Cyclometallation Reactions. XXI. Some Chemistry of Binuclear Manganese Complexes Derived From Azobenzene: X-Ray Crystal-Structures of {Mn (CO)4}2(μ- C6H4N=NC6H4) and {Mn (CO)4}{ Mn (CO)3[P(OPh)3]}(μ-C6H4N=NC6H4)

1988 ◽  
Vol 41 (9) ◽  
pp. 1407 ◽  
Author(s):  
MI Bruce ◽  
MJ Liddell ◽  
MR Snow ◽  
ERT Tiekink
Keyword(s):  
Crystal Structures ◽  
Binuclear Complex ◽  
Hydrogen Transfer ◽  
Monoclinic Space Group ◽  
Subsequent Reaction ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Cell Dimensions ◽  
Unit Cell Dimensions

The reaction between azobenzene and Mn (CH2Ph)(CO)5, carried out in refluxing n-octane, afforded the binuclear complex {Mn (CO)4}2(μ- C6H4N=NC6H4) (2) as the first isolable product; subsequent reaction with azobenzene gave Mn (C6H4N= NPh )(CO)4. With P( OPh )3, the binuclear complex undergoes CO substitution but not hydrogen transfer, to give {Mn (CO)4}{ Mn (CO)3[P(OPh)3]}(μ-C6H4N=NC6H4)(3). The X-ray crystal structures of the title complexes have been determined. Compound (2) crystallizes in the monoclinic space group P21/c with unit cell dimensions a 10.161(2), b 23.586(4), c 13.091(4)Ǻ, β 97.10(2)° with Z = 6; crystals of (3) are triclinic, space group Pī , a 12.886(3), b 13.920(3), c 10.428(7)Ǻ, α 97.11(4),β 102.60(4), γ 81.78(2)°. The structures were refined by a full-matrix least-squares procedure to final R 0.041 and Rw 0.048 for 3459 reflections with I ≥ 2.5σ(I) for (2), and R 0.095 and Rw 0.106 for 3406 reflections for (3).

Metal-selenolate chemistry: stereochemistry of adamantane-type clusters of formula [(μ-SePh)6(MSePh)4]2− (M = Zn and Cd)

1992 ◽  
Vol 70 (3) ◽  
pp. 792-801 ◽  
Author(s):  
Jagadese J. Vittal ◽  
Philip A. W. Dean ◽  
Nicholas C. Payne
Keyword(s):  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Bridging Ligands ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Space Groups ◽  
X Ray Crystallography ◽  
Cell Dimensions ◽  
Minimum Number

The structures of three tetramethylammonium salts containing anions of formula [(μ-SePh)6(MSePh)4]2− (M = Zn and Cd) were determined by single crystal X-ray diffraction techniques. The Zn salt crystallizes in different space groups depending upon the solvent combination used in the synthesis. Thus crystals of (Me4N)2[Zn4(SePh)10], 1, grown from a mixture of methanol, acetonitrile, and acetone are triclinic, space group [Formula: see text] with cell dimensions a = 13.214(2), b = 23.859(2), c = 13.072(1) Å, α = 91.134(8), β = 113.350(8), γ = 79.865(9)°, and Z = 2. In the absence of acetone, a solvated crystal (Me4N)2[Zn4(SePh)10]•CH3CN, 2, is formed, which belongs to the monoclinic space group P21/n with a = 14.248(1), b = 39.722(2), c = 13.408(1) Å, β = 97.132(5)°, and Z = 4. The Cd salt (Me4N)2[Cd4(SePh)10], 3, crystallizes in the monoclinic space group P21/c, with a = 20.830(2), b = 14.282(1), c = 25.872(1) Å, β = 99.626(6)°, and Z = 4. These three salts are the first examples of homoleptic, tetranuclear selenolatometal(II) anions with (μ-Se)6M4 cages of adamantane-type stereochemistry. In each case the phenyl substituents of the bridging ligands adopt the configuration [aae, aae, aee, aee], which has the minimum number of two 1,3-axial–axial non-bonding substituent interactions. Keywords: selenolate complexes, synthesis, X-ray crystallography, isomerism, adamantane stereochemistry.

Kristallstrukturen der iodierten closo-Hexaborate trans-(Ph4P)2[B6H4I2], mer-(Ph4P)2[B6H3I3] · 2 CH2Cl2, trans-(Ph4P)2[B6H2I4] · 2 CH3CN und (CH2Py2)[B6HI5]/Crystal Structures of the Iodized closo-Hexaborates trans-(Ph4P)2[B6H4I2], mer-(Ph4P)2[B6H3I3] · 2 CH2Cl2, trans-(Ph4P )2[B6H2I4] · 2 CH3CN and (CH2Py2)[B6HI5]

1998 ◽  
Vol 53 (2) ◽  
pp. 206-210 ◽  
Author(s):  
D. Sonnak ◽  
W. Preetz
Keyword(s):  
Single Crystals ◽  
Crystal Structures ◽  
Monoclinic Space Group ◽  
Orthorhombic Space Group ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Structure Determinations

Abstract X-ray structure determinations have been performed on single crystals of trans-(Ph4P)2-[B6H4I2] (1) (triclinic, space group P1̄, a = 9.9680(12), b = 10.9690(11), c = 11.0470(14) Å,α = 88.167(9), β = 80.466(12), γ = 68.839(11)°, Z = 1), mer-(Ph4P)2[B6H3I3] · 2 CH2Cl2 (2)(triclinic, space group P1̄, a = 11.8694(11), b = 15.1699(13), c = 17.051(2) Å, α = 75.118(9), β = 71.953(10), γ = 69.331(8)°, Z = 2), trans-(Ph4P )2[B6H2I4] · 2 CH3CN (3) (monoclinic, space group P21/n, a = 14.9665(10), b = 7.6783(10), c = 23.385(3) Å, β = 95.78(9)°, Z = 2), and (CH2Py2)[B6HI5] (4) (orthorhombic, space group Pnma, a = 13.660(2), b = 11.8711(13), c = 13.839(2) Å, Z = 4). The B6 octahedra are compressed in the direction of the B-I bonds, resulting in shortened diagonal B ··· B distances with average values of the groups I-B ··· B-I = 2.37 and I-B ··· B-H = 2.43 Å as compared with H-B ··· B-H = 2.49 Å.

Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalysen von trans-[PtX2(acac)2], X = CI, Br, I, SCN / Crystal Structures, Vibrational Spectra and Normal Coordinate Analyses of trans-[PtX2(acac)2], X = Cl, Br, I, SCN

1996 ◽  
Vol 51 (10) ◽  
pp. 1400-1406 ◽  
Author(s):  
D. Rickert ◽  
W. Preetz
Keyword(s):  
Crystal Structures ◽  
Normal Modes ◽  
Force Constants ◽  
Monoclinic Space Group ◽  
Normal Coordinate ◽  
Triclinic Space Group ◽  
Valence Force ◽  
Space Group ◽  
X Ray ◽  
Modes Of Vibration

The crystal structures of trans-[PtCl2(acac)2](monoclinic, space group P21/c, a - 7.616(5), b = 12.759(5), c = 7.892(5) Å, β = 118.459(5)°, Z = 2), trans-[PtBr2(acac)2] (triclinic, space group P1̅, a = 7.502(5), b = 7.665(5), c = 8.155(5) Å, α = 114~508(5), β = 94.537(5), γ = 117.669(5)°. Z = 1) and trans-[Pt(SCN)2(acac)2] (triclinic, space group P1̅ , a = 7.9095(10), b = 7.9393( 10), c = 7.9631 Å, a = 114.051 (10), β = 100.955(10), γ = 100.573(10)°, Z = 1) have been determined by single crystal X-ray diffraction analysis. The crystal structure of trans- [Ptl2(acac)2] is known from the literature. To enhance the spectroscopic resolution, the IR and Raman spectra of the four complexes have been measured at low temperature (10 K). Using the X-ray data, normal coordinate analyses based on a modified valence force field have been performed and the normal modes of vibration for the octahedral skeleton [PtX2O4] have been assigned. With a set of 19 or 23 force constants taking into account the inner-ligand vibrations a good agreement between observed and calculated frequencies has been achieved. The valence force constants are e.g.fd (PtCl) = 2.16, fd (PtBr) = 1.45, fd (PtI) = 1.01, fd (PtS) = 1.80 mdyn/Å, and fd (PtO) ranges from 1.89 to 1.91 mdyn/Å.

Darstellung, Schwingungsspektren und Normalkoordinatenanalyse von bindungsisomeren Halogenoselenocyanatorhenaten(IV) sowie Kristallstrukturen von mer-(Ph4P)2[ReCl3(NCSe)2cis (SeCN)] und mer-(n-Bu4N)2[ReCl3I(NCSe)2cis] / Synthesis, Vibrational Spectra and Normal Coordinate Analysis of Linkage Isomeric Halogenoselenocyanatorhenates(IV) and Crystal Structures of mer-(Ph4P)2[ReCl3(NCSe)2cis (SeCN)] and mer-(n-Bu4N)2[ReCl3I(NCSe)2cis]

1999 ◽  
Vol 54 (10) ◽  
pp. 1222-1228 ◽  
Author(s):  
S. Strueß ◽  
W. Preetz
Keyword(s):  
Crystal Structures ◽  
Exchange Chromatography ◽  
Normal Coordinate Analysis ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Normal Coordinate ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Diethylaminoethyl Cellulose

By treatment of fac-[ReCl3I3]2- with (SeCN)2 indichloromethane fac-[ReCl3(NCSe)3]2- (1), mer-[ReCl3(NCSe)2cis (SeCN)]2- (2) and mer-[ReCl3I(NCSe)2cis]2- (3) are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structures of mer-(Ph-P)2[ReCl3(NCSe)2cis(SeCN)] (triclinic, space group Pl̅, a = 16.099(1), b = 16.729(3), c =21.026(2) Å, α = 70.194(10), ß = 73.958(10), γ = 83.929(10)°, Z = 4) and mer-(n-Bu4N)2[ReCl3|(NCSe)2cis] (monoclinic, space group P21/c, a = 11.838(1), b = 12.796(2), c = 30.767(2) Å, ß = 97.419(6)°, Z = 4) have been determined by single crystal X-ray diffraction analysis. Based on the molecular parameters of the X-ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu4N) salts have been assigned by normal coordinate analysis. The valence force constants are fd(ReN) = 1.79 (1), 1.71 (2), 1.71 (3) and fd(ReSe) = 1.15 (2) mdyn/Å.

scholarly journals Kristallstrukturen der Tetrachloroniccolate (PPh4)2[NiCl4] und [Na-15-Krone-5]2[NiCl4] / Crystal Structures of the Tetrachloroniccolates (PPh4)2[NiCl4] and [Na- 15-Crown-5]2[NiCl4]

1990 ◽  
Vol 45 (7) ◽  
pp. 995-999 ◽  
Author(s):  
Karin Ruhlandt-Senge ◽  
Ulrich Müller
Keyword(s):  
Crown Ether ◽  
Crystal Structures ◽  
Monoclinic Space Group ◽  
Sodium Ions ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Positional Disorder ◽  
Cl Atoms

The title compounds were obtained from NiS + PPh4Cl + HCl in dichloromethane, from NiCl2 and PPh4Cl and from NiCl2 + Na2S + 15-crown-5 in acetonitrile or CH2Cl2, respectively. Their crystal structures were determined by X-ray diffraction. (PPh4)2[NiCl4]: monoclinic, space group C 2/c, Z = 4, a = 1094.9(3), b = 1946.1(4), c = 2033.5(5) pm, β = 91.48(3)°; R = 0.07 for 2895 unique observed reflexions. [Na-15-crown-5]2[NiCl4]: triclinic, space group P1̄, Z = 2, a = 987.6(1), b = 998.0(1), c = 1779.9(2) pm, α = 104.17(1), β = 95.43(1), γ = 109.95(1)°; R = 0.090 for 4155 unique observed reflexions. In both cases, the [NiCl4]2- ions have distorted tetrahedral structures. With PPh4+ as the cation the distortion corresponds to a twisted tetrahedron which fulfils the point symmetry D2, the deviation from a flattened D2d-tetrahedron being small. In (PPh4)2[NiCl4] cations and anions alternate in layers parallel to (001). In [Na-15-crown-5]2[NiCl4] two of the Cl atoms of the anion are coordinated to sodium ions; one of the crown ether molecules shows positional disorder.

Isoselenocyanatoborate -Kristallstrukturen von (n-Bu4N)[BH(NCSe)3] und (Ph4P)[B3H7(NCSe)] / Isoselenocyanatoborates -Crystal Structures of (n-Bu4N)[BH(NCSe)3] and (Ph4P)[B3H7(NCSe)]

1998 ◽  
Vol 53 (3) ◽  
pp. 271-274 ◽  
Author(s):  
B. Steuer ◽  
W. Preetz
Keyword(s):  
Single Crystals ◽  
Crystal Structures ◽  
Elemental Selenium ◽  
Monoclinic Space Group ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Structure Determinations ◽  
Average Bond

Abstract The treatment of [B6H6]2- with an excess of (SCN)2 in dichloromethane in the presence of solid KOH gives the hexaisoselenocyanatodiborate anion [B2(NCSe)6]2- as an intermediate (δ(11B) = -10.3 ppm), from which [BH(NCSe)3]- and elemental selenium are formed. The X-ray structure determinations on single crystals of (n-Bu4N)2[BH(NCSe)3] (1) (triclinic, space group Pi with a = 8.512(2), b = 10.885(3), c = 14.895(4) Å, α = 79.52(2), β = 74.86(2), γ = 86.768(2)°, Z = 2) and (Ph4P)[B3H7(NCSe)] (2) (monoclinic, space group C2, a = 7.686(5), b = 10.366(3), c = 17.533(3) A, β = 108.89°, Z = 4) show that the selenocyanate groups are coordinated exclusively via the N atoms with average bond lengths of B-N = 1.52, C-N = 1.15, C-Se = 1.75 A and angles N-C-Se = 179°, B-N-C = 168.7 - 176.8°. The N-B-N angles of 1 range from 107.5 to 109.5°.

Kristallstrukturen, Schwingungsspektren und Normalkoordinaten- analysen von cis- und trans-[OsX2(acac)2], X = Cl, Br, I / Crystal Structures, Vibrational Spectra and Normal Coordinate Analyses of cis- and trans-[OsX2(acac)2], X = Cl, Br, I

1997 ◽  
Vol 52 (8) ◽  
pp. 965-974 ◽  
Author(s):  
K Dallmann ◽  
W Preetz
Keyword(s):  
Crystal Structures ◽  
Normal Modes ◽  
Force Constants ◽  
Monoclinic Space Group ◽  
Normal Coordinate ◽  
Triclinic Space Group ◽  
Valence Force ◽  
Space Group ◽  
X Ray ◽  
Modes Of Vibration

The crystal structures of trans-[OsCl2(acac)2] (triclinic, space group P1̄, a = 7.4114(5), b = 7.6419(9), c = 7.9944(6) Å, α = 62.692(7), β = 87.687(6), γ = 60.667(6)°, Z = 1), trans-[OsBr2(acac)2] (triclinic, space group P1̄, a = 7.467(3), b = 7.621(3), c = 8.260(3) Å, α = 115.03(3), β = 92.78(3), γ = 117.91(3)°, Z = 1), cis-[OsCl2(acac)2] (monoclinic, space group C2/c, a = 13.8532(13), b = 7.7990(8), c = 13.6202(12) Å, β = 108.375(10)°, Z = 4) and cis-[OsBr2(acac)2] (monoclinic, space group C2/c, a = 13.944(2), b = 8.0347(13), c = 13.743(2) Å, β = 106.757(12)°, Z = 4) have been determined by single crystal X-ray diffraction analysis. To enhance the spectroscopic resolution, the IR and Raman spectra of the six complexes have been measured at low temperature (10 K). Using the molecular parameters of the X-ray determinations normal coordinate analyses based on a modified valence force field have been performed for trans-[OsCl2(acac)2], trans-[OsBr2(acac)2] and cis-[OsCl2(acac)2], and the normal modes of vibration assigned. With sets of 31 or 32 force constants, taking into account the innerligand vibrations, a good agreement between observed and calculated frequencies has been achieved. The valence force constants for the X-Os-X axes are fd(OsCl) = 1.81, fd(OsBr) =1.61 mdyn/Å, and for the Cl′-Os-O* axis are fd(OsCl’) = 1.94, fd(OsO*) = 2.81 mdyn/Å and fd(OsO) ranges from 3.27 to 3.31 mdyn/Å.

X-Ray structure of tris(acetonitrile)tricarbonylrhenium(I) tetrafluoroborate

1977 ◽  
Vol 55 (1) ◽  
pp. 111-114 ◽  
Author(s):  
Lillian Y. Y. Chan ◽  
E. E. Isaacs ◽  
W. A. G. Graham
Keyword(s):  
Least Squares ◽  
Unit Cell ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Cell Dimensions ◽  
The Mean ◽  
Unit Cell Dimensions ◽  
Cell Data ◽  
Unit Cell Data

Reaction of [n-Bu4N]2[Re4(CO)16] with AgBF4 in acetonitrile affords the compound [(CH3CN)3Re(CO)3][BF4]. The latter crystallizes in monoclinic space group P21/c with unit cell dimensions a = 11.021(5) Å, b = 11.136(5) Å, c = 12.980(6) Å, β = 96.906(25)°, and four molecules per unit cell. Data were collected by counter methods and the structure was refined using least-squares procedures to give R = 0.041. The rhenium cation is approximately octahedrally coordinated by six facially arranged ligands. The mean rhenium–nitrogen distance is 2.13 Å, and the mean rhenium–nitrogen–carbon angle in the coordinated acetonitrile is 174.7°.

Kristallstrukturen, Schwingungsspektren und Normalkoordinaten- analysen von trans-[OsO2(ox)2]2– und trans-[OsO2(mal)2]2–/ Crystal Structures, Vibrational Spectra and Normal Coordinate Analyses of trans-[OsO2(ox)2]2– and trans -[OsO2(mal)2]2–

1998 ◽  
Vol 53 (8) ◽  
pp. 823-828 ◽  
Author(s):  
A. Strueß ◽  
W. Preetz
Keyword(s):  
Crystal Structures ◽  
Vibrational Spectra ◽  
Room Temperature ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Normal Coordinate ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Ir And Raman

Abstract The crystal structures of trans-(Ph4P)2[OsO2(ox)2] (monoclinic, space group P21/n, a = 12.281(2), b = 14.5440(13), c = 13.9810(12) Å, β = 100.000(8)°, Z = 2) and trans- (n-Bu4N)2[OsO2(mal)2] (triclinic, space group P1̄, a = 10.365(4),b = 10.707(3), c - 11.473(5) A, a = 73.00(2), β = 64.44(3), 7 = 82.55(3)°, Z = 1) have been determined by single crystal X-ray diffraction analysis. The IR and Raman spectra of these complexes were measured at room temperature. Based on the molecular parameters of the X-ray determinations normal coordinate analyses have been performed and the vibrations assigned. The valence force constants of [OsO2(ox)2]2- are fd(Os=O) = 6.7, fd(Os-O) = 2.9, fd(C-O) = 5.05, fd(C=O) = 11.2 and fd(C-C) = 4.7 mdyn/Å and of [OsO2(mal)2]2- fd(Os=O) = 6.7, fd(Os-O) = 2.9, fd(C-O) = 4.86, fd(C=O) =11.1 and fd(C-C) = 4.07 mdyn/Å.

Structures of 2,6-disubstituted naphthalenes

1999 ◽  
Vol 55 (1) ◽  
pp. 85-94 ◽  
Author(s):  
James A. Kaduk ◽  
Joseph T. Golab
Keyword(s):  
Crystal Structures ◽  
Ester Group ◽  
Carboxyl Groups ◽  
Monoclinic Space Group ◽  
Ring Plane ◽  
Orthorhombic Space Group ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
The Mean

The crystal structures of 2,6-naphthalenedicarboxylic acid (NDA) and dimethyl 2,6-naphthalenedicarboxylate (NDC) have been solved ab initio using a combination of X-ray powder diffraction and computational chemistry techniques. These two crystal structures, and that of 2,6-dimethylnaphthalene (DMN), have been refined by the Rietveld technique. DMN crystallizes in the orthorhombic space group Pbca, with a = 7.4544 (4), b = 6.0826 (6), c = 20.0946 (12) Å, V = 911.1 (1) Å3 and Z = 4. The structure consists of a herringbone stacking parallel to a, resulting in loosely bound layers perpendicular to c. NDA crystallizes in the triclinic space group P1¯, with a = 3.7061 (8), b = 7.4688 (14), c = 8.5352 (22) Å, α = 86.62 (2), β = 85.49 (2), γ = 87.99 (2)°, V = 235.00 (6) Å3 and Z = 1. The structure consists of loosely packed hydrogen-bonded chains along [11¯1]. NDC crystallizes in the monoclinic space group P21/c, with a = 13.41931 (14), b = 6.14869 (5), c = 7.15257 (5) Å, β = 100.400 (1)°, V = 580.47 (1) Å3 at 300 K and Z = 2. The structure consists of layers of NDC molecules perpendicular to a. The ester group is twisted 20° out of the mean ring plane in NDC. The conformations of the carboxyl groups in NDA and NDC differ. MP2 calculations suggest that the observed twist in NDC corresponds to an increase in conformational energy of 9 kJ mol−1.

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