Pentacarbonyl(di-2-pyridyl­amine)tungsten(0)

In the title molecular complex, (I), the W atom is in an octahedral environment with four equatorial carbonyl ligands and a fifth in an axial position trans to the monodentate dipyridyl­amine ligand. The long dimension of this last bisects the angle between two of the equatorial carbonyl groups and while the non-bonded pyridyl N atom is directed away from the W atom, the bridging amine group is directed towards it. Thus, in addition to the N atom to which it is attached, the amino H has two nearest neighbour C atoms of equatorial carbonyl groups but does not participate in hydrogen bonding in any real or usual sense. The W-C bond distance for the axial carbonyl group is notably less than those of the equatorial groups.

S1. Comment

For the most part, the bond distances and angles of the title compound are in no way remarkable. On the other hand W1—C5 of the axial carbonyl group (1.967 (7) Å) is appreciably shorter than the W—C bond lengths of the equatorial groups which are in the range 2.020 (7) to 2.063 (8) Å. There is however no comparable distinction in the carbony C—O bond lengths. The orientation of the dipyridylamine ligand at 90 ° to the equatorial plane of the complex with the non-bonding pyridyl N directed away from the metal atom and the bridging NH group directed towards it is most likely determined by steric effects. The long dimension of the dipyridyl ligand bisects the angle between the C3—O3 and C4—O4 equatorial carbonyl groups. As a result, in addition to the N to which it is attached, the amino H has two nearest neighbour non-H (C3 and C4 at 2.30 (6) and 2.78 (6) Å respectively). For convenience the molecular geometry in the vicinity of the amino H is reported in the manner appropriate to the description of H-bonds but the distances and angles reported in this way suggest that H-bonding in any real or usual sense is entirely absent.

S2. Experimental

The title compound was prepared by the addition of dipyridylamine to a solution of W(CO)₅(THF) in THF, followed by removal of solvent under reduced pressure. The resulting yellow solid was recrystallized from deaerated toluene. W(CO)₅(THF) was prepared by photolysis of W(CO)₆ in argon purged THF.

S3. Refinement

H were initially placed in calculated positions and while H1 of the amino group was refined isotropically in the normal manner the remaining H were refined with a riding model.

Computing details

Data collection: Nicolet P3 Software (Nicolet, 1980); cell refinement: Nicolet P3 Software (Nicolet, 1980); data reduction: RDNIC (Howie, 1980); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

2,2'-Dipyridylaminepentacarbonyltungsten(0)

Crystal data

[W(C10H9N3)(CO)5]	F(000) = 936
Mr = 495.10	Dx = 2.032 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.812 (11) Å	Cell parameters from 14 reflections
b = 7.185 (7) Å	θ = 10.2–12.5°
c = 17.835 (15) Å	µ = 7.17 mm^−1
β = 99.61 (7)°	T = 298 K
V = 1619 (3) Å^3	Block, green yellow
Z = 4	0.52 × 0.26 × 0.26 mm

Data collection

Nicolet P3 diffractometer	2799 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.041
Graphite monochromator	θmax = 27.6°, θmin = 1.8°
θ–2θ scans	h = 0→16
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
Tmin = 0.071, Tmax = 0.151	l = −23→22
3904 measured reflections	2 standard reflections every 50 reflections
3748 independent reflections	intensity decay: random variation +−2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.082	Calculated w = 1/[σ^2(Fo^2) + (0.0367P)^2 + 0.3862P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
3748 reflections	Δρmax = 0.99 e Å^−3
222 parameters	Δρmin = −0.60 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: heavy-atom method	Extinction coefficient: 0.0038 (2)

Special details

Experimental. Scan rates, dependent on prescan intensity (Ip), were in the range 58.6 (Ip>2500) to 5.33 (Ip<150) ° 2θ min^-1. Scan widths, dependent on 2θ, were in the range 2.4 to 2.75 ° 2θ. Stationary crystal, stationary counter background counts were taken on either side of the peak each for 25% of the total (peak plus background) count time.

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.

All H were initially placed in calculated positions (AFIX 43). Thereafter aryl H were refined with a riding model with U_iso 1.2 x Uequ of the C to which they were attached whereas the amino H (H1) was refined isotropically in the normal manner.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
W1	0.318564 (18)	0.22037 (4)	0.066959 (14)	0.04187 (11)
O1	0.4187 (4)	0.4078 (9)	−0.0664 (3)	0.0791 (17)
O2	0.3786 (5)	−0.1699 (9)	0.0044 (4)	0.090 (2)
O3	0.2638 (4)	0.0174 (8)	0.2132 (3)	0.0723 (15)
O4	0.2912 (5)	0.6237 (8)	0.1339 (3)	0.0791 (17)
O5	0.5455 (4)	0.2314 (9)	0.1620 (3)	0.0843 (19)
N1	0.0619 (4)	0.2760 (8)	0.0862 (3)	0.0480 (13)
H1	0.125 (5)	0.253 (8)	0.118 (4)	0.043 (17)*
N2	0.1541 (4)	0.2166 (7)	−0.0107 (3)	0.0454 (12)
N3	−0.1179 (4)	0.3072 (9)	0.0976 (4)	0.0620 (16)
C1	0.3795 (5)	0.3436 (10)	−0.0194 (4)	0.0493 (15)
C2	0.3531 (6)	−0.0355 (11)	0.0255 (4)	0.0567 (18)
C3	0.2784 (5)	0.0898 (9)	0.1583 (4)	0.0498 (16)
C4	0.2967 (5)	0.4823 (11)	0.1091 (4)	0.0544 (17)
C5	0.4618 (5)	0.2281 (10)	0.1274 (4)	0.0566 (17)
C6	0.1548 (6)	0.1851 (10)	−0.0866 (4)	0.0553 (17)
H6	0.2193	0.1591	−0.1017	0.066*
C7	0.0677 (6)	0.1897 (11)	−0.1404 (4)	0.068 (2)
H7	0.0724	0.1716	−0.1913	0.082*
C8	−0.0287 (6)	0.2220 (11)	−0.1181 (5)	0.067 (2)
H8	−0.0901	0.2249	−0.1542	0.080*
C9	−0.0343 (5)	0.2497 (9)	−0.0433 (4)	0.0569 (18)
H9	−0.0992	0.2706	−0.0279	0.068*
C10	0.0589 (5)	0.2463 (8)	0.0098 (4)	0.0440 (15)
C11	−0.0170 (5)	0.2879 (9)	0.1312 (4)	0.0493 (15)
C12	0.0137 (6)	0.2787 (11)	0.2086 (4)	0.0615 (19)
H12	0.0847	0.2654	0.2296	0.074*
C13	−0.0617 (7)	0.2894 (13)	0.2542 (6)	0.085 (3)
H13	−0.0428	0.2829	0.3068	0.102*
C14	−0.1657 (7)	0.3101 (15)	0.2212 (6)	0.093 (3)
H14	−0.2186	0.3212	0.2508	0.112*
C15	−0.1894 (6)	0.3138 (13)	0.1440 (6)	0.084 (3)
H15	−0.2604	0.3214	0.1221	0.101*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
W1	0.03809 (14)	0.05104 (17)	0.03725 (15)	0.00048 (12)	0.00855 (9)	0.00116 (13)
O1	0.084 (4)	0.099 (5)	0.060 (3)	−0.014 (3)	0.028 (3)	0.011 (3)
O2	0.115 (5)	0.074 (4)	0.089 (5)	0.027 (4)	0.039 (4)	−0.015 (4)
O3	0.077 (4)	0.086 (4)	0.059 (3)	0.008 (3)	0.025 (3)	0.020 (3)
O4	0.108 (5)	0.060 (4)	0.073 (4)	−0.001 (3)	0.027 (3)	−0.016 (3)
O5	0.049 (3)	0.132 (6)	0.068 (4)	−0.011 (3)	−0.003 (3)	0.025 (4)
N1	0.035 (2)	0.059 (3)	0.049 (3)	0.003 (2)	0.003 (2)	0.005 (3)
N2	0.046 (3)	0.046 (3)	0.045 (3)	−0.001 (2)	0.009 (2)	0.000 (3)
N3	0.041 (3)	0.068 (4)	0.079 (4)	0.007 (3)	0.014 (3)	0.001 (3)
C1	0.045 (3)	0.052 (4)	0.051 (4)	0.002 (3)	0.011 (3)	0.000 (3)
C2	0.061 (4)	0.064 (5)	0.050 (4)	0.004 (4)	0.023 (3)	−0.001 (4)
C3	0.044 (3)	0.051 (4)	0.057 (4)	0.008 (3)	0.015 (3)	0.002 (3)
C4	0.056 (4)	0.066 (5)	0.043 (4)	−0.005 (3)	0.015 (3)	−0.003 (4)
C5	0.049 (4)	0.070 (5)	0.052 (4)	−0.005 (3)	0.011 (3)	0.011 (4)
C6	0.063 (4)	0.056 (5)	0.047 (4)	−0.001 (3)	0.010 (3)	−0.010 (3)
C7	0.075 (5)	0.081 (6)	0.042 (4)	−0.010 (4)	−0.006 (4)	−0.002 (4)
C8	0.065 (5)	0.070 (5)	0.056 (4)	−0.009 (4)	−0.017 (4)	0.008 (4)
C9	0.045 (3)	0.061 (5)	0.060 (4)	−0.001 (3)	−0.005 (3)	0.002 (4)
C10	0.043 (3)	0.038 (4)	0.050 (4)	−0.003 (2)	0.005 (3)	0.003 (3)
C11	0.045 (3)	0.042 (3)	0.063 (4)	0.000 (3)	0.016 (3)	−0.005 (3)
C12	0.051 (4)	0.081 (5)	0.053 (4)	−0.007 (4)	0.011 (3)	−0.013 (4)
C13	0.076 (6)	0.115 (8)	0.071 (6)	−0.003 (5)	0.033 (5)	−0.015 (6)
C14	0.068 (5)	0.127 (9)	0.095 (8)	−0.003 (5)	0.042 (5)	−0.025 (7)
C15	0.041 (4)	0.104 (7)	0.111 (8)	0.001 (4)	0.027 (4)	−0.006 (6)

Geometric parameters (Å, º)

W1—C5	1.967 (7)	N2—C10	1.347 (8)
W1—C3	2.020 (7)	N2—C6	1.375 (9)
W1—C1	2.041 (7)	N3—C15	1.335 (10)
W1—C2	2.057 (8)	N3—C11	1.338 (9)
W1—C4	2.063 (8)	C6—C7	1.344 (10)
W1—N2	2.320 (6)	C7—C8	1.379 (11)
O1—C1	1.144 (8)	C8—C9	1.363 (11)
O2—C2	1.106 (9)	C9—C10	1.395 (9)
O3—C3	1.152 (8)	C11—C12	1.371 (11)
O4—C4	1.115 (9)	C12—C13	1.365 (11)
O5—C5	1.145 (8)	C13—C14	1.372 (13)
N1—C10	1.374 (9)	C14—C15	1.359 (13)
N1—C11	1.395 (8)	N1—H1	0.92 (6)
C5—W1—C3	84.9 (3)	O2—C2—W1	175.3 (7)
C5—W1—C1	87.8 (3)	O3—C3—W1	174.5 (6)
C3—W1—C1	172.3 (2)	O4—C4—W1	175.8 (7)
C5—W1—C2	89.2 (3)	O5—C5—W1	179.3 (7)
C3—W1—C2	88.5 (3)	C7—C6—N2	123.9 (7)
C1—W1—C2	89.1 (3)	C6—C7—C8	118.4 (7)
C5—W1—C4	86.9 (3)	C9—C8—C7	120.2 (7)
C3—W1—C4	93.5 (3)	C8—C9—C10	118.9 (7)
C1—W1—C4	88.4 (3)	N2—C10—N1	114.6 (5)
C2—W1—C4	175.4 (3)	N2—C10—C9	122.0 (7)
C5—W1—N2	176.5 (2)	N1—C10—C9	123.3 (6)
C3—W1—N2	98.5 (2)	N3—C11—C12	123.3 (7)
C1—W1—N2	88.8 (2)	N3—C11—N1	119.1 (7)
C2—W1—N2	90.2 (2)	C12—C11—N1	117.6 (6)
C4—W1—N2	93.6 (2)	C13—C12—C11	119.0 (8)
C10—N1—C11	132.7 (6)	C12—C13—C14	118.9 (9)
C10—N2—C6	116.6 (6)	C15—C14—C13	118.3 (8)
C10—N2—W1	127.6 (4)	N3—C15—C14	124.5 (8)
C6—N2—W1	115.8 (4)	C10—N1—H1	118 (4)
C15—N3—C11	115.9 (7)	C11—N1—H1	107 (4)
O1—C1—W1	176.3 (6)
C5—W1—N2—C10	−152 (4)	N2—W1—C4—O4	−170 (9)
C3—W1—N2—C10	40.2 (5)	C3—W1—C5—O5	109 (49)
C1—W1—N2—C10	−142.2 (5)	C1—W1—C5—O5	−69 (49)
C2—W1—N2—C10	128.7 (5)	C2—W1—C5—O5	20 (49)
C4—W1—N2—C10	−53.9 (5)	C4—W1—C5—O5	−157 (49)
C5—W1—N2—C6	26 (4)	N2—W1—C5—O5	−59 (51)
C3—W1—N2—C6	−141.7 (5)	C10—N2—C6—C7	2.7 (10)
C1—W1—N2—C6	35.9 (5)	W1—N2—C6—C7	−175.7 (6)
C2—W1—N2—C6	−53.2 (5)	N2—C6—C7—C8	−2.2 (12)
C4—W1—N2—C6	124.2 (5)	C6—C7—C8—C9	0.5 (12)
C5—W1—C1—O1	31 (10)	C7—C8—C9—C10	0.5 (11)
C3—W1—C1—O1	14 (11)	C6—N2—C10—N1	179.6 (5)
C2—W1—C1—O1	−58 (10)	W1—N2—C10—N1	−2.2 (7)
C4—W1—C1—O1	118 (10)	C6—N2—C10—C9	−1.6 (9)
N2—W1—C1—O1	−148 (10)	W1—N2—C10—C9	176.6 (4)
C5—W1—C2—O2	−23 (9)	C11—N1—C10—N2	−170.6 (6)
C3—W1—C2—O2	−108 (9)	C11—N1—C10—C9	10.6 (11)
C1—W1—C2—O2	65 (9)	C8—C9—C10—N2	0.1 (10)
C4—W1—C2—O2	8 (11)	C8—C9—C10—N1	178.8 (6)
N2—W1—C2—O2	153 (9)	C15—N3—C11—C12	−1.2 (11)
C5—W1—C3—O3	2 (7)	C15—N3—C11—N1	178.6 (7)
C1—W1—C3—O3	20 (8)	C10—N1—C11—N3	−13.7 (11)
C2—W1—C3—O3	92 (7)	C10—N1—C11—C12	166.1 (7)
C4—W1—C3—O3	−84 (7)	N3—C11—C12—C13	0.1 (12)
N2—W1—C3—O3	−178 (6)	N1—C11—C12—C13	−179.8 (7)
C5—W1—C4—O4	6 (9)	C11—C12—C13—C14	−0.3 (13)
C3—W1—C4—O4	91 (9)	C12—C13—C14—C15	1.8 (15)
C1—W1—C4—O4	−82 (9)	C11—N3—C15—C14	2.9 (14)
C2—W1—C4—O4	−25 (11)	C13—C14—C15—N3	−3.2 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···C3	0.92 (6)	2.30 (6)	3.154 (8)	154 (5)
N1—H1···C4	0.92 (6)	2.78 (6)	3.317 (9)	119 (5)