![](/logos/buttonlogos/cross.png)
![](/logos/buttonlogos/cross.png)
metal-organic compounds
Bis[1,2-bis(dimethylphosphino)ethane]dichloridonitrosyltungsten(0) chloride
aAnorganisch-Chemisches Institut der Universität Zürich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland
*Correspondence e-mail: oblacque@aci.uzh.ch
In the 2(NO)(C6H16P2)2]Cl, the seven-coordinated tungsten(II) center displays a distorted pentagonal–bipyramidal geometry with trans nitrosyl and chloride ligands. The NO and Cl ligands are disordered over two positions; the site occupancy factors are 0.6 and 0.4.
of the title compound, [WClRelated literature
For related trans-chloridonitrosyl-tungsten complexes, see: Chen et al. (2007). For related trans-chloridonitrosyl-bis(1,2-bis(dimethylphosphino)ethane)molybdenum complexes, see: Liang et al. (2003
, 2006
). For related literature, see: Bencze & Kohàn (1982
); Carmona et al. (1989
); Hunter & Legzdins (1984
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: IPDS Software (Stoe & Cie, 1999); cell IPDS Software; data reduction: X-RED in IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997
); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997
); molecular graphics: PLATON (Spek, 2003
); software used to prepare material for publication: SHELXL97.
Supporting information
https://doi.org/10.1107/S1600536807067128/su2037sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807067128/su2037Isup2.hkl
[W(Cl)2(NO)(dmpe)2]Cl was prepared from complex [W(Cl)3(NO)(CH3CN)2], which is easily synthesized by the reaction of W(Cl)6 with NO gas in dichloromethane in the presence of acetonitrile at room temperature (Bencze & Kohàn, 1982; Hunter & Legzdins, 1984). 5.00 g (12.6 mmol) of WCl6 and 1.32 ml (25.2 mmol) of acetonitrile were dissolved in 180 ml of dichloromethane in a 500 ml three-necked flask. Nitric oxide was passed through the solution, which was stirred at room temperature until the dark purple colour of the solution turned to the light green precipitate after ca 1 h. The volume of the final mixture was reduced to 50 ml in vacuo and the mixture was then cooled to 0°C for 15 min. The precipitate was isolated by filtration and the collected solid was washed with cold dichloromethane (2 x 10 ml at 0°C) and then with hexane (4 x 20 ml) at room temperature. Final drying of the solid under vacuum for 18 h afforded the yellow-green [W(Cl)3(NO)(CH3CN)2] compound. 0.356 g (0.88 mmol) of [W(Cl)3(NO)(NCCH3)2] was dissolved in 20 ml of tetrahydrofurane in a Young tap Schlenk and the dmpe ligand (0.38 ml, 2.20 mmol) was syringed into the solution. After 24 h of stirring at room temperature, the solution was filtered off and the solvent was removed under vacuum. The resulting precipitate was extracted with dichloromethane and crystallized in dichloromethane at room temperature to give yellow crystals of compound (I).
Yield: 0.491 g (90%).
IR (cm-1, CH2Cl2): 1608 (NO).
1H NMR (200.0 MHz, CD2Cl2, 25°C): d 2.09 (m, 8H, P(CH2)2P), 2.01 (m, 12H, PCH3) and 1.86 (m, 12H, PCH3).
31P{1H} NMR (80.9 MHz, CD2Cl2, 25°C): d 43.8 (m, P(CH2)2P) and 21.9 (m, P(CH2)2P), 2JPN = 27.6 Hz; 1JPW = 200 Hz.
13C{1H} NMR (50.3 MHz, CD2Cl2, 25°C): d 33.4 (m, P(CH2)2P), 24.3 (m, P(CH2)2P), 13.2 (m, PCH3) and 11.5 (m, PCH3).
Anal. Calcd for C12H32Cl3P4NOW: C, 23.22; H, 5.16; N, 2.26. Found: C, 23.26; H, 5.28; N, 2.37.
The H atom were included in calculated positions and treated as riding atoms with C—H distances = 0.98 - 0.99Å and Uiso(H) = 1.2Ueq(C) for CH2 and 1.5Ueq(C) for the CH3 groups. A positional disorder was refined for the trans NO and Cl ligands with occupancy factors of 0.6:0.4.
The title compound [W(Cl)2(NO)(dmpe)2](Cl) (I) was obtained by the reaction of [W(Cl)3(NO)(NCCH3)2] with 2.5 equivalents of dmpe at room temperature in tetrahydrofurane. The tungsten center has transformed into a seven coordination environment and exhibits a distorted pentagonal bipyramidal geometry, where the four phosphorus atoms and one chloride form the pentagon, and the trans nitrosyl and chloride ligands are at the apexes (Figure 1). This geometry is clearly different to that observed for the related compound Mo(Cl)3(NO)(PMe3)3, for which the
is described as a capped-octahedron (Carmona et al., 1989). The five equatorial atoms, P1, P2, P3, P4, and Cl1 are in an approximately planar array and the corresponding equatorial angles are in the range 68.5 - 76.5°. The two Cl—W—P bond angles of 68.84 (4) and 68.56 (4)° are smaller than the theoretical average angle of 72°, while all three P—W—P angles are larger (73.07 (4) - 76.49 (3)°). The nitrosyl group is located trans to one chloride ligand and they are positionally disordered in a ratio 0.6:0.4 (Chen et al., 2007). One chloride ion acts as a counterion and is not coordinated, resulting in a tungsten center in the +2.For related trans-chloridonitrosyl-tungsten complexes, see: Chen et al. (2007). For related trans-chloridonitrosyl-bis(1,2-bis(dimethylphosphino)ethane)molybdenum complexes, see: Liang et al. (2003, 2006). For related literature, see: Bencze & Kohàn (1982); Carmona et al. (1989); Hunter & Legzdins (1984).
Data collection: IPDS Software (Stoe & Cie, 1999); cell
IPDS Software (Stoe & Cie, 1999); data reduction: X-RED in IPDS Software (Stoe & Cie, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).[WCl2(NO)(C6H16P2)2]Cl | F(000) = 1216 |
Mr = 620.46 | Dx = 1.850 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 8000 reflections |
a = 8.0929 (7) Å | θ = 2.4–28.0° |
b = 26.118 (2) Å | µ = 5.83 mm−1 |
c = 10.5703 (10) Å | T = 183 K |
β = 94.19 (1)° | Plate, yellow |
V = 2228.3 (3) Å3 | 0.20 × 0.15 × 0.07 mm |
Z = 4 |
Stoe IPDS diffractometer | 3937 independent reflections |
Radiation source: fine-focus sealed tube | 3353 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
φ oscillation scan | θmax = 25.0°, θmin = 2.5° |
Absorption correction: numerical (Coppens et al., 1965) | h = −9→9 |
Tmin = 0.410, Tmax = 0.723 | k = −30→30 |
7761 measured reflections | l = 0→12 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.060 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0359P)2] where P = (Fo2 + 2Fc2)/3 |
3937 reflections | (Δ/σ)max = 0.001 |
217 parameters | Δρmax = 0.83 e Å−3 |
0 restraints | Δρmin = −1.28 e Å−3 |
[WCl2(NO)(C6H16P2)2]Cl | V = 2228.3 (3) Å3 |
Mr = 620.46 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.0929 (7) Å | µ = 5.83 mm−1 |
b = 26.118 (2) Å | T = 183 K |
c = 10.5703 (10) Å | 0.20 × 0.15 × 0.07 mm |
β = 94.19 (1)° |
Stoe IPDS diffractometer | 3937 independent reflections |
Absorption correction: numerical (Coppens et al., 1965) | 3353 reflections with I > 2σ(I) |
Tmin = 0.410, Tmax = 0.723 | Rint = 0.035 |
7761 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.060 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.83 e Å−3 |
3937 reflections | Δρmin = −1.28 e Å−3 |
217 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
W1 | 0.14034 (2) | 0.138353 (6) | 0.190758 (14) | 0.01228 (7) | |
P1 | 0.28028 (14) | 0.05181 (4) | 0.24110 (10) | 0.0148 (2) | |
P2 | 0.08089 (15) | 0.11528 (4) | 0.41984 (10) | 0.0187 (2) | |
P3 | 0.28985 (14) | 0.11874 (4) | −0.00872 (10) | 0.0153 (2) | |
P4 | 0.05122 (15) | 0.20805 (4) | 0.02694 (10) | 0.0201 (2) | |
Cl1 | −0.03756 (17) | 0.20441 (5) | 0.28354 (11) | 0.0320 (3) | |
C1 | 0.1747 (6) | 0.01929 (18) | 0.3647 (4) | 0.0263 (11) | |
H1A | 0.0601 | 0.0104 | 0.3331 | 0.032* | |
H1B | 0.2337 | −0.0127 | 0.3898 | 0.032* | |
C2 | 0.1720 (6) | 0.05517 (19) | 0.4784 (4) | 0.0258 (11) | |
H2A | 0.2859 | 0.0610 | 0.5164 | 0.031* | |
H2B | 0.1050 | 0.0402 | 0.5438 | 0.031* | |
C3 | 0.4913 (6) | 0.0544 (2) | 0.3091 (4) | 0.0266 (11) | |
H3A | 0.5357 | 0.0196 | 0.3182 | 0.040* | |
H3B | 0.4941 | 0.0708 | 0.3926 | 0.040* | |
H3C | 0.5588 | 0.0742 | 0.2534 | 0.040* | |
C4 | 0.2717 (7) | 0.00030 (18) | 0.1264 (5) | 0.0311 (12) | |
H4A | 0.3430 | 0.0086 | 0.0581 | 0.047* | |
H4B | 0.1574 | −0.0041 | 0.0908 | 0.047* | |
H4C | 0.3102 | −0.0315 | 0.1681 | 0.047* | |
C5 | 0.1471 (7) | 0.1608 (2) | 0.5415 (5) | 0.0357 (13) | |
H5A | 0.0950 | 0.1940 | 0.5221 | 0.054* | |
H5B | 0.2679 | 0.1644 | 0.5447 | 0.054* | |
H5C | 0.1144 | 0.1486 | 0.6237 | 0.054* | |
C6 | −0.1376 (6) | 0.1041 (2) | 0.4354 (5) | 0.0323 (12) | |
H6A | −0.1580 | 0.1016 | 0.5254 | 0.048* | |
H6B | −0.1709 | 0.0720 | 0.3924 | 0.048* | |
H6C | −0.2021 | 0.1325 | 0.3967 | 0.048* | |
C7 | 0.3072 (6) | 0.17713 (19) | −0.1023 (4) | 0.0273 (11) | |
H7A | 0.3815 | 0.2019 | −0.0554 | 0.033* | |
H7B | 0.3546 | 0.1690 | −0.1837 | 0.033* | |
C8 | 0.1377 (6) | 0.19998 (19) | −0.1269 (4) | 0.0273 (11) | |
H8A | 0.0664 | 0.1770 | −0.1818 | 0.033* | |
H8B | 0.1450 | 0.2335 | −0.1700 | 0.033* | |
C9 | 0.1887 (6) | 0.07605 (19) | −0.1249 (4) | 0.0286 (11) | |
H9A | 0.2509 | 0.0755 | −0.2011 | 0.043* | |
H9B | 0.0757 | 0.0881 | −0.1473 | 0.043* | |
H9C | 0.1848 | 0.0415 | −0.0894 | 0.043* | |
C10 | 0.5051 (6) | 0.1013 (2) | 0.0067 (5) | 0.0287 (11) | |
H10A | 0.5169 | 0.0670 | 0.0435 | 0.043* | |
H10B | 0.5664 | 0.1259 | 0.0621 | 0.043* | |
H10C | 0.5495 | 0.1016 | −0.0771 | 0.043* | |
C11 | 0.1231 (7) | 0.27186 (18) | 0.0718 (5) | 0.0337 (12) | |
H11A | 0.0917 | 0.2959 | 0.0030 | 0.051* | |
H11B | 0.2440 | 0.2715 | 0.0876 | 0.051* | |
H11C | 0.0725 | 0.2826 | 0.1490 | 0.051* | |
C12 | −0.1699 (6) | 0.2108 (2) | −0.0142 (5) | 0.0316 (12) | |
H12A | −0.2282 | 0.2161 | 0.0627 | 0.047* | |
H12B | −0.2066 | 0.1785 | −0.0545 | 0.047* | |
H12C | −0.1944 | 0.2392 | −0.0732 | 0.047* | |
Cl3 | 0.54253 (16) | 0.09564 (5) | 0.66427 (11) | 0.0299 (3) | |
Cl21 | −0.0944 (3) | 0.08497 (11) | 0.1146 (2) | 0.0243 (8) | 0.597 (5) |
N11 | 0.3280 (12) | 0.1748 (4) | 0.2417 (8) | 0.020 (2) | 0.597 (5) |
O11 | 0.4639 (12) | 0.1916 (4) | 0.2679 (8) | 0.051 (3) | 0.597 (5) |
Cl22 | 0.3926 (7) | 0.18470 (18) | 0.2565 (4) | 0.0243 (8) | 0.403 (5) |
N12 | −0.0356 (16) | 0.0967 (5) | 0.1383 (12) | 0.020 (2) | 0.403 (5) |
O12 | −0.1463 (16) | 0.0674 (6) | 0.1024 (13) | 0.051 (3) | 0.403 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
W1 | 0.01609 (10) | 0.01170 (10) | 0.00949 (9) | 0.00126 (7) | 0.00396 (6) | −0.00089 (6) |
P1 | 0.0185 (6) | 0.0143 (5) | 0.0119 (5) | 0.0007 (4) | 0.0024 (4) | 0.0001 (4) |
P2 | 0.0244 (6) | 0.0205 (6) | 0.0122 (5) | −0.0016 (5) | 0.0078 (4) | −0.0001 (4) |
P3 | 0.0178 (6) | 0.0186 (6) | 0.0099 (5) | 0.0015 (4) | 0.0046 (4) | 0.0001 (4) |
P4 | 0.0278 (7) | 0.0147 (6) | 0.0184 (6) | 0.0052 (5) | 0.0066 (5) | 0.0039 (4) |
Cl1 | 0.0477 (8) | 0.0254 (6) | 0.0252 (6) | 0.0177 (6) | 0.0176 (5) | 0.0007 (5) |
C1 | 0.033 (3) | 0.019 (2) | 0.027 (3) | −0.002 (2) | 0.008 (2) | 0.005 (2) |
C2 | 0.029 (3) | 0.032 (3) | 0.017 (2) | −0.003 (2) | 0.0082 (19) | 0.0006 (19) |
C3 | 0.021 (2) | 0.037 (3) | 0.022 (2) | 0.007 (2) | −0.0004 (19) | 0.004 (2) |
C4 | 0.051 (3) | 0.017 (2) | 0.025 (3) | 0.006 (2) | −0.001 (2) | −0.0013 (19) |
C5 | 0.054 (4) | 0.032 (3) | 0.021 (2) | −0.004 (3) | 0.003 (2) | −0.006 (2) |
C6 | 0.027 (3) | 0.037 (3) | 0.035 (3) | 0.001 (2) | 0.016 (2) | 0.006 (2) |
C7 | 0.035 (3) | 0.027 (3) | 0.022 (2) | −0.002 (2) | 0.011 (2) | 0.000 (2) |
C8 | 0.041 (3) | 0.024 (3) | 0.017 (2) | 0.006 (2) | 0.004 (2) | 0.0076 (19) |
C9 | 0.038 (3) | 0.030 (3) | 0.017 (2) | 0.001 (2) | 0.001 (2) | −0.001 (2) |
C10 | 0.023 (2) | 0.040 (3) | 0.025 (2) | 0.005 (2) | 0.0107 (19) | 0.002 (2) |
C11 | 0.053 (3) | 0.014 (2) | 0.035 (3) | −0.001 (2) | 0.009 (2) | 0.003 (2) |
C12 | 0.031 (3) | 0.031 (3) | 0.033 (3) | 0.011 (2) | 0.004 (2) | 0.012 (2) |
Cl3 | 0.0378 (7) | 0.0303 (7) | 0.0229 (6) | 0.0086 (5) | 0.0107 (5) | 0.0059 (5) |
Cl21 | 0.016 (2) | 0.0332 (14) | 0.0231 (12) | 0.0016 (14) | −0.0007 (12) | −0.0017 (10) |
N11 | 0.010 (5) | 0.034 (4) | 0.017 (4) | −0.002 (4) | 0.004 (3) | −0.002 (3) |
O11 | 0.027 (5) | 0.073 (5) | 0.052 (4) | −0.004 (4) | −0.006 (4) | −0.018 (4) |
Cl22 | 0.016 (2) | 0.0332 (14) | 0.0231 (12) | 0.0016 (14) | −0.0007 (12) | −0.0017 (10) |
N12 | 0.010 (5) | 0.034 (4) | 0.017 (4) | −0.002 (4) | 0.004 (3) | −0.002 (3) |
O12 | 0.027 (5) | 0.073 (5) | 0.052 (4) | −0.004 (4) | −0.006 (4) | −0.018 (4) |
W1—P1 | 2.5665 (11) | C3—H3B | 0.9800 |
W1—P2 | 2.5745 (11) | C3—H3C | 0.9800 |
W1—P3 | 2.5583 (11) | C4—H4A | 0.9800 |
W1—P4 | 2.5788 (11) | C4—H4B | 0.9800 |
W1—Cl1 | 2.4935 (11) | C4—H4C | 0.9800 |
W1—Cl21 | 2.445 (3) | C5—H5A | 0.9800 |
W1—Cl22 | 2.431 (5) | C5—H5B | 0.9800 |
W1—N11 | 1.840 (11) | C5—H5C | 0.9800 |
W1—N12 | 1.845 (13) | C6—H6A | 0.9800 |
N11—O11 | 1.198 (15) | C6—H6B | 0.9800 |
N12—O12 | 1.218 (17) | C6—H6C | 0.9800 |
P1—C3 | 1.805 (5) | C7—C8 | 1.502 (7) |
P1—C4 | 1.809 (5) | C7—H7A | 0.9900 |
P1—C1 | 1.823 (5) | C7—H7B | 0.9900 |
P2—C5 | 1.803 (5) | C8—H8A | 0.9900 |
P2—C6 | 1.812 (5) | C8—H8B | 0.9900 |
P2—C2 | 1.823 (5) | C9—H9A | 0.9800 |
P3—C10 | 1.796 (5) | C9—H9B | 0.9800 |
P3—C9 | 1.810 (5) | C9—H9C | 0.9800 |
P3—C7 | 1.829 (5) | C10—H10A | 0.9800 |
P4—C12 | 1.812 (5) | C10—H10B | 0.9800 |
P4—C11 | 1.817 (5) | C10—H10C | 0.9800 |
P4—C8 | 1.829 (5) | C11—H11A | 0.9800 |
C1—C2 | 1.525 (7) | C11—H11B | 0.9800 |
C1—H1A | 0.9900 | C11—H11C | 0.9800 |
C1—H1B | 0.9900 | C12—H12A | 0.9800 |
C2—H2A | 0.9900 | C12—H12B | 0.9800 |
C2—H2B | 0.9900 | C12—H12C | 0.9800 |
C3—H3A | 0.9800 | ||
N11—W1—N12 | 174.8 (4) | P2—C2—H2A | 110.3 |
N11—W1—Cl21 | 175.3 (3) | C1—C2—H2B | 110.3 |
N12—W1—Cl22 | 173.3 (5) | P2—C2—H2B | 110.3 |
Cl22—W1—Cl21 | 173.87 (10) | H2A—C2—H2B | 108.6 |
N11—W1—Cl1 | 90.8 (3) | P1—C3—H3A | 109.5 |
N12—W1—Cl1 | 94.1 (4) | P1—C3—H3B | 109.5 |
Cl21—W1—Cl1 | 93.84 (7) | H3A—C3—H3B | 109.5 |
Cl22—W1—Cl1 | 92.29 (11) | P1—C3—H3C | 109.5 |
N11—W1—P3 | 85.1 (2) | H3A—C3—H3C | 109.5 |
N12—W1—P3 | 92.0 (4) | H3B—C3—H3C | 109.5 |
Cl22—W1—P3 | 84.12 (11) | P1—C4—H4A | 109.5 |
Cl21—W1—P3 | 91.00 (6) | P1—C4—H4B | 109.5 |
Cl1—W1—P3 | 141.64 (4) | H4A—C4—H4B | 109.5 |
N11—W1—P1 | 93.0 (3) | P1—C4—H4C | 109.5 |
N12—W1—P1 | 82.1 (4) | H4A—C4—H4C | 109.5 |
Cl22—W1—P1 | 91.76 (11) | H4B—C4—H4C | 109.5 |
Cl21—W1—P1 | 83.48 (6) | P2—C5—H5A | 109.5 |
Cl1—W1—P1 | 141.86 (4) | P2—C5—H5B | 109.5 |
P1—W1—P2 | 73.07 (4) | H5A—C5—H5B | 109.5 |
P1—W1—P3 | 76.49 (3) | P2—C5—H5C | 109.5 |
N11—W1—P2 | 93.0 (3) | H5A—C5—H5C | 109.5 |
N12—W1—P2 | 87.2 (4) | H5B—C5—H5C | 109.5 |
Cl22—W1—P2 | 93.34 (11) | P2—C6—H6A | 109.5 |
Cl21—W1—P2 | 88.97 (6) | P2—C6—H6B | 109.5 |
Cl1—W1—P2 | 68.84 (4) | H6A—C6—H6B | 109.5 |
P3—W1—P2 | 149.37 (4) | P2—C6—H6C | 109.5 |
N11—W1—P4 | 90.9 (3) | H6A—C6—H6C | 109.5 |
N12—W1—P4 | 92.5 (4) | H6B—C6—H6C | 109.5 |
Cl22—W1—P4 | 91.62 (11) | C8—C7—P3 | 108.6 (3) |
Cl21—W1—P4 | 90.52 (7) | C8—C7—H7A | 110.0 |
Cl1—W1—P4 | 68.56 (4) | P3—C7—H7A | 110.0 |
P3—W1—P4 | 73.37 (4) | C8—C7—H7B | 110.0 |
P1—W1—P4 | 149.15 (3) | P3—C7—H7B | 110.0 |
P2—W1—P4 | 137.26 (4) | H7A—C7—H7B | 108.3 |
C3—P1—C4 | 106.5 (2) | C7—C8—P4 | 107.2 (3) |
C3—P1—C1 | 102.2 (2) | C7—C8—H8A | 110.3 |
C4—P1—C1 | 97.9 (2) | P4—C8—H8A | 110.3 |
C3—P1—W1 | 116.09 (17) | C7—C8—H8B | 110.3 |
C4—P1—W1 | 121.42 (16) | P4—C8—H8B | 110.3 |
C1—P1—W1 | 109.64 (16) | H8A—C8—H8B | 108.5 |
C5—P2—C6 | 106.4 (3) | P3—C9—H9A | 109.5 |
C5—P2—C2 | 103.5 (2) | P3—C9—H9B | 109.5 |
C6—P2—C2 | 101.7 (2) | H9A—C9—H9B | 109.5 |
C5—P2—W1 | 116.77 (18) | P3—C9—H9C | 109.5 |
C6—P2—W1 | 111.95 (17) | H9A—C9—H9C | 109.5 |
C2—P2—W1 | 114.95 (15) | H9B—C9—H9C | 109.5 |
C10—P3—C9 | 107.0 (2) | P3—C10—H10A | 109.5 |
C10—P3—C7 | 98.5 (2) | P3—C10—H10B | 109.5 |
C9—P3—C7 | 101.3 (2) | H10A—C10—H10B | 109.5 |
C10—P3—W1 | 119.33 (16) | P3—C10—H10C | 109.5 |
C9—P3—W1 | 117.72 (17) | H10A—C10—H10C | 109.5 |
C7—P3—W1 | 109.79 (16) | H10B—C10—H10C | 109.5 |
C12—P4—C11 | 108.6 (3) | P4—C11—H11A | 109.5 |
C12—P4—C8 | 103.1 (2) | P4—C11—H11B | 109.5 |
C11—P4—C8 | 101.6 (2) | H11A—C11—H11B | 109.5 |
C12—P4—W1 | 114.33 (17) | P4—C11—H11C | 109.5 |
C11—P4—W1 | 113.81 (17) | H11A—C11—H11C | 109.5 |
C8—P4—W1 | 114.16 (15) | H11B—C11—H11C | 109.5 |
C2—C1—P1 | 108.2 (3) | P4—C12—H12A | 109.5 |
C2—C1—H1A | 110.1 | P4—C12—H12B | 109.5 |
P1—C1—H1A | 110.1 | H12A—C12—H12B | 109.5 |
C2—C1—H1B | 110.1 | P4—C12—H12C | 109.5 |
P1—C1—H1B | 110.1 | H12A—C12—H12C | 109.5 |
H1A—C1—H1B | 108.4 | H12B—C12—H12C | 109.5 |
C1—C2—P2 | 106.9 (3) | O11—N11—W1 | 169.1 (8) |
C1—C2—H2A | 110.3 | O12—N12—W1 | 176.9 (15) |
N11—W1—P1—C3 | 2.3 (3) | Cl22—W1—P3—C9 | 175.1 (2) |
N12—W1—P1—C3 | −179.4 (4) | Cl21—W1—P3—C9 | −1.2 (2) |
Cl22—W1—P1—C3 | 3.0 (2) | Cl1—W1—P3—C9 | −98.7 (2) |
Cl21—W1—P1—C3 | 179.16 (18) | P1—W1—P3—C9 | 81.82 (19) |
Cl1—W1—P1—C3 | −92.92 (18) | P2—W1—P3—C9 | 88.4 (2) |
P3—W1—P1—C3 | 86.56 (18) | P4—W1—P3—C9 | −91.47 (19) |
P2—W1—P1—C3 | −89.93 (18) | N11—W1—P3—C7 | −68.8 (3) |
P4—W1—P1—C3 | 99.15 (18) | N12—W1—P3—C7 | 115.6 (5) |
N11—W1—P1—C4 | −129.7 (3) | Cl22—W1—P3—C7 | −69.9 (2) |
N12—W1—P1—C4 | 48.6 (5) | Cl21—W1—P3—C7 | 113.84 (19) |
Cl22—W1—P1—C4 | −128.9 (3) | Cl1—W1—P3—C7 | 16.37 (19) |
Cl21—W1—P1—C4 | 47.2 (2) | P1—W1—P3—C7 | −163.11 (18) |
Cl1—W1—P1—C4 | 135.1 (2) | P2—W1—P3—C7 | −156.49 (18) |
P3—W1—P1—C4 | −45.4 (2) | P4—W1—P3—C7 | 23.60 (18) |
P2—W1—P1—C4 | 138.1 (2) | N11—W1—P4—C12 | −154.6 (3) |
P4—W1—P1—C4 | −32.8 (2) | N12—W1—P4—C12 | 29.4 (5) |
N11—W1—P1—C1 | 117.5 (3) | Cl22—W1—P4—C12 | −155.9 (2) |
N12—W1—P1—C1 | −64.3 (4) | Cl21—W1—P4—C12 | 29.8 (2) |
Cl22—W1—P1—C1 | 118.2 (2) | Cl1—W1—P4—C12 | −64.1 (2) |
Cl21—W1—P1—C1 | −65.69 (18) | P3—W1—P4—C12 | 120.7 (2) |
Cl1—W1—P1—C1 | 22.23 (19) | P1—W1—P4—C12 | 107.9 (2) |
P3—W1—P1—C1 | −158.29 (17) | P2—W1—P4—C12 | −59.2 (2) |
P2—W1—P1—C1 | 25.23 (17) | N11—W1—P4—C11 | −29.1 (3) |
P4—W1—P1—C1 | −145.69 (18) | N12—W1—P4—C11 | 154.9 (5) |
N11—W1—P2—C5 | 30.3 (3) | Cl22—W1—P4—C11 | −30.3 (2) |
N12—W1—P2—C5 | −154.9 (5) | Cl21—W1—P4—C11 | 155.4 (2) |
Cl22—W1—P2—C5 | 31.7 (2) | Cl1—W1—P4—C11 | 61.5 (2) |
Cl21—W1—P2—C5 | −153.9 (2) | P3—W1—P4—C11 | −113.7 (2) |
Cl1—W1—P2—C5 | −59.4 (2) | P1—W1—P4—C11 | −126.5 (2) |
P3—W1—P2—C5 | 115.8 (2) | P2—W1—P4—C11 | 66.4 (2) |
P1—W1—P2—C5 | 122.6 (2) | N11—W1—P4—C8 | 87.0 (3) |
P4—W1—P2—C5 | −64.3 (2) | N12—W1—P4—C8 | −89.0 (4) |
N11—W1—P2—C6 | 153.4 (3) | Cl22—W1—P4—C8 | 85.7 (2) |
N12—W1—P2—C6 | −31.9 (5) | Cl21—W1—P4—C8 | −88.5 (2) |
Cl22—W1—P2—C6 | 154.8 (2) | Cl1—W1—P4—C8 | 177.56 (19) |
Cl21—W1—P2—C6 | −30.9 (2) | P3—W1—P4—C8 | 2.37 (19) |
Cl1—W1—P2—C6 | 63.6 (2) | P1—W1—P4—C8 | −10.4 (2) |
P3—W1—P2—C6 | −121.1 (2) | P2—W1—P4—C8 | −177.56 (19) |
P1—W1—P2—C6 | −114.4 (2) | C3—P1—C1—C2 | 68.8 (4) |
P4—W1—P2—C6 | 58.8 (2) | C4—P1—C1—C2 | 177.6 (4) |
N11—W1—P2—C2 | −91.2 (3) | W1—P1—C1—C2 | −54.9 (4) |
N12—W1—P2—C2 | 83.6 (5) | P1—C1—C2—P2 | 53.9 (4) |
Cl22—W1—P2—C2 | −89.8 (2) | C5—P2—C2—C1 | −160.7 (3) |
Cl21—W1—P2—C2 | 84.53 (19) | C6—P2—C2—C1 | 89.0 (4) |
Cl1—W1—P2—C2 | 179.05 (18) | W1—P2—C2—C1 | −32.2 (4) |
P3—W1—P2—C2 | −5.7 (2) | C10—P3—C7—C8 | −179.3 (3) |
P1—W1—P2—C2 | 1.03 (18) | C9—P3—C7—C8 | 71.3 (4) |
P4—W1—P2—C2 | 174.18 (18) | W1—P3—C7—C8 | −53.8 (3) |
N11—W1—P3—C10 | 43.7 (3) | P3—C7—C8—P4 | 54.2 (4) |
N12—W1—P3—C10 | −132.0 (5) | C12—P4—C8—C7 | −158.3 (3) |
Cl22—W1—P3—C10 | 42.6 (2) | C11—P4—C8—C7 | 89.3 (4) |
Cl21—W1—P3—C10 | −133.7 (2) | W1—P4—C8—C7 | −33.7 (4) |
Cl1—W1—P3—C10 | 128.8 (2) | Cl22—W1—N11—O11 | 2 (10) |
P1—W1—P3—C10 | −50.6 (2) | Cl1—W1—N11—O11 | 174 (4) |
P2—W1—P3—C10 | −44.0 (2) | P3—W1—N11—O11 | −44 (4) |
P4—W1—P3—C10 | 136.1 (2) | P1—W1—N11—O11 | 32 (4) |
N11—W1—P3—C9 | 176.1 (3) | P2—W1—N11—O11 | 105 (4) |
N12—W1—P3—C9 | 0.5 (5) | P4—W1—N11—O11 | −118 (4) |
Experimental details
Crystal data | |
Chemical formula | [WCl2(NO)(C6H16P2)2]Cl |
Mr | 620.46 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 183 |
a, b, c (Å) | 8.0929 (7), 26.118 (2), 10.5703 (10) |
β (°) | 94.19 (1) |
V (Å3) | 2228.3 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.83 |
Crystal size (mm) | 0.20 × 0.15 × 0.07 |
Data collection | |
Diffractometer | Stoe IPDS |
Absorption correction | Numerical (Coppens et al., 1965) |
Tmin, Tmax | 0.410, 0.723 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7761, 3937, 3353 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.060, 0.98 |
No. of reflections | 3937 |
No. of parameters | 217 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.83, −1.28 |
Computer programs: X-RED in IPDS Software (Stoe & Cie, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003).
W1—P1 | 2.5665 (11) | W1—Cl21 | 2.445 (3) |
W1—P2 | 2.5745 (11) | W1—Cl22 | 2.431 (5) |
W1—P3 | 2.5583 (11) | W1—N11 | 1.840 (11) |
W1—P4 | 2.5788 (11) | W1—N12 | 1.845 (13) |
W1—Cl1 | 2.4935 (11) | ||
P1—W1—P2 | 73.07 (4) | Cl1—W1—P4 | 68.56 (4) |
P1—W1—P3 | 76.49 (3) | P3—W1—P4 | 73.37 (4) |
Cl1—W1—P2 | 68.84 (4) |
Acknowledgements
We thank the University of Zürich and the Swiss National Science Foundation for financial support.
References
Bencze, L. & Kohàn, J. (1982). Inorg. Chim. Acta, 65, L17–L19. CrossRef CAS Web of Science Google Scholar
Carmona, E., Gutiérrez-Puebla, E., Monge, A., Pérez, P. J. & Sanchez, L. J. (1989). Inorg. Chem. 28, 2120–2127. CSD CrossRef CAS Web of Science Google Scholar
Chen, Z., Schmalle, H. W., Fox, T., Blacque, O. & Berke, H. (2007). J. Organomet. Chem. 692, 4875–4885. Web of Science CSD CrossRef CAS Google Scholar
Coppens, P., Leiserowitz, L. & Rabinovich, D. (1965). Acta Cryst. 18, 1035–1038. CrossRef CAS IUCr Journals Web of Science Google Scholar
Hunter, A. D. & Legzdins, P. (1984). Inorg. Chem. 23, 4198–4204. CrossRef CAS Web of Science Google Scholar
Liang, F., Schmalle, H. W. & Berke, H. (2006). Eur. J. Inorg. Chem. 24, 5081–5088. Web of Science CSD CrossRef Google Scholar
Liang, F., Schmalle, H. W., Fox, T. & Berke, H. (2003). Organometallics, 22, 3382–3393. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (1999). IPDS Software. Version 2.92. Stoe & Cie, Darmstadt, Germany. Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The title compound [W(Cl)2(NO)(dmpe)2](Cl) (I) was obtained by the reaction of [W(Cl)3(NO)(NCCH3)2] with 2.5 equivalents of dmpe at room temperature in tetrahydrofurane. The tungsten center has transformed into a seven coordination environment and exhibits a distorted pentagonal bipyramidal geometry, where the four phosphorus atoms and one chloride form the pentagon, and the trans nitrosyl and chloride ligands are at the apexes (Figure 1). This geometry is clearly different to that observed for the related compound Mo(Cl)3(NO)(PMe3)3, for which the coordination polyhedron is described as a capped-octahedron (Carmona et al., 1989). The five equatorial atoms, P1, P2, P3, P4, and Cl1 are in an approximately planar array and the corresponding equatorial angles are in the range 68.5 - 76.5°. The two Cl—W—P bond angles of 68.84 (4) and 68.56 (4)° are smaller than the theoretical average angle of 72°, while all three P—W—P angles are larger (73.07 (4) - 76.49 (3)°). The nitrosyl group is located trans to one chloride ligand and they are positionally disordered in a ratio 0.6:0.4 (Chen et al., 2007). One chloride ion acts as a counterion and is not coordinated, resulting in a tungsten center in the oxidation state +2.