Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802020123/bt6200sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802020123/bt6200Isup2.hkl |
CCDC reference: 202280
A Schlenk tube was charged with a mixture of trans-[Mo(dppe)2(N2)2] (663 mg, 0.699 mmol) and [N(n—Bu)4](NCS) (211 mg, 0.702 mmol). THF (40 ml) was added to the mixture and the resulting clear orange solution was stirred at ambient temperature overnight under an N2 atmosphere. Within ca 20 min, the color of the solution changed to deep red. At the end of the reaction, the solution was concentrated to half of its volume and stored for 2 h at 237 K to afford a mixture of yellow and red–black crystalline material. The supernatant dark-red solution was decanted, treated with toluene (35 ml) and then stirred for 1–2 minutes in air. Dark-green single crystals of (1α) were obtained upon cooling the resulting yellow solution for 3 d at 237 K.
The disordered toluene solvate molecule occupies two close half-occupancy positions, which are related by inversion symmetry. Only five resolved atomic positions could be localized and refined isotropically with an adequate site-occupancy model. Restraints for distances and angles in the molecule were applied.
Recently, we have shown that the reactions of the dinitrogen complexes trans-[M(dppe)2(N2)2] [M = Mo, W; dppe is ethane-1,2-diylbis(diphenylphosphane), Ph2PCH2CH2PPh2] with the germanium(II) halides Cp*GeX (Cp* = C5Me5; X = Cl, Br, I) afford the germylyne complexes trans-[X(dppe)2M≡Ge—(η1-Cp*)] (Filippou, Philippopoulos et al., 2000; Filippou, Portius et al., 2002). Furthermore, the tungsten derivative trans-[I(dppe)2W≡Ge—(η1-Cp*)] was shown to undergo iodide/pseudohalide ligand exchange with an excess of M'Y (M' = Na, K; Y = CN, NCO, N3, NCS) to yield the germylyne complexes trans-[Y(dppe)2W≡Ge—(η1-Cp*)] (Filippou, Philippopoulos et al., 2002). Looking for an alternative approach to the analogous molybdenum compounds, we prepared the anionic dinitrogen complex [N(n—Bu)4][Mo(NCS)(dppe)2(N2)], following the method of Chatt et al. (1980). Exposure of this complex to air was reported to give trans-[Mo(NCS)2(dppe)2], (1), which was characterized by IR spectroscopy and elemental analysis (Chatt et al., 1980). However, the molecular structure of (1) remained unknown until today. Dark-green single crystals of the toluene solvate of (1), viz. (1α), were obtained from a THF/toluene solution upon cooling from 293 to 238 K. The title compound, (1α), crystallizes in the same space group (P21/c) as the chloro complex trans-[MoCl2(dppe)2]·2C4H8O (Filippou, Portius et al., 2000). The 16 valence-electron complex (1) reveals a distorted octahedral geometry at the Mo atom, which bears two trans-arranged N-bonded thiocyanate ligands and lies on a crystallographic center of symmetry. Distortion is evidenced in the tilt of the axial isothiocyanate ligands with respect to the equatorial plane spanned by the four P atoms, the angle between the N—Mo—N' axis and the P4 plane being 82.9°. A similar tilt of the axial chloro ligands (80.5°) was observed in trans-[MoCl2(dppe)2]·2C4H8O (Filippou, Portius et al., 2000). The isothiocyanate ligands feature an almost linear Mo—N—C1—S array in (1α), with Mo—N—C1 and N—C1—S angles of 176.2 (3) and 178.0 (4)°, respectively. The Mo—N bonds of (1α) [2.086 (3) Å] are slightly shorter than those of the few other structurally characterized molybdenum(II) isothiocyanate complexes (Bino & Cotton, 1979; Müller & Mohan, 1981) and the mean Mo—P bond length of (1α) (2.503 Å) compares well with that of trans-[MoCl2(dppe)2]·2C4H8O (average Mo—P = 2.499 Å; Filippou, Portius et al., 2000) or trans-[MoCl2(dppe)2]·CH2Cl2 (average Mo—P = 2.497 Å; Nardelli et al., 1980).
Data collection: STADI4 (Stoe & Cie, 1997); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.
[Mo(NCS)2(C26H24P2)2]·C7H8 | F(000) = 1140 |
Mr = 1101.02 | Dx = 1.374 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.6277 (13) Å | Cell parameters from 72 reflections |
b = 17.017 (2) Å | θ = 14.0–14.8° |
c = 16.755 (2) Å | µ = 0.49 mm−1 |
β = 104.172 (11)° | T = 180 K |
V = 2661.5 (6) Å3 | Block, black |
Z = 2 | 0.68 × 0.62 × 0.48 mm |
Stoe STADI-4 diffractometer | 3796 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed X-ray tube | Rint = 0.098 |
Planar graphite monochromator | θmax = 25.3°, θmin = 1.7° |
2θ/ω scans | h = −11→11 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→20 |
Tmin = 0.733, Tmax = 0.800 | l = −2→20 |
4828 measured reflections | 3 standard reflections every 120 min |
4820 independent reflections | intensity decay: 3.8% |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0348P)2 + 3.8899P] where P = (Fo2 + 2Fc2)/3 |
4820 reflections | (Δ/σ)max = 0.001 |
306 parameters | Δρmax = 0.74 e Å−3 |
5 restraints | Δρmin = −0.43 e Å−3 |
[Mo(NCS)2(C26H24P2)2]·C7H8 | V = 2661.5 (6) Å3 |
Mr = 1101.02 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.6277 (13) Å | µ = 0.49 mm−1 |
b = 17.017 (2) Å | T = 180 K |
c = 16.755 (2) Å | 0.68 × 0.62 × 0.48 mm |
β = 104.172 (11)° |
Stoe STADI-4 diffractometer | 3796 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.098 |
Tmin = 0.733, Tmax = 0.800 | 3 standard reflections every 120 min |
4828 measured reflections | intensity decay: 3.8% |
4820 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 5 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.74 e Å−3 |
4820 reflections | Δρmin = −0.43 e Å−3 |
306 parameters |
Experimental. During data collection the crystal was in cold N2 gas of a cryostream cooler (Oxford Cryosystems). Measurement: 2Θ/ω-scan,ratio=1.0,width(ω)=1.75–1.9° |
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) | |
C1 | 0.2192 (4) | 0.5707 (2) | 0.3717 (2) | 0.0354 (8) | |
C2 | 0.1881 (4) | 0.4709 (2) | 0.5650 (2) | 0.0334 (8) | |
H2A | 0.1309 | 0.4732 | 0.6067 | 0.040* | |
H2B | 0.1313 | 0.4956 | 0.5139 | 0.040* | |
C3 | 0.2181 (4) | 0.3853 (2) | 0.5480 (2) | 0.0353 (8) | |
H3A | 0.1283 | 0.3604 | 0.5166 | 0.042* | |
H3B | 0.2499 | 0.3570 | 0.6010 | 0.042* | |
C4 | 0.4313 (4) | 0.2789 (2) | 0.5255 (2) | 0.0321 (8) | |
C5 | 0.5761 (4) | 0.2663 (2) | 0.5518 (3) | 0.0487 (10) | |
H5 | 0.6407 | 0.3082 | 0.5503 | 0.058* | |
C6 | 0.6294 (5) | 0.1928 (3) | 0.5805 (3) | 0.0601 (12) | |
H6 | 0.7299 | 0.1848 | 0.5983 | 0.072* | |
C7 | 0.5374 (5) | 0.1321 (2) | 0.5830 (2) | 0.0513 (10) | |
H7 | 0.5736 | 0.0821 | 0.6034 | 0.062* | |
C8 | 0.3931 (5) | 0.1438 (2) | 0.5559 (3) | 0.0554 (11) | |
H8 | 0.3288 | 0.1017 | 0.5570 | 0.067* | |
C9 | 0.3409 (5) | 0.2157 (2) | 0.5272 (3) | 0.0513 (11) | |
H9 | 0.2404 | 0.2227 | 0.5080 | 0.062* | |
C10 | 0.2561 (4) | 0.3498 (2) | 0.3844 (2) | 0.0346 (8) | |
C11 | 0.3200 (5) | 0.3023 (2) | 0.3360 (2) | 0.0495 (10) | |
H11 | 0.4130 | 0.2815 | 0.3583 | 0.059* | |
C12 | 0.2495 (6) | 0.2850 (3) | 0.2557 (3) | 0.0707 (15) | |
H12 | 0.2943 | 0.2531 | 0.2227 | 0.085* | |
C13 | 0.1132 (7) | 0.3145 (3) | 0.2235 (3) | 0.0796 (17) | |
H13 | 0.0634 | 0.3015 | 0.1688 | 0.096* | |
C14 | 0.0493 (5) | 0.3627 (3) | 0.2705 (3) | 0.0675 (14) | |
H14 | −0.0434 | 0.3838 | 0.2479 | 0.081* | |
C15 | 0.1210 (4) | 0.3801 (2) | 0.3502 (2) | 0.0463 (10) | |
H15 | 0.0770 | 0.4134 | 0.3823 | 0.056* | |
C16 | 0.2873 (4) | 0.6237 (2) | 0.6201 (2) | 0.0353 (8) | |
C17 | 0.1865 (4) | 0.6597 (2) | 0.5570 (2) | 0.0414 (9) | |
H17 | 0.1520 | 0.6328 | 0.5063 | 0.050* | |
C18 | 0.1358 (4) | 0.7343 (2) | 0.5672 (3) | 0.0500 (10) | |
H18 | 0.0667 | 0.7581 | 0.5236 | 0.060* | |
C19 | 0.1849 (5) | 0.7742 (2) | 0.6402 (3) | 0.0557 (11) | |
H19 | 0.1499 | 0.8253 | 0.6470 | 0.067* | |
C20 | 0.2845 (5) | 0.7397 (3) | 0.7027 (3) | 0.0628 (13) | |
H20 | 0.3185 | 0.7670 | 0.7531 | 0.075* | |
C21 | 0.3366 (5) | 0.6646 (2) | 0.6931 (2) | 0.0499 (10) | |
H21 | 0.4062 | 0.6414 | 0.7369 | 0.060* | |
C22 | 0.4318 (4) | 0.4881 (2) | 0.7067 (2) | 0.0336 (8) | |
C23 | 0.5762 (4) | 0.5028 (2) | 0.7431 (2) | 0.0380 (8) | |
H23 | 0.6314 | 0.5334 | 0.7147 | 0.046* | |
C24 | 0.6390 (5) | 0.4731 (2) | 0.8202 (2) | 0.0514 (11) | |
H24 | 0.7371 | 0.4837 | 0.8448 | 0.062* | |
C25 | 0.5596 (6) | 0.4281 (3) | 0.8616 (3) | 0.0619 (13) | |
H25 | 0.6033 | 0.4069 | 0.9143 | 0.074* | |
C26 | 0.4171 (6) | 0.4140 (3) | 0.8264 (3) | 0.0594 (12) | |
H26 | 0.3627 | 0.3835 | 0.8552 | 0.071* | |
C27 | 0.3517 (5) | 0.4438 (2) | 0.7494 (2) | 0.0469 (10) | |
H27 | 0.2530 | 0.4341 | 0.7259 | 0.056* | |
C28 | −0.0776 (19) | 0.4379 (9) | 0.0514 (11) | 0.140 (6)* | 0.50 |
H28 | −0.1097 | 0.3872 | 0.0653 | 0.168* | 0.50 |
C29 | −0.1165 (9) | 0.5006 (6) | 0.0944 (6) | 0.144 (3)* | |
H29A | −0.1717 | 0.4988 | 0.1354 | 0.173* | 0.50 |
H29B | −0.1435 | 0.4498 | 0.1085 | 0.173* | 0.50 |
H29C | −0.1265 | 0.5229 | 0.1461 | 0.173* | 0.50 |
H29D | −0.2216 | 0.4958 | 0.0766 | 0.173* | 0.50 |
C30 | −0.0644 (19) | 0.5707 (9) | 0.0696 (11) | 0.151 (7)* | 0.50 |
H30 | −0.0760 | 0.6196 | 0.0965 | 0.181* | 0.50 |
C31 | −0.0004 (12) | 0.5598 (7) | 0.0069 (7) | 0.173 (4)* | |
H31 | 0.0270 | 0.6080 | −0.0147 | 0.208* | |
C32 | −0.0400 (14) | 0.5014 (10) | 0.0341 (8) | 0.097 (4)* | 0.50 |
N | 0.3213 (3) | 0.54434 (17) | 0.41527 (17) | 0.0307 (6) | |
P1 | 0.35788 (9) | 0.37521 (5) | 0.48864 (5) | 0.0279 (2) | |
P2 | 0.35653 (9) | 0.52638 (5) | 0.60272 (5) | 0.0290 (2) | |
S | 0.07691 (11) | 0.61012 (7) | 0.31294 (7) | 0.0554 (3) | |
Mo | 0.5000 | 0.5000 | 0.5000 | 0.02374 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.040 (2) | 0.038 (2) | 0.0334 (19) | −0.0087 (16) | 0.0173 (17) | 0.0026 (16) |
C2 | 0.0275 (17) | 0.0388 (19) | 0.0376 (19) | −0.0052 (14) | 0.0152 (15) | −0.0025 (15) |
C3 | 0.0365 (19) | 0.039 (2) | 0.0348 (19) | −0.0106 (16) | 0.0161 (15) | −0.0037 (16) |
C4 | 0.0371 (19) | 0.0317 (19) | 0.0278 (17) | −0.0042 (15) | 0.0086 (15) | −0.0012 (14) |
C5 | 0.045 (2) | 0.034 (2) | 0.067 (3) | −0.0062 (18) | 0.015 (2) | 0.0027 (19) |
C6 | 0.051 (3) | 0.043 (3) | 0.082 (3) | 0.010 (2) | 0.007 (2) | 0.009 (2) |
C7 | 0.074 (3) | 0.034 (2) | 0.045 (2) | 0.001 (2) | 0.013 (2) | 0.0083 (18) |
C8 | 0.067 (3) | 0.035 (2) | 0.063 (3) | −0.011 (2) | 0.013 (2) | 0.011 (2) |
C9 | 0.048 (2) | 0.037 (2) | 0.066 (3) | −0.0104 (18) | 0.008 (2) | 0.011 (2) |
C10 | 0.044 (2) | 0.0287 (18) | 0.0305 (18) | −0.0114 (16) | 0.0081 (16) | 0.0007 (14) |
C11 | 0.071 (3) | 0.040 (2) | 0.036 (2) | 0.002 (2) | 0.010 (2) | −0.0059 (17) |
C12 | 0.115 (4) | 0.054 (3) | 0.039 (2) | 0.003 (3) | 0.011 (3) | −0.013 (2) |
C13 | 0.108 (4) | 0.076 (4) | 0.038 (3) | −0.018 (3) | −0.015 (3) | −0.008 (2) |
C14 | 0.058 (3) | 0.082 (4) | 0.051 (3) | −0.011 (3) | −0.010 (2) | 0.007 (3) |
C15 | 0.042 (2) | 0.052 (3) | 0.042 (2) | −0.0077 (19) | 0.0060 (18) | 0.0005 (19) |
C16 | 0.0372 (19) | 0.0331 (19) | 0.042 (2) | −0.0023 (15) | 0.0226 (16) | −0.0024 (16) |
C17 | 0.043 (2) | 0.038 (2) | 0.046 (2) | 0.0003 (17) | 0.0181 (18) | −0.0040 (17) |
C18 | 0.049 (2) | 0.043 (2) | 0.061 (3) | 0.0055 (19) | 0.020 (2) | 0.000 (2) |
C19 | 0.068 (3) | 0.035 (2) | 0.072 (3) | 0.001 (2) | 0.032 (3) | −0.009 (2) |
C20 | 0.084 (3) | 0.048 (3) | 0.059 (3) | 0.001 (2) | 0.022 (3) | −0.019 (2) |
C21 | 0.064 (3) | 0.045 (2) | 0.041 (2) | 0.000 (2) | 0.015 (2) | −0.0086 (18) |
C22 | 0.047 (2) | 0.0286 (19) | 0.0268 (17) | −0.0003 (15) | 0.0128 (15) | −0.0038 (14) |
C23 | 0.049 (2) | 0.040 (2) | 0.0264 (17) | 0.0051 (18) | 0.0120 (15) | −0.0041 (16) |
C24 | 0.066 (3) | 0.052 (3) | 0.034 (2) | 0.020 (2) | 0.008 (2) | −0.0030 (18) |
C25 | 0.104 (4) | 0.049 (3) | 0.033 (2) | 0.029 (3) | 0.020 (2) | 0.0110 (19) |
C26 | 0.102 (4) | 0.043 (2) | 0.043 (2) | −0.006 (2) | 0.036 (3) | 0.0051 (19) |
C27 | 0.068 (3) | 0.043 (2) | 0.037 (2) | −0.007 (2) | 0.026 (2) | −0.0024 (17) |
N | 0.0336 (16) | 0.0329 (16) | 0.0277 (15) | −0.0038 (13) | 0.0117 (13) | −0.0018 (12) |
P1 | 0.0312 (4) | 0.0272 (5) | 0.0270 (4) | −0.0060 (4) | 0.0104 (4) | −0.0012 (3) |
P2 | 0.0311 (4) | 0.0319 (5) | 0.0266 (4) | −0.0042 (4) | 0.0119 (4) | −0.0035 (3) |
S | 0.0364 (5) | 0.0718 (8) | 0.0558 (7) | 0.0041 (5) | 0.0072 (5) | 0.0259 (6) |
Mo | 0.0257 (2) | 0.0247 (2) | 0.02231 (19) | −0.00377 (17) | 0.00874 (14) | −0.00124 (17) |
C1—N | 1.161 (4) | C19—C20 | 1.367 (6) |
C1—S | 1.624 (4) | C19—H19 | 0.9500 |
C2—C3 | 1.526 (5) | C20—C21 | 1.396 (6) |
C2—P2 | 1.848 (3) | C20—H20 | 0.9500 |
C2—H2A | 0.9900 | C21—H21 | 0.9500 |
C2—H2B | 0.9900 | C22—C27 | 1.394 (5) |
C3—P1 | 1.867 (3) | C22—C23 | 1.398 (5) |
C3—H3A | 0.9900 | C22—P2 | 1.834 (3) |
C3—H3B | 0.9900 | C23—C24 | 1.381 (5) |
C4—C5 | 1.372 (5) | C23—H23 | 0.9500 |
C4—C9 | 1.388 (5) | C24—C25 | 1.384 (6) |
C4—P1 | 1.831 (4) | C24—H24 | 0.9500 |
C5—C6 | 1.393 (6) | C25—C26 | 1.375 (7) |
C5—H5 | 0.9500 | C25—H25 | 0.9500 |
C6—C7 | 1.368 (6) | C26—C27 | 1.385 (6) |
C6—H6 | 0.9500 | C26—H26 | 0.9500 |
C7—C8 | 1.366 (6) | C27—H27 | 0.9500 |
C7—H7 | 0.9500 | C28—C31i | 1.371 (18) |
C8—C9 | 1.365 (6) | C28—C29 | 1.389 (13) |
C8—H8 | 0.9500 | C28—H28 | 0.9638 |
C9—H9 | 0.9500 | C29—C32 | 1.389 (12) |
C10—C15 | 1.386 (5) | C29—C30 | 1.396 (13) |
C10—C11 | 1.392 (5) | C29—H29A | 0.9665 |
C10—P1 | 1.832 (3) | C29—H29B | 0.9497 |
C11—C12 | 1.382 (6) | C29—H29C | 0.9719 |
C11—H11 | 0.9500 | C29—H29D | 0.9853 |
C12—C13 | 1.385 (7) | C30—C31 | 1.354 (14) |
C12—H12 | 0.9500 | C30—C32 | 1.37 (2) |
C13—C14 | 1.381 (7) | C30—H30 | 0.9652 |
C13—H13 | 0.9500 | C31—C32i | 1.356 (16) |
C14—C15 | 1.378 (6) | C31—C28i | 1.371 (18) |
C14—H14 | 0.9500 | C31—H31 | 0.9587 |
C15—H15 | 0.9500 | C32—C31i | 1.356 (16) |
C16—C21 | 1.387 (5) | N—Mo | 2.086 (3) |
C16—C17 | 1.390 (5) | P1—Mo | 2.5081 (9) |
C16—P2 | 1.835 (4) | P2—Mo | 2.4971 (9) |
C17—C18 | 1.387 (5) | Mo—Nii | 2.086 (3) |
C17—H17 | 0.9500 | Mo—P2ii | 2.4971 (9) |
C18—C19 | 1.377 (6) | Mo—P1ii | 2.5081 (9) |
C18—H18 | 0.9500 | ||
N—C1—S | 178.0 (4) | C27—C22—C23 | 119.3 (3) |
C3—C2—P2 | 111.2 (2) | C27—C22—P2 | 122.7 (3) |
C3—C2—H2A | 109.4 | C23—C22—P2 | 118.0 (3) |
P2—C2—H2A | 109.4 | C24—C23—C22 | 120.3 (4) |
C3—C2—H2B | 109.4 | C24—C23—H23 | 119.9 |
P2—C2—H2B | 109.4 | C22—C23—H23 | 119.9 |
H2A—C2—H2B | 108.0 | C23—C24—C25 | 120.2 (4) |
C2—C3—P1 | 112.4 (2) | C23—C24—H24 | 119.9 |
C2—C3—H3A | 109.1 | C25—C24—H24 | 119.9 |
P1—C3—H3A | 109.1 | C26—C25—C24 | 119.8 (4) |
C2—C3—H3B | 109.1 | C26—C25—H25 | 120.1 |
P1—C3—H3B | 109.1 | C24—C25—H25 | 120.1 |
H3A—C3—H3B | 107.8 | C25—C26—C27 | 121.0 (4) |
C5—C4—C9 | 117.8 (3) | C25—C26—H26 | 119.5 |
C5—C4—P1 | 121.7 (3) | C27—C26—H26 | 119.5 |
C9—C4—P1 | 120.5 (3) | C26—C27—C22 | 119.5 (4) |
C4—C5—C6 | 120.7 (4) | C26—C27—H27 | 120.2 |
C4—C5—H5 | 119.7 | C22—C27—H27 | 120.2 |
C6—C5—H5 | 119.7 | C31i—C28—C29 | 127.8 (15) |
C7—C6—C5 | 120.2 (4) | C31i—C28—H28 | 117.4 |
C7—C6—H6 | 119.9 | C29—C28—H28 | 114.8 |
C5—C6—H6 | 119.9 | C32—C28—H29B | 105.8 |
C8—C7—C6 | 119.5 (4) | C28—C29—C30 | 109.8 (10) |
C8—C7—H7 | 120.2 | C28—C29—H29A | 127.5 |
C6—C7—H7 | 120.2 | C30—C29—H29A | 122.7 |
C9—C8—C7 | 120.3 (4) | C32—C29—H29B | 114.6 |
C9—C8—H8 | 119.9 | C30—C29—H29C | 93.1 |
C7—C8—H8 | 119.9 | H29B—C29—H29C | 92.3 |
C8—C9—C4 | 121.6 (4) | C28—C29—H29D | 99.6 |
C8—C9—H9 | 119.2 | C32—C29—H29D | 118.0 |
C4—C9—H9 | 119.2 | C30—C29—H29D | 113.5 |
C15—C10—C11 | 118.6 (4) | H29C—C29—H29D | 89.1 |
C15—C10—P1 | 122.4 (3) | C31—C30—C29 | 112.3 (13) |
C11—C10—P1 | 118.9 (3) | C31—C30—H30 | 127.3 |
C12—C11—C10 | 120.6 (4) | C29—C30—H30 | 120.4 |
C12—C11—H11 | 119.7 | C32—C31—C28i | 125.2 (14) |
C10—C11—H11 | 119.7 | C30—C31—H31 | 113.3 |
C11—C12—C13 | 119.7 (5) | C32i—C31—H31 | 109.1 |
C11—C12—H12 | 120.2 | C31i—C32—C29 | 129.1 (16) |
C13—C12—H12 | 120.2 | C1—N—Mo | 176.2 (3) |
C14—C13—C12 | 120.3 (4) | C4—P1—C10 | 100.52 (16) |
C14—C13—H13 | 119.8 | C4—P1—C3 | 99.91 (16) |
C12—C13—H13 | 119.8 | C10—P1—C3 | 104.00 (16) |
C15—C14—C13 | 119.5 (5) | C4—P1—Mo | 125.01 (11) |
C15—C14—H14 | 120.2 | C10—P1—Mo | 115.26 (11) |
C13—C14—H14 | 120.2 | C3—P1—Mo | 109.43 (11) |
C14—C15—C10 | 121.2 (4) | C22—P2—C16 | 104.17 (16) |
C14—C15—H15 | 119.4 | C22—P2—C2 | 104.63 (16) |
C10—C15—H15 | 119.4 | C16—P2—C2 | 101.09 (16) |
C21—C16—C17 | 118.3 (4) | C22—P2—Mo | 115.71 (11) |
C21—C16—P2 | 122.3 (3) | C16—P2—Mo | 123.73 (11) |
C17—C16—P2 | 119.4 (3) | C2—P2—Mo | 105.06 (11) |
C18—C17—C16 | 120.8 (4) | Nii—Mo—N | 180.000 (1) |
C18—C17—H17 | 119.6 | Nii—Mo—P2 | 95.70 (8) |
C16—C17—H17 | 119.6 | N—Mo—P2 | 84.30 (8) |
C19—C18—C17 | 120.4 (4) | Nii—Mo—P2ii | 84.30 (8) |
C19—C18—H18 | 119.8 | N—Mo—P2ii | 95.70 (8) |
C17—C18—H18 | 119.8 | P2—Mo—P2ii | 180.0 |
C20—C19—C18 | 119.5 (4) | Nii—Mo—P1ii | 84.88 (8) |
C20—C19—H19 | 120.2 | N—Mo—P1ii | 95.12 (8) |
C18—C19—H19 | 120.2 | P2—Mo—P1ii | 100.31 (3) |
C19—C20—C21 | 120.6 (4) | P2ii—Mo—P1ii | 79.69 (3) |
C19—C20—H20 | 119.7 | Nii—Mo—P1 | 95.12 (8) |
C21—C20—H20 | 119.7 | N—Mo—P1 | 84.88 (8) |
C16—C21—C20 | 120.4 (4) | P2—Mo—P1 | 79.69 (3) |
C16—C21—H21 | 119.8 | P2ii—Mo—P1 | 100.31 (3) |
C20—C21—H21 | 119.8 | P1ii—Mo—P1 | 180.0 |
P2—C2—C3—P1 | −46.3 (3) | C11—C10—P1—Mo | 91.4 (3) |
C9—C4—C5—C6 | −1.2 (6) | C2—C3—P1—C4 | 151.6 (3) |
P1—C4—C5—C6 | 179.2 (3) | C2—C3—P1—C10 | −104.9 (3) |
C4—C5—C6—C7 | −0.2 (7) | C2—C3—P1—Mo | 18.8 (3) |
C5—C6—C7—C8 | 1.1 (7) | C27—C22—P2—C16 | 90.4 (3) |
C6—C7—C8—C9 | −0.6 (7) | C23—C22—P2—C16 | −91.0 (3) |
C7—C8—C9—C4 | −0.7 (7) | C27—C22—P2—C2 | −15.3 (3) |
C5—C4—C9—C8 | 1.6 (6) | C23—C22—P2—C2 | 163.3 (3) |
P1—C4—C9—C8 | −178.8 (3) | C27—C22—P2—Mo | −130.4 (3) |
C15—C10—C11—C12 | −0.7 (6) | C23—C22—P2—Mo | 48.2 (3) |
P1—C10—C11—C12 | −176.8 (3) | C21—C16—P2—C22 | 22.0 (3) |
C10—C11—C12—C13 | −0.8 (7) | C17—C16—P2—C22 | −160.9 (3) |
C11—C12—C13—C14 | 1.8 (8) | C21—C16—P2—C2 | 130.3 (3) |
C12—C13—C14—C15 | −1.3 (8) | C17—C16—P2—C2 | −52.6 (3) |
C13—C14—C15—C10 | −0.2 (7) | C21—C16—P2—Mo | −113.0 (3) |
C11—C10—C15—C14 | 1.2 (6) | C17—C16—P2—Mo | 64.1 (3) |
P1—C10—C15—C14 | 177.2 (3) | C3—C2—P2—C22 | −70.5 (3) |
C21—C16—C17—C18 | −0.6 (5) | C3—C2—P2—C16 | −178.5 (2) |
P2—C16—C17—C18 | −177.8 (3) | C3—C2—P2—Mo | 51.8 (3) |
C16—C17—C18—C19 | 0.2 (6) | C22—P2—Mo—Nii | −8.71 (15) |
C17—C18—C19—C20 | 0.1 (7) | C16—P2—Mo—Nii | 121.69 (16) |
C18—C19—C20—C21 | 0.1 (7) | C2—P2—Mo—Nii | −123.53 (15) |
C17—C16—C21—C20 | 0.7 (6) | C22—P2—Mo—N | 171.29 (15) |
P2—C16—C21—C20 | 177.8 (3) | C16—P2—Mo—N | −58.31 (16) |
C19—C20—C21—C16 | −0.4 (7) | C2—P2—Mo—N | 56.47 (15) |
C27—C22—C23—C24 | 0.7 (5) | C22—P2—Mo—P1ii | −94.52 (13) |
P2—C22—C23—C24 | −178.0 (3) | C16—P2—Mo—P1ii | 35.88 (15) |
C22—C23—C24—C25 | 0.5 (6) | C2—P2—Mo—P1ii | 150.66 (12) |
C23—C24—C25—C26 | −1.1 (6) | C22—P2—Mo—P1 | 85.48 (13) |
C24—C25—C26—C27 | 0.5 (7) | C16—P2—Mo—P1 | −144.12 (15) |
C25—C26—C27—C22 | 0.6 (6) | C2—P2—Mo—P1 | −29.34 (12) |
C23—C22—C27—C26 | −1.2 (5) | C4—P1—Mo—Nii | −14.26 (15) |
P2—C22—C27—C26 | 177.4 (3) | C10—P1—Mo—Nii | −139.49 (15) |
C5—C4—P1—C10 | 121.5 (3) | C3—P1—Mo—Nii | 103.77 (15) |
C9—C4—P1—C10 | −58.1 (3) | C4—P1—Mo—N | 165.74 (15) |
C5—C4—P1—C3 | −132.1 (3) | C10—P1—Mo—N | 40.51 (15) |
C9—C4—P1—C3 | 48.3 (3) | C3—P1—Mo—N | −76.23 (15) |
C5—C4—P1—Mo | −9.8 (4) | C4—P1—Mo—P2 | −109.14 (14) |
C9—C4—P1—Mo | 170.6 (3) | C10—P1—Mo—P2 | 125.63 (14) |
C15—C10—P1—C4 | 138.3 (3) | C3—P1—Mo—P2 | 8.89 (13) |
C11—C10—P1—C4 | −45.7 (3) | C4—P1—Mo—P2ii | 70.86 (14) |
C15—C10—P1—C3 | 35.2 (3) | C10—P1—Mo—P2ii | −54.37 (14) |
C11—C10—P1—C3 | −148.8 (3) | C3—P1—Mo—P2ii | −171.11 (13) |
C15—C10—P1—Mo | −84.5 (3) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mo(NCS)2(C26H24P2)2]·C7H8 |
Mr | 1101.02 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 180 |
a, b, c (Å) | 9.6277 (13), 17.017 (2), 16.755 (2) |
β (°) | 104.172 (11) |
V (Å3) | 2661.5 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.49 |
Crystal size (mm) | 0.68 × 0.62 × 0.48 |
Data collection | |
Diffractometer | Stoe STADI-4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.733, 0.800 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4828, 4820, 3796 |
Rint | 0.098 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.101, 1.09 |
No. of reflections | 4820 |
No. of parameters | 306 |
No. of restraints | 5 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.74, −0.43 |
Computer programs: STADI4 (Stoe & Cie, 1997), STADI4, X-RED (Stoe & Cie, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1999), SHELXL97.
Recently, we have shown that the reactions of the dinitrogen complexes trans-[M(dppe)2(N2)2] [M = Mo, W; dppe is ethane-1,2-diylbis(diphenylphosphane), Ph2PCH2CH2PPh2] with the germanium(II) halides Cp*GeX (Cp* = C5Me5; X = Cl, Br, I) afford the germylyne complexes trans-[X(dppe)2M≡Ge—(η1-Cp*)] (Filippou, Philippopoulos et al., 2000; Filippou, Portius et al., 2002). Furthermore, the tungsten derivative trans-[I(dppe)2W≡Ge—(η1-Cp*)] was shown to undergo iodide/pseudohalide ligand exchange with an excess of M'Y (M' = Na, K; Y = CN, NCO, N3, NCS) to yield the germylyne complexes trans-[Y(dppe)2W≡Ge—(η1-Cp*)] (Filippou, Philippopoulos et al., 2002). Looking for an alternative approach to the analogous molybdenum compounds, we prepared the anionic dinitrogen complex [N(n—Bu)4][Mo(NCS)(dppe)2(N2)], following the method of Chatt et al. (1980). Exposure of this complex to air was reported to give trans-[Mo(NCS)2(dppe)2], (1), which was characterized by IR spectroscopy and elemental analysis (Chatt et al., 1980). However, the molecular structure of (1) remained unknown until today. Dark-green single crystals of the toluene solvate of (1), viz. (1α), were obtained from a THF/toluene solution upon cooling from 293 to 238 K. The title compound, (1α), crystallizes in the same space group (P21/c) as the chloro complex trans-[MoCl2(dppe)2]·2C4H8O (Filippou, Portius et al., 2000). The 16 valence-electron complex (1) reveals a distorted octahedral geometry at the Mo atom, which bears two trans-arranged N-bonded thiocyanate ligands and lies on a crystallographic center of symmetry. Distortion is evidenced in the tilt of the axial isothiocyanate ligands with respect to the equatorial plane spanned by the four P atoms, the angle between the N—Mo—N' axis and the P4 plane being 82.9°. A similar tilt of the axial chloro ligands (80.5°) was observed in trans-[MoCl2(dppe)2]·2C4H8O (Filippou, Portius et al., 2000). The isothiocyanate ligands feature an almost linear Mo—N—C1—S array in (1α), with Mo—N—C1 and N—C1—S angles of 176.2 (3) and 178.0 (4)°, respectively. The Mo—N bonds of (1α) [2.086 (3) Å] are slightly shorter than those of the few other structurally characterized molybdenum(II) isothiocyanate complexes (Bino & Cotton, 1979; Müller & Mohan, 1981) and the mean Mo—P bond length of (1α) (2.503 Å) compares well with that of trans-[MoCl2(dppe)2]·2C4H8O (average Mo—P = 2.499 Å; Filippou, Portius et al., 2000) or trans-[MoCl2(dppe)2]·CH2Cl2 (average Mo—P = 2.497 Å; Nardelli et al., 1980).