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Acta Cryst. (2007). E63, m1476    [ doi:10.1107/S1600536807019320 ]

Chloridobis[1,2-bis(diphenylphosphino)ethane](ethylimido)molybdenum(IV) tetraphenylborate acetonitrile disolvate

K. Mersmann, C. Näther and F. Tuczek

Abstract top

In the crystal structure of the title compound, [Mo(C2H5N)Cl(C26H24P2)2](C24H20B)·2C2H3N, C82H79N3BClP4Mo, the Mo atom is surrounded by four P atoms of two crystallographically independent 1,2-bis(diphenylphosphino)ethane ligands, one Cl atom and one N atom of an ethylimido ligand in a distorted octahedral geomtery.

Comment top

The structure determination of this compound was undertaken as part of a project on the asymmetric reduction of dinitrogen via the Chatt cycle (Mersmann et al., 2006). Imido complexes are problematic intermediates in this cycle because of their very negative reduction potentials (Alias et al., 1997). For practical reasons it is instructive to study alkylimido complexes. During these investigations we obtained big crystals of the title compound in order to perform polarized absorption spectroscopy. An absoption band at 510 nm possesses unexpected differences in intensity under polarization along the a- and b axis of this molecule. Furthermore a vibrational fine structure of about 530 cm−1 was observed on the absorption band, which is attributed to a Mo—N—C bending vibration.

The crystal structure of the title compound consists of discrete [Mo(Cl)(NC2H5)(P2C26H24)2]+ cations and tetraphenylborate anions. The molybdenum atoms are coordinated by four phosphorous atoms of two crystallographically independent 1,2-bis(diphenylphosphino)ethane ligands, one nitrogen atom of an ethylimido ligand and one chlorine atom within distorted octahedra (Fig. 1). All bond lengths and angles are in good agreement with those retrieved from the CSD database (conquest version 1.8, 2007; Bruno et al., 2002) The Mo1—N1 bond lengths of 1.732 (2) Å strongly indicate that this is a Mo—N triple bond. There are two additional acetonitrile ligands per formula unit within the structure, that are located in holes of the crystal. These solvent molecules exhibit slightly enlarged anisotropic displacement parameters indicating some static or dynamic disorder.

Related literature top

For related literature, see: Alias et al. (1997); Allen & Kennard (1993); Chatt & Dilworth (1977); George & Noble (1978); Mersmann et al. (2006).

Experimental top

Under an inert gas atmosphere, 120 mg (0,127 mmol) of the nitrido complex [Mo(N)(Cl)(dppe)2], prepared following literature procedures (George et al., 1978; Chatt et al., 1977), were dissolved in 15 ml thf. Some drops of ethyliodide were added and the solution was stirred for 3 h. Afterwards the reaction mixture was evaporated to dryness and the residue was redissolved in 30 ml of acetonitrile. After addition of 50 mg (0,15 mmol) sodium tetraphenylborate the product crystallizes in rectangular plates.

Refinement top

The hydrogen atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined isotropic with Ueq = 1.2 Ueq(C) for aromatic and methylene H atoms and Ueq = 1.5 Ueq(C) for methyl H atoms using a riding model with C—H = 0.95 Å for aromatic, C—H = 0.99 Å for methylene and C—H = 0.98 Å for methyl H atoms. Both carbon atoms of the ethylimido ligand are disordered in two positions and were refined using a split model.

Computing details top

Data collection: IPDS Program Package (Stoe & Cie, 1998); cell refinement: IPDS Program Package; data reduction: IPDS Program Package; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1998); software used to prepare material for publication: CIFTAB in SHELXTL.

Figures top
[Figure 1] Fig. 1. : Crystal structure of compound I with labelling and displacement ellipsoids drawn at the 50% probability level. The hydrogen atoms are omitted for clarity.
Chloridobis[1,2-bis(diphenylphosphino)ethane](ethylimido)molybdenum(IV) tetraphenylborate acetonitrile disolvate top
Crystal data top
[Mo(C2H5N)Cl(C26H24P2)2](C24H20B)·2C2H3NF(000) = 2864
Mr = 1372.56Dx = 1.299 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 15.3299 (12) ÅCell parameters from 8000 reflections
b = 21.5840 (11) Åθ = 11.3–24.3°
c = 21.3439 (16) ŵ = 0.36 mm−1
β = 96.387 (9)°T = 170 K
V = 7018.4 (8) Å3Block, red
Z = 40.2 × 0.15 × 0.1 mm
Data collection top
Stoe IPDS-1
diffractometer		15159 independent reflections
Radiation source: fine-focus sealed tube12034 reflections with I > 2σ(I)
graphiteRint = 0.043
φ scansθmax = 27.0°, θmin = 2.1°
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 1998)		h = −19→18
Tmin = 0.929, Tmax = 0.941k = −23→27
48449 measured reflectionsl = −27→27
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.101 w = 1/[σ2(Fo2) + (0.0633P)2 + 1.19P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.005
15159 reflectionsΔρmax = 0.62 e Å−3
850 parametersΔρmin = −0.68 e Å−3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0024 (2)
Crystal data top
[Mo(C2H5N)Cl(C26H24P2)2](C24H20B)·2C2H3NV = 7018.4 (8) Å3
Mr = 1372.56Z = 4
Monoclinic, P21/nMo Kα radiation
a = 15.3299 (12) ŵ = 0.36 mm−1
b = 21.5840 (11) ÅT = 170 K
c = 21.3439 (16) Å0.2 × 0.15 × 0.1 mm
β = 96.387 (9)°
Data collection top
Stoe IPDS-1
diffractometer		15159 independent reflections
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 1998)		12034 reflections with I > 2σ(I)
Tmin = 0.929, Tmax = 0.941Rint = 0.043
48449 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.101Δρmax = 0.62 e Å−3
S = 1.01Δρmin = −0.68 e Å−3
15159 reflectionsAbsolute structure: ?
850 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Mo10.498959 (11)0.407142 (8)0.224115 (7)0.01628 (6)
Cl10.47025 (4)0.40693 (3)0.10929 (2)0.02676 (12)
N10.52061 (19)0.40494 (9)0.30548 (9)0.0443 (6)
C910.5682 (3)0.40422 (19)0.37061 (19)0.0293 (8)0.60
H91A0.59670.44470.38090.035*0.60
H91B0.61350.37140.37470.035*0.60
C920.4978 (4)0.3913 (3)0.4132 (2)0.0538 (13)0.60
H92A0.52430.39000.45720.081*0.60
H92B0.47000.35130.40190.081*0.60
H92C0.45350.42420.40830.081*0.60
C91'0.4942 (4)0.3962 (3)0.3708 (3)0.0281 (12)0.40
H91C0.47280.35350.37680.034*0.40
H91D0.44830.42610.37960.034*0.40
C92'0.5809 (5)0.4085 (4)0.4127 (3)0.050 (2)0.40
H92D0.57140.40400.45720.075*0.40
H92E0.60110.45060.40520.075*0.40
H92F0.62530.37860.40250.075*0.40
P10.39118 (3)0.49746 (2)0.21967 (2)0.01916 (11)
P20.35534 (3)0.34829 (3)0.22543 (2)0.02065 (12)
C10.28036 (15)0.46342 (11)0.21360 (12)0.0289 (5)
H1A0.23850.49390.22770.035*
H1B0.26100.45260.16910.035*
C20.28130 (15)0.40533 (10)0.25447 (11)0.0270 (5)
H2A0.22130.38790.25270.032*
H2B0.30140.41590.29890.032*
C30.38091 (14)0.55426 (10)0.15561 (9)0.0219 (4)
C40.41413 (16)0.61398 (11)0.16549 (10)0.0267 (5)
H40.44160.62560.20590.032*
C50.40713 (19)0.65652 (12)0.11648 (11)0.0377 (6)
H50.42930.69740.12350.045*
C60.3682 (2)0.63965 (13)0.05778 (11)0.0407 (6)
H60.36240.66910.02450.049*
C70.33749 (19)0.58018 (13)0.04703 (11)0.0388 (6)
H70.31220.56850.00610.047*
C80.34333 (16)0.53753 (11)0.09556 (10)0.0305 (5)
H80.32170.49670.08800.037*
C90.39205 (14)0.54671 (10)0.28972 (9)0.0227 (4)
C100.46220 (15)0.54570 (11)0.33647 (10)0.0267 (5)
H100.51110.51960.33210.032*
C110.46172 (18)0.58257 (11)0.38987 (11)0.0336 (5)
H110.50960.58090.42220.040*
C120.39177 (19)0.62165 (11)0.39600 (11)0.0350 (6)
H120.39110.64630.43280.042*
C130.32302 (18)0.62475 (12)0.34869 (12)0.0360 (6)
H130.27580.65250.35230.043*
C140.32282 (16)0.58740 (11)0.29599 (11)0.0296 (5)
H140.27500.58950.26370.036*
C150.29625 (15)0.31922 (11)0.15219 (10)0.0265 (5)
C160.20557 (16)0.32541 (13)0.13927 (12)0.0369 (6)
H160.17340.34790.16730.044*
C170.1625 (2)0.29883 (15)0.08555 (14)0.0498 (8)
H170.10080.30370.07660.060*
C180.2080 (2)0.26536 (15)0.04495 (13)0.0497 (8)
H180.17750.24690.00850.060*
C190.2979 (2)0.25859 (14)0.05704 (12)0.0448 (7)
H190.32940.23530.02930.054*
C200.34173 (17)0.28634 (12)0.11043 (11)0.0340 (5)
H200.40370.28270.11840.041*
C210.34541 (14)0.28166 (10)0.27740 (10)0.0248 (4)
C220.36671 (16)0.22305 (11)0.25682 (12)0.0330 (5)
H220.38630.21830.21640.040*
C230.35970 (17)0.17142 (12)0.29471 (15)0.0429 (7)
H230.37580.13170.28070.051*
C240.3292 (2)0.17804 (15)0.35267 (15)0.0514 (8)
H240.32330.14270.37840.062*
C250.3075 (2)0.23580 (15)0.37329 (13)0.0479 (7)
H250.28610.24010.41320.057*
C260.31648 (16)0.28802 (12)0.33636 (11)0.0323 (5)
H260.30280.32790.35150.039*
P30.63851 (3)0.46729 (2)0.21345 (2)0.01898 (11)
P40.60205 (3)0.31874 (2)0.20681 (2)0.02002 (11)
C310.72697 (14)0.41003 (10)0.22556 (11)0.0269 (5)
H31A0.78270.42840.21500.032*
H31B0.73510.39680.27020.032*
C320.70217 (15)0.35445 (11)0.18297 (11)0.0282 (5)
H32A0.75060.32390.18670.034*
H32B0.69180.36810.13850.034*
C330.65835 (14)0.50534 (10)0.13959 (9)0.0232 (4)
C340.74278 (15)0.51344 (12)0.12320 (11)0.0310 (5)
H340.79130.49590.14870.037*
C350.75663 (17)0.54724 (13)0.06962 (12)0.0363 (6)
H350.81460.55230.05860.044*
C360.68722 (18)0.57335 (12)0.03251 (11)0.0346 (6)
H360.69720.5966−0.00380.041*
C370.60335 (18)0.56560 (12)0.04823 (11)0.0346 (5)
H370.55520.58360.02270.041*
C380.58884 (16)0.53159 (12)0.10132 (10)0.0295 (5)
H380.53060.52620.11160.035*
C390.67054 (13)0.52817 (10)0.27102 (9)0.0211 (4)
C400.71922 (15)0.51613 (11)0.32870 (10)0.0276 (5)
H400.73730.47500.33930.033*
C410.74138 (17)0.56396 (13)0.37068 (11)0.0359 (6)
H410.77470.55540.40990.043*
C420.71564 (18)0.62372 (12)0.35619 (12)0.0367 (6)
H420.73190.65640.38500.044*
C430.66570 (18)0.63605 (11)0.29926 (12)0.0348 (5)
H430.64660.67710.28930.042*
C440.64374 (16)0.58848 (11)0.25710 (11)0.0283 (5)
H440.60990.59720.21810.034*
C450.57533 (14)0.25804 (10)0.14803 (10)0.0242 (4)
C460.57037 (18)0.27257 (12)0.08388 (11)0.0341 (5)
H460.58530.31300.07110.041*
C470.5437 (2)0.22822 (13)0.03898 (12)0.0428 (7)
H470.54080.2384−0.00450.051*
C480.52136 (19)0.16919 (13)0.05671 (12)0.0405 (6)
H480.50310.13900.02560.049*
C490.52576 (18)0.15443 (12)0.12001 (12)0.0369 (6)
H490.51000.11410.13240.044*
C500.55329 (16)0.19857 (11)0.16568 (11)0.0292 (5)
H500.55700.18790.20910.035*
C510.64005 (15)0.27452 (10)0.27751 (10)0.0253 (5)
C520.58005 (17)0.26072 (11)0.31972 (10)0.0310 (5)
H520.52240.27730.31310.037*
C530.6037 (2)0.22294 (12)0.37139 (12)0.0402 (6)
H530.56210.21320.39970.048*
C540.6877 (2)0.19962 (12)0.38149 (13)0.0492 (8)
H540.70410.17390.41700.059*
C550.7475 (2)0.21340 (15)0.34061 (15)0.0555 (9)
H550.80530.19710.34790.067*
C560.72490 (19)0.25093 (14)0.28856 (13)0.0427 (6)
H560.76710.26050.26060.051*
B10.48127 (15)−0.08729 (11)0.17146 (11)0.0203 (4)
C610.50020 (13)−0.03005 (10)0.22225 (10)0.0215 (4)
C620.56562 (15)0.01470 (10)0.22030 (11)0.0272 (5)
H620.60060.01400.18630.033*
C630.58165 (17)0.06050 (11)0.26652 (13)0.0366 (6)
H630.62700.08990.26340.044*
C640.53206 (18)0.06319 (12)0.31651 (12)0.0380 (6)
H640.54290.09420.34800.046*
C650.46630 (17)0.01994 (12)0.32005 (12)0.0366 (6)
H650.43110.02140.35390.044*
C660.45152 (15)−0.02579 (11)0.27405 (11)0.0289 (5)
H660.4065−0.05540.27790.035*
C670.38780 (14)−0.07824 (10)0.12653 (9)0.0216 (4)
C680.36469 (15)−0.12151 (11)0.07866 (10)0.0281 (5)
H680.4037−0.15490.07350.034*
C690.28697 (17)−0.11773 (13)0.03827 (10)0.0345 (6)
H690.2736−0.14830.00660.041*
C700.22974 (16)−0.06959 (14)0.04446 (11)0.0358 (6)
H700.1765−0.06680.01720.043*
C710.25019 (15)−0.02557 (13)0.09041 (11)0.0324 (5)
H710.21100.00780.09490.039*
C720.32856 (14)−0.02987 (11)0.13057 (10)0.0246 (4)
H720.34180.00130.16160.030*
C730.55772 (14)−0.09069 (10)0.12310 (10)0.0230 (4)
C740.56174 (15)−0.04456 (11)0.07683 (10)0.0273 (5)
H740.5204−0.01170.07490.033*
C750.62368 (16)−0.04511 (13)0.03393 (11)0.0339 (5)
H750.6241−0.01290.00360.041*
C760.68469 (17)−0.09249 (13)0.03532 (12)0.0372 (6)
H760.7272−0.09320.00620.045*
C770.68259 (16)−0.13894 (13)0.07998 (12)0.0356 (5)
H770.7242−0.17170.08160.043*
C780.61981 (15)−0.13791 (11)0.12256 (11)0.0279 (5)
H780.6193−0.17060.15230.034*
C790.47921 (13)−0.15040 (10)0.21425 (9)0.0205 (4)
C800.54757 (15)−0.16243 (11)0.26222 (10)0.0275 (5)
H800.5954−0.13420.26810.033*
C810.54804 (16)−0.21383 (12)0.30136 (11)0.0331 (5)
H810.5958−0.22030.33300.040*
C820.47913 (17)−0.25576 (12)0.29447 (12)0.0353 (5)
H820.4793−0.29100.32110.042*
C830.41032 (16)−0.24545 (11)0.24836 (11)0.0309 (5)
H830.3622−0.27340.24350.037*
C840.41126 (14)−0.19410 (10)0.20891 (10)0.0239 (4)
H840.3636−0.18850.17690.029*
N20.2933 (3)0.2066 (3)0.54874 (19)0.1073 (15)
C930.3490 (3)0.2388 (2)0.53754 (18)0.0772 (12)
C940.4213 (3)0.2788 (3)0.5230 (3)0.1022 (16)
H94A0.45230.29480.56230.153*
H94B0.39790.31340.49660.153*
H94C0.46210.25480.50030.153*
N30.5099 (5)0.1161 (4)0.4785 (2)0.178 (3)
C950.4699 (4)0.0975 (3)0.5157 (2)0.0936 (16)
C960.4198 (4)0.0808 (3)0.5645 (3)0.121 (2)
H96A0.45650.08310.60500.182*
H96B0.39800.03840.55760.182*
H96C0.37000.10930.56480.182*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mo10.01982 (9)0.01424 (9)0.01485 (9)0.00141 (7)0.00219 (6)−0.00022 (6)
Cl10.0357 (3)0.0260 (3)0.0177 (2)−0.0009 (2)−0.00102 (19)−0.00043 (19)
N10.0904 (19)0.0166 (10)0.0249 (10)0.0166 (11)0.0015 (11)−0.0020 (8)
C910.031 (2)0.031 (2)0.026 (2)0.0033 (17)0.0032 (16)0.0022 (16)
C920.060 (3)0.071 (4)0.033 (3)−0.011 (3)0.014 (2)0.005 (2)
C91'0.040 (4)0.028 (3)0.016 (3)−0.001 (3)0.003 (2)0.005 (2)
C92'0.051 (4)0.076 (6)0.022 (3)−0.009 (4)−0.008 (3)0.004 (3)
P10.0214 (3)0.0154 (3)0.0211 (2)0.0021 (2)0.00404 (19)0.00153 (19)
P20.0205 (3)0.0159 (3)0.0263 (3)0.0004 (2)0.0058 (2)0.0011 (2)
C10.0241 (11)0.0187 (11)0.0441 (13)0.0015 (9)0.0046 (9)0.0048 (9)
C20.0247 (11)0.0187 (11)0.0398 (12)0.0025 (9)0.0130 (9)0.0026 (9)
C30.0230 (10)0.0192 (10)0.0238 (10)0.0026 (8)0.0044 (8)0.0013 (8)
C40.0360 (12)0.0213 (11)0.0238 (10)−0.0013 (10)0.0071 (9)0.0007 (8)
C50.0609 (17)0.0218 (12)0.0325 (12)−0.0044 (12)0.0150 (11)0.0029 (9)
C60.0618 (18)0.0324 (14)0.0295 (12)0.0070 (13)0.0117 (12)0.0122 (10)
C70.0539 (16)0.0381 (15)0.0228 (11)0.0070 (12)−0.0026 (10)0.0033 (10)
C80.0377 (13)0.0250 (12)0.0276 (11)0.0023 (10)−0.0019 (9)0.0000 (9)
C90.0297 (11)0.0174 (10)0.0224 (9)0.0020 (9)0.0093 (8)0.0022 (8)
C100.0318 (12)0.0212 (11)0.0280 (10)0.0019 (9)0.0071 (9)−0.0018 (8)
C110.0438 (14)0.0272 (13)0.0297 (11)−0.0033 (11)0.0034 (10)−0.0026 (9)
C120.0565 (16)0.0229 (12)0.0284 (11)−0.0003 (11)0.0169 (11)−0.0036 (9)
C130.0465 (15)0.0273 (13)0.0376 (13)0.0116 (11)0.0191 (11)0.0003 (10)
C140.0344 (12)0.0269 (12)0.0287 (11)0.0089 (10)0.0083 (9)0.0033 (9)
C150.0263 (11)0.0213 (11)0.0314 (11)−0.0042 (9)0.0010 (9)0.0036 (9)
C160.0279 (12)0.0377 (15)0.0439 (14)−0.0041 (11)−0.0009 (10)0.0093 (11)
C170.0376 (15)0.060 (2)0.0479 (16)−0.0145 (14)−0.0142 (12)0.0151 (14)
C180.0580 (18)0.0558 (19)0.0316 (13)−0.0279 (15)−0.0111 (13)0.0091 (12)
C190.0565 (18)0.0440 (16)0.0337 (13)−0.0173 (14)0.0035 (12)−0.0068 (11)
C200.0329 (12)0.0339 (14)0.0345 (12)−0.0068 (11)0.0008 (10)−0.0054 (10)
C210.0183 (10)0.0223 (11)0.0338 (11)−0.0011 (9)0.0022 (8)0.0056 (9)
C220.0280 (12)0.0222 (12)0.0490 (14)0.0004 (10)0.0058 (10)0.0047 (10)
C230.0314 (13)0.0207 (13)0.0739 (19)−0.0018 (11)−0.0050 (12)0.0114 (12)
C240.0483 (17)0.0387 (17)0.0651 (19)−0.0092 (14)−0.0028 (14)0.0293 (14)
C250.0494 (17)0.0516 (19)0.0428 (14)−0.0097 (14)0.0055 (12)0.0212 (13)
C260.0311 (12)0.0338 (13)0.0322 (11)−0.0037 (10)0.0052 (9)0.0076 (10)
P30.0181 (2)0.0159 (3)0.0224 (2)0.0006 (2)0.00004 (19)−0.00067 (19)
P40.0214 (3)0.0157 (3)0.0230 (2)0.0019 (2)0.00261 (19)−0.00274 (19)
C310.0201 (10)0.0193 (11)0.0403 (12)0.0006 (9)−0.0004 (9)−0.0030 (9)
C320.0239 (11)0.0211 (11)0.0406 (12)0.0015 (9)0.0074 (9)−0.0041 (9)
C330.0254 (11)0.0202 (11)0.0245 (10)−0.0051 (9)0.0048 (8)−0.0046 (8)
C340.0260 (11)0.0339 (13)0.0335 (12)−0.0064 (10)0.0046 (9)−0.0047 (10)
C350.0352 (13)0.0388 (15)0.0374 (13)−0.0126 (11)0.0158 (10)−0.0047 (11)
C360.0504 (15)0.0298 (13)0.0248 (11)−0.0124 (11)0.0103 (10)−0.0032 (9)
C370.0418 (14)0.0341 (14)0.0275 (11)−0.0033 (11)0.0025 (10)0.0045 (10)
C380.0295 (12)0.0321 (13)0.0275 (11)−0.0013 (10)0.0054 (9)0.0044 (9)
C390.0176 (9)0.0203 (10)0.0253 (10)−0.0012 (8)0.0026 (8)−0.0017 (8)
C400.0299 (11)0.0275 (12)0.0249 (10)0.0067 (10)0.0005 (9)−0.0023 (9)
C410.0369 (13)0.0421 (15)0.0269 (11)0.0070 (12)−0.0044 (10)−0.0099 (10)
C420.0406 (14)0.0338 (14)0.0353 (12)−0.0036 (11)0.0025 (10)−0.0162 (10)
C430.0459 (14)0.0197 (11)0.0390 (13)0.0011 (11)0.0055 (11)−0.0042 (9)
C440.0325 (12)0.0219 (11)0.0294 (11)0.0012 (9)−0.0014 (9)−0.0010 (9)
C450.0251 (10)0.0201 (11)0.0280 (10)0.0025 (9)0.0058 (8)−0.0062 (8)
C460.0494 (15)0.0270 (12)0.0287 (11)−0.0083 (11)0.0171 (10)−0.0072 (9)
C470.0626 (18)0.0392 (15)0.0291 (12)−0.0108 (14)0.0165 (12)−0.0130 (11)
C480.0524 (16)0.0319 (14)0.0386 (13)−0.0087 (12)0.0111 (12)−0.0176 (11)
C490.0449 (15)0.0214 (12)0.0440 (14)−0.0041 (11)0.0034 (11)−0.0065 (10)
C500.0350 (12)0.0204 (11)0.0318 (11)−0.0002 (10)0.0020 (9)−0.0031 (9)
C510.0296 (11)0.0168 (10)0.0276 (10)0.0031 (9)−0.0049 (8)−0.0041 (8)
C520.0369 (13)0.0241 (12)0.0301 (11)−0.0002 (10)−0.0048 (9)0.0043 (9)
C530.0628 (18)0.0246 (13)0.0309 (12)−0.0033 (12)−0.0057 (11)0.0051 (10)
C540.080 (2)0.0257 (13)0.0349 (13)0.0163 (14)−0.0223 (14)0.0003 (10)
C550.0589 (19)0.0484 (19)0.0532 (17)0.0296 (16)−0.0195 (15)−0.0048 (14)
C560.0395 (14)0.0445 (16)0.0420 (14)0.0175 (13)−0.0045 (11)−0.0025 (12)
B10.0185 (11)0.0177 (11)0.0252 (11)−0.0002 (9)0.0043 (8)0.0006 (8)
C610.0185 (9)0.0161 (10)0.0293 (10)0.0013 (8)0.0005 (8)0.0000 (8)
C620.0242 (11)0.0195 (11)0.0368 (12)−0.0025 (9)−0.0012 (9)0.0029 (9)
C630.0338 (13)0.0196 (12)0.0530 (15)−0.0059 (10)−0.0107 (11)−0.0011 (10)
C640.0413 (14)0.0243 (13)0.0445 (14)0.0063 (11)−0.0120 (11)−0.0127 (10)
C650.0403 (14)0.0330 (14)0.0366 (13)0.0053 (11)0.0050 (10)−0.0103 (10)
C660.0272 (11)0.0238 (12)0.0362 (12)−0.0026 (9)0.0065 (9)−0.0066 (9)
C670.0210 (10)0.0234 (11)0.0212 (9)−0.0035 (8)0.0064 (8)0.0012 (8)
C680.0286 (11)0.0288 (12)0.0271 (11)−0.0002 (10)0.0036 (9)−0.0035 (9)
C690.0370 (13)0.0426 (15)0.0229 (10)−0.0090 (12)−0.0012 (9)−0.0042 (10)
C700.0233 (11)0.0559 (17)0.0276 (11)−0.0025 (11)−0.0003 (9)0.0059 (11)
C710.0257 (11)0.0433 (15)0.0293 (11)0.0079 (11)0.0074 (9)0.0055 (10)
C720.0229 (10)0.0271 (12)0.0250 (10)0.0019 (9)0.0073 (8)−0.0003 (8)
C730.0213 (10)0.0208 (11)0.0272 (10)−0.0028 (8)0.0045 (8)−0.0019 (8)
C740.0242 (11)0.0272 (12)0.0309 (11)−0.0033 (9)0.0054 (9)0.0012 (9)
C750.0339 (13)0.0396 (14)0.0291 (11)−0.0113 (11)0.0077 (10)0.0013 (10)
C760.0315 (12)0.0476 (16)0.0355 (12)−0.0091 (12)0.0169 (10)−0.0090 (11)
C770.0289 (12)0.0366 (14)0.0431 (13)0.0029 (11)0.0122 (10)−0.0082 (11)
C780.0261 (11)0.0247 (12)0.0342 (11)0.0000 (9)0.0085 (9)−0.0016 (9)
C790.0203 (10)0.0173 (10)0.0250 (10)−0.0009 (8)0.0077 (8)−0.0037 (8)
C800.0256 (11)0.0230 (12)0.0331 (11)−0.0064 (9)−0.0001 (9)0.0030 (9)
C810.0321 (12)0.0304 (13)0.0356 (12)0.0024 (10)−0.0010 (10)0.0058 (10)
C820.0430 (14)0.0219 (12)0.0427 (13)−0.0012 (11)0.0127 (11)0.0098 (10)
C830.0318 (12)0.0180 (11)0.0441 (13)−0.0054 (9)0.0096 (10)0.0011 (9)
C840.0219 (10)0.0191 (11)0.0310 (10)−0.0031 (8)0.0050 (8)−0.0026 (8)
N20.090 (3)0.153 (5)0.077 (2)−0.033 (3)−0.001 (2)0.018 (3)
C930.075 (3)0.094 (3)0.059 (2)0.000 (3)−0.007 (2)0.002 (2)
C940.086 (3)0.096 (4)0.119 (4)−0.018 (3)−0.015 (3)0.004 (3)
N30.176 (6)0.278 (9)0.083 (3)−0.106 (6)0.030 (3)−0.022 (4)
C950.095 (3)0.107 (4)0.078 (3)−0.044 (3)0.002 (3)0.004 (3)
C960.107 (4)0.115 (5)0.145 (5)0.001 (4)0.035 (4)0.051 (4)
Geometric parameters (Å, °) top
Mo1—N11.732 (2)C37—C381.389 (3)
Mo1—Cl12.4413 (5)C37—H370.9500
Mo1—P42.5308 (6)C38—H380.9500
Mo1—P32.5342 (6)C39—C441.387 (3)
Mo1—P22.5447 (6)C39—C401.391 (3)
Mo1—P12.5503 (6)C40—C411.384 (3)
N1—C911.496 (4)C40—H400.9500
N1—C91'1.507 (6)C41—C421.374 (4)
C91—C921.513 (6)C41—H410.9500
C91—H91A0.9900C42—C431.388 (4)
C91—H91B0.9900C42—H420.9500
C92—H92A0.9800C43—C441.382 (3)
C92—H92B0.9800C43—H430.9500
C92—H92C0.9800C44—H440.9500
C91'—C92'1.540 (9)C45—C501.390 (3)
C91'—H91C0.9900C45—C461.399 (3)
C91'—H91D0.9900C46—C471.384 (3)
C92'—H92D0.9800C46—H460.9500
C92'—H92E0.9800C47—C481.383 (4)
C92'—H92F0.9800C47—H470.9500
P1—C31.830 (2)C48—C491.382 (4)
P1—C91.833 (2)C48—H480.9500
P1—C11.842 (2)C49—C501.394 (3)
P2—C151.828 (2)C49—H490.9500
P2—C21.829 (2)C50—H500.9500
P2—C211.833 (2)C51—C521.389 (3)
C1—C21.527 (3)C51—C561.392 (3)
C1—H1A0.9900C52—C531.387 (3)
C1—H1B0.9900C52—H520.9500
C2—H2A0.9900C53—C541.376 (4)
C2—H2B0.9900C53—H530.9500
C3—C81.393 (3)C54—C551.367 (5)
C3—C41.393 (3)C54—H540.9500
C4—C51.387 (3)C55—C561.388 (4)
C4—H40.9500C55—H550.9500
C5—C61.376 (4)C56—H560.9500
C5—H50.9500B1—C791.642 (3)
C6—C71.378 (4)B1—C671.645 (3)
C6—H60.9500B1—C731.647 (3)
C7—C81.381 (3)B1—C611.648 (3)
C7—H70.9500C61—C621.396 (3)
C8—H80.9500C61—C661.404 (3)
C9—C101.383 (3)C62—C631.399 (3)
C9—C141.395 (3)C62—H620.9500
C10—C111.391 (3)C63—C641.378 (4)
C10—H100.9500C63—H630.9500
C11—C121.382 (4)C64—C651.382 (4)
C11—H110.9500C64—H640.9500
C12—C131.378 (4)C65—C661.393 (3)
C12—H120.9500C65—H650.9500
C13—C141.384 (3)C66—H660.9500
C13—H130.9500C67—C721.393 (3)
C14—H140.9500C67—C681.400 (3)
C15—C201.386 (3)C68—C691.393 (3)
C15—C161.393 (3)C68—H680.9500
C16—C171.382 (4)C69—C701.376 (4)
C16—H160.9500C69—H690.9500
C17—C181.376 (5)C70—C711.376 (4)
C17—H170.9500C70—H700.9500
C18—C191.381 (4)C71—C721.399 (3)
C18—H180.9500C71—H710.9500
C19—C201.392 (3)C72—H720.9500
C19—H190.9500C73—C781.395 (3)
C20—H200.9500C73—C741.409 (3)
C21—C261.387 (3)C74—C751.391 (3)
C21—C221.390 (3)C74—H740.9500
C22—C231.388 (4)C75—C761.384 (4)
C22—H220.9500C75—H750.9500
C23—C241.378 (5)C76—C771.386 (4)
C23—H230.9500C76—H760.9500
C24—C251.375 (5)C77—C781.395 (3)
C24—H240.9500C77—H770.9500
C25—C261.391 (4)C78—H780.9500
C25—H250.9500C79—C841.401 (3)
C26—H260.9500C79—C801.405 (3)
P3—C391.829 (2)C80—C811.388 (3)
P3—C311.832 (2)C80—H800.9500
P3—C331.833 (2)C81—C821.386 (4)
P4—C511.825 (2)C81—H810.9500
P4—C451.828 (2)C82—C831.378 (4)
P4—C321.839 (2)C82—H820.9500
C31—C321.528 (3)C83—C841.393 (3)
C31—H31A0.9900C83—H830.9500
C31—H31B0.9900C84—H840.9500
C32—H32A0.9900N2—C931.147 (6)
C32—H32B0.9900C93—C941.465 (7)
C33—C381.389 (3)C94—H94A0.9800
C33—C341.389 (3)C94—H94B0.9800
C34—C351.392 (3)C94—H94C0.9800
C34—H340.9500N3—C951.129 (6)
C35—C361.375 (4)C95—C961.408 (7)
C35—H350.9500C96—H96A0.9800
C36—C371.375 (4)C96—H96B0.9800
C36—H360.9500C96—H96C0.9800
N1—Mo1—Cl1178.20 (7)C38—C33—P3119.92 (17)
N1—Mo1—P494.16 (8)C34—C33—P3121.44 (17)
Cl1—Mo1—P484.136 (19)C33—C34—C35120.3 (2)
N1—Mo1—P391.98 (10)C33—C34—H34119.9
Cl1—Mo1—P388.31 (2)C35—C34—H34119.9
P4—Mo1—P379.981 (19)C36—C35—C34120.6 (2)
N1—Mo1—P292.57 (10)C36—C35—H35119.7
Cl1—Mo1—P287.16 (2)C34—C35—H35119.7
P4—Mo1—P2100.388 (19)C35—C36—C37119.6 (2)
P3—Mo1—P2175.395 (18)C35—C36—H36120.2
N1—Mo1—P196.28 (8)C37—C36—H36120.2
Cl1—Mo1—P185.432 (19)C36—C37—C38120.2 (2)
P4—Mo1—P1169.537 (17)C36—C37—H37119.9
P3—Mo1—P198.915 (18)C38—C37—H37119.9
P2—Mo1—P179.879 (18)C37—C38—C33120.9 (2)
C91—N1—C91'44.9 (3)C37—C38—H38119.6
C91—N1—Mo1162.0 (3)C33—C38—H38119.6
C91'—N1—Mo1152.9 (3)C44—C39—C40118.8 (2)
N1—C91—C92104.7 (3)C44—C39—P3118.66 (16)
N1—C91—H91A110.8C40—C39—P3122.54 (17)
C92—C91—H91A110.8C41—C40—C39120.1 (2)
N1—C91—H91B110.8C41—C40—H40119.9
C92—C91—H91B110.8C39—C40—H40119.9
H91A—C91—H91B108.9C42—C41—C40120.7 (2)
C91—C92—H92A109.5C42—C41—H41119.6
C91—C92—H92B109.5C40—C41—H41119.6
H92A—C92—H92B109.5C41—C42—C43119.6 (2)
C91—C92—H92C109.5C41—C42—H42120.2
H92A—C92—H92C109.5C43—C42—H42120.2
H92B—C92—H92C109.5C44—C43—C42119.9 (2)
N1—C91'—C92'102.3 (5)C44—C43—H43120.1
N1—C91'—H91C111.3C42—C43—H43120.1
C92'—C91'—H91C111.3C43—C44—C39120.9 (2)
N1—C91'—H91D111.3C43—C44—H44119.6
C92'—C91'—H91D111.3C39—C44—H44119.6
H91C—C91'—H91D109.2C50—C45—C46118.9 (2)
C91'—C92'—H92D109.5C50—C45—P4121.23 (17)
C91'—C92'—H92E109.5C46—C45—P4119.65 (17)
H92D—C92'—H92E109.5C47—C46—C45120.2 (2)
C91'—C92'—H92F109.5C47—C46—H46119.9
H92D—C92'—H92F109.5C45—C46—H46119.9
H92E—C92'—H92F109.5C46—C47—C48120.7 (2)
C3—P1—C9102.30 (10)C46—C47—H47119.6
C3—P1—C1102.27 (10)C48—C47—H47119.6
C9—P1—C1102.22 (11)C49—C48—C47119.5 (2)
C3—P1—Mo1122.78 (7)C49—C48—H48120.2
C9—P1—Mo1117.84 (7)C47—C48—H48120.2
C1—P1—Mo1106.64 (7)C48—C49—C50120.3 (2)
C15—P2—C2104.69 (11)C48—C49—H49119.9
C15—P2—C21100.46 (10)C50—C49—H49119.9
C2—P2—C21103.10 (10)C45—C50—C49120.4 (2)
C15—P2—Mo1120.59 (8)C45—C50—H50119.8
C2—P2—Mo1103.77 (8)C49—C50—H50119.8
C21—P2—Mo1121.91 (7)C52—C51—C56119.0 (2)
C2—C1—P1109.72 (15)C52—C51—P4118.34 (17)
C2—C1—H1A109.7C56—C51—P4122.5 (2)
P1—C1—H1A109.7C53—C52—C51120.5 (2)
C2—C1—H1B109.7C53—C52—H52119.7
P1—C1—H1B109.7C51—C52—H52119.7
H1A—C1—H1B108.2C54—C53—C52119.8 (3)
C1—C2—P2109.03 (15)C54—C53—H53120.1
C1—C2—H2A109.9C52—C53—H53120.1
P2—C2—H2A109.9C55—C54—C53120.2 (2)
C1—C2—H2B109.9C55—C54—H54119.9
P2—C2—H2B109.9C53—C54—H54119.9
H2A—C2—H2B108.3C54—C55—C56120.8 (3)
C8—C3—C4119.1 (2)C54—C55—H55119.6
C8—C3—P1120.41 (17)C56—C55—H55119.6
C4—C3—P1120.47 (16)C55—C56—C51119.6 (3)
C5—C4—C3120.1 (2)C55—C56—H56120.2
C5—C4—H4119.9C51—C56—H56120.2
C3—C4—H4119.9C79—B1—C67110.70 (17)
C6—C5—C4120.1 (2)C79—B1—C73111.75 (17)
C6—C5—H5120.0C67—B1—C73105.93 (16)
C4—C5—H5120.0C79—B1—C61105.59 (16)
C5—C6—C7120.3 (2)C67—B1—C61111.88 (17)
C5—C6—H6119.9C73—B1—C61111.11 (17)
C7—C6—H6119.9C62—C61—C66115.1 (2)
C6—C7—C8120.2 (2)C62—C61—B1124.99 (19)
C6—C7—H7119.9C66—C61—B1119.80 (19)
C8—C7—H7119.9C61—C62—C63122.6 (2)
C7—C8—C3120.2 (2)C61—C62—H62118.7
C7—C8—H8119.9C63—C62—H62118.7
C3—C8—H8119.9C64—C63—C62120.5 (2)
C10—C9—C14118.6 (2)C64—C63—H63119.8
C10—C9—P1120.90 (16)C62—C63—H63119.8
C14—C9—P1120.43 (17)C63—C64—C65118.8 (2)
C9—C10—C11120.5 (2)C63—C64—H64120.6
C9—C10—H10119.8C65—C64—H64120.6
C11—C10—H10119.8C64—C65—C66120.2 (2)
C12—C11—C10120.1 (2)C64—C65—H65119.9
C12—C11—H11119.9C66—C65—H65119.9
C10—C11—H11119.9C65—C66—C61122.8 (2)
C13—C12—C11119.9 (2)C65—C66—H66118.6
C13—C12—H12120.0C61—C66—H66118.6
C11—C12—H12120.0C72—C67—C68115.5 (2)
C12—C13—C14120.0 (2)C72—C67—B1125.79 (19)
C12—C13—H13120.0C68—C67—B1118.65 (19)
C14—C13—H13120.0C69—C68—C67122.8 (2)
C13—C14—C9120.8 (2)C69—C68—H68118.6
C13—C14—H14119.6C67—C68—H68118.6
C9—C14—H14119.6C70—C69—C68119.7 (2)
C20—C15—C16118.9 (2)C70—C69—H69120.2
C20—C15—P2119.25 (17)C68—C69—H69120.2
C16—C15—P2121.66 (19)C69—C70—C71119.5 (2)
C17—C16—C15119.9 (3)C69—C70—H70120.2
C17—C16—H16120.1C71—C70—H70120.2
C15—C16—H16120.1C70—C71—C72120.2 (2)
C18—C17—C16120.7 (3)C70—C71—H71119.9
C18—C17—H17119.6C72—C71—H71119.9
C16—C17—H17119.6C67—C72—C71122.2 (2)
C17—C18—C19120.2 (3)C67—C72—H72118.9
C17—C18—H18119.9C71—C72—H72118.9
C19—C18—H18119.9C78—C73—C74115.3 (2)
C18—C19—C20119.2 (3)C78—C73—B1124.84 (19)
C18—C19—H19120.4C74—C73—B1119.84 (19)
C20—C19—H19120.4C75—C74—C73122.8 (2)
C15—C20—C19121.0 (2)C75—C74—H74118.6
C15—C20—H20119.5C73—C74—H74118.6
C19—C20—H20119.5C76—C75—C74120.1 (2)
C26—C21—C22119.1 (2)C76—C75—H75119.9
C26—C21—P2121.87 (18)C74—C75—H75120.0
C22—C21—P2118.99 (18)C75—C76—C77118.8 (2)
C23—C22—C21120.7 (3)C75—C76—H76120.6
C23—C22—H22119.7C77—C76—H76120.6
C21—C22—H22119.7C76—C77—C78120.4 (2)
C24—C23—C22119.7 (3)C76—C77—H77119.8
C24—C23—H23120.1C78—C77—H77119.8
C22—C23—H23120.1C73—C78—C77122.5 (2)
C25—C24—C23120.0 (3)C73—C78—H78118.7
C25—C24—H24120.0C77—C78—H78118.7
C23—C24—H24120.0C84—C79—C80115.0 (2)
C24—C25—C26120.7 (3)C84—C79—B1125.00 (18)
C24—C25—H25119.7C80—C79—B1119.97 (18)
C26—C25—H25119.7C81—C80—C79122.7 (2)
C21—C26—C25119.7 (3)C81—C80—H80118.7
C21—C26—H26120.1C79—C80—H80118.7
C25—C26—H26120.1C82—C81—C80120.3 (2)
C39—P3—C31104.53 (10)C82—C81—H81119.8
C39—P3—C33101.42 (10)C80—C81—H81119.8
C31—P3—C33103.45 (11)C83—C82—C81118.9 (2)
C39—P3—Mo1118.30 (7)C83—C82—H82120.5
C31—P3—Mo1105.12 (8)C81—C82—H82120.5
C33—P3—Mo1121.96 (7)C82—C83—C84120.1 (2)
C51—P4—C45102.66 (10)C82—C83—H83120.0
C51—P4—C32104.39 (11)C84—C83—H83120.0
C45—P4—C32103.92 (10)C83—C84—C79123.0 (2)
C51—P4—Mo1114.87 (7)C83—C84—H84118.5
C45—P4—Mo1122.99 (7)C79—C84—H84118.5
C32—P4—Mo1106.16 (8)N2—C93—C94178.7 (6)
C32—C31—P3108.33 (15)C93—C94—H94A109.5
C32—C31—H31A110.0C93—C94—H94B109.5
P3—C31—H31A110.0H94A—C94—H94B109.5
C32—C31—H31B110.0C93—C94—H94C109.5
P3—C31—H31B110.0H94A—C94—H94C109.5
H31A—C31—H31B108.4H94B—C94—H94C109.5
C31—C32—P4108.95 (16)N3—C95—C96173.9 (7)
C31—C32—H32A109.9C95—C96—H96A109.5
P4—C32—H32A109.9C95—C96—H96B109.5
C31—C32—H32B109.9H96A—C96—H96B109.5
P4—C32—H32B109.9C95—C96—H96C109.5
H32A—C32—H32B108.3H96A—C96—H96C109.5
C38—C33—C34118.4 (2)H96B—C96—H96C109.5
Table 1
Selected geometric parameters (Å, °) top
Mo1—N11.732 (2)Mo1—P32.5342 (6)
Mo1—Cl12.4413 (5)Mo1—P22.5447 (6)
Mo1—P42.5308 (6)Mo1—P12.5503 (6)
N1—Mo1—Cl1178.20 (7)P4—Mo1—P2100.388 (19)
N1—Mo1—P494.16 (8)P3—Mo1—P2175.395 (18)
Cl1—Mo1—P484.136 (19)N1—Mo1—P196.28 (8)
N1—Mo1—P391.98 (10)Cl1—Mo1—P185.432 (19)
Cl1—Mo1—P388.31 (2)P4—Mo1—P1169.537 (17)
P4—Mo1—P379.981 (19)P3—Mo1—P198.915 (18)
N1—Mo1—P292.57 (10)P2—Mo1—P179.879 (18)
Cl1—Mo1—P287.16 (2)
Acknowledgements top

This work is supported by the state of Schleswig-Holstein and the DFG (project No. TU58/12–2).

references
References top

Alias, Y., Ibrahim, S. K., Queiros, M. A., Fonseca, A., Talarmin, J., Volant, F. & Pickett, C. J. (1997). J. Chem. Soc. Dalton Trans. pp. 4807–4815.

Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389–397.

Bruker (1998). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Chatt, J. & Dilworth, J. R. (1977). J. Indian Chem. Soc. 54, 13–18.

George, T. A. & Noble, M. E. (1978). Inorg. Chem. 17, 1678–1679.

Mersmann, K., Hauser, A., Lehnert, N. & Tuczek, F. (2006). Inorg. Chem. 45, 5044–5056.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Stoe & Cie (1998). X-SHAPE (Version 1.03) and IPDS Program Package (Version 2.89). Stoe & Cie, Darmstadt, Germany.