Penta-carbon-yl{3-[(2S)-1-methyl-pyrrolidin-2-yl]pyridine}tungsten(0).

The title compound, [W(C(10)H(14)N(2))(CO)(5)], contains five carbonyl ligands and a nicotine ligand in an octa-hedral arrangement around the tungsten atom. The metal atom shows cis angles in the range 87.30 (16)-94.2 (2)°, and trans angles between 175.2 (2) and 178.1 (4)°. The W-CO bond trans to the pyridine N atom [1.987 (6) Å] is noticeably shorter than the others, which range between 2.036 (3) and 2.064 (3) Å, possibly due to the well-known trans effect. The distance between the W atom and the pyridine N atom is 2.278 (4) Å.

Related literature

Attempts to understand and mimic the nature of nitro­gen fixation have led to studies on the responsible enzyme, nitro­genase (Jennings, 1991 ▶; Schrock, 2006 ▶). As part of this work, we have investigated the reactions of the precursor tungsten halogenidocarbonyl derivative, [W(CO)4 X 2]2, with nitro­gen bases. For possible reaction mechanisms, see: Abel et al. (1963 ▶); Baker (1998 ▶); Heyns & Buchholtz (1976 ▶); Tripathi & Srivasatva (1970 ▶). For the preparation of tungsten dichlorido­tetracarbonyl [W(CO)4Cl2], see: Colton & Tomkins (1966 ▶).

Experimental

Crystal data

[W(C10H14N2)(CO)5]

M = 486.13

Monoclinic,

a = 6.6303 (1) Å

b = 10.6720 (2) Å

c = 11.6748 (2) Å

β = 96.636 (1)°

V = 820.56 (2) Å3

Z = 2

Cu Kα radiation

μ = 13.29 mm−1

T = 100 K

0.28 × 0.25 × 0.19 mm

Data collection

Bruker SMART CCD APEXII area-detector diffractometer

Absorption correction: numerical (SADABS; Sheldrick, 2008a ▶) T min = 0.119, T max = 0.185

6704 measured reflections

2676 independent reflections

2673 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.014

wR(F 2) = 0.033

S = 1.13

2676 reflections

210 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.44 e Å−3

Δρmin = −0.53 e Å−3

Absolute structure: Flack (1983 ▶), 1225 Friedel pairs

Flack parameter: 0.041 (9)

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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810010974/ez2203sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810010974/ez2203Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[W(C10H14N2)(CO)5]	F(000) = 464
Mr = 486.13	Dx = 1.968 Mg m−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2yb	Cell parameters from 6772 reflections
a = 6.6303 (1) Å	θ = 3.8–66.8°
b = 10.6720 (2) Å	µ = 13.29 mm−1
c = 11.6748 (2) Å	T = 100 K
β = 96.636 (1)°	Plate, yellow
V = 820.56 (2) Å3	0.28 × 0.25 × 0.19 mm
Z = 2

Bruker SMART CCD APEXII area-detector diffractometer	2676 independent reflections
Radiation source: fine-focus sealed tube	2673 reflections with I > 2σ(I)
graphite	Rint = 0.020
φ and ω scans	θmax = 66.8°, θmin = 3.8°
Absorption correction: numerical (SADABS; Sheldrick, 2008a)	h = −7→7
Tmin = 0.119, Tmax = 0.185	k = −12→12
6704 measured reflections	l = −13→11

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.014	w = 1/[σ2(Fo2) + (0.0071P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.033	(Δ/σ)max < 0.001
S = 1.13	Δρmax = 0.44 e Å−3
2676 reflections	Δρmin = −0.53 e Å−3
210 parameters	Extinction correction: SHELXTL (Sheldrick, 2008b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraint	Extinction coefficient: 0.00053 (7)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1225 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.041 (9)

Experimental. 'crystal mounted on a Cryoloop using Paratone-N'

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 > 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.

	x	y	z	Uiso*/Ueq
W1	0.975072 (14)	0.99294 (4)	0.798344 (8)	0.01869 (6)
C1	1.1233 (8)	1.1176 (5)	0.9028 (5)	0.0212 (12)
O1	1.2053 (6)	1.1868 (3)	0.9687 (3)	0.0307 (8)
N1	0.7925 (6)	0.8443 (4)	0.6915 (4)	0.0218 (9)
C2	0.8653 (6)	1.1332 (4)	0.6881 (4)	0.0206 (10)
O2	0.8203 (4)	1.2112 (3)	0.6253 (2)	0.0327 (6)
N2	0.3021 (3)	0.5061 (4)	0.6952 (2)	0.0230 (6)
C3	1.2185 (4)	0.9810 (7)	0.7074 (2)	0.0238 (9)
O3	1.3582 (3)	0.9783 (5)	0.6594 (2)	0.0384 (8)
C4	1.1080 (9)	0.8553 (5)	0.9047 (6)	0.0233 (12)
O4	1.1972 (6)	0.7822 (3)	0.9596 (3)	0.0337 (8)
C5	0.7301 (4)	1.0112 (5)	0.8913 (2)	0.0204 (11)
O5	0.5952 (4)	1.0199 (2)	0.9427 (2)	0.0327 (8)
C6	0.7783 (5)	0.8398 (3)	0.5751 (3)	0.0244 (7)
H6	0.8463	0.9017	0.5355	0.029*
C7	0.6690 (5)	0.7487 (3)	0.5122 (3)	0.0289 (7)
H7	0.6611	0.7487	0.4304	0.035*
C8	0.5703 (5)	0.6569 (3)	0.5682 (3)	0.0245 (7)
H8	0.4963	0.5924	0.5258	0.029*
C9	0.5815 (5)	0.6609 (3)	0.6876 (3)	0.0204 (6)
C10	0.6930 (4)	0.7558 (3)	0.7446 (3)	0.0190 (6)
H10	0.7001	0.7587	0.8263	0.023*
C11	0.4868 (5)	0.5628 (3)	0.7575 (3)	0.0204 (6)
H11	0.4530	0.6007	0.8312	0.025*
C12	0.6199 (5)	0.4479 (3)	0.7839 (3)	0.0285 (8)
H12A	0.7203	0.4626	0.8522	0.034*
H12B	0.6931	0.4261	0.7174	0.034*
C13	0.4704 (5)	0.3435 (4)	0.8078 (3)	0.0283 (8)
H13A	0.4955	0.2666	0.7642	0.034*
H13B	0.4821	0.3232	0.8911	0.034*
C14	0.2606 (5)	0.3988 (3)	0.7666 (3)	0.0246 (7)
H14A	0.1746	0.3365	0.7210	0.030*
H14B	0.1908	0.4258	0.8329	0.030*
C15	0.1310 (5)	0.5916 (4)	0.6783 (3)	0.0321 (8)
H15A	0.0156	0.5494	0.6343	0.048*
H15B	0.1687	0.6655	0.6359	0.048*
H15C	0.0930	0.6174	0.7535	0.048*

	U11	U22	U33	U12	U13	U23
W1	0.01884 (8)	0.01807 (8)	0.01892 (8)	−0.00160 (9)	0.00110 (4)	−0.00046 (9)
C1	0.017 (2)	0.024 (3)	0.022 (3)	0.0024 (17)	0.0021 (17)	0.0015 (18)
O1	0.0287 (18)	0.0293 (18)	0.033 (2)	−0.0064 (14)	0.0007 (14)	−0.0016 (14)
N1	0.021 (2)	0.0222 (18)	0.0211 (18)	0.0006 (15)	−0.0020 (14)	−0.0023 (12)
C2	0.021 (2)	0.0141 (18)	0.025 (2)	0.0005 (17)	−0.0033 (17)	0.0001 (13)
O2	0.0357 (14)	0.0301 (15)	0.0304 (15)	0.0040 (12)	−0.0037 (11)	0.0013 (12)
N2	0.0172 (10)	0.0248 (18)	0.0262 (12)	−0.0042 (15)	−0.0002 (8)	0.0002 (15)
C3	0.0216 (12)	0.028 (3)	0.0223 (14)	0.0030 (19)	0.0068 (10)	0.0013 (18)
O3	0.0368 (12)	0.042 (2)	0.0386 (13)	0.0094 (16)	0.0119 (9)	0.0142 (15)
C4	0.024 (2)	0.018 (2)	0.026 (3)	−0.0011 (18)	−0.0001 (18)	0.0026 (17)
O4	0.042 (2)	0.0292 (17)	0.0269 (19)	−0.0006 (15)	−0.0089 (14)	0.0064 (14)
C5	0.0202 (12)	0.022 (3)	0.0200 (14)	−0.0013 (14)	0.0070 (10)	−0.0048 (14)
O5	0.0327 (12)	0.031 (3)	0.0349 (14)	−0.0026 (10)	0.0071 (9)	−0.0025 (9)
C6	0.0282 (17)	0.0266 (19)	0.0185 (19)	−0.0014 (14)	0.0029 (13)	0.0036 (14)
C7	0.0345 (19)	0.035 (2)	0.0170 (18)	−0.0022 (15)	0.0021 (13)	−0.0001 (13)
C8	0.0281 (17)	0.0268 (18)	0.0175 (18)	−0.0031 (14)	−0.0016 (12)	−0.0027 (12)
C9	0.0167 (14)	0.0233 (17)	0.0209 (18)	0.0029 (12)	0.0005 (11)	−0.0001 (12)
C10	0.0199 (15)	0.0220 (17)	0.0150 (16)	0.0017 (12)	0.0019 (11)	−0.0005 (11)
C11	0.0196 (16)	0.0228 (18)	0.0190 (18)	−0.0019 (14)	0.0025 (11)	−0.0026 (14)
C12	0.0234 (17)	0.0250 (18)	0.037 (2)	−0.0056 (13)	0.0013 (14)	0.0076 (12)
C13	0.0271 (19)	0.027 (2)	0.030 (2)	−0.0056 (13)	0.0005 (14)	0.0053 (13)
C14	0.0224 (16)	0.0218 (17)	0.0299 (19)	−0.0067 (13)	0.0039 (13)	−0.0018 (13)
C15	0.0243 (17)	0.0310 (19)	0.040 (2)	0.0035 (14)	0.0013 (14)	0.0027 (15)

W1—C1	1.987 (6)	C7—H7	0.9500
W1—C3	2.035 (3)	C8—C9	1.388 (5)
W1—C2	2.052 (5)	C8—H8	0.9500
W1—C4	2.055 (6)	C9—C10	1.379 (5)
W1—C5	2.064 (3)	C9—C11	1.507 (5)
W1—N1	2.278 (4)	C10—H10	0.9500
C1—O1	1.156 (7)	C11—C12	1.522 (4)
N1—C10	1.344 (5)	C11—H11	1.0000
N1—C6	1.352 (6)	C12—C13	1.539 (5)
C2—O2	1.126 (6)	C12—H12A	0.9900
N2—C15	1.451 (5)	C12—H12B	0.9900
N2—C14	1.460 (5)	C13—C14	1.536 (4)
N2—C11	1.480 (4)	C13—H13A	0.9900
C3—O3	1.138 (4)	C13—H13B	0.9900
C4—O4	1.132 (7)	C14—H14A	0.9900
C5—O5	1.138 (4)	C14—H14B	0.9900
C6—C7	1.374 (5)	C15—H15A	0.9800
C6—H6	0.9500	C15—H15B	0.9800
C7—C8	1.384 (5)	C15—H15C	0.9800
C1—W1—C3	89.8 (2)	C10—C9—C11	118.9 (3)
C1—W1—C2	90.6 (3)	C8—C9—C11	123.0 (3)
C3—W1—C2	87.9 (2)	N1—C10—C9	124.0 (3)
C1—W1—C4	87.75 (12)	N1—C10—H10	118.0
C3—W1—C4	87.7 (2)	C9—C10—H10	118.0
C2—W1—C4	175.3 (2)	N2—C11—C9	113.0 (3)
C1—W1—C5	88.7 (2)	N2—C11—C12	101.4 (3)
C3—W1—C5	178.1 (3)	C9—C11—C12	113.7 (2)
C2—W1—C5	90.97 (18)	N2—C11—H11	109.5
C4—W1—C5	93.4 (2)	C9—C11—H11	109.5
C1—W1—N1	175.2 (2)	C12—C11—H11	109.5
C3—W1—N1	94.2 (2)	C11—C12—C13	104.5 (3)
C2—W1—N1	92.12 (11)	C11—C12—H12A	110.9
C4—W1—N1	89.8 (3)	C13—C12—H12A	110.9
C5—W1—N1	87.30 (16)	C11—C12—H12B	110.9
O1—C1—W1	176.2 (5)	C13—C12—H12B	110.9
C10—N1—C6	117.2 (4)	H12A—C12—H12B	108.9
C10—N1—W1	119.7 (3)	C14—C13—C12	104.1 (3)
C6—N1—W1	123.1 (3)	C14—C13—H13A	110.9
O2—C2—W1	174.5 (4)	C12—C13—H13A	110.9
C15—N2—C14	112.0 (2)	C14—C13—H13B	110.9
C15—N2—C11	113.5 (3)	C12—C13—H13B	110.9
C14—N2—C11	103.9 (3)	H13A—C13—H13B	109.0
O3—C3—W1	177.1 (6)	N2—C14—C13	104.9 (3)
O4—C4—W1	173.8 (5)	N2—C14—H14A	110.8
O5—C5—W1	179.3 (5)	C13—C14—H14A	110.8
N1—C6—C7	122.3 (3)	N2—C14—H14B	110.8
N1—C6—H6	118.9	C13—C14—H14B	110.8
C7—C6—H6	118.9	H14A—C14—H14B	108.8
C6—C7—C8	119.8 (3)	N2—C15—H15A	109.5
C6—C7—H7	120.1	N2—C15—H15B	109.5
C8—C7—H7	120.1	H15A—C15—H15B	109.5
C7—C8—C9	118.7 (3)	N2—C15—H15C	109.5
C7—C8—H8	120.7	H15A—C15—H15C	109.5
C9—C8—H8	120.7	H15B—C15—H15C	109.5
C10—C9—C8	118.1 (3)
C3—W1—C1—O1	−139 (7)	C1—W1—C5—O5	−122 (22)
C2—W1—C1—O1	133 (7)	C3—W1—C5—O5	−159 (22)
C4—W1—C1—O1	−51 (7)	C2—W1—C5—O5	147 (22)
C5—W1—C1—O1	42 (7)	C4—W1—C5—O5	−35 (22)
N1—W1—C1—O1	8(9)	N1—W1—C5—O5	55 (22)
C1—W1—N1—C10	−11 (3)	C10—N1—C6—C7	−0.5 (6)
C3—W1—N1—C10	135.7 (3)	W1—N1—C6—C7	179.4 (3)
C2—W1—N1—C10	−136.2 (3)	N1—C6—C7—C8	−0.6 (6)
C4—W1—N1—C10	48.1 (3)	C6—C7—C8—C9	1.2 (5)
C5—W1—N1—C10	−45.3 (3)	C7—C8—C9—C10	−0.8 (5)
C1—W1—N1—C6	169 (2)	C7—C8—C9—C11	−177.5 (3)
C3—W1—N1—C6	−44.1 (4)	C6—N1—C10—C9	1.0 (5)
C2—W1—N1—C6	44.0 (4)	W1—N1—C10—C9	−178.9 (2)
C4—W1—N1—C6	−131.8 (4)	C8—C9—C10—N1	−0.3 (5)
C5—W1—N1—C6	134.8 (4)	C11—C9—C10—N1	176.5 (3)
C1—W1—C2—O2	71 (4)	C15—N2—C11—C9	−69.3 (3)
C3—W1—C2—O2	−18 (4)	C14—N2—C11—C9	168.8 (3)
C4—W1—C2—O2	2(7)	C15—N2—C11—C12	168.6 (3)
C5—W1—C2—O2	160 (4)	C14—N2—C11—C12	46.7 (3)
N1—W1—C2—O2	−113 (4)	C10—C9—C11—N2	152.7 (3)
C1—W1—C3—O3	−7(10)	C8—C9—C11—N2	−30.6 (5)
C2—W1—C3—O3	84 (10)	C10—C9—C11—C12	−92.4 (4)
C4—W1—C3—O3	−94 (10)	C8—C9—C11—C12	84.2 (4)
C5—W1—C3—O3	30 (13)	N2—C11—C12—C13	−35.7 (3)
N1—W1—C3—O3	176 (10)	C9—C11—C12—C13	−157.3 (3)
C1—W1—C4—O4	−71 (5)	C11—C12—C13—C14	12.4 (4)
C3—W1—C4—O4	19 (5)	C15—N2—C14—C13	−162.2 (3)
C2—W1—C4—O4	−1(8)	C11—N2—C14—C13	−39.3 (3)
C5—W1—C4—O4	−159 (5)	C12—C13—C14—N2	15.9 (4)
N1—W1—C4—O4	113 (5)