Self-assemblies of Ni(II) with phenanthroline and maleate anions: [Ni(H2O)3(phen)L] ⋅ H2O (1) and [Ni(H2O)2(phen)L] ⋅ 2H2O (2) with H2L = maleic acid

The complex [Ni(H₂O)₃(phen)(C₄H₂O₄)] H₂O (1), which was obtained by reaction of phenanthroline, Ni(NO₃)₂ 6H₂O, and maleic acid in CH₃OH/H₂O at pH = 7.05, crystallized in the monoclinic space group P2₁ (no. 4) with cell dimensions: a = 9.350(1) Å, b = 7.631(1) Å, c = 12.821(1) Å, = 106.25(1), and D _calc = 1.607 g/cm³ for Z = 2. The Ni atoms are each octahe drally coordinated by one chelating phen ligand, three H₂O molecules and one monodentate maleato ligand to form [Ni(H₂O)₃(phen)(C₄H₂O₄)] complex molecules with d(Ni–O) = 2.038–2.090 Å, d(Ni–N) = 2.066, 2.089 Å. The formed complex molecules are, via the intermolecular hydrogen bonds, assembled into columnar 1D chains. Interdigitation of the chelating phen ligands of the neighboring chains leads to 2D layers and the crystal H₂O molecules are hydrogen bonded to the oxygen atoms of the maleate not coordinated to the Ni atom. However, reaction of NiCO₃, phen, and maleic acid in CH₃OH/H₂O at pH = 6.33 afforded [Ni(H₂O)₂(phen)(C₄H₂O₄)] 2H₂O (2), which crystallized in the triclinic space group (no. 2) with cell dimensions: a = 7.971(1) Å, b = 8.237(1) Å, c = 13.304(1) Å, = 81.005(6)°, = 87.877(8)°, = 78.322(8)°, and D _calc = 1.671 g/cm³ for Z = 2. The Ni atoms are each octahedrally coordinated by two N atoms of one phen ligand and four O atoms of two H₂O molecules and two bis–monodentate maleato ligands with d(Ni–O) = 2.041–2.120 Å and d(Ni–N) = 2.095 Å. The Ni atoms are bridged by the maleato ligands to generate 1D ¹ [Ni(H₂O)₂(phen)(C₄H₂O₄)_2/2] chains along [100]. The supramolecular assemblies of the 1D chains via – stacking inter- actions result in thick 2D layers parallel to (001), between which the noncoordinating H₂O molecules are sandwiched. The paramagnetic [Ni(H₂O)₂(phen)(C₄H₂O₄)_2/2] 2H₂O (2) obeys the Curie–Weiss law _m(T-) = 1.139cm³ mol^–1 K with the Weiss constant = –0.95 K.     

Hydrogen bonding in labdane diterpenoids, labda-7,12(E),14-triene-17-oic acid and labda-12(Z),14,17-triene-18-oic acid

Two labdane diterpenoids, labda-7,12(E),14-triene-17-oic acid (1) and labda-12(Z),14,17-triene-18-oic acid (2), C₂₀H₃₀O₂, have been isolated from Croton oblongifolius. Both 1 and 2 crystallized in the monoclinic system, space group C2, with cell dimensions of a = 21.912(1) Å, b = 7.4002(4) Å, c = 11.5079(7) Å, = 101.999(1)^o and a = 21.308(2) Å, b = 11.9067(9) Å, c = 7.5606(6) Å, = 100.763(1)^o, respectively. Compound 1, a rare example of carboxylic group bound to a cyclohexene ring, forms an infinite intermolecular hydrogen-bonded polymer [O1 O2(–x + 1/2, y + 1/2, –z + 2) 2.697(2) Å], whereas molecules of compound 2 are linked to form an asymmetric hydrogen-bonded dimer [O1 O2(–x, y, –z) 2.657(3) Å].     

Synthesis and crystal structure of Bi(mpo)3 (Hmpo = 2-mercaptopyridine N-oxide)

The synthesis as well as crystal and molecular structure of [Bi(C₅H₄NOS)₃] are reported. The complex crystallizes in the monoclinic system, space group P2₁/n with lattice parameters a = 9.6521(3) Å, b = 10.0659(4) Å, c = 18.4484(7) Å, = 102.13(6)°, and D _calc = 2.227 Mg · m^–3 for Z = 4. It is clear from the packing diagram that the title compound is a dimer via the secondary coordination. Surrounding Bi atom, three five-membered ring planes (Bi,O,N,C,S) make a dihedral angle of 55.91, 54.72, and 26.13° respectively. The whole crystal presents a three-dimensional network structure as each molecule produces four weak C–H O hydrogen bonds and a weak C–H S hydrogen bond.     

Structures of transition and alkaline earth metal salts of 5-aminonaphthalene-2-sulfonate and 6-aminonaphthalene-1, 3-disulfonate: Some unusual coordination behaviors

Salts of 5-aminonaphthalene-2-sulfonate with divalent Mg, Mn, Co, and Ni cations have been crystallized and their structures determined by single crystal X-ray methods. The Mg, Mn, and Co salts are isostructural. Crystal data for hexaaquamagnesium(II) 5-aminonaphthalene-2-sulfonate hexahydrate, [Mg(H₂O)₆](H₂NC₁₀H₆SO₃)₂·6H₂O: monoclinic, P2₁/c, Z=2, a=14.1329(18) ?, b=8.5789(11) ?, c=12.4880(17) ?, β=93.374(3)°, V=1511.5(3) ?³; hexaaquamanganese(II) 5-aminonaphthalene-2-sulfonate hexahydrate, [Mn(H₂O)₆](H₂NC₁₀H₆SO₃)₂·6H₂O: monoclinic, P2₁/c, Z=2, a=14.249(3) ?, b=8.5940(17) ?, c=12.505(3) ?, β=93.30(3)°, V=1528.8(6) ?³; hexaaquacobalt(II) 5-aminonaphthalene-2-sulfonate hexahydrate, [Co(H₂O)₆](H₂NC₁₀H₆SO₃)₂·6H₂O: monoclinic, P2₁/c, Z=2, a=14.1406(18) ?, b=8.5674(11) ?, c=12.4960(16) ?, β=93.297(2)°, V=1511.4(3) ?³. The structures are composed of alternating layers of octahedral metal–aqua complexes and sulfonate anions linked by hydrogen bonds. The three water molecules of crystallization are associated with the hexaaquametal cations and sulfonate O atoms. The repeat unit along the a-axis is a single layer. The Ni salt [crystal data for tetraaquabis(5-aminonaphthalene-2-sulfonato-N)nickel(II) dihydrate, [Ni(H₂O)₄(H₂NC₁₀H₆SO₃)₂]·2H₂O: triclinic, , Z=1, a=6.8524(10) ?, b=8.3094(12) ?, c=11.4832(17) ?, α=69.003(2)°, β=76.570(3)°, γ=83.952(2)°, V=593.56(15) ?³] has a very different structure with direct coordination of the amine N atom to Ni, a modified stacking pattern, and fewer free water molecules. Ag and Ni salts of an amine-substituted naphthalenedisulfonate have also been characterized. Crystal data for diaqua(6-ammonionaphthalene-1,3-disulfonato-O)silver(I) hydrate,[Ag(H₂O)₂(H₃NC₁₀H₅(SO₃)₂)]·0.42H₂O: monoclinic, P2₁/c, Z=2, a=9.099(3) ?, b=21.406(6) ?, c=7.629(2) ?, β=110.178(4)°, V=1394.9(7) ?³; tetraaquabis (6-ammonionaphthalene-1,3-disulfonato-O)nickel(II)tetrahydrate, [Ni(H₂O)₄(H₂NC₁₀H₅ (SO₃)₂)₂]·4H₂O: triclinic,, Z=1, a=6.7971(17) ?, b=10.661(3) ?, c=11.165(3) ?, α=68.308(4)°, β=88.292(5)°, γ=84.896(5)°, V=748.8(3) ?³. The silver salt contains six coordinate metal centers each of which bonds to four sulfonate O atoms from three different anions and two water molecules. The nickel salt contains octahedral cations with four water molecules and two trans sulfonate O atoms. Both structures are layered, but differently from each other and from those of the monofunctional naphthalenesulfonate salts.Unusual coordination of a sulfonate group to a transition metal and coordination of an amine group to nickel but not to cobalt or manganese have been observed in a series of metal aminonaphthalenesulfonate salts     

Synthesis and crystal structure of a new two-dimensional chromium(III) network through hydrogen bonds

A new chromium(III) complex, [Cr(ox)(bdmpza)(H₂O)], (ox = oxalate dianion and bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate, respectively), has been synthesized and characterized by X-ray crystallography. This compound crystallizes in the monoclinic space group P2₁/c, with a = 7.008(3) Å, b = 14.229(5) Å, c = 16.497(7) Å, = 101.588(7)°, V = 1611.5(11) ų, Z = 4. The chromium atom has a distorted octahedral environment with different coordination atoms. Bis(3,5-dimethylpyrazol-1-yl)acetate anion is a tridentate ligand, and the oxalate group acts as a chelating bidentate ligand. This compound also forms an infinite two-dimensional network through O–H O hydrogen bonds. The lengths of the hydrogen bonds are 2.765(5) and 2.733(5) Å, respectively.     

The crystal structure of 5-amino-2-nitrobenzoic acid

The crystal structure of 5-amino-2-nitrobenzoic acid (5A2NB) was determined by the X-ray diffraction method. The 5-amino-2-nitrobenzoic acid crystallizes in the monoclinic P2₁/c space group with a = 3.898(2) Å, b = 13.531(3) Å, c = 14.301(3) Å, and = 90.83(3)°. The adjacent molecules form a cyclic dimmer by intermolecular hydrogen bonds of type O—HsO with their carboxyl groups. In the crystal structure NH₂ group forms a three-center hydrogen bond with oxygen atoms of NO₂ group. The IR spectrum and thermal properties of acid are discussed.     

Hydrogen-bond networks in the mono- and diprotonated cyclic diamine [9]aneN2S

The hydrogen-bond networks in the mono- and diprotonated cyclic diamine, 1-thia-4,7-diazacyclononane, [9]aneN₂S, have been examined. Crystals of the monoprotonated, form [9]aneN₂S HCl, contain a ribbon-like network of alternating strong and weak intermolecular N H Cl hydrogen bonds and weak intramolecular N H N hydrogen bonds. Crystal data for [9]aneN₂S HCl: monoclinic, a = 6.6640(6) Å, b = 10.3493(9) Å, c = 6.9807(6) Å, = 108.847(1)°, V = 455.63(7) ų, space group P2₁, Z = 2. In the di-protonated form, [9]aneN₂S 2HBr, the ribbon-like network comprises strong intermolecular and weak intramolecular N H Br hydrogen bonds. Crystal data for [9]aneN₂S 2HBr: orthorhombic, a = 12.5918(13) Å, b = 8.0753(9) Å, c = 10.6856(11) Å, V = 1086.5(2) ų, space group Pnma, Z = 4. The chloride anions of [9]aneN₂S HCl align in interlocking columns in the a- and c-direction whereas the bromide anions in [9]aneN₂S 2HBr occupy channels in the b-direction.     

Synthesis and structure of [(nitrito-O,O′) bis(di-2-pyridylamine)copper(II)] nitrite

The synthesis and molecular structure of the title compound, [(nitrito-O,O) (dpa)₂Cu(II)] (NO₂), 1, is reported. Compound 1 crystallized in the orthorhombic space group Pccn with a = 11.397(5) Å, b = 12.256(6) Å, c = 14.876(8) Å, and V = 2077.9(17) ų with Z = 4. The distorted octahedral copper(II) cations are linked through a hydrogen-bonded polymer network. The polymer network is formed through the amine N–H of the cations and hydrogen bonded to the N–HO nitrite anions.     

Synthesis and X-ray structure analysis of 2-acetylamino-benzoic acid

The title compound crystallizes in the orthorhombic space group Fdd2 with unit cell parameters a = 10.848(1) Å, b = 30.264(1) Å and c = 10.577(1) Å, V = 3472.47(2) ų, and Z = 4. The final reliability index is 0.030 for 700 observed reflections. Nitrogen of the amide group and carbon atom of the acid group deviate significantly below and above the plane of the phenyl ring. The crystal cohesion is accentuated by N—HO and O—HO hydrogen bonds.     

Rotational disorder in 1,5-dihydroxy xanthone

The crystal structure of 1,5-dihydroxy xanthone obtained from Callophyllum trapezifolium has been determined (C₁₃H₈O₄), Mr = 228.21, a = 5.547(5), b = 5.186(5), c = 16.487(5) Å, = 91.40(1), Z = 2 and V = 474.1(6) ų. The xanthone molecule is planar and exhibits rotational disorder in the crystal. The packing of the molecules in the crystal lattice is due to inter- and intramolecular O–H O hydrogen bonds forming infinite chains.     

Preparation, characterization, and X-ray structure analysis of diethylenetriammonium tetrathiomolybdate

The interaction of H₂S gas with aqueous ammonium heptamolybdate solution in the presence of diethylenetriamine (dien) led to the formation of diethylenetriammonium tetrathiomolybdate crystals. The elemental analyses, UV-Visible, IR, and ¹H NMR spectra suggested the presence of organic cation and (MoS₄)^2– moiety. The ¹H NMR revealed the presence of two sets of symmetrical A₂X₂ multiple patterns. The compound crystallizes in the monoclinic system with space group Pn, a = 7.196(6), b = 7.532(3), c = 11.525(10) Å, = 90°, = 90.17(3)°, = 90°, V = 624.78(8) ų, and Z = 2, wR ₁ = 0.0261 and wR ₂ = 0.0698. The structure consists of tetrahedral tetrathiomolybdate anions, which form an extended three-dimensional network in the solid state with Mo–SH–N hydrogen bonding with the organic cation.     

Structure of hexakis(imidazole)cadmium(II) carbonate trihydrate: [Cd(Im)6]CO3 ⋅ 3H2O

The crystal and molecular structure of the title compound [Cd(Im)₆]CO₃ 3H₂O, where Im = imidazole, has been determined by X-ray crystallography. The crystal structure consists of discrete Cd(Im)₆ ²⁺ cations, CO₃ ^2– anions and three uncoordinated water molecules. It crystallizes in the hexagonal system, space group P6₃/m, with lattice parameters a = 9.0552(l) Å, c = 21.745(l) Å, and Z = 2; The Cd(II) ion assumes centrosymmetric octahedron geometry. The bond distance of Cd–N is 2.361(l) Å. A three-dimensional intermolecular hydrogen bond network is formed between the free carbonate anions, the imidazole ligands, and the free water molecules.     

Crystal structure of di(N-benzyl piperidinium) pentachloroantimonate(III) dihydrate

The salt di(N-benzyl piperidinium) pentachloroantimonate(III) dihydrate crystallizes in the orthorhombic system with space group Cmc2₁, the unit cell dimensions are: a = 29.383(1), b = 10.509(2), c = 9.941(1) Å, with Z = 8. The structure shows a layer arrangement perpendicular to the a axis: planes of SbCl₆ octahedra alternate with planes of [C₁₂H₁₇N]⁺ cations. The SbCl₆ octahedra are connected through a O(W)–HCl hydrogen bonds and a chlorine bridge, so that infinite unidimensional chains of composition [SbCl₅(H₂O)₂]^2n– _n are formed in the structure along the c direction. These chains are connected to [C₁₂H₁₇N]⁺ entities by N–HCl and N–HO(W) hydrogen bonds, forming a three-dimensional network. It was found that lengths of Sb–Cl bonds may differ from each other. The differences shown as a distortion of the SbCl₆ octahedra were attributed to the Sb(III) lone electron pair stereoactivity.     

Structure, thermal behavior, and IR investigations of (C6H9N2)H2PO4

Chemical preparation, X-ray single-crystal, thermal behavior, and IR spectroscopy studies of a new dihydrogenmonophosphate associated to an organic cation, the 3-(ammoniummethyl)pyridine dihydrogenmonophosphate (denoted as AMPP) are described. The AMPP crystallizes in the monoclinic system with P2₁/c space group. The unit cell dimensions are a = 5.8465(2) Å, b = 19.9776(9) Å, c = 7.3103(3) Å, = 90.848(3)° with V = 853.74(4) ų and Z = 4. The structure has been solved using direct method and refined to a reliability R factor of 0.0393. The structure of AMPP includes three types of hydrogen bonds. The first one, O H O, links the H₂PO₄ groups to form infinite inorganic chains [H₂PO₄]n ^n–, parallel to the c axis. The two other types, O H N and N H O assemble inorganic chains so as to build up a three-dimensional arrangement.     

Crystal structures and supramolecular assembly of 1:2 piperazine with o- and p-nitrophenol

1:2 Cocrystals of piperazine (PPN) with o- and p-nitrophenol (oNPH and pNPH) were obtained from aqueous solution. The co-crystal structure of PPN, 2pNPH, and 2H₂O is triclinic space group : a = 6.401(1) Å, b = 6.7515(1) Å, c = 11.219(1) Å, = 100.37(1)°, = 97.10(1)°, = 99.99(1)°,V= 465.5(1) ų, Z = 2. Refinement led to a final conventional R value of 0.0365 for 2081 reflections. PPN, 2oNPH, and 2H₂O cocrystallize in the monoclinic space group P2₁ : a = 7.753(1) Å, b = 10.888(2) Å, c = 11.378(2) Å, = 92.89(1)°, V = 953.1(3) ų, Z = 2. Refinement led to a final conventional R value of 0.0347 for 1978 reflections. It was found in both cocrystals that the hydroxyl H-atom of pNPH and oNPH was transferred to a N-atom of PPN, forming new ionic complexes PPNH₂ ²⁺2(oNP^–) and PPNH₂ ²⁺2(pNP^–), respectively.     

Crystal and molecular structure of [Cu2(3,5-dihydroxybenzoate)4 (acetonitrile)2] ⋅ 8H2O

The crystal and molecular structure of the title compound, [Cu₂(3,5-dihydroxybenzoate)₄ (acetonitrile)₂] 8H₂O 1, is reported. Crystal data for 1: tetragonal, space group I 4/m, a = 11.720(2) Å, c = 15.304(3) Å, V = 2102.4(6), and D _c = 1.53 g/cm³, for Z = 2. The metal and organic components crystallize to form a Cu paddle-wheel complex, of idealized D_4h symmetry, that assembles in the solid-state, along with eight equivalents of water, to form a 3D hydrogen-bonded network held together by O–H O hydrogens bonds. The metal complexes pack to form a 2D layered structure.     

Crystal structures of two substituted key intermediates of phenothiazine derivatives

The key intermediates, in the synthesis of phenothiazines, 5-hydroxy-5-methyl 3(phenyl) 2,4-N-dimethylcarbamoyl cyclohexanone, C₁₇H₂₂O₄N₂ (I), and 5-hydroxy-5-methyl 3(2-methylphenyl) 2,4-N-dimethylcarbamoyl cyclohexanone, C₁₈H₂₄O₄N₂ (II), contain essentially substituted cyclohexanone rings in chair conformation with approximately perpendicular oriented phenyl rings. The carbamoyl groups are aligned in opposite directions to facilitate the formation of intramolecular C–HO interaction and O–HO hydrogen bonding. The molecules are linked in helical fashion by an N–HO type intermolecular hydrogen bonding framework. Crystal data: [I], orthorhombic, space group Pbca, a = 9.278(1), b = 19.094(2), c = 19.802(2) Å, V = 3508.0(6) ų, Z = 8 and d = 1.206 Mg m^–3, R = 0.074 (wR = 0.137) for 208 parameters and 1190 observed reflections with I 2 (I); [II], monoclinic, space group P2₁/n, a = 10.523(1), b = 9.005(1), c = 19.771(2) Å, = 94.96(6)°, V = 1866.5(3) ų, Z = 4 and d = 1.183 Mg m^–3, R = 0.062 (wR = 0.131) for 217 parameters and 2276 observed reflections with I 2 (I).     

Synthesis and structural properties of a 1-D copper(I) coordination polymer

A coordination polymer catena-chloro(4-pyridinecarboxylic acid)copper(I): [Cu(C₆H₅ O₂N)Cl]_n (1) has been prepared directly by reacting Cu^IICl₂ 2H₂O and 4-cyanopyridine in the presence of disodium maleate under hydrothermal conditions at 140°C. Crystal data for 1 are as follows: monoclinic, P2₁/n, a = 16.4623(9) Å, b = 3.7795(2) Å, c = 24.7612(11) Å, = 101.534(1)°, V = 1509.5(1) ų, Z = 4, D _calc. = 1.955 g cm^–3, R1 = 0.0511, wR2 = 0.1060 for all 2666 reflections. In this 1-D stair-polymer, two [Cu–Cl–Cu]_n zigzag chains are held together by weak interchain Cu–Cl bonds. The 4-pyridinecarboxylic acid ligands derived from the 4-CNpy molecules coordinate to the approximately tetrahedral Cu(I) centers through pyridyl-N atoms. The carboxyl ends of 4-pyridinecarboxylic acid participate in interchain hydrogen-bonding interactions to form a 2-D supramolecular network.     

2-[(trifluoroacetyl)amino]benzoquinone and the hydrochloride and perchlorate salts of 2-aminohydroquinone

Hydrogen bonding parameters for the title materials are reported. 2-[(trifluoroacetyl)amino]benzoquinone crystallizes in the monoclinic space group P2 ₁/c, with a = 18.195(4), b = 5.110(1), c = 9.635(2), = 104.22(3)°, V = 868.4(3) ų, and Z = 4. This compound exhibits two weak intramolecular hydrogen bonds. The first is between a hydrogen atom of the quinone ring and the carbonyl oxygen of the trifluoroacetamide group; it has a distance of 2.24 Å and a C—HsO angle of 122°. The second is between the hydrogen atom of the trifluoroacetamide group and a quinone carbonyl group; it has a distance of 2.26 Å and a N—HsO angle of 107°. 2-Aminohydroquinone hydrochloride crystallizes in the orthorhombic space group Pca2₁, with a = 16.220(3), b = 5.211(1), c = 8.719(2), V = 737.0(2) ų, and Z = 4. 2-Aminohydroquinone perchlorate crystallizes in the orthorhombic space group P2₁2₁2₁, with a = 7.110(1), b = 7.139(1), c = 18.043(4), V = 915.8(3) ų, and Z = 4. All active hydrogens of the two salts exhibit intermolecular hydrogen bonds that serve to organize a three-dimensional framework for each case.     

Synthesis and crystal structure of an unsymmetric dysprosium(III) cryptate

Synthesis, crystal and molecular structure of [Dy(H₃L)(NO₃)(H₂O)](ClO₄)₂ H₂O are reported. The complex crystallizes in the orthorhombic system, space group Pbca with lattice parameters a = 16.8036(3) Å, b = 20.9756(3) Å, c = 25.1113(4) Å, and D _calc = 1.797 Mg m^–3 for Z = 8. The coordination number of dysprosium(III) is 9, and its coordination geometry is a distorted monocapped square antiprisms. In the cryptate, a water molecule acts as a guest molecule encapsulated in the cryptate.