Copper(II) Complexes with N-(3-Hydroximino-2-methylbutan-2-yl)methylamine (HL): Synthesis and Properties. Crystal and Molecular Structures of [Cu(HL)Cl2] and [Cu(HL)(H2O)2SO4]n

Paramagnetic copper(II) complexes with N-(3-hydroximino-2-methylbutan-2-yl)methylamine (HL), namely, Cu(HL)Cl₂(I), Cu(HL)(SO₄) · 2H₂O (II), and Cu(HL)(NO₃)₂(III), were obtained. The crystal structures of I and II were determined. The blue crystals of these compounds are monoclinic. For I(C₆H₁₄Cl₂CuN₂O): a = 8.820(1) Å, b = 6.511(1) Å, c = 18.255(2) Å, = 92.86(1)° V = 1047.0(2) ų, space group P2₁/c, _calcd = 1.679 g/cm³, Z = 4 for R ₁ = 0.0250; for II(C₆H₁₈CuN₂O₇S): a = 9.999(2) Å, b = 9.927(2) Å, c = 12.963(3) Å, = 106.37(3)°, V = 1234.5(4) ų, space group P2₁/c, _calcd = 1.753 g/cm³, Z = 4 for R ₁ = 0.0324. Crystals of I have a molecular structure. The Cu coordination polyhedron is a square bipyramid (2N + 2Cl + Cl + Cl) due to additional contacts with two Cl atoms from the neighboring molecules. Structure II is built from polymeric chains. The environment of the Cu atom is a distorted cis-octahedron (2N + 2O(H₂O) + 2O(SO₄)). Complexes I–IIIare characterized by IR and EPR spectroscopy.     

The Crystal Structures of Rubidium and 4-Amino-1,2,4-Triazolium Tetrafluoroantimonates(III)

The crystal structures of complex antimony(III) fluorides RbSbF₄ (I) and (C₂N₄H₅)SbF₄ (II) were determined. The crystals of I and II are monoclinic; for I: a = 4.628(1) Å, b = 6.167(1) Å, c = 7.922(1) Å, = 100.582(3)°, V = 222.24(7) ų, Z = 2, (calcd.) = 4.23 g/cm³, (exp.) = 4.25 g/cm³, F(000) = 248, space group P2₁/m, R = 0.0395; for II: a = 4.678(1) Å, b = 7.339(4) Å, c = 10.185(1) Å, = 90.88(2)°, V = 349.6(2) ų, Z = 2, (calcd.) = 2.69 g/cm³, (exp.) = 2.70 g/cm³, F(000) = 264, space group P2₁. The structure of I is formed by Rb⁺ cations and [SbF₄] ^n– _n anionic chains composed of SbF₅E octahedra with two bridging fluorine atoms. The structure of IIis formed by (C₂N₄H₅)⁺ cations and isolated [SbF₄]^– anions in which the antimony polyhedra are SbF₄E trigonal bipyramids. The relationship between the crystal structures and electrophysical and biological properties of single-charged cation tetrafluoroantimonates(III) was studied.     

Nickel(II) Diisobutyldithiophosphinate Complexes with Hexamethylenetetramine and Triethylenediamine: Synthesis and Properties. Crystal and Molecular Structure of [Ni2(C6H12N4){(i-C4H9)2PS2}4]

The paramagnetic compounds [Ni₂(HMTA)(i-Bu₂PS₂)₄] (I) and [Ni₂(TEDA)(i-Bu₂PS₂)₄] (II) (_eff = 3.11 and 3.23 _B, respectively) were synthesized by reacting diamagnetic Ni(i-Bu₂PS₂)₂ with hexamethylenetetramine (HMTA) and triethylenediamine (TEDA) in ethanol. The crystal structure of I was established by single-crystal X-ray diffraction analysis (CAD4 diffractometer, MoK radiation, 1483 F _hkl, R = 0.0648). The crystals are monoclinic: a = 35.212(7) Å, b = 9.313(2) Å, c = 22.622(5) Å; = 129.97(3)°, V = 5685(2) ų, Z = 4, (calcd) = 1.281 g/cm³, space group C2/c. The structure is built of discrete binuclear molecules. The coordination polyhedron of the Ni atom is a distorted tetragonal pyramid with four S atoms of two bidentate cyclic ligands i-Bu₂PS₂ ^– in the base and the N atom of the bidentate bridging ligand HMTA at the axial vertex. Complexes I and II have similar electronic reflection spectra, which agrees with the C _4v symmetry of the ligand field.     

Ni(II) Complexes with Diisobutyldithiophosphinate Ions and o-Phenanthroline Molecules. Structure of [Ni(Phen)2(i-Bu2PS2)](i-Bu2PS2)

Paramagnetic compounds [Ni(Phen)(i-Bu₂PS₂)₂] (I), [Ni(Phen)₂(i-Bu₂PS₂)](i-Bu₂PS₂) (II), and [Ni(Phen)₃](i-Bu₂PS₂)₂ (III) (_eff = 3.03–3.14 _B) were synthesized by reacting Ni(i-Bu₂PS₂)₂ chelate with Phen. Their single crystals were grown. X-ray diffraction analysis of II was performed (CAD4 diffractometer, K radiation, 1181 F _hkl, R = 0.0378). The crystals are monoclinic: a = 14.039(2) Å, b = 18.030(2) Å, c = 18.118(2) Å = 105.52(1)°, V = 4418.9(9) ų, Z = 4, (calcd) = 1.259 g/cm³, space group P2₁/c. The structure is built of individual [Ni(Phen)₂(i-Bu₂PS₂)]⁺ cations and i-Bu₂PS₂ ^- anions. The coordination polyhedron of NiN₄S₂ is a distorted octahedron with four N atoms of two bidentate chelate ligands (Phen molecules) and with two S atoms of a bidentate cyclic ligand i-Bu₂PS₂ ^-. The electronic spectroscopy data for molecular complex I and ionic complex III suggest the octahedral structure of the NiN₂S₄ and NiN₆ chromophores, respectively.     

Structure of Complexes Formed in the CuX2–Cu–N-Allylisoquinolinium Chloride System (X = Cl,Br)

The crystals of N-allylisoquinolinium chlorides of the compositions [C₉H₇N(C₃H₅)]₂Cu^IICl₄ (I), [C₉H₇N(C₃H₅)]Cu^ICl₂ · H₂O (II), and [C₉H₇N(C₃H₅)]Cu^ICl_1.43Br_0.57 · H₂O (III) were prepared by alternating-current electrosynthesis. X-ray diffraction analysis (using diffractometer models DARCH1 for I, STOE for II, and KUMA/CCD for III, MoK radiation) showed that the crystals of I are monoclinic, space group P2₁/n, a = 14.91(1) Å, b = 10.41(1) Å, c = 16.90(1) Å, = 109.73(8)°, V = 2470(8) ų, Z = 4. The crystals of isostructural compounds II and III are triclinic, space group P, Z = 2; crystals II: a = 7.2446(6) Å, b = 7.4379(6) Å, c = 12.110(1) Å, = 80.95(1)°, = 85.55(1)°, = 86.60(1)°, V = 641.8(2) ų; crystals III: a = 7.253(2) Å, b = 7.459(4) Å, c = 12.151(5) Å, = 80.82(4)°, = 83.73(3)°, = 86.81(4)°, V = 644.6(9) ų. The structure of I is composed of Cu^IICl₄ ^2– tetrahedra and N-allylisoquinolinium cations united by C–H···Cl hydrogen bonds in corrugated layers. The crystal structures of -complexesII and III are built of [C₉H₇(C₃H₅)]₂Cu₂ ^IX₄ dimers, which form layers along the c axis due to the C–H···X hydrogen bonds. An important role in the structure formation is played by water molecules, which crosslink the organometallic layers to form a three-dimensional framework through the O–H···X contacts.     

Rh(I) carbonyl carboxylato complexes: Spectral and structural characteristics. Some reactions of coordinated formate group

Complexes [Rh(µ-RCOO)(CO₂)]₂ , where R = H, CH₃,CF₃ (I, II, III, respectively) are synthesized by reacting anhydrous carboxylic acids with Rh(Acac)(CO₂) crystals. In compounds I, II, III, and trans-Rh(RCOO)(PPh₃)₂(CO), where R = H, CH₃, CF₃ (IV, V, VI, respectively), (CO) and ¹J(CRh) increase and ¹³C decreases with the increasing electronegativity of R (CH₃ < H < CF₃). In the case complexes IV, V, and VI, the values of ³¹P and ¹ J(PRh) decrease in the same order. Complexes I and V are studied by X-ray diffraction analysis. Intramolecular (2.946 Å) and intermolecular (3.127 Å) Rh-Rh distances in a columnar structure I are close, i.e., the structure contains infinite chains of metal atoms. Interaction of IV with chlorinated solvents results in trans-RhCl(PPh₃)₂(CO). When heated with an excess of PPh₃ in propanol-2, compound IV transforms to HRh(PPh₃)₃(CO). The latter reaction was suggested as a basis of a new method that can be used to obtain HRh(PPh₃)₃(CO).Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 2, 2005, pp. 132–142.Original Russian Text Copyright © 2005 by Varshavskii, Cherkasova, Podkorytov, Korlyukov, Khrustalev, Nikolskii.     

Neptunium(V) Carbamide Complexes. The structure of [NpO2(HCOO){OC(NH2)2}3]

A new complex of Np(V) [NpO₂(HCOO){OC(NH₂)₂}₃] (I) was synthesized and its crystal structure was determined: a = 6.674(1) Å, b = 13.164(2) Å, c = 7.020(1) Å, = 101.35(1)°, space group P2₁, Z = 2, V = 604.7(2) ų, R = 0.048, wR(F ²) = 0.128. The structure consists of infinite chains of [NpO₂(HCOO){OC(NH₂)₂}₃]. The coordination polyhedron of the Np atom is a pentagonal bipyramid with the O atoms of three carbamide molecules and two formate ions in the equatorial plane. The absorption spectra were measured in IR and near-IR regions for compound I and for the [NpO₂Cl{OC(NH₂)₂}₄] complex, whose structure was reported in the previous publication.     

Synthesis and Crystal Structures of Copper(I) Complexes with N-Allylhexamethylenetetraminium Chloride Obtained in Different Acidic Media

The crystals of [(CH₂)₆N₄(C₃H₅)]Cu₂Cl₃ (I), [(CH₂)₆N₄(C₃H₅)]Cu₂Cl₃ (II), and [(CH₂)₆N₄(C₃H₅)]CuCl₂ (III) complexes were electrochemically synthesized (ac) from CuCl₂ · 2H₂O and N-allylhexamethylenetetraminium chloride in ethanol solutions at pH 6, 4.5, and 3. Their structures were determined using X-ray diffraction analysis (DARCh diffractometer, MoK radiation, /2 scan mode). Complex Icrystallizes in the monoclinic system: space group A2/a, a = 24.812(6) Å, b = 8.855(3) Å, c = 12.080(2) Å, = 89.21(3)°, and Z = 8. Complex II crystallizes in the triclinic system: space group P , a = 7.618(2) Å, b = 7.048(2) Å, c = 13.150(3) Å, = 97.50(2)°, = 92.70(2)°, = 100.74(2)°, and Z = 2. The crystals of complex III are orthorhombic: space group Pmn2₁, a = 7.478(2) Å, b = 8.827(2) Å, c = 9.662(3) Å, Z = 2. The organic cation in complex I acts as a tridentate ,,-ligand; that in complex II, as a bidentate ,-ligand. In complex III, the organic cation is involved in coordination with the copper(I) atom only through one nitrogen atom.     

Crystal Structure of Thallium Tridecafluorotetraantimonate(III) TlSb4F13

The crystal structure of thallium fluoroantimonate(III) complex TlSb₄F₁₃ (I), which is isostructural to KSb₄F₁₃ (II), is determined. Crystals I are tetragonal: a = 9.634(2) Å, c = 6.590(2) Å, V = 611.7(2) ų, Z = 2, (calcd) = 5.094 g/cm³, F(000) = 804.0, space group I4¯. The structure consists of tetrameric [Sb₄F₁₃]^– anions formed by SbF₃ groups connected by the fluoride ion and the l⁺ cations.     

Complexation with hydroxy host compounds,part 5. Structures and thermal analyses of 1,2,3,4,5-pentaphenylcyclopenta-2,4-dien-1-ol and its inclusion compounds with water and dimethylsulphoxide

The crystal and molecular structures of the title host compound (I), C₃₅H₂₆O, and its inclusion complexes with water (II), C₃₅H₂₆O·H₂O and dimethylsulphoxide (III), C₃₅H₂₆O·C₂H₆OS are reported. (I) is monoclinicC2/c,a = 9.725(1),b = 20.031(3),c = 26.545(3) Å, = 90.60(1)⁰,V = 5170 ų,Z = 8; (II) is triclinic, ,a = 10.206(1),b = 10.324(2),c = 14.425(2) Å, = 101.68(1), = 89.92(2), = 116.34(1)⁰,V = 1327 ų,Z = 2; (III) is monoclinicP2₁/n,a = 17.832(5),b = 10.109(3),c = 17.901(5) Å, = 111.93(2)⁰,V = 2993 ų,Z =4. The structures were solved by direct methods and refined to final residuals of 0.045, 0.048, and 0.071, respectively. Thermal analysis of the complexes corroborates the crystallographic results.     

Pentakis(carbamide)dioxoneptunium(V) Nitrate [NpO2{OC(NH2)2}5](NO3): Synthesis,Crystal Structure,and Some Properties

X-ray diffraction and spectroscopic data for a new Np(V) compound, namely, [NpO₂{OC(NH₂)₂}₅](NO₃) (I) are presented. Crystals are monoclinic, space group P2₁, a = 11.142(2) Å, b = 7.6379(9) Å, c = 11.143(2) Å, = 108.9(1)°, Z = 2, V = 897.1(2) ų. The neptunium atom has a typical pentagonal-bipyramidal environment with five oxygen atoms of the carbamide molecules in the equatorial plane. The nitrate ion is in the outer sphere. Carbamide is a strong molecular ligand with respect to Np(V) and hence, cation–cation bonds of the NpO₂ ⁺ ions are not realized in structure I. The wave length of the f–f transition in the electronic absorption spectra of crystalline complex I and Np(V) in a saturated carbamide solution is virtually the same and is equal to 991 nm.     

Monomeric [Ni(2,2"-Bipy){(i-C4H9)2PS2}2] and [Ni(Pz)2{(i-C4H9)2PS2}2] and Polymeric [Ni(Pz){(i-C4H9)2PS2}2]nComplexes (Pz = Pyrazine): Synthesis,Structures, and Properties

Diamagnetic [Ni(i-Bu₂PS₂)₂] compound (I) in ethanol reacts with 2,2"-bipyridine or pyrazine to give the paramagnetic complexes [Ni(2,2"-Bipy)(i-Bu₂PS₂)₂] (II), [Ni(Pz)₂(i-Bu₂PS₂)₂] (III), and [Ni(Pz)(i-Bu₂PS₂)₂] _n (IV) (_eff= 2.91–3.12 _B). Single crystals of IIwere grown for X-ray diffraction study. The crystals are monoclinic, a= 14.669(3) Å, b= 19.693(4) Å, c= 12.155(2) Å, = 107.51(3)°, V= 3348(1) ų, Z= 4; _calcd= 1.257 g/cm³, space group P2₁/c. The structure is built from monomeric molecules. The coordination polyhedron of the Ni atom is a distorted octahedron formed by four S atoms of two bidentate chelating i-Bu₂PS^– ₂ligands and by two N atoms of bidentate cyclic 2,2"-Bipy. Preliminary data for complexes IIIand IVindicate that they also contain an octahedral NiN₂S₄fragment. The structures of complexes I(square planar) and ofII–IV(octahedral) were confirmed by data from electron spectroscopy. Electronic absorption spectra were used to determine the rankings of the i-Bu₂PS^– ₂ions and Pz on a spectrochemical scale.     

Synthesis and Crystal Structure of Acid Phosphites RbH2PO3, CsH2PO3, and TlH2PO3

The reaction of Rb, Cs, or Tl carbonates with a solution of phosphorous acid gave crystalline acid phosphites RbH₂PO₃(I), CsH₂PO₃(II), and TlH₂PO₃(III). The crystal structures of the compounds were studied by a single-crystal X-ray diffraction analysis at 150 K: I, monoclinic system, a= 7.530(2) Å, b= 8.634(2) Å, c= 12.426(2) Å, = 102.46(3)°, V= 788.8(3) ų, Z= 8, space group P2₁/c, R ₁= 0.0409; II, monoclinic system, a= 7.930(2) Å, b= 8.929(2) Å, c= 13.163(3) Å, = 104.84(3)°, V= 900.9(4) ų, Z= 8, space group P2₁/c, R ₁= 0.0239; III, orthorhombic system, a= 6.603(1) Å, b= 6.785(1) Å, c= 8.836(2) Å, V= 395.9(1) ų, Z= 4, space group Pna2₁, R ₁= 0.0350. The PHO₃tretrahedra in structures I–IIIare joined via hydrogen bonds into infinite zigzag-like chains [HPHO₃] ^n– _n, which form layers alternating with layers of metal cations. The layers of anionic chains are wavelike in Iand IIand planar in III. Apparently, IIIis not isostructural to Ior IIdue to the fact that Tl(I) has a stereochemically active pair of electrons.     

Synthesis and Structure of Acetonitrile Solvates of Copper(II) Monofluoroacetate and Silver(I) Trifluoroacetate, [Cu2(CH2FCOO)4· 2CH3CN](CH3CN) and Ag3(CF3COO)3(CH3CN)2

Compounds [Cu₂(CH₂FCOO)₄· 2CH₃CN](CH₃CN) (I) and Ag₃(CF₃COO)₃(CH₃CN)₂(II) were synthesized and studied by X-ray structural analysis. Crystals Iare monoclinic, space group C2/c, a= 27.854(6), b= 8.286(2), c= 19.428(4) Å, = 106.82(3)°, V= 4292(2) ų, Z= 8, R ₁= 0.0426; crystals IIare triclinic, space group , a= 8.676(2), b= 9.819(2), c= 11.961(2) Å, = 95.27(3), = 109.59(3)°, = 104.60(3)°, V= 911.4(3) ų, Z= 2, R ₁= 0.0252. Structure Iis composed of the structural units (lanterns) typical of copper(II) carboxylates. The presence of an additional acetonitrile molecule noncoordinated by the copper atoms makes it possible to consider compound Ias a lattice clathrate. Structure IIhas no analogs among the silver carboxylates. It simultaneously contains silver atoms with coordination numbers varying from 2 to 4.     

Kristallstruktur von Trimethylisocyanursäure, (CH3NCO)3, und von Trichlorisocyanursäure-1/2-Ethylenchlorid, (ClNCO)3·1/2C2H4Cl2

X-ray crystal structure analyses of (CH₃NCO)₃ (M) and (ClNCO)₃·1/2C₂H₄Cl₂ (C) were carried out at room temperature (MoK, graphite monochromator, =0.71069 Å): 1.M=171.16, monochlinic, P2₁/c,a=14.848 (1) Å,b=13.400 (2) Å,c=8.149 (1) Å, =100.87 (1)°,V=1 592.3 ų,Z=8,F(000)=720,d _x =1.428 Mgm^–3, =76m^–1,R=6.51%,R _w =7.01% (964 reflections, 218 parameters). 2.M=281.89, monochlinic, P 2₁/c,a=9.416 (3) Å,b=5.728 (1) Å,c=18.199 (8) Å, =98.64 (2)°,V=970.4 Å₃,Z=4,F(000)=556,d _x =1.929 Mgm^–3, =1.11 mm^–1,R=3.96%,R _w =3.44% (605 reflections, 132 parameters). The ring systems together with the C atoms of the methyl groups in (M) and with the Cl atoms in (C) are planar and have D_3h-symmetry. Bond lengths and bond angles are discussed with regard to¹⁴N-NQR,³⁵Cl-NQR and vibrational spectroscopic data.

     

Synthesis and crystal structure of copper halide complexes with triethylallylammonium (teaa) chloride: [(teaa)Cu3ICl4], [(teaa)Cu3IBr3.86Cl0.14], and (teaa)2CuIICl4

The results of X-ray diffraction analysis of novel triethylallylammonium chloride compounds with copper(I) chloride, copper(I) bromide, and copper(II) chloride are reported. The [(CH₃CH₂)₃(CH₂=CHCH₂xN]Cu ₃ ^I Cl₄ and [(CH₃CH₂)₃(CH₂=CHCH₂Cu ₃ ^I Br_3.86)Cl_0.14 -complexes are isostructural: space group P2₁/a; a= 17.58(1) Å, b = 12.059(8)Å, c = 7.184(4) Å, = 98.37(5)° and a = 17.972(9) Å, b=12.479(8) Å, c = 7.290(5) Å, = 98.81(5)°, respectively. ²-Coordination of the copper atom by the olefinic bond plays a key role in the structural ordering of the tetraalkylammonium cation. In contrast, the structure of {(CH₃CH₂)₃x(CH₂=CHCH₂)N}₂Cu^IICl₄ (P4₂/nmc; a = 8.839(3) Å, c =15.660(9) Å) follows the ionic salt pattern.Original Russian Text Copyright © 2004 by L. M. Babkov, I. I. Gnatyuk, G. A. Puchkovskaya, and S. V. TrukhachevTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 398–405, May–June, 2004.     

Destruction of the propylenediamine ring upon the chlorination of the platinum(IV) tetramine complex [PtpnPy2Cl2]Cl2

The chlorination of an aqueous solution of [PtpnPy₂Cl₂]Cl₂ affords the platinum(IV) dichloroamine complex [PtPy₂(NCl₂)₂Cl₂](I), as the major reaction product formed due to the complete destruction of the five-membered chelate ring. Complex I is obtained in the pure state from acetonitrile. In addition, the [PtPy(NH₂-CH(CH₃)-CH(CH₃)-NH₂)Cl₃]Cl · 1/2 H₂O complex (II) is isolated from the mother liquor upon chlorination. Complex I reacts rapidly with concentrated HCl to form the tetramine complex [PtPy₂(NH₃)₂Cl₂](CF₃SO₃)₂ · 1/2 H₂O(III). The X-ray diffraction study is carried out for complexes I, II, and III. Complex I crystallizes in the monoclinic crystal system: space group C2/c, a = 7.4529(4), b = 15.2143(9), c = 14.9965(8) Å, β = 99.866(1)°, V = 1675.3(2) ų, Z = 4; R _hkl = 0.040. The crystals of complex II are triclinic: space group P $ \bar 1 The chlorination of an aqueous solution of [PtpnPy₂Cl₂]Cl₂ affords the platinum(IV) dichloroamine complex [PtPy₂(NCl₂)₂Cl₂](I), as the major reaction product formed due to the complete destruction of the five-membered chelate ring. Complex I is obtained in the pure state from acetonitrile. In addition, the [PtPy(NH₂-CH(CH₃)-CH(CH₃)-NH₂)Cl₃]Cl · 1/2 H₂O complex (II) is isolated from the mother liquor upon chlorination. Complex I reacts rapidly with concentrated HCl to form the tetramine complex [PtPy₂(NH₃)₂Cl₂](CF₃SO₃)₂ · 1/2 H₂O(III). The X-ray diffraction study is carried out for complexes I, II, and III. Complex I crystallizes in the monoclinic crystal system: space group C2/c, a = 7.4529(4), b = 15.2143(9), c = 14.9965(8) ?, β = 99.866(1)°, V = 1675.3(2) ?³, Z = 4; R _hkl = 0.040. The crystals of complex II are triclinic: space group P , a = 8.163(2), b = 8.656(2), c = 10.638(2) ?, α = 78.30(3)°, β = 83.95(3)°, γ = 84.68(3)°, V = 730.0(3) ?³, Z = 2; R _hkl = 0.026. The crystals of complex III are monoclinic: space group C2/c, a = 11.946(2), b = 19.624(4), c = 10.034(2) ?, β = 95.96(3)°, V = 2339.5(8) ?³, Z = 4; R _hkl = 0.043. The IR spectra of all the compounds synthesized are studied. Original Russian Text ? I.B. Baranovskii, M.D. Surazhskaya, M.A. Golubnichaya, G.G. Aleksandrov, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 12, pp. 2000–2007.     

Thiourea N- and S-Derivatives as Ligands: Synthesis and Crystal Structure of 4CuCl · 6All–NHCSNH2 and [(All–NH)2C–SC2H5]Cu2ClxBr3 – x (x = 0.765, All is Allyl)

Crystals of the compounds 4CuCl · 6CH₂=CH–CH₂–NHCSNH₂ (I) and [(CH₂=CH–CH₂–NH)₂C–SC₂H₅]Cu₂Cl _x Br_{3 – x} (x = 0.765) (II) were synthesized by the ac electrochemical method, and their crystal structures were determined (CuK and MoK radiation, 2575 and 1090 unique reflections with F 4(F), R = 0.050 and 0.028 for I and II, respectively). Complex I crystallizes in space group C2/c, a = 17.230(7) Å, b = 12.258(5) Å, c = 42.95(2) Å, = 97.48(4)°, V = 8994(7) ų, Z = 8. The structure of -complex II is described by space group P2₁/n, a = 10.633(5) Å, b = 9.280(5) Å, c = 16.024(4) Å, = 102.16(3)°, V = 1546(1) ų, Z = 4. Complex I is built from isolated units of the aforementioned composition; every allylthiourea molecule coordinates two metal atoms through the sulfur atom. The distorted tetrahedral surrounding of every Cu(I) atom involves three S atoms and one Cl atom. The N,N"-diallyl-S-ethylisotiouronium cation coordinates two copper atoms through the C=C bonds, 1.32(1) and 1.35(1)Å, uniting the cuprohalide chains in layers. The structure of complex II is very close to the structure of the previously studied -complex of diallylammonium [H⁺L]Cu₂Cl₃.     

Crystal Structures of Ammonium and Cesium Pentadecafluorotetraantimonates(III)

Antimony(III) fluoride complexes with compositions (NH₄)₃Sb₄F₁₅(I) and Cs₃Sb₄F₁₅(II) are structurally characterized. Crystals Iare triclinic: a= 8.317(3) Å, b= 10.419(6) Å, c= 10.826(3) Å, = 63.71(4)°, = 73.24(3)°, = 77.42(5)°, Z= 2, _calcd= 3.42 g/cm³, _exp= 3.45 g/cm³, space group P , R= 0.051; crystals IIare monoclinic: a= 8.079(2) Å, b= 29.116(8) Å, c= 8.162(2) Å, = 117.08(2)°, Z= 4, _calcd= 4.549 g/cm³, _exp= 4.50 g/cm³, space group P2₁/c, R= 0.036. Structure Iis composed of SbF₄E and SbF₅E polyhedra combined into tetranuclear chains; crystals IIconsist of SbF₄E polyhedra, two of which form a dimer Sb₂F₇E₂, while the other two are isolated (E is the antimony lone electron pair).     

Synthesis,Crystal and Molecular Structures of [Co(MH)2(Thio)2][BF4] · H2O and [Co(DH)2(NH3)2][BF4]

Crystal structures of [Co(MH)₂(Thio)₂][BF₄] · H₂O (I) and [Co(DH)₂(NH₃)₂][BF₄] (II), where MH^– is H₃C–C(NOH)–C(NO^–)–H and DH^– is H₃C–C(NOH)–C(NO^–)–CH₃, were determined by X-ray diffraction. The crystals are monoclinic, space group C2/c, unit cell parameters (for I and II, respectively): a = 22.018(2) Å, b = 7.943(1) Å, c = 11.681(1) Å, = 92.68(1)° and a = 21.436(2) Å, b = 6.400(2) Å, c = 12.389(2) Å, = 113.13(1)°. In both cases, the Co(III) coordination polyhedron is a centrosymmetrical trans-octahedron, N₄S₂ for I and N₆ for II. In the crystals of I and II, the complex cations and the outer-sphere [BF₄]^– anions (and the crystal water molecules in I) form elaborate hydrogen bonding system.