μ-Oxido-bis­[chlorido(4,4′-di-tert-butyl-2,2′-bipyridine-κ2N,N′)dioxido­molybdenum(VI)] 0.2-hydrate

Gomes, A.C.; Fernandes, J.A.; Gamelas, C.A.; Gonçalves, I.S.; Almeida Paz, F.A.

doi:10.1107/S1600536811046952

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages m1738-m1739

https://doi.org/10.1107/S1600536811046952

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μ-Oxido-bis[chlorido(4,4′-di-tert-butyl-2,2′-bipyridine-κ²N,N′)dioxidomolybdenum(VI)] 0.2-hydrate

Ana C. Gomes,^a José A. Fernandes,^a Carla A. Gamelas,^b Isabel S. Gonçalves ^a and Filipe A. Almeida Paz ^a ^*

^aDepartment of Chemistry, University of Aveiro, CICECO, 3810-193 Aveiro, Portugal, and ^bEscola Superior de Tecnologia, Instituto Politécnico de Setúbal, 2910-761 Setúbal, Portugal
^*Correspondence e-mail: filipe.paz@ua.pt

(Received 4 November 2011; accepted 7 November 2011; online 12 November 2011)

The title hydrate, [Mo₂Cl₂O₅(C₁₈H₂₄N₂)₂]·0.2H₂O, has been isolated as the oxidation product of [Mo(η³-C₃H₅)Cl(CO)₂(di-t-Bu-bipy)] (where di-t-Bu-bipy is 4,4′-di-tert-butyl-2,2′-bipyridine). A μ-oxide ligand bridges two similar MoCl(di-t-Bu-bipy)O₂ units, having the terminal oxide ligands mutually cis, and the chloride and μ-oxide trans to each other. In the binuclear complex, the coordination geometries of the metal atoms can be described as highly distorted octahedra. Individual complexes co-crystallize with a partially occupied water molecule of crystallization (occupancy factor = 0.20; H atoms not located), with the crystal packing being mediated by the need to effectively fill the available space. A number of weak C—H⋯O and C—H⋯Cl interactions are present.

Related literature

For general background to dioxidomolybdenum(VI) complexes, see: Arzoumanian et al. (2006 ); Jeyakumar & Chand (2009 ); Kühn et al. (2002 ); Rodrigues et al. (2004 ). For studies on molybdenum complexes from our research groups, see: Coelho et al. (2011 ); Fernandes et al. (2011a ,b , 2011 ); Gago et al. (2009 ); Nunes et al. (2003 ); Pereira et al. (2007 ).

Experimental

Crystal data

[Mo₂Cl₂O₅(C₁₈H₂₄N₂)₂]·0.2H₂O
M_r = 883.17
Monoclinic, P 2₁ /n
a = 16.9997 (7) Å
b = 12.7444 (6) Å
c = 18.4609 (8) Å
β = 99.582 (2)°
V = 3943.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.82 mm⁻¹
T = 150 K
0.08 × 0.06 × 0.03 mm

Data collection

Bruker X8 KappaCCD APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.938, T_max = 0.976
54239 measured reflections
10578 independent reflections
7469 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.086
S = 1.02
10578 reflections
463 parameters
18 restraints
H-atom parameters constrained
Δρ_max = 0.96 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Table 1
Selected bond lengths (Å)

Mo1—O1	1.8920 (19)
Mo1—O2	1.6972 (19)
Mo1—O3	1.696 (2)
Mo1—N1	2.330 (2)
Mo1—N2	2.323 (2)
Mo1—Cl1	2.4895 (8)
Mo2—O1	1.9274 (19)
Mo2—O4	1.6975 (19)
Mo2—O5	1.694 (2)
Mo2—N3	2.328 (2)
Mo2—N4	2.304 (2)
Mo2—Cl2	2.4283 (8)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C27—H27⋯O1ⁱ	0.95	2.52	3.341 (3)	145
C34—H34A⋯Cl1ⁱⁱ	0.98	2.77	3.748 (4)	174
C35—H35A⋯O4ⁱ	0.98	2.54	3.421 (4)	149
C12—H12C⋯O1W	0.98	2.69	3.641 (16)	163
C18—H18B⋯O1W	0.98	2.10	2.970 (18)	147
O1W⋯Cl2ⁱ			3.573 (18)
O1W⋯O5ⁱⁱⁱ			3.236 (17)
Symmetry codes: (i) -x, -y+1, -z; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT-Plus (Bruker, 2005 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811046952/tk5013sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811046952/tk5013Isup2.hkl

checkCIF report

Comment top

Dioxomolybdenum(VI) complexes are known to be highly active catalysts in the epoxidation of olefins (Kühn et al., 2002; Jeyakumar & Chand, 2009). In these complexes the active metal-oxo functional group may appear with two distinct structural motifs: as a terminal oxo (Mo═O) or as a bridging µ-oxo (Mo—O—Mo). Compounds with the latter type of bridging group are significantly less studied but have been shown to be intermediates in a handful of interesting catalytic systems (Nunes et al., 2003). Following our on-going interest in the study of this type of family of compounds (Fernandes et al., 2010a,b, 2011) we have recently described the synthesis and structural details of the oxo-µ-oxo complexes [Mo₂O₄(µ-O)Cl₂(DMF)₄] (Gago et al., 2009), [Mo₂O₄(µ-O)Cl₂(pyrazole)₄] (Pereira et al., 2007), and [Mo₂O₄(µ-O)Cl₂(PzPy)₂] (where PzPy stands for 2-(3-pyrazolyl)pyridine) (Coelho et al., 2011). Noteworthy, these complexes were found to be highly active in epoxidation catalysis with tert-butylhydroperoxide. The title compound, a µ-oxo dimer with empirical formula [Mo₂O₄(µ-O)Cl₂(di-t-Bu-bipy)₂] (where di-t-Bu-bipy stands for 4,4'-di-tert-butyl-2,2'-bipyridine) which simultaneously contains terminal Mo═O oxo groups and a bridging µ-oxo one, has been recently synthesized by Arzoumanian et al. (2006) and we now wish to report its crystal structure at the low temperature of 150 K.

The asymmetric unit of the title compound comprises a whole binuclear molecular entity, C₃₆H₄₈Cl₂Mo₂N₄O₅, and a partially occupied (20%) water molecule of crystallization. The binuclear complex is formed by two crystallographically independent Mo(VI) centres bridged via a µ-oxo group imposing a Mo···Mo distance of 3.6273 (4) Å. The chemical environment of these metallic centers is very similar, being composed of a pair of cis-positioned terminal oxo ligands, a chlorido and a N,N-chelating 4,4'-di-tert-butyl-2,2'-bipyridine (di-t-Bu-bipy) molecule as depicted in Fig. 1. The coordination environments around the metal centers can be described as highly distorted octahedra due to, on the one hand, the existence of chlorido ligands (trans-positioned with respect to the µ-oxo ligand) and, on the other, to the typical trans effect of the Mo═O groups: while the Mo—O_bridge distances are 1.8920 (19) and 1.9274 (19) Å, the Mo—O_terminal distances range from 1.694 (2) to 1.6975 (19) Å; the Mo—Cl distances are 2.4895 (8) and 2.4283 (8) Å and the Mo—N bonds range from 2.304 (2) to 2.330 (2) Å. The cis and trans octahedral angles are in the ranges of 68.95 (8) to 107.35 (10)° and 157.51 (6) to 160.69 (9)°, respectively. The Mo1—O1—Mo2 kink angle through the µ-oxo bridge is 143.50 (10)° which, to the best of our knowledge, constitutes the smallest reported to date for related binuclear dioxomolybdenum(VI) complexes: the analogous value for [Mo₂O₄(µ-O)Cl₂(DMF)₄] is ca 175° and that for [Mo₂O₄(µ-O)Cl₂(pyrazole)₄] is ca 151°, and those for the two conformers of [Mo₂O₄(µ-O)Cl₂(PzPy)₂] are ca 156 and 180°. We attribute this structural feature to the considerable steric hindrance associated with the di-t-Bu-bipy moieties, mostly due to the pendant —CH₃ groups. In this context, the two average planes containing the aromatic rings of the two crystallographically independent di-t-Bu-bipy molecules subtend an angle of ca 34°, which contrasts with the parallel nature observed for the two conformers of [Mo₂O₄(µ-O)Cl₂(PzPy)₂]. Noteworthy, the torsion angles N1—Mo1···Mo2—N4 and N2—Mo1···Mo2—N3 are -18.40 (7) and -157.03 (9)°, respectively.

The crystal packing is mainly driven by the need to effectively fill the available space (van de Waals contacts) in conjunction with several weak supramolecular interactions, namely weak C—H···O and C—H···Cl hydrogen bonding interactions (light blue dashed lines in Fig. 2; see Table 2 for geometric details). The water molecule of crystallization (O1W), which is only statistically present in 1/5 of the asymmetric units, accepts the hydrogen donation from adjacent C—H groups and also acts as hydrogen bond donor to Cl2 and O5 of neighboring molecules (violet dashed lines in Figure 2; see Table 2 for geometrical details). Even though the location of the water molecule permits its full site occupancy, we postulate that the absence of suitable hydrogen bonding partners in the binuclear complexes contributes significantly for its partial occupancy in the crystal structure.

Related literature top

For general background to dioxomolybdenum(VI) complexes, see: Arzoumanian et al. (2006); Jeyakumar & Chand (2009); Kühn et al. (2002); Rodrigues et al. (2004). For studies on molybdenum complexes from our research groups, see: Coelho et al. (2011); Fernandes et al. (2010a,b, 2011); Gago et al. (2009); Nunes et al. (2003); Pereira et al. (2007).

Experimental top

Chemicals were purchased from commercial sources and used as received. The compound [Mo(η³-C₃H₅)Cl(CO)₂(di-t-Bu-bipy)] (1) was prepared following a literature method (Rodrigues et al., 2004). Thus, 70% aqueous tert-butylhydroperoxide (TBHP) (0.64 mL, 4.60 mmol) was added dropwise to a stirred solution of 1 (0.23 g, 0.46 mmol) in CH₃CN (20 mL). After stirring at ambient temperature for 15 h, the resultant yellow solution was filtered off, concentrated, and a very pale yellow solid precipitated after the addition of n-hexane and diethyl ether. The precipitate was filtered, washed with n-hexane and diethyl ether, and vacuum-dried. Yield: 0.14 g, 69%.

The same product (as confirmed by a comparison of FT–IR and ¹H NMR spectra, and microanalysis data) was obtained by using a decane solution of TBHP (5–6 M, 10 equiv.) instead of the aqueous solution, with 1 dissolved in CH₂Cl₂ under otherwise similar conditions (the excess of TBHP was destroyed with MnO₂).

Anal. Calcd. for C₃₆H₄₈N₄Cl₂Mo₂O₅.0.2H₂O (in %): C, 48.96; H, 5.52; N, 6.34. Found (in %): C, 49.47; H, 5.52; N, 6.28. The FT–IR and ¹H NMR spectral data were in agreement with published data (Arzoumanian et al., 2006).

Suitable crystals were obtained by the slow diffusion of diethyl ether into a concentrated solution of the compound in CH₂Cl₂ with a small layer of n-hexane.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 2006); data reduction: SAINT-Plus (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Asymmetric unit of the title compound showing all non-hydrogen atoms represented as thermal ellipsoids drawn at the 50% probability level. The water molecule has a site occupancy factor = 0.20. Hydrogen atoms are represented as small spheres with arbitrary radii and the atomic labeling is provided for all non-hydrogen atoms.
	Fig. 2. Crystal packing of the title compound viewed in perspective along [010] direction. The highly distorted {MoCl₂N₂O₂} coordination polyhedra are represented as translucent octahedra for clarity. Supramolecular contacts interconnecting adjacent chemical moieties are represented as dashed lines: C—H···O and C—H···Cl in light blue; O_water···O and O_water···Cl in violet.

µ-Oxido-bis[chlorido(4,4'-di-tert-butyl-2,2'-bipyridine- κ²N,N')dioxidomolybdenum(VI)] 0.2-hydrate top

Crystal data top

[Mo₂Cl₂O₅(C₁₈H₂₄N₂)₂]·0.2H₂O	F(000) = 1808
M_r = 883.17	D_x = 1.487 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9903 reflections
a = 16.9997 (7) Å	θ = 2.8–29.1°
b = 12.7444 (6) Å	µ = 0.82 mm⁻¹
c = 18.4609 (8) Å	T = 150 K
β = 99.582 (2)°	Block, yellow
V = 3943.8 (3) Å³	0.08 × 0.06 × 0.03 mm
Z = 4

Data collection top

Bruker X8 KappaCCD APEXII diffractometer	10578 independent reflections
Radiation source: fine-focus sealed tube	7469 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ω and φ scans	θ_max = 29.1°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −23→23
T_min = 0.938, T_max = 0.976	k = −16→17
54239 measured reflections	l = −24→25

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0315P)² + 3.406P] where P = (F_o² + 2F_c²)/3
10578 reflections	(Δ/σ)_max = 0.001
463 parameters	Δρ_max = 0.96 e Å⁻³
18 restraints	Δρ_min = −0.67 e Å⁻³

Crystal data top

[Mo₂Cl₂O₅(C₁₈H₂₄N₂)₂]·0.2H₂O	V = 3943.8 (3) Å³
M_r = 883.17	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 16.9997 (7) Å	µ = 0.82 mm⁻¹
b = 12.7444 (6) Å	T = 150 K
c = 18.4609 (8) Å	0.08 × 0.06 × 0.03 mm
β = 99.582 (2)°

Data collection top

Bruker X8 KappaCCD APEXII diffractometer	10578 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	7469 reflections with I > 2σ(I)
T_min = 0.938, T_max = 0.976	R_int = 0.050
54239 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	18 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.02	Δρ_max = 0.96 e Å⁻³
10578 reflections	Δρ_min = −0.67 e Å⁻³
463 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mo1	0.161140 (13)	0.78289 (2)	0.101763 (13)	0.02009 (7)
Mo2	0.153567 (14)	0.63578 (2)	−0.067460 (14)	0.02215 (7)
Cl1	0.16494 (4)	0.87386 (6)	0.22163 (4)	0.02652 (16)
Cl2	0.21012 (5)	0.51282 (7)	−0.14517 (4)	0.03473 (19)
N1	0.11178 (12)	0.65491 (18)	0.17242 (13)	0.0210 (5)
N2	0.02749 (13)	0.81233 (19)	0.10764 (13)	0.0213 (5)
N3	0.27507 (13)	0.59963 (19)	0.00696 (13)	0.0223 (5)
N4	0.14638 (12)	0.48235 (19)	−0.00290 (12)	0.0211 (5)
O1	0.12571 (10)	0.69242 (15)	0.02171 (10)	0.0224 (4)
O2	0.25605 (11)	0.73982 (17)	0.12818 (11)	0.0276 (5)
O3	0.16755 (12)	0.89784 (16)	0.05679 (12)	0.0311 (5)
O4	0.06091 (11)	0.61851 (17)	−0.11680 (11)	0.0297 (5)
O5	0.19330 (13)	0.74344 (18)	−0.10133 (12)	0.0360 (5)
C1	0.15948 (16)	0.5835 (2)	0.21063 (16)	0.0238 (6)
H1	0.2115	0.5743	0.1992	0.029*
C2	0.13739 (16)	0.5228 (2)	0.26543 (17)	0.0245 (6)
H2	0.1739	0.4736	0.2910	0.029*
C3	0.06192 (16)	0.5334 (2)	0.28335 (16)	0.0263 (7)
C4	0.01067 (16)	0.6030 (3)	0.23986 (17)	0.0297 (7)
H4	−0.0432	0.6088	0.2472	0.036*
C5	0.03666 (15)	0.6629 (2)	0.18700 (16)	0.0235 (6)
C6	−0.01214 (16)	0.7471 (2)	0.14631 (16)	0.0232 (6)
C7	−0.09241 (16)	0.7619 (3)	0.14974 (17)	0.0292 (7)
H7	−0.1198	0.7126	0.1751	0.035*
C8	−0.13296 (16)	0.8487 (3)	0.11624 (17)	0.0298 (7)
C9	−0.09027 (17)	0.9162 (3)	0.07927 (17)	0.0295 (7)
H9	−0.1152	0.9770	0.0561	0.035*
C10	−0.01101 (17)	0.8954 (2)	0.07589 (16)	0.0245 (6)
H10	0.0171	0.9427	0.0497	0.029*
C11	0.03393 (19)	0.4783 (3)	0.34808 (19)	0.0385 (8)
C12	0.0029 (3)	0.5616 (4)	0.3962 (2)	0.0777 (16)
H12A	0.0464	0.6095	0.4158	0.117*
H12B	−0.0172	0.5273	0.4370	0.117*
H12C	−0.0403	0.6013	0.3666	0.117*
C13	−0.0336 (2)	0.4023 (4)	0.3180 (2)	0.0666 (14)
H13A	−0.0763	0.4408	0.2868	0.100*
H13B	−0.0547	0.3701	0.3590	0.100*
H13C	−0.0129	0.3474	0.2890	0.100*
C14	0.1016 (2)	0.4186 (3)	0.3952 (2)	0.0461 (10)
H14A	0.1204	0.3627	0.3659	0.069*
H14B	0.0822	0.3878	0.4376	0.069*
H14C	0.1456	0.4669	0.4123	0.069*
C15	−0.22161 (17)	0.8645 (3)	0.1206 (2)	0.0397 (9)
C16	−0.2495 (2)	0.9713 (4)	0.0924 (4)	0.0971 (19)
H16A	−0.3076	0.9757	0.0886	0.146*
H16B	−0.2348	0.9824	0.0438	0.146*
H16C	−0.2243	1.0252	0.1264	0.146*
C17	−0.2693 (2)	0.7825 (4)	0.0698 (3)	0.0681 (13)
H17A	−0.2527	0.7118	0.0870	0.102*
H17B	−0.2590	0.7920	0.0195	0.102*
H17C	−0.3264	0.7914	0.0706	0.102*
C18	−0.2369 (3)	0.8407 (6)	0.1960 (3)	0.106 (2)
H18A	−0.2121	0.8948	0.2301	0.159*
H18B	−0.2142	0.7720	0.2115	0.159*
H18C	−0.2946	0.8397	0.1960	0.159*
C19	0.33976 (16)	0.6593 (2)	0.00679 (17)	0.0274 (7)
H19	0.3352	0.7203	−0.0232	0.033*
C20	0.41289 (16)	0.6358 (3)	0.04836 (17)	0.0279 (7)
H20	0.4572	0.6806	0.0465	0.033*
C21	0.42233 (15)	0.5476 (2)	0.09269 (16)	0.0241 (6)
C22	0.35406 (15)	0.4888 (2)	0.09491 (16)	0.0243 (6)
H22	0.3568	0.4295	0.1265	0.029*
C23	0.28184 (15)	0.5150 (2)	0.05182 (15)	0.0206 (6)
C24	0.20800 (15)	0.4519 (2)	0.04866 (15)	0.0209 (6)
C25	0.20205 (15)	0.3673 (2)	0.09379 (15)	0.0213 (6)
H25	0.2459	0.3494	0.1307	0.026*
C26	0.13233 (16)	0.3073 (2)	0.08606 (15)	0.0211 (6)
C27	0.07065 (16)	0.3385 (2)	0.03097 (16)	0.0234 (6)
H27	0.0223	0.2995	0.0223	0.028*
C28	0.07950 (15)	0.4252 (2)	−0.01084 (16)	0.0232 (6)
H28	0.0360	0.4457	−0.0473	0.028*
C29	0.50289 (16)	0.5150 (3)	0.13790 (18)	0.0304 (7)
C30	0.50366 (18)	0.5490 (3)	0.21771 (19)	0.0435 (9)
H30A	0.5534	0.5256	0.2481	0.065*
H30B	0.4582	0.5174	0.2359	0.065*
H30C	0.4999	0.6256	0.2201	0.065*
C31	0.57226 (17)	0.5677 (3)	0.1089 (2)	0.0420 (9)
H31A	0.5688	0.6439	0.1147	0.063*
H31B	0.5696	0.5505	0.0568	0.063*
H31C	0.6229	0.5423	0.1367	0.063*
C32	0.51307 (18)	0.3958 (3)	0.1352 (2)	0.0428 (9)
H32A	0.5029	0.3722	0.0840	0.064*
H32B	0.4752	0.3619	0.1624	0.064*
H32C	0.5676	0.3770	0.1575	0.064*
C33	0.12703 (17)	0.2135 (2)	0.13614 (16)	0.0260 (6)
C34	0.1347 (2)	0.2522 (3)	0.21501 (17)	0.0394 (9)
H34A	0.1857	0.2888	0.2288	0.059*
H34B	0.1325	0.1923	0.2479	0.059*
H34C	0.0908	0.3006	0.2192	0.059*
C35	0.04774 (18)	0.1555 (3)	0.11683 (17)	0.0319 (7)
H35A	0.0043	0.2012	0.1265	0.048*
H35B	0.0490	0.0919	0.1469	0.048*
H35C	0.0391	0.1362	0.0647	0.048*
C36	0.1950 (2)	0.1374 (3)	0.1283 (2)	0.0459 (9)
H36A	0.1899	0.1143	0.0771	0.069*
H36B	0.1922	0.0763	0.1601	0.069*
H36C	0.2464	0.1729	0.1428	0.069*
O1W	−0.1847 (9)	0.6639 (13)	0.2975 (10)	0.078 (5)	0.20

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.01580 (10)	0.02716 (14)	0.01656 (13)	−0.00222 (10)	0.00054 (8)	−0.00064 (11)
Mo2	0.02064 (11)	0.02864 (15)	0.01613 (13)	0.00094 (10)	0.00001 (9)	0.00249 (11)
Cl1	0.0231 (3)	0.0348 (4)	0.0201 (4)	−0.0005 (3)	−0.0010 (3)	−0.0053 (3)
Cl2	0.0354 (4)	0.0461 (5)	0.0232 (4)	0.0068 (4)	0.0064 (3)	−0.0019 (4)
N1	0.0157 (10)	0.0261 (14)	0.0201 (13)	−0.0015 (9)	0.0001 (9)	−0.0008 (10)
N2	0.0193 (11)	0.0258 (14)	0.0169 (13)	0.0015 (9)	−0.0026 (9)	−0.0009 (10)
N3	0.0197 (11)	0.0278 (14)	0.0197 (13)	−0.0008 (10)	0.0042 (9)	−0.0008 (10)
N4	0.0175 (10)	0.0289 (14)	0.0150 (12)	−0.0024 (9)	−0.0030 (9)	0.0006 (10)
O1	0.0183 (9)	0.0286 (12)	0.0188 (11)	0.0011 (8)	−0.0015 (8)	−0.0022 (8)
O2	0.0177 (9)	0.0421 (13)	0.0222 (11)	−0.0017 (9)	0.0009 (8)	−0.0067 (9)
O3	0.0377 (12)	0.0301 (12)	0.0259 (12)	−0.0038 (9)	0.0067 (10)	0.0005 (9)
O4	0.0260 (10)	0.0400 (13)	0.0199 (11)	0.0023 (9)	−0.0052 (8)	−0.0001 (9)
O5	0.0374 (12)	0.0373 (14)	0.0332 (13)	−0.0015 (10)	0.0059 (10)	0.0100 (11)
C1	0.0184 (12)	0.0276 (17)	0.0244 (16)	0.0005 (11)	0.0008 (11)	−0.0013 (13)
C2	0.0202 (13)	0.0260 (16)	0.0257 (17)	0.0038 (11)	−0.0011 (12)	0.0026 (13)
C3	0.0223 (13)	0.0332 (18)	0.0221 (16)	0.0011 (12)	0.0001 (12)	0.0064 (13)
C4	0.0164 (13)	0.043 (2)	0.0296 (18)	0.0021 (12)	0.0049 (12)	0.0090 (14)
C5	0.0167 (12)	0.0327 (17)	0.0204 (15)	−0.0003 (11)	0.0008 (11)	0.0024 (13)
C6	0.0195 (13)	0.0300 (17)	0.0189 (15)	0.0008 (11)	−0.0007 (11)	0.0022 (12)
C7	0.0168 (13)	0.044 (2)	0.0259 (17)	0.0010 (13)	0.0016 (12)	0.0048 (14)
C8	0.0201 (13)	0.043 (2)	0.0248 (17)	0.0051 (13)	−0.0012 (12)	−0.0036 (14)
C9	0.0282 (15)	0.0311 (18)	0.0256 (17)	0.0071 (13)	−0.0059 (13)	0.0003 (14)
C10	0.0277 (14)	0.0245 (16)	0.0189 (16)	−0.0003 (12)	−0.0032 (12)	−0.0014 (12)
C11	0.0338 (17)	0.051 (2)	0.033 (2)	0.0093 (16)	0.0107 (14)	0.0173 (17)
C12	0.107 (4)	0.090 (4)	0.047 (3)	0.053 (3)	0.043 (3)	0.033 (3)
C13	0.0322 (19)	0.099 (4)	0.070 (3)	−0.011 (2)	0.0104 (19)	0.048 (3)
C14	0.0408 (19)	0.058 (3)	0.040 (2)	0.0081 (17)	0.0077 (16)	0.0235 (19)
C15	0.0185 (14)	0.059 (2)	0.040 (2)	0.0117 (15)	0.0008 (13)	0.0013 (18)
C16	0.037 (2)	0.072 (3)	0.186 (6)	0.021 (2)	0.029 (3)	0.006 (4)
C17	0.0261 (17)	0.096 (4)	0.083 (3)	−0.005 (2)	0.0089 (19)	−0.006 (3)
C18	0.048 (2)	0.219 (6)	0.056 (3)	0.055 (3)	0.023 (2)	0.010 (4)
C19	0.0246 (14)	0.0271 (17)	0.0318 (18)	0.0008 (12)	0.0084 (13)	0.0010 (14)
C20	0.0179 (13)	0.0360 (18)	0.0302 (18)	−0.0029 (12)	0.0057 (12)	−0.0050 (14)
C21	0.0188 (13)	0.0330 (18)	0.0198 (16)	0.0008 (12)	0.0013 (11)	−0.0062 (13)
C22	0.0201 (13)	0.0294 (17)	0.0230 (16)	0.0016 (12)	0.0025 (11)	−0.0003 (13)
C23	0.0175 (12)	0.0281 (16)	0.0160 (15)	0.0000 (11)	0.0020 (10)	−0.0008 (12)
C24	0.0186 (12)	0.0260 (16)	0.0163 (15)	−0.0006 (11)	−0.0024 (10)	−0.0034 (12)
C25	0.0201 (12)	0.0250 (16)	0.0166 (14)	−0.0008 (11)	−0.0033 (11)	0.0003 (12)
C26	0.0221 (13)	0.0240 (16)	0.0161 (15)	−0.0014 (11)	0.0000 (11)	−0.0022 (12)
C27	0.0204 (13)	0.0268 (17)	0.0212 (16)	−0.0040 (11)	−0.0018 (11)	−0.0022 (12)
C28	0.0189 (12)	0.0306 (17)	0.0178 (15)	−0.0008 (11)	−0.0039 (11)	−0.0023 (13)
C29	0.0168 (13)	0.045 (2)	0.0282 (18)	0.0030 (13)	0.0011 (12)	−0.0047 (15)
C30	0.0240 (15)	0.072 (3)	0.031 (2)	0.0066 (16)	−0.0046 (14)	−0.0089 (18)
C31	0.0182 (14)	0.064 (3)	0.043 (2)	0.0004 (15)	0.0031 (14)	0.0020 (19)
C32	0.0232 (15)	0.052 (2)	0.051 (2)	0.0094 (15)	−0.0012 (15)	−0.0005 (18)
C33	0.0273 (14)	0.0306 (17)	0.0182 (15)	−0.0062 (13)	−0.0013 (11)	0.0023 (13)
C34	0.0481 (19)	0.046 (2)	0.0210 (18)	−0.0263 (16)	−0.0025 (15)	−0.0002 (15)
C35	0.0388 (17)	0.0327 (19)	0.0199 (17)	−0.0130 (14)	−0.0075 (13)	0.0037 (14)
C36	0.0426 (19)	0.034 (2)	0.060 (3)	0.0063 (16)	0.0040 (18)	0.0164 (18)
O1W	0.055 (9)	0.079 (12)	0.105 (14)	−0.006 (8)	0.029 (9)	0.015 (10)

Geometric parameters (Å, º) top

Mo1—O1	1.8920 (19)	C15—C17	1.541 (5)
Mo1—O2	1.6972 (19)	C16—H16A	0.9800
Mo1—O3	1.696 (2)	C16—H16B	0.9800
Mo1—N1	2.330 (2)	C16—H16C	0.9800
Mo1—N2	2.323 (2)	C17—H17A	0.9800
Mo1—Cl1	2.4895 (8)	C17—H17B	0.9800
Mo2—O1	1.9274 (19)	C17—H17C	0.9800
Mo2—O4	1.6975 (19)	C18—H18A	0.9800
Mo2—O5	1.694 (2)	C18—H18B	0.9800
Mo2—N3	2.328 (2)	C18—H18C	0.9800
Mo2—N4	2.304 (2)	C19—C20	1.381 (4)
Mo2—Cl2	2.4283 (8)	C19—H19	0.9500
N1—C1	1.339 (3)	C20—C21	1.384 (4)
N1—C5	1.352 (3)	C20—H20	0.9500
N2—C10	1.329 (4)	C21—C22	1.388 (4)
N2—C6	1.347 (4)	C21—C29	1.537 (4)
N3—C19	1.337 (4)	C22—C23	1.388 (4)
N3—C23	1.353 (4)	C22—H22	0.9500
N4—C28	1.338 (3)	C23—C24	1.484 (4)
N4—C24	1.350 (3)	C24—C25	1.377 (4)
C1—C2	1.375 (4)	C25—C26	1.397 (4)
C1—H1	0.9500	C25—H25	0.9500
C2—C3	1.384 (4)	C26—C27	1.391 (4)
C2—H2	0.9500	C26—C33	1.523 (4)
C3—C4	1.399 (4)	C27—C28	1.371 (4)
C3—C11	1.529 (4)	C27—H27	0.9500
C4—C5	1.369 (4)	C28—H28	0.9500
C4—H4	0.9500	C29—C31	1.529 (4)
C5—C6	1.482 (4)	C29—C32	1.531 (5)
C6—C7	1.389 (4)	C29—C30	1.534 (5)
C7—C8	1.393 (4)	C30—H30A	0.9800
C7—H7	0.9500	C30—H30B	0.9800
C8—C9	1.378 (4)	C30—H30C	0.9800
C8—C15	1.536 (4)	C31—H31A	0.9800
C9—C10	1.385 (4)	C31—H31B	0.9800
C9—H9	0.9500	C31—H31C	0.9800
C10—H10	0.9500	C32—H32A	0.9800
C11—C14	1.524 (4)	C32—H32B	0.9800
C11—C13	1.533 (5)	C32—H32C	0.9800
C11—C12	1.534 (6)	C33—C34	1.522 (4)
C12—H12A	0.9800	C33—C35	1.526 (4)
C12—H12B	0.9800	C33—C36	1.534 (4)
C12—H12C	0.9800	C34—H34A	0.9800
C13—H13A	0.9800	C34—H34B	0.9800
C13—H13B	0.9800	C34—H34C	0.9800
C13—H13C	0.9800	C35—H35A	0.9800
C14—H14A	0.9800	C35—H35B	0.9800
C14—H14B	0.9800	C35—H35C	0.9800
C14—H14C	0.9800	C36—H36A	0.9800
C15—C18	1.490 (6)	C36—H36B	0.9800
C15—C16	1.504 (6)	C36—H36C	0.9800

O3—Mo1—O2	106.53 (10)	C18—C15—C17	105.9 (4)
O3—Mo1—O1	100.49 (9)	C16—C15—C17	107.4 (4)
O2—Mo1—O1	101.02 (9)	C8—C15—C17	107.5 (3)
O3—Mo1—N2	91.51 (9)	C15—C16—H16A	109.5
O2—Mo1—N2	158.31 (9)	C15—C16—H16B	109.5
O1—Mo1—N2	87.03 (8)	H16A—C16—H16B	109.5
O3—Mo1—N1	159.54 (9)	C15—C16—H16C	109.5
O2—Mo1—N1	91.52 (9)	H16A—C16—H16C	109.5
O1—Mo1—N1	85.02 (8)	H16B—C16—H16C	109.5
N2—Mo1—N1	68.95 (8)	C15—C17—H17A	109.5
O3—Mo1—Cl1	92.21 (8)	C15—C17—H17B	109.5
O2—Mo1—Cl1	90.71 (7)	H17A—C17—H17B	109.5
O1—Mo1—Cl1	159.37 (6)	C15—C17—H17C	109.5
N2—Mo1—Cl1	76.36 (6)	H17A—C17—H17C	109.5
N1—Mo1—Cl1	77.70 (6)	H17B—C17—H17C	109.5
O5—Mo2—O4	107.35 (10)	C15—C18—H18A	109.5
O5—Mo2—O1	100.46 (10)	C15—C18—H18B	109.5
O4—Mo2—O1	99.73 (9)	H18A—C18—H18B	109.5
O5—Mo2—N4	159.56 (9)	C15—C18—H18C	109.5
O4—Mo2—N4	92.48 (9)	H18A—C18—H18C	109.5
O1—Mo2—N4	80.46 (8)	H18B—C18—H18C	109.5
O5—Mo2—N3	90.52 (9)	N3—C19—C20	122.7 (3)
O4—Mo2—N3	160.69 (9)	N3—C19—H19	118.7
O1—Mo2—N3	83.69 (8)	C20—C19—H19	118.7
N4—Mo2—N3	69.21 (8)	C19—C20—C21	120.7 (3)
O5—Mo2—Cl2	94.77 (8)	C19—C20—H20	119.7
O4—Mo2—Cl2	91.29 (7)	C21—C20—H20	119.7
O1—Mo2—Cl2	157.51 (6)	C20—C21—C22	116.2 (3)
N4—Mo2—Cl2	79.53 (6)	C20—C21—C29	123.0 (3)
N3—Mo2—Cl2	79.71 (6)	C22—C21—C29	120.8 (3)
C1—N1—C5	117.1 (2)	C21—C22—C23	121.1 (3)
C1—N1—Mo1	121.85 (18)	C21—C22—H22	119.4
C5—N1—Mo1	119.91 (18)	C23—C22—H22	119.4
C10—N2—C6	118.2 (2)	N3—C23—C22	121.3 (3)
C10—N2—Mo1	121.46 (19)	N3—C23—C24	115.0 (2)
C6—N2—Mo1	120.28 (18)	C22—C23—C24	123.6 (3)
C19—N3—C23	117.9 (2)	N4—C24—C25	121.7 (2)
C19—N3—Mo2	122.4 (2)	N4—C24—C23	115.1 (2)
C23—N3—Mo2	119.71 (17)	C25—C24—C23	123.2 (2)
C28—N4—C24	117.8 (2)	C24—C25—C26	120.9 (2)
C28—N4—Mo2	121.53 (18)	C24—C25—H25	119.6
C24—N4—Mo2	120.46 (18)	C26—C25—H25	119.6
Mo1—O1—Mo2	143.50 (10)	C27—C26—C25	116.2 (3)
N1—C1—C2	123.7 (3)	C27—C26—C33	123.6 (2)
N1—C1—H1	118.2	C25—C26—C33	120.1 (2)
C2—C1—H1	118.2	C28—C27—C26	120.1 (3)
C1—C2—C3	119.9 (3)	C28—C27—H27	119.9
C1—C2—H2	120.0	C26—C27—H27	119.9
C3—C2—H2	120.0	N4—C28—C27	123.3 (3)
C2—C3—C4	116.0 (3)	N4—C28—H28	118.4
C2—C3—C11	124.3 (3)	C27—C28—H28	118.4
C4—C3—C11	119.6 (3)	C31—C29—C32	109.0 (3)
C5—C4—C3	121.2 (3)	C31—C29—C30	109.2 (3)
C5—C4—H4	119.4	C32—C29—C30	109.2 (3)
C3—C4—H4	119.4	C31—C29—C21	111.2 (3)
N1—C5—C4	121.8 (3)	C32—C29—C21	110.2 (3)
N1—C5—C6	114.9 (2)	C30—C29—C21	108.1 (2)
C4—C5—C6	123.0 (3)	C29—C30—H30A	109.5
N2—C6—C7	121.4 (3)	C29—C30—H30B	109.5
N2—C6—C5	115.4 (2)	H30A—C30—H30B	109.5
C7—C6—C5	123.1 (3)	C29—C30—H30C	109.5
C6—C7—C8	120.3 (3)	H30A—C30—H30C	109.5
C6—C7—H7	119.8	H30B—C30—H30C	109.5
C8—C7—H7	119.8	C29—C31—H31A	109.5
C9—C8—C7	117.0 (3)	C29—C31—H31B	109.5
C9—C8—C15	123.1 (3)	H31A—C31—H31B	109.5
C7—C8—C15	119.9 (3)	C29—C31—H31C	109.5
C8—C9—C10	120.0 (3)	H31A—C31—H31C	109.5
C8—C9—H9	120.0	H31B—C31—H31C	109.5
C10—C9—H9	120.0	C29—C32—H32A	109.5
N2—C10—C9	123.0 (3)	C29—C32—H32B	109.5
N2—C10—H10	118.5	H32A—C32—H32B	109.5
C9—C10—H10	118.5	C29—C32—H32C	109.5
C14—C11—C3	111.8 (3)	H32A—C32—H32C	109.5
C14—C11—C13	109.9 (3)	H32B—C32—H32C	109.5
C3—C11—C13	108.6 (3)	C34—C33—C26	108.7 (3)
C14—C11—C12	108.4 (3)	C34—C33—C35	108.2 (3)
C3—C11—C12	108.5 (3)	C26—C33—C35	112.2 (2)
C13—C11—C12	109.8 (3)	C34—C33—C36	110.4 (3)
C11—C12—H12A	109.5	C26—C33—C36	108.5 (3)
C11—C12—H12B	109.5	C35—C33—C36	108.8 (3)
H12A—C12—H12B	109.5	C33—C34—H34A	109.5
C11—C12—H12C	109.5	C33—C34—H34B	109.5
H12A—C12—H12C	109.5	H34A—C34—H34B	109.5
H12B—C12—H12C	109.5	C33—C34—H34C	109.5
C11—C13—H13A	109.5	H34A—C34—H34C	109.5
C11—C13—H13B	109.5	H34B—C34—H34C	109.5
H13A—C13—H13B	109.5	C33—C35—H35A	109.5
C11—C13—H13C	109.5	C33—C35—H35B	109.5
H13A—C13—H13C	109.5	H35A—C35—H35B	109.5
H13B—C13—H13C	109.5	C33—C35—H35C	109.5
C11—C14—H14A	109.5	H35A—C35—H35C	109.5
C11—C14—H14B	109.5	H35B—C35—H35C	109.5
H14A—C14—H14B	109.5	C33—C36—H36A	109.5
C11—C14—H14C	109.5	C33—C36—H36B	109.5
H14A—C14—H14C	109.5	H36A—C36—H36B	109.5
H14B—C14—H14C	109.5	C33—C36—H36C	109.5
C18—C15—C16	114.4 (4)	H36A—C36—H36C	109.5
C18—C15—C8	110.3 (3)	H36B—C36—H36C	109.5
C16—C15—C8	110.9 (3)

O3—Mo1—N1—C1	−154.4 (3)	N1—C5—C6—N2	−8.0 (4)
O2—Mo1—N1—C1	−2.2 (2)	C4—C5—C6—N2	166.9 (3)
O1—Mo1—N1—C1	98.8 (2)	N1—C5—C6—C7	174.8 (3)
N2—Mo1—N1—C1	−172.5 (2)	C4—C5—C6—C7	−10.3 (5)
Cl1—Mo1—N1—C1	−92.6 (2)	N2—C6—C7—C8	−3.5 (5)
O3—Mo1—N1—C5	13.1 (4)	C5—C6—C7—C8	173.5 (3)
O2—Mo1—N1—C5	165.3 (2)	C6—C7—C8—C9	1.2 (5)
O1—Mo1—N1—C5	−93.7 (2)	C6—C7—C8—C15	−179.8 (3)
N2—Mo1—N1—C5	−5.0 (2)	C7—C8—C9—C10	0.8 (5)
Cl1—Mo1—N1—C5	74.9 (2)	C15—C8—C9—C10	−178.2 (3)
O3—Mo1—N2—C10	3.8 (2)	C6—N2—C10—C9	−1.7 (4)
O2—Mo1—N2—C10	150.5 (3)	Mo1—N2—C10—C9	−179.0 (2)
O1—Mo1—N2—C10	−96.7 (2)	C8—C9—C10—N2	−0.6 (5)
N1—Mo1—N2—C10	177.5 (2)	C2—C3—C11—C14	5.6 (5)
Cl1—Mo1—N2—C10	95.7 (2)	C4—C3—C11—C14	−171.7 (3)
O3—Mo1—N2—C6	−173.5 (2)	C2—C3—C11—C13	−115.8 (4)
O2—Mo1—N2—C6	−26.7 (4)	C4—C3—C11—C13	67.0 (4)
O1—Mo1—N2—C6	86.1 (2)	C2—C3—C11—C12	125.0 (4)
N1—Mo1—N2—C6	0.3 (2)	C4—C3—C11—C12	−52.2 (4)
Cl1—Mo1—N2—C6	−81.6 (2)	C9—C8—C15—C18	−138.6 (4)
O5—Mo2—N3—C19	−1.0 (2)	C7—C8—C15—C18	42.5 (5)
O4—Mo2—N3—C19	157.1 (3)	C9—C8—C15—C16	−10.8 (5)
O1—Mo2—N3—C19	−101.5 (2)	C7—C8—C15—C16	170.3 (4)
N4—Mo2—N3—C19	176.4 (2)	C9—C8—C15—C17	106.4 (4)
Cl2—Mo2—N3—C19	93.7 (2)	C7—C8—C15—C17	−72.6 (4)
O5—Mo2—N3—C23	179.7 (2)	C23—N3—C19—C20	2.2 (4)
O4—Mo2—N3—C23	−22.2 (4)	Mo2—N3—C19—C20	−177.1 (2)
O1—Mo2—N3—C23	79.2 (2)	N3—C19—C20—C21	0.1 (5)
N4—Mo2—N3—C23	−3.0 (2)	C19—C20—C21—C22	−2.8 (4)
Cl2—Mo2—N3—C23	−85.6 (2)	C19—C20—C21—C29	177.6 (3)
O5—Mo2—N4—C28	−171.6 (3)	C20—C21—C22—C23	3.2 (4)
O4—Mo2—N4—C28	−5.4 (2)	C29—C21—C22—C23	−177.2 (3)
O1—Mo2—N4—C28	94.0 (2)	C19—N3—C23—C22	−1.8 (4)
N3—Mo2—N4—C28	−179.2 (2)	Mo2—N3—C23—C22	177.6 (2)
Cl2—Mo2—N4—C28	−96.3 (2)	C19—N3—C23—C24	−179.5 (3)
O5—Mo2—N4—C24	13.8 (4)	Mo2—N3—C23—C24	−0.1 (3)
O4—Mo2—N4—C24	179.9 (2)	C21—C22—C23—N3	−1.0 (4)
O1—Mo2—N4—C24	−80.6 (2)	C21—C22—C23—C24	176.5 (3)
N3—Mo2—N4—C24	6.2 (2)	C28—N4—C24—C25	−2.3 (4)
Cl2—Mo2—N4—C24	89.1 (2)	Mo2—N4—C24—C25	172.5 (2)
O3—Mo1—O1—Mo2	60.75 (19)	C28—N4—C24—C23	176.7 (2)
O2—Mo1—O1—Mo2	−48.57 (19)	Mo2—N4—C24—C23	−8.5 (3)
N2—Mo1—O1—Mo2	151.74 (18)	N3—C23—C24—N4	5.4 (4)
N1—Mo1—O1—Mo2	−139.15 (18)	C22—C23—C24—N4	−172.2 (3)
Cl1—Mo1—O1—Mo2	−172.16 (6)	N3—C23—C24—C25	−175.6 (3)
O5—Mo2—O1—Mo1	−40.34 (19)	C22—C23—C24—C25	6.8 (4)
O4—Mo2—O1—Mo1	−150.18 (18)	N4—C24—C25—C26	2.1 (4)
N4—Mo2—O1—Mo1	118.93 (18)	C23—C24—C25—C26	−176.8 (3)
N3—Mo2—O1—Mo1	49.02 (18)	C24—C25—C26—C27	−0.1 (4)
Cl2—Mo2—O1—Mo1	91.5 (2)	C24—C25—C26—C33	179.6 (3)
C5—N1—C1—C2	−3.3 (4)	C25—C26—C27—C28	−1.7 (4)
Mo1—N1—C1—C2	164.5 (2)	C33—C26—C27—C28	178.7 (3)
N1—C1—C2—C3	0.4 (5)	C24—N4—C28—C27	0.5 (4)
C1—C2—C3—C4	3.8 (4)	Mo2—N4—C28—C27	−174.3 (2)
C1—C2—C3—C11	−173.6 (3)	C26—C27—C28—N4	1.5 (5)
C2—C3—C4—C5	−5.2 (5)	C20—C21—C29—C31	−18.8 (4)
C11—C3—C4—C5	172.3 (3)	C22—C21—C29—C31	161.6 (3)
C1—N1—C5—C4	1.8 (4)	C20—C21—C29—C32	−139.8 (3)
Mo1—N1—C5—C4	−166.3 (2)	C22—C21—C29—C32	40.6 (4)
C1—N1—C5—C6	176.7 (2)	C20—C21—C29—C30	101.0 (4)
Mo1—N1—C5—C6	8.6 (3)	C22—C21—C29—C30	−78.6 (4)
C3—C4—C5—N1	2.6 (5)	C27—C26—C33—C34	−117.4 (3)
C3—C4—C5—C6	−172.0 (3)	C25—C26—C33—C34	62.9 (3)
C10—N2—C6—C7	3.7 (4)	C27—C26—C33—C35	2.2 (4)
Mo1—N2—C6—C7	−178.9 (2)	C25—C26—C33—C35	−177.4 (3)
C10—N2—C6—C5	−173.5 (2)	C27—C26—C33—C36	122.4 (3)
Mo1—N2—C6—C5	3.8 (3)	C25—C26—C33—C36	−57.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C27—H27···O1ⁱ	0.95	2.52	3.341 (3)	145
C34—H34A···Cl1ⁱⁱ	0.98	2.77	3.748 (4)	174
C35—H35A···O4ⁱ	0.98	2.54	3.421 (4)	149
C12—H12C···O1W	0.98	2.69	3.641 (16)	163
C18—H18B···O1W	0.98	2.10	2.970 (18)	147
O1W···Cl2ⁱ			3.573 (18)
O1W···O5ⁱⁱⁱ			3.236 (17)

Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1/2, y−1/2, −z+1/2; (iii) x−1/2, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Mo₂Cl₂O₅(C₁₈H₂₄N₂)₂]·0.2H₂O
M_r	883.17
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	16.9997 (7), 12.7444 (6), 18.4609 (8)
β (°)	99.582 (2)
V (Å³)	3943.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.82
Crystal size (mm)	0.08 × 0.06 × 0.03

Data collection
Diffractometer	Bruker X8 KappaCCD APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.938, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	54239, 10578, 7469
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.086, 1.02
No. of reflections	10578
No. of parameters	463
No. of restraints	18
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.96, −0.67

Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (Bruker, 2006), SAINT-Plus (Bruker, 2005), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2009).

Selected bond lengths (Å) top

Mo1—O1	1.8920 (19)	Mo2—O1	1.9274 (19)
Mo1—O2	1.6972 (19)	Mo2—O4	1.6975 (19)
Mo1—O3	1.696 (2)	Mo2—O5	1.694 (2)
Mo1—N1	2.330 (2)	Mo2—N3	2.328 (2)
Mo1—N2	2.323 (2)	Mo2—N4	2.304 (2)
Mo1—Cl1	2.4895 (8)	Mo2—Cl2	2.4283 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C27—H27···O1ⁱ	0.95	2.52	3.341 (3)	145
C34—H34A···Cl1ⁱⁱ	0.98	2.77	3.748 (4)	174
C35—H35A···O4ⁱ	0.98	2.54	3.421 (4)	149
C12—H12C···O1W	0.98	2.69	3.641 (16)	163
C18—H18B···O1W	0.98	2.10	2.970 (18)	147
O1W···Cl2ⁱ	.	.	3.573 (18)	.
O1W···O5ⁱⁱⁱ	.	.	3.236 (17)	.

Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1/2, y−1/2, −z+1/2; (iii) x−1/2, −y+3/2, z+1/2.

Acknowledgements

We are grateful to the Fundação para a Ciência e a Tecnologia (FCT/FEDER and POCI, Portugal) for their general financial support to CICECO, and for the post-doctoral research grant No. SFRH/BPD/63736/2009 (to JAF). Thanks are also due to the FCT for specific funding toward the purchase of the single-crystal diffractometer.

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