{N,N-Bis­[(diphenyl­phosphino)meth­yl]­aniline}tetra­carbonyl­molybdenum(0)

Sanchez Ballester, N.M.; Elsegood, M.R.J.; Smith, M.B.; Brown, G.M.

doi:10.1107/S1600536807006101

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 63| Part 3| March 2007| Pages m719-m721

https://doi.org/10.1107/S1600536807006101

{N,N-Bis[(diphenylphosphino)methyl]aniline}tetracarbonylmolybdenum(0)

Noelia M. Sanchez Ballester,^a Mark R. J. Elsegood,^a ^* Martin B. Smith ^a and Gavin M. Brown ^a

^aChemistry Department, Loughborough University, Leicestershire LE11 3TU, England
^*Correspondence e-mail: m.r.j.elsegood@lboro.ac.uk

(Received 30 January 2007; accepted 5 February 2007; online 14 February 2007)

The title compound, [Mo(CO)₄{Ph₂PCH₂N(Ph)CH₂PPh₂}] or [Mo(C₃₂H₂₉NP₂)(CO)₄], is a tetracarbonylmolybdenum(0) complex of a chelating ditertiary phosphine with a P—C—N—C—P backbone. The geometry at the Mo centre is octahedral, while both diphenylphosphino centres coordinate in a cis fashion.

Comment

Organometallic compounds containing the group 6 metals Mo, Cr and W have been extensively studied over the past few decades for a variety of substitution reactions, one example being with phosphine ligands. Ligand substitution reactions have been accomplished in several ways, including under thermal or photolysis conditions, or displacement of labile precursors [e.g. piperidine, norbornadiene (nbd), THF, CH₃CN] from appropriate Mo starting materials. Thus, neutral, octahedral compounds of the general type Mo(CO)_n(PR₃)_6-n (n = 3–5) can be obtained using monodentate tertiary phosphines. Of these, one particular class of compound of interest are the tetracarbonylmolybdenum(0) diphosphine complexes Mo(CO)₄(P—P) [P—P is a symmetric (Bookham et al., 1993 ; Fernández et al., 1996 ; Gaw et al., 2000 , 2002 ; Powell et al., 1992 ) or non-symmetric ligand (Affandi et al., 1989 )]. Recent interest has also focused on tetracarbonylmolybdenum(0) complexes with bidentate ligands bearing group 15 (Heinze & Jacob, 2002 ) or group 16 donor centres (Heuer et al., 2002 ). We describe here the synthesis of Mo(CO)₄{Ph₂PCH₂N(Ph)CH₂PPh₂}, (1), and its single-crystal X-ray structure.

The molecular structure of compound (1) is shown in Fig. 1, with selected geometric data in Table 1, together with those for the related compounds Mo(CO₄){Ph₂P(CH₂)₃PPh₂}, (2) (Ueng & Hwang, 1991 ), and Mo(CO₄){Ph₂PCH₂C(CH₂)CH₂PPh₂}, (3) (Bookham et al., 1993). The structure of (1) comprises a cis-chelating Ph₂PCH₂N(Ph)CH₂PPh₂ ligand and four terminal CO ligands. The Mo—P bond lengths in (1) are slightly shorter than those of (2) and (3). The variations in Mo—C distances are as expected for the different π-acceptor properties of CO and –PPh₂ groups. The Mo—C—O bond angles are all close to linear. The P—Mo—P bite angle is similar to those of (2) and (3). As anticipated, this bite angle is enlarged with respect to those found in complexes of the type Mo(CO)₄{Ph₂PN(R)PPh₂} [R = H, P—Mo—P 65.29 (6)°; R = 2-MeOC₆H₄, P—Mo—P = 65.78 (2)°] in which the chelating Ph₂PN(R)PPh₂ ligands adopt near planar four-membered ring conformations (Gaw et al., 2000; Knorr & Strohmann, 1999 ). The six-membered chelate ring in (1) adopts a chair conformation with N1 above the P₂C₂ mean plane by 0.736 (3) Å and Mo below the plane by 0.986 (2) Å. The Mo—P—C—N—C—P metallacyclic ring is similar to those previously seen for other M—P—C—N—C—P compounds (Zhang et al., 2002 ). The N-arene is twisted about the N1—C18 axis by 47.2 (2)° with respect to the central heterocycle.

Figure 1
The molecular structure of (1), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. All H atoms have been omitted for clarity.

Experimental

A solution of Mo(CO)₄(nbd) (0.0613 g, 0.206 mmol) and Ph₂PCH₂N(Ph)CH₂PPh₂ (0.101 g, 0.206 mmol) in CH₂Cl₂ (10 ml) was stirred for 12 h at room temperature under N₂. The volume was reduced to ca 2–3 ml under reduced pressure. Addition of diethyl ether (20 ml) and petroleum ether (b.p. 333–353 K, 10 ml) gave a pale-yellow solid which was collected by suction filtration. Yield 0.071 g, 50%. X-ray quality crystals of (1) were obtained by slow evaporation of the CH₂Cl₂/diethyl ether/petroleum ether filtrate. Calculated for C₃₆H₂₉MoNO₄P₂·0.5C₆H₁₄: C 63.25, H 4.90, N 1.89; found: C 63.09, H 4.75, N 1.87%.

Crystal data

[Mo(C₃₂H₂₉NP₂)(CO)₄]
M_r = 697.48
Triclinic, $[P \overline 1]$
a = 10.2072 (6) Å
b = 11.2800 (7) Å
c = 14.5527 (9) Å
α = 100.047 (1)°
β = 93.162 (1)°
γ = 101.316 (1)°
V = 1610.84 (17) Å³
Z = 2
D_x = 1.438 Mg m⁻³
Synchrotron radiation
λ = 0.6910 Å
μ = 0.55 mm⁻¹
T = 120 (2) K
Plate, colourless
0.15 × 0.06 × 0.03 mm

Data collection

Bruker APEX II CCD diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.923, T_max = 0.984
19074 measured reflections
10047 independent reflections
8204 reflections with I > 2σ(I)
R_int = 0.065
θ_max = 31.0°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.164
S = 1.00
10047 reflections
397 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0783P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.97 e Å⁻³

Table 1
Selected geometric parameters (Å, °) for (1) and a comparison with reported compounds (2) and (3)

	(1)	(2)	(3)
Mo—C(trans to C)	2.016 (3)/2.043 (3)	2.035 (7)/2.023 (7)	2.016 (4)/2.030 (4)
Mo—C(trans to P)	2.007 (3)/1.994 (3)	1.968 (5)/1.968 (5)	1.999 (4)/1.986 (4)
Mo—P	2.5005 (8)/2.4986 (8)	2.538 (1)/2.538 (1)	2.5199 (11)/2.5094 (13)
C—Mo—C(trans to C)	178.21 (12)	174.8 (3)	171.0 (2)
C—Mo—C(cis, av.)	89.72 (13)	88.7 (2)	88.3 (2)
P—Mo—P	86.75 (2)	89.74 (4)	85.14 (4)
(1) This work. (2) Ueng & Hwang (1991). (3) Bookham et al. (1993).

H atoms were positioned geometrically (C—H = 0.95 Å for aryl H and 0.99 Å for methylene H), and refined using a riding model. U_iso(H) values were set to 1.2U_eq(C).

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks global, 1. DOI: https://doi.org/10.1107/S1600536807006101/bt2263sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S1600536807006101/bt22631sup2.hkl

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

{N,N-bis[(diphenylphosphino)methyl]aniline}tetracarbonylmolybdenum(0) top

Crystal data top

[Mo(C₃₂H₂₉NP₂)(CO)₄]	Z = 2
M_r = 697.48	F(000) = 712
Triclinic, P1	D_x = 1.438 Mg m⁻³
Hall symbol: -P 1	Synchrotron radiation, λ = 0.6910 Å
a = 10.2072 (6) Å	Cell parameters from 4141 reflections
b = 11.2800 (7) Å	θ = 2.4–29.2°
c = 14.5527 (9) Å	µ = 0.55 mm⁻¹
α = 100.047 (1)°	T = 120 K
β = 93.162 (1)°	Plate, colourless
γ = 101.316 (1)°	0.15 × 0.06 × 0.03 mm
V = 1610.84 (17) Å³

Data collection top

Bruker APEX II CCD diffractometer	10047 independent reflections
Radiation source: Daresbury SRS station 9.8	8204 reflections with I > 2σ(I)
Silicon 111 monochromator	R_int = 0.065
ω rotation with narrow frames scans	θ_max = 31.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −15→15
T_min = 0.923, T_max = 0.984	k = −16→16
19074 measured reflections	l = −21→21

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.164	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0783P)²] where P = (F_o² + 2F_c²)/3
10047 reflections	(Δ/σ)_max = 0.001
397 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.97 e Å⁻³

Special details top

Experimental. ¹H NMR (400 MHz, CDCl₃, p.p.m.): δ 7.54–6.02 (arom. H, 25H, m), 3.99 (CH₂, 4H, s). ³¹P{¹H} NMR (162 MHz, CDCl₃, p.p.m.): δ 18.8. IR ν_max (KBr, cm^-1): 2024, 1927, 1901, 1885 (CO). Calculated for C₃₆H₂₉MoNO₄P₂·0.5C₆H₁₄: C, 63.25; H, 4.90; N, 1.89. Found: C, 63.09; H, 4.75; N, 1.87%.

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
Mo1	−0.13066 (2)	0.85871 (2)	0.688421 (16)	0.01970 (8)
C1	−0.1835 (3)	1.0108 (3)	0.6580 (2)	0.0247 (6)
O1	−0.2141 (2)	1.0981 (2)	0.64239 (18)	0.0354 (5)
C2	−0.2241 (3)	0.8728 (3)	0.8072 (2)	0.0296 (6)
O2	−0.2767 (3)	0.8813 (3)	0.8753 (2)	0.0477 (7)
C3	−0.2992 (3)	0.7540 (3)	0.6186 (2)	0.0253 (6)
O3	−0.3979 (2)	0.6962 (2)	0.57755 (18)	0.0379 (6)
C4	−0.0417 (3)	0.8423 (3)	0.5657 (2)	0.0250 (6)
O4	0.0025 (3)	0.8353 (3)	0.49443 (17)	0.0362 (5)
P1	−0.05987 (7)	0.67674 (7)	0.73650 (5)	0.02001 (15)
C5	−0.1977 (3)	0.5496 (3)	0.7452 (2)	0.0236 (6)
C6	−0.2651 (4)	0.4766 (3)	0.6616 (2)	0.0344 (7)
H6	−0.2382	0.4934	0.6029	0.041*
C7	−0.3715 (4)	0.3796 (4)	0.6649 (3)	0.0418 (9)
H7	−0.4158	0.3292	0.6082	0.050*
C8	−0.4136 (4)	0.3557 (3)	0.7501 (3)	0.0372 (8)
H8	−0.4865	0.2894	0.7517	0.045*
C9	−0.3492 (3)	0.4286 (3)	0.8324 (3)	0.0322 (7)
H9	−0.3780	0.4123	0.8907	0.039*
C10	−0.2417 (3)	0.5265 (3)	0.8305 (2)	0.0281 (6)
H10	−0.1988	0.5771	0.8875	0.034*
C11	0.0602 (3)	0.5999 (3)	0.6749 (2)	0.0233 (5)
C12	0.0658 (3)	0.4767 (3)	0.6789 (2)	0.0310 (7)
H12	−0.0026	0.4271	0.7054	0.037*
C13	0.1717 (4)	0.4291 (3)	0.6437 (3)	0.0381 (8)
H13	0.1745	0.3459	0.6458	0.046*
C14	0.2736 (4)	0.4995 (4)	0.6056 (3)	0.0393 (8)
H14	0.3472	0.4662	0.5838	0.047*
C15	0.2665 (4)	0.6200 (4)	0.5997 (2)	0.0348 (7)
H15	0.3343	0.6686	0.5719	0.042*
C16	0.1609 (3)	0.6692 (3)	0.6344 (2)	0.0281 (6)
H16	0.1574	0.7517	0.6304	0.034*
C17	0.0254 (3)	0.7136 (3)	0.8578 (2)	0.0224 (5)
H17A	−0.0370	0.7426	0.9021	0.027*
H17B	0.0463	0.6375	0.8744	0.027*
N1	0.1492 (2)	0.8075 (2)	0.86898 (17)	0.0220 (5)
C18	0.2662 (3)	0.7786 (3)	0.9091 (2)	0.0209 (5)
C19	0.3125 (3)	0.6768 (3)	0.8644 (2)	0.0279 (6)
H19	0.2619	0.6251	0.8103	0.034*
C20	0.4310 (3)	0.6502 (3)	0.8977 (2)	0.0303 (7)
H20	0.4608	0.5806	0.8663	0.036*
C21	0.5060 (3)	0.7235 (3)	0.9761 (3)	0.0331 (7)
H21	0.5878	0.7055	0.9984	0.040*
C22	0.4607 (3)	0.8236 (3)	1.0219 (2)	0.0321 (7)
H22	0.5114	0.8739	1.0765	0.038*
C23	0.3413 (3)	0.8522 (3)	0.9892 (2)	0.0261 (6)
H23	0.3115	0.9214	1.0214	0.031*
C24	0.1326 (3)	0.9344 (3)	0.8885 (2)	0.0227 (5)
H24A	0.2187	0.9886	0.9173	0.027*
H24B	0.0650	0.9421	0.9341	0.027*
P2	0.07867 (7)	0.98633 (7)	0.78070 (5)	0.01930 (15)
C25	0.2311 (3)	1.0066 (3)	0.71928 (19)	0.0204 (5)
C26	0.3469 (3)	0.9680 (3)	0.7441 (2)	0.0253 (6)
H26	0.3504	0.9278	0.7961	0.030*
C27	0.4581 (3)	0.9880 (3)	0.6929 (2)	0.0299 (6)
H27	0.5370	0.9614	0.7103	0.036*
C28	0.4542 (3)	1.0466 (3)	0.6169 (2)	0.0312 (7)
H28	0.5307	1.0612	0.5829	0.037*
C29	0.3375 (3)	1.0839 (3)	0.5905 (2)	0.0323 (7)
H29	0.3338	1.1231	0.5380	0.039*
C30	0.2263 (3)	1.0632 (3)	0.6417 (2)	0.0274 (6)
H30	0.1465	1.0880	0.6235	0.033*
C31	0.0780 (3)	1.1464 (3)	0.8338 (2)	0.0220 (5)
C32	0.1966 (3)	1.2350 (3)	0.8529 (2)	0.0260 (6)
H32	0.2789	1.2128	0.8374	0.031*
C33	0.1961 (3)	1.3553 (3)	0.8943 (2)	0.0296 (6)
H33	0.2778	1.4150	0.9066	0.036*
C34	0.0770 (3)	1.3888 (3)	0.9178 (2)	0.0286 (6)
H34	0.0767	1.4714	0.9457	0.034*
C35	−0.0418 (3)	1.3012 (3)	0.9006 (2)	0.0303 (7)
H35	−0.1235	1.3234	0.9176	0.036*
C36	−0.0412 (3)	1.1803 (3)	0.8581 (2)	0.0265 (6)
H36	−0.1230	1.1207	0.8457	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.01699 (13)	0.01926 (13)	0.02395 (14)	0.00605 (9)	0.00209 (9)	0.00448 (9)
C1	0.0199 (13)	0.0262 (14)	0.0310 (15)	0.0079 (11)	0.0041 (11)	0.0093 (12)
O1	0.0315 (12)	0.0337 (13)	0.0472 (14)	0.0153 (10)	0.0040 (10)	0.0153 (11)
C2	0.0296 (16)	0.0209 (14)	0.0385 (17)	0.0065 (12)	0.0082 (13)	0.0030 (12)
O2	0.0563 (18)	0.0376 (15)	0.0491 (16)	0.0070 (13)	0.0307 (14)	0.0031 (12)
C3	0.0203 (13)	0.0273 (14)	0.0282 (14)	0.0049 (11)	0.0016 (11)	0.0058 (11)
O3	0.0255 (12)	0.0391 (14)	0.0435 (14)	0.0008 (10)	−0.0041 (10)	0.0016 (11)
C4	0.0193 (13)	0.0258 (14)	0.0295 (15)	0.0056 (11)	−0.0013 (11)	0.0039 (11)
O4	0.0342 (13)	0.0491 (15)	0.0275 (12)	0.0129 (11)	0.0063 (9)	0.0069 (11)
P1	0.0200 (3)	0.0180 (3)	0.0222 (3)	0.0049 (3)	0.0013 (3)	0.0032 (3)
C5	0.0230 (13)	0.0165 (12)	0.0311 (15)	0.0042 (10)	0.0028 (11)	0.0039 (11)
C6	0.0343 (17)	0.0308 (17)	0.0325 (17)	−0.0022 (14)	−0.0014 (13)	0.0021 (13)
C7	0.039 (2)	0.0361 (19)	0.041 (2)	−0.0067 (16)	−0.0017 (15)	−0.0008 (15)
C8	0.0309 (17)	0.0238 (15)	0.054 (2)	0.0000 (13)	0.0072 (15)	0.0061 (15)
C9	0.0290 (16)	0.0278 (15)	0.0442 (19)	0.0089 (13)	0.0138 (14)	0.0121 (14)
C10	0.0268 (15)	0.0243 (14)	0.0346 (16)	0.0077 (12)	0.0033 (12)	0.0064 (12)
C11	0.0263 (14)	0.0227 (13)	0.0211 (13)	0.0101 (11)	0.0003 (10)	−0.0005 (10)
C12	0.0340 (17)	0.0263 (15)	0.0324 (16)	0.0135 (13)	0.0005 (13)	−0.0022 (12)
C13	0.048 (2)	0.0319 (17)	0.0355 (18)	0.0215 (16)	−0.0026 (15)	−0.0046 (14)
C14	0.0382 (19)	0.046 (2)	0.0367 (18)	0.0245 (17)	0.0052 (14)	−0.0017 (15)
C15	0.0322 (17)	0.044 (2)	0.0315 (17)	0.0158 (15)	0.0071 (13)	0.0049 (14)
C16	0.0265 (15)	0.0299 (15)	0.0289 (15)	0.0096 (12)	0.0030 (11)	0.0040 (12)
C17	0.0224 (13)	0.0199 (13)	0.0249 (13)	0.0042 (10)	−0.0006 (10)	0.0052 (10)
N1	0.0235 (12)	0.0159 (10)	0.0259 (12)	0.0054 (9)	−0.0018 (9)	0.0014 (9)
C18	0.0199 (13)	0.0186 (12)	0.0260 (13)	0.0060 (10)	0.0016 (10)	0.0071 (10)
C19	0.0308 (16)	0.0224 (14)	0.0304 (15)	0.0078 (12)	−0.0014 (12)	0.0031 (11)
C20	0.0307 (16)	0.0256 (15)	0.0387 (17)	0.0142 (13)	0.0018 (13)	0.0080 (13)
C21	0.0217 (14)	0.0341 (17)	0.0459 (19)	0.0052 (13)	−0.0012 (13)	0.0160 (15)
C22	0.0264 (15)	0.0322 (16)	0.0361 (17)	0.0045 (13)	−0.0073 (13)	0.0073 (13)
C23	0.0241 (14)	0.0256 (14)	0.0278 (14)	0.0054 (11)	−0.0023 (11)	0.0046 (11)
C24	0.0243 (13)	0.0195 (12)	0.0255 (13)	0.0089 (11)	0.0000 (10)	0.0032 (10)
P2	0.0188 (3)	0.0167 (3)	0.0234 (3)	0.0065 (3)	0.0023 (3)	0.0031 (3)
C25	0.0181 (12)	0.0182 (12)	0.0232 (13)	0.0029 (10)	0.0002 (9)	0.0009 (10)
C26	0.0229 (14)	0.0230 (14)	0.0318 (15)	0.0081 (11)	0.0022 (11)	0.0061 (11)
C27	0.0216 (14)	0.0322 (16)	0.0373 (17)	0.0112 (12)	0.0058 (12)	0.0034 (13)
C28	0.0236 (15)	0.0338 (17)	0.0332 (16)	0.0011 (12)	0.0057 (12)	0.0025 (13)
C29	0.0287 (16)	0.0376 (18)	0.0287 (16)	0.0030 (14)	0.0002 (12)	0.0061 (13)
C30	0.0226 (14)	0.0290 (15)	0.0304 (15)	0.0042 (12)	0.0013 (11)	0.0068 (12)
C31	0.0249 (14)	0.0186 (12)	0.0237 (13)	0.0083 (10)	0.0015 (10)	0.0036 (10)
C32	0.0243 (14)	0.0211 (13)	0.0318 (15)	0.0079 (11)	0.0002 (11)	0.0001 (11)
C33	0.0342 (16)	0.0177 (13)	0.0362 (17)	0.0062 (12)	0.0002 (13)	0.0030 (12)
C34	0.0431 (18)	0.0201 (13)	0.0255 (14)	0.0150 (13)	0.0024 (12)	0.0028 (11)
C35	0.0348 (17)	0.0286 (15)	0.0329 (16)	0.0175 (13)	0.0088 (13)	0.0063 (12)
C36	0.0272 (15)	0.0229 (14)	0.0309 (15)	0.0101 (12)	0.0036 (11)	0.0034 (11)

Geometric parameters (Å, º) top

Mo1—C3	1.994 (3)	N1—C24	1.455 (4)
Mo1—C1	2.007 (3)	C18—C23	1.395 (4)
Mo1—C2	2.016 (3)	C18—C19	1.398 (4)
Mo1—C4	2.043 (3)	C19—C20	1.385 (4)
Mo1—P2	2.4986 (8)	C19—H19	0.9500
Mo1—P1	2.5005 (8)	C20—C21	1.377 (5)
C1—O1	1.145 (4)	C20—H20	0.9500
C2—O2	1.152 (4)	C21—C22	1.382 (5)
C3—O3	1.156 (4)	C21—H21	0.9500
C4—O4	1.151 (4)	C22—C23	1.400 (4)
P1—C11	1.823 (3)	C22—H22	0.9500
P1—C5	1.828 (3)	C23—H23	0.9500
P1—C17	1.865 (3)	C24—P2	1.860 (3)
C5—C10	1.393 (4)	C24—H24A	0.9900
C5—C6	1.403 (4)	C24—H24B	0.9900
C6—C7	1.392 (5)	P2—C25	1.832 (3)
C6—H6	0.9500	P2—C31	1.838 (3)
C7—C8	1.387 (5)	C25—C26	1.388 (4)
C7—H7	0.9500	C25—C30	1.394 (4)
C8—C9	1.378 (5)	C26—C27	1.395 (4)
C8—H8	0.9500	C26—H26	0.9500
C9—C10	1.401 (4)	C27—C28	1.387 (5)
C9—H9	0.9500	C27—H27	0.9500
C10—H10	0.9500	C28—C29	1.394 (5)
C11—C16	1.389 (4)	C28—H28	0.9500
C11—C12	1.413 (4)	C29—C30	1.396 (4)
C12—C13	1.383 (5)	C29—H29	0.9500
C12—H12	0.9500	C30—H30	0.9500
C13—C14	1.384 (6)	C31—C32	1.389 (4)
C13—H13	0.9500	C31—C36	1.391 (4)
C14—C15	1.392 (5)	C32—C33	1.386 (4)
C14—H14	0.9500	C32—H32	0.9500
C15—C16	1.387 (4)	C33—C34	1.386 (5)
C15—H15	0.9500	C33—H33	0.9500
C16—H16	0.9500	C34—C35	1.385 (5)
C17—N1	1.462 (4)	C34—H34	0.9500
C17—H17A	0.9900	C35—C36	1.397 (4)
C17—H17B	0.9900	C35—H35	0.9500
N1—C18	1.419 (4)	C36—H36	0.9500

C3—Mo1—C1	90.78 (13)	C18—N1—C17	117.0 (2)
C3—Mo1—C2	89.67 (13)	C24—N1—C17	115.5 (2)
C1—Mo1—C2	91.66 (13)	C23—C18—C19	118.4 (3)
C3—Mo1—C4	88.59 (12)	C23—C18—N1	122.4 (3)
C1—Mo1—C4	87.92 (12)	C19—C18—N1	119.1 (3)
C2—Mo1—C4	178.21 (12)	C20—C19—C18	120.9 (3)
C3—Mo1—P2	177.99 (9)	C20—C19—H19	119.5
C1—Mo1—P2	90.49 (9)	C18—C19—H19	119.5
C2—Mo1—P2	88.74 (10)	C21—C20—C19	120.7 (3)
C4—Mo1—P2	93.01 (8)	C21—C20—H20	119.6
C3—Mo1—P1	91.92 (9)	C19—C20—H20	119.6
C1—Mo1—P1	176.40 (9)	C20—C21—C22	119.1 (3)
C2—Mo1—P1	85.98 (9)	C20—C21—H21	120.4
C4—Mo1—P1	94.52 (9)	C22—C21—H21	120.4
P2—Mo1—P1	86.75 (2)	C21—C22—C23	121.0 (3)
O1—C1—Mo1	178.7 (3)	C21—C22—H22	119.5
O2—C2—Mo1	179.6 (3)	C23—C22—H22	119.5
O3—C3—Mo1	178.1 (3)	C18—C23—C22	119.8 (3)
O4—C4—Mo1	176.2 (3)	C18—C23—H23	120.1
C11—P1—C5	103.40 (14)	C22—C23—H23	120.1
C11—P1—C17	99.70 (13)	N1—C24—P2	112.1 (2)
C5—P1—C17	101.38 (14)	N1—C24—H24A	109.2
C11—P1—Mo1	122.17 (10)	P2—C24—H24A	109.2
C5—P1—Mo1	114.87 (10)	N1—C24—H24B	109.2
C17—P1—Mo1	112.43 (9)	P2—C24—H24B	109.2
C10—C5—C6	119.2 (3)	H24A—C24—H24B	107.9
C10—C5—P1	122.8 (2)	C25—P2—C31	101.21 (13)
C6—C5—P1	117.8 (2)	C25—P2—C24	103.34 (13)
C7—C6—C5	119.8 (3)	C31—P2—C24	98.14 (13)
C7—C6—H6	120.1	C25—P2—Mo1	117.00 (9)
C5—C6—H6	120.1	C31—P2—Mo1	118.07 (10)
C8—C7—C6	120.7 (3)	C24—P2—Mo1	116.15 (10)
C8—C7—H7	119.7	C26—C25—C30	119.3 (3)
C6—C7—H7	119.7	C26—C25—P2	124.5 (2)
C9—C8—C7	119.7 (3)	C30—C25—P2	116.2 (2)
C9—C8—H8	120.2	C25—C26—C27	120.2 (3)
C7—C8—H8	120.2	C25—C26—H26	119.9
C8—C9—C10	120.5 (3)	C27—C26—H26	119.9
C8—C9—H9	119.8	C28—C27—C26	120.4 (3)
C10—C9—H9	119.8	C28—C27—H27	119.8
C5—C10—C9	120.0 (3)	C26—C27—H27	119.8
C5—C10—H10	120.0	C27—C28—C29	119.8 (3)
C9—C10—H10	120.0	C27—C28—H28	120.1
C16—C11—C12	118.8 (3)	C29—C28—H28	120.1
C16—C11—P1	118.8 (2)	C28—C29—C30	119.6 (3)
C12—C11—P1	121.8 (2)	C28—C29—H29	120.2
C13—C12—C11	119.4 (3)	C30—C29—H29	120.2
C13—C12—H12	120.3	C25—C30—C29	120.6 (3)
C11—C12—H12	120.3	C25—C30—H30	119.7
C12—C13—C14	121.6 (3)	C29—C30—H30	119.7
C12—C13—H13	119.2	C32—C31—C36	118.8 (3)
C14—C13—H13	119.2	C32—C31—P2	120.9 (2)
C13—C14—C15	118.9 (3)	C36—C31—P2	120.3 (2)
C13—C14—H14	120.5	C33—C32—C31	120.7 (3)
C15—C14—H14	120.5	C33—C32—H32	119.6
C16—C15—C14	120.2 (3)	C31—C32—H32	119.6
C16—C15—H15	119.9	C34—C33—C32	120.3 (3)
C14—C15—H15	119.9	C34—C33—H33	119.9
C15—C16—C11	121.0 (3)	C32—C33—H33	119.9
C15—C16—H16	119.5	C35—C34—C33	119.7 (3)
C11—C16—H16	119.5	C35—C34—H34	120.2
N1—C17—P1	113.2 (2)	C33—C34—H34	120.2
N1—C17—H17A	108.9	C34—C35—C36	119.9 (3)
P1—C17—H17A	108.9	C34—C35—H35	120.0
N1—C17—H17B	108.9	C36—C35—H35	120.0
P1—C17—H17B	108.9	C31—C36—C35	120.6 (3)
H17A—C17—H17B	107.8	C31—C36—H36	119.7
C18—N1—C24	118.7 (2)	C35—C36—H36	119.7

C2—Mo1—P1—C11	−171.65 (15)	C19—C20—C21—C22	0.8 (5)
C4—Mo1—P1—C11	10.07 (14)	C20—C21—C22—C23	−0.9 (5)
P2—Mo1—P1—C11	−82.69 (12)	C19—C18—C23—C22	0.7 (5)
C3—Mo1—P1—C5	−27.57 (14)	N1—C18—C23—C22	−175.7 (3)
C2—Mo1—P1—C5	61.96 (15)	C21—C22—C23—C18	0.1 (5)
C4—Mo1—P1—C5	−116.31 (14)	C18—N1—C24—P2	133.9 (2)
P2—Mo1—P1—C5	150.92 (11)	C17—N1—C24—P2	−79.5 (3)
C3—Mo1—P1—C17	−142.82 (13)	N1—C24—P2—C25	−73.8 (2)
C2—Mo1—P1—C17	−53.29 (14)	N1—C24—P2—C31	−177.4 (2)
C4—Mo1—P1—C17	128.44 (13)	N1—C24—P2—Mo1	55.7 (2)
P2—Mo1—P1—C17	35.67 (10)	C1—Mo1—P2—C25	−94.18 (13)
C11—P1—C5—C10	121.7 (3)	C2—Mo1—P2—C25	174.17 (14)
C17—P1—C5—C10	18.7 (3)	C4—Mo1—P2—C25	−6.24 (14)
Mo1—P1—C5—C10	−102.7 (3)	P1—Mo1—P2—C25	88.13 (11)
C11—P1—C5—C6	−61.4 (3)	C1—Mo1—P2—C31	27.08 (14)
C17—P1—C5—C6	−164.4 (3)	C2—Mo1—P2—C31	−64.56 (14)
Mo1—P1—C5—C6	74.2 (3)	C4—Mo1—P2—C31	115.03 (14)
C10—C5—C6—C7	−2.4 (5)	P1—Mo1—P2—C31	−150.61 (11)
P1—C5—C6—C7	−179.4 (3)	C1—Mo1—P2—C24	143.22 (13)
C5—C6—C7—C8	1.3 (6)	C2—Mo1—P2—C24	51.58 (14)
C6—C7—C8—C9	−0.2 (6)	C4—Mo1—P2—C24	−128.83 (13)
C7—C8—C9—C10	0.0 (5)	P1—Mo1—P2—C24	−34.46 (10)
C6—C5—C10—C9	2.2 (5)	C31—P2—C25—C26	111.6 (3)
P1—C5—C10—C9	179.1 (2)	C24—P2—C25—C26	10.3 (3)
C8—C9—C10—C5	−1.0 (5)	Mo1—P2—C25—C26	−118.7 (2)
C5—P1—C11—C16	163.2 (2)	C31—P2—C25—C30	−69.5 (2)
C17—P1—C11—C16	−92.5 (3)	C24—P2—C25—C30	−170.7 (2)
Mo1—P1—C11—C16	31.9 (3)	Mo1—P2—C25—C30	60.3 (2)
C5—P1—C11—C12	−26.2 (3)	C30—C25—C26—C27	1.3 (4)
C17—P1—C11—C12	78.1 (3)	P2—C25—C26—C27	−179.8 (2)
Mo1—P1—C11—C12	−157.5 (2)	C25—C26—C27—C28	0.0 (5)
C16—C11—C12—C13	0.9 (5)	C26—C27—C28—C29	−1.0 (5)
P1—C11—C12—C13	−169.7 (3)	C27—C28—C29—C30	0.8 (5)
C11—C12—C13—C14	0.8 (5)	C26—C25—C30—C29	−1.5 (5)
C12—C13—C14—C15	−2.2 (6)	P2—C25—C30—C29	179.5 (2)
C13—C14—C15—C16	2.0 (5)	C28—C29—C30—C25	0.5 (5)
C14—C15—C16—C11	−0.4 (5)	C25—P2—C31—C32	−25.4 (3)
C12—C11—C16—C15	−1.1 (5)	C24—P2—C31—C32	80.1 (3)
P1—C11—C16—C15	169.8 (3)	Mo1—P2—C31—C32	−154.4 (2)
C11—P1—C17—N1	69.0 (2)	C25—P2—C31—C36	156.5 (2)
C5—P1—C17—N1	174.9 (2)	C24—P2—C31—C36	−98.0 (3)
Mo1—P1—C17—N1	−61.9 (2)	Mo1—P2—C31—C36	27.5 (3)
P1—C17—N1—C18	−128.0 (2)	C36—C31—C32—C33	−0.8 (5)
P1—C17—N1—C24	84.9 (3)	P2—C31—C32—C33	−179.0 (2)
C24—N1—C18—C23	22.5 (4)	C31—C32—C33—C34	0.4 (5)
C17—N1—C18—C23	−123.5 (3)	C32—C33—C34—C35	0.6 (5)
C24—N1—C18—C19	−153.9 (3)	C33—C34—C35—C36	−1.1 (5)
C17—N1—C18—C19	60.1 (4)	C32—C31—C36—C35	0.3 (5)
C23—C18—C19—C20	−0.8 (5)	P2—C31—C36—C35	178.4 (2)
N1—C18—C19—C20	175.7 (3)	C34—C35—C36—C31	0.7 (5)
C18—C19—C20—C21	0.1 (5)

Table 1 top

Selected geometric parameters (Å, °) for (1) and a comparison with reported compounds (2) and (3)

	1	2	3
Mo—C(trans to C)	2.016 (3)/2.043 (3)	2.035 (7)/2.023 (7)	2.016 (4)/2.030 (4)
Mo—C(trans to P)	2.007 (3)/1.994 (3)	1.968 (5)/1.968 (5)	1.999 (4)/1.986 (4)
Mo—P	2.5005 (8)/2.4986 (8)	2.538 (1)/2.538 (1)	2.5199 (11)/2.5094 (13)
C—Mo—C(trans to C)	178.21 (12)	174.8 (3)	171.0 (2)
C—Mo—C(cis, av.)	89.72 (13)	88.7 (2)	88.3 (2)
P—Mo—P	86.75 (2)	89.74 (4)	85.14 (4)

(1) this work; (2) Ueng & Hwang (1991); (3) Bookham et al. (1993).

Acknowledgements

We acknowledge the EPSRC and Loughborough University for the provision of studentships (GMB, NMSB). The authors acknowledge Dr John Warren and Dr Timothy Prior for scientific support at Daresbury Laboratory Station 9.8 during the data collection of (1).

References

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