fac-Tricarbonyl[bis(2-pyridylmethyl) ether-N,O,N']molybdenum(0)

Reaction of bis(2-pyridylmethyl) ether with [Mo(CO)₃­(Me­CN)₃] in MeCN gives the title compound, [Mo(C₁₂H₁₂-N₂O)(CO)₃], (I), as a yellow crystalline product. Compound (I) has been characterized by ¹H NMR and IR spectroscopy, and single-crystal X-ray crystallography. In contrast with other examples of low-valent early transition metal complexes of ethers, the ether linkage of (I) appears relatively inert. Nevertheless, the weak donor property of the ether ligand is evidenced by a trans effect manifested as a short Mo-CO bond length for the carbonyl ligand trans to the ether ligand.

S1. Comment

Low-valent early transition metals (e.g. zero-valent group six metals) generally prefer to be ligated by soft donors, preferably π-acids. Ethers are particularly poor ligands for such metals since they are generally weak Lewis bases, they bear hard donor atoms, and they are incapable of charge-balancing via back donation. These properties of ethers have been advantageous in the development of hemi-labile ligands (Chadwell et al., 1996; Dunbar et al., 1990, 1994; Mason et al., 1991). In the present study, a relatively stable ether complex has been synthesized by employing the chelating ligand bis(2-pyridylmethyl) ether (bpme). In contrast to other metal-ether complexes that react with nitriles (Anderson & Kumar, 1984; Dunbar et al., 1990; Lindner et al., 1987), the title compound is synthesized in acetonitrile, and its ether ligand shows no propensity for substitution by donor solvents.

The ¹H-NMR spectrum of (I) is comparable to that of the free bpme ligand, although the methylene groups of (I) are diastereotopic. At 300 MHz, the methylene region is second-order. The chemical shifts and coupling constants for the methylene groups of (I) that are reported in the experimental section were derived from the second-order spectrum. The infrared spectrum of (I) as a KBr pellet exhibits a sharp band at 1905 cm⁻¹ and a broad, multi-featured band at 1800 cm⁻¹. These carbonyl vibrational frequencies are quite low. For comparison, the carbonyl stretching frequencies for [Mo(CO)₃L] where L = η⁶-benzene (Barbeau & Turcotte, 1976), 1,4,7-trithiacyclononane (ttcn) (Ashby et al., 1986; Ashby & Lichtenberger, 1985) and 1,4,7-triazacyclononane (tacn) (Chandhuri et al., 1984) occur at 1985 and 1912, 1915 and 1783, and 1850 and 1730 cm⁻¹, respectively. Thus, the overall donor/acceptor ability of the bpme ligand is comparable to a soft σ-donor such as ttcn. Hard σ-donors such as tacn deliver considerably more electron density to the metal that is ultimately nullified in part by back-donation to the carbonyl ligands.

The Mo—N bond lengths of (I), 2.253 (2) and 2.265 (2) Å, are statistically equivalent to the average Mo—N distance of 2.266 (5) Å that has been found for 25 Mo(0)-pyridyl bonds (which range from 2.197 to 2.353 Å) (Allen & Kennard, 1993). In contrast, the Mo—O bond length of (I), 2.290 (2) Å, is somewhat shorter than those previously reported for six Mo(0)-ether linkages (which range from 2.316 to 2.363 Å) (Allen & Kennard, 1993). This shorter bond length may reflect a tighter binding of the O-donor of bpme. Interestingly, a trans effect is observed for (I) with respect to the Mo-carbonyl bond lengths. The Mo—CO that is trans to the ether ligand, 1.915 (3) Å, is statistically shorter than the two that are trans to pyridyl ligands, 1.939 (3) and 1.955 (3) Å. A similar trans effect is observed for other zero-valent group six metal carbonyl complexes that bear ether ligands. Thus for [Cr(CO)₅(THF)], the Cr—(trans-CO) bond length is 1.812 (5) Å, whereas the average Cr—(cis-CO) bond length is 1.899 (11) Å (Schubert et al., 1978). For a compound that is perhaps more closely related to (I), {Mo(CO)₃[(Ph₂CH₂P(CH₂CH₂OEt)₂]₂}, one finds the Mo—CO bond lengths for the CO ligands that are trans to phosphine ligands, 1.964 (4) and 1.968 (4) Å, are longer than that for the CO that is trans to an ether ligand, 1.914 (4) Å (Chadwell et al., 1996). A similar situation is observed for a related W compound where two 1.98 (1) Å bond lengths are observed for CO ligands trans to phosphine-donors and 1.91 (1) Å for a CO ligand that is trans to an ether-donor (Mason et al., 1991). The crystal structure of [Mo(CO)₄(P(C₆H₂(OMe)₃)₃] nicely illustrates the comparative effects of CO, PR3 and OR2 on metal-carbonyl bond lengths (Dunbar et al., 1994). Since ether ligands are ineffectual π-donors, the short M—CO bond lengths for the carbonyl ligands trans to ether ligands may be attributed to a weak M—O σ bond.

S2. Experimental

Preparation of bis(2-pyridylmethyl) ether (bpme): to dry THF (20 ml) was added NaH (0.6 g of a 60% wt suspension in oil, 15 mmol) and 2-pyridylcarbinol (1.5 ml, 1.7 g, 15 mmol). After refluxing for 2 h, the solution was cooled to room temperature and 2-pyridylmethyl-p-toluenesulfonate (4.0 g, 15 mmol; preparation deposited) was added. The mixture was refluxed 2 d. After cooling to room temperature, water (50 ml) was added, and the product was extracted with ether (2 x 50 ml). The organic layer was dried with CaCl₂, and the ether was removed on a rotary evaporator to give the crude product as a yellow oil. The crude oil was dissolved in 5% aqueous HCl (100 ml) and an organic impurity was removed by extraction with ether (2 x 50 ml). The aqueous layer was neutralized with aqueous NaOH. The product was extracted with ether (2 x 50 ml), the organic layer was dried with CaCl₂, and the ether was removed on a rotary evaporator to give the product as a colorless oil (19% yield). ¹H NMR (CDCl₃, 293 K, 300 MHz): d 8.55 (d, 1H, J = 4 Hz); 7.70 (td, 1H, J = 8, J' = 2 Hz); 7.51 (d, 1H, J = 8 Hz); 7.22 (dd, 1H, J = 5, J' = 7 Hz); 4.77 (s, 2H).

Preparation of tricarbonyl[bis(2-pyridylmethyl) ether-N,O,N']molybdenum(0), (I): acetonitrile (30 ml) and Mo(CO)₆ (309 mg, 1.17 mmol) were added to a Schlenk flask. The resulting solution was freeze-pump-thawed and the flask was placed in an 353 K oil bath. After 1 h, the flask was removed from the oil bath, the solution was frozen, and the CO that had evolved was pumped away. The flask was returned to the oil bath and the process of removing the CO was repeated twice more. The ligand (250 mg, 1.25 mmol) was added, the solution was freeze-pump-thawed, and the sealed flask was returned to the oil bath for 1 h. The resulting yellow precipitate was collected on a Schlenk frit, washed with dry pentane and dried under vacuum (47% yield). ¹H NMR (acetone-d₆, 293 K, 300 MHz): d 8.91 (d, 1H, J = 5 Hz); 7.79 (td, 1H, J = 8, J' = 2 Hz); 7.38 (d, 1H, J = 8 Hz);7.30 (t, 1H, J = 8 Hz); 5.52, 5.15 (AB, 2H, J = 16 Hz). IR(KBr) 1905 (s), 1800 (br) cm⁻¹. Analysis calculated for C₁₅H₁₂N₂O₄Mo (fw = 548.20): C 32.86, H 2.21°. Found: C 33.41, H 2.96°.

S3. Refinement

Based on systematic absences of 0kl, k = 2n + 1, h0l, l = 2n + 1, and hk0, h = 2n + 1 the space group was uniquely determined to be Pbca (#61). The H atoms were located in the difference map and refined isotropically; C—H distances are in the range 0.90 (3)–1.05 (4) Å. Absorption correction was not applied since it was judged to be insignificant.

Computing details

Data collection: XSCANS (Siemens 1994a); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Siemens 1994b); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. Molecular structure and labeling scheme showing 50% probability displacement ellipsoids. H atoms are omitted for clarity.

(I)

Crystal data

[Mo(C12H12N2O)(CO)3]	Dx = 1.659 Mg m^−3
Mr = 380.21	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 38 reflections
a = 13.864 (1) Å	θ = 10.6–25.0°
b = 13.339 (1) Å	µ = 0.88 mm^−1
c = 16.464 (1) Å	T = 198 K
V = 3044.7 (4) Å^3	Plate, yellow
Z = 8	0.36 × 0.28 × 0.24 mm
F(000) = 1520

Data collection

Siemens P4 diffractometer	Rint = 0.022
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.5°
Graphite monochromator	h = −1→16
2θ/ω scans	k = −1→15
3376 measured reflections	l = −19→1
2660 independent reflections	3 standard reflections every 97 reflections
2196 reflections with I > 2σ(I)	intensity decay: 6.7%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.024	Hydrogen site location: difference Fourier map
wR(F^2) = 0.061	All H-atom parameters refined
S = 1.07	Calculated w = 1/[σ^2(Fo^2) + (0.0289P)^2 + 0.7814P] where P = (Fo^2 + 2Fc^2)/3
2655 reflections	(Δ/σ)max = 0.010
247 parameters	Δρmax = 0.40 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

Special details

Experimental. Acetonitrile was distilled from P₂O₅, then distilled from CaH₂, and finally vacuum transferred into the Schlenk flask that was used for the reaction. Tetrahydrofuran (THF) was predried over CaCl₂, then distilled from sodium benzophenone ketal. The 2-pyridylcarbinol was freshly distilled under vacuum before use. The other reagents were used as received from Aldrich. ¹H-NMR spectra were recorded on a Varian XL-300 using the residual CHCl₃ (7.25 p.p.m.) or acetone-d5 (2.05 p.p.m.) as internal standards. The NMR sample of (I) was prepared in a tube that had been glass-blown onto a Schlenk adapter. The solution was freeze-pump-thawed and the tube was flame-sealed under vacuum. The infrared spectrum of (I) was obtained on a Bio-Rad 175 C s pectrophotometer as a KBR pellet that was prepared in a glovebox under argon.

Preparation of 2-pyridylmethyl-p-touluenesulfonate: to dry THF (150 ml) was added NaH (8.5 g of a 60% wt suspension in oil, 210 mmol). A solution of 2-pyridylcarbinol (20.0 ml, 22.6 g, 210 mmol) in THF (30 ml) was added dropwise over a period of 30 min. After 1 h of stirring at room temperature, p-toluenesulfonyl chloride (40.0 g, 210 mmol) was added and the mixture was refluxed overnight. After cooling to room temperature, water (250 ml) was added, and the product was extracted with ether (2 x 100 ml). The organic layer was dried with CaCl₂, and the ether was removed on a rotary evaporator. The product was recrystallized from diethyl ether and pentane to give a colorless crystalline solid in 66% yield. ¹H NMR (CDCl₃, 293 K, 300 MHz): d 8.51 (d, 1H, J = 5 Hz); 7.83 (d, 2H, J = 8 Hz); 7.70 (t, 1H, J = 6 Hz); 7.43 (d, 1H, J = 8 Hz); 7.34 (d, 2H, J = 8 Hz); 7.22 (m, 1H); 5.14 (s, 2H); 2.45 (s, 3H).

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 on F² for ALL reflections except for 5 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating _refine_ls_R_factor_gt 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 (Ų)

	x	y	z	Uiso*/Ueq
Mo1	0.036449 (14)	0.23082 (2)	0.145273 (13)	0.03527 (9)
N1	−0.03950 (14)	0.2682 (2)	0.26240 (14)	0.0407 (5)
N2	−0.0415 (2)	0.3727 (2)	0.10793 (13)	0.0422 (5)
O1	0.11758 (13)	0.36238 (14)	0.20283 (10)	0.0465 (4)
O3	−0.1072 (2)	0.0708 (2)	0.08466 (14)	0.0657 (6)
O4	0.1675 (2)	0.0572 (2)	0.2064 (2)	0.0811 (7)
O5	0.1505 (2)	0.2018 (2)	−0.01524 (13)	0.0642 (6)
C1	0.1050 (2)	0.3625 (3)	0.2899 (2)	0.0556 (8)
C2	0.1005 (3)	0.4554 (3)	0.1621 (2)	0.0659 (9)
C3	−0.0516 (2)	0.1309 (2)	0.1068 (2)	0.0435 (6)
C4	0.1166 (2)	0.1211 (2)	0.1858 (2)	0.0493 (7)
C5	0.1066 (2)	0.2141 (2)	0.0443 (2)	0.0424 (6)
C11	0.0040 (2)	0.3336 (2)	0.3129 (2)	0.0428 (6)
C12	−0.0395 (2)	0.3673 (3)	0.3834 (2)	0.0519 (7)
C13	−0.1299 (2)	0.3329 (3)	0.4024 (2)	0.0604 (8)
C14	−0.1751 (2)	0.2668 (3)	0.3515 (2)	0.0563 (8)
C15	−0.1287 (2)	0.2364 (2)	0.2824 (2)	0.0460 (6)
C21	0.0005 (2)	0.4606 (2)	0.1256 (2)	0.0471 (6)
C22	−0.0432 (3)	0.5509 (2)	0.1086 (2)	0.0644 (9)
C23	−0.1335 (3)	0.5518 (3)	0.0752 (2)	0.0706 (10)
C24	−0.1778 (2)	0.4625 (2)	0.0573 (2)	0.0632 (9)
C25	−0.1303 (2)	0.3750 (2)	0.0741 (2)	0.0481 (6)
H1'	0.116 (2)	0.428 (3)	0.310 (2)	0.074 (11)*
H1"	0.152 (3)	0.311 (3)	0.312 (2)	0.083 (11)*
H2'	0.109 (3)	0.514 (3)	0.204 (2)	0.078 (11)*
H2"	0.150 (3)	0.464 (3)	0.117 (2)	0.090 (12)*
H12	−0.011 (2)	0.414 (3)	0.4146 (18)	0.056 (9)*
H13	−0.159 (2)	0.359 (3)	0.449 (2)	0.073 (10)*
H14	−0.236 (3)	0.237 (2)	0.364 (2)	0.068 (10)*
H15	−0.160 (2)	0.193 (2)	0.2437 (17)	0.051 (8)*
H22	−0.009 (3)	0.612 (3)	0.120 (2)	0.078 (11)*
H23	−0.163 (2)	0.613 (3)	0.068 (2)	0.080 (11)*
H24	−0.244 (3)	0.460 (3)	0.030 (2)	0.094 (12)*
H25	−0.156 (2)	0.308 (2)	0.0574 (17)	0.052 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.02889 (13)	0.03483 (14)	0.04207 (14)	−0.00280 (8)	−0.00089 (9)	−0.00431 (9)
N1	0.0350 (11)	0.0414 (12)	0.0456 (12)	0.0000 (9)	−0.0001 (9)	0.0013 (10)
N2	0.0413 (12)	0.0360 (11)	0.0491 (13)	−0.0028 (9)	0.0029 (10)	−0.0033 (10)
O1	0.0406 (10)	0.0501 (11)	0.0488 (10)	−0.0108 (9)	0.0012 (8)	−0.0075 (9)
O3	0.0629 (14)	0.0536 (13)	0.0805 (15)	−0.0242 (11)	−0.0183 (12)	0.0040 (11)
O4	0.078 (2)	0.066 (2)	0.100 (2)	0.0236 (14)	−0.0180 (14)	0.0079 (14)
O5	0.0569 (12)	0.0764 (15)	0.0593 (13)	0.0010 (11)	0.0126 (11)	−0.0134 (12)
C1	0.046 (2)	0.073 (2)	0.049 (2)	−0.013 (2)	0.0005 (13)	−0.016 (2)
C2	0.065 (2)	0.053 (2)	0.080 (2)	−0.021 (2)	−0.017 (2)	0.007 (2)
C3	0.0415 (14)	0.0415 (15)	0.047 (2)	0.0005 (12)	−0.0026 (11)	0.0054 (13)
C4	0.0428 (15)	0.052 (2)	0.053 (2)	−0.0025 (14)	−0.0022 (13)	−0.0046 (14)
C5	0.0347 (12)	0.0403 (15)	0.052 (2)	−0.0020 (11)	−0.0015 (12)	−0.0057 (12)
C11	0.0388 (13)	0.046 (2)	0.0437 (14)	0.0021 (12)	−0.0055 (11)	−0.0018 (12)
C12	0.054 (2)	0.058 (2)	0.0439 (14)	0.0035 (14)	−0.0035 (13)	−0.0059 (15)
C13	0.050 (2)	0.082 (2)	0.049 (2)	0.009 (2)	0.0087 (14)	−0.001 (2)
C14	0.0376 (15)	0.075 (2)	0.056 (2)	−0.0011 (15)	0.0046 (13)	0.005 (2)
C15	0.0339 (13)	0.051 (2)	0.053 (2)	−0.0032 (12)	−0.0028 (12)	0.0054 (13)
C21	0.0484 (15)	0.042 (2)	0.051 (2)	−0.0060 (13)	0.0021 (13)	−0.0054 (13)
C22	0.078 (2)	0.039 (2)	0.077 (2)	−0.007 (2)	0.000 (2)	−0.006 (2)
C23	0.077 (2)	0.046 (2)	0.088 (2)	0.015 (2)	0.000 (2)	0.004 (2)
C24	0.051 (2)	0.054 (2)	0.085 (2)	0.008 (2)	−0.005 (2)	0.009 (2)
C25	0.0395 (14)	0.044 (2)	0.061 (2)	−0.0017 (12)	−0.0027 (13)	−0.0006 (14)

Geometric parameters (Å, º)

Mo1—C3	1.915 (3)	C2—H2'	1.05 (4)
Mo1—C5	1.939 (3)	C2—H2"	1.02 (4)
Mo1—C4	1.955 (3)	C11—C12	1.383 (4)
Mo1—N1	2.253 (2)	C12—C13	1.371 (4)
Mo1—N2	2.265 (2)	C12—H12	0.90 (3)
Mo1—O1	2.290 (2)	C13—C14	1.369 (5)
N1—C15	1.348 (3)	C13—H13	0.94 (3)
N1—C11	1.348 (3)	C14—C15	1.369 (4)
N2—C21	1.341 (4)	C14—H14	0.95 (4)
N2—C25	1.350 (3)	C15—H15	0.96 (3)
O1—C2	1.430 (4)	C21—C22	1.376 (4)
O1—C1	1.444 (3)	C22—C23	1.367 (5)
O3—C3	1.170 (3)	C22—H22	0.96 (4)
O4—C4	1.157 (4)	C23—C24	1.372 (5)
O5—C5	1.165 (3)	C23—H23	0.92 (4)
C1—C11	1.501 (4)	C24—C25	1.369 (4)
C1—H1'	0.94 (3)	C24—H24	1.01 (3)
C1—H1"	1.01 (4)	C25—H25	1.01 (3)
C2—C21	1.513 (5)
C3—Mo1—C5	87.49 (11)	H2'—C2—H2"	109 (3)
C3—Mo1—C4	87.33 (12)	O3—C3—Mo1	178.2 (2)
C5—Mo1—C4	85.47 (11)	O4—C4—Mo1	176.3 (3)
C3—Mo1—N1	98.01 (10)	O5—C5—Mo1	178.0 (2)
C5—Mo1—N1	173.59 (9)	N1—C11—C12	122.2 (3)
C4—Mo1—N1	98.02 (10)	N1—C11—C1	115.3 (2)
C3—Mo1—N2	100.83 (10)	C12—C11—C1	122.4 (3)
C5—Mo1—N2	95.92 (10)	C13—C12—C11	118.8 (3)
C4—Mo1—N2	171.76 (10)	C13—C12—H12	120 (2)
N1—Mo1—N2	79.88 (8)	C11—C12—H12	121 (2)
C3—Mo1—O1	169.56 (9)	C14—C13—C12	119.7 (3)
C5—Mo1—O1	101.32 (9)	C14—C13—H13	123 (2)
C4—Mo1—O1	98.84 (10)	C12—C13—H13	117 (2)
N1—Mo1—O1	72.88 (7)	C15—C14—C13	119.0 (3)
N2—Mo1—O1	72.92 (8)	C15—C14—H14	118 (2)
C15—N1—C11	117.6 (2)	C13—C14—H14	123 (2)
C15—N1—Mo1	124.6 (2)	N1—C15—C14	122.7 (3)
C11—N1—Mo1	117.5 (2)	N1—C15—H15	116.1 (17)
C21—N2—C25	117.8 (2)	C14—C15—H15	121.1 (17)
C21—N2—Mo1	117.7 (2)	N2—C21—C22	122.0 (3)
C25—N2—Mo1	124.4 (2)	N2—C21—C2	116.3 (3)
C2—O1—C1	116.4 (3)	C22—C21—C2	121.6 (3)
C2—O1—Mo1	112.9 (2)	C23—C22—C21	119.5 (3)
C1—O1—Mo1	110.6 (2)	C23—C22—H22	122 (2)
O1—C1—C11	111.3 (2)	C21—C22—H22	119 (2)
O1—C1—H1'	109 (2)	C22—C23—C24	119.2 (3)
C11—C1—H1'	107 (2)	C22—C23—H23	118 (2)
O1—C1—H1"	106 (2)	C24—C23—H23	123 (2)
C11—C1—H1"	110 (2)	C25—C24—C23	118.8 (3)
H1'—C1—H1"	114 (3)	C25—C24—H24	120 (2)
O1—C2—C21	112.3 (2)	C23—C24—H24	122 (2)
O1—C2—H2'	108.7 (18)	N2—C25—C24	122.7 (3)
C21—C2—H2'	109.4 (19)	N2—C25—H25	114.9 (16)
O1—C2—H2"	109 (2)	C24—C25—H25	122.2 (16)
C21—C2—H2"	109 (2)
C3—Mo1—N1—C15	−10.3 (2)	O1—Mo1—C3—O3	−9 (8)
C5—Mo1—N1—C15	138.7 (8)	C3—Mo1—C4—O4	108 (4)
C4—Mo1—N1—C15	−98.7 (2)	C5—Mo1—C4—O4	20 (4)
N2—Mo1—N1—C15	89.4 (2)	N1—Mo1—C4—O4	−155 (4)
O1—Mo1—N1—C15	164.5 (2)	N2—Mo1—C4—O4	−80 (4)
C3—Mo1—N1—C11	175.5 (2)	O1—Mo1—C4—O4	−81 (4)
C5—Mo1—N1—C11	−35.5 (9)	C3—Mo1—C5—O5	−90 (7)
C4—Mo1—N1—C11	87.1 (2)	C4—Mo1—C5—O5	−2 (7)
N2—Mo1—N1—C11	−84.9 (2)	N1—Mo1—C5—O5	121 (6)
O1—Mo1—N1—C11	−9.8 (2)	N2—Mo1—C5—O5	170 (7)
C3—Mo1—N2—C21	−179.9 (2)	O1—Mo1—C5—O5	96 (7)
C5—Mo1—N2—C21	−91.3 (2)	C15—N1—C11—C12	0.5 (4)
C4—Mo1—N2—C21	7.9 (8)	Mo1—N1—C11—C12	175.2 (2)
N1—Mo1—N2—C21	83.8 (2)	C15—N1—C11—C1	177.1 (3)
O1—Mo1—N2—C21	8.7 (2)	Mo1—N1—C11—C1	−8.3 (3)
C3—Mo1—N2—C25	4.8 (2)	O1—C1—C11—N1	31.9 (4)
C5—Mo1—N2—C25	93.4 (2)	O1—C1—C11—C12	−151.5 (3)
C4—Mo1—N2—C25	−167.4 (6)	N1—C11—C12—C13	0.0 (5)
N1—Mo1—N2—C25	−91.5 (2)	C1—C11—C12—C13	−176.3 (3)
O1—Mo1—N2—C25	−166.6 (2)	C11—C12—C13—C14	−0.3 (5)
C3—Mo1—O1—C2	−76.3 (5)	C12—C13—C14—C15	0.0 (5)
C5—Mo1—O1—C2	70.9 (2)	C11—N1—C15—C14	−0.8 (4)
C4—Mo1—O1—C2	158.0 (2)	Mo1—N1—C15—C14	−175.0 (2)
N1—Mo1—O1—C2	−106.3 (2)	C13—C14—C15—N1	0.6 (5)
N2—Mo1—O1—C2	−21.9 (2)	C25—N2—C21—C22	−1.4 (4)
C3—Mo1—O1—C1	56.2 (6)	Mo1—N2—C21—C22	−177.1 (2)
C5—Mo1—O1—C1	−156.6 (2)	C25—N2—C21—C2	−179.0 (3)
C4—Mo1—O1—C1	−69.5 (2)	Mo1—N2—C21—C2	5.4 (3)
N1—Mo1—O1—C1	26.2 (2)	O1—C2—C21—N2	−24.9 (4)
N2—Mo1—O1—C1	110.6 (2)	O1—C2—C21—C22	157.6 (3)
C2—O1—C1—C11	91.7 (3)	N2—C21—C22—C23	2.1 (5)
Mo1—O1—C1—C11	−38.9 (3)	C2—C21—C22—C23	179.6 (3)
C1—O1—C2—C21	−98.0 (3)	C21—C22—C23—C24	−1.6 (6)
Mo1—O1—C2—C21	31.6 (4)	C22—C23—C24—C25	0.4 (6)
C5—Mo1—C3—O3	−157 (8)	C21—N2—C25—C24	0.2 (4)
C4—Mo1—C3—O3	118 (8)	Mo1—N2—C25—C24	175.5 (2)
N1—Mo1—C3—O3	20 (8)	C23—C24—C25—N2	0.3 (5)
N2—Mo1—C3—O3	−61 (8)