1¯ with a = 7.504(3), b = 11.936(4), c = 7.304(2) Å, = 93.09(2), = 110.49(2), = 99.04(2)°, V = 601.1(3) ų, Z = 2, and D _x = 1.818(1) g cm^–3. In both compounds there are chains of molecules held together by CN···I interactions, with N···I distances of 3.15 and 3.26 Å, respectively. The chains form similar two-dimensional sheets, which, however, stack differently in the two compounds.     

Crystal structure of NH3(CH2)2NH3BiCl5·2H2O

The ethylenediammonium pentachlorobismuthate(III) dihydrate salt is monoclinic with the following unit cell dimensions: a = 10.902(8)Å, b = 7.926(6)Å, c = 15.199(6)Å, = 96.40(1)°, space group P2₁/n with Z = 4. The structure shows a layer arrangement parallel to the axis: planes of the [Bi₂Cl₁₀]^4– bioctahedra alternate with planes of [NH₃(CH₂)₂NH₃]²⁺ dications. The [Bi₂Cl₁₀]^4– bioctahedra are connected through O(W)–H··· Cl hydrogen bonds, so that infinite unidimensional chains of composition [Bi₂Cl₁₀(H₂O)₂] _n ^4n– are formed in the structure parallel to the axis. These chains are themselves interconnected by means of the N–H···Cl bonds originating from the [NH₃(CH₂)₂NH₃]²⁺ entities, forming a three-dimensional network.     

Crystal structure and characterization of [Co(saccharinate)2(L1)(H2O)2] n solvate: A new microporous coordination polymer generated from 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene (L1) and [Co(saccharinate)2·4H2O]·2H2O

A new microporous coordination polymer, [Co(saccharinate)₂(L1)(H₂O)₂] _n solvate, has been prepared from the reaction of the N,N bidentate ligand 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene (L1) with [Co(saccharinate)₂·4H₂O]·2H₂O in a methylene chloride/ethanol solvent mixture. The compound crystallizes in the triclinic system, space group P-1, with lattice parameters a = 7.6893(5) Å, b = 11.0169(7) Å, c = 11.2369(7) Å, = 66.2610(10)°, = 74.4160(10)°, = 74.6740(10)°. The structure consists of one-dimensional chains composed of octahedrally coordinated Co(II) centers linked by L1. The packing of these chains, along with intrachain and interchain hydrogen bonds, generates a 3-D framework with infinite channels that are occupied by disordered guest molecules. The compound was further characterized by IR spectroscopy and DTA/TGA.     

Synthesis and crystal structures of four nickel(II) 1,5-naphthalenedisulfonate compounds

Four nickle(II) 1,5-naphthalenedisulfonate (1,5nds) complexes, namely [Ni(H₂O)₆] (1,5nds) (1), trans-[Ni(en)₂(H₂O)₂](1,5nds)·2H₂O (2), [Ni(tren)(H₂O)₂](1,5nds)·H₂O (3), and [Ni(dien)₂](1,5nds)·2H₂O (4), where en = ethylenediamine, tren = tris(2-aminoethyl)amine, and dien = diethylenetriamine, have been synthesized and structurally characterized. Compound 1 crystallizes in space group P2₁/c, with a = 13.200(2) Å, b = 6.6197(10) Å, c = 9.6001(14) Å, and = 92.005(3)° compound 2 crystallizes in space group C2/c, with a = 15.698(2) Å, b = 13.006(2) Å, c = 12.845(2) Å, and = 119.262(4) Å compound 3 crystallizes in space group P , with a = 8.8971(10) Å, b = 11.5440(13) Å, c = 11.9169(14) Å, = 77.254(2)°, = 74.079(2)°, and = 82.162(2)° compound 4 crystallizes in space group P2₁/c, with a = 10.3600(13) Å, b = 12.5650(16) Å, c = 9.9853(12) Å, and = 103.599(2)°. Compound 1 crystallizes in a typical inorganic–organic layered structure adopted by metal naphthalenesulfonate, while compounds 2–4 crystallize in a hybrid inorganic–organic pattern. Unlike their Cu²⁺ analogue, the sulfonate does not coordinate directly to Ni²⁺. The hydrogen bonds formed between sulfonate and water molecules are the predominant packing forces for all structures. The inherited inversion center of the 1,5nds anion is carried into the crystal structure and results in centrosymmetric crystallization of all compounds.     

Redetermination of the crystal structure of [Na4(H2O)14]SnS4: a compound containing a novel chain of aquated sodium ions

[Na₄(H₂O)₁₄]SnS₄ is obtained by the reaction of Na₂S·9H₂O with SnCl₄·5H₂O in aqueous solution at 21°C. It crystallizes in the space group Cc with a = 8.621(2) Å, b = 23.543(5) Å, c = 11.358(2) Å, = 110.58(3)° and V = 2158.2 ų with Z = 2. Refinement of 3826 unique reflections from a racemically twinned crystal yielded a final value of R₁ = 0.0464 (|F| > 4) and wR₂ = 0.104 and a goodness of fit of 1.125. The structure consists of a Na⁺/H₂O network supporting the tetrahedral SnS₄ ^4– anions. Water molecules or sulfide ions octahedrally coordinate each of the four crystallographically independent Na⁺ ions. The dominant feature of the structure is the existence of zigzag chains of edgeshared Na octahedra. These chains are tied together into a three-dimensional network by bridging Na(H₂O)₆ octahedra and individual H₂O molecules.     

Nickel(II) complexes with N,N,O-donor Schiff bases. Self-assembly to two-dimensional network via hydrogen bonding

The syntheses, characterization and crystal structures of two mononuclear nickel(II) complexes are described. Reactions of Ni(O₂CCH₃)₂⋅4H₂O with the Schiff bases derived from 2-pyridinecarbaldehyde and ortho-aminophenol (Hpaap) and 2-pyridinecarbaldehyde and ortho-aminobenzoic acid (Hpaab) in methanolic media afford the complexes in good yields. The elemental analysis, magnetic moments, and spectral features of the complexes are consistent with the formulae [Ni(paap)₂]⋅CH₃COOH⋅H₂O and [Ni(paab)₂]⋅2H₂O. Crystal data for [Ni(paap)₂]⋅CH₃COOH⋅H₂O: monoclinic, P2₁/c, a = 9.675(2) Å, b = 17.109(5) Å, c = 14.403(4) Å, β = 92.903(11)^∘, V = 2381.1(11) ų, and Z = 4 and for [Ni(paab)₂]⋅2H₂O: triclinic, P 1, a = 9.834(3) Å, b = 11.319(3) Å, c = 13.130(4) Å, α = 84.68(3), β = 67.54(3), γ = 85.49(2)^∘, V = 1343.4(6) ų, and Z = 2. In each complex, two tridentate monoanionic meridionally spanning ligands form a distorted octahedral N₄O₂ coordination sphere around the metal ion. In [Ni(paap)₂]⋅CH₃COOH⋅H₂O, two metal coordinated phenolate-O atoms are hydrogen bonded to CH₃COOH and H₂O, respectively. Intramolecular C–H⋅ < eqid1 > ⋅O interactions involving the water molecule and the C–H from azomethine and aromatic fragments lead to a two-dimensional network of [Ni(paap)₂]⋅CH₃COOH⋅H₂O in the crystal lattice. An uncoordinated carboxylate O-atom in [Ni(paab)₂]⋅2H₂O is hydrogen bonded to both water molecules. One of the water molecules is again hydrogen bonded to the corresponding symmetry related water molecule forming a dimer. The azomethine groups and the metal coordinated carboxylate-O atoms in [Ni(paab)₂] are involved in intermolecular C–H⋅ < eqid2 > ⋅O interactions forming a chain-like arrangement of the molecules. The water dimers act as bridges between these chains and a two-dimensional network of [Ni(paab)₂]⋅2H₂O is formed.