trans-Di-μ-acetato-[μ-N,N-bis­(diphenyl­phosphino)aniline]bis­[chlorido­molybdenum(II)](Mo—Mo)–dichloro­methane–tetra­hydro­furan (1/0.3/1.7)

Hapke, M.; Wöhl, A.; Peitz, S.; Spannenberg, A.; Rosenthal, U.

doi:10.1107/S1600536809007016

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page m357

doi:10.1107/S1600536809007016

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trans-Di-μ-acetato-[μ-N,N-bis(diphenylphosphino)aniline]bis[chloridomolybdenum(II)](Mo—Mo)–dichloromethane–tetrahydrofuran (1/0.3/1.7)

Marko Hapke,^a ^* Anina Wöhl,^b Stephan Peitz,^a Anke Spannenberg ^a and Uwe Rosenthal ^a

^aLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany, and ^bLinde AG, Linde Engineering Division, Dr.-Carl-von-Linde-Strasse 6-14, 82049 Pullach, Germany
^*Correspondence e-mail: marko.hapke@catalysis.de

(Received 24 February 2009; accepted 25 February 2009; online 6 March 2009)

The molecular structure of the title compound, [Mo₂(CH₃COO)₂Cl₂(C₃₀H₂₅NP₂)]·0.3CH₂Cl₂·1.7C₄H₈O, features an Mo—Mo dumbbell bridged by two acetate groups which are trans to each other. Perpendicular to the plane spanned by the acetate groups, the Ph₂PN(Ph)PPh₂ ligand bridges both Mo atoms, having a P—N—P angle of 114.09 (19)°. In a trans position to the PNP ligand are two Cl atoms, one on each molybdenum centre. The Mo—Mo bond distance is 2.1161 (9) Å, within the range known for Mo—Mo quadruple bonds. The Mo complex is located on a crystallographic twofold rotation axis which runs through the N—C bond of the ligand. The site occupation factors of the disordered solvent molecules were fixed to 0.15 for dichloromethane and 0.85 for tetrahydrofuran.

Related literature

For derivatives of the title compound, mostly with monodentate phosphane ligands, see Green et al. (1982 ). For the synthesis and structural evaluation of dimolybdenum species containing two trans-standing PNP ligands, see: Cotton et al. (1996 , 2006 ), Arnold et al. (1996 ), Wu et al. (1997 ). For the catalytic properties of the PNP ligand systems with middle and late transition metals, see: Wöhl et al. (2009 ). For the free ligand, see Fei et al. (2003 ).

Experimental

Crystal data

[Mo₂(C₂H₃O₂)₂Cl₂(C₃₀H₂₅NP₂)]·0.3CH₂Cl₂·1.7C₄H₈O
M_r = 990.37
Monoclinic, C 2/c
a = 15.769 (3) Å
b = 13.913 (3) Å
c = 20.108 (4) Å
β = 107.32 (3)°
V = 4211.3 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 200 K
0.20 × 0.15 × 0.10 mm

Data collection

Stoe IPDS-II diffractometer
Absorption correction: none
33618 measured reflections
4834 independent reflections
3695 reflections with I > 2σ(I)
R_int = 0.076

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.076
S = 0.90
4834 reflections
263 parameters
22 restraints
H-atom parameters constrained
Δρ_max = 0.99 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2005 ); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2005); program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809007016/bt2886sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007016/bt2886Isup2.hkl

checkCIF report

Comment top

In the chemistry of molecular compounds containing two metal atoms sharing a metal-metal-bond, chelating ligands have found wide-spread use (Cotton et al. 2006). Ligands containing the "PNP" moiety as the structural motif of the coordination unit have been used in a number of cases for the bridging of the metal-metal unit. In all cases, the Mo—Mo bond was symmetrically bridged by two PNP units, which are arranged in trans-position. In most cases the common precursor for the preparation of the diphosphine complexes was Mo(OAc)₄, from which by addition of TMSCl two acetato groups were removed and the free coordination sites occupied by the PNP ligands (Arnold et al. 1996, Wu et al. 1997 and Cotton et al. 1996). We became interested into PNP complexes during our studies on the selective oligomerization of ethene via transition metal-catalyzed tri- or tetramerization, yielding 1-hexene or 1-octene (Wöhl et al. 2009). Our initial experimental work was focusing on a chromium-based catalyst system (CrCl₃(THF)₃/Ph₂PN(iPr)PPh₂/MAO) where we also investigated the use of dinuclear chromium complexes. However, for reasons of comparison we wanted to examine comparable molybdenum complexes that contain the PNP ligand moiety. During these experiments we discovered, that by the procedure described below we were able to isolate a molybdenum complex, that contains only one PNP ligand, Ph₂PN(Ph)PPh₂, to bridge the two Mo centres, which has to the best of our knowledge not been described yet for PNP ligands. The molecular structure features a Mo—Mo unit which is bridged by two acetato groups which are trans to each other (Fig. 1). Perpendicular to the plane spanned by the acetato groups the Ph₂PN(Ph)PPh₂ ligand is bridging both Mo atoms, having a P—N—P angle of 114.09 (19)°, nearly the same as found in the free ligand (Fei et al. 2003). In trans-position to the PNP ligand are two chlorine atoms located, one at each molybdenum center. The Mo—Mo bond distance is 2.1161 (9) Å and within the range known for Mo—Mo quadruple bonds. The asymmetric unit of the title compound contains a half molecule of [(Ph₂PN(Ph)PPh₂)(OAC)₂Cl₂Mo₂] besides THF and CH₂Cl₂ as lattice solvent with occupancies 0.85:0.15.

Related literature top

For derivatives of the title compound, mostly with monodentate phosphane ligands, see Green et al. (1982). For the synthesis and structural evaluation of dimolybdenum species containing two trans-standing PNP ligands, see: Cotton et al. (1996, 2006), Arnold et al. (1996), Wu et al. (1997) . For the catalytic properties of the PNP ligand systems with middle and late transition metals, see: Wöhl et al. (2009). For the free ligand, see Fei et al. (2003).

Experimental top

Molybdenum(II)-acetate (200 mg, 0.467 mmol) and N,N-bis(diphenylphosphino)-phenylamine (2.5 equiv., 540 mg, 1.17 mmol) were weighted into a Schlenk flask and 25–30 ml dry THF added. To this green-yellow suspension trimethylsilylchloride (15 equiv., 0.9 ml, 7 mmol) was added via syringe and the reaction mixture stirred at room temperature. The colour of the solution was changing to yellow-orange, red and after a couple of minutes she became red-violett. After 10 minutes a red-violett precipitate started to appear while stirring was continued. After standing without stirring over night the reaction mixture was filtrated under argon and the violet solid product washed with 20 ml portions of THF and n-hexane twice each. The violet solid was dried in high vacuo giving a fine powder (328 mg). The compound was characterized by NMR (¹H, ¹³C and ³¹P NMR; solvent: CDCl₃). Suitable crystals for X-ray analysis have been grown by diffusion of THF into a solution of the complex in CH₂Cl₂.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-RED (Stoe & Cie, 2005); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound showing the atom-labelling scheme (operator for generating equivalent atoms: -x + 2, y, -z + 3/2). Anisotropic displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms and solvent molecules are omitted for clarity.

trans-Di-µ-acetato-[µ-N,N- bis(diphenylphosphino)aniline]bis[chloridomolybdenum(II)](Mo—Mo)– dichloromethane–tetrahydrofuran (1/0.3/1.7) top

Crystal data top

[Mo₂(C₂H₃O₂)₂Cl₂(C₃₀H₂₅NP₂)]·0.3CH₂Cl₂·1.7C₄H₈O	F(000) = 2010
M_r = 990.37	D_x = 1.562 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 20698 reflections
a = 15.769 (3) Å	θ = 1.9–29.7°
b = 13.913 (3) Å	µ = 0.88 mm⁻¹
c = 20.108 (4) Å	T = 200 K
β = 107.32 (3)°	Prism, red
V = 4211.3 (15) Å³	0.20 × 0.15 × 0.10 mm
Z = 4

Data collection top

Stoe IPDS-II diffractometer	3695 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.076
Graphite monochromator	θ_max = 27.5°, θ_min = 2.0°
ω scans	h = −20→20
33618 measured reflections	k = −18→18
4834 independent reflections	l = −26→26

Refinement top

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H-atom parameters constrained
S = 0.90	w = 1/[σ²(F_o²) + (0.0436P)²] where P = (F_o² + 2F_c²)/3
4834 reflections	(Δ/σ)_max = 0.001
263 parameters	Δρ_max = 0.99 e Å⁻³
22 restraints	Δρ_min = −0.72 e Å⁻³

Crystal data top

[Mo₂(C₂H₃O₂)₂Cl₂(C₃₀H₂₅NP₂)]·0.3CH₂Cl₂·1.7C₄H₈O	V = 4211.3 (15) Å³
M_r = 990.37	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 15.769 (3) Å	µ = 0.88 mm⁻¹
b = 13.913 (3) Å	T = 200 K
c = 20.108 (4) Å	0.20 × 0.15 × 0.10 mm
β = 107.32 (3)°

Data collection top

Stoe IPDS-II diffractometer	3695 reflections with I > 2σ(I)
33618 measured reflections	R_int = 0.076
4834 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	22 restraints
wR(F²) = 0.076	H-atom parameters constrained
S = 0.90	Δρ_max = 0.99 e Å⁻³
4834 reflections	Δρ_min = −0.72 e Å⁻³
263 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C23	0.3316 (18)	0.371 (2)	−0.0151 (15)	0.038 (6)*	0.15
H23A	0.3312	0.3382	0.0286	0.046*	0.15
H23B	0.3456	0.3216	−0.0458	0.046*	0.15
Cl2	0.4164 (8)	0.4554 (9)	0.0049 (6)	0.094 (3)*	0.15
Cl3	0.1952 (10)	0.4261 (14)	−0.0668 (7)	0.075 (3)*	0.15
C1	0.9245 (2)	0.6337 (2)	0.60553 (15)	0.0224 (6)
C2	0.8729 (2)	0.7137 (2)	0.57764 (17)	0.0314 (7)
H2	0.8335	0.7400	0.6005	0.038*
C3	0.8792 (3)	0.7547 (3)	0.51670 (18)	0.0387 (8)
H3	0.8430	0.8084	0.4973	0.046*
C4	0.9374 (3)	0.7184 (3)	0.48376 (18)	0.0402 (8)
H4	0.9416	0.7475	0.4421	0.048*
C5	0.9894 (3)	0.6402 (3)	0.51100 (17)	0.0359 (8)
H5	1.0299	0.6156	0.4884	0.043*
C6	0.9827 (2)	0.5971 (2)	0.57136 (15)	0.0288 (6)
H6	1.0179	0.5424	0.5896	0.035*
C7	0.81890 (18)	0.6061 (2)	0.69921 (15)	0.0222 (5)
C8	0.7406 (2)	0.5965 (2)	0.64439 (17)	0.0289 (6)
H8	0.7430	0.5795	0.5992	0.035*
C9	0.6595 (2)	0.6117 (2)	0.6561 (2)	0.0353 (7)
H9	0.6063	0.6044	0.6187	0.042*
C10	0.6545 (2)	0.6371 (2)	0.7204 (2)	0.0366 (8)
H10	0.5984	0.6492	0.7272	0.044*
C11	0.7316 (2)	0.6452 (2)	0.7757 (2)	0.0365 (8)
H11	0.7284	0.6623	0.8206	0.044*
C12	0.8134 (2)	0.6282 (2)	0.76538 (17)	0.0282 (7)
H12	0.8660	0.6317	0.8037	0.034*
C13	1.0000	0.7507 (3)	0.7500	0.0267 (9)
C14	0.9682 (2)	0.8011 (2)	0.7974 (2)	0.0369 (8)
H14	0.9462	0.7675	0.8299	0.044*
C15	0.9689 (3)	0.9006 (3)	0.7968 (3)	0.0540 (10)
H15	0.9475	0.9349	0.8294	0.065*
C16	1.0000	0.9505 (4)	0.7500	0.0633 (19)
H16	1.0000	1.0187	0.7500	0.076*
C17	0.85381 (19)	0.3927 (2)	0.79476 (16)	0.0246 (6)
C18	0.7734 (2)	0.3832 (2)	0.81938 (19)	0.0344 (8)
H18A	0.7293	0.4316	0.7963	0.052*
H18B	0.7904	0.3928	0.8699	0.052*
H18C	0.7479	0.3188	0.8080	0.052*
Cl1	0.93542 (6)	0.23863 (6)	0.65324 (4)	0.03252 (18)
Mo1	0.958490 (16)	0.400753 (17)	0.697846 (12)	0.01851 (7)
N1	1.0000	0.6457 (2)	0.7500	0.0215 (7)
O1	0.84401 (13)	0.38946 (15)	0.72997 (11)	0.0243 (4)
O2	1.07046 (13)	0.40319 (15)	0.66069 (10)	0.0247 (4)
P1	0.92644 (5)	0.57906 (5)	0.68785 (4)	0.01836 (15)
O3	0.2246 (4)	0.4448 (4)	0.0103 (3)	0.0979 (17)	0.85
C19	0.1975 (9)	0.4284 (11)	−0.0537 (6)	0.112 (2)	0.85
H19A	0.1902	0.4890	−0.0807	0.134*	0.85
H19B	0.1401	0.3938	−0.0664	0.134*	0.85
C20	0.2727 (5)	0.3642 (6)	−0.0674 (5)	0.1111 (19)	0.85
H20A	0.2642	0.2953	−0.0590	0.133*	0.85
H20B	0.2768	0.3727	−0.1153	0.133*	0.85
C21	0.3560 (7)	0.4072 (6)	−0.0112 (4)	0.1117 (19)	0.85
H21A	0.3885	0.4538	−0.0317	0.134*	0.85
H21B	0.3971	0.3564	0.0139	0.134*	0.85
C22	0.3065 (6)	0.4577 (6)	0.0368 (5)	0.1097 (19)	0.85
H22A	0.3263	0.4299	0.0842	0.132*	0.85
H22B	0.3200	0.5273	0.0402	0.132*	0.85

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0244 (15)	0.0238 (13)	0.0181 (13)	−0.0015 (11)	0.0048 (11)	0.0007 (11)
C2	0.0309 (17)	0.0338 (17)	0.0303 (16)	0.0057 (13)	0.0105 (14)	0.0055 (13)
C3	0.043 (2)	0.0373 (18)	0.0342 (18)	0.0079 (16)	0.0095 (16)	0.0154 (15)
C4	0.056 (2)	0.0410 (19)	0.0262 (16)	−0.0023 (17)	0.0164 (16)	0.0088 (15)
C5	0.049 (2)	0.0379 (18)	0.0269 (16)	0.0041 (15)	0.0212 (16)	0.0022 (14)
C6	0.0342 (16)	0.0287 (14)	0.0244 (14)	0.0008 (14)	0.0101 (12)	0.0002 (13)
C7	0.0200 (13)	0.0201 (13)	0.0274 (14)	0.0030 (11)	0.0084 (11)	0.0029 (12)
C8	0.0263 (15)	0.0279 (15)	0.0312 (15)	0.0001 (13)	0.0065 (12)	0.0036 (14)
C9	0.0209 (15)	0.0302 (17)	0.051 (2)	−0.0003 (13)	0.0051 (14)	0.0109 (15)
C10	0.0255 (17)	0.0290 (16)	0.062 (2)	0.0052 (13)	0.0224 (17)	0.0091 (16)
C11	0.038 (2)	0.0346 (18)	0.046 (2)	0.0028 (15)	0.0255 (17)	0.0008 (15)
C12	0.0257 (16)	0.0307 (16)	0.0295 (16)	0.0012 (12)	0.0102 (13)	−0.0018 (12)
C13	0.021 (2)	0.022 (2)	0.033 (2)	0.000	−0.0004 (17)	0.000
C14	0.0351 (19)	0.0263 (16)	0.047 (2)	0.0040 (14)	0.0081 (15)	−0.0044 (15)
C15	0.050 (2)	0.0286 (18)	0.082 (3)	0.0070 (18)	0.018 (2)	−0.013 (2)
C16	0.053 (4)	0.018 (2)	0.115 (6)	0.000	0.020 (4)	0.000
C17	0.0256 (15)	0.0190 (13)	0.0329 (15)	0.0001 (12)	0.0142 (12)	−0.0007 (12)
C18	0.0268 (16)	0.0380 (19)	0.0456 (19)	−0.0021 (13)	0.0218 (15)	−0.0013 (15)
Cl1	0.0342 (4)	0.0274 (4)	0.0401 (4)	−0.0066 (3)	0.0173 (3)	−0.0114 (3)
Mo1	0.01940 (12)	0.01871 (11)	0.01876 (11)	0.00004 (10)	0.00775 (8)	−0.00079 (10)
N1	0.0215 (17)	0.0169 (16)	0.0244 (17)	0.000	0.0043 (14)	0.000
O1	0.0209 (10)	0.0244 (10)	0.0297 (11)	−0.0014 (8)	0.0108 (8)	−0.0007 (9)
O2	0.0267 (11)	0.0268 (10)	0.0242 (10)	0.0012 (9)	0.0133 (8)	0.0008 (9)
P1	0.0183 (3)	0.0193 (3)	0.0178 (3)	0.0008 (2)	0.0057 (3)	0.0006 (3)
O3	0.075 (3)	0.140 (5)	0.076 (3)	0.007 (3)	0.018 (3)	0.049 (3)
C19	0.110 (4)	0.079 (4)	0.124 (4)	0.013 (3)	−0.001 (4)	0.020 (4)
C20	0.112 (4)	0.078 (3)	0.119 (4)	0.016 (3)	−0.004 (3)	0.020 (3)
C21	0.115 (4)	0.080 (3)	0.113 (4)	0.019 (3)	−0.005 (3)	0.024 (3)
C22	0.118 (4)	0.080 (3)	0.109 (4)	0.020 (3)	−0.001 (3)	0.025 (3)

Geometric parameters (Å, º) top

C23—Cl2	1.74 (3)	C14—H14	0.9500
C23—Cl3	2.23 (3)	C15—C16	1.372 (5)
C23—H23A	0.9900	C15—H15	0.9500
C23—H23B	0.9900	C16—C15ⁱ	1.372 (5)
C1—C2	1.395 (4)	C16—H16	0.9500
C1—C6	1.396 (4)	C17—O1	1.266 (4)
C1—P1	1.813 (3)	C17—O2ⁱ	1.270 (4)
C2—C3	1.382 (5)	C17—C18	1.498 (4)
C2—H2	0.9500	C18—H18A	0.9800
C3—C4	1.378 (5)	C18—H18B	0.9800
C3—H3	0.9500	C18—H18C	0.9800
C4—C5	1.375 (5)	Cl1—Mo1	2.4146 (9)
C4—H4	0.9500	Mo1—O1	2.096 (2)
C5—C6	1.385 (4)	Mo1—O2	2.1124 (19)
C5—H5	0.9500	Mo1—Mo1ⁱ	2.1161 (9)
C6—H6	0.9500	Mo1—P1	2.5278 (9)
C7—C12	1.393 (4)	N1—P1	1.704 (2)
C7—C8	1.395 (4)	N1—P1ⁱ	1.704 (2)
C7—P1	1.817 (3)	O2—C17ⁱ	1.270 (4)
C8—C9	1.384 (4)	O3—C19	1.251 (8)
C8—H8	0.9500	O3—C22	1.255 (8)
C9—C10	1.365 (5)	C19—C20	1.573 (8)
C9—H9	0.9500	C19—H19A	0.9900
C10—C11	1.386 (6)	C19—H19B	0.9900
C10—H10	0.9500	C20—C21	1.573 (8)
C11—C12	1.386 (4)	C20—H20A	0.9900
C11—H11	0.9500	C20—H20B	0.9900
C12—H12	0.9500	C21—C22	1.575 (8)
C13—C14ⁱ	1.390 (4)	C21—H21A	0.9900
C13—C14	1.390 (4)	C21—H21B	0.9900
C13—N1	1.461 (5)	C22—H22A	0.9900
C14—C15	1.384 (5)	C22—H22B	0.9900

Cl2—C23—Cl3	116.3 (16)	O1—C17—C18	118.7 (3)
Cl2—C23—H23A	108.2	O2ⁱ—C17—C18	119.2 (3)
Cl3—C23—H23A	108.2	C17—C18—H18A	109.5
Cl2—C23—H23B	108.2	C17—C18—H18B	109.5
Cl3—C23—H23B	108.2	H18A—C18—H18B	109.5
H23A—C23—H23B	107.4	C17—C18—H18C	109.5
C2—C1—C6	118.9 (3)	H18A—C18—H18C	109.5
C2—C1—P1	123.4 (2)	H18B—C18—H18C	109.5
C6—C1—P1	117.5 (2)	O1—Mo1—O2	175.75 (8)
C3—C2—C1	120.0 (3)	O1—Mo1—Mo1ⁱ	91.72 (6)
C3—C2—H2	120.0	O2—Mo1—Mo1ⁱ	90.85 (6)
C1—C2—H2	120.0	O1—Mo1—Cl1	89.78 (6)
C4—C3—C2	120.6 (3)	O2—Mo1—Cl1	86.16 (6)
C4—C3—H3	119.7	Mo1ⁱ—Mo1—Cl1	110.39 (2)
C2—C3—H3	119.7	O1—Mo1—P1	85.87 (6)
C5—C4—C3	120.2 (3)	O2—Mo1—P1	97.15 (6)
C5—C4—H4	119.9	Mo1ⁱ—Mo1—P1	97.405 (18)
C3—C4—H4	119.9	Cl1—Mo1—P1	151.98 (3)
C4—C5—C6	119.9 (3)	C13—N1—P1	122.96 (10)
C4—C5—H5	120.0	C13—N1—P1ⁱ	122.95 (10)
C6—C5—H5	120.0	P1—N1—P1ⁱ	114.09 (19)
C5—C6—C1	120.5 (3)	C17—O1—Mo1	117.50 (19)
C5—C6—H6	119.8	C17ⁱ—O2—Mo1	117.26 (18)
C1—C6—H6	119.8	N1—P1—C1	105.33 (12)
C12—C7—C8	118.9 (3)	N1—P1—C7	104.61 (11)
C12—C7—P1	119.5 (2)	C1—P1—C7	105.38 (14)
C8—C7—P1	121.4 (2)	N1—P1—Mo1	113.53 (10)
C9—C8—C7	119.8 (3)	C1—P1—Mo1	115.62 (10)
C9—C8—H8	120.1	C7—P1—Mo1	111.43 (10)
C7—C8—H8	120.1	C19—O3—C22	117.0 (9)
C10—C9—C8	121.1 (3)	O3—C19—C20	103.9 (8)
C10—C9—H9	119.4	O3—C19—H19A	111.0
C8—C9—H9	119.4	C20—C19—H19A	111.0
C9—C10—C11	119.8 (3)	O3—C19—H19B	111.0
C9—C10—H10	120.1	C20—C19—H19B	111.0
C11—C10—H10	120.1	H19A—C19—H19B	109.0
C12—C11—C10	120.0 (3)	C21—C20—C19	99.7 (8)
C12—C11—H11	120.0	C21—C20—H20A	111.8
C10—C11—H11	120.0	C19—C20—H20A	111.8
C11—C12—C7	120.4 (3)	C21—C20—H20B	111.8
C11—C12—H12	119.8	C19—C20—H20B	111.8
C7—C12—H12	119.8	H20A—C20—H20B	109.5
C14ⁱ—C13—C14	119.4 (4)	C20—C21—C22	98.6 (7)
C14ⁱ—C13—N1	120.3 (2)	C20—C21—H21A	112.0
C14—C13—N1	120.3 (2)	C22—C21—H21A	112.0
C15—C14—C13	119.6 (4)	C20—C21—H21B	112.0
C15—C14—H14	120.2	C22—C21—H21B	112.0
C13—C14—H14	120.2	H21A—C21—H21B	109.7
C16—C15—C14	121.1 (4)	O3—C22—C21	108.2 (7)
C16—C15—H15	119.5	O3—C22—H22A	110.1
C14—C15—H15	119.5	C21—C22—H22A	110.1
C15ⁱ—C16—C15	119.2 (5)	O3—C22—H22B	110.1
C15ⁱ—C16—H16	120.4	C21—C22—H22B	110.1
C15—C16—H16	120.4	H22A—C22—H22B	108.4
O1—C17—O2ⁱ	122.1 (3)

C6—C1—C2—C3	0.8 (5)	C13—N1—P1—C7	−64.90 (10)
P1—C1—C2—C3	176.0 (3)	P1ⁱ—N1—P1—C7	115.09 (10)
C1—C2—C3—C4	−1.3 (6)	C13—N1—P1—Mo1	173.409 (15)
C2—C3—C4—C5	0.6 (6)	P1ⁱ—N1—P1—Mo1	−6.593 (15)
C3—C4—C5—C6	0.6 (6)	C2—C1—P1—N1	−83.1 (3)
C4—C5—C6—C1	−1.1 (5)	C6—C1—P1—N1	92.2 (3)
C2—C1—C6—C5	0.4 (5)	C2—C1—P1—C7	27.2 (3)
P1—C1—C6—C5	−175.1 (3)	C6—C1—P1—C7	−157.5 (2)
C12—C7—C8—C9	1.9 (5)	C2—C1—P1—Mo1	150.7 (2)
P1—C7—C8—C9	175.9 (2)	C6—C1—P1—Mo1	−34.0 (3)
C7—C8—C9—C10	0.6 (5)	C12—C7—P1—N1	−31.0 (3)
C8—C9—C10—C11	−1.8 (5)	C8—C7—P1—N1	155.1 (2)
C9—C10—C11—C12	0.5 (5)	C12—C7—P1—C1	−141.8 (2)
C10—C11—C12—C7	2.1 (5)	C8—C7—P1—C1	44.3 (3)
C8—C7—C12—C11	−3.3 (5)	C12—C7—P1—Mo1	92.1 (2)
P1—C7—C12—C11	−177.3 (2)	C8—C7—P1—Mo1	−81.8 (3)
C14ⁱ—C13—C14—C15	−0.2 (3)	O1—Mo1—P1—N1	109.43 (7)
N1—C13—C14—C15	179.8 (3)	O2—Mo1—P1—N1	−73.57 (7)
C13—C14—C15—C16	0.4 (6)	Mo1ⁱ—Mo1—P1—N1	18.23 (4)
C14—C15—C16—C15ⁱ	−0.2 (3)	Cl1—Mo1—P1—N1	−168.85 (5)
C14ⁱ—C13—N1—P1	−74.23 (17)	O1—Mo1—P1—C1	−128.66 (13)
C14—C13—N1—P1	105.77 (17)	O2—Mo1—P1—C1	48.34 (13)
C14ⁱ—C13—N1—P1ⁱ	105.77 (17)	Mo1ⁱ—Mo1—P1—C1	140.14 (11)
C14—C13—N1—P1ⁱ	−74.23 (17)	Cl1—Mo1—P1—C1	−46.94 (13)
O2ⁱ—C17—O1—Mo1	0.6 (4)	O1—Mo1—P1—C7	−8.37 (12)
C18—C17—O1—Mo1	−179.0 (2)	O2—Mo1—P1—C7	168.62 (11)
Mo1ⁱ—Mo1—O1—C17	4.7 (2)	Mo1ⁱ—Mo1—P1—C7	−99.57 (11)
Cl1—Mo1—O1—C17	115.1 (2)	Cl1—Mo1—P1—C7	73.34 (12)
P1—Mo1—O1—C17	−92.6 (2)	C22—O3—C19—C20	37.3 (15)
Mo1ⁱ—Mo1—O2—C17ⁱ	7.9 (2)	O3—C19—C20—C21	−32.7 (13)
Cl1—Mo1—O2—C17ⁱ	−102.4 (2)	C19—C20—C21—C22	18.7 (10)
P1—Mo1—O2—C17ⁱ	105.5 (2)	C19—O3—C22—C21	−23.9 (12)
C13—N1—P1—C1	45.93 (11)	C20—C21—C22—O3	−1.3 (9)
P1ⁱ—N1—P1—C1	−134.07 (11)

Symmetry code: (i) −x+2, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Mo₂(C₂H₃O₂)₂Cl₂(C₃₀H₂₅NP₂)]·0.3CH₂Cl₂·1.7C₄H₈O
M_r	990.37
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	15.769 (3), 13.913 (3), 20.108 (4)
β (°)	107.32 (3)
V (Å³)	4211.3 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.88
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Stoe IPDS-II diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	33618, 4834, 3695
R_int	0.076
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.076, 0.90
No. of reflections	4834
No. of parameters	263
No. of restraints	22
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.99, −0.72

Computer programs: X-AREA (Stoe & Cie, 2005), X-RED (Stoe & Cie, 2005), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the Leibniz-Institut für Katalyse e. V. an der Universität Rostock.

References

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