Crystal structure of (2,2′-bi­pyridine-κ2N,N′)-trans-bis­(tert-butyl­dimethyl­sil­yloxy)-cis-dioxidomolybdenum(VI)

Minyaev, M.E.; Vinogradov, A.A.; Nifant'ev, I.E.; Churakov, A.V.

doi:10.1107/S2056989018008472

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Volume 74| Part 7| July 2018| Pages 970-972

https://doi.org/10.1107/S2056989018008472

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Crystal structure of (2,2′-bipyridine-κ²N,N′)-trans-bis(tert-butyldimethylsilyloxy)-cis-dioxidomolybdenum(VI)

Mikhail E. Minyaev,^a ^* Alexander A. Vinogradov,^a Ilya E. Nifant'ev ^a,^b and Andrei V. Churakov ^c

^aA.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky Prospect, 119991, Moscow, Russian Federation, ^bChemistry Department, M.V. Lomonosov Moscow State University, 1 Leninskie Gory Str., Building 3, Moscow 119991, Russian Federation, and ^cN.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31 Leninsky Prospect, Moscow 119991, Russian Federation
^*Correspondence e-mail: mminyaev@mail.ru

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 25 May 2018; accepted 8 June 2018; online 15 June 2018)

In the title compound, [(^tBuSiMe₂O)₂MoO₂(2,2′-bipyridine)] or [Mo(C₆H₁₅OSi)₂O₂(C₁₀H₈N₂)], the Mo^VI atom has a distorted octahedral environment with the siloxy substituents occupying the trans positions. The complex contains a rare (R₃SiO)₂MO₂ (M = Mo, W) structural motif and was formed in a reaction between sodium molybdate and tert-butyldimethylsilyl chloride in the presence of 2,2-bipyridine. In the crystal, neighbouring molecules are linked by C—H⋯O=Mo hydrogen bonds, forming chains propagating along the a-axis direction.

Keywords: crystal structure; molybdenum(VI); rare structural motif; coordination compounds; NMR; hydrogen bonding..

CCDC reference: 1833969

1. Chemical context

Bulky siloxy ligands are of interest as they can stabilize transition metal complexes with low coordination numbers, providing attractive structures and chemistry (Eppley et al., 1991 ; Neithamer et al., 1989 ; Huang & DeKock, 1993 ). The structural and reactivity studies of cis-M^VIO₂ and cis-M^VIOS complexes (M = Mo, W), including siloxy derivatives, are essential for understanding the activity of specific enzymes (Thapper et al., 1999 ; Miao et al., 2000 ). Both Mo^VIO₂ and Mo siloxy derivatives have attracted attention as precursors, or as real catalytic species, in various catalytic applications (Heppekausen et al., 2012 ; Arzoumanian et al., 2008 ; Coelho et al., 2011 ; Bruno et al., 2006 ). Herein, we report on the crystal structure and synthesis of the title complex, (^tBuSiMe₂O)₂MoO₂(bipy) (I).

It was prepared by a one-pot reaction of sodium molybdate (Na₂MoO₄) with 2,2-bipyridine (bipy) in acetonitrile followed by addition of tert-butyldimethylsilyl chloride (Fig. 1).

Figure 1
Synthesis of [(^tBuSiMe₂O)₂MoO₂(2,2′-bipyridine)] (I)

2. Structural commentary

A view of the molecular structure of the 16-electron complex (^tBuSiMe₂O)₂MoO₂(bipy) (I) is given in Fig. 2, and selected geometrical parameters are given in Table 1. The bipy ligand is not planar, but instead twisted about the C5—C6 bond with a dihedral angle of 9.76 (14)° between the two pyridine rings. The Mo environment resembles a distorted octahedron with the bulky siloxy ligands occupying the trans positions. The X—Mo—X bond angles lie in the ranges 77.30 (7)–79.91 (7)° for O_Si—Mo1—N, 97.22 (8)–98.38 (9) for O_Si—Mo1—O_Mo=O, 90.23 (7)–94.24 (7) for O_Mo=O—Mo1—N (cis) and 159.26 (7)–163.31 (7) for O_Mo=O—Mo1—N (trans). The Mo=O double bonds are, as expected, shorter by ca 0.20 Å than the Mo—O_Si single bonds (Table 1), while the Mo—N bond lengths are the longest.

Table 1
Selected geometric parameters (Å, °)

Mo1—O1	1.9001 (17)	Mo1—O4	1.7073 (16)
Mo1—O2	1.9149 (17)	Mo1—N1	2.3508 (18)
Mo1—O3	1.7058 (17)	Mo1—N2	2.3523 (18)

O1—Mo1—O2	153.41 (7)	O3—Mo1—N1	159.26 (7)
O1—Mo1—O3	98.38 (9)	O4—Mo1—N1	94.24 (7)
O1—Mo1—O4	97.22 (8)	O1—Mo1—N2	79.53 (7)
O2—Mo1—O3	98.38 (8)	O2—Mo1—N2	79.91 (7)
O2—Mo1—O4	97.63 (8)	O3—Mo1—N2	90.23 (7)
O3—Mo1—O4	106.46 (8)	O4—Mo1—N2	163.31 (7)
O1—Mo1—N1	77.30 (7)	N1—Mo1—N2	69.07 (6)
O2—Mo1—N1	79.72 (7)

Figure 2
The molecular structure of the title complex (I)

. Displacement ellipsoids are drawn at the 50% probability level and, for clarity, H atoms have been omitted.

The Mo—X bond lengths in five known complexes of types (Ph₃SiO)₂MoO₂(L) and (Ph₃SiO)₂MoO₂(py)₂ (where L is a κ²N,N′-coordinated ligand, py is pyridine; CSD refcodes are LEKCEL, SOKPAK, WIXCEL, WIXCIP and ZASHAE; see Section 4, Database survey below) vary from 1.695 to 1.705 Å for Mo=O, 1.923 to 1.939 Å for Mo—O_Si and 2.336–2.407 Å for Mo—N. Slightly shorter Mo—O bond lengths are found in the complexes (Ph₃SiO)₂MoO₂(PPh₃) (PERGAU; 1.678 and 1.678 Å for Mo=O, 1.903 and 1.922 Å for Mo—O_Si) and (Ph₃SiO)₂MoO₂ (PERFUN; 1.690 Å for Mo=O and 1.816 Å for Mo—O_Si), likely because of the reduced number of coordinated σ-donating atoms. The title complex exhibits similar Mo=O and Mo—N bond lengths to those in (Ph₃SiO)₂MoO₂(L), but the Mo—O_Si bond lengths are shorter by ca 0.02 Å, probably as a result of the lower steric influence of the ^tBuSiMe₂O ligand than that of Ph₃SiO. The X—Mo—X bond angles in (I) and those in (Ph₃SiO)₂MoO₂(L) are also similar.

3. Supramolecular features

In the crystal, neighbouring molecules are linked by C—H⋯O=Mo hydrogen bonds, forming chains along the a-axis direction (Fig. 3 and Table 2). Similar Mo=O⋯H_Ar interactions can be found in the (Ph₃SiO)₂MoO₂(L) complexes mentioned above. Other non-valent intermolecular short contacts present in the structure of (I) are less significant.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O4ⁱ	0.95	2.38	3.260 (3)	153
C7—H7⋯O3ⁱ	0.95	2.59	3.189 (3)	122
C7—H7⋯O4ⁱ	0.95	2.55	3.494 (3)	170
C8—H8⋯O3ⁱ	0.95	2.55	3.168 (3)	123
Symmetry code: (i) x+1, y, z.

Figure 3
A view along the b axis of the crystal packing of the title complex (I)

. Only the H atoms involved in hydrogen bonding (dashed lines; see Table 2

) are included.

4. Database survey

Crystal structures possessing the (R₃SiO)₂M(=O)₂ structural motif (M = Cr, Mo or W; R is alkyl/aryl) are quite rare. Nine such structures have been described to date in the Cambridge Structural Database (CSD Version 5.39, latest update February 2018; Groom et al., 2016 ), which have only R = Ph. There are two complexes of the type (Ph₃SiO)₂MO₂ without additional σ-donors (M = Mo, CSD refcode PERFUN: Huang & DeKock, 1993; M = Cr, PSILCR: Stensland & Kierkegaard, 1970 ), two complexes with σ-donating monodentate ligands, viz. (Ph₃SiO)₂MoO₂(PPh₃) (PERGAU: Huang & DeKock, 1993), (Ph₃SiO)₂MoO₂(py)₂ (py molecules cis; WIXCIP: Thapper et al., 1999) and five (Ph₃SiO)₂MO₂(L) complexes (where M = Mo and W; L is a κ²N,N′-bidentate ligand). They include (Ph₃SiO)₂MoO₂(bipy) (LEKCEL: Heppekausen et al., 2012), (Ph₃SiO)₂MoO₂(4,4′-^tBu₂bipy) (SOKPAK: Arzoumanian et al., 2008), (Ph₃SiO)₂MoO₂(phen) (phen is 1,10-phenanthroline; WIXCEL: Thapper et al., 1999), (Ph₃SiO)₂WO₂(3,4,7,8-Me₄phen)(MELGEP: Miao et al., 2000) and (Ph₃SiO)₂MoO₂(pzpy) (pzpy is 2-(1H-pyrazol-3-yl)pyridine; ZASHAE: Coelho et al., 2011).

5. Synthesis and crystallization

The title Mo^VI complex was synthesized by a modification of previously reported methods for an analogous complex (Huang & DeKock, 1993; Bruno et al., 2006). Details of the synthesis are illustrated in Fig. 1. Under an argon atmosphere, a stirred mixture of anhydrous sodium molybdate (0.41 g, 2.0 mmol) and 2,2-bipyridine (0.310 g, 2.0 mmol) in CH₃CN (15 ml) was cooled to 273 K and a solution of tert-butyldimethylsilyl chloride (0.603 g, 4.00 mmol) in CH₃CN (10 ml) was slowly added. The obtained suspension was allowed to warm slowly to room temperature and was stirred overnight. All volatiles were removed under reduced pressure. The residue was extracted with THF (50 ml) and filtered. The filtrates were concentrated and cooled to 248 K to afford colourless crystals of (I) (yield 0.850 g, 1.55 mmol, 78%).

¹H NMR (CD₂Cl₂, 298K) δ: −0.45 (s, 12H), 0.55 (s, 18H), 7.60 (t, 2H), 8.08 (t, 2H), 8.19 (m, 2H), 8.29 (d, 2H). ¹³C{¹H} NMR (CD₂Cl₂, 298K) δ: −4.3, 19.5, 25.9, 122.0, 126.1, 139.8, 150.9. See the Supporting information for ¹H and ¹³C{¹H} NMR spectra. Analysis found (calculated for C₂₂H₃₈MoN₂O₄Si₂): C 48.65 (48.33), H 7.30 (7.01), N 5.28% (5.12%).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were found from difference-Fourier maps but positioned geometrically and refined as riding: C—H = 0.95–0.98 Å with U_iso(H) = 1.5U_eq(C-methyl) and 1.2U_eq(C) for other H atoms. A rotating group model was applied for the methyl groups. Reflections 001, 010 and 0 $[\overline{1}]$ 1 were omitted from the refinement as they were affected by the beam stop.

Table 3
Experimental details

Crystal data
Chemical formula	[Mo(C₆H₁₅OSi)₂O₂(C₁₀H₈N₂)]
M_r	546.66
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	150
a, b, c (Å)	8.4027 (8), 12.8657 (13), 14.4266 (14)
α, β, γ (°)	113.144 (2), 91.133 (2), 105.501 (2)
V (Å³)	1368.1 (2)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.59
Crystal size (mm)	0.37 × 0.16 × 0.01

Data collection
Diffractometer	Bruker SMART APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.612, 0.797
No. of measured, independent and observed [I > 2σ(I)] reflections	14073, 6550, 5158
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.075, 1.01
No. of reflections	6550
No. of parameters	290
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.76
Computer programs: APEX2 and SAINT (Bruker, 2008), SHELXS and SHELXTL (Sheldrick, 2008 ), SHELXL2017/1 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ), and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1833969

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S2056989018008472/su5447sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018008472/su5447Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018008472/su5447Isup3.cdx

NMR spectra. DOI: https://doi.org/10.1107/S2056989018008472/su5447sup4.pdf

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2017/1 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2017/1 (Sheldrick, 2015) and publCIF (Westrip, 2010).

(2,2'-Bipyridine-κ²N,N')-trans-bis(tert-\ butyldimethylsilyloxy)-cis-dioxiomolybdenum(VI) top

Crystal data top

[Mo(C₆H₁₅OSi)₂O₂(C₁₀H₈N₂)]	Z = 2
M_r = 546.66	F(000) = 572
Triclinic, P1	D_x = 1.327 Mg m⁻³
a = 8.4027 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.8657 (13) Å	Cell parameters from 4261 reflections
c = 14.4266 (14) Å	θ = 2.5–30.2°
α = 113.144 (2)°	µ = 0.59 mm⁻¹
β = 91.133 (2)°	T = 150 K
γ = 105.501 (2)°	Plate, colourless
V = 1368.1 (2) Å³	0.37 × 0.16 × 0.01 mm

Data collection top

Bruker SMART APEXII diffractometer	6550 independent reflections
Radiation source: fine-focus sealed tube	5158 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 28.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→11
T_min = 0.612, T_max = 0.797	k = −16→16
14073 measured reflections	l = −19→19

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0328P)² + 0.2626P] where P = (F_o² + 2F_c²)/3
6550 reflections	(Δ/σ)_max = 0.001
290 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.76 e Å⁻³

Special details top

Experimental. All synthetic manipulations were conducted under an argon atmosphere, using a dry box and standard Schlenk and vacuum line techniques. THF was predried over NaOH and distilled from potassium/benzophenoneketyl under argon. CH3CN was distilled from calcium hydride under argon. CD2Cl2 was carefully distilled from LiAlH4 and stored over 4?Å molecular sieves. The Mo complex was synthesized by a modification of previously reported methods for an analogous complex (Huang & DeKock, 1993; Bruno et al., 2006). Elemental (C, H, N) analysis was performed with a PerkinElmer 2400 Series II elemental CHNS/O analyzer. NMR spectra were recorded with a Bruker AVANCE 400 spectrometer at 298K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.52976 (2)	0.50708 (2)	0.72617 (2)	0.02159 (6)
Si1	0.49782 (9)	0.23030 (6)	0.72652 (5)	0.03018 (16)
Si2	0.76259 (8)	0.79213 (6)	0.75979 (5)	0.02501 (15)
N1	0.7113 (2)	0.44628 (16)	0.60828 (14)	0.0215 (4)
N2	0.7921 (2)	0.53749 (17)	0.80986 (14)	0.0212 (4)
O1	0.5091 (2)	0.35145 (15)	0.71423 (14)	0.0351 (4)
O2	0.6496 (2)	0.65577 (14)	0.72517 (12)	0.0294 (4)
O3	0.4593 (2)	0.55966 (17)	0.84064 (13)	0.0349 (4)
O4	0.36694 (19)	0.46985 (16)	0.63499 (13)	0.0329 (4)
C1	0.6609 (3)	0.3972 (2)	0.50836 (18)	0.0292 (5)
H1	0.555036	0.397932	0.484733	0.035*
C2	0.7559 (3)	0.3452 (3)	0.43764 (19)	0.0398 (7)
H2	0.716631	0.310979	0.366791	0.048*
C3	0.9084 (3)	0.3443 (3)	0.4724 (2)	0.0458 (8)
H3	0.975418	0.307597	0.425645	0.055*
C4	0.9640 (3)	0.3968 (2)	0.57561 (19)	0.0350 (6)
H4	1.070137	0.397791	0.600557	0.042*
C5	0.8626 (3)	0.4483 (2)	0.64229 (17)	0.0220 (5)
C6	0.9120 (3)	0.5063 (2)	0.75423 (17)	0.0213 (5)
C7	1.0721 (3)	0.5303 (2)	0.79989 (18)	0.0302 (6)
H7	1.155480	0.508329	0.759516	0.036*
C8	1.1091 (3)	0.5865 (3)	0.90479 (19)	0.0365 (7)
H8	1.218304	0.604139	0.937403	0.044*
C9	0.9851 (3)	0.6166 (2)	0.96145 (19)	0.0335 (6)
H9	1.007172	0.654825	1.033667	0.040*
C10	0.8284 (3)	0.5901 (2)	0.91123 (17)	0.0266 (5)
H10	0.742823	0.609994	0.950338	0.032*
C11	0.5902 (4)	0.2679 (3)	0.8581 (3)	0.0663 (10)
H11A	0.540588	0.323552	0.907140	0.099*
H11B	0.711021	0.304435	0.866646	0.099*
H11C	0.567837	0.195617	0.869773	0.099*
C12	0.6180 (5)	0.1462 (3)	0.6336 (3)	0.0723 (11)
H12A	0.735789	0.193257	0.648619	0.108*
H12B	0.573603	0.130178	0.564370	0.108*
H12C	0.607803	0.071187	0.638913	0.108*
C13	0.2713 (4)	0.1436 (3)	0.7013 (2)	0.0406 (7)
C14	0.1814 (4)	0.2076 (4)	0.7858 (3)	0.0682 (11)
H14A	0.062089	0.164346	0.770465	0.102*
H14B	0.197187	0.287983	0.790677	0.102*
H14C	0.227105	0.211773	0.850591	0.102*
C15	0.2504 (5)	0.0183 (3)	0.6950 (3)	0.0739 (12)
H15A	0.131507	−0.026089	0.680629	0.111*
H15B	0.298124	0.024024	0.760015	0.111*
H15C	0.308173	−0.022823	0.640459	0.111*
C16	0.1928 (4)	0.1339 (3)	0.6008 (3)	0.0663 (11)
H16A	0.073361	0.091631	0.589027	0.099*
H16B	0.246525	0.090336	0.545051	0.099*
H16C	0.208028	0.213434	0.603852	0.099*
C17	0.7485 (4)	0.8299 (3)	0.6479 (2)	0.0395 (7)
H17A	0.779816	0.771938	0.589129	0.059*
H17B	0.824427	0.909248	0.664271	0.059*
H17C	0.633928	0.828417	0.631510	0.059*
C18	0.9844 (3)	0.8106 (2)	0.8014 (2)	0.0341 (6)
H18A	1.028364	0.758651	0.745049	0.051*
H18B	0.989910	0.789604	0.859472	0.051*
H18C	1.051098	0.893156	0.821405	0.051*
C19	0.6780 (3)	0.8919 (2)	0.86890 (19)	0.0323 (6)
C20	0.7706 (4)	1.0223 (3)	0.8951 (2)	0.0536 (8)
H20A	0.729747	1.073145	0.953875	0.080*
H20B	0.750759	1.040231	0.836610	0.080*
H20C	0.890478	1.036863	0.911493	0.080*
C21	0.4918 (4)	0.8679 (3)	0.8387 (2)	0.0483 (8)
H21A	0.447629	0.919161	0.895310	0.072*
H21B	0.432569	0.784734	0.822421	0.072*
H21C	0.475998	0.884299	0.778858	0.072*
C22	0.6998 (4)	0.8661 (3)	0.96252 (19)	0.0405 (7)
H22A	0.657102	0.918716	1.019096	0.061*
H22B	0.818368	0.879441	0.981903	0.061*
H22C	0.637747	0.783454	0.946496	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.01231 (9)	0.02799 (12)	0.02539 (11)	0.00788 (7)	0.00225 (7)	0.01080 (9)
Si1	0.0280 (4)	0.0293 (4)	0.0335 (4)	0.0066 (3)	0.0005 (3)	0.0146 (3)
Si2	0.0272 (3)	0.0270 (4)	0.0230 (3)	0.0095 (3)	0.0036 (3)	0.0115 (3)
N1	0.0166 (9)	0.0228 (10)	0.0218 (10)	0.0062 (8)	0.0006 (7)	0.0058 (8)
N2	0.0171 (9)	0.0242 (10)	0.0222 (10)	0.0083 (8)	0.0025 (7)	0.0081 (8)
O1	0.0257 (9)	0.0324 (10)	0.0488 (12)	0.0036 (8)	0.0011 (8)	0.0218 (9)
O2	0.0305 (9)	0.0267 (9)	0.0312 (10)	0.0125 (8)	0.0051 (7)	0.0096 (8)
O3	0.0221 (9)	0.0522 (12)	0.0308 (10)	0.0149 (8)	0.0078 (7)	0.0148 (9)
O4	0.0193 (8)	0.0445 (11)	0.0343 (10)	0.0114 (8)	−0.0014 (7)	0.0147 (9)
C1	0.0229 (12)	0.0337 (14)	0.0254 (13)	0.0094 (11)	−0.0037 (10)	0.0062 (11)
C2	0.0383 (15)	0.0523 (18)	0.0196 (13)	0.0182 (14)	0.0001 (11)	0.0027 (12)
C3	0.0340 (15)	0.067 (2)	0.0266 (14)	0.0262 (15)	0.0069 (11)	0.0026 (14)
C4	0.0223 (12)	0.0529 (18)	0.0266 (13)	0.0184 (12)	0.0041 (10)	0.0086 (12)
C5	0.0152 (10)	0.0256 (13)	0.0236 (12)	0.0063 (9)	0.0022 (9)	0.0084 (10)
C6	0.0178 (10)	0.0255 (12)	0.0213 (11)	0.0081 (9)	0.0023 (9)	0.0094 (10)
C7	0.0190 (11)	0.0462 (16)	0.0267 (13)	0.0161 (11)	0.0041 (9)	0.0123 (12)
C8	0.0219 (12)	0.0586 (19)	0.0277 (14)	0.0165 (12)	−0.0023 (10)	0.0139 (13)
C9	0.0312 (13)	0.0473 (17)	0.0206 (12)	0.0160 (12)	−0.0001 (10)	0.0102 (12)
C10	0.0240 (12)	0.0349 (14)	0.0228 (12)	0.0140 (11)	0.0064 (9)	0.0104 (11)
C11	0.064 (2)	0.074 (3)	0.059 (2)	0.0102 (19)	−0.0221 (18)	0.034 (2)
C12	0.068 (2)	0.055 (2)	0.093 (3)	0.029 (2)	0.037 (2)	0.022 (2)
C13	0.0400 (15)	0.0408 (17)	0.0405 (16)	−0.0009 (13)	−0.0004 (12)	0.0249 (14)
C14	0.0435 (19)	0.092 (3)	0.070 (2)	0.0143 (19)	0.0225 (18)	0.038 (2)
C15	0.065 (2)	0.053 (2)	0.103 (3)	−0.0100 (18)	0.003 (2)	0.050 (2)
C16	0.054 (2)	0.070 (2)	0.057 (2)	−0.0134 (18)	−0.0222 (17)	0.0308 (19)
C17	0.0412 (15)	0.0485 (18)	0.0363 (16)	0.0132 (14)	0.0044 (12)	0.0252 (14)
C18	0.0304 (13)	0.0425 (16)	0.0315 (14)	0.0087 (12)	0.0056 (11)	0.0188 (12)
C19	0.0362 (14)	0.0296 (14)	0.0300 (14)	0.0148 (12)	0.0033 (11)	0.0080 (11)
C20	0.077 (2)	0.0313 (17)	0.0459 (19)	0.0173 (16)	0.0028 (16)	0.0084 (14)
C21	0.0469 (17)	0.054 (2)	0.0408 (17)	0.0332 (16)	0.0069 (13)	0.0051 (15)
C22	0.0516 (17)	0.0431 (17)	0.0249 (14)	0.0232 (14)	0.0093 (12)	0.0062 (12)

Geometric parameters (Å, º) top

Mo1—O1	1.9001 (17)	C11—H11B	0.9800
Mo1—O2	1.9149 (17)	C11—H11C	0.9800
Mo1—O3	1.7058 (17)	C12—H12A	0.9800
Mo1—O4	1.7073 (16)	C12—H12B	0.9800
Mo1—N1	2.3508 (18)	C12—H12C	0.9800
Mo1—N2	2.3523 (18)	C13—C14	1.521 (5)
Si1—O1	1.6152 (18)	C13—C16	1.525 (4)
Si1—C11	1.860 (3)	C13—C15	1.540 (4)
Si1—C12	1.867 (3)	C14—H14A	0.9800
Si1—C13	1.876 (3)	C14—H14B	0.9800
Si2—O2	1.6219 (18)	C14—H14C	0.9800
Si2—C18	1.870 (3)	C15—H15A	0.9800
Si2—C17	1.871 (3)	C15—H15B	0.9800
Si2—C19	1.891 (3)	C15—H15C	0.9800
N1—C1	1.332 (3)	C16—H16A	0.9800
N1—C5	1.344 (3)	C16—H16B	0.9800
N2—C10	1.335 (3)	C16—H16C	0.9800
N2—C6	1.347 (3)	C17—H17A	0.9800
C1—C2	1.381 (3)	C17—H17B	0.9800
C1—H1	0.9500	C17—H17C	0.9800
C2—C3	1.372 (4)	C18—H18A	0.9800
C2—H2	0.9500	C18—H18B	0.9800
C3—C4	1.380 (3)	C18—H18C	0.9800
C3—H3	0.9500	C19—C21	1.530 (4)
C4—C5	1.387 (3)	C19—C22	1.531 (4)
C4—H4	0.9500	C19—C20	1.535 (4)
C5—C6	1.482 (3)	C20—H20A	0.9800
C6—C7	1.387 (3)	C20—H20B	0.9800
C7—C8	1.382 (3)	C20—H20C	0.9800
C7—H7	0.9500	C21—H21A	0.9800
C8—C9	1.380 (3)	C21—H21B	0.9800
C8—H8	0.9500	C21—H21C	0.9800
C9—C10	1.379 (3)	C22—H22A	0.9800
C9—H9	0.9500	C22—H22B	0.9800
C10—H10	0.9500	C22—H22C	0.9800
C11—H11A	0.9800

O1—Mo1—O2	153.41 (7)	H11A—C11—H11C	109.5
O1—Mo1—O3	98.38 (9)	H11B—C11—H11C	109.5
O1—Mo1—O4	97.22 (8)	Si1—C12—H12A	109.5
O2—Mo1—O3	98.38 (8)	Si1—C12—H12B	109.5
O2—Mo1—O4	97.63 (8)	H12A—C12—H12B	109.5
O3—Mo1—O4	106.46 (8)	Si1—C12—H12C	109.5
O1—Mo1—N1	77.30 (7)	H12A—C12—H12C	109.5
O2—Mo1—N1	79.72 (7)	H12B—C12—H12C	109.5
O3—Mo1—N1	159.26 (7)	C14—C13—C16	108.3 (3)
O4—Mo1—N1	94.24 (7)	C14—C13—C15	109.6 (3)
O1—Mo1—N2	79.53 (7)	C16—C13—C15	109.2 (3)
O2—Mo1—N2	79.91 (7)	C14—C13—Si1	109.7 (2)
O3—Mo1—N2	90.23 (7)	C16—C13—Si1	109.4 (2)
O4—Mo1—N2	163.31 (7)	C15—C13—Si1	110.6 (2)
N1—Mo1—N2	69.07 (6)	C13—C14—H14A	109.5
O1—Si1—C11	108.92 (14)	C13—C14—H14B	109.5
O1—Si1—C12	109.23 (15)	H14A—C14—H14B	109.5
C11—Si1—C12	109.27 (19)	C13—C14—H14C	109.5
O1—Si1—C13	107.15 (11)	H14A—C14—H14C	109.5
C11—Si1—C13	111.06 (15)	H14B—C14—H14C	109.5
C12—Si1—C13	111.14 (16)	C13—C15—H15A	109.5
O2—Si2—C18	110.49 (11)	C13—C15—H15B	109.5
O2—Si2—C17	107.57 (11)	H15A—C15—H15B	109.5
C18—Si2—C17	110.27 (12)	C13—C15—H15C	109.5
O2—Si2—C19	109.25 (11)	H15A—C15—H15C	109.5
C18—Si2—C19	109.30 (12)	H15B—C15—H15C	109.5
C17—Si2—C19	109.94 (13)	C13—C16—H16A	109.5
C1—N1—C5	119.01 (19)	C13—C16—H16B	109.5
C1—N1—Mo1	121.42 (15)	H16A—C16—H16B	109.5
C5—N1—Mo1	119.10 (14)	C13—C16—H16C	109.5
C10—N2—C6	118.84 (19)	H16A—C16—H16C	109.5
C10—N2—Mo1	121.80 (14)	H16B—C16—H16C	109.5
C6—N2—Mo1	119.28 (14)	Si2—C17—H17A	109.5
Si1—O1—Mo1	169.53 (12)	Si2—C17—H17B	109.5
Si2—O2—Mo1	163.13 (11)	H17A—C17—H17B	109.5
N1—C1—C2	122.8 (2)	Si2—C17—H17C	109.5
N1—C1—H1	118.6	H17A—C17—H17C	109.5
C2—C1—H1	118.6	H17B—C17—H17C	109.5
C3—C2—C1	118.2 (2)	Si2—C18—H18A	109.5
C3—C2—H2	120.9	Si2—C18—H18B	109.5
C1—C2—H2	120.9	H18A—C18—H18B	109.5
C2—C3—C4	119.8 (2)	Si2—C18—H18C	109.5
C2—C3—H3	120.1	H18A—C18—H18C	109.5
C4—C3—H3	120.1	H18B—C18—H18C	109.5
C3—C4—C5	118.9 (2)	C21—C19—C22	108.6 (2)
C3—C4—H4	120.5	C21—C19—C20	109.5 (2)
C5—C4—H4	120.5	C22—C19—C20	109.4 (2)
N1—C5—C4	121.3 (2)	C21—C19—Si2	109.38 (18)
N1—C5—C6	116.11 (19)	C22—C19—Si2	109.81 (17)
C4—C5—C6	122.6 (2)	C20—C19—Si2	110.15 (19)
N2—C6—C7	121.4 (2)	C19—C20—H20A	109.5
N2—C6—C5	115.85 (18)	C19—C20—H20B	109.5
C7—C6—C5	122.7 (2)	H20A—C20—H20B	109.5
C8—C7—C6	119.3 (2)	C19—C20—H20C	109.5
C8—C7—H7	120.4	H20A—C20—H20C	109.5
C6—C7—H7	120.4	H20B—C20—H20C	109.5
C9—C8—C7	119.0 (2)	C19—C21—H21A	109.5
C9—C8—H8	120.5	C19—C21—H21B	109.5
C7—C8—H8	120.5	H21A—C21—H21B	109.5
C10—C9—C8	118.7 (2)	C19—C21—H21C	109.5
C10—C9—H9	120.6	H21A—C21—H21C	109.5
C8—C9—H9	120.6	H21B—C21—H21C	109.5
N2—C10—C9	122.7 (2)	C19—C22—H22A	109.5
N2—C10—H10	118.6	C19—C22—H22B	109.5
C9—C10—H10	118.6	H22A—C22—H22B	109.5
Si1—C11—H11A	109.5	C19—C22—H22C	109.5
Si1—C11—H11B	109.5	H22A—C22—H22C	109.5
H11A—C11—H11B	109.5	H22B—C22—H22C	109.5
Si1—C11—H11C	109.5

C11—Si1—O1—Mo1	−16.0 (7)	N2—C6—C7—C8	0.5 (4)
C12—Si1—O1—Mo1	−135.2 (6)	C5—C6—C7—C8	178.9 (2)
C13—Si1—O1—Mo1	104.3 (6)	C6—C7—C8—C9	0.5 (4)
C18—Si2—O2—Mo1	68.6 (4)	C7—C8—C9—C10	−0.4 (4)
C17—Si2—O2—Mo1	−171.0 (3)	C6—N2—C10—C9	1.7 (4)
C19—Si2—O2—Mo1	−51.7 (4)	Mo1—N2—C10—C9	−175.1 (2)
C5—N1—C1—C2	1.7 (4)	C8—C9—C10—N2	−0.7 (4)
Mo1—N1—C1—C2	−170.4 (2)	O1—Si1—C13—C14	−67.7 (2)
N1—C1—C2—C3	0.1 (4)	C11—Si1—C13—C14	51.2 (3)
C1—C2—C3—C4	−1.4 (5)	C12—Si1—C13—C14	173.0 (2)
C2—C3—C4—C5	0.9 (5)	O1—Si1—C13—C16	51.0 (3)
C1—N1—C5—C4	−2.2 (4)	C11—Si1—C13—C16	169.8 (2)
Mo1—N1—C5—C4	170.10 (19)	C12—Si1—C13—C16	−68.3 (3)
C1—N1—C5—C6	178.9 (2)	O1—Si1—C13—C15	171.3 (2)
Mo1—N1—C5—C6	−8.9 (3)	C11—Si1—C13—C15	−69.9 (3)
C3—C4—C5—N1	0.9 (4)	C12—Si1—C13—C15	52.0 (3)
C3—C4—C5—C6	179.8 (3)	O2—Si2—C19—C21	−53.3 (2)
C10—N2—C6—C7	−1.6 (4)	C18—Si2—C19—C21	−174.34 (19)
Mo1—N2—C6—C7	175.28 (19)	C17—Si2—C19—C21	64.5 (2)
C10—N2—C6—C5	179.9 (2)	O2—Si2—C19—C22	65.7 (2)
Mo1—N2—C6—C5	−3.2 (3)	C18—Si2—C19—C22	−55.3 (2)
N1—C5—C6—N2	7.9 (3)	C17—Si2—C19—C22	−176.46 (19)
C4—C5—C6—N2	−171.0 (2)	O2—Si2—C19—C20	−173.69 (18)
N1—C5—C6—C7	−170.6 (2)	C18—Si2—C19—C20	65.3 (2)
C4—C5—C6—C7	10.4 (4)	C17—Si2—C19—C20	−55.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O4ⁱ	0.95	2.38	3.260 (3)	153
C7—H7···O3ⁱ	0.95	2.59	3.189 (3)	122
C7—H7···O4ⁱ	0.95	2.55	3.494 (3)	170
C8—H8···O3ⁱ	0.95	2.55	3.168 (3)	123
C10—H10···O3	0.95	2.61	3.118 (3)	114

Symmetry code: (i) x+1, y, z.

Funding information

Funding for this research was provided by: the TIPS RAS State Plan.

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