Structure,magnetic and IR studies of copper(II) diphenylphosphate dihydrate,Cu(DPhP)2·(H2O)2

The title compound has been synthesized, and characterized by means of X-ray, magnetic, and IR-spectroscopic measurements.The crystals of Cu(DPhP)₂(H₂O)₂(DPhP=diphenylphosphate) are monoclinic, space groupI2/c witha=24.126(6),b=8.510(2),c=12.333(3) Å,=90.73(5)° andZ=4. The structure was solved by the heavy-atom technique, and refined by full-matrix least-squares calculations to a finalR of 0.040 for 1494 reflections.The complex is centrosymmetric, and the Cu atom at a center of symmetry is four-fold coordinated with two oxygen atoms from two phosphate groups and two water molecules. The coordination about the Cu atom is square-planar, with Cu-O and Cu-O(W) distances 1.926(3) and 1.912(3) Å, respectively.The O(2) phosphate oxygen is an acceptor of two H bonds; one of them is an intramolecular O(W)-H(2)O(2) of 2.714(4) Å, and the other is an intermolecularO(W)-H(1)O(2ⁱ) of 2.667(4) Å. Their presence is also deduced from the IR spectrum of this compound at 3250 and 3000 cm^–1, respectively.The calculated magnetic moment value of 1.92 B.M. corresponds to that of the monomeric copper(II) complexes including those of some alkyl phosphates.     

Structure of bis(O,O′-diisopropyldithiophosphato-S,S′) (1,10-phenanthroline-N1,N10)zinc(II) complex, [Zn(phen)(S2P(OiPr)2)2]

The crystal and molecular structure of [Zn(phen)(S₂P(OiPr)₂)₂] (Phen = 1,10-phenanthroline) has been determined by X-ray crystallography. It crystallizes in the Monoclinic system, space group C2/c, with lattice parameters a = 19.315(4), b = 10.438(2), c = 16.567(3)Å, = 102.89 (3)°, and Z = 4. The complex has C₂ symmetry. The coordination geometry of each Zn atom, by two S atoms from two (O,O-diisopropyldithiophosphato) anions and by two N atoms from phenanthroline ligand, is that of a slightly distorted tetrahedron [Zn—S 2.2914(8)Å Zn—N 2.111(2)Å]. The Zn···S distances to the noncoordinated S atoms are long: 3.5276 Å, which are indicated that there are much weaker interactions between them.     

Structure of a Cu(II)-containing peptide,diaquo-gly-l-tyr Cu(II) dihydrate, [Cu(C11N2O4H13)(H2O)2·2H2O

The structure of the Cu(II) complex of gly-l-tyr [Cu(C₁₁N₂O₄H₁₃) (H₂O)₂]·2H₂O has been solved by X-ray diffraction methods. The compound crystallizes in the orthorhombic space groupP2₁2₁2₁ witha=11.970(2) Å,b=12.485(2) Å andc=10.418(3) Å, respectively, (MoK)=0.710 Å,D _c =1.59 Mgm^–3,D _m =1.59 Mgm^–3, finalR=0.04. The structure was solved by heavy atom (Cu) phased Fourier and refined by full-matrix least squares methods. The coordination geometry of the ligand around the Cu(II) ion has been established as a distorted tetragonal pyramid. The peptide molecule behaves as a tridentate ligand via its amino (N2), amido (N1) nitrogens and carboxyl (O2) oxygens. The peptide nitrogen is found to be deprotonated.     

Structure of the adduct of bis(O,O′-diisopropyldithiophosphato) metal with pyridine: Ni[(iPrO)2PS2]2(py)2 and Cd[(iPrO)2PS2]2 (py)2(py = pyridine)

The crystal and molecular structures of the complex of [Ni{(iPrO)₂dtp}₂(py)₂] and [Cd{(iPrO)₂dtp}₂(py)₂] (dtp = dithiophosphate, py = pyridine) have been determined by X-ray crystallography. They are isomorphous. The crystal structures are very similar and consist of discrete molecules of [Ni{(iPrO)₂dtp}₂(py)₂] and [Cd{(iPrO)₂dtp}₂(py)₂], respectively. They both crystallize in the monoclinic system, space group P2₁/c, the former with lattice parameters a = 6.489(1) Å, b = 14.830(3) Å, c = 16.386(3) Å, = 99.74(3), and Z = 2; the latter with a = 6.461(3) Å, b = 14.583(4) Å, c = 17.433(4) Å, = 99.55(3)°, and Z = 2. They all display distorted octahedral geometry around the central metal atom. In the complexes, two O,O-diisopropyl dithiophosphate ions act as bidentate ligands with their S atoms coordinated to metal. Each forms a four-membered chelate ring in the equatorial plane. The N atoms from two pyridine ligands are axially coordinated to the metal atom. The Ni–S bond distances are 2.5137(10) and 2.5386(9) Å, and the Ni–N bond distances are 2.127(3) Å. The Cd–S(1) and Cd–S(2) bond distance are 2.694(1) and 2.704(1) Å, respectively, and the Cd–N bond distances are 2.399(3) Å. The IR spectra data is in agreement with the structural data.     

Phenylmercury(II) dithiophosphates. Crystal structure of (O,O′-diethyldithiophosphate) phenylmercury(II)

The phenylmercury(II) derivatives PhHgS₂P(OR)₂ (R=C₂H₅, C₆H₁₁ and C₆H₅) have been synthesized. (O,O-diethyldithiophosphate) phenylmercury(II), C₁₀H₁₅HgO₂PS₂, crystallizes in the monoclinic space groupP2₁/c (n° 14) witha=7.330(5),b=18.085(2),c=11.552(4)Å,=105.96(5)°,V=1472.3(6)ų,Z=4,D=2.088 g.cm^–3. The mercury atom is coordinated to the phenyl carbon atom and to a ligand sulphur atom in an almost linear arrangement (C-Hg-S angle, 176.0(2)°. The ligand is almost monodentate, its second sulphur atom only being involved in a weak secondary intermolecular bond.IR and Raman studies of the other two compounds suggest the same coordination scheme. Positive ion FAB and¹³C,³¹P and¹⁹⁹Hg NMR spectra are also discussed.     

Crystal structure of neptunium(V) sulfate hexahydrate, (NpO2)2SO4 · 6H2O

Single crystals of (NpO₂)₂SO₄ · 6H₂O are obtained, and their structure is determined. The structure is built of NpO ₂ ⁺ dioxo cations, SO ₄ ^2? anions, and molecules of coordination and crystallization water. The NpO ₂ ⁺ ions are linked into cationic ribbons stretched along the [001] direction. In the ribbons, neptunoyl ions of one type act as monodentate ligands, whereas neptunoyl ions of the other type coordinate the neighboring neptunoyl groups by two oxygen atoms. The Np(1) and Np(2) atoms have oxygen environments in the shape of a pentagonal bipyramid whose equatorial plane consists of oxygen atoms of the neighboring dioxo cations, sulfate ions, and water molecules. The sulfate ion acts as a bidentate ligand bridging the two neighboring atoms Np(1) and Np(2). Six water molecules are revealed in the structure; one of them is a crystallization water molecule. Hydrogen bonds link cationic ribbons into a three-dimensional network.     

Metal-pyrimidine interaction: synthesis and crystal structure of a cadmium complex of trimethoprim ([CdBr2(TMP)2(H2O)2]·H2O, TMP = trimethoprim)

The crystal structure of a cadmium complex of trimethoprim ([CdBr₂(TMP)₂(H₂O)₂] · H₂O, TMP = trimethoprim) has been determined from X-ray diffraction data using MoK radiation. The crystals are monoclinic, C2/c, with a = 7.7811(11), b = 15.439(3) c = 29.645(6)Å, = 97.23(2)° and Z = 4. Trimethoprim (2,3-diamino(3,4,5trimethoxybenzyl)pyrimidine) acts as a monodentate ligand. Cadmium is coordinated to N(1) atoms of two trimethoprim moieties. The octahetral coordination geometry around cadmium is completed by two Br-ions and two water molecules. The complex has a two-fold axis coinciding with a crystallographic two-fold axis. There is an interligand hydrogen bond between the bromide ion and the 2-amino group of the pyrimidine.     

Synthesis of [Mn(O2CCH2CH2CO2)(2,2′-bipyridyl) (H2O)2]n·H2O

The title compound exists as a 1D coordination polymer consisting of succinate anions, manganese cations and 2,2-bipyridyl molecules. Twelve water molecules are present in the unit cell and are part of a hydrogen bonding system. Some of these waters are binding to manganese cations while others are only participating in hydrogen bonding. The structure has a monoclinic space group P2₁/c with a = 8.2750(3) Å, b = 11.5104(3) Å and c = 16.9113(6) Å, = 95.2727(16); V = 1603.96(9) ų and Z = 4.     

三维孔道结构(H3 NCH2 CH2 NH3)2(H3 NCH2 CH2 NH2)[VⅢ(H2O)2(VⅣ O)8(OH)4(H(P,B)O4)4((P,B)O4)4(H2O)2]·3H2O的水热合成及晶体化学研究 --(2)晶体结构与晶体化学

在单晶X射线衍射实验的基础上,对孔道结构化合物V9P8-en的类质同象物V9(P,B)8-en的晶体结构和晶体化学进行了深入研究.结果表明,该化合物的晶体学数据为:P2(1)/n,a=1.43134(9)nm,b=1.01256(6)nm,c=1.83156(12)nm,β=90.280(2)°,V=2.6545(3)nm3,Z=2,R=0.0540,wR2=0.1551.结构中,沿着三个结晶轴方向发育复杂而规整的三维孔道,最大孔径达1.83nm(∥b轴),质子化乙二胺和水分子居于孔道中.硼部分替代四面体配位的磷,替代率为B8:P8=0.1838:7.8162;其中B与{P-OH}位P的替代量大于与[P-O]位P的替代量.相对于V9P8-en来说,V9(P,B)8-en的晶胞参数发生了变化,导致b轴增长(1.0150→1.0256nm)和c轴缩短(1.8374→1.8316nm),同时β角变小(90.39→90.278(2)°).二者的化学计量比也不同,体现在结构与孔容的关系、电荷平衡、满足亲水-疏水作用的结晶水的数量及有机模板分子的赋存状态等方面都有差异.     

Crystal structure of triaquamaleatostrontium(II) monohydrate, [Sr(C4H2O4)(OH2)3]·H2O

[Sr(C₄H₂O₄)(OH₂)₃]·H₂O is monoclinic, P2₁/n, witha=11.476(2),b=7.027(1),c=12.344(2) Å, =115.74(3)°,V=896.67 ų,Z=4. The Sr atom is surrounded by nine oxygen atoms which come from four different maleate anions and three water molecules. The Sr–O distances range from 2.546(2) to 2.808(2) Å. The C–O distances are equal within the standard deviation 1.263(3) to 1.258(3) Å). In the maleate anion, the planes that contain the carboxylate groups form an angle of 74.44(9)°. Both carboxylate groups deviate significantly from planarity. The different coordination modes of the carboxylate group and the extensive hydrogen bonding present are responsible for the polymeric nature of the structure.     

Synthesis, crystal structure, and thermal analyses of triaqua-(1,10-phenanthroline-N,N′) succinatomanganese(II) dihydrate, [Mn(H2O)3(phen)(C4H4O4)]·2H2O

[Mn(H₂O)₃(phen)(C₄H₄O₄)]·2H₂O was obtained by reaction of freshly prepared MnCO₃, phen and succinic acid in CH₃OH/H₂O (1:1 v/v), and its crystal structure has been determined by single crystal X-ray diffraction methods. The title mixed ligand complex crystallizes in the triclinic space group with cell dimensions a = 7.590(1) Å, b = 9.324(1) Å, c = 13.917(1) Å, = 85.64(1)°, = 74.56(1)°, = 77.10(1)°, and D _calc = 1.584 g/cm³ for Z = 2. The crystal structure consists of the [Mn(H₂O)₃(phen)(C₄H₄O₄)] complex molecules and lattice H₂O molecules. The Mn atoms are each octahedrally coordinated by two N atoms of one phen ligand and four O atoms of three H₂O molecules and one succinato ligand with d(Mn—N) = 2.271 and 2.299 Å, and d(Mn—O) = 2.133–2.239 Å. Through intermolecular hydrogen bondings, the complex molecules are interlinked to form 2D layers, which are assembled by – stacking interactions into 3D framework with tunnels occupied by the lattice H₂O molecules. Thermal analyses showed that the title compound decomposes in two steps over the range 25–600°C upon heating in flowing Ar.     

Growth,Properties, and Structure of Cadmium Sulfamate Cd(NH2SO3)2 · 2H2O

Crystallography Reports - The temperature dependence of the solubility of Cd(NH2SO3)2 compound in the range from 25 to 80°C has been determined. It is found that Cd(NH2SO3)2 · 2H2O and...     

Synthesis and crystal structure of trans-bis(O, O′-diisopropylthiophosphoryl-1H-imidazole-N3) bis(O,O′-diisopropyldithiophosphato) nickel(II) complex: Ni[N3-ImSP(OiPr)2]2[S2P(OiPr)2]2 (Im = imidazole; iPr = isopropyl)

The mononuclear complex, Ni[N³-ImSP(OiPr)₂]₂[S₂P(OiPr)₂]₂ (Im = imidazole; iPr = isopropyl), was unexpectedly obtained in a reaction of bis(O,O-diisopropyl-dithiophosphato) nickel(II) complex with imidazole ligand, and its structure was determined by X-ray crystallography. It crystallizes in the triclinic system, space group P , with lattice parameters a = 12.437(3) Å, b = 13.181(3) Å, c = 8.4580(17) Å, = 93.16(3)°, = 101.93(3)°, = 65.26(3)°, and Z = 1. The Ni atom has almost perfect octahedral coordination geometry and is coordinated by two N atoms of imidazole from two O,O-diisopropylthiophosphoryl-1H-imidazole ligands in axial positions and four S atoms from two (O,O-diisopropyldithiophosphato) anions which act as bidentate ligands forming a four-membered chelate ring in the equatorial plane. The Ni—S bond distances are 2.469(1) and 2.507(1) Å, and the Ni—N bond distances are 2.097(2) Å. The IR spectra data are in agreement with the structural data.     

三维孔道结构(H3NCH2CH2NH3)2(H3NCH2CH2NH2)[VⅢ(H2O)2(VⅣO)8(OH)4(H(P,B)O4)4(P,B)O4)4(H2O)2]·3H2O的水热合成及晶体化学研究——(1)水热合成与产物表征

为了探讨化学成份对VPO体系孔道结构化合物结构稳定性的影响,根据酸碱平衡原理进行了合成实验设计;利用V2O5、H3PO4、H3BO3等简单的无机前驱物、乙二胺作结构导向剂,水热法合成了孔道结构钒硼磷酸盐化合物(H3NCH2CH2NH3)2(H3NCH2CH2NH2)[VⅢ(H2O)2(VⅣO)8(OH)4(H(P,B)O4)4((P,B)O4)4(H2O)2]·3H2O(简称V9(P,B)8-en).典型的反应起始物摩尔比为n(V2O5):n(H3BO3):n(H3PO4):n(en):n(H2O)=0.89:3.50:3.50:3.60:265(pH值为6.5),在175℃、自生压力条件下恒温晶化6.5d(最终pH值为5.9).通过电子探针、粉末X射线衍射、红外吸收光谱、原子占位度修正等方法,对产物的化学成份、物相及其结构等进行了实验研究.证实V9(P,B)8-en为V9P8-en的类质同象化合物,不同晶粒中B与P的含量有差别,B与P之比为O.1:7.9～2.54:5.46(原子比),但恒有V:(P+B)≈9:8.表明通过合理设计和控制合成条件,可在保持V9P8-en基本结构不变的前提下通过同晶取代引入新的化学成份,并由此探讨成份与结构稳定性的关系.     

Refined crystal structure of lovozerite Na2CaZr[Si6O12(OH,O)6] · H2O

The structure of Na,Ca,Zr-silicate lovozerite, Na₂CaZr[Si₆O₁₂(OH,O)₆] · H₂O, from the Khibiny alkaline massif (the Kola Peninsula) was refined by single-crystal X-ray diffraction analysis (Syntex $P\bar 1$ diffractometer, λMoK _α radiation, 2θ/θ scanning technique). The refinement (R _hkl = 0.077, 1531 independent reflections; anisotropic thermal parameters) confirmed the trigonal system proposed for the mineral earlier (sp. gr. R3; a = 10.18(1) Å, c = 13.13(2) Å, Z = 3) and revealed the presence of two additional positions (C and B) statistically occupied by Ca and Na atoms (and partly by Mn) and H₂O molecules, respectively.     

Crystal and molecular structure of four copper(II) ethylenediaminedisuccinates, [Cu2(RR,SS-Edds)] · 6H2O, Ba2[Cu(RR,SS-Edds)](ClO4)2 · 8H2O, Ba[Cu(SS-HEdds)]ClO4 · 2H2O, and Ba3[Cu2(RR,SS-Edds)2](ClO4)2 · 6H2O

Four Cu(II) complexes with the RR,SS-Edds ^4? and SS-HEdds ^3? anions are synthesized, and their crystal structures are studied. In the compounds [Cu2(RR,SS-Edds)] · 6H₂O (I) and Ba2[Cu(RR,SS-Edds)](ClO₄)₂ · 8H₂O (II), the ligand forms hexacoordinate chelate [Cu(Edds)]^2? complexes with the N atoms and O atoms of the propionate groups in the equatorial positions and the O atoms of the acetate groups in the axial vertices. In the compounds Ba[Cu(SS-HEdds)]ClO₄ · 2H₂O (III) and Ba3[Cu2(RR,SS-Edds)₂](ClO₄)₂ · 6H₂O (IV), one of the propionate arms, the protonated arm in III and the deprotonated arm in IV, does not enter into the coordination sphere of the Cu atom. An acetate arm moves to its position in the equatorial plane, and the free axial vertex is occupied by an O atom of the perchlorate ion. In I–IV, the lengths of the equatorial Cu-N and Cu-O bonds fall in the ranges 1.970–2.014 and 1.921–1.970 Å, respectively. The axial Cu-O bonds with the acetate groups and ClO ₄ ^? anions are elongated to 2.293–2.500 and 2.727–2.992 Å, respectively. In structure I, the second Cu atom acts as a counterion forming bonds with the O atoms of two water molecules and three O atoms of the Edds ligands. In II–IV, the Ba²⁺ cations are hydrated and bound to the O atoms of the anionic complexes and (except for one of the cations in IV) ClO ₄ ^? anions. The coordination number of the Ba cations is nine. The structural units in I–IV are connected into layers. In I, an extended system of hydrogen bonds links the layers into a framework. In II and III, the layers are linked only by weak hydrogen bonds, one bond per structural unit. In IV, ClO ₄ ^? anions are bound to the Ba and Cu atoms of neighboring layers, thus serving as bridges between the layers.     

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.     

Differential metathesis reactions of 2,2′-bipyridine and 1,10-phenanthroline complexes of cobalt(II) and nickel(II): cocrystallization of ionization isomers {[cis-Ni(phen)2(H2O)2][cis-Ni(phen)2(H2O)Cl]} (PF6)3⋅4.5H2O, and a synthetic route to asymmetric tris-substituted complexes

Addition of ammonium hexafluorophosphate to aqueous solutions of M(chelate)Cl₂ [chelate = 2,2-bipyridine and 1,10-phenanthroline, M = Co(II) and Ni(II)] produce different metathesis products. Tris-substituted chelate complexes are produced in the case of bipyridine; however {[cis-M(phen)₂Cl(H₂O)][ cis-M(phen)₂(H₂O)₂]}(PF₆)₃4.5H₂O, a unique example of cocrystallized ionization isomers, is produced with phenanthroline. Extended hydrogen bonding interactions connect [M(phen)₂Cl(H₂O)]⁺ and [M(phen)₂(H₂O)₂]²⁺ cations in the crystal lattice. Because metathesis reactions using phenanthroline produce disubstituted complexes, the convenient synthesis of symmetric [Ni(phen)₃]²⁺ and asymmetric [Ni(phen)₂(5-nitrophenanthroline)]²⁺ is described.