Home Physical Sciences Crystal structure of [(1,2-bis(dicyclohexylphosphino)-1,2-dicarba-closo-dodecaborane-κ2P,P′]dibromidonickel(II)), C26H54B10NiBr2P2
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Crystal structure of [(1,2-bis(dicyclohexylphosphino)-1,2-dicarba-closo-dodecaborane-κ2P,P′]dibromidonickel(II)), C26H54B10NiBr2P2

  • Yang Liguo EMAIL logo , Liu Qingyun , Wang Xin , Liu Nana and Dai Yuqiang
Published/Copyright: February 12, 2018

Abstract

C26H54B10NiBr2P2, monoclinic, C2/c (no. 15), a = 13.064(7) Å, b = 15.655(8) Å, c = 16.652(9) Å, β = 95.830(7)°, V = 3388(3) Å3, Z = 4, Rgt(F) = 0.0603, wRref(F2) = 0.1364, T = 298(2) K.

CCDC no.: 684375

The title crystal structure is shown in the figure (hydrogen atoms are omitted for clarity). Tables 1 and 2 contain details on crystal structure and measurement conditions and a list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Red block
Size:0.80 × 0.15 × 0.13 mm
Wavelength:Mo radiation (0.71073 Å)
μ:3.05 mm−1
Diffractometer, scan mode:Bruker SMART, φ and ω-scans
θmax, completeness:25°, >99%
N(hkl)measured, N(hkl)unique, Rint:8640, 2963, 0.099
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 1801
N(param)refined:186
Programs:Bruker programs [1], SHELX [2, 3]
Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

AtomxyzUiso*/Ueq
Ni10.00000.07819(7)0.75000.0249(3)
P10.11912(12)0.17176(10)0.73674(9)0.0234(4)
B10.1181(6)0.3693(4)0.8010(5)0.0331(19)
H10.19500.36940.83480.040*
B20.1008(6)0.3682(5)0.6941(5)0.0301(18)
H20.16670.36730.65790.036*
B3−0.0151(5)0.3120(4)0.6646(4)0.0260(17)
H3−0.02570.27360.60910.031*
B4−0.0140(6)0.4246(5)0.6636(5)0.0351(19)
H4−0.02290.46110.60680.042*
B50.0680(6)0.4604(5)0.7482(5)0.036(2)
H50.11200.52020.74680.043*
Br10.12757(6)−0.02587(4)0.75610(5)0.0478(3)
C10.0648(5)0.2824(3)0.7468(3)0.0233(15)
C20.2415(4)0.1677(4)0.8032(3)0.0246(14)
H2A0.27260.11310.79010.030*
C30.2255(5)0.1600(4)0.8926(4)0.0349(16)
H3A0.17490.11590.89970.042*
H3B0.19970.21360.91170.042*
C40.3274(6)0.1374(5)0.9418(4)0.0463(19)
H4A0.31740.13630.99870.056*
H4B0.34880.08080.92670.056*
C50.4104(6)0.2003(5)0.9284(4)0.056(2)
H5A0.47450.18170.95770.067*
H5B0.39280.25540.94970.067*
C60.4258(5)0.2100(5)0.8401(4)0.046(2)
H6A0.45080.15660.81990.055*
H6B0.47710.25360.83400.055*
C70.3249(5)0.2346(4)0.7909(4)0.0350(17)
H7A0.33530.23780.73410.042*
H7B0.30280.29030.80790.042*
C80.1536(5)0.1629(4)0.6306(4)0.0281(15)
H80.16070.22100.61000.034*
C90.0674(5)0.1184(4)0.5756(4)0.0337(16)
H9A0.05800.06090.59520.040*
H9B0.00340.14920.57820.040*
C100.0918(6)0.1142(5)0.4881(4)0.050(2)
H10A0.03740.08350.45620.060*
H10B0.09420.17170.46660.060*
C110.1931(6)0.0705(6)0.4808(5)0.058(2)
H11A0.20880.07310.42520.069*
H11B0.18770.01080.49550.069*
C120.2804(6)0.1120(5)0.5351(4)0.051(2)
H12A0.34320.07960.53230.061*
H12B0.29190.16940.51610.061*
C130.2550(5)0.1156(4)0.6221(4)0.0391(18)
H13A0.31050.14420.65470.047*
H13B0.25010.05780.64240.047*

Source of material

The ligand, 1,2-(PCycl2)2-1,2-C2B10H10, was synthesized according to the literature known method [4]. NiBr2⋅2H2O (0.10 mmol) was added to a suspension of 1,2-(PCycl2)2-1,2-C2B10H10 (0.10 mmol) in chloromethane (10 mL). The mixture was stirred for 6 h at room temperature under the protection of dry nitrogen. Then a colourless solution formed. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a dichloromethane-n-hexane solution. (24.4 mg, 40.9°) m.p. 188–189 K. FTIR (KBr) v (cm−l): 2980, 2960, 2920, 2865 (C—H); 2610, 2600, 2582, 2552 (B—H); 1071 (C—P).

Experimental details

All H atoms were placed geometrically and treated as riding on their parent atoms, with B—H 1.10, C—H 0.96, with Uiso(H) = 1.2Ueq(B), Uiso(H) = 1.5Ueq(C).

Discussion

Polyhedral heteroboranes have been the subject of research for over 40 years [5]. A subset of this extensive class of compounds in dicarba-closo-dodecaboranes, commonly referred to as carboranes [6], [7], [8]. An extensive field of carborane chemistry has developed, concerned with substitution of the C—H or B—H vertices of these clusters, and the products have potential applications in many diverse areas, including medicinal chemistry, esp. boron neutron capture treatment (BNCT) of tumor, special polymers, agents for the extraction of metal ions, supramolecular chemistry and as ligands for metals [9, 10] . The closo carborane diphosphine 1,2-(PPh2)2-1,2-C2B10H10 reported in 1963 for the first time is a typical bidentate phosphine ligand. Because of its ability to form stable five-member chelate rings between the ligand and the metal atom, this diphosphine ligand has become the intensely studied carborane derivative in coordination chemistry.

The figure depicts a perspective of the title complex showing the atom numbering. The environment of the Ni atom is four coordinated, in which two positions are occupied by the chelating closo diphosphine ligand 1,2-(PCycl2)2-1,2-C2B10H10, and the other two come from the bromido ligands at cis position. The mean deviation 0.553 Å from the plane P1P2NiO1O2 and the dihedral angle 11.41° between the two planes P1NiP2 and Br1NiBr2 show that the coordination sphere of the Ni atom is distorted square-planar. The distances of the Ni—Br (2.3254(13) Å) and P—Ni (2.1647(19) Å) are very close to the corresponding distances 2.328(2) and 2.148(5) Å in the complex dibromo[1,2-bis(diphenylphosphino)ethane]nickel(II) [11]. The angles of Br(1)—Ni(1)—Br(2) (91.05(7)°) and P(1)—Ni(1)—P(2) (94.83(10)°) are also comparable to the homologous values in similar complexes [12].

Acknowledgements

This work was supported by Henan science and technology project (Nos. 172102210161, 172102210160, 172102310166) and the Research Fund of Anyang Institute of Technology (No. YJJ2016014).

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Received: 2017-8-21
Accepted: 2018-1-30
Published Online: 2018-2-12
Published in Print: 2018-3-28

©2018 Yang Liguo et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 License.

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