Synthesis and Crystal Structures of Copper(II) Complexes Derived from 5-Methoxy-2-[(2-morpholin-4-ylethylimino)methyl]phenolate and (2-Morpholin-4-ylethyl)-(1-pyridin-2-ylethylidene)amine

Abstract  

A pair of copper(II) complexes, [CuL¹(ONO₂)(OH₂)] 1 and [CuBrL²N₃] 2, where L¹ is 5-methoxy-2-[(2-morpholin-4-ylethylimino)methyl]phenolate, and L² is (2-morpholin-4-ylethyl)-(1-pyridin-2-ylethylidene)amine, have been synthesized and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic space group P2₁/c, with a = 10.496(2), b = 19.113(3), c = 8.586(2) ?, β = 105.186(10)°. Complex 2 crystallizes in the monoclinic space group C2/c, with a = 16.606(3), b = 7.357(2), c = 26.043(5) ?, β = 94.996(2)°. The Cu atom in each complex is five-coordinate in a square pyramidal geometry.     

Absolute Configuration of Two Eudesmane Derivatives from <Emphasis Type="Italic">Verbesina turbacensis</Emphasis> H.B.K.

Abstract  

Two compounds isolated from the aerial parts of Verbesina turbacensis H.B.K, are reported in this work. Both compounds crystallize in the orthorhombic system, space group P2₁2₁2₁. Compound (1), 6β-[cinnamoyloxy]-3β,4α-dihydroxyeudesmane, formula C₂₄H₃₄O_4, has unit cell parameters a = 9.6234(2), b = 12.3137(3) and c = 18.6277(5) Å, V = 2207.38(9) Å³, Z = 4. On the other hand, 6β-[cinnamoyloxy]-eudesman-15-oic acid (2), formula C₂₄H₃₂O_4, has cell parameters a = 8.7035(3), b = 14.2020(4), c = 17.1590(5) Å, V = 2120.97(11) Å³, Z = 4.     

Synthesis,Crystal Structures and Magnetic Properties of Two Three-Dimensional Cerium(III) and Erbium(III) Coordination Polymers

Abstract  

Two lanthanide(III) coordination polymers, namely [Ce(pzdc)_1.5(H₂O)] _n (1), [Er(pzdc)(μ₂-OH)(H₂O)] _n ·nH₂O (2) (H₂pzdc = pyrazine-2,5-dicarboxylic acid), have been hydrothermally synthesized and characterized by single crystal X-ray diffraction and magnetic measurements. Polymer 1 crystallizes in triclinic space group P-1, with a = 6.2875(6), b = 6.7396(6), c = 13.3858(14) Å, α = 82.858(4), β = 83.118(4), γ = 63.452(4)°, V = 502.16(8) Å³, and Z = 2. Polymer 2 crystallizes in monoclinic space group P2(1)/c, with a = 11.706(4), b = 6.151(2), c = 14.063(5) Å, β = 92.255(3), V = 502.16(8) Å³, and Z = 4. Single-crystal X-ray diffraction studies show that compound 1 possess a 3D framework structure consisted of double chains. Compound 2 features a 3D open framework structure with a dinuclear Er(III) secondary building unit. Magnetic studies for complex 1 show stronger antiferromagnetic coupling between the Ce(III) ions.     

Order and Disorder in the Structures of Two Crystal Polymorphs of the Adduct Bis(Quinolinium-2-Carboxylate) DL-Malic Acid

Abstract  

The structures of two polymorphs of the anhydrous cocrystal adduct of bis(quinolinium-2-carboxylate) DL-malic acid, one triclinic the other monoclinic and disordered, have been determined at 200 K. Crystals of the triclinic polymorph 1 have space group P-1, with Z = 1 in a cell with dimensions a = 4.4854(4), b = 9.8914(7), c = 12.4670(8) ?, α = 79.671(5), β = 83.094(6), γ = 88.745(6)°. Crystals of the monoclinic polymorph 2 have space group P2₁/c, with Z = 2 in a cell with dimensions a = 13.3640(4), b = 4.4237(12), c = 18.4182(5) ?, β = 100.782(3)°. Both structures comprise centrosymmetric cyclic hydrogen-bonded quinolinic acid zwitterion dimers [graph set R₂²(10)] and 50% disordered malic acid molecules which lie across crystallographic inversion centres. However, the oxygen atoms of the malic acid carboxylic groups in 2 are 50% rotationally disordered whereas in 1 these are ordered. There are similar primary malic acid carboxyl O–H···O_{quinaldic acid} hydrogen-bonding chain interactions in each polymorph, extended into two-dimensional structures but in 1 this involves centrosymmetric cyclic head-to-head malic acid hydroxyl-carboxyl O–H···O interactions [graph set R₂²(10)] whereas in 2 the links are through single hydroxy-carboxyl hydrogen bonds.     

The Crystal Structures of Some 1-Aryl-5-methyl-1,2,3-triazole Derivatives

Abstract  The two 1-aryl-5-methyl-1,2,3-triazole derivatives were prepared by the 1-aryl-5-methyl-1,2,3-triazol-4-carboxylic acids 3. The yielded products 4a–b were confirmed by NMR, MS, IR spectra. We investigated the crystalline structure of compounds 4a and 4b. Compound 4a, C₉H₈BrN₃, Mr = 238.09, crystallizes in the monoclinic space group P2(1)/n with unit cell parameters a = 11.660(2), b = 7.668(2), c = 11.818(2) ?, α = 90.00, β = 116.01(3), γ = 90.00o. V = 949.6(3) ?³, Z = 4, Dx = 1.665 Mg m⁻³. The final R was 0.0477. Compound 4b, C₁₃H₁₁N₃, Mr = 209.25, crystallized in the orthorhombic space group Pbca with unit cell parameters a = 10.373(2) ?, b = 11.691(2) ?, c = 17.579(4) ?, α = 90.00o, β = 90.00o, γ = 90.00o, V = 2131.8(7) ?³, Z = 8, D _m = 1.304 Mg m⁻³. The final R was 0.0565. Index Abstract  The two 1-aryl-5-methyl-1,2,3-triazole derivatives were prepared by the 1-aryl-5-methyl-1,2,3-triazol-4-carboxylic acids 3. The yielded products 4a–b were confirmed by NMR, MS, IR spectra. We investigated the crystalline structure of compounds 4a and 4b. Compound 4a, C9H8BrN3, Mr = 238.09, crystallizes in the monoclinic space group P2(1)/n with unit cell parameters a = 11.660(2), b = 7.668(2), c = 11.818(2)  ?, α = 90.00, β = 116.01(3), γ =90.00o. V = 949.6(3) ?³, Z = 4, Dx = 1.665 Mg m⁻³. The final R was 0.0477. Compound 4b, C13H11N3, Mr = 209.25, crystallized in the orthorhombic space group Pbca with unit cell parameters a = 10.373(2) ?, b = 11.691(2) ?, c = 17.579(4) ?, α = 90.00o, β = 90.00o, γ = 90.00o, V = 2131.8(7) ?³, Z = 8, D _m = 1.304 Mg m⁻³. The final R was 0.0565.      

Unusual Co-Crystallization of both Monomeric and Dimeric Forms of Cu[PhN(py)quin]Cl<Subscript>2</Subscript>

Abstract  

The aryl functionalized diquinolyl amine MesN(quin)₂ (1) and the pyridyl-quinolyl amine (2,6-iPr₂C₆H₃)N(py)quin (2) have been prepared via palladium catalyzed cross-coupling of substituted anilines with 2-chloroquinoline. The HBF₄ acid salts of (2,6-ⁱPr₂C₆H₃)N(quin)₂ (3) and MesN(py)quin (4), as well as the copper complex [Cu{PhN(py)quin}Cl₂] (5) have been prepared in order to probe the effect that ligand coordination has on its geometry. The molecular structures of each have been determined by X-ray crystallography. The free ligands 1 and 2 crystallize in three-bladed propellar conformations, having smaller degrees of “pitch” between the two heterocycles than either has with the aryl “blade”, allowing for greater heterocycle π-system overlap with the amine lone pair. Acid confinement of similar ligands in 3 and 4 results in forced coplanarity of the two heterocycles, which coordinate the HBF₄ proton in an asymmetric fashion. The copper complex 5 crystallizes with both monomeric and dimeric forms present in the asymmetric unit. Crystal data: (1) Space group P2₁/c, a = 14.058(3), b = 12.202(2), c = 12.831(3) ?, β = 104.61(3)°, V = 2129.8(8) ?³, Z = 4, R = 0.0596, wR₂ = 0.1453. (2) Space group P2₁/c, a = 22.250(4), b = 8.628(2), c = 23.031(5) ?, β = 92.88(3)°, V = 4370(2) ?³, Z = 8, R = 0.0514, wR₂ = 0.1323. (3) Space group Pbca, a = 13.886(3), b = 18.016(4), c = 21.347(4) ?, V = 5340(2) ?³, Z = 8, R = 0.0722, wR₂ = 0.1635. (4) Space group P2₁/c, a = 10.629(2), b = 18.489(4), c = 10.907(2) ?, β = 92.88(3), V = 2140.6(7) ?³, Z = 4, R = 0.0551, wR₂ = 0.1531. (5) Space group \text P[`1]{\text P}\bar{1}, a = 9.706(2), b = 11.325(2), c = 17.322(4) ?, α = 98.28(3), β = 94.85(3), γ = 91.83(3)°, V = 1875.6(7) ?³, Z = 1, R = 0.0481, wR₂ = 0.0946.     

A Facile Synthesis and Crystallographic Analysis of Seven Trityl Phosphorus Compounds and Two Nickel(II) Phosphine Side-Products

Abstract  The syntheses and X-ray analyses of triphenylmethyl (trityl=Tr) phosphorus compounds are reported and the structural similarities, differences and ³¹P chemical shifts compared. A series of seven trityl-substituted phosphorus-containing compounds have been characterized by single crystal X-ray diffraction. Ph₃CPPh₂, 1, a bulky P(III) compound crystallizes in the triclinic space group , a = 7.5624(6) ?, b = 9.5470(8) ?, c = 16.9722(14) ?, α = 83.4720(10)°, β = 80.541(2)°, γ = 68.1580(10)°, the borane complex of 1, 2, Ph₃CPPh₂(BH₃) crystallizes as monoclinic colorless crystals, P2₁/c, a = 10.0972(12) ?, b = 9.6955(12) ?, c = 25.197(3) ?, β = 90.258(2)°. The analogous methyl substituted, 3, Ph₃CPMe₂(BH₃) is monoclinic, C₂/c, a = 15.628(3) ?, b = 12.770(3) ?, c = 18.406(4) ?, β = 103.968(3)°. Compounds 4–7 are trityl substituted P(V) compounds: Ph₃CP(Ph)(O)(OH), 4, crystallizes in the triclinic space group , a = 8.9847(18) ?, b = 9.7443(19) ?, c = 12.786(3) ?, α = 72.045(3)°, β = 72.031(3)°, γ = 78.769(3)°. Esterification of 4 affords TrCP(O)(Ph)OBn 5, space group, P2₁/c, a = 7.9196(5) ?, b = 31.701(2) ?, c = 19.8062(13) ?, β = 99.7750(10)°. A phosphonate diester was also characterized, Ph₃CP(O)(OEt)₂, 6, triclinic, , a = 7.9521(17) ?, b = 9.2205(19) ?, c = 14.471(3) ?, α = 85.906(4)°, β = 83.031(4)°, γ = 68.283(4)°. Treatment of the trityl H-phosphinic acid, Ph₃CPO₂H_2, with elemental selenium yields yellow crystals of 7, [Ph₃CP(O)(OH)Se]_2, P2₁/c, a = 9.0603(4) ?, b = 22.3652(11) ?, c = 16.9134(7) ?, β = 107.035(2)°. In our efforts to isolate a nickel-phosphine complex, two Ni(II) complexes were crystallographically analyzed, [Ni(OP(H)Ph₂)₆]₂BF₄ ⁻ 8 and 9. Complex 8 with an uncoordinated BF₄ ⁻ ion crystallizes as yellow orthorhombic crystals, Pbca, a = 18.8247(12) ?, b = 18.5518(12) ?, c = 21.0976(14) ?, while crystals of 9 are trigonal, , a = b = 13.1545(12) ?, c = 68.461(9) ?. Graphical Abstract  The syntheses and X-ray analyses of triphenylmethyl (trityl=Tr) phosphorus compounds are reported and the structural similarities, differences and ³¹P chemical shifts compared.      

Crystal Structures of a Series of 1,1-Spiro-bis(1,2,3,4-tetrahydronaphthalene)-Based Derivatives

Abstract  

The structures of four spirobisnaphthalenes based monomers 1, 2, 3a and 3b are reported. Each compound represents a methoxylated precursor which after deprotection led to the formation of a monomer successfully used for the synthesis of Polymers of intrinsic microporosity. The spiro-centre represents the site of contortion that, since its rigidity, leads to inefficient packing in the solid state inducing microporosity in the final polymer. Compound 1 crystallized in the monoclinic P2/c space group with unit cell parameters a = 8.1659(19) ?, b = 7.5298(18) ?, c = 19.130(5) ?, β = 97.935(4)°, V = 1165.0(5) ?³, Z = 2, D = 1.210 Mg m⁻³. Compound 2 crystallized in the monoclinic P2₁/n space group with unit cell parameters a = 12.6940(9) ?, b = 7.7267(6) ?, c = 19.9754(15) ?, β = 97.220(1)°, V = 1943.7(3) ?³, Z = 4, D = 1.355 Mg m⁻³. Compound 3a crystallized in the monoclinic P2₁/c space group with unit cell parameters a = 16.8137(14) ?, b = 10.5577(9) ?, c = 31.344(3) ?, β = 103.618(1)°, V = 5407.5(8) ?³, Z = 8, D = 1.308 Mg m⁻³. Compound 3b crystallized in the monoclinic Pc space group with unit cell parameters a = 15.594 ?, b = 12.564 ?, c = 18.339 ?, β = 90.224(1)°, V = 3593.0 ?³, Z = 4, D = 1.236 Mg m⁻³.     

Cross Coupling of Substituted Anilines with Quinoline: Synthesis and Structural Characterization of HN(py)quin,PhN(py)quin,MesN(py)quin,and [PhN(py)(H-quin)]BF<Subscript>4</Subscript>

Abstract  

The molecular structure of (2,6-ⁱPr₂C₆H₃)N(quin)₂ (1) and both the methanol and toluene solvates of its copper complex [Cu{(2,6-ⁱPr₂C₆H₃)N(quin)₂}₂]BF₄, 2·MeOH and 2.2(C₆H₅Me), respectively, have been determined. The quinolyl rings in 1 adopt anti-syn (C_Ar–N–C–N_quin) conformation as a result of π–π stacking. The cation in 2·MeOH crystallizes on a C₂ axis, while the cation in 2·2(C₆H₅Me) is crystallographically independent. As a result of intramolecular π–π stacking there are significant changes within the coordination geometry about the copper centers between the two solvates, suggesting that the coordination around copper is supple. Crystal data: 1 group P2₁/c, a = 8.614(1), b = 16.137(3), c = 17.601(4) ?, β = 93.32(3)°, V = 2,442.5(9) ?³, Z = 4, R = 0.0544, wR ₂ = 0.1340. 2·MeOH group P3₂21, a = 13.254(1), b = 13.254(1), c = 27.214(5) ?, V = 4,140(1) ?³, Z = 3, R = 0.0392, wR ₂ = 0.0917. 2.2(C₆H₅Me) group P1, a = 11.677(2), b = 16.261(3), c = 17.077(3) ?, α = 93.63(3), β = 97.30(3), γ = 96.26(3)°, V = 3,187(1) ?³, Z = 4, R = 0.0526, wR ₂ = 0.1221.     

Copper(II) and lead(II) complexes of 4,4′-bipyridine-<Emphasis Type="Italic">N,N</Emphasis>′-dioxide

Cu(II) and Pb(II) complexes of 4,4′-bipyridine-N,N′-dioxide have been prepared using a solvent-layering system. [Cu₂Cl₄(bpdo)₃(H₂O)₂] . 2(CH₃)₂SO (1) crystallises in P-1, a=8.731(2), b=8.943(2), c=14.408(3) ?, α=102.85(3), β=97.49(3), γ=109.77(3)°. The Cu(II) complex is a z-shaped discrete molecule with a DMSO molecule hydrogen bonded to the host through coordinated water molecule. Crystallisation of PbCl₂, PbBr₂ and PbI₂ with bpdo afforded isostructural 2D coordination polymers. [PbCl₂(bpdo)]_n is monoclinic, C2/c with a=16.3274(7), b=4.0708(1), c=18.6146(8) ?, β=93.73(1)°; [PbBr₂(bpdo)]_n is monoclinic, C2/c with a=16.403(3), b=4.2412(8), c=18.846(4) ?, β=92.59(3)° and [PbI₂(bpdo)]_n is monoclinic, C2/c with a=16.438(3), b=4.538(1), c=18.973(4) ?, β=91.04(3)°. The adjacent metal centres of these polymers are bridged by coordinated Cl⁻, Br⁻ or I⁻ anions as well as by bpdo ligands. These polymers possess no conventional hydrogen bonds.     

Phenylamido and Diphenylamido Complexes of Chromium(II)

Abstract  Addition LiNHPh to a [(NacNac)Cr(μ-I)]₂ [NacNac = 2,4 pentane-N-N′-bis(2,6-diisopropylphenyl) ketiminato] in THF yields a dimeric anilido complex, 1, that crystallizes in P2₁/n with unit cell parameters a = 13.390(2) ?, b = 26.298(5) ?, c = 21.326(4) ?, β = 93.905(4)°, V = 7492(2) ?³ and Z = 4. The same reaction in the presence of aniline yields a monomeric anilido complex, 2, with a coordinated aniline molecule. Complex 2 crystallizes in P2 ₁ /c with unit cell parameters a = 28.530(5) ?, b = 10.8116(18) ?, c = 26.492(5) ?, β = 115.685(3)°, V = 7364(2) ?³ and Z = 8. Addition of aniline to isolated 1 yields 2. Addition of LiNPh₂ to [(NacNac)Cr(μ-I)]₂ in THF yields a monomeric complex that crystallizes in P2₁/n with the unit cell parameters a = 11.152(6) ?, b = 23.820(12) ?, c = 17.915(9) ?, β = 106.223(9)°, V = 4569(4) ?³ and Z = 4. All complexes have been spectroscopically and structurally characterized. Graphical Abstract  Addition of LiNHPh or LiNPh₂ to [(NacNac)Cr(μ-I)]₂ yields a dimeric or a monomeric complex whereas addition of LiNHPh in the presence of aniline yields the monomeric anilido complex.      

Self-Assembly of Two Isomorphous Thiocyanate Complexes of Co(II) and Ni(II) with 3-Hydroxypicolinamide

Abstract  

The synthesis, thermal and spectral characterization, and crystal structure of isomorphous thiocyanate cobalt(II) and nickel(II) complexes with 3-hydroxypicolinamide (3-OHpia), [M(C₆H₆N₂O₂)₂(NCS)₂]·2H₂O, are reported. The metal(II) ions are chelated by two cis-oriented 3-OHpia and two thiocyanate ligands in distorted octahedral geometry. The distortion within the coordination sphere is mainly imposed by formation of the chelate rings. The compounds crystallize in monoclinic space group P2/c with two symmetrically independent molecules and a = 14.4945(2) ?, b = 8.5906(1) ?, c = 16.3865(3) ?, β = 105.987(2)°, Z = 4 (1) and a = 14.4927(5) ?, b = 8.5912(3) ?, c = 16.2712(6) ?, β = 105.740(4)°, Z = 4 (2). Commonly observed supramolecular amide synthons are not robust enough to accommodate thiocyanate ions and H₂O molecules. But instead, neutral complexes are linked through hydrogen bonds leading to two different hydrogen bonding ribbon motifs involving amide moieties and H₂O molecules [C(8)R ₂²(12) along c axis] and amide moieties and thiocyanate ions [C(8)R ₂²(16) along b axis] for symmetrically related molecules labelled as 1 [Co1 (1) and Ni1 (2)] and 2 [Co2 (1) and Ni2 (2)], respectively.     

Two Polymorphs of 1-(2-Methyl-3-oxoisoindolin-5-yl)urea

Abstract  

4-Ureidophthalimide or ureido isoindolin-1-one based ligands were shown by NMR spectroscopy and theoretical studies to bind the CG base pairs in the major groove. To examine this hydrogen-bonded complex, we cocrystallized 5-fluorocytosine, 9-methylguanine and 1-(2-methyl-3-oxoisoindolin-5-yl)urea. Two polymorphs of the latter compound were obtained during the cocrystallization attempts. Both crystallized in monoclinic space groups: form Ia in P2₁/c with cell parameters of a = 11.382(2), b = 6.042(1), c = 14.102(2) ? and β = 96.51(1)°, and form Ib in P2₁/n with cell parameters of a = 7.092(1), b = 11.643(2), c = 11.580(2) ? and β = 93.48(1)°. An identical molecular conformation of the two polymorphs is observed. Both polymorphs have an R ₂²(8) N–H···O interaction linking the urea fragments of two molecules to a centrosymmetric dimer. Nevertheless, the crystal packing for both forms is completely different. In Ia, two dimers are connected by two R ₂¹(6) N–H···O bonds simultaneously to a shifted ribbon motif, whereas in Ib the two R ₂¹(6) interactions link two molecules from two different dimers.     

Structure of 2-[(Phenyl)-(3,5-Dimethyl-Pyrazol-1-yl)-Methyl]-Malonic Acid Diethyl Ester

Abstract  

The titled new functionalized ligand of type 2-[(phenyl)-(3,5-dimethyl-pyrazol-1-yl)-methyl]-malonic acid diethyl ester (4) is prepared in good yield through condensation of 3,5-dimethyl-pyrazole, with 2-arylidene-malonic acid diethyl esters 3. The structure of 4 was determined by spectral (IR, ¹H and ¹³C NMR), elemental analyses and X-ray diffraction data. The title compound (4) crystallizes in the monoclinic space group P2₁/a, with a = 7.9253 (2), b = 17.1299 (5), c = 13.4522 (4) ?, β = 90.220 (2)°, V = 1,826.25 (9) ?³, Z = 4 and with R _int = 0.021. The molecular conformation shows two possible pockets ready to coordinate two metal atoms. The crystal structure of (4) is stabilized by inter-molecular C–H⋯O and C–H⋯N hydrogen bonding.     

Histamine Molecule and Dianion Oxalate are Efficient Blocks for Building 2D Supramolecular Networks

Abstract  

One salt and two Cu(II) complexes (H₂hsm)(ox), 1, [Cu(hsm)(ox)], 2, and [Cu(hsm)(ox)H₂O], 3, have been synthesized and X-ray characterized (hsm is histamine and ox²⁻ is the oxalate dianion). Starting from the prochiral tetracoordinated complex 2, pentacoordinated complex 3 crystallizes as a racemic mixture of the enantiomeric Δ and Λ isomers, in space group P2₁/c. In all cases, the side chain of the hsm group is gauche, allowing the formation of strong hydrogen bonds in the salt 1, and to chelate the metal center in complexes 2 and 3. The combination hsm/ox seems to favor the formation of 2D supramolecular structures (planes or wavy planes), through efficient networks of N–H···O hydrogen bonds. Cell parameters: 1, P2₁/c, a = 6.260 (2) ?, b = 11.500 (4) ?, c = 12.525 (4) ?, β = 104.047 (17)o; 2, C2/c, a = 10.7966 (13) ?, b = 15.5622 (16) ?, c = 11.3996 (15) ?, β = 106.261 (11)o; 3, P2₁/c, a = 7.0627 (6) ?, b = 7.1323 (6) ?, c = 20.0296 (19) ?, β = 91.529 (7)o.     

Piperazinium Chlorocuprates(I)

Abstract  The formation from aqueous solution of networks containing piperazinium hydrochlorides with copper(I) chloride is described. Four new X-ray crystal structures are reported: (H₂Pip)[Cu₂Cl₄] (two isomeric phases: 1A and 1B), (H₂MePip)[Cu₃Cl₅] (2), and (H₂Me₂Pip)[Cu₄Cl₆] (3) (Pip = piperazine, MePip = N-methylpiperazine, Me₂Pip = N,N′-dimethylpiperazine. In 1A (P-1, a = 6.3141(2), b = 6.8248(2), c = 6.9067(2), α = 90.707(2), β = 110.748(2), γ = 110.799(2), V = 256.918(13), Z = 2) corner-sharing Cu₂Cl₂ rhomboid dimers form infinite chains running parallel to the a-axis. In 1B (Pbcn, a = 9.9442(6), b = 8.0622(5), c = 13.1301(7), V = 1052.67(11), Z = 8) the Cu₂Cl₂ dimers are linked by μ-Cl into Cu₆Cl₈ rings which form hexagonally tiled sheets running parallel to the a,b-plane. In 2 (P-1, a = 8.0815(7), b = 9.6584(9), c = 9.7900(8), α = 70.231(4), β = 77.180(4), γ = 70.587(4), V = 673.05(10), Z = 2) alternating Cu₃Cl₃ and Cu₄Cl₄ rings are fused to form ribbons that run parallel to the a-axis. Copper-copper interactions are present. In 3 (C2/c, a = 17.4026(6), b = 10.5295(4), c = 11.7501(8), β = 131.5490(10), V = 1611.35(14), Z = 8) relatively long Cu···Cl interactions connect Cu₄Cl₆ “adamantane” units into chains running parallel to the c-axis. In all cases the piperazinium ions are independent from the chlorocuprate structures, but they do show N–H···Cl interactions. Index Abstract  The synthesis and network structures of four piperazinium hydrochlorides with copper(I) chloride are presented.      

Synthesis and Crystal Structure of Phenolato-Bridged Dinuclear Copper(II) Complex with (2-Hydroxybenzyl)(2-pyridylmethyl)amine

Abstract  

The tridentate Schiff base phenol-containing ligand (2-hydroxybenzyl)(2-pyridylmethyl)amine (Hbpa) reacts with copper(II) perchlorate to give the phenolato-bridged dinuclear complex [Cu(bpa)(H₂O)]₂·2ClO₄ (1). Each copper(II) ion exhibits a distorted square-pyramidal environment, being coordinated by two nitrogen atoms and two phenolato oxygen atoms of the two deprotonated bpa ligands, and one oxygen atom of the water molecule. It crystallizes in the triclinic system P-1 with a = 7.8790(6), b = 8.9345(7), c = 12.0207(9) ?, α = 69.158(1), β = 85.307(1), γ = 76.629(1)°, V = 769.39(10) ?³, Z = 1. Cyclic voltammetry of 1 gives two oxidation and two reduced processes.     

Pentacarbonyl(trimethylamine)chromium and Pentacarbonyl(trimethylamine)Molybdenum

Abstract  

Pentacarbonyl(trimethylamine)chromium (1) and pentacarbonyl(trimethylamine)molybdenum (2) are isomorphous and crystallize in the space group P2₁/n, a = 6.8267(14) ?, b = 11.269(2) ?, c = 14.692(3) ?, β = 102.89(3)°, V = 1,101.8(4) ?³, Z = 4 for 1 and a = 6.949(5) ?, b = 11.362(5) ?, c = 14.927(5) ?, β = 102.639(5)°, V = 1,150.0(10) ?³, Z = 4 for 2; both compounds possess distorted octahedral molecular geometries that result from the steric influence of the coordinated amine ligand.     

Solvothermal Syntheses and Crystal Structures of Neodymium Thiostannates [Nd(dien)3]2[(Sn2S6)Cl2] and [Nd(dien)3]2[(Sn2S6)(SH)2]

Abstract  

Two neodymium thiostannates [Nd(dien)₃]₂[(Sn₂S₆)Cl₂] (1) and [Nd(dien)₃]₂[(Sn₂S₆)(SH)₂] (2) (dien = diethylenetriamine) were synthesized by the reaction of tin and sulfur in the presence of NdCl₃ and Nd₂O₃, respectively under solvothermal conditions. Compounds 1 and 2 crystallize in monoclinic space group P2₁/n. Crystallographic data for 1: a = 11.6722(16), b = 15.119(2), c = 14.1566(19) ?, β = 96.213(3)°, V = 2483.6(6) ?³, Z = 4. For 2: a = 11.7190(14), b = 15.2168(19), c = 14.2209(18) ?, β = 95.775(4)°, V = 2523.1(5) ?³, Z = 4. The nine-coordinate [Nd(trien)₃]³⁺ complex cation formed in situ acts as the counter ion to the [Sn₂S₆]⁴⁻ anion. The [Nd(dien)₃]³⁺, [Sn₂S₆]⁴⁻ and Cl^– (or SH^–) ions form a 3-dimensional network structure through the N–H···S and N–H···Cl hydrogen bonds.     

Nickel(II) and cobalt(II) nitrate and chloride networks with 2-aminopyrimidine

The coordination chemistry of 2-aminopyrimidine (PymNH₂) with nickel(II) and cobalt(II) nitrate and chloride is reported, including seven new X-ray crystal structures. Two [Ni(NO₃)₂(PymNH₂)₂(OH₂)] isomers were found (A: C2/c, a=13.3006(5), b=7.9727(3), c=28.5453(11), β=101.758(2), V=2963.48(19), Z=8 and B·1/2 acetone: P2₁/c, a=7.66060(10), b=10.6792(2), c=20.6790(3), β=100.2970(10), 1664.48(5), Z=4). In both cases one nitrate is monodentate and the other is chelating and the PymNH₂ ligands coordinate through ring nitrogen atoms. Hydrogen bonding results in double sheet structure for isomer A, and a three dimensional channeled network for isomer B. [Co(NO₃)₂(PymNH₂)₂(OH₂)] (C2/c, a=13.3507(2), b=7.99520(10), c=28.6734(3), β=102.3540(10), V=2989.77(7), Z=8) is isostructural to Ni isomer A. [CoCl₂(PymNH₂)] (Cmcm, a=3.6139(2), b=14.3170(7), c=12.9986(7), V=672.55(6), Z=4) is a sheet coordination network, consisting of corner-sharing chains of Co₂(μ-Cl)₂ bridged by PymNH₂ through ring nitrogen atoms; [CoCl₂(PymNH₂)₂] (C2/c, a=11.2774(6), b=6.5947(4), c=16.5687(9), β=92.269(3), V=1231.27(12), Z=4) is a tetrahedral molecule knit into a ribbon structures through pairs of hydrogen bonds. Isostructural trans-[NiCl₂(PymNH₂)₄] (C2/c, a=7.67760(10), b=18.7224(3), c=15.0418(2), β=99.6740(10), V=2131.41(5), Z=4) and trans-[CoCl₂(PymNH₂)₄] (C2/c, a=7.69120(10), b=18.5957(2), c=15.1091(2), β=99.5280(10), V=2131.14(5), Z=4) are simple octahedral molecules, with hydrogen-bonding producing sheet structures.