(4,4′,6,6′-Tetra-tert-butyl-2,2′-{[2-(di­methyl­amino)­ethyl]­nitrilo­bis­(methyl­ene)}diphenolato)dioxidomolyb­denum(VI) chloro­form monosolvate

Lei, X.; Chelamalla, N.

doi:10.1107/S160053681104092X

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page m1510

doi:10.1107/S160053681104092X

Open

access

(4,4′,6,6′-Tetra-tert-butyl-2,2′-{[2-(dimethylamino)ethyl]nitrilobis(methylene)}diphenolato)dioxidomolybdenum(VI) chloroform monosolvate

Xiangyang Lei ^a ^* and Nagasree Chelamalla ^a

^aDepartment of Chemistry & Biochemistry, Lamar University, Beaumont, TX 77710, USA
^*Correspondence e-mail: xlei@lamar.edu

(Received 12 August 2011; accepted 4 October 2011; online 12 October 2011)

In the title compound, [Mo(C₃₄H₅₄N₂O₂)O₂]·CHCl₃, the molybdenum(VI) ion exhibits a cis-dioxide distorted octahedral geometry. Two anionic phenolate O-atom donors and two neutral N-atom donors of the ligand are trans and cis, respectively. The Mo=O bond lengths and the O=Mo=O bond angle are typical for six-coordinated dioxomolybdenum(VI) complexes. The Mo—N bond lengths are longer than 2.30 Å, as expected for a trans O=Mo—N structure.

Related literature

For molybdenum coordination complexes as catalysts, see: Wong et al. (2010 ); Rappe & Goddard (1982 ). For the synthesis of the ligand, see: Tshuva et al. (2001 ). For incorporation of the molybdenum center into redox enzymes, see: Tucci et al. (1998 ); Schultz et al. (1993 ). For spectroscopic and NMR data, see: Lehtonen et al. (2006 ). For related structures, see: Hinshaw et al. (1989 ); Lehtonen & Sillanpää (2005 ).

Experimental

Crystal data

[Mo(C₃₄H₅₄N₂O₂)O₂]·CHCl₃
M_r = 770.10
Orthorhombic, P n a 2₁
a = 24.3475 (10) Å
b = 13.9748 (6) Å
c = 11.0267 (4) Å
V = 3751.9 (3) Å³
Z = 4
Cu Kα radiation
μ = 5.12 mm⁻¹
T = 110 K
0.50 × 0.20 × 0.02 mm

Data collection

Bruker MWPC area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.184, T_max = 0.904
79926 measured reflections
5548 independent reflections
5061 reflections with I > 2σ(I)
R_int = 0.081
θ_max = 60.0°

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.078
S = 1.00
5548 reflections
421 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.51 e Å⁻³
Absolute structure: Flack (1983 ), 2649 Friedel pairs
Flack parameter: 0.000 (9)

Data collection: FRAMBO (Bruker, 1999 ); cell refinement: FRAMBO; data reduction: SAINT (Bruker, 2004 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); 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/S160053681104092X/jj2100sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681104092X/jj2100Isup2.hkl

checkCIF report

Comment top

Molybdenum coordination complexes have attracted considerable attention because they can catalyze a variety of chemical reactions such as olefin epoxidation (Wong et al. 2010) and olefin metathesis (Rappe & Goddard, 1982) reactions. In addition, molybdenum is also a necessary element in diverse biological systems whereby the molybdenum center is incorporated into various redox enzymes such as DMSO reductase (Tucci et al. 1998) and xanthine oxidase (Schultz et al. 1993). A number of related dioxomolybdenum(VI) complexes with tetradentate ligands have been reported (Hinshaw et al. 1989; Lehtonen & Sillanpää, 2005).

While the X-ray structure of the title compound is described here, its synthesis, IR, and ¹H & ¹³C NMR data have been reported (Lehtonen et al. 2006). The title complex contains one crystallographically unique molybdenum ion in a cis-dioxo distorted octahedral geometry. The aminobis(phenolate) moiety is coordinated to the MoO₂²⁺ unit as a tripodal tetradentate ligand though two anionic phenolate oxygen donors (trans to each other) and two neutral nitrogen donors (cis to each other). The Mo=O bond lengths (1.702 (2) and 1.702 (3) Å for Mo=O3 and Mo=O4, respectively) and the O=Mo=O bond angle (108.33 (13)°) are typical for six-coordinated dioxomolybdenum(VI) complexes. The bond lengths of Mo—N1 and Mo—N2 are 2.392 (3) and 2.422 (3) Å, respectively, both of which are > 2.30 Å as expected for the trans O=Mo—N structure as well as a distorted octahedral geometry.

Related literature top

For molybdenum coordination complexes as catalysts, see: Wong et al. (2010); Rappe & Goddard (1982). For the synthesis of the ligand, see: Tshuva et al. (2001). For incorporation of the molybdenum center into redox enzymes, see: Tucci et al. (1998); Schultz et al. (1993); For spectroscopic and NMR data, see: Lehtonen et al. (2006). For related structures, see: Hinshaw et al. (1989); Lehtonen & Sillanpää (2005).

Experimental top

To a solution of 0.52 g (1.00 mmol) of 6,6'-(2-(dimethylamino)ethylazanediyl)bis(methylene)bis(2,4-di-tert-butylphenol) (Tshuva et al. 2001) in 10 ml of CH₂Cl₂ and 10 ml of CH₃OH was added 0.33 g (1.06 mmol) of MoO₂(acac)₂. The resulting orange solution was stirred overnight at room temperature. The yellow solid (0.61 g) was collected by filtration and washed with cold methanol. Single crystals suitable for X-ray diffraction were obtained by recrystallization from CHCl₃/hexanes.

Computing details top

Data collection: FRAMBO (Bruker, 1999); cell refinement: FRAMBO (Bruker, 1999); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); 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. A view of the molecular structure. Ellipsoids are drawn at the 30% probability level. Hydrogen atoms were omitted for clarity.

(4,4',6,6'-Tetra-tert-butyl-2,2'-{[2- (dimethylamino)ethyl]nitrilobis(methylene)}diphenolato)dioxidomolybdenum(VI) chloroform monosolvate top

Crystal data top

[Mo(C₃₄H₅₄N₂O₂)O₂]·CHCl₃	F(000) = 1616
M_r = 770.10	D_x = 1.363 Mg m⁻³
Orthorhombic, Pna2₁	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2c -2n	Cell parameters from 9879 reflections
a = 24.3475 (10) Å	θ = 3.6–62.7°
b = 13.9748 (6) Å	µ = 5.12 mm⁻¹
c = 11.0267 (4) Å	T = 110 K
V = 3751.9 (3) Å³	Plate, yellow
Z = 4	0.50 × 0.20 × 0.02 mm

Data collection top

Bruker MWPC area-detector diffractometer	5548 independent reflections
Radiation source: fine-focus sealed tube	5061 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.081
ϕ and ω scans	θ_max = 60.0°, θ_min = 4.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −27→27
T_min = 0.184, T_max = 0.904	k = −15→15
79926 measured reflections	l = −12→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.078	w = 1/[σ²(F_o²) + (0.054P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
5548 reflections	Δρ_max = 0.81 e Å⁻³
421 parameters	Δρ_min = −0.51 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 2649 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.000 (9)

Crystal data top

[Mo(C₃₄H₅₄N₂O₂)O₂]·CHCl₃	V = 3751.9 (3) Å³
M_r = 770.10	Z = 4
Orthorhombic, Pna2₁	Cu Kα radiation
a = 24.3475 (10) Å	µ = 5.12 mm⁻¹
b = 13.9748 (6) Å	T = 110 K
c = 11.0267 (4) Å	0.50 × 0.20 × 0.02 mm

Data collection top

Bruker MWPC area-detector diffractometer	5548 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	5061 reflections with I > 2σ(I)
T_min = 0.184, T_max = 0.904	R_int = 0.081
79926 measured reflections	θ_max = 60.0°

Refinement top

R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.078	Δρ_max = 0.81 e Å⁻³
S = 1.00	Δρ_min = −0.51 e Å⁻³
5548 reflections	Absolute structure: Flack (1983), 2649 Friedel pairs
421 parameters	Absolute structure parameter: 0.000 (9)
1 restraint

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 > 2σ(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	0.426810 (10)	0.838846 (17)	−0.50398 (3)	0.01403 (9)
Cl1	0.59086 (5)	0.19093 (10)	−0.37928 (12)	0.0456 (3)
Cl2	0.62313 (6)	0.38887 (9)	−0.37779 (18)	0.0700 (5)
Cl3	0.70222 (5)	0.24265 (8)	−0.43262 (11)	0.0380 (3)
O1	0.37192 (9)	0.93850 (17)	−0.4855 (3)	0.0161 (6)
O2	0.48994 (10)	0.76272 (18)	−0.4523 (3)	0.0198 (6)
O3	0.38528 (10)	0.74922 (18)	−0.5542 (2)	0.0195 (6)
O4	0.45879 (11)	0.8885 (2)	−0.6260 (2)	0.0223 (6)
N1	0.47151 (12)	0.9508 (2)	−0.3729 (3)	0.0135 (7)
N2	0.39503 (13)	0.8003 (2)	−0.3016 (3)	0.0171 (7)
C1	0.42256 (14)	1.0851 (3)	−0.4926 (5)	0.0205 (9)
C2	0.37556 (14)	1.0319 (2)	−0.5192 (4)	0.0176 (9)
C3	0.33115 (15)	1.0736 (3)	−0.5830 (3)	0.0159 (9)
C4	0.33686 (16)	1.1685 (3)	−0.6165 (4)	0.0188 (9)
H4	0.3075	1.1973	−0.6600	0.023*
C5	0.38261 (16)	1.2249 (3)	−0.5909 (4)	0.0198 (9)
C6	0.42495 (15)	1.1812 (3)	−0.5263 (4)	0.0202 (11)
H6	0.4563	1.2179	−0.5047	0.024*
C7	0.47454 (16)	1.0452 (3)	−0.4337 (4)	0.0199 (9)
H7A	0.5032	1.0411	−0.4972	0.024*
H7B	0.4873	1.0924	−0.3731	0.024*
C8	0.27985 (16)	1.0155 (3)	−0.6168 (4)	0.0184 (9)
C9	0.23863 (16)	1.0749 (3)	−0.6897 (4)	0.0230 (9)
H9A	0.2064	1.0356	−0.7085	0.035*
H9B	0.2558	1.0964	−0.7653	0.035*
H9BC	0.2273	1.1306	−0.6419	0.035*
C10	0.24975 (14)	0.9810 (3)	−0.5024 (5)	0.0239 (8)
H10A	0.2181	0.9419	−0.5260	0.036*
H10B	0.2371	1.0364	−0.4557	0.036*
H10C	0.2748	0.9426	−0.4528	0.036*
C11	0.29541 (17)	0.9285 (3)	−0.6952 (4)	0.0213 (9)
H11A	0.2619	0.8972	−0.7245	0.032*
H11B	0.3168	0.8831	−0.6465	0.032*
H11C	0.3174	0.9498	−0.7645	0.032*
C12	0.38648 (18)	1.3300 (3)	−0.6294 (4)	0.0252 (10)
C13	0.3754 (2)	1.3935 (3)	−0.5203 (5)	0.0456 (14)
H13A	0.3805	1.4606	−0.5432	0.068*
H13B	0.4010	1.3771	−0.4549	0.068*
H13C	0.3376	1.3836	−0.4924	0.068*
C14	0.3457 (2)	1.3543 (3)	−0.7301 (5)	0.0437 (14)
H14A	0.3502	1.4215	−0.7537	0.066*
H14B	0.3082	1.3439	−0.7008	0.066*
H14C	0.3526	1.3131	−0.8004	0.066*
C15	0.4439 (2)	1.3524 (3)	−0.6790 (5)	0.0355 (12)
H15A	0.4457	1.4198	−0.7031	0.053*
H15B	0.4513	1.3118	−0.7496	0.053*
H15C	0.4714	1.3399	−0.6161	0.053*
C16	0.52969 (15)	0.9236 (3)	−0.3376 (4)	0.0192 (9)
H16A	0.5495	0.9822	−0.3125	0.023*
H16B	0.5281	0.8804	−0.2665	0.023*
C17	0.56204 (14)	0.8750 (3)	−0.4370 (4)	0.0170 (9)
C18	0.54237 (14)	0.7891 (3)	−0.4836 (4)	0.0178 (9)
C19	0.57446 (15)	0.7309 (3)	−0.5608 (4)	0.0190 (9)
C20	0.62607 (15)	0.7660 (3)	−0.5902 (4)	0.0176 (9)
H20	0.6489	0.7279	−0.6407	0.021*
C21	0.64651 (16)	0.8541 (3)	−0.5501 (4)	0.0174 (9)
C22	0.61418 (15)	0.9075 (3)	−0.4715 (3)	0.0182 (10)
H22	0.6275	0.9666	−0.4409	0.022*
C23	0.55331 (17)	0.6345 (3)	−0.6097 (4)	0.0217 (9)
C24	0.5097 (2)	0.6521 (3)	−0.7063 (5)	0.0348 (12)
H24A	0.4975	0.5908	−0.7399	0.052*
H24B	0.5252	0.6916	−0.7713	0.052*
H24C	0.4783	0.6853	−0.6699	0.052*
C25	0.52917 (19)	0.5717 (3)	−0.5084 (6)	0.0384 (10)
H25A	0.5227	0.5070	−0.5395	0.058*
H25B	0.4944	0.5992	−0.4806	0.058*
H25C	0.5550	0.5688	−0.4404	0.058*
C26	0.59983 (19)	0.5767 (3)	−0.6685 (5)	0.0329 (12)
H26A	0.5860	0.5136	−0.6923	0.049*
H26B	0.6300	0.5690	−0.6104	0.049*
H26C	0.6132	0.6106	−0.7405	0.049*
C27	0.70438 (16)	0.8849 (3)	−0.5894 (4)	0.0208 (9)
C28	0.70892 (19)	0.8820 (4)	−0.7288 (4)	0.0339 (11)
H28A	0.7468	0.8962	−0.7530	0.051*
H28B	0.6841	0.9297	−0.7641	0.051*
H28C	0.6987	0.8181	−0.7579	0.051*
C29	0.71837 (17)	0.9870 (3)	−0.5474 (4)	0.0252 (10)
H29A	0.7545	1.0052	−0.5788	0.038*
H29B	0.7189	0.9892	−0.4586	0.038*
H29C	0.6906	1.0316	−0.5781	0.038*
C30	0.74679 (15)	0.8160 (3)	−0.5365 (4)	0.0239 (11)
H30A	0.7837	0.8361	−0.5610	0.036*
H30B	0.7397	0.7512	−0.5667	0.036*
H30C	0.7442	0.8164	−0.4478	0.036*
C31	0.43785 (16)	0.9580 (3)	−0.2602 (4)	0.0197 (9)
H31A	0.4032	0.9923	−0.2783	0.024*
H31B	0.4582	0.9952	−0.1985	0.024*
C32	0.42489 (17)	0.8604 (3)	−0.2109 (4)	0.0196 (9)
H32A	0.4595	0.8281	−0.1876	0.024*
H32B	0.4020	0.8671	−0.1371	0.024*
C33	0.33508 (16)	0.8180 (3)	−0.2903 (4)	0.0207 (9)
H33A	0.3218	0.7915	−0.2133	0.031*
H33B	0.3158	0.7872	−0.3578	0.031*
H33C	0.3281	0.8871	−0.2922	0.031*
C34	0.40419 (19)	0.6974 (3)	−0.2756 (4)	0.0273 (10)
H34A	0.3912	0.6827	−0.1936	0.041*
H34B	0.4435	0.6830	−0.2816	0.041*
H34C	0.3839	0.6585	−0.3345	0.041*
C35	0.64330 (19)	0.2714 (3)	−0.3474 (4)	0.0322 (11)
H35	0.6526	0.2663	−0.2594	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.01303 (14)	0.01394 (14)	0.01511 (14)	−0.00271 (11)	−0.00087 (19)	−0.00026 (19)
Cl1	0.0472 (7)	0.0482 (7)	0.0413 (8)	−0.0196 (6)	0.0070 (6)	−0.0063 (6)
Cl2	0.0577 (9)	0.0264 (7)	0.1258 (15)	0.0056 (6)	0.0374 (10)	0.0150 (8)
Cl3	0.0442 (7)	0.0329 (6)	0.0368 (6)	0.0014 (5)	0.0031 (6)	0.0034 (6)
O1	0.0132 (12)	0.0155 (12)	0.0196 (17)	−0.0015 (9)	−0.0039 (12)	0.0029 (13)
O2	0.0140 (13)	0.0168 (14)	0.0287 (15)	−0.0036 (11)	0.0027 (12)	−0.0061 (12)
O3	0.0168 (13)	0.0163 (14)	0.0253 (14)	−0.0043 (11)	−0.0024 (12)	−0.0040 (12)
O4	0.0237 (16)	0.0274 (16)	0.0160 (14)	−0.0045 (13)	0.0041 (13)	0.0004 (13)
N1	0.0130 (16)	0.0124 (16)	0.0151 (16)	−0.0018 (13)	0.0032 (15)	−0.0010 (14)
N2	0.0199 (18)	0.0163 (17)	0.0150 (17)	−0.0020 (14)	0.0007 (15)	0.0021 (15)
C1	0.0195 (18)	0.0191 (18)	0.023 (2)	0.0011 (15)	0.000 (2)	0.004 (2)
C2	0.0219 (18)	0.0100 (17)	0.021 (3)	−0.0029 (13)	0.002 (2)	−0.005 (2)
C3	0.012 (2)	0.019 (2)	0.017 (2)	0.0016 (16)	0.0024 (17)	−0.0024 (18)
C4	0.017 (2)	0.023 (2)	0.016 (2)	0.0072 (17)	0.0020 (18)	0.0049 (18)
C5	0.026 (2)	0.015 (2)	0.019 (2)	0.0030 (17)	0.0015 (19)	0.0021 (18)
C6	0.0181 (18)	0.0177 (19)	0.025 (3)	−0.0039 (15)	−0.0005 (19)	0.0019 (19)
C7	0.020 (2)	0.015 (2)	0.024 (2)	0.0032 (16)	0.002 (2)	0.0037 (18)
C8	0.020 (2)	0.019 (2)	0.016 (2)	−0.0001 (17)	−0.0019 (18)	−0.0014 (18)
C9	0.017 (2)	0.026 (2)	0.027 (2)	−0.0010 (18)	−0.0070 (19)	0.001 (2)
C10	0.0185 (18)	0.0254 (19)	0.0278 (19)	0.0013 (15)	0.004 (3)	0.004 (3)
C11	0.019 (2)	0.024 (2)	0.021 (2)	0.0018 (18)	−0.0032 (18)	−0.0062 (19)
C12	0.028 (2)	0.013 (2)	0.034 (2)	0.0008 (17)	0.000 (2)	0.0013 (19)
C13	0.078 (4)	0.018 (2)	0.041 (3)	0.012 (2)	0.005 (3)	−0.001 (3)
C14	0.054 (3)	0.025 (3)	0.052 (3)	−0.006 (2)	−0.015 (3)	0.018 (2)
C15	0.036 (3)	0.024 (3)	0.047 (3)	−0.002 (2)	0.003 (2)	0.010 (2)
C16	0.016 (2)	0.019 (2)	0.022 (2)	−0.0004 (16)	−0.0020 (18)	−0.0059 (18)
C17	0.0076 (19)	0.020 (2)	0.023 (2)	0.0022 (16)	−0.0013 (17)	−0.0043 (19)
C18	0.0163 (19)	0.0179 (19)	0.019 (3)	0.0002 (15)	−0.0003 (18)	−0.0011 (18)
C19	0.016 (2)	0.022 (2)	0.0189 (19)	0.0057 (17)	−0.0060 (18)	−0.0044 (18)
C20	0.016 (2)	0.020 (2)	0.016 (2)	0.0086 (17)	−0.0001 (17)	−0.0037 (18)
C21	0.014 (2)	0.021 (2)	0.0174 (19)	0.0063 (17)	−0.0048 (16)	0.0043 (16)
C22	0.0174 (19)	0.0164 (19)	0.021 (3)	0.0004 (16)	−0.0033 (16)	−0.0059 (16)
C23	0.022 (2)	0.017 (2)	0.026 (2)	0.0048 (17)	−0.008 (2)	−0.0032 (19)
C24	0.034 (3)	0.033 (3)	0.037 (3)	0.013 (2)	−0.016 (2)	−0.019 (2)
C25	0.053 (3)	0.019 (2)	0.043 (3)	−0.0036 (18)	0.003 (4)	−0.012 (3)
C26	0.032 (3)	0.020 (2)	0.047 (3)	0.007 (2)	−0.010 (2)	−0.017 (2)
C27	0.014 (2)	0.028 (2)	0.020 (2)	0.0030 (17)	0.0020 (18)	0.0025 (19)
C28	0.026 (2)	0.052 (3)	0.024 (3)	0.001 (2)	0.007 (2)	0.004 (2)
C29	0.018 (2)	0.026 (2)	0.031 (2)	0.0006 (17)	0.0062 (18)	0.0032 (19)
C30	0.0125 (19)	0.028 (2)	0.031 (3)	0.0056 (16)	0.0024 (18)	−0.0025 (19)
C31	0.017 (2)	0.021 (2)	0.021 (2)	−0.0024 (17)	0.0019 (18)	−0.0041 (18)
C32	0.019 (2)	0.025 (2)	0.014 (2)	−0.0050 (18)	0.0008 (17)	0.0066 (18)
C33	0.015 (2)	0.025 (2)	0.022 (2)	−0.0053 (17)	0.0033 (18)	0.0001 (19)
C34	0.037 (3)	0.017 (2)	0.028 (2)	0.001 (2)	−0.003 (2)	0.009 (2)
C35	0.050 (3)	0.021 (2)	0.026 (2)	−0.005 (2)	−0.001 (2)	0.000 (2)

Geometric parameters (Å, º) top

Mo1—O3	1.702 (2)	C15—H15B	0.9800
Mo1—O4	1.702 (3)	C15—H15C	0.9800
Mo1—O1	1.941 (2)	C16—C17	1.512 (5)
Mo1—O2	1.954 (3)	C16—H16A	0.9900
Mo1—N1	2.392 (3)	C16—H16B	0.9900
Mo1—N2	2.422 (3)	C17—C18	1.391 (5)
Cl1—C35	1.737 (4)	C17—C22	1.401 (5)
Cl2—C35	1.746 (4)	C18—C19	1.413 (6)
Cl3—C35	1.761 (5)	C19—C20	1.387 (5)
O1—C2	1.360 (4)	C19—C23	1.540 (6)
O2—C18	1.373 (4)	C20—C21	1.400 (5)
N1—C7	1.482 (5)	C20—H20	0.9500
N1—C31	1.492 (5)	C21—C22	1.388 (5)
N1—C16	1.517 (5)	C21—C27	1.536 (5)
N2—C34	1.483 (5)	C22—H22	0.9500
N2—C33	1.486 (5)	C23—C24	1.525 (6)
N2—C32	1.495 (5)	C23—C26	1.535 (6)
C1—C6	1.395 (5)	C23—C25	1.538 (7)
C1—C2	1.396 (5)	C24—H24A	0.9800
C1—C7	1.528 (6)	C24—H24B	0.9800
C2—C3	1.416 (5)	C24—H24C	0.9800
C3—C4	1.384 (5)	C25—H25A	0.9800
C3—C8	1.536 (5)	C25—H25B	0.9800
C4—C5	1.393 (6)	C25—H25C	0.9800
C4—H4	0.9500	C26—H26A	0.9800
C5—C6	1.394 (6)	C26—H26B	0.9800
C5—C12	1.531 (5)	C26—H26C	0.9800
C6—H6	0.9500	C27—C30	1.528 (5)
C7—H7A	0.9900	C27—C29	1.537 (6)
C7—H7B	0.9900	C27—C28	1.541 (6)
C8—C9	1.531 (5)	C28—H28A	0.9800
C8—C10	1.536 (6)	C28—H28B	0.9800
C8—C11	1.539 (5)	C28—H28C	0.9800
C9—H9A	0.9800	C29—H29A	0.9800
C9—H9B	0.9800	C29—H29B	0.9800
C9—H9BC	0.9800	C29—H29C	0.9800
C10—H10A	0.9800	C30—H30A	0.9800
C10—H10B	0.9800	C30—H30B	0.9800
C10—H10C	0.9800	C30—H30C	0.9800
C11—H11A	0.9800	C31—C32	1.501 (6)
C11—H11B	0.9800	C31—H31A	0.9900
C11—H11C	0.9800	C31—H31B	0.9900
C12—C13	1.519 (7)	C32—H32A	0.9900
C12—C14	1.528 (7)	C32—H32B	0.9900
C12—C15	1.534 (7)	C33—H33A	0.9800
C13—H13A	0.9800	C33—H33B	0.9800
C13—H13B	0.9800	C33—H33C	0.9800
C13—H13C	0.9800	C34—H34A	0.9800
C14—H14A	0.9800	C34—H34B	0.9800
C14—H14B	0.9800	C34—H34C	0.9800
C14—H14C	0.9800	C35—H35	1.0000
C15—H15A	0.9800

O3—Mo1—O4	108.33 (13)	C17—C16—H16A	108.7
O3—Mo1—O1	98.81 (11)	N1—C16—H16A	108.7
O4—Mo1—O1	96.06 (12)	C17—C16—H16B	108.7
O3—Mo1—O2	99.29 (11)	N1—C16—H16B	108.7
O4—Mo1—O2	95.31 (12)	H16A—C16—H16B	107.6
O1—Mo1—O2	154.36 (12)	C18—C17—C22	119.4 (3)
O3—Mo1—N1	161.44 (12)	C18—C17—C16	118.4 (3)
O4—Mo1—N1	90.18 (12)	C22—C17—C16	121.6 (3)
O1—Mo1—N1	77.33 (10)	O2—C18—C17	117.3 (3)
O2—Mo1—N1	79.73 (10)	O2—C18—C19	120.7 (3)
O3—Mo1—N2	86.91 (12)	C17—C18—C19	121.9 (3)
O4—Mo1—N2	164.76 (12)	C20—C19—C18	116.0 (4)
O1—Mo1—N2	80.96 (11)	C20—C19—C23	122.0 (3)
O2—Mo1—N2	82.04 (11)	C18—C19—C23	122.0 (3)
N1—Mo1—N2	74.57 (10)	C19—C20—C21	124.0 (4)
C2—O1—Mo1	128.0 (2)	C19—C20—H20	118.0
C18—O2—Mo1	120.8 (2)	C21—C20—H20	118.0
C7—N1—C31	110.1 (3)	C22—C21—C20	117.9 (4)
C7—N1—C16	107.0 (3)	C22—C21—C27	123.1 (4)
C31—N1—C16	108.4 (3)	C20—C21—C27	118.9 (3)
C7—N1—Mo1	109.3 (2)	C21—C22—C17	120.6 (4)
C31—N1—Mo1	107.3 (2)	C21—C22—H22	119.7
C16—N1—Mo1	114.6 (2)	C17—C22—H22	119.7
C34—N2—C33	107.0 (3)	C24—C23—C26	107.7 (4)
C34—N2—C32	110.0 (3)	C24—C23—C25	109.5 (4)
C33—N2—C32	109.1 (3)	C26—C23—C25	106.8 (3)
C34—N2—Mo1	110.2 (2)	C24—C23—C19	109.7 (3)
C33—N2—Mo1	110.8 (2)	C26—C23—C19	111.2 (3)
C32—N2—Mo1	109.6 (2)	C25—C23—C19	111.9 (4)
C6—C1—C2	119.4 (4)	C23—C24—H24A	109.5
C6—C1—C7	115.5 (3)	C23—C24—H24B	109.5
C2—C1—C7	125.0 (3)	H24A—C24—H24B	109.5
O1—C2—C1	120.5 (3)	C23—C24—H24C	109.5
O1—C2—C3	118.8 (3)	H24A—C24—H24C	109.5
C1—C2—C3	120.7 (3)	H24B—C24—H24C	109.5
C4—C3—C2	116.8 (3)	C23—C25—H25A	109.5
C4—C3—C8	121.6 (3)	C23—C25—H25B	109.5
C2—C3—C8	121.6 (3)	H25A—C25—H25B	109.5
C3—C4—C5	124.6 (4)	C23—C25—H25C	109.5
C3—C4—H4	117.7	H25A—C25—H25C	109.5
C5—C4—H4	117.7	H25B—C25—H25C	109.5
C4—C5—C6	116.5 (4)	C23—C26—H26A	109.5
C4—C5—C12	122.4 (4)	C23—C26—H26B	109.5
C6—C5—C12	121.1 (4)	H26A—C26—H26B	109.5
C5—C6—C1	121.9 (4)	C23—C26—H26C	109.5
C5—C6—H6	119.1	H26A—C26—H26C	109.5
C1—C6—H6	119.1	H26B—C26—H26C	109.5
N1—C7—C1	118.5 (3)	C30—C27—C21	109.6 (3)
N1—C7—H7A	107.7	C30—C27—C29	108.7 (3)
C1—C7—H7A	107.7	C21—C27—C29	112.2 (3)
N1—C7—H7B	107.7	C30—C27—C28	108.4 (3)
C1—C7—H7B	107.7	C21—C27—C28	109.9 (3)
H7A—C7—H7B	107.1	C29—C27—C28	108.0 (4)
C9—C8—C10	106.8 (3)	C27—C28—H28A	109.5
C9—C8—C3	111.9 (3)	C27—C28—H28B	109.5
C10—C8—C3	110.8 (3)	H28A—C28—H28B	109.5
C9—C8—C11	107.1 (3)	C27—C28—H28C	109.5
C10—C8—C11	109.3 (3)	H28A—C28—H28C	109.5
C3—C8—C11	110.7 (3)	H28B—C28—H28C	109.5
C8—C9—H9A	109.5	C27—C29—H29A	109.5
C8—C9—H9B	109.5	C27—C29—H29B	109.5
H9A—C9—H9B	109.5	H29A—C29—H29B	109.5
C8—C9—H9BC	109.5	C27—C29—H29C	109.5
H9A—C9—H9BC	109.5	H29A—C29—H29C	109.5
H9B—C9—H9BC	109.5	H29B—C29—H29C	109.5
C8—C10—H10A	109.5	C27—C30—H30A	109.5
C8—C10—H10B	109.5	C27—C30—H30B	109.5
H10A—C10—H10B	109.5	H30A—C30—H30B	109.5
C8—C10—H10C	109.5	C27—C30—H30C	109.5
H10A—C10—H10C	109.5	H30A—C30—H30C	109.5
H10B—C10—H10C	109.5	H30B—C30—H30C	109.5
C8—C11—H11A	109.5	N1—C31—C32	110.8 (3)
C8—C11—H11B	109.5	N1—C31—H31A	109.5
H11A—C11—H11B	109.5	C32—C31—H31A	109.5
C8—C11—H11C	109.5	N1—C31—H31B	109.5
H11A—C11—H11C	109.5	C32—C31—H31B	109.5
H11B—C11—H11C	109.5	H31A—C31—H31B	108.1
C13—C12—C14	109.3 (4)	N2—C32—C31	111.7 (3)
C13—C12—C5	109.2 (4)	N2—C32—H32A	109.3
C14—C12—C5	112.0 (4)	C31—C32—H32A	109.3
C13—C12—C15	109.0 (4)	N2—C32—H32B	109.3
C14—C12—C15	106.7 (4)	C31—C32—H32B	109.3
C5—C12—C15	110.5 (3)	H32A—C32—H32B	107.9
C12—C13—H13A	109.5	N2—C33—H33A	109.5
C12—C13—H13B	109.5	N2—C33—H33B	109.5
H13A—C13—H13B	109.5	H33A—C33—H33B	109.5
C12—C13—H13C	109.5	N2—C33—H33C	109.5
H13A—C13—H13C	109.5	H33A—C33—H33C	109.5
H13B—C13—H13C	109.5	H33B—C33—H33C	109.5
C12—C14—H14A	109.5	N2—C34—H34A	109.5
C12—C14—H14B	109.5	N2—C34—H34B	109.5
H14A—C14—H14B	109.5	H34A—C34—H34B	109.5
C12—C14—H14C	109.5	N2—C34—H34C	109.5
H14A—C14—H14C	109.5	H34A—C34—H34C	109.5
H14B—C14—H14C	109.5	H34B—C34—H34C	109.5
C12—C15—H15A	109.5	Cl1—C35—Cl2	111.3 (3)
C12—C15—H15B	109.5	Cl1—C35—Cl3	110.1 (2)
H15A—C15—H15B	109.5	Cl2—C35—Cl3	110.0 (2)
C12—C15—H15C	109.5	Cl1—C35—H35	108.5
H15A—C15—H15C	109.5	Cl2—C35—H35	108.5
H15B—C15—H15C	109.5	Cl3—C35—H35	108.5
C17—C16—N1	114.4 (3)

O3—Mo1—O1—C2	−136.2 (3)	C16—N1—C7—C1	172.9 (4)
O4—Mo1—O1—C2	−26.5 (3)	Mo1—N1—C7—C1	48.2 (4)
O2—Mo1—O1—C2	89.4 (4)	C6—C1—C7—N1	167.6 (4)
N1—Mo1—O1—C2	62.3 (3)	C2—C1—C7—N1	−15.7 (7)
N2—Mo1—O1—C2	138.4 (3)	C4—C3—C8—C9	0.4 (5)
O3—Mo1—O2—C18	133.7 (3)	C2—C3—C8—C9	−177.7 (4)
O4—Mo1—O2—C18	24.1 (3)	C4—C3—C8—C10	−118.6 (4)
O1—Mo1—O2—C18	−91.9 (3)	C2—C3—C8—C10	63.2 (5)
N1—Mo1—O2—C18	−65.1 (3)	C4—C3—C8—C11	119.9 (4)
N2—Mo1—O2—C18	−140.8 (3)	C2—C3—C8—C11	−58.3 (5)
O3—Mo1—N1—C7	−138.1 (3)	C4—C5—C12—C13	102.5 (5)
O4—Mo1—N1—C7	37.9 (2)	C6—C5—C12—C13	−76.6 (5)
O1—Mo1—N1—C7	−58.3 (2)	C4—C5—C12—C14	−18.7 (6)
O2—Mo1—N1—C7	133.3 (2)	C6—C5—C12—C14	162.1 (4)
N2—Mo1—N1—C7	−142.2 (2)	C4—C5—C12—C15	−137.6 (4)
O3—Mo1—N1—C31	−18.7 (5)	C6—C5—C12—C15	43.3 (6)
O4—Mo1—N1—C31	157.3 (2)	C7—N1—C16—C17	−85.1 (4)
O1—Mo1—N1—C31	61.2 (2)	C31—N1—C16—C17	156.2 (3)
O2—Mo1—N1—C31	−107.3 (2)	Mo1—N1—C16—C17	36.3 (4)
N2—Mo1—N1—C31	−22.8 (2)	N1—C16—C17—C18	−60.3 (5)
O3—Mo1—N1—C16	101.8 (4)	N1—C16—C17—C22	128.1 (4)
O4—Mo1—N1—C16	−82.2 (3)	Mo1—O2—C18—C17	64.7 (4)
O1—Mo1—N1—C16	−178.4 (3)	Mo1—O2—C18—C19	−114.9 (3)
O2—Mo1—N1—C16	13.2 (2)	C22—C17—C18—O2	−176.6 (3)
N2—Mo1—N1—C16	97.7 (3)	C16—C17—C18—O2	11.6 (5)
O3—Mo1—N2—C34	54.6 (3)	C22—C17—C18—C19	3.0 (6)
O4—Mo1—N2—C34	−126.1 (5)	C16—C17—C18—C19	−168.8 (4)
O1—Mo1—N2—C34	154.0 (3)	O2—C18—C19—C20	177.7 (3)
O2—Mo1—N2—C34	−45.2 (3)	C17—C18—C19—C20	−1.9 (6)
N1—Mo1—N2—C34	−126.7 (3)	O2—C18—C19—C23	−2.1 (6)
O3—Mo1—N2—C33	−63.7 (2)	C17—C18—C19—C23	178.4 (4)
O4—Mo1—N2—C33	115.6 (5)	C18—C19—C20—C21	−1.2 (6)
O1—Mo1—N2—C33	35.8 (2)	C23—C19—C20—C21	178.5 (4)
O2—Mo1—N2—C33	−163.5 (2)	C19—C20—C21—C22	3.1 (6)
N1—Mo1—N2—C33	115.0 (2)	C19—C20—C21—C27	−179.9 (4)
O3—Mo1—N2—C32	175.9 (3)	C20—C21—C22—C17	−2.0 (6)
O4—Mo1—N2—C32	−4.9 (6)	C27—C21—C22—C17	−178.8 (4)
O1—Mo1—N2—C32	−84.7 (2)	C18—C17—C22—C21	−1.0 (6)
O2—Mo1—N2—C32	76.0 (2)	C16—C17—C22—C21	170.6 (4)
N1—Mo1—N2—C32	−5.4 (2)	C20—C19—C23—C24	−106.9 (5)
Mo1—O1—C2—C1	−46.0 (6)	C18—C19—C23—C24	72.9 (5)
Mo1—O1—C2—C3	133.2 (3)	C20—C19—C23—C26	12.1 (5)
C6—C1—C2—O1	−179.0 (4)	C18—C19—C23—C26	−168.2 (4)
C7—C1—C2—O1	4.5 (7)	C20—C19—C23—C25	131.4 (4)
C6—C1—C2—C3	1.9 (7)	C18—C19—C23—C25	−48.9 (5)
C7—C1—C2—C3	−174.7 (4)	C22—C21—C27—C30	112.4 (4)
O1—C2—C3—C4	−179.4 (4)	C20—C21—C27—C30	−64.4 (5)
C1—C2—C3—C4	−0.2 (6)	C22—C21—C27—C29	−8.4 (5)
O1—C2—C3—C8	−1.2 (6)	C20—C21—C27—C29	174.7 (3)
C1—C2—C3—C8	178.0 (4)	C22—C21—C27—C28	−128.7 (4)
C2—C3—C4—C5	−0.5 (6)	C20—C21—C27—C28	54.5 (5)
C8—C3—C4—C5	−178.8 (4)	C7—N1—C31—C32	168.7 (3)
C3—C4—C5—C6	−0.4 (6)	C16—N1—C31—C32	−74.5 (4)
C3—C4—C5—C12	−179.5 (4)	Mo1—N1—C31—C32	49.8 (3)
C4—C5—C6—C1	2.1 (6)	C34—N2—C32—C31	155.2 (3)
C12—C5—C6—C1	−178.7 (4)	C33—N2—C32—C31	−87.7 (4)
C2—C1—C6—C5	−2.9 (7)	Mo1—N2—C32—C31	33.8 (4)
C7—C1—C6—C5	174.0 (4)	N1—C31—C32—N2	−58.0 (4)
C31—N1—C7—C1	−69.4 (5)

Experimental details

Crystal data
Chemical formula	[Mo(C₃₄H₅₄N₂O₂)O₂]·CHCl₃
M_r	770.10
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	110
a, b, c (Å)	24.3475 (10), 13.9748 (6), 11.0267 (4)
V (Å³)	3751.9 (3)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	5.12
Crystal size (mm)	0.50 × 0.20 × 0.02

Data collection
Diffractometer	Bruker MWPC area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.184, 0.904
No. of measured, independent and observed [I > 2σ(I)] reflections	79926, 5548, 5061
R_int	0.081
θ_max (°)	60.0
(sin θ/λ)_max (Å⁻¹)	0.562

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.078, 1.00
No. of reflections	5548
No. of parameters	421
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.81, −0.51
Absolute structure	Flack (1983), 2649 Friedel pairs
Absolute structure parameter	0.000 (9)

Computer programs: FRAMBO (Bruker, 1999), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

We thank the Welch Foundation (V-004) for financial support. We are very grateful to Dr Joseph Reibenspies at Texas A & M University for the X-ray crystallographic analysis. The X-ray diffractometers, small angle scattering instrumentation and crystallographic computing systems in the X-ray Diffraction Laboratory at the Department of Chemistry, Texas A & M University were purchased with funds provided by the National Science Foundation (CHE-9807975, CHE-0079822 and CHE-0215838).

References

Bruker (1999). FRAMBO. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2008). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Hinshaw, C. J., Peng, G., Singh, R., Spence, J. T., Enemark, J. H., Bruck, M., Kristofzski, J., Merbs, S. L., Ortega, R. B. & Wexler, P. A. (1989). Inorg. Chem. 28, 4483–4491. CSD CrossRef CAS Web of Science Google Scholar
Lehtonen, A. & Sillanpää, R. (2005). Polyhedron, 24, 257–265. Web of Science CSD CrossRef CAS Google Scholar
Lehtonen, A., Wasberg, M. & Sillanpää, R. (2006). Polyhedron, 25, 767–775. Web of Science CSD CrossRef CAS Google Scholar
Rappe, A. K. & Goddard, W. A. (1982). J. Am. Chem. Soc. 104, 448–456. CrossRef CAS Web of Science Google Scholar
Schultz, B. E., Gheller, S. F., Muetterties, M. C., Scott, M. J. & Holm, R. H. (1993). J. Am. Chem. Soc. 115, 2714–2722. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tshuva, E., Goldberg, I. & Kol, M. (2001). Organometallics, 20, 3017–3028. Web of Science CSD CrossRef CAS Google Scholar
Tucci, G. C., Donahue, J. P. & Holm, R. H. (1998). Inorg. Chem. 37, 1602–1608. Web of Science CrossRef CAS Google Scholar
Wong, Y. L., Tong, L. H., Dilworth, J. R., Ng, D. K. P. & Lee, H. K. (2010). Dalton Trans. 39, 4602–4611. Web of Science CSD CrossRef CAS PubMed Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.