Structure of the neutral metal complex Pt(dddt)2

A neutral metal complex, [Pt(dddt)₂]° (1), has been obtained by oxidation of the [Pt(dddt)₂]^– anion with excess (Bu₄N)AuBr₄ in nitrobenzene. Crystallographic data for 1a=17.854(9) Å,b=18.409(9) Å,c=4.717(5) Å, =68.83(2)°, space group P2₁/n,Z=4,d _calc=2.55 g/cm³. In1 two independent centrosymmetric [Pt(dddt)₂]° molecules are packed in stacks that form layers parallel to the (110) plane. The molecules of1 in the layers have shortened S...S contacts 3.491(9) Å, and 3.594(10) Å. The average bond lengths Pt-S 2.242(7) Å, S-C 1.71(2) Å and C=C 1.40(3) Å, together with the square-planar coordination of Pt in PtS₄, suggest considerable conjugation in the metal cycles.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1207–1209, July, 1993.     

Zur Kristallchemie der Triäthanolaminkomplexe

-Sn[(OC₂H₄)₂NC₂H₄OH]₂ crystallizes with space group Pccn and cell dimensionsa=16.35 (2),b=7.26 (1),c=12.82 (1) Å andZ=4. The structure was solved by the heavy atom technique (571 observed reflections, R₁=5.9%). Tin is octahedrally coordinated by four oxygen and two nitrogen atoms (Sn–O 2.01; 2.04 Å, Sn–N 2.33 Å) of the triethanolamine molecules. The complexes possess a crystallographic two-fold axis of rotation. They are linked by hydrogen bonds, thus forming infinite chains parallel to the twofold axis.

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Mit 1 Abbildung     

Nickel complexes of 1-methylimidazoline-2(3H)-thione: crystal structures of trans-dichlorotetrakis(1-methylimidazoline-2(3H)-thione)nickel(II) and tetrakis[1-methylimidazoline-2(3H)-thione]nickel(II) tetrafluoroborate

Summary Crystal structures have been determined for two nickel complexes of the monodentate S-donating ligand 1-methyl imidazoline-2(3H)-thione (mimtH). The parainagnetic trans-octahedral complex, [Ni(mimtH)₄Cl₂], crystallises in an orthorhombic unit cell (a=12.459(1),b=13.078(1),c=15.406(1)Å, V=2510.24ų,Z=4, space group Pbca). Final conventional R from 1848 observed data [F>4(F)] is 0.0273. The Ni–Cl distance is. 2.537(1) Å and the mean Ni–S distance is 2.479 Å.The diamagnetic complex, [Ni(mimtH)₄](BF₄)₂, contains a distorted square-planar cation which is H-bonded. to [BF₄]^– anions. The complex crystallises in an orthorhombic unit cell [a=9.810(1),b=14.585(1),c=20.120(2)Å, V=2878.8ų,Z=4, space group Pbcn]. Final conventional R from 1756 observed data [F>4(F)] is 0.0629. The average Ni–S distance is 2.216Å.     

Crystal structure of 4-ethylvanadatrane-1-one

An X-ray diffraction study of a substituted vanadatrane-1-one (space groupPna2₁,R= 0.019 for 1394 reflections, the absolute structure was determined) showed that the geometry of its atrane framework is similar to that of the Si- and Ge-analogs. The bond lengths are: V=O, 1.614(2) Å; VN, 2.329(2) Å; V-O, 1.800–1.806(2) Å. The deviation of the V atom having distorted trigonal bipyramidal coordination from the equatorial plane of the O atoms is 0.35 Å, the 0=VN bond angle is 179.4(1)°.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1477–1479, August, 1993.     

Crystal structure of copper(II) bis-hexafluoroacetylacetonate

An X-ray diffraction investigation has performed for copper(II) bis-hexafluoroacetylacetonate (Bruker AXS P4 automatic diffractometer, MoK radiation, t = –25°C). Crystal data for C₁₀H₂CuF₁₂O₄: a = 5.530(1) Å, b = 6.038(1) Å, c = 11.266(2) Å, = 95.948(3)°, = 101.743(3)°, = 92.298(3)°, space group; P1, V = 365.6(1) ų, Z = 1, d _calc = 2.169 g/cm³. The square-planar environment of the copper atom (Cu-O_av 1.912 Å, O-Cu-O_av 93°) is completed to bipyramidal by two fluorine atoms of the neighboring molecules, Cu...F 2.71 Å and 2.75 Å.Original Russian Text Copyright © 2004 by S. A. Gromilov, I. A. Baidina, P. A. Stabnikov, and G. V. RomanenkoTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 502–507, May–June 2004.     

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.     

The structure of binuclear molybdenum(VI) oxocomplexes with dianionic tridentate Schiff bases

Summary The new Mo^VI complex [Mo(O) (-O) (SAE)]₂ was prepared and characterized by means of spectroscopic (i.r.,¹Hn.m.r.) and crystallographic measurements. Crystals of the [Mo(C₉H₈NO₂)(H₂O)]₂, M=582.3, orthorhombic, space group Pbca,a=13.108(4),b=8.982(2),c=16.842(4) Å, v=1982.9 ų, z=4, D_m=1.93(2), D_c=1.95 g cm^–3, MoK =0.71069 Å, =1.3 mm^–1, F(000)=1152, T=295K, R=0.035 for 2413 reflections.The crystal structure consists of [Mo(O)(-O)(L)]₂, in dimeric units. The coordination geometry around each molybdenum atom is distorted octahedral with Mo–O (terminal) and Mo–O (bridge) distances of 1.694(3) and 1.760(3) Å, respectively, and with the angle O(1)–Mo–O(2) of 105.6(1)^o, typical for manycis-dioxocomplexes of Mo^VI. The asymmetric bridge is characterized by the following parameters: Mo–O(2)ⁱ and Mo–Moⁱ distances equal 2.408(3) and 3.319(3) Å, respectively, and the Mo–O(2)–Moⁱ and O(2)–Mo–O(2)ⁱ angles equal 104.5(1)^o and 75.5(1)^o, respectively.The i. r. and Raman spectra of molybdenum complexes with an asymmetric double oxygen bridge display a strong absorption the 800–850 cm^–1 range.     

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.     

Iron(II) complexes of imidazoline-2-thiones: the crystal structure of dichlorobis(1-methylimidazoline-2-thione)iron(II)

Summary Imidazoline-2-thione (imtH ₂) and 1-methylimidazoline-2-thione (mimtH) react with FeCl₂·4H₂O in rigorously anhydrous media producing complexes of general formula Fe(LH)₂Cl₂.Infrared and electronic spectra as well as room temperature magnetic moments are consistent with mononuelear, pseudotetrahedral species. The crystal structure of [Fe(mimHH)₂Cl₂] confirms this arrangement. The complex crystallises in a triclinic unit cell (a=7.376(2),b=7.595(2),c=15.043(4) Å. =76.80(1)°, =79.60(1)°, =61.90(1)°; V=721.13 ų; space group=P1, Z=2). Final conventional R from 2267 observed data (F >4(F)) is 0.0271. Average bond lengths are 2.353 Å (Fe–S) and 2.265 Å (Fe–Cl). Angles at the metal range from 91.5(1)° to 114.5(1)°.Thermal degradation of the complexes in flowing air involves sequential loss of halogen and ligand with -Fe₂O₃ as the final product. The decomposition is exothermic in flowing dinitrogen.     

Synthesis and structure of a three-dimensional coordination polymer [Ag<Subscript>3</Subscript>hmt<Subscript>3</Subscript>(μ<Subscript>3</Subscript>-btc)]·5H<Subscript>2</Subscript>O

A new coordination polymer [Ag₃hmt₃(₃-btc)]·5H₂O (1 )(hmt = hexamethylenetetramine, btc = 1,3,5-benzenetricarboxyl)has been successfully synthesized. Crystal data: P2₁/a , a = 11.9906(2) Å, b = 17.3689(2) Å, c = 16.96100(10) Å, = 101.9820(14)°, V = 3455.40(7) ų, Z = 4, Dc = 2.002 mg/m³. In the hexagonal structure of the Ag-hmt unit, each Ag-hmt unit comprises three Ag atoms and three hmt ligands. The ₃-btc ligands bridge the adjacent two-dimensional honeycomb-like Ag-hmt layers to form three-dimensional networks. Structural analysis shows that hydrogen bonds play a key role for the structural stability of the compounds.Original Russian Text Copyright © 2004 by Shoubo Qin, Sheming Lu, Yanxiong Ke, Jianmin Li, Shuxi Zhou, Xintao Wu, and Wenxin DuTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 566–571, May–June 2004.     

Polymeric Tin(II) Complexes with Dibasic Nitrogen-Containing Organic Cations. Synthesis and Crystal Structure of (C10H10N2)0.5[SnF(SO4]

The (C₁₀H₁₀N₂)_0.5[SnF(SO₄)] compound was synthesized via reaction of SnF₂ with 4,4"-bipyridine (C₁₀H₈N₂) in a diluted sulfuric acid solution (pH 3) and its X-ray diffraction analysis was carried out. The Sn²⁺ atoms coordinate one fluorine atom (Sn–F 2.062(2) Å) and two oxygen atoms of two sulfate groups (Sn–O 2.149(2) and 2.313(3) Å) thus forming the coordination polyhedron as a trigonal bipyramid with a stereochemically active unshared electron pair in its vertex. The sulfate groups act as bidentate bridges and join the neighboring Sn²⁺ complexes into infinite chains of [SnF(SO₄)] ^n– _n anions combined in pairs through the Sn–F contacts (2.450(2) Å) to form ribbons whose voids contain two-charge 4,4"-bipyridinium cations.     

Diaqua[N,N-di(2-carboxyethyl)-o-anisidinato]copper(II) Dihydrate [Cu(o-Andp)(H2O)2] · 2H2O: Synthesis and Crystal Structure

Crystals of [Cu(o-Andp)(H₂O)₂] · 2H₂O (where o-Andp^2–is -anisidine-N,N-di-3-propionate) were synthesized and studied using X-ray diffraction analysis. The crystals are triclinic: a= 12.063(1) Å, b= 12.483(3) Å, c= 13.586(2) Å, = 91.29(1)°, = 111.67(1)°, = 104.00(1)°, V= 1830.5(5) ų, space group P , Z= 2, and R= 0.0528 for 5965 reflections with I2(I). The two crystallographically independent complexes are isostructural. The tetragonal–bipyramidal coordination of copper(III) involves three O atoms, the N atom of the tetradentate ligand o-Andp^2–, and two O atoms from water. The aminodipropionate group of the ligand (average Cu–O 1.939 Å and Cu–N 2.051 Å) and one of the coordinated water molecules (Cu–O(w) 1.991 Å) lie in the equatorial plane. The second water molecule (Cu–O(w) 2.32 Å) and the methoxy O atom of o-Andp^2–(Cu–O 2.37 Å) are in the apical positions of the bipyramid.     

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 Structure of Hexafluosilicates of Protonated Thiosemicarbazide and 2,5-Diamino-1,3,4-thiadiazole Produced in the Reaction of Thiosemicarbazide with Fluosilicic Acid

The structure of the crystal complex (L¹H)₂(L²H)(SiF₆)_1.5(L¹is thiosemicarbazide, L²is 2,5-diamino-1,3,4-thiadiazole) was studied by X-ray diffraction analysis. The complex was prepared by reacting an aqueous solution of L¹with 45% fluosilicic acid. The crystals are monoclinic: a= 16.080(3) Å, b= 5.4860(8) Å, c= 20.079(4) Å, = 91.46(1)°, Z= 4, space group P2/n, R= 0.0427. The components of the ionic structure of the complex are L¹H⁺and L²H⁺cations and SiF^2– ₆anions combined by a system of H bonds of the NH···S and NH···F types, the -nitrogen atom of the hydrazine fragment and the endocyclic nitrogen atom of the heterocycle being the protonation centers in L¹H⁺and L²H⁺, respectively. The bond lengths in the SiF^2– ₆anions range within 1.621(6)–1.691(2) Å.     

Steric and Electronic Influences in Os3(CO)11(PR3) Structures

The structures of Os₃(CO)₁₁(PR₃) with R=F, OPh, Et, p-C₆H₄Me, o-C₆H₄Me, p-C₆H₄(CF₃) and C₆H₁₁, and with PR₃=P(OCH₂)₃CMe have been determined. The Os–Os bond lengths in these compounds are compared to the Os–Os lengths for the other structures of Os₃(CO)₁₁(PR₃) clusters reported in the literature. In most cases, the Os–Os bond length remote from the P ligand [range, 2.8666(4)–2.9044(4) Å] and that in the pseudo-trans position [range, 2.8712(5)–2.900(1) Å] show little variation as the steric and electronic properties of the P ligand are varied. The Os–Os length cis to PR₃ shows more variation [range, 2.879(1)–2.9429(4) Å] and is sensitive to both the size and the -donor/-acceptor properties of the PR₃ ligand: larger or better donor PR₃ ligands cause an increase in the Os–Os bond length. The Os–P distances [range, 2.15(2)–2.478(1) Å] show a similar dependence on the steric and electronic properties of the PR₃ ligand.     

Analysis of atomic displacement parameters and molecular motion in crystals. Part 2. X-ray crystal structure of K2Ru(SO4)2 * 6H2O at 160 K and 295 K

Atomic displacement parameters determined from a single-crystal X-ray-diffraction study on K₂Ru(SO₄)₂ * 6H₂O are analyzed in the molecular mean field approximation. The motion of SO₂ ^2– can be described with a rigid-body model, whereas for [Ru(H₂O)₆]²⁺ internal stretching motion and coupling between stretching motion and overall translation are found to be necessary for explaining the observed atomic displacement parameters. Frequencies and force constants of internal motion are not significantly affected by such couplings. K₂Ru(SO₄)₂ * 6H₂O crystallizes in the monoclinic space groupP2₁/c (No. 14), witha = 6.1211(7)Å,b = 12.226(2) Å,c = 8.916(2)Å, = 105.11(1)°,Z = 2 at 160 K anda = 6.1402(7)Å,b = 12.274(2)Å,c = 8.957(1)Å, = 105.25(1)°,Z = 2 at 295 K. The structure was refined to a finalR(F) of 0.017 at 160 K and of 0.019 at 295 K for 1438 and 1299 observed reflections withF ₀ > 6(F₀) and sin / > 0.617 Å^1–.     

Crystal Structure of Ammonium Undecafluorotriantimonate(III) (NH4)2Sb3F11

The crystal structure of a novel antimony(III) fluoride complex, ammonium undecafluorotriantimonate(III) (NH₄)₂Sb₃F₁₁, was determined. The crystals are triclinic: a = 7.780(2) Å, b = 8.370(2) Å, c = 10.620(1) Å, = 71.06(1)°, = 89.03(1)°, = 63.58(1)°, V = 579.1(2) ų, Z = 2, (calcd) = 3.500 g/cm³, (exp) = 3.51 g/cm³, F(000) = 548.0, space group P . The structure consists of anionic [Sb₃F₁₁]^2– chains and ammonium cations combined into a framework by the N–H···F hydrogen bonds.     

The crystal structure of tetraphenylarsonium tricyanooxopyridine-2-carboxylatotungstate(IV) dihydrate

Summary The structure of (AsPh₄)₂[WO(CN)₃(Pic)] · 2H₂O has been determined from three dimensional x-ray data. The cell dimensions are:a=17.699(8),b=13.546(6),c= 13.590(6) Å, =117.39(8), = 71.54(7) and = 115.04(8)°, space group P¯1, Z = 2, The structure was solved from 5279 observed reflections. The anisotropic refinement converged to R = 0.060.The [WO(CN)₃(Pic)]^2–-ion is a distorted octahedron. The structure indicates that the aqua group in [WO(CN)₄(H₂O)]^2– was displaced by an oxygen atom of the carboxylate of 2-picolinate, while a cyanide ligand was substituted by the pyridine nitrogen atom. Themer-arrangement of the three cyanide ligands has two normaltrans W-C_av = 2.17(2) Å bond distances and a significant shorter W-C = 2.042(18) Å bond trans to the W-N [2.188(18) Å] bond. The W=O and W-O bond lengths are 1.676(9)Å and 2.171 Å, respectively.     

Crystal and molecular structure of the simple cation-radical salt ethylenedithiopropylenedithiotetrathiafulvalene trichloromercurate (EPT)HgCl3

The new cation-radical salt (EPT)HgCl₃ is prepared. Its structure and electrical conductivity are studied. The crystal structure of (EPT)HgCl₃ contains (EPT)⁺ in the chair conformation and trigonal planar HgCl₃ ^– packed into organic and inorganic layers alternating along thea axis. Shortened intermolecular contacts join HgCl₃ ^– into infinite chains along the c axis (Hg...Cl, 3.289 and 3.387 Å), form stacks (S...S, 3.536 and 3.597 Å) and layers (S...S, 3.427–3.498 Å) of EPT⁺ cation-radicals, and create cation-anion interactions between neighboring layers in the crystal (Cl...S, 3.396–3.521 Å, Cl...C, 3.360 Å). The configuration of the bonds around Hg in HgCl₃ ^– is distorted trigonal planar: Hg-Cl, 2.342(3)–2.449(3) Å, Cl-Hg-Cl, 110.7(1)–137.4(1). The Hg atom lies out of the plane of the Cl atoms by 0.015 Å. The conductivity of (EPT)HgCl₃ at 20°C is ₃₀₀ 5·10^–2 (·cm)^–1. The dependence of conductivity on temperature is semiconducting in nature.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2055–2061, September, 1991.     

Crystal and Molecular Structure of Bis(O,O"-diisopropyldithiophosphato-S,S")(dimethylglyoximato-N,N")rhodium(III)

The crystal and molecular structure of bis(O,O"-diisopropyldithiophosphato-S,S")(dimethylglyoximato-N,N")rhodium(III) (I) was studied using X-ray diffraction analysis: space group P2₁/c, a = 13.644 Å, b = 10.350 Å, c = 20.906 Å, = 109.02°, Z = 4. The structure was solved by the direct method and anisotropically refined by the full-matrix least-squares method to R = 0.029 using 5447 independent reflections (CAD-4 autodiffractometer, MoK ). Compound I is a mononuclear tris-chelate complex whose three ligands are singly charge anions. The individual molecule of the complex has a noncrystallographic two-fold axis; its Rh atom is coordinated by four S atoms and two N atoms, forming a distorted octahedron. The average coordination bond lengths are Rh–S 2.402 and Rh–N 2.023 Å. The molecules in structureI are joined into infinite chains via weak intramolecular C–H···S hydrogen bonds and intermolecular N–O–H···O–N hydrogen bonds.