Bis[1,3-bis­(2,4,6-trimethyl­phen­yl)-2,3-dihydro-1H-imidazol-2-yl­idene]dichloridodinitro­syltungsten(II) tetra­hydro­furan-d8 monosolvate

Fraga-Hernández, J.; Blacque, O.; Berke, H.

doi:10.1107/S1600536810050099

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page m31

https://doi.org/10.1107/S1600536810050099

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Bis[1,3-bis(2,4,6-trimethylphenyl)-2,3-dihydro-1H-imidazol-2-ylidene]dichloridodinitrosyltungsten(II) tetrahydrofuran-d₈ monosolvate

Javier Fraga-Hernández,^a Olivier Blacque ^a ^* and Heinz Berke ^a

^aInstitut of Inorganic Chemistry, University of Zürich, Winterthurerstrasse 190, 8057 Zürich, Switzerland
^*Correspondence e-mail: oblacque@aci.uzh.ch

(Received 15 November 2010; accepted 30 November 2010; online 4 December 2010)

The molecular structure of the title compound, [WCl₂(NO)₂(C₂₁H₂₄N₂)₂]·C₄D₈O, displays a distorted octahedral arrangement around the W atom with two trans 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes) carbene ligands in axial positions. The four equatorial positions are occupied by nitrosyl and chloride ligands, which are trans to each other. The C_carbene—W—C_carbene bond angle of 173.44 (18)° and the Cl—W—N_nitrosyl bond angles of 171.34 (11) and 171.32 (13)° deviate only slightly from linearity. The distortion comes from the nitrosyl and chloride ligands which are not fully coplanar since the two N atoms deviate from the WCl₂ plane by −0.279 (4) and 0.272 (4) Å, respectively. An intermolecular C—H⋯O interaction connects the organometallic molecule and the tetrahydrofuran-d₈ solvent molecule.

Related literature

For the synthesis, characterization and reactivity of dinitrosyl tungsten complexes in various oxidation states, see: Fraga-Hernández (2007 ). For tungsten complexes with N-heterocyclic (NHC) carbenes, see: Nonnenmacher et al. (2005 ); Hahn et al. (2005 ); Wu et al. (2007 ). For an overview of the first organometallic nitrosyls, see: Enemark & Feltham (1974 ); Richter-Addo & Legzdins (1988 ); Berke & Burger (1994 ).

Experimental

Crystal data

[WCl₂(NO)₂(C₂₁H₂₄N₂)₂]·C₄D₈O
M_r = 1003.72
Triclinic, $[P \overline 1]$
a = 11.3861 (7) Å
b = 13.0517 (9) Å
c = 17.0448 (11) Å
α = 81.245 (8)°
β = 72.473 (7)°
γ = 68.983 (7)°
V = 2251.9 (3) Å³
Z = 2
Mo Kα radiation
μ = 2.73 mm⁻¹
T = 183 K
0.25 × 0.15 × 0.08 mm

Data collection

Stoe IPDS diffractometer
Absorption correction: numerical (Coppens et al., 1965 ) T_min = 0.568, T_max = 0.816
44725 measured reflections
7466 independent reflections
6365 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.076
S = 1.12
7466 reflections
535 parameters
H-atom parameters constrained
Δρ_max = 1.00 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O3	0.93	2.40	3.320 (7)	172

Data collection: EXPOSE in IPDS Software (Stoe & Cie, 1999 ); cell refinement: CELL in IPDS Software; data reduction: INTEGRATE in IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97, WinGX (Farrugia, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810050099/fj2368sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810050099/fj2368Isup2.hkl

checkCIF report

Comment top

In the course of our efforts on the synthesis of novel dinitrosyl hydride and dihydride tungsten derivatives bearing sterically demanding and highly donating phosphine ligands or N-heterocyclic (NHC) carbene ligands, the title compound W(NO)₂Cl₂(IMes)₂.C₄D₈O was synthesized as an intermediate species by the reaction of the coordination polymer dinitrosyldichlorotungsten [W(NO)₂Cl₂]_n with 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes), purified and characterized by several spectroscopic techniques and single-crystal X-ray diffraction.

The molecular structure of the title compound, C₄₂H₄₈Cl₂N₆O₂W.C₄D₈O, displays a distorted octahedral arrangement around the W center with two trans 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene ligands in axial positions, and the four equatorial positions are occupied by trans nitrosyl and chloride ligands (Fig. 1). The C_carbene—W—C_carbene bond angle of 173.44 (18)° and the Cl—W—N_nitrosyl bond angles of 171.34 (11) and 171.32 (13)° deviates only slightly from linearity. The distortion comes from the nitrosyl and chloride ligands which are not fully coplanar since N1 and N2 deviate from the Cl1—W1—Cl2 plane by -0.279 (4) and +0.272 (4) Å, respectively. The five-membered rings of the carbene ligands are almost perpendicular to each other, the dihedral angle between the mean planes C1/N3/C2/C3/N4 and C22/N5/C23/C25/N6 is 74.2 (2)°. Each ring adopts an eclipsed conformation with one linear Cl—W—N_NO moiety, the dihedral angles between the mean planes Cl1/W1/N2/C1 and C1/N3/C2/C3/N4, and between Cl2/W1/N1/C22 and C22/N5/C23/C25/N6, are 15.8 (2) and 5.2 (2)°, respectively.

In the crystal structure, intermolecular C—H···O interactions connect the metal-organic molecules and the tetrahydrofurane-d₈ solvent molecules (Table 1).

Related literature top

For the synthesis, characterization and reactivity of dinitrosyl tungsten complexes in various oxidation states, see: Fraga-Hernández (2007). For tungsten complexes with N-heterocyclic (NHC) carbenes, see: Nonnenmacher et al. (2005); Hahn et al. (2005); Wu et al. (2007). For an overview of the first organometallic nitrosyls, see: Enemark & Feltham (1974); Richter-Addo & Legzdins (1988); Berke & Burger (1994).

Experimental top

To a stirred suspension of [W(NO)₂Cl₂]_n (128.4 mg, 0.408 mmol) in 15 ml THF was added dropwise a solution of IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (248 mg, 0.815 mmol) in THF (5 ml) over a period of 15 minutes. Gradually, the solution intensified in color and a floculent black residue formed. The reaction mixture was stirred at room temperature for 6 h to obtain a deep green solution whose IR spectrum exhibited vibrations at 1737 and 1624 cm^-1 attributable to nitrosyl groups. The volatiles were removed under vacuum, and the residue was extracted with 25 ml of toluene. The dark green solution was filtered through celite and dried under vacuum. The solid was recrystallized in CH₂Cl₂/pentane, leaving a fraction of green crystals, which where washed with pentane (2 x 3 ml) and dried in vacuo to afford 312.8 mg of [W(NO)₂Cl₂(IMes)₂] (83%).

IR (ATR, 22°C, cm^-1): 1737 (NO), 1624 (NO).

¹H NMR (THF-d₈, 300 MHz, 22°C): δ 6.97 (s, NCH, 4H, ³J_HH = 0.6 Hz), 6.78 (s, ArH, 8H), 2.25 (s, 4-CH₃, 12H), 1.99 (s, 2,6-CH₃, 24H).

¹³C {¹H} NMR (benzene-d₆, 125.8 MHz, 22°C): δ 182.6 (s, NCN), 139.6 (s, Mes C-1), 134.6 (s, Mes C-4), 129.8 (s, Mes C-2,6), 128.9 (s, Mes C-3,5), 122.4 (s, NCC), 21.0 (s, 4-CH₃), 17.4 (s, 2,6-CH₃).

Elemental analysis (%) calculated for C₄₂H₄₈Cl₂N₆O₂W: C (54.62), H (5.24), N (9.10); found C (54.83), H (5.44), N (9.02).

Structure description top

In the crystal structure, intermolecular C—H···O interactions connect the metal-organic molecules and the tetrahydrofurane-d₈ solvent molecules (Table 1).

For the synthesis, characterization and reactivity of dinitrosyl tungsten complexes in various oxidation states, see: Fraga-Hernández (2007). For tungsten complexes with N-heterocyclic (NHC) carbenes, see: Nonnenmacher et al. (2005); Hahn et al. (2005); Wu et al. (2007). For an overview of the first organometallic nitrosyls, see: Enemark & Feltham (1974); Richter-Addo & Legzdins (1988); Berke & Burger (1994).

Computing details top

Data collection: EXPOSE in IPDS Software (Stoe & Cie, 1999); cell refinement: CELL in IPDS Software (Stoe & Cie, 1999); data reduction: INTEGRATE in IPDS Software (Stoe & Cie, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).

Figures top

Fig. 1. View of the title compound showing the labeling of the non-H atoms and 20% probability ellipsoids.

Bis[1,3-bis(2,4,6-trimethylphenyl)-2,3-dihydro-1H-imidazol- 2-ylidene]dichloridodinitrosyltungsten(II) tetrahydrofuran-d₈ monosolvate top

Crystal data top

[WCl₂(NO)₂(C₂₁H₂₄N₂)₂]·C₄D₈O	Z = 2
M_r = 1003.72	F(000) = 1012
Triclinic, P1	D_x = 1.48 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.3861 (7) Å	Cell parameters from 7997 reflections
b = 13.0517 (9) Å	θ = 3.0–30.3°
c = 17.0448 (11) Å	µ = 2.73 mm⁻¹
α = 81.245 (8)°	T = 183 K
β = 72.473 (7)°	Plate, green
γ = 68.983 (7)°	0.25 × 0.15 × 0.08 mm
V = 2251.9 (3) Å³

Data collection top

Stoe IPDS diffractometer	7466 independent reflections
Radiation source: fine-focus sealed tube	6365 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
φ oscillation scan	θ_max = 25°, θ_min = 3.0°
Absorption correction: numerical (Coppens et al., 1965)	h = −12→13
T_min = 0.568, T_max = 0.816	k = −15→15
44725 measured reflections	l = 0→20

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.026	w = 1/[σ²(F_o²) + (0.0434P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.076	(Δ/σ)_max = 0.001
S = 1.12	Δρ_max = 1.00 e Å⁻³
7466 reflections	Δρ_min = −0.42 e Å⁻³
535 parameters

Crystal data top

[WCl₂(NO)₂(C₂₁H₂₄N₂)₂]·C₄D₈O	γ = 68.983 (7)°
M_r = 1003.72	V = 2251.9 (3) Å³
Triclinic, P1	Z = 2
a = 11.3861 (7) Å	Mo Kα radiation
b = 13.0517 (9) Å	µ = 2.73 mm⁻¹
c = 17.0448 (11) Å	T = 183 K
α = 81.245 (8)°	0.25 × 0.15 × 0.08 mm
β = 72.473 (7)°

Data collection top

Stoe IPDS diffractometer	7466 independent reflections
Absorption correction: numerical (Coppens et al., 1965)	6365 reflections with I > 2σ(I)
T_min = 0.568, T_max = 0.816	R_int = 0.046
44725 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.076	H-atom parameters constrained
S = 1.12	Δρ_max = 1.00 e Å⁻³
7466 reflections	Δρ_min = −0.42 e Å⁻³
535 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.

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

	x	y	z	U_iso*/U_eq
W1	0.748163 (17)	0.774765 (17)	0.734179 (12)	0.02191 (7)
Cl1	0.74039 (11)	0.82743 (12)	0.59143 (8)	0.0377 (3)
Cl2	0.63266 (11)	0.96649 (11)	0.76621 (9)	0.0401 (3)
N1	0.8115 (4)	0.6268 (4)	0.7123 (3)	0.0350 (10)
O1	0.8406 (4)	0.5351 (3)	0.7034 (3)	0.0607 (13)
N2	0.7786 (4)	0.7372 (4)	0.8350 (3)	0.0434 (12)
O2	0.8123 (5)	0.7087 (5)	0.8966 (3)	0.0757 (17)
C1	0.5416 (4)	0.7669 (4)	0.7755 (3)	0.0235 (10)
N3	0.4669 (3)	0.7666 (4)	0.8548 (2)	0.0287 (9)
C2	0.3430 (5)	0.7670 (5)	0.8590 (3)	0.0442 (15)
H2	0.2756	0.7681	0.9065	0.057*
C3	0.3397 (5)	0.7653 (5)	0.7825 (3)	0.0434 (15)
H3	0.2693	0.7645	0.766	0.056*
N4	0.4603 (3)	0.7649 (4)	0.7312 (2)	0.0286 (9)
C4	0.5013 (4)	0.7590 (4)	0.9315 (3)	0.0258 (10)
C5	0.5675 (4)	0.6562 (4)	0.9616 (3)	0.0302 (11)
C6	0.5887 (5)	0.6493 (5)	1.0389 (3)	0.0381 (12)
H6	0.6348	0.5816	1.0595	0.049*
C7	0.5432 (5)	0.7401 (5)	1.0858 (3)	0.0399 (14)
C8	0.4749 (5)	0.8402 (5)	1.0539 (3)	0.0393 (14)
H8	0.4437	0.9018	1.085	0.051*
C9	0.4517 (4)	0.8518 (4)	0.9777 (3)	0.0310 (12)
C10	0.6143 (6)	0.5546 (5)	0.9139 (4)	0.0431 (13)
H10A	0.5501	0.5573	0.8871	0.056*
H10B	0.6279	0.4907	0.9508	0.056*
H10C	0.695	0.5509	0.8732	0.056*
C11	0.5614 (6)	0.7296 (7)	1.1711 (4)	0.062 (2)
H11A	0.5813	0.7919	1.1796	0.081*
H11B	0.6319	0.6635	1.1766	0.081*
H11C	0.4826	0.7268	1.2112	0.081*
C12	0.3677 (5)	0.9606 (5)	0.9488 (4)	0.0460 (15)
H12A	0.2829	0.9572	0.9538	0.06*
H12B	0.4075	0.9766	0.8923	0.06*
H12C	0.3591	1.0174	0.982	0.06*
C13	0.4801 (4)	0.7632 (4)	0.6427 (3)	0.0271 (11)
C14	0.5257 (4)	0.6605 (4)	0.6083 (3)	0.0325 (12)
C15	0.5311 (5)	0.6613 (5)	0.5253 (3)	0.0393 (14)
H15	0.5628	0.5948	0.5	0.051*
C16	0.4906 (4)	0.7580 (5)	0.4795 (3)	0.0371 (13)
C17	0.4438 (4)	0.8572 (5)	0.5170 (3)	0.0352 (12)
H17	0.4162	0.9224	0.4865	0.046*
C18	0.4374 (4)	0.8611 (4)	0.5994 (3)	0.0279 (11)
C19	0.5644 (6)	0.5538 (5)	0.6569 (4)	0.0484 (15)
H19A	0.6345	0.5503	0.6786	0.063*
H19B	0.5927	0.4938	0.6218	0.063*
H19C	0.491	0.5489	0.7015	0.063*
C20	0.4971 (5)	0.7543 (7)	0.3890 (4)	0.0550 (18)
H20A	0.5867	0.7257	0.3579	0.071*
H20B	0.4579	0.8271	0.3678	0.071*
H20C	0.4509	0.7077	0.3844	0.071*
C21	0.3868 (5)	0.9700 (4)	0.6394 (4)	0.0393 (13)
H21A	0.3122	0.9721	0.6852	0.051*
H21B	0.362	1.0287	0.6	0.051*
H21C	0.454	0.9783	0.6584	0.051*
C22	0.9457 (4)	0.8013 (4)	0.6851 (3)	0.0218 (10)
N5	0.9786 (3)	0.8939 (3)	0.6796 (2)	0.0223 (8)
C23	1.1098 (4)	0.8746 (4)	0.6391 (3)	0.0253 (10)
H23	1.1533	0.9255	0.6276	0.033*
C24	1.1615 (4)	0.7697 (4)	0.6197 (3)	0.0268 (11)
H24	1.2479	0.7333	0.5926	0.035*
N6	1.0612 (3)	0.7249 (3)	0.6478 (2)	0.0223 (8)
C25	0.9052 (4)	0.9987 (4)	0.7170 (3)	0.0238 (10)
C26	0.9017 (4)	1.0074 (4)	0.7986 (3)	0.0271 (11)
C27	0.8452 (5)	1.1120 (4)	0.8294 (3)	0.0322 (12)
H27	0.8398	1.1197	0.8839	0.042*
C28	0.7966 (5)	1.2048 (4)	0.7820 (3)	0.0323 (11)
C29	0.8005 (4)	1.1917 (4)	0.7015 (3)	0.0304 (11)
H29	0.7662	1.2532	0.6695	0.04*
C30	0.8543 (4)	1.0889 (4)	0.6676 (3)	0.0255 (10)
C31	0.9567 (6)	0.9102 (5)	0.8509 (4)	0.0428 (14)
H31A	0.8997	0.867	0.8675	0.056*
H31B	0.9645	0.9345	0.8989	0.056*
H31C	1.0412	0.8663	0.8201	0.056*
C32	0.7440 (6)	1.3177 (5)	0.8157 (4)	0.0492 (15)
H32A	0.713	1.3119	0.8747	0.064*
H32B	0.6735	1.3634	0.7932	0.064*
H32C	0.8122	1.3496	0.8008	0.064*
C33	0.8575 (5)	1.0771 (4)	0.5809 (3)	0.0359 (12)
H33A	0.9425	1.0721	0.5453	0.047*
H33B	0.7931	1.1399	0.5636	0.047*
H33C	0.839	1.0118	0.5782	0.047*
C34	1.0899 (4)	0.6077 (4)	0.6418 (3)	0.0251 (10)
C35	1.1166 (4)	0.5382 (4)	0.7091 (3)	0.0285 (11)
C36	1.1433 (4)	0.4258 (4)	0.7025 (3)	0.0335 (11)
H36	1.1591	0.3774	0.7471	0.044*
C37	1.1465 (4)	0.3850 (4)	0.6306 (3)	0.0327 (12)
C38	1.1286 (4)	0.4567 (4)	0.5636 (3)	0.0308 (11)
H38	1.1363	0.429	0.5145	0.04*
C39	1.0993 (4)	0.5699 (4)	0.5670 (3)	0.0263 (10)
C40	1.1198 (6)	0.5791 (5)	0.7860 (4)	0.0409 (13)
H40A	1.1826	0.6167	0.7722	0.053*
H40B	1.144	0.518	0.8239	0.053*
H40C	1.035	0.6288	0.8111	0.053*
C41	1.1681 (6)	0.2642 (4)	0.6278 (4)	0.0447 (14)
H41A	1.0854	0.2524	0.6445	0.058*
H41B	1.2198	0.2224	0.6645	0.058*
H41C	1.2129	0.2409	0.5727	0.058*
C42	1.0835 (5)	0.6465 (5)	0.4932 (3)	0.0356 (12)
H42A	0.9999	0.7033	0.5065	0.046*
H42B	1.0891	0.6065	0.4487	0.046*
H42C	1.1513	0.679	0.4771	0.046*
O3	0.0873 (4)	0.7653 (5)	1.0168 (3)	0.0734 (15)
C43	−0.0328 (7)	0.8164 (9)	1.0722 (5)	0.086 (3)
D43A	−0.0682	0.8929	1.0547	0.112*
D43B	−0.0216	0.8134	1.1268	0.112*
C44	−0.1204 (9)	0.7577 (10)	1.0733 (7)	0.100 (3)
D44A	−0.1681	0.7896	1.0321	0.129*
D44B	−0.1823	0.7596	1.127	0.129*
C45	−0.0341 (12)	0.6449 (9)	1.0546 (8)	0.111 (4)
D45A	−0.0705	0.6081	1.0275	0.145*
D45B	−0.0153	0.6018	1.1037	0.145*
C46	0.0864 (10)	0.6674 (9)	0.9966 (6)	0.098 (3)
D46A	0.1649	0.6084	1.0027	0.127*
D46B	0.0832	0.6722	0.9399	0.127*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
W1	0.01818 (9)	0.02470 (11)	0.02314 (10)	−0.00853 (6)	−0.00253 (6)	−0.00466 (7)
Cl1	0.0302 (6)	0.0598 (9)	0.0275 (6)	−0.0210 (6)	−0.0064 (5)	−0.0024 (6)
Cl2	0.0273 (6)	0.0348 (7)	0.0563 (8)	−0.0127 (5)	0.0022 (5)	−0.0182 (7)
N1	0.0211 (19)	0.031 (3)	0.048 (3)	−0.0105 (17)	−0.0039 (18)	0.006 (2)
O1	0.039 (2)	0.036 (2)	0.103 (4)	−0.0160 (18)	−0.001 (2)	−0.018 (3)
N2	0.030 (2)	0.067 (3)	0.040 (3)	−0.028 (2)	−0.009 (2)	0.004 (3)
O2	0.063 (3)	0.149 (5)	0.038 (3)	−0.065 (3)	−0.026 (2)	0.028 (3)
C1	0.025 (2)	0.024 (2)	0.023 (2)	−0.0101 (18)	−0.0046 (18)	−0.002 (2)
N3	0.0227 (18)	0.039 (2)	0.028 (2)	−0.0139 (17)	−0.0039 (16)	−0.006 (2)
C2	0.028 (3)	0.078 (4)	0.034 (3)	−0.031 (3)	0.000 (2)	−0.005 (3)
C3	0.027 (2)	0.076 (4)	0.035 (3)	−0.029 (3)	−0.003 (2)	−0.008 (3)
N4	0.0233 (18)	0.039 (2)	0.027 (2)	−0.0157 (17)	−0.0064 (16)	−0.001 (2)
C4	0.022 (2)	0.035 (3)	0.020 (2)	−0.0131 (19)	−0.0006 (17)	−0.003 (2)
C5	0.030 (2)	0.036 (3)	0.024 (3)	−0.015 (2)	0.0027 (19)	−0.007 (2)
C6	0.032 (3)	0.048 (3)	0.028 (3)	−0.010 (2)	−0.001 (2)	−0.004 (3)
C7	0.029 (2)	0.065 (4)	0.027 (3)	−0.017 (3)	−0.002 (2)	−0.012 (3)
C8	0.033 (3)	0.049 (3)	0.038 (3)	−0.019 (2)	0.004 (2)	−0.022 (3)
C9	0.025 (2)	0.036 (3)	0.032 (3)	−0.014 (2)	0.0021 (19)	−0.009 (2)
C10	0.053 (3)	0.030 (3)	0.037 (3)	−0.011 (2)	0.000 (2)	−0.007 (3)
C11	0.045 (3)	0.108 (6)	0.035 (3)	−0.022 (4)	−0.009 (3)	−0.021 (4)
C12	0.038 (3)	0.037 (3)	0.050 (4)	−0.007 (2)	0.003 (3)	−0.006 (3)
C13	0.018 (2)	0.037 (3)	0.029 (3)	−0.0124 (19)	−0.0073 (18)	−0.004 (2)
C14	0.023 (2)	0.036 (3)	0.040 (3)	−0.010 (2)	−0.012 (2)	−0.001 (3)
C15	0.026 (2)	0.050 (4)	0.041 (3)	−0.006 (2)	−0.008 (2)	−0.019 (3)
C16	0.025 (2)	0.057 (4)	0.031 (3)	−0.013 (2)	−0.006 (2)	−0.011 (3)
C17	0.027 (2)	0.046 (3)	0.034 (3)	−0.015 (2)	−0.008 (2)	0.003 (3)
C18	0.017 (2)	0.034 (3)	0.034 (3)	−0.0109 (18)	−0.0037 (18)	−0.007 (2)
C19	0.051 (3)	0.038 (3)	0.060 (4)	−0.011 (3)	−0.023 (3)	−0.004 (3)
C20	0.037 (3)	0.092 (5)	0.036 (3)	−0.016 (3)	−0.011 (2)	−0.014 (4)
C21	0.034 (3)	0.036 (3)	0.050 (3)	−0.012 (2)	−0.012 (2)	−0.005 (3)
C22	0.025 (2)	0.023 (2)	0.019 (2)	−0.0075 (18)	−0.0062 (17)	−0.005 (2)
N5	0.0192 (17)	0.023 (2)	0.025 (2)	−0.0072 (14)	−0.0049 (15)	−0.0036 (18)
C23	0.022 (2)	0.029 (3)	0.028 (2)	−0.0136 (18)	−0.0053 (18)	−0.001 (2)
C24	0.020 (2)	0.033 (3)	0.029 (3)	−0.0113 (19)	−0.0028 (18)	−0.007 (2)
N6	0.0208 (17)	0.021 (2)	0.024 (2)	−0.0065 (15)	−0.0043 (15)	−0.0034 (18)
C25	0.020 (2)	0.022 (2)	0.030 (3)	−0.0092 (17)	−0.0040 (18)	−0.006 (2)
C26	0.027 (2)	0.031 (3)	0.027 (3)	−0.0130 (19)	−0.0074 (19)	−0.003 (2)
C27	0.038 (3)	0.034 (3)	0.027 (3)	−0.015 (2)	−0.006 (2)	−0.008 (2)
C28	0.032 (2)	0.028 (3)	0.035 (3)	−0.012 (2)	−0.001 (2)	−0.007 (2)
C29	0.030 (2)	0.025 (3)	0.031 (3)	−0.0079 (19)	−0.004 (2)	0.000 (2)
C30	0.025 (2)	0.026 (3)	0.026 (2)	−0.0119 (19)	−0.0013 (18)	−0.003 (2)
C31	0.054 (3)	0.041 (3)	0.033 (3)	−0.009 (3)	−0.018 (3)	−0.005 (3)
C32	0.054 (3)	0.037 (3)	0.052 (4)	−0.013 (3)	−0.004 (3)	−0.017 (3)
C33	0.048 (3)	0.029 (3)	0.029 (3)	−0.011 (2)	−0.011 (2)	0.000 (2)
C34	0.0168 (19)	0.023 (2)	0.031 (3)	−0.0033 (17)	−0.0021 (18)	−0.004 (2)
C35	0.024 (2)	0.028 (3)	0.031 (3)	−0.0050 (19)	−0.0072 (19)	−0.001 (2)
C36	0.029 (2)	0.028 (3)	0.040 (3)	−0.004 (2)	−0.011 (2)	0.000 (3)
C37	0.029 (2)	0.023 (3)	0.044 (3)	−0.0068 (19)	−0.007 (2)	−0.007 (3)
C38	0.029 (2)	0.030 (3)	0.031 (3)	−0.009 (2)	−0.002 (2)	−0.010 (2)
C39	0.020 (2)	0.027 (3)	0.029 (3)	−0.0057 (18)	−0.0021 (18)	−0.007 (2)
C40	0.057 (3)	0.030 (3)	0.040 (3)	−0.011 (2)	−0.023 (3)	0.000 (3)
C41	0.051 (3)	0.026 (3)	0.055 (4)	−0.008 (2)	−0.017 (3)	−0.006 (3)
C42	0.042 (3)	0.036 (3)	0.028 (3)	−0.011 (2)	−0.007 (2)	−0.006 (3)
O3	0.052 (3)	0.111 (5)	0.061 (3)	−0.040 (3)	−0.003 (2)	−0.008 (3)
C43	0.061 (4)	0.134 (8)	0.074 (5)	−0.039 (5)	−0.015 (4)	−0.023 (6)
C44	0.083 (6)	0.138 (10)	0.093 (7)	−0.063 (6)	−0.026 (5)	0.020 (7)
C45	0.138 (9)	0.084 (7)	0.124 (9)	−0.066 (7)	−0.037 (8)	0.037 (7)
C46	0.107 (7)	0.088 (7)	0.084 (7)	−0.017 (6)	−0.023 (6)	−0.008 (6)

Geometric parameters (Å, º) top

W1—N2	1.815 (5)	N5—C25	1.449 (5)
W1—N1	1.856 (4)	C23—C24	1.332 (7)
W1—C1	2.278 (4)	C23—H23	0.93
W1—C22	2.284 (4)	C24—N6	1.392 (6)
W1—Cl2	2.4315 (12)	C24—H24	0.93
W1—Cl1	2.4449 (13)	N6—C34	1.457 (6)
N1—O1	1.143 (6)	C25—C30	1.391 (7)
N2—O2	1.188 (6)	C25—C26	1.401 (7)
C1—N3	1.364 (6)	C26—C27	1.392 (7)
C1—N4	1.369 (6)	C26—C31	1.490 (8)
N3—C2	1.390 (6)	C27—C28	1.385 (8)
N3—C4	1.453 (6)	C27—H27	0.93
C2—C3	1.319 (8)	C28—C29	1.395 (7)
C2—H2	0.93	C28—C32	1.509 (7)
C3—N4	1.387 (6)	C29—C30	1.393 (7)
C3—H3	0.93	C29—H29	0.93
N4—C13	1.459 (6)	C30—C33	1.497 (7)
C4—C5	1.389 (7)	C31—H31A	0.96
C4—C9	1.392 (7)	C31—H31B	0.96
C5—C6	1.393 (7)	C31—H31C	0.96
C5—C10	1.505 (7)	C32—H32A	0.96
C6—C7	1.382 (8)	C32—H32B	0.96
C6—H6	0.93	C32—H32C	0.96
C7—C8	1.385 (9)	C33—H33A	0.96
C7—C11	1.508 (8)	C33—H33B	0.96
C8—C9	1.379 (8)	C33—H33C	0.96
C8—H8	0.93	C34—C35	1.388 (7)
C9—C12	1.507 (8)	C34—C39	1.398 (7)
C10—H10A	0.96	C35—C36	1.402 (7)
C10—H10B	0.96	C35—C40	1.504 (7)
C10—H10C	0.96	C36—C37	1.393 (7)
C11—H11A	0.96	C36—H36	0.93
C11—H11B	0.96	C37—C38	1.379 (8)
C11—H11C	0.96	C37—C41	1.513 (7)
C12—H12A	0.96	C38—C39	1.399 (7)
C12—H12B	0.96	C38—H38	0.93
C12—H12C	0.96	C39—C42	1.496 (7)
C13—C18	1.377 (7)	C40—H40A	0.96
C13—C14	1.403 (7)	C40—H40B	0.96
C14—C15	1.396 (8)	C40—H40C	0.96
C14—C19	1.500 (8)	C41—H41A	0.96
C15—C16	1.384 (8)	C41—H41B	0.96
C15—H15	0.93	C41—H41C	0.96
C16—C17	1.386 (8)	C42—H42A	0.96
C16—C20	1.529 (8)	C42—H42B	0.96
C17—C18	1.392 (7)	C42—H42C	0.96
C17—H17	0.93	O3—C46	1.376 (11)
C18—C21	1.513 (7)	O3—C43	1.403 (9)
C19—H19A	0.96	C43—C44	1.454 (12)
C19—H19B	0.96	C43—D43A	0.97
C19—H19C	0.96	C43—D43B	0.97
C20—H20A	0.96	C44—C45	1.467 (15)
C20—H20B	0.96	C44—D44A	0.97
C20—H20C	0.96	C44—D44B	0.97
C21—H21A	0.96	C45—C46	1.526 (14)
C21—H21B	0.96	C45—D45A	0.97
C21—H21C	0.96	C45—D45B	0.97
C22—N5	1.370 (6)	C46—D46A	0.97
C22—N6	1.370 (5)	C46—D46B	0.97
N5—C23	1.390 (5)

N2—W1—N1	89.2 (2)	C22—N5—C25	130.6 (3)
N2—W1—C1	95.23 (17)	C23—N5—C25	117.6 (3)
N1—W1—C1	89.24 (16)	C24—C23—N5	107.3 (4)
N2—W1—C22	89.32 (17)	C24—C23—H23	126.3
N1—W1—C22	95.56 (16)	N5—C23—H23	126.3
C1—W1—C22	173.44 (18)	C23—C24—N6	106.8 (4)
N2—W1—Cl2	92.77 (17)	C23—C24—H24	126.6
N1—W1—Cl2	171.34 (11)	N6—C24—H24	126.6
C1—W1—Cl2	82.19 (12)	C22—N6—C24	111.4 (4)
C22—W1—Cl2	92.89 (11)	C22—N6—C34	128.5 (4)
N2—W1—Cl1	171.32 (13)	C24—N6—C34	119.8 (3)
N1—W1—Cl1	91.09 (15)	C30—C25—C26	122.7 (4)
C1—W1—Cl1	93.45 (12)	C30—C25—N5	118.5 (4)
C22—W1—Cl1	82.02 (12)	C26—C25—N5	118.4 (4)
Cl2—W1—Cl1	88.23 (5)	C27—C26—C25	117.1 (5)
O1—N1—W1	174.1 (4)	C27—C26—C31	120.6 (4)
O2—N2—W1	173.0 (4)	C25—C26—C31	122.3 (4)
N3—C1—N4	102.8 (3)	C28—C27—C26	122.4 (5)
N3—C1—W1	126.0 (3)	C28—C27—H27	118.8
N4—C1—W1	131.2 (3)	C26—C27—H27	118.8
C1—N3—C2	111.8 (4)	C27—C28—C29	118.3 (4)
C1—N3—C4	129.8 (4)	C27—C28—C32	121.0 (5)
C2—N3—C4	118.2 (4)	C29—C28—C32	120.7 (5)
C3—C2—N3	106.6 (4)	C30—C29—C28	121.9 (5)
C3—C2—H2	126.7	C30—C29—H29	119.1
N3—C2—H2	126.7	C28—C29—H29	119.1
C2—C3—N4	107.6 (4)	C25—C30—C29	117.5 (4)
C2—C3—H3	126.2	C25—C30—C33	121.7 (4)
N4—C3—H3	126.2	C29—C30—C33	120.8 (5)
C1—N4—C3	111.2 (4)	C26—C31—H31A	109.5
C1—N4—C13	131.2 (4)	C26—C31—H31B	109.5
C3—N4—C13	117.7 (4)	H31A—C31—H31B	109.5
C5—C4—C9	121.9 (4)	C26—C31—H31C	109.5
C5—C4—N3	118.6 (4)	H31A—C31—H31C	109.5
C9—C4—N3	118.9 (4)	H31B—C31—H31C	109.5
C4—C5—C6	117.7 (4)	C28—C32—H32A	109.5
C4—C5—C10	122.0 (5)	C28—C32—H32B	109.5
C6—C5—C10	120.3 (5)	H32A—C32—H32B	109.5
C7—C6—C5	122.0 (5)	C28—C32—H32C	109.5
C7—C6—H6	119	H32A—C32—H32C	109.5
C5—C6—H6	119	H32B—C32—H32C	109.5
C6—C7—C8	118.1 (5)	C30—C33—H33A	109.5
C6—C7—C11	121.1 (6)	C30—C33—H33B	109.5
C8—C7—C11	120.8 (5)	H33A—C33—H33B	109.5
C9—C8—C7	122.3 (5)	C30—C33—H33C	109.5
C9—C8—H8	118.8	H33A—C33—H33C	109.5
C7—C8—H8	118.8	H33B—C33—H33C	109.5
C8—C9—C4	117.9 (5)	C35—C34—C39	123.1 (4)
C8—C9—C12	120.1 (5)	C35—C34—N6	118.0 (4)
C4—C9—C12	121.9 (5)	C39—C34—N6	118.7 (5)
C5—C10—H10A	109.5	C34—C35—C36	117.2 (5)
C5—C10—H10B	109.5	C34—C35—C40	122.5 (5)
H10A—C10—H10B	109.5	C36—C35—C40	120.3 (5)
C5—C10—H10C	109.5	C37—C36—C35	121.6 (5)
H10A—C10—H10C	109.5	C37—C36—H36	119.2
H10B—C10—H10C	109.5	C35—C36—H36	119.2
C7—C11—H11A	109.5	C38—C37—C36	118.8 (5)
C7—C11—H11B	109.5	C38—C37—C41	121.5 (5)
H11A—C11—H11B	109.5	C36—C37—C41	119.8 (5)
C7—C11—H11C	109.5	C37—C38—C39	122.2 (5)
H11A—C11—H11C	109.5	C37—C38—H38	118.9
H11B—C11—H11C	109.5	C39—C38—H38	118.9
C9—C12—H12A	109.5	C34—C39—C38	116.9 (5)
C9—C12—H12B	109.5	C34—C39—C42	121.4 (4)
H12A—C12—H12B	109.5	C38—C39—C42	121.7 (4)
C9—C12—H12C	109.5	C35—C40—H40A	109.5
H12A—C12—H12C	109.5	C35—C40—H40B	109.5
H12B—C12—H12C	109.5	H40A—C40—H40B	109.5
C18—C13—C14	123.1 (4)	C35—C40—H40C	109.5
C18—C13—N4	118.6 (4)	H40A—C40—H40C	109.5
C14—C13—N4	117.7 (5)	H40B—C40—H40C	109.5
C15—C14—C13	116.5 (5)	C37—C41—H41A	109.5
C15—C14—C19	120.4 (5)	C37—C41—H41B	109.5
C13—C14—C19	123.0 (5)	H41A—C41—H41B	109.5
C16—C15—C14	122.1 (5)	C37—C41—H41C	109.5
C16—C15—H15	119	H41A—C41—H41C	109.5
C14—C15—H15	119	H41B—C41—H41C	109.5
C15—C16—C17	119.0 (5)	C39—C42—H42A	109.5
C15—C16—C20	120.0 (5)	C39—C42—H42B	109.5
C17—C16—C20	121.0 (6)	H42A—C42—H42B	109.5
C16—C17—C18	121.3 (5)	C39—C42—H42C	109.5
C16—C17—H17	119.4	H42A—C42—H42C	109.5
C18—C17—H17	119.4	H42B—C42—H42C	109.5
C13—C18—C17	118.0 (4)	C46—O3—C43	108.7 (6)
C13—C18—C21	121.3 (5)	O3—C43—C44	107.3 (8)
C17—C18—C21	120.7 (5)	O3—C43—D43A	110.3
C14—C19—H19A	109.5	C44—C43—D43A	110.3
C14—C19—H19B	109.5	O3—C43—D43B	110.3
H19A—C19—H19B	109.5	C44—C43—D43B	110.3
C14—C19—H19C	109.5	D43A—C43—D43B	108.5
H19A—C19—H19C	109.5	C43—C44—C45	104.5 (8)
H19B—C19—H19C	109.5	C43—C44—D44A	110.9
C16—C20—H20A	109.5	C45—C44—D44A	110.9
C16—C20—H20B	109.5	C43—C44—D44B	110.9
H20A—C20—H20B	109.5	C45—C44—D44B	110.9
C16—C20—H20C	109.5	D44A—C44—D44B	108.9
H20A—C20—H20C	109.5	C44—C45—C46	100.1 (8)
H20B—C20—H20C	109.5	C44—C45—D45A	111.8
C18—C21—H21A	109.5	C46—C45—D45A	111.8
C18—C21—H21B	109.5	C44—C45—D45B	111.8
H21A—C21—H21B	109.5	C46—C45—D45B	111.8
C18—C21—H21C	109.5	D45A—C45—D45B	109.5
H21A—C21—H21C	109.5	O3—C46—C45	107.8 (8)
H21B—C21—H21C	109.5	O3—C46—D46A	110.1
N5—C22—N6	103.2 (3)	C45—C46—D46A	110.1
N5—C22—W1	130.8 (3)	O3—C46—D46B	110.1
N6—C22—W1	125.8 (3)	C45—C46—D46B	110.1
C22—N5—C23	111.2 (3)	D46A—C46—D46B	108.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O3	0.93	2.40	3.320 (7)	172

Experimental details

Crystal data
Chemical formula	[WCl₂(NO)₂(C₂₁H₂₄N₂)₂]·C₄D₈O
M_r	1003.72
Crystal system, space group	Triclinic, P1
Temperature (K)	183
a, b, c (Å)	11.3861 (7), 13.0517 (9), 17.0448 (11)
α, β, γ (°)	81.245 (8), 72.473 (7), 68.983 (7)
V (Å³)	2251.9 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.73
Crystal size (mm)	0.25 × 0.15 × 0.08

Data collection
Diffractometer	Stoe IPDS
Absorption correction	Numerical (Coppens et al., 1965)
T_min, T_max	0.568, 0.816
No. of measured, independent and observed [I > 2σ(I)] reflections	44725, 7466, 6365
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.076, 1.12
No. of reflections	7466
No. of parameters	535
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.00, −0.42

Computer programs: EXPOSE in IPDS Software (Stoe & Cie, 1999), CELL in IPDS Software (Stoe & Cie, 1999), INTEGRATE in IPDS Software (Stoe & Cie, 1999), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O3	0.93	2.40	3.320 (7)	172

Acknowledgements

Financial support by the University of Zürich is gratefully acknowledged.

References

Berke, H. & Burger, P. (1994). Comments Inorg. Chem. 16, 279–312. CrossRef CAS Web of Science Google Scholar
Coppens, P., Leiserowitz, L. & Rabinovich, D. (1965). Acta Cryst. 18, 1035–1038. CrossRef CAS IUCr Journals Web of Science Google Scholar
Enemark, J. H. & Feltham, R. D. (1974). Coord. Chem. Rev. 13, 339–406. CrossRef CAS Web of Science Google Scholar
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