Penta­carbonyl­(N,N-dimethyl­benzyl­amine)tungsten

Mahmud, T.; Iqbal, J.; Irshad, M.; Elsegood, M.R.J.; McKee, V.

doi:10.1107/S1600536805025560

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 61| Part 9| September 2005| Pages m1789-m1791

https://doi.org/10.1107/S1600536805025560

Pentacarbonyl(N,N-dimethylbenzylamine)tungsten

Tariq Mahmud,^a Javed Iqbal,^a Muhammad Irshad,^a Mark R. J. Elsegood ^b and Vickie McKee ^b ^*

^aInstitute of Chemistry, University of the Punjab, Lahore 54590, Pakistan, and ^bChemistry Department, Loughborough University, Loughborough, Leicestershire LE11 3TU, England
^*Correspondence e-mail: v.mckee@lboro.ac.uk

(Received 8 August 2005; accepted 10 August 2005; online 17 August 2005)

The title compound, [W(C₉H₁₃N)(CO)₅], was prepared by irradiation of W(CO)₆ in tetrahydrofuran in the presence of N,N-dimethylbenzylamine. The geometry at the W atom is approximately octahedral, with the cis bond angles in the range 86.3 (3)–95.6 (2)°. The bond to the tertiary amine is long [2.371 (5) Å] and, as might be expected, the bond to the trans carbonyl is quite short [W—C = 1.964 (7) Å]. The remaining W—CO bonds lie in the range 2.033 (6)–2.049 (6) Å. Similar bonding patterns have been observed in related W(CO)₅(amine) complexes,

Comment

(N,N-Dimethylbenzylamine)pentacarbonyltungsten was prepared by irradiation of W(CO)₆ in tetrahydrofuran (THF) in the presence of the amine. Presumably, the reaction proceeds via an intermediate THF complex (Aroney et al., 1994 , and references therein):

W(CO)₆ + THF → W(CO)₅(THF) + CO

W(CO)₅(THF) + C₉H₁₃N → W(CO)₅(C₉H₁₃N) + THF.

Although a number of cyclometallated complexes of tungsten with this ligand have been reported previously (van der Schaaf et al., 1993 ), no carbonyl complex has been structurally characterized. Also, in our hands, no cyclometallated complex was isolated.

The structure of (N,N-dimethylbenzylamine)pentacarbonyltungsten, (I), is shown in Fig. 1. The geometry at the W atom is approximately octahedral, with the cis bond angles in the range 86.3 (3)–95.6 (2)°. The bond to the tertiary amine is long [2.371 (5) Å] and, as might be expected, the bond to the trans carbonyl is quite short [W1—C10 = 1.964 (7) Å]. The remaining W—CO bonds lie in the range 2.033 (6)–2.049 (6) Å. Similar bonding patterns have been observed in related W(CO)₅(amine) complexes [see, for example, Long et al. (2002 ) and Moralejo et al. (1991 )]. There are no obvious π–π or edge-to-face interactions.

Figure 1
Perspective view of the the complex, with displacement ellipsoids drawn at the 50% probability level.

Experimental

W(CO)₆ (0.351 g, 1.0 mmol) and N,N-dimethylbenzylamine (0.30 ml, 2.0 mmol) were dissolved in sodium-dried THF (20 ml). The mixture was stirred under N₂ and irradiated with UV light for 4 h, yielding a yellow solution. The progress of the reaction was monitored by following the CO stretching band at 1975 cm⁻¹ by IR. The volume of the solvent was reduced under vacuum and n-hexane added to induce crystallization (yield 0.078 g, 17%). The sample was not pure and did not give satisfactory microanalysis. The EI mass spectrum of the complex showed a cluster corresponding to the parent ion W(C₆H₅CH₂N(CH₃)₂)(CO)₅ centered at m/e 459 and the isotope pattern matched that predicted from theory. Clusters corresponding to sequential loss of CO groups were observed at m/e of 431 [W(C₆H₅CH₂N(CH₃)₂)(CO)₄], 403 [W(C₆H₅CH₂N(CH₃)₂(CO)₃] and 375 [W(C₆H₅CH₂N(CH₃)₂)(CO)₂]. Clusters at m/e 345, 317 and 135 were assigned to W(C₆H₅CH₂N)(CO)₂, W(C₆H₅CH₂N)(CO) and [C₆H₅CH₂N(CH₃)₂ + H⁺], respectively. Clusters corresponding to W(CO)₆, W(CO)₅, W(CO)₄, W(CO)₃, W(CO)₂, W(CO) and W were also observed. The W(CO)₆ was most likely present as an impurity in the sample. ¹H NMR (CDCl₃): 2.78 (s, 6H, CH₃), 4.22 (s, 2H, CH₂), 7.25–7.34 (m, 5H, aromatic). ¹³C NMR: 55.3 (CH₃), 73.6 (CH₂), 128.5 (aromatic C₃, C₅), 129.0 (aromatic C₄), 132.0 (aromatic, C₂, C₆), 191, 199, 202 (carbonyl). IR (KBr, cm⁻¹): 3425 (m), 1952 (m), 1060 (w), 932 (m), 853 (m) 774 (m), 592 (s).

Crystal data

[W(C₉H₁₃N)(CO)₅]
M_r = 459.10
Orthorhombic, P b c a
a = 13.7829 (11) Å
b = 12.5247 (10) Å
c = 18.2985 (14) Å
V = 3158.8 (4) Å³
Z = 8
D_x = 1.931 Mg m⁻³
Mo Kα radiation
Cell parameters from 4675 reflections
θ = 2.5–28.1°
μ = 7.33 mm⁻¹
T = 150 (2) K
Plate, yellow
0.28 × 0.20 × 0.05 mm

Data collection

Bruker SMART 1000 CCD diffractometer
ω rotation with narrow-frame scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.233, T_max = 0.711
18147 measured reflections
3870 independent reflections
2534 reflections with I > 2σ(I)
R_int = 0.059
θ_max = 29.0°
h = −13 → 18
k = −16 → 16
l = −24 → 22

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.074
S = 1.03
3870 reflections
192 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0125P)² + 14.4005P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 1.10 e Å⁻³
Δρ_min = −0.85 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

W1—N1	2.371 (5)
W1—C10	1.964 (7)
W1—C11	2.041 (6)
W1—C12	2.034 (6)
W1—C13	2.033 (6)
W1—C14	2.048 (6)
O10—C10	1.157 (9)
O11—C11	1.144 (8)
O12—C12	1.152 (8)
O13—C13	1.156 (7)
O14—C14	1.142 (7)
N1—C1	1.492 (9)
N1—C2	1.496 (9)
N1—C3	1.514 (8)

N1—W1—C10	176.8 (2)
N1—W1—C11	93.9 (2)
N1—W1—C12	89.8 (2)
N1—W1—C13	91.5 (2)
N1—W1—C14	95.6 (2)
C10—W1—C11	88.4 (3)
C10—W1—C12	88.0 (3)
C10—W1—C13	86.3 (3)
C10—W1—C14	86.7 (3)
C11—W1—C12	174.8 (3)
C11—W1—C13	90.5 (2)
C11—W1—C14	86.8 (2)
C12—W1—C13	93.1 (3)
C12—W1—C14	89.1 (3)
C13—W1—C14	172.6 (3)
W1—N1—C1	110.0 (4)
W1—N1—C2	111.7 (4)
W1—N1—C3	109.1 (4)
C1—N1—C2	107.4 (5)
C1—N1—C3	109.3 (5)
C2—N1—C3	109.3 (5)
N1—C3—C4	115.8 (6)
W1—C10—O10	177.2 (6)
W1—C11—O11	176.4 (6)
W1—C12—O12	174.0 (6)
W1—C13—O13	173.9 (6)
W1—C14—O14	174.5 (5)

H atoms bonded to C atoms were inserted at calculated positions and refined using a riding model. The constrained C—H distances were 0.95, 0.98 and 0.99 Å for aryl, methyl, and methylene H atoms, respectively. The H atoms of methylene and aryl groups were refined with U_iso(H) = 1.2U_eq(C) and those of the methyl groups with U_iso(H) = 1.5U_eq(C). The highest residual electron-density peak is 0.88 Å from the W atom.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805025560/hg6224sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805025560/hg6224Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

(N,N-dimethylbenzylamine)pentacarbonyltungsten top

Crystal data top

[W(C₉H₁₃N)(CO)₅]	F(000) = 1744
M_r = 459.10	D_x = 1.931 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4675 reflections
a = 13.7829 (11) Å	θ = 2.5–28.1°
b = 12.5247 (10) Å	µ = 7.33 mm⁻¹
c = 18.2985 (14) Å	T = 150 K
V = 3158.8 (4) Å³	Plate, yellow
Z = 8	0.28 × 0.20 × 0.05 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	3870 independent reflections
Radiation source: sealed tube	2534 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
ω rotation with narrow frames scans	θ_max = 29.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −13→18
T_min = 0.233, T_max = 0.711	k = −16→16
18147 measured reflections	l = −24→22

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0125P)² + 14.4005P] where P = (F_o² + 2F_c²)/3
3870 reflections	(Δ/σ)_max = 0.001
192 parameters	Δρ_max = 1.10 e Å⁻³
0 restraints	Δρ_min = −0.85 e Å⁻³

Special details top

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
W1	0.07804 (2)	0.77665 (2)	0.20210 (1)	0.0237 (1)
O10	0.0153 (4)	0.8367 (4)	0.0435 (3)	0.0530 (19)
O11	0.1652 (3)	1.0111 (4)	0.2164 (3)	0.0460 (18)
O12	0.0043 (4)	0.5425 (4)	0.1638 (3)	0.050 (2)
O13	−0.1313 (3)	0.8659 (4)	0.2432 (3)	0.0437 (17)
O14	0.2815 (3)	0.7141 (4)	0.1313 (3)	0.0410 (17)
N1	0.1143 (4)	0.7259 (4)	0.3239 (3)	0.0270 (14)
C1	0.0264 (5)	0.6796 (7)	0.3594 (4)	0.048 (3)
C2	0.1456 (6)	0.8194 (5)	0.3690 (4)	0.046 (3)
C3	0.1944 (5)	0.6432 (5)	0.3230 (4)	0.0313 (19)
C4	0.2273 (5)	0.6028 (5)	0.3973 (4)	0.032 (2)
C5	0.3071 (5)	0.6478 (6)	0.4319 (4)	0.041 (3)
C6	0.3377 (6)	0.6098 (7)	0.4996 (5)	0.056 (3)
C7	0.2906 (6)	0.5259 (7)	0.5324 (4)	0.055 (3)
C8	0.2133 (6)	0.4800 (6)	0.4991 (5)	0.051 (3)
C9	0.1813 (5)	0.5179 (5)	0.4313 (4)	0.039 (2)
C10	0.0410 (5)	0.8148 (5)	0.1018 (4)	0.0323 (19)
C11	0.1338 (4)	0.9266 (5)	0.2138 (4)	0.032 (2)
C12	0.0289 (5)	0.6265 (5)	0.1815 (4)	0.0330 (19)
C13	−0.0554 (4)	0.8303 (5)	0.2320 (4)	0.032 (2)
C14	0.2101 (4)	0.7340 (5)	0.1599 (3)	0.0283 (19)
H1A	0.00200	0.62020	0.32980	0.0720*
H1B	−0.02380	0.73470	0.36340	0.0720*
H1C	0.04330	0.65360	0.40830	0.0720*
H2A	0.16320	0.79500	0.41810	0.0680*
H2B	0.09240	0.87090	0.37230	0.0680*
H2C	0.20190	0.85340	0.34600	0.0680*
H3A	0.25120	0.67420	0.29760	0.0380*
H3B	0.17200	0.58130	0.29380	0.0380*
H5	0.34110	0.70490	0.40920	0.0500*
H6	0.39160	0.64210	0.52330	0.0670*
H7	0.31220	0.50010	0.57850	0.0660*
H8	0.18070	0.42200	0.52190	0.0620*
H9	0.12730	0.48490	0.40820	0.0470*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
W1	0.0238 (1)	0.0235 (1)	0.0238 (1)	−0.0016 (1)	0.0004 (1)	0.0004 (1)
O10	0.055 (3)	0.068 (4)	0.036 (3)	−0.005 (3)	−0.006 (3)	0.013 (3)
O11	0.048 (3)	0.028 (2)	0.062 (4)	−0.008 (2)	−0.003 (3)	0.002 (2)
O12	0.064 (4)	0.028 (3)	0.057 (4)	−0.014 (2)	−0.007 (3)	−0.007 (2)
O13	0.029 (3)	0.047 (3)	0.055 (3)	0.005 (2)	0.003 (2)	0.005 (3)
O14	0.034 (3)	0.047 (3)	0.042 (3)	0.005 (2)	0.011 (2)	−0.002 (3)
N1	0.026 (2)	0.028 (2)	0.027 (3)	0.001 (2)	0.001 (2)	0.000 (3)
C1	0.032 (4)	0.075 (5)	0.037 (5)	0.001 (4)	0.006 (3)	0.018 (4)
C2	0.066 (5)	0.034 (4)	0.038 (4)	0.017 (4)	−0.012 (4)	−0.015 (3)
C3	0.033 (3)	0.027 (3)	0.034 (4)	0.006 (3)	0.002 (3)	−0.005 (3)
C4	0.038 (4)	0.030 (3)	0.027 (4)	0.012 (3)	−0.001 (3)	0.001 (3)
C5	0.035 (4)	0.053 (5)	0.036 (4)	0.005 (3)	0.002 (3)	0.004 (4)
C6	0.049 (5)	0.074 (6)	0.044 (5)	0.011 (4)	−0.014 (4)	−0.007 (5)
C7	0.063 (6)	0.069 (6)	0.032 (5)	0.026 (5)	−0.004 (4)	0.011 (4)
C8	0.064 (5)	0.047 (4)	0.042 (5)	0.010 (4)	0.006 (4)	0.016 (4)
C9	0.048 (4)	0.026 (3)	0.043 (5)	0.001 (3)	−0.006 (4)	0.005 (3)
C10	0.029 (3)	0.032 (3)	0.036 (4)	−0.009 (3)	0.004 (3)	0.005 (3)
C11	0.029 (3)	0.037 (4)	0.031 (4)	0.003 (3)	0.004 (3)	−0.005 (3)
C12	0.031 (3)	0.034 (3)	0.034 (4)	−0.001 (3)	0.001 (3)	0.008 (3)
C13	0.030 (4)	0.033 (3)	0.032 (4)	−0.007 (3)	0.001 (3)	0.004 (3)
C14	0.033 (3)	0.025 (3)	0.027 (4)	−0.002 (3)	−0.002 (3)	−0.003 (3)

Geometric parameters (Å, º) top

W1—N1	2.371 (5)	C5—C6	1.393 (12)
W1—C10	1.964 (7)	C6—C7	1.373 (12)
W1—C11	2.041 (6)	C7—C8	1.355 (12)
W1—C12	2.034 (6)	C8—C9	1.400 (11)
W1—C13	2.033 (6)	C1—H1A	0.9800
W1—C14	2.048 (6)	C1—H1B	0.9800
O10—C10	1.157 (9)	C1—H1C	0.9800
O11—C11	1.144 (8)	C2—H2A	0.9800
O12—C12	1.152 (8)	C2—H2B	0.9800
O13—C13	1.156 (7)	C2—H2C	0.9800
O14—C14	1.142 (7)	C3—H3A	0.9900
N1—C1	1.492 (9)	C3—H3B	0.9900
N1—C2	1.496 (9)	C5—H5	0.9500
N1—C3	1.514 (8)	C6—H6	0.9500
C3—C4	1.520 (10)	C7—H7	0.9500
C4—C5	1.389 (10)	C8—H8	0.9500
C4—C9	1.386 (9)	C9—H9	0.9500

N1—W1—C10	176.8 (2)	W1—C11—O11	176.4 (6)
N1—W1—C11	93.9 (2)	W1—C12—O12	174.0 (6)
N1—W1—C12	89.8 (2)	W1—C13—O13	173.9 (6)
N1—W1—C13	91.5 (2)	W1—C14—O14	174.5 (5)
N1—W1—C14	95.6 (2)	N1—C1—H1A	109.00
C10—W1—C11	88.4 (3)	N1—C1—H1B	109.00
C10—W1—C12	88.0 (3)	N1—C1—H1C	109.00
C10—W1—C13	86.3 (3)	H1A—C1—H1B	109.00
C10—W1—C14	86.7 (3)	H1A—C1—H1C	110.00
C11—W1—C12	174.8 (3)	H1B—C1—H1C	109.00
C11—W1—C13	90.5 (2)	N1—C2—H2A	109.00
C11—W1—C14	86.8 (2)	N1—C2—H2B	110.00
C12—W1—C13	93.1 (3)	N1—C2—H2C	109.00
C12—W1—C14	89.1 (3)	H2A—C2—H2B	110.00
C13—W1—C14	172.6 (3)	H2A—C2—H2C	109.00
W1—N1—C1	110.0 (4)	H2B—C2—H2C	109.00
W1—N1—C2	111.7 (4)	N1—C3—H3A	108.00
W1—N1—C3	109.1 (4)	N1—C3—H3B	108.00
C1—N1—C2	107.4 (5)	C4—C3—H3A	108.00
C1—N1—C3	109.3 (5)	C4—C3—H3B	108.00
C2—N1—C3	109.3 (5)	H3A—C3—H3B	107.00
N1—C3—C4	115.8 (6)	C4—C5—H5	120.00
C3—C4—C5	120.6 (6)	C6—C5—H5	120.00
C3—C4—C9	121.4 (6)	C5—C6—H6	120.00
C5—C4—C9	118.0 (7)	C7—C6—H6	120.00
C4—C5—C6	120.5 (7)	C6—C7—H7	120.00
C5—C6—C7	120.5 (8)	C8—C7—H7	120.00
C6—C7—C8	120.0 (8)	C7—C8—H8	120.00
C7—C8—C9	120.2 (7)	C9—C8—H8	120.00
C4—C9—C8	120.9 (7)	C4—C9—H9	119.00
W1—C10—O10	177.2 (6)	C8—C9—H9	120.00

C11—W1—N1—C1	129.4 (5)	C1—N1—C3—C4	−60.3 (7)
C11—W1—N1—C2	10.3 (5)	C2—N1—C3—C4	57.0 (7)
C11—W1—N1—C3	−110.7 (4)	N1—C3—C4—C5	−95.4 (8)
C12—W1—N1—C1	−54.3 (5)	N1—C3—C4—C9	87.0 (8)
C12—W1—N1—C2	−173.4 (5)	C3—C4—C9—C8	178.8 (7)
C12—W1—N1—C3	65.6 (4)	C5—C4—C9—C8	1.1 (10)
C13—W1—N1—C1	38.8 (5)	C9—C4—C5—C6	−1.6 (11)
C13—W1—N1—C2	−80.3 (5)	C3—C4—C5—C6	−179.3 (7)
C13—W1—N1—C3	158.7 (4)	C4—C5—C6—C7	1.3 (12)
C14—W1—N1—C1	−143.5 (5)	C5—C6—C7—C8	−0.5 (13)
C14—W1—N1—C2	97.5 (5)	C6—C7—C8—C9	0.0 (12)
C14—W1—N1—C3	−23.5 (4)	C7—C8—C9—C4	−0.4 (12)
W1—N1—C3—C4	179.4 (4)

Acknowledgements

The authors thank the University of the Punjab, Lahore, Pakistan, and the Charles Wallace Pakistan Trust for financial support, and are also grateful to Loughborough University for providing facilities and to the EPSRC Mass Spectrometry Service Centre, University of Wales, Swansea, for the mass spectrum.

References

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