Crystal structures of the new diphosphates,K2NiP2O7 and K6Sr2Ni5(P2O7)5

Crystalline K₂NiP₂O₇ (I): monoclinic, P2₁,a=9.230(2),b=17.540(8),c=8.319(9)Å, =91.44(2)°,Z=8,d _calc=3.067 g cm^–3, MoK =0.71069Å,R/R _w=6.5/9.4%, is characterized by the existence of face sharing NiO₆ octahedra with Ni–Ni separation of 2.827 Å (Ni–O; 1.93(2)–2.17(2)Å). K⁺ is seen in sites of seven, six, and fivefold coordination (K–O, averages; 2.83(2), 2.81(2), and 2.77(2)Å, respectively) P₂O₇ ^4– groups are observed in semieclipsed conformation. K₆Sr₂Ni₅(P₂O₇)₅ (II) crystallizes in monoclinic space group P2₁/c;a=11.038(7),b=9.533(13),c=7.438(2)Å, =100.13(4)°,D _calc=3.309 g cm^–3,Z=2,R/R _w=6.4/8.1%. Nickel atoms are distributed on planes parallel to the crystallographic (100) plane at =0 and =0.5. On the planes, =0, Ni²⁺ ions form successive linked trimers of edge sharing NiO₆ octahedra (Ni–Ni, 3.018(1), 3.008(1)Å; Ni–O, av 2.07(2)Å). The intermediate planes (=0.5) contain isolated and six coordinate Ni²⁺ ions (Ni–O av. 2.09(2)Å). Seven-coordinate potassium ions (K–O, av. 2.74(2)Å) are located on intermediate planes at =0.25 and 0.75. P₂O₇ ^4– groups are found in eclipsed conformation. Strontium atoms are located between nickel and potassium planes and are surrounded by seven oxygen atoms (Sr–O, av. 2.586(2)Å).     

Gas-solid structure differences in the donor-acceptor complex (CH3)2HN−SO2

The crystal structure of the donor — acceptor adduct (CH₃)₂HN–SO₂ is reported. Crystals of the compound are clear prisms, space group Pna2₁; at –96°C,a=9.894(1),b=6.051(2),c=16.478(3) Å,D=1.469 g/cm³,V=786.6(5) Å,Z=8. The unit cell contains two crystallographically independent adducts, with N–S bond lengths of 2.015(3) Å and 1.991(3) Å. The average value, 2.00(1) Å is 0.33(4) Å shorter than the 2.34(3) Å value previously determined from microwave spectroscopy of the gas phase species, revealing a large medium effect on the length of the donor — acceptor bond. The structural results are compared with published data for the trimethylamine — SO₂ adduct, and discussed in terms of existing experimental and theoretical results for other donor — acceptor systems.     

Primary to secondary sphere coordination of 18-crown-6 to lanthanide (III) nitrates: Structural analysis of [Pr(NO3)3-(18-crown-6)] and [M(NO3)3(OH2)3]·18-crown-6 (M=Y,Eu, Tb−Lu)

The direct reaction of hydrated lanthanide nitrate salts with 18-crown-6 in 31 CH₃CNCH₃OH has resulted in the isolation and structural characterization of [Pr(NO₃)₃(18-crown-6)] and [M(NO₃)₃(OH₂)₃]·18-crown-6 (M=Y, Eu, Tb–Lu). (The Eu and Yb analogs were confirmed with preliminary cell data only.) [Pr(NO₃)₃(18-crown-6)] is 12-coordinate icosahedral and crystallizes in the orthorhombic space group Pbca with (at 20°C)a=12.230(2),b=15.598(4),c=21.777(9)Å andD _calc=1.89 g cm^–3 forZ=8. The seven isostructural [Pr(NO₃)₃(18-crown-6)] complexes all contain 9-coordinate capped square antiprismatic metal centers hydrogen bonded via the bound water molecules to D_3d 18-crown-6 within the lattice to form hydrogen bonded polymeric chains. Each complex is orthorhombic Pnma with cell parameters as follows: M=Tb (20°C):a=15.242(6),b=14.253(11),c=11.070(6)Å,D _calc=1.83 g cm^–3 forZ=4; M=Dy (20°C):a=15.248(3),b=14.239(5),c=11.058(3)Å,D _calc=1.84 g cm^–3 forZ=4; M=Y (19°C):a=15.260(2),b=14.238(2),c=11.048(3) Å,D _calc=1.64 g cm^–3 for Z=4; M=Ho (20°C):a=15.226(4),b=14.208(15),c=11.028(3)Å,D _calc=1.86 g cm^–3 forZ=4; M=Er (20°C):a=15.250(3),b=14.208(7),c=11.028(3)Å,D _calc=1.87 g cm^–3 forZ=4; M=Tm (20°C):a=15.246(6),b=14.190(16),c=11.013(6) Å,D _calc=1.88 g cm^–3 forZ=4; M=Lu (21°C):a=15.244(9),b=14.158(6),c=10.980(7)Å,D _calc=1.90 g cm^–3 forZ=4.     

The crystal structure of a magnesium(II) ethyl diglyme complex

Dibromo[1,1-oxybix[2-ethoxyethane]-O,O,O]-(tetrahydrofuran-O) magnesium, C₁₂H₂₆O₄MgBr₂, crystallizes in space group Pbca witha=7.402(1),b=16.726(2),c=29.248(3) Å,V=3620.9(12) ų,Z=8. The structure was refined toR=0.083 andR _w =0.055 for 1880 observed reflections. Magnesium is octahedrally coordinated by twocis bromine atoms and four oxygen atoms, three from the meridional ethyl diglyme and one from tetrahydrofuran. The Mg–Br distances are 2.614(3)trans to thf and 2.529(3) Åtrans to the central O of the diglyme. The Br–Mg–Br angle is 97.9(1)° and the Mg–O(thf) distance is 2.196(6) Å. The O–Mg–O bite angles subtended by the diglyme are 75.3(2) and 75.7(2)°. The Mg–O(ethyl diglyme) distances are 2.127(6), 2.136(6), and 2.090(6) Å.     

Crystal and molecular structure of tetrakis-(phenylenethiourea)tellurium(II) perchlorate hexahydrate,C28H24N8O8S4Cl2Te·6H2O

The synthesis and structural characterization of the title compound, C₂₈H₂₄N₈O₈S₄Cl₂Te·6H₂O are reported. The crystals are triclinic, space group P¯1 (No. 2), withZ=1 in a unit cell of dimensionsa=10.312(7),b=7.144(6),c=14.256(7) Å,=83.04(5),=92.15(5), and=101.25(6)°,V _c =1022 ų. The structure was solved by Fourier methods, and refined by full-matrix least squares toR=0.073 andR _w =0.077 for 1305 unique reflections. The tellurium atom in the molecule lies at a crystallographic center of symmetry, and is bonded to four phenylenethiourea sulfur atoms in a near square-planar arrangement with Te-S(1)=2.666(5), Te-S(2)=2.675(6) Å, and S(1)-Te-S(2)=88.7(3)°. The ligands behave as thiones. The crystal packing is stabilized by the extensive hydrogen bonding involving oxygen and nitrogen atoms. The Cl-O bond lengths are 1.29-1.36 Å and the O-Cl-O angles are 90–130° in the ClO₄ ^– moiety, and differ considerably from the normal values of 1.44 Å and 109°, respectively.     

Crystal structure of 751-1751-1751-1751-2751-2751-2

The title compound crystallizes in the centrosymmetric triclinic space group (No. 2) witha=10.818(1)Å,b=10.876(1)Å,c=11.072(2)Å, =98.74(1)°, =98.83(1)°, =96.61(1)°,V=125906(3)ų andZ=2. Interatomic distances include Fe–P=2.243(2)Å, Fe–CO=1.771(6)–1.781(5)Å, Fe–C(C₅H₅)=2.074(6)–2.103(5)Å and P–F=1.511(6)–1.571(4)Å.     

Synthesis and crystal structure of 1-acetyl-3-bromo-3-phenylazetidine and 1-phenyl-2-(N-acetyl-N-formyl)-aminoethanone

1-Acetyl-3-bromo-3-phenylazetidine (1), C₁₁H₁₂BrNO, has been synthesized and characterized by spectroscopic methods and single crystal X-ray analysis. It crystallizes in the space group P2 ₁/c with a = 8.633(1), b = 7.461(1), c = 17.204(1) Å, = 98.403(7)°, V = 1096.2(2) ų, Z = 4, D _calc = 1.540 g cm^–3. The azetidine ring is nearly planar since the four atoms are within ±0.039(5) Å of the mean square plane calculated for the heterocycle. The attempt to obtain a highly strained 2-azetine derivative from the above compound gave, surprisingly, 1-phenyl-2-(N-acetyl-N-formyl)-aminoethanone (2), C₁₁H₁₁NO₃. This compound has been also characterized by spectroscopic methods and single crystal X-ray analysis. It crystallizes in the space group P2₁2₁2₁, with a = 5.4719(3), b = 8.3205(6), c = 23.298(3) Å, V = 1060.7(2) ų, Z = 4, D _calc = 1.286 g cm^–3. The aminoethanone residue is in a near planar conformation where the torsion angles are 7(2)° for N–C–C–=O and –173(2)° for N–C–C–C(Ph).     

Chiral bisphosphanes XII: Synthesis and molecular structure of cis-{rac,trans-1,2-bis[bis(morpholin-4-yl)-phosphino]cyclopentane}dimethylplatinum(II), cis-[C5H8{P[N(C2H4)2O-cyclo]2}2Pt(CH3)2]

Crystals of the title compound are monoclinic, space group P2₁/c, with a = 10.2621(8), b = 15.372(5), c = 17.612(2) Å, = 95.928(9)°, and Z = 4. Coordination about the central metal deviates slightly from ideal square-planar geometry. The five-membered chelate ring adopts an envelope conformation with one of the two P atoms (P1) deviating from the least-squares plane spanned by the central metal, the bridging CH carbons, and donor atom P2. While the morpholino substituents at the latter show little axial-equatorial discrimination for their orientation with respect to the coordination plane, the spatial alignments of the N(C₂H₄)₂O rings attached to P1 differ significantly between a more equatorial and a more axial disposition. The conformationally dissimilar arrangement of the two P donor groups within the envelope-like chelate ring manifests itself in unequal Pt–P bond lengths: d(Pt–P1) = 2.2677(16), d(Pt–P2) = 2.2825(16) Å. The Pt–CH₃ distances amount to 2.114(6) (trans to P2) and 2.141(6) Å (trans to P1), respectively.     

Solid state structure of oxalato-(bis(dicyclohexylphosphino)-ethane) platinum(II)-acetonitrile solvate

C₃₀H₅₁NO₄P₂Pt-[C₂H₃N], orthorhombic,Pbca, a=16.132(1),b=16.610(2),c=24.001(2) Å.Z=8,D _c=1.54 g cm^–3,R=0.042,R _w=0.048, GOF=1.33. The platinaoxalate (PtC₂O₂) ring fragment is essentially planar with Pt–O bond lengths of 2.067(8) and 2.058(7) Å.     

The structure of a tetrabromotetrahydrodibenzocyclooctene

5, 6, 11, 12-Tetrabromo-5, 6, 11, 12-tetrahydrodibenzo[a, e]cyclooctene, C₁₆H₁₂Br₄, crystallizes in monoclinic space group P2₁/c witha=8.6917(7),b=15.135(2),c=12.892(2) Å, =101.836(8)°, V=1660.0(7) ų,Z=4. The structure was refined toR=0.058 for 3137 observed reflections. The molecule has approximate C₂ symmetry, with the eight-membered ring adopting the twist-boat conformation. The planes of the two phenyl rings form a dihedral angle of 117.3(2)°, C–Br distances range 1.965(5)–1.981(5) Å.     

Crystal structure of aquo (hydroxo) (ethylenediaminetetraacetato) sodium(I) tin(IV), NaSn(OH)(edta)(H2O)

NaSn(OH)(edta)(H₂O) is monoclinic, space groupP2₁/c, witha=9.747(3)Å,b=9.121(3)Å,c=16.430(6)Å, =98.69(4)°, ų, andZ=4. The coordination environment of Sn(IV) is a capped octahedron. Sn–O distances range from 1.990(6)Å to 2.351(7)Å. Na(I) is five coordinated to three different edta molecules. Na–O distances range from 2.283(9)Å to 2.414(7)Å. The edta ligand presents the E, G/R conformation. The crystal structure is composed of sheets parallel to (001): inside a sheet Sn(OH)(edta) molecules are connected to each other by the Na(I) interactions.     

Schiff bases and their complexes with metal ions. Part II. Structures of N-n-butyl-2-hydroxy-1-naphthaldimine and bis[N-n-pentyl-2-hydroxy-1-naphthaldiminato]nickel(II)

The Schiff base ligand (1), [C₁₅H₁₇NO] crystallizes in the monoclinic space group P2₁/c witha=10.054(3),b=10.313(3), c=13.173(4)Å, =107.42(4)°,V=1303.2(7)ų,Z=4,Dx=1.159 g cm^–3, and (MoK)=0.674 cm^–1. The C2-O[1.23(1)Å] and C3–C4 [1.33(2)Å] bond lengths are short, due to its quinoidal structure. In the Schiff base nickel complex (2), [Ni(C₁₆H₁₈NO)₂] the asymmetric unit is comprised of two half-complexes. It crystallizes in the triclinic space group witha=5.124(3),b=16.227(3),c=16.886(4)Å, =95.47(8), =96.00(1), =90.71(4)°,V=1389.6(9) ų,Z=2,Dx=1.289 g cm^–3, and (MoK) =12.1 cm^–1. The coordination of the Ni(II) ions are square planar with bond angles between 87.9(1) and 92.1(1)°. The Ni–O and Ni–N distances are 1.819(2), 1.922(2) and 1.823(2), 1.914(3)Å in these two complexes.     

A twist boat: Structure and conformation oftrans-2,4,6-tris(trichloromethyl)-1,3,5-trithian

Trans-2,4,6-tris(trichloromethyl)-1,3,5-trithian, (CCl₃·CHS)₃, has been prepared free from persistent impurification bycis-trans-2,4,6-tris(trichloromethyl)-1,3,5-oxadithian and its conformation determined by single crystal x-ray crystallography. The title compound is orthorhombic,Pbca, a=10.479(10),b=27.957(14),c=11.093(3) Å,V=3250 ų,Z=8. The structure was solved by direct methods, from data collected at room temperature on an Enraf-Nonius CAD4 diffractometer, and refined by full-matrix least squares to a finalR value at 0.074 using 1186 reflections. The molecule exhibits a twist boat conformation with the –CCl₃ groups occupying pseudoequatorial positions. The torsion angles in the trithian ring are successively 29(1), –79(1), 41(1), 41(1), –84(1), 39(1)°. Average values are: S-C 1.82(2), C(ring)-C(Cl₃) 1.56(4), C-Cl 1.76(2) Å, S-C-S 112.7(2)°. The C-S-C angles are 97.4(7), 101.4(7), 97.3(7)°.     

Molecular and crystal structure of Cp2Mo(mto), mto=monothiooxalate

Compoundl, Cp₂Mo(mto) is obtained by the reaction of Cp₂MoCl₂ with methanol solutions of potassium dithiooxalate in air. Red platelike crystals of Cp₂Mo(mto) were grown by the slow diffusion of pentane into a CH₂Cl₂ solution ofl and have been studied by X-ray crystallography: space group, P2₁/n,a=7.578(1),b=10.551(2),c=14.090(3) Å, =94.38(2)°,V=1123.1(4) ų,Z=4. The mto ligand chelates to the Mo atom through one oxygen atom and the sulfur atom. The two Cp rings form dihedral angles of 24° with the least-squares plane of the mto ligand. The Mo–O and Mo–S bond distances are 2.193(5) and 2.449(2) Å, respectively.     

The molecular structure of acetato[2-(pyridin-2′-yl)phenyl]mercury(II)

The crystal structure of the title compound was determined by X-ray crystallography. The compound crystallizes in the monoclinic crystal system witha=8.152(4),b=17.994(7),c=8.634(9) Å, =108.92(5)°, space group P2₁/c (N:14),V=1198.02 ų,Z=4. The mercuryl(II) atom forms two strong, almost colinear bonds (bond angle 176.1(4)°) with a carbon of the phenyl ring (Hg–C=1.99(1) Å) and one of the acetate oxygen atoms (Hg–O(1)=2.005(7) Å). These primary bonds are supplemented by secondary intramolecular interactions with the pyridine nitrogen (Hg...N=2.727(9) Å) and the other acetate oxygen (Hg...O(2)=2.925(8) Å), although the latter is very weak and the acetate anion therefore practically monodentate. Weak additional intermolecular Hg–C and Hg–O(1)interactions contribute to the lattice structure.     

The crystal structure of tris(4-methylpyridine) tricarbonylmolybdenum(0)

The title compound, Mo(4-CH₃C₅H₄N)₃(CO)₃, is monoclinic, P2₁/c, with cell dimensionsa=10.385(1),b=13.572(2),c=15.522(2) Å, =105.08(1)°,Z=4. The complex isfac-octahedral with approximate three-fold symmetry. The Mo–C bond lengths are 1.901–1.904(7) Å, distinctly shorter than in the parent Mo(CO)₆, and the Mo–N bond lengths are 2.297–2.331(5) Å.     

Crystal structure of dicyclohexylammonium 2-mercaptobenzoatotriphenylstannate

Dicyclohexylammonium 2-mercaptobenzoatotriphenylstannate crystallizes in the monoclinicP2₁/n space group (a=11.171(2),b=17.891(5),c=17.190(3)Å;=105.08(2)°). The asymmetric unit consists of a [(cyclo-C₆H₁₁)₂NH₂]⁺ cation hydrogen bonded (NO1=2.803(4) Å) to the stannate anion; the [(C₆H₅)₃Sn]⁺ group is covalently linked to the sulfur end (Sn-S=2.427(1)Å) of the [SC₆H₄C(O2)O1]^–2 moiety. The tin is five-coordinate in a distortedcis-trigonal bipyramidal environment in which the carboxyl O2 atom (Sn-O2=2.704(3)Å) and theipso-carbon of a phenyl ring occupy apical positions (O2-Sn-C1=168.7(1)°); the Sn-C_axial bond (Sn-C1=2.179(3)Å) is longer than the Sn-C_equatorial bonds (2.136(4), 2.139(3)Å). The stannate anion is linked to an adjacent cation (NO1=2.880(4)Å) to form a tightly held three-dimensional network structure.     

The preparation, characterization, and X-ray structural analysis of dichlorobis[1-methyl-3-(2-propyl) -2(3H)-imidazolethione]mercury(II)

A new compound of mercury(II) chloride complexed to 1-methyl-3-(2-propyl) -2(3H)-imidazolethione (mipit) has been prepared and characterized via standard methods and X-ray crystallography. The structural significance of this study is that it shows one of the few monomeric examples of a mercury(II) chloride thione complex reported to date. The compound crystallizes in space group P2₁/c with a = 17.143(6) Å, b = 17.047(6) Å, c = 14.759(5) Å, = 105.899(5)°, V = 4148(2) ų, Z = 8. The coordination sphere is distorted tetrahedral with Hg–S bonds and Hg–Cl bond distances falling within the normally expected ranges. Bond angles ranged from 108.11(4)° to 115.51(4)° with the widest angle being observed for the S–Hg–S linkage. Ligand bond distances and angles including the C=S distance are within the normally expected values observed for this compound.     

Crystal and molecular structure of methylene bis(piperidine-dithiocarbamate), C13H22N2S4

Reaction of anhydrous sodium piperidine dithiocarbamate with methylene chloride yields methylene bis(piperidine dithiocarbamate). The crystals, C₁₃H₂₂N₂S₄ (M=334.57), are monoclinic with space group ,a=6.421(3),b=29.321(7),c=9.022(4)Å,=109.05(3)°,V=1605.6 ų,Z=4,D _c =1.384 g cm^–3,F(000)=712,T=295°K (Mo-K)=0.71069 Å,=5.62 cm^–1 andR=0.032 for 1734 reflections. The molecular structure shows that the methylenic group is bonded to two planar moieties at distances of 1.782(3) and 1.803(3)Å with an S-CH₂-S angle of 114.7(2)°. The configuration about each N atom is planar rather than pyramidal. The two C-N bond lengths adjacent to the C=S bonds are both very short 1.330(4) and 1.336(4) Å indicating the influence of the C=S bond on C-N bond lengths. The six-membered piperidine ring has a classical chair conformation with average C-C distance of 1.511 (5)Å.     

Crystal structures of p-chloro- and p-bromobenzaldehyde

p-Chloro- and p-bromobenzaldehyde form isomorphous monoclinic crystals, space groupP2 ₁/a. For p-Cl at –96°C,a=12.945(3),b=3.833(3),c=26.503(9) Å, =103.68(2)°,Z=8,V=1278(2) ų,Dx=1.461(2) g cm^–3, refinement on 2714 reflections,R=0.047. For p-Br at –96°C,a=12.754(5),b=3.919(3),c=27.317(12) Å, =103.28(3)°,Z=8,V=1329(2) ų,Dx=1.849(3) g cm^–3, refinement on 1519 reflections,R=0.062. The molecules do not differ significantly from planarity. They pack in stacks with Cl...Cl or Br...Br contacts at one end and CH...O contacts that are suggestive of hydrogen bonds at the other. There are no O...Cl or O...Br contacts.