Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702185X/bt2358sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680702185X/bt2358Isup2.hkl |
CCDC reference: 650616
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.007 Å
- R factor = 0.061
- wR factor = 0.135
- Data-to-parameter ratio = 19.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The preparation of I was carried out as follows. A solution of Mo(CO)4(norbornadiene) (0.0408 g, 0.136 mmol) and Ph2P(CH2)3PPh2 (0.0559 g, 0.135 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. 60–80°C, 10 ml) gave a pale yellow solid which was collected by suction filtration. Yield: 0.0749 g, 89%. Suitable X-ray quality crystals of 1 were obtained by slow evaporation of the CH2Cl2/diethyl ether/petroleum ether filtrate. Selected data for I: 31P{1H} NMR (162 MHz, CDCl3): δ(P) 25.1 p.p.m. IR νmax (KBr)/cm-1: 2018, 1919, 1891, 1854 (CO).
H atoms were placed in geometric positions (C—H distance = 0.95 Å for aryl H; 0.99 Å for methylene H) using a riding model. Uiso values were set to 1.2Ueq.
Ditertiary phosphines are valuable synthetic tools widely used in coordination chemistry and homogeneous catalysis. (Sekabunga et al., 2002; Wu & Li, 2003; Balch et al., 1990). A number of Mo—P—C—X—C—P (X = N or C) forming a six-membered chelated metallocycle have been described in the literature (Sanchez-Ballester et al., 2007; Ueng & Hwang, 1991). A second polymorph of Mo(CO)4{Ph2P(CH2)3PPh2} I has been structurally determined (Figure 1), with selected geometric data in Table 1, together with those for the related compounds Mo(CO4){Ph2P(CH2)3PPh2}, I' (Ueng & Hwang, 1991), and [Mo(CO4){Ph2PCH2N(Ph)CH2PPh2}], II (Sanchez-Ballester et al., 2007). The Mo—P bond lengths and P—Mo—P bite angle in (I) are similar to (I') but slightly longer than 2. The six-membered chelate ring in (I) adopts a chair conformation with C14 above the P2C2 mean plane by 0.747 (6)Å and Mo below the plane by 0.764 (3) Å. Figures 2 and 3 show packing plots of (I) and (I') viewed along the crystallographic b and c axes respectively. These show the substantial differences in packing between the two polymorphs. In (I) adjacent molecules are off-set and canted by 26° with respect to the ab plane with a whole molecule in the asymmetric unit, while in (I') molecules lie directly stacked in parallel columns with individual molecules lying on mirror planes.
In summary, we have reported the crystal structure of a new monoclinic, polymorph I that displays very similar Mo—P/Mo—CO bond lengths, bond angles and core molecular conformation to the known orthorhombic, polymorph I' (Ueng & Hwang, 1991), but substantial differences in crystal packing.
An orthorhombic polymorph (Ueng & Hwang, 1991) has been reported previously and shows a different packing arrangement in which molecules are lying directly stacked in parallel columns with individual molecules lying on mirror planes. See also Sekabunga et al., 2002, Wu & Li, 2003, and Balch et al., 1990 for broader information on phospines in catalysis and Sanchez Ballester et al., 2007 for a closely related structure.
Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; 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.
[Mo(C27H26P2)(CO)4] | F(000) = 1264 |
Mr = 620.40 | Dx = 1.421 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 6633 reflections |
a = 15.5925 (6) Å | θ = 2.9–27.5° |
b = 8.8293 (3) Å | µ = 0.60 mm−1 |
c = 21.0760 (6) Å | T = 120 K |
β = 91.979 (2)° | Block, colourless |
V = 2899.82 (17) Å3 | 0.10 × 0.05 × 0.03 mm |
Z = 4 |
Bruker-Nonius 95mm CCD camera on κ-goniostat diffractometer | 6604 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 5497 reflections with I > 2σ(I) |
10cm confocal mirrors monochromator | Rint = 0.076 |
φ and ω scans | θmax = 27.6°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −20→20 |
Tmin = 0.965, Tmax = 0.982 | k = −11→11 |
33177 measured reflections | l = −27→27 |
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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.17 | w = 1/[σ2(Fo2) + 15.4402P] where P = (Fo2 + 2Fc2)/3 |
6604 reflections | (Δ/σ)max = 0.001 |
343 parameters | Δρmax = 1.34 e Å−3 |
0 restraints | Δρmin = −0.72 e Å−3 |
[Mo(C27H26P2)(CO)4] | V = 2899.82 (17) Å3 |
Mr = 620.40 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 15.5925 (6) Å | µ = 0.60 mm−1 |
b = 8.8293 (3) Å | T = 120 K |
c = 21.0760 (6) Å | 0.10 × 0.05 × 0.03 mm |
β = 91.979 (2)° |
Bruker-Nonius 95mm CCD camera on κ-goniostat diffractometer | 6604 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 5497 reflections with I > 2σ(I) |
Tmin = 0.965, Tmax = 0.982 | Rint = 0.076 |
33177 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.17 | w = 1/[σ2(Fo2) + 15.4402P] where P = (Fo2 + 2Fc2)/3 |
6604 reflections | Δρmax = 1.34 e Å−3 |
343 parameters | Δρmin = −0.72 e Å−3 |
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 | ||
Mo1 | 0.80343 (2) | 0.83793 (4) | 0.487754 (16) | 0.01481 (11) | |
C1 | 0.9296 (3) | 0.6703 (5) | 0.3555 (2) | 0.0186 (8) | |
C2 | 0.9387 (3) | 0.5816 (5) | 0.3015 (2) | 0.0242 (10) | |
H2 | 0.8974 | 0.5055 | 0.2916 | 0.029* | |
C3 | 1.0067 (3) | 0.6023 (6) | 0.2622 (2) | 0.0303 (11) | |
H3 | 1.0117 | 0.5404 | 0.2256 | 0.036* | |
C4 | 1.0675 (3) | 0.7125 (6) | 0.2758 (2) | 0.0287 (11) | |
H4 | 1.1143 | 0.7271 | 0.2488 | 0.034* | |
C5 | 1.0595 (3) | 0.8013 (5) | 0.3293 (2) | 0.0246 (10) | |
H5 | 1.1016 | 0.8763 | 0.3392 | 0.029* | |
C6 | 0.9911 (3) | 0.7827 (5) | 0.3685 (2) | 0.0207 (9) | |
H6 | 0.9858 | 0.8465 | 0.4045 | 0.025* | |
C7 | 0.7567 (3) | 0.5721 (5) | 0.3543 (2) | 0.0184 (9) | |
C8 | 0.7362 (3) | 0.4209 (5) | 0.3431 (2) | 0.0225 (9) | |
H8 | 0.7663 | 0.3438 | 0.3661 | 0.027* | |
C9 | 0.6719 (3) | 0.3813 (6) | 0.2986 (2) | 0.0300 (11) | |
H9 | 0.6579 | 0.2777 | 0.2917 | 0.036* | |
C10 | 0.6289 (3) | 0.4922 (6) | 0.2646 (2) | 0.0315 (12) | |
H10 | 0.5855 | 0.4651 | 0.2340 | 0.038* | |
C11 | 0.6485 (3) | 0.6432 (6) | 0.2749 (2) | 0.0295 (11) | |
H11 | 0.6186 | 0.7195 | 0.2513 | 0.035* | |
C12 | 0.7115 (3) | 0.6835 (5) | 0.3196 (2) | 0.0237 (9) | |
H12 | 0.7243 | 0.7875 | 0.3268 | 0.028* | |
P1 | 0.84233 (7) | 0.63373 (12) | 0.41003 (5) | 0.0155 (2) | |
C13 | 0.8838 (3) | 0.4563 (5) | 0.4452 (2) | 0.0177 (8) | |
H13A | 0.8924 | 0.3829 | 0.4105 | 0.021* | |
H13B | 0.9407 | 0.4771 | 0.4656 | 0.021* | |
C14 | 0.8270 (3) | 0.3816 (5) | 0.4945 (2) | 0.0191 (9) | |
H14A | 0.7668 | 0.3834 | 0.4780 | 0.023* | |
H14B | 0.8442 | 0.2742 | 0.4992 | 0.023* | |
C15 | 0.8309 (3) | 0.4562 (5) | 0.5601 (2) | 0.0189 (9) | |
H15A | 0.8920 | 0.4738 | 0.5723 | 0.023* | |
H15B | 0.8081 | 0.3834 | 0.5910 | 0.023* | |
P2 | 0.77312 (7) | 0.63617 (12) | 0.56842 (5) | 0.0163 (2) | |
C16 | 0.6601 (3) | 0.5822 (5) | 0.5736 (2) | 0.0202 (9) | |
C17 | 0.6009 (3) | 0.6958 (6) | 0.5873 (2) | 0.0298 (11) | |
H17 | 0.6197 | 0.7978 | 0.5917 | 0.036* | |
C18 | 0.5153 (3) | 0.6608 (7) | 0.5947 (2) | 0.0349 (12) | |
H18 | 0.4757 | 0.7387 | 0.6041 | 0.042* | |
C19 | 0.4870 (3) | 0.5118 (7) | 0.5882 (2) | 0.0325 (12) | |
H19 | 0.4283 | 0.4877 | 0.5938 | 0.039* | |
C20 | 0.5442 (3) | 0.4000 (6) | 0.5738 (2) | 0.0301 (11) | |
H20 | 0.5247 | 0.2987 | 0.5684 | 0.036* | |
C21 | 0.6308 (3) | 0.4339 (5) | 0.5667 (2) | 0.0228 (9) | |
H21 | 0.6699 | 0.3553 | 0.5573 | 0.027* | |
C22 | 0.8008 (3) | 0.6718 (5) | 0.65245 (19) | 0.0187 (8) | |
C23 | 0.8620 (3) | 0.7794 (5) | 0.6713 (2) | 0.0235 (10) | |
H23 | 0.8875 | 0.8415 | 0.6403 | 0.028* | |
C24 | 0.8860 (3) | 0.7965 (6) | 0.7353 (2) | 0.0273 (10) | |
H24 | 0.9280 | 0.8699 | 0.7474 | 0.033* | |
C25 | 0.8495 (3) | 0.7081 (6) | 0.7811 (2) | 0.0274 (11) | |
H25 | 0.8659 | 0.7204 | 0.8246 | 0.033* | |
C26 | 0.7884 (3) | 0.6010 (6) | 0.7628 (2) | 0.0283 (11) | |
H26 | 0.7626 | 0.5397 | 0.7939 | 0.034* | |
C27 | 0.7647 (3) | 0.5830 (5) | 0.6990 (2) | 0.0238 (10) | |
H27 | 0.7232 | 0.5088 | 0.6871 | 0.029* | |
C28 | 0.8256 (3) | 0.9952 (5) | 0.4224 (2) | 0.0184 (9) | |
O1 | 0.8362 (2) | 1.0873 (4) | 0.38470 (15) | 0.0285 (8) | |
C29 | 0.9276 (3) | 0.8437 (5) | 0.5207 (2) | 0.0185 (8) | |
O2 | 0.9971 (2) | 0.8496 (4) | 0.53965 (16) | 0.0288 (7) | |
C30 | 0.7700 (3) | 0.9967 (5) | 0.5489 (2) | 0.0202 (9) | |
O3 | 0.7490 (2) | 1.0904 (4) | 0.58319 (15) | 0.0297 (8) | |
C31 | 0.6779 (3) | 0.8437 (5) | 0.4551 (2) | 0.0229 (9) | |
O4 | 0.6091 (2) | 0.8598 (5) | 0.43742 (18) | 0.0382 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.01750 (18) | 0.00963 (18) | 0.01729 (18) | −0.00135 (15) | 0.00041 (12) | −0.00034 (14) |
C1 | 0.019 (2) | 0.015 (2) | 0.022 (2) | 0.0007 (17) | 0.0004 (16) | 0.0038 (17) |
C2 | 0.023 (2) | 0.020 (2) | 0.030 (2) | −0.0005 (18) | 0.0050 (18) | −0.0030 (18) |
C3 | 0.029 (3) | 0.030 (3) | 0.032 (3) | 0.004 (2) | 0.010 (2) | −0.006 (2) |
C4 | 0.025 (3) | 0.029 (3) | 0.032 (3) | 0.002 (2) | 0.010 (2) | 0.008 (2) |
C5 | 0.019 (2) | 0.020 (2) | 0.035 (3) | −0.0004 (18) | −0.0008 (18) | 0.0070 (19) |
C6 | 0.021 (2) | 0.016 (2) | 0.025 (2) | −0.0005 (17) | 0.0015 (17) | 0.0013 (17) |
C7 | 0.020 (2) | 0.016 (2) | 0.019 (2) | −0.0021 (17) | 0.0033 (16) | −0.0028 (16) |
C8 | 0.024 (2) | 0.018 (2) | 0.026 (2) | −0.0045 (18) | 0.0024 (17) | −0.0054 (18) |
C9 | 0.029 (3) | 0.030 (3) | 0.031 (3) | −0.010 (2) | 0.001 (2) | −0.013 (2) |
C10 | 0.025 (3) | 0.043 (3) | 0.026 (2) | −0.009 (2) | −0.0016 (19) | −0.007 (2) |
C11 | 0.031 (3) | 0.032 (3) | 0.025 (2) | 0.000 (2) | −0.0042 (19) | 0.005 (2) |
C12 | 0.026 (2) | 0.020 (2) | 0.025 (2) | −0.0025 (19) | −0.0012 (18) | 0.0013 (18) |
P1 | 0.0170 (5) | 0.0107 (5) | 0.0190 (5) | −0.0010 (4) | 0.0008 (4) | −0.0002 (4) |
C13 | 0.018 (2) | 0.013 (2) | 0.022 (2) | −0.0013 (16) | 0.0010 (16) | 0.0005 (16) |
C14 | 0.025 (2) | 0.008 (2) | 0.025 (2) | −0.0022 (16) | 0.0045 (17) | −0.0011 (16) |
C15 | 0.023 (2) | 0.013 (2) | 0.021 (2) | −0.0002 (17) | 0.0013 (16) | 0.0029 (16) |
P2 | 0.0189 (5) | 0.0117 (5) | 0.0182 (5) | −0.0013 (4) | 0.0007 (4) | −0.0002 (4) |
C16 | 0.017 (2) | 0.024 (2) | 0.020 (2) | −0.0036 (18) | 0.0009 (16) | 0.0048 (17) |
C17 | 0.031 (3) | 0.025 (3) | 0.034 (3) | 0.001 (2) | 0.005 (2) | −0.002 (2) |
C18 | 0.022 (2) | 0.045 (3) | 0.038 (3) | 0.005 (2) | 0.008 (2) | 0.003 (2) |
C19 | 0.019 (2) | 0.047 (3) | 0.032 (3) | −0.006 (2) | 0.0029 (19) | 0.005 (2) |
C20 | 0.027 (3) | 0.032 (3) | 0.031 (3) | −0.015 (2) | 0.000 (2) | 0.005 (2) |
C21 | 0.028 (2) | 0.018 (2) | 0.023 (2) | −0.0052 (19) | −0.0010 (17) | 0.0011 (17) |
C22 | 0.022 (2) | 0.013 (2) | 0.020 (2) | 0.0055 (18) | 0.0012 (16) | −0.0030 (16) |
C23 | 0.028 (2) | 0.016 (2) | 0.026 (2) | −0.0014 (19) | −0.0006 (18) | −0.0018 (18) |
C24 | 0.032 (3) | 0.021 (2) | 0.029 (2) | 0.000 (2) | −0.0040 (19) | −0.0054 (19) |
C25 | 0.035 (3) | 0.027 (3) | 0.019 (2) | 0.010 (2) | −0.0027 (19) | −0.0040 (18) |
C26 | 0.035 (3) | 0.030 (3) | 0.020 (2) | 0.004 (2) | 0.0072 (19) | 0.0017 (19) |
C27 | 0.023 (2) | 0.024 (2) | 0.025 (2) | −0.0018 (19) | 0.0029 (18) | −0.0003 (18) |
C28 | 0.021 (2) | 0.015 (2) | 0.019 (2) | −0.0014 (17) | 0.0004 (16) | −0.0009 (16) |
O1 | 0.045 (2) | 0.0165 (17) | 0.0241 (17) | 0.0013 (15) | 0.0010 (14) | 0.0027 (13) |
C29 | 0.022 (2) | 0.0091 (19) | 0.025 (2) | −0.0034 (17) | 0.0009 (17) | 0.0002 (16) |
O2 | 0.0236 (18) | 0.0283 (19) | 0.0342 (18) | −0.0024 (15) | −0.0047 (14) | 0.0040 (15) |
C30 | 0.022 (2) | 0.016 (2) | 0.023 (2) | −0.0033 (18) | 0.0022 (17) | 0.0017 (17) |
O3 | 0.043 (2) | 0.0217 (18) | 0.0245 (17) | 0.0036 (16) | 0.0052 (15) | −0.0011 (14) |
C31 | 0.025 (2) | 0.019 (2) | 0.025 (2) | −0.0050 (19) | −0.0034 (17) | −0.0011 (18) |
O4 | 0.0215 (18) | 0.046 (2) | 0.046 (2) | −0.0021 (17) | −0.0058 (16) | 0.0017 (18) |
Mo1—C30 | 1.985 (5) | C14—C15 | 1.532 (6) |
Mo1—C28 | 1.995 (4) | C14—H14A | 0.9900 |
Mo1—C29 | 2.035 (4) | C14—H14B | 0.9900 |
Mo1—C31 | 2.052 (5) | C15—P2 | 1.838 (4) |
Mo1—P2 | 2.5185 (11) | C15—H15A | 0.9900 |
Mo1—P1 | 2.5239 (11) | C15—H15B | 0.9900 |
C1—C2 | 1.392 (6) | P2—C16 | 1.832 (4) |
C1—C6 | 1.401 (6) | P2—C22 | 1.836 (4) |
C1—P1 | 1.840 (4) | C16—C21 | 1.393 (6) |
C2—C3 | 1.380 (6) | C16—C17 | 1.401 (7) |
C2—H2 | 0.9500 | C17—C18 | 1.384 (7) |
C3—C4 | 1.382 (7) | C17—H17 | 0.9500 |
C3—H3 | 0.9500 | C18—C19 | 1.393 (8) |
C4—C5 | 1.381 (7) | C18—H18 | 0.9500 |
C4—H4 | 0.9500 | C19—C20 | 1.371 (8) |
C5—C6 | 1.381 (6) | C19—H19 | 0.9500 |
C5—H5 | 0.9500 | C20—C21 | 1.396 (7) |
C6—H6 | 0.9500 | C20—H20 | 0.9500 |
C7—C8 | 1.391 (6) | C21—H21 | 0.9500 |
C7—C12 | 1.400 (6) | C22—C27 | 1.390 (6) |
C7—P1 | 1.831 (4) | C22—C23 | 1.394 (6) |
C8—C9 | 1.394 (6) | C23—C24 | 1.396 (6) |
C8—H8 | 0.9500 | C23—H23 | 0.9500 |
C9—C10 | 1.375 (8) | C24—C25 | 1.381 (7) |
C9—H9 | 0.9500 | C24—H24 | 0.9500 |
C10—C11 | 1.384 (7) | C25—C26 | 1.388 (7) |
C10—H10 | 0.9500 | C25—H25 | 0.9500 |
C11—C12 | 1.385 (7) | C26—C27 | 1.389 (7) |
C11—H11 | 0.9500 | C26—H26 | 0.9500 |
C12—H12 | 0.9500 | C27—H27 | 0.9500 |
P1—C13 | 1.841 (4) | C28—O1 | 1.152 (5) |
C13—C14 | 1.537 (6) | C29—O2 | 1.143 (5) |
C13—H13A | 0.9900 | C30—O3 | 1.154 (5) |
C13—H13B | 0.9900 | C31—O4 | 1.133 (6) |
C30—Mo1—C28 | 90.68 (17) | P1—C13—H13B | 108.3 |
C30—Mo1—C29 | 91.63 (18) | H13A—C13—H13B | 107.4 |
C28—Mo1—C29 | 91.88 (17) | C15—C14—C13 | 114.8 (4) |
C30—Mo1—C31 | 86.08 (19) | C15—C14—H14A | 108.6 |
C28—Mo1—C31 | 86.41 (18) | C13—C14—H14A | 108.6 |
C29—Mo1—C31 | 177.12 (17) | C15—C14—H14B | 108.6 |
C30—Mo1—P2 | 90.11 (13) | C13—C14—H14B | 108.6 |
C28—Mo1—P2 | 178.65 (13) | H14A—C14—H14B | 107.5 |
C29—Mo1—P2 | 89.19 (12) | C14—C15—P2 | 116.9 (3) |
C31—Mo1—P2 | 92.56 (13) | C14—C15—H15A | 108.1 |
C30—Mo1—P1 | 178.66 (13) | P2—C15—H15A | 108.1 |
C28—Mo1—P1 | 89.88 (13) | C14—C15—H15B | 108.1 |
C29—Mo1—P1 | 89.56 (12) | P2—C15—H15B | 108.1 |
C31—Mo1—P1 | 92.75 (13) | H15A—C15—H15B | 107.3 |
P2—Mo1—P1 | 89.30 (4) | C16—P2—C22 | 100.5 (2) |
C2—C1—C6 | 118.1 (4) | C16—P2—C15 | 104.9 (2) |
C2—C1—P1 | 120.7 (3) | C22—P2—C15 | 98.03 (19) |
C6—C1—P1 | 121.2 (3) | C16—P2—Mo1 | 115.30 (14) |
C3—C2—C1 | 121.3 (4) | C22—P2—Mo1 | 119.13 (15) |
C3—C2—H2 | 119.4 | C15—P2—Mo1 | 116.30 (14) |
C1—C2—H2 | 119.4 | C21—C16—C17 | 118.6 (4) |
C2—C3—C4 | 120.2 (5) | C21—C16—P2 | 123.5 (4) |
C2—C3—H3 | 119.9 | C17—C16—P2 | 117.9 (4) |
C4—C3—H3 | 119.9 | C18—C17—C16 | 120.5 (5) |
C5—C4—C3 | 119.3 (4) | C18—C17—H17 | 119.7 |
C5—C4—H4 | 120.4 | C16—C17—H17 | 119.7 |
C3—C4—H4 | 120.4 | C17—C18—C19 | 120.3 (5) |
C6—C5—C4 | 120.9 (4) | C17—C18—H18 | 119.9 |
C6—C5—H5 | 119.5 | C19—C18—H18 | 119.9 |
C4—C5—H5 | 119.5 | C20—C19—C18 | 119.6 (5) |
C5—C6—C1 | 120.3 (4) | C20—C19—H19 | 120.2 |
C5—C6—H6 | 119.9 | C18—C19—H19 | 120.2 |
C1—C6—H6 | 119.9 | C19—C20—C21 | 120.6 (5) |
C8—C7—C12 | 118.6 (4) | C19—C20—H20 | 119.7 |
C8—C7—P1 | 123.5 (3) | C21—C20—H20 | 119.7 |
C12—C7—P1 | 117.9 (3) | C16—C21—C20 | 120.4 (5) |
C7—C8—C9 | 120.7 (5) | C16—C21—H21 | 119.8 |
C7—C8—H8 | 119.7 | C20—C21—H21 | 119.8 |
C9—C8—H8 | 119.7 | C27—C22—C23 | 118.2 (4) |
C10—C9—C8 | 119.9 (5) | C27—C22—P2 | 119.8 (3) |
C10—C9—H9 | 120.0 | C23—C22—P2 | 121.8 (3) |
C8—C9—H9 | 120.0 | C22—C23—C24 | 120.4 (4) |
C9—C10—C11 | 120.2 (5) | C22—C23—H23 | 119.8 |
C9—C10—H10 | 119.9 | C24—C23—H23 | 119.8 |
C11—C10—H10 | 119.9 | C25—C24—C23 | 120.8 (5) |
C10—C11—C12 | 120.2 (5) | C25—C24—H24 | 119.6 |
C10—C11—H11 | 119.9 | C23—C24—H24 | 119.6 |
C12—C11—H11 | 119.9 | C24—C25—C26 | 119.1 (4) |
C11—C12—C7 | 120.4 (4) | C24—C25—H25 | 120.5 |
C11—C12—H12 | 119.8 | C26—C25—H25 | 120.5 |
C7—C12—H12 | 119.8 | C25—C26—C27 | 120.3 (4) |
C7—P1—C1 | 100.96 (19) | C25—C26—H26 | 119.9 |
C7—P1—C13 | 104.1 (2) | C27—C26—H26 | 119.9 |
C1—P1—C13 | 98.26 (19) | C26—C27—C22 | 121.2 (5) |
C7—P1—Mo1 | 116.27 (14) | C26—C27—H27 | 119.4 |
C1—P1—Mo1 | 118.66 (15) | C22—C27—H27 | 119.4 |
C13—P1—Mo1 | 115.81 (14) | O1—C28—Mo1 | 178.3 (4) |
C14—C13—P1 | 115.8 (3) | O2—C29—Mo1 | 178.7 (4) |
C14—C13—H13A | 108.3 | O3—C30—Mo1 | 178.2 (4) |
P1—C13—H13A | 108.3 | O4—C31—Mo1 | 174.2 (4) |
C14—C13—H13B | 108.3 | ||
C6—C1—C2—C3 | 0.7 (7) | C13—C14—C15—P2 | 75.6 (4) |
P1—C1—C2—C3 | −176.3 (4) | C14—C15—P2—C16 | 77.7 (4) |
C1—C2—C3—C4 | 0.0 (8) | C14—C15—P2—C22 | −179.1 (3) |
C2—C3—C4—C5 | 0.1 (8) | C14—C15—P2—Mo1 | −50.9 (4) |
C3—C4—C5—C6 | −0.9 (7) | C30—Mo1—P2—C16 | 81.8 (2) |
C4—C5—C6—C1 | 1.6 (7) | C29—Mo1—P2—C16 | 173.4 (2) |
C2—C1—C6—C5 | −1.4 (6) | C31—Mo1—P2—C16 | −4.3 (2) |
P1—C1—C6—C5 | 175.5 (3) | P1—Mo1—P2—C16 | −97.04 (17) |
C12—C7—C8—C9 | −0.2 (7) | C30—Mo1—P2—C22 | −37.9 (2) |
P1—C7—C8—C9 | −178.0 (3) | C29—Mo1—P2—C22 | 53.8 (2) |
C7—C8—C9—C10 | 0.8 (7) | C31—Mo1—P2—C22 | −124.0 (2) |
C8—C9—C10—C11 | −0.6 (8) | P1—Mo1—P2—C22 | 143.33 (16) |
C9—C10—C11—C12 | −0.1 (8) | C30—Mo1—P2—C15 | −154.9 (2) |
C10—C11—C12—C7 | 0.7 (7) | C29—Mo1—P2—C15 | −63.2 (2) |
C8—C7—C12—C11 | −0.6 (7) | C31—Mo1—P2—C15 | 119.1 (2) |
P1—C7—C12—C11 | 177.4 (4) | P1—Mo1—P2—C15 | 26.34 (16) |
C8—C7—P1—C1 | 99.0 (4) | C22—P2—C16—C21 | −106.0 (4) |
C12—C7—P1—C1 | −78.8 (4) | C15—P2—C16—C21 | −4.7 (4) |
C8—C7—P1—C13 | −2.5 (4) | Mo1—P2—C16—C21 | 124.6 (3) |
C12—C7—P1—C13 | 179.7 (3) | C22—P2—C16—C17 | 71.7 (4) |
C8—C7—P1—Mo1 | −131.1 (3) | C15—P2—C16—C17 | 173.0 (4) |
C12—C7—P1—Mo1 | 51.0 (4) | Mo1—P2—C16—C17 | −57.7 (4) |
C2—C1—P1—C7 | −34.5 (4) | C21—C16—C17—C18 | 0.7 (7) |
C6—C1—P1—C7 | 148.6 (4) | P2—C16—C17—C18 | −177.1 (4) |
C2—C1—P1—C13 | 71.7 (4) | C16—C17—C18—C19 | −0.2 (8) |
C6—C1—P1—C13 | −105.2 (4) | C17—C18—C19—C20 | −0.9 (8) |
C2—C1—P1—Mo1 | −162.8 (3) | C18—C19—C20—C21 | 1.4 (8) |
C6—C1—P1—Mo1 | 20.3 (4) | C17—C16—C21—C20 | −0.2 (7) |
C28—Mo1—P1—C7 | −83.9 (2) | P2—C16—C21—C20 | 177.4 (3) |
C29—Mo1—P1—C7 | −175.8 (2) | C19—C20—C21—C16 | −0.8 (7) |
C31—Mo1—P1—C7 | 2.5 (2) | C16—P2—C22—C27 | 35.7 (4) |
P2—Mo1—P1—C7 | 95.04 (16) | C15—P2—C22—C27 | −71.1 (4) |
C28—Mo1—P1—C1 | 36.9 (2) | Mo1—P2—C22—C27 | 162.6 (3) |
C29—Mo1—P1—C1 | −55.0 (2) | C16—P2—C22—C23 | −148.8 (4) |
C31—Mo1—P1—C1 | 123.3 (2) | C15—P2—C22—C23 | 104.4 (4) |
P2—Mo1—P1—C1 | −144.21 (16) | Mo1—P2—C22—C23 | −21.8 (4) |
C28—Mo1—P1—C13 | 153.4 (2) | C27—C22—C23—C24 | 0.1 (7) |
C29—Mo1—P1—C13 | 61.5 (2) | P2—C22—C23—C24 | −175.5 (4) |
C31—Mo1—P1—C13 | −120.2 (2) | C22—C23—C24—C25 | −0.3 (7) |
P2—Mo1—P1—C13 | −27.70 (16) | C23—C24—C25—C26 | 0.2 (7) |
C7—P1—C13—C14 | −75.1 (3) | C24—C25—C26—C27 | 0.2 (7) |
C1—P1—C13—C14 | −178.7 (3) | C25—C26—C27—C22 | −0.5 (7) |
Mo1—P1—C13—C14 | 53.8 (3) | C23—C22—C27—C26 | 0.3 (7) |
P1—C13—C14—C15 | −77.1 (4) | P2—C22—C27—C26 | 176.0 (4) |
Experimental details
Crystal data | |
Chemical formula | [Mo(C27H26P2)(CO)4] |
Mr | 620.40 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 120 |
a, b, c (Å) | 15.5925 (6), 8.8293 (3), 21.0760 (6) |
β (°) | 91.979 (2) |
V (Å3) | 2899.82 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.60 |
Crystal size (mm) | 0.10 × 0.05 × 0.03 |
Data collection | |
Diffractometer | Bruker-Nonius 95mm CCD camera on κ-goniostat |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.965, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 33177, 6604, 5497 |
Rint | 0.076 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.135, 1.17 |
No. of reflections | 6604 |
No. of parameters | 343 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + 15.4402P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.34, −0.72 |
Computer programs: COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, SHELXTL (Bruker, 2000), SHELXTL and local programs.
1 | 1' | 2 | |
Mo—C(trans to C) | 2.035 (4)/2.052 (5) | 2.035 (7)/2.023 (7) | 2.016 (3)/2.043 (3) |
Mo—C(trans to P) | 1.995 (4)/1.985 (5) | 1.968 (5)/1.968 (5) | 2.007 (3)/1.994 (3) |
Mo—P | 2.5239 (11)/2.5185 (11) | 2.538 (1)/2.538 (1) | 2.5005 (8)/2.4986 (8) |
C—Mo—C(trans to C) | 177.12 (17) | 174.8 (3) | 178.21 (12) |
C—Mo—C(cis, av.) | 89.34 (18) | 88.7 (2) | 89.72 (13) |
P—Mo—P | 89.30 (4) | 89.74 (4) | 86.75 (2) |
Notes: (I) this work; (I') orthorhombic polymorph (Ueng & Hwang, 1991); (II) [Mo(CO4){Ph2PCH2N(Ph)CH2PPh2}] (Sanchez-Ballester et al., 2007). |
Ditertiary phosphines are valuable synthetic tools widely used in coordination chemistry and homogeneous catalysis. (Sekabunga et al., 2002; Wu & Li, 2003; Balch et al., 1990). A number of Mo—P—C—X—C—P (X = N or C) forming a six-membered chelated metallocycle have been described in the literature (Sanchez-Ballester et al., 2007; Ueng & Hwang, 1991). A second polymorph of Mo(CO)4{Ph2P(CH2)3PPh2} I has been structurally determined (Figure 1), with selected geometric data in Table 1, together with those for the related compounds Mo(CO4){Ph2P(CH2)3PPh2}, I' (Ueng & Hwang, 1991), and [Mo(CO4){Ph2PCH2N(Ph)CH2PPh2}], II (Sanchez-Ballester et al., 2007). The Mo—P bond lengths and P—Mo—P bite angle in (I) are similar to (I') but slightly longer than 2. The six-membered chelate ring in (I) adopts a chair conformation with C14 above the P2C2 mean plane by 0.747 (6)Å and Mo below the plane by 0.764 (3) Å. Figures 2 and 3 show packing plots of (I) and (I') viewed along the crystallographic b and c axes respectively. These show the substantial differences in packing between the two polymorphs. In (I) adjacent molecules are off-set and canted by 26° with respect to the ab plane with a whole molecule in the asymmetric unit, while in (I') molecules lie directly stacked in parallel columns with individual molecules lying on mirror planes.
In summary, we have reported the crystal structure of a new monoclinic, polymorph I that displays very similar Mo—P/Mo—CO bond lengths, bond angles and core molecular conformation to the known orthorhombic, polymorph I' (Ueng & Hwang, 1991), but substantial differences in crystal packing.