Pentacarbonyl(4-phenylpyridine)­tungsten(0) and pentacarbonyl(2-phenylpyridine)chromium(0)

In penta­carbonyl(4-phenyl­pyridine)­tungsten(0), [W­(C₁₁H₉N)(CO)₅], the mol­ecules have mm site symmetry and the pyridine ligand, with m symmetry, is completely planar. In penta­carbonyl(2-phenyl­pyridine)­chromium(0), [Cr(C₁₁­H₉N)(CO)₅], the mol­ecules are in general positions and the phenyl and pyridine rings of the ligand are twisted by 67.7 (3)° with respect to one another by rotation about the C-C bond joining them. In both compounds, the axial M-C_carbonyl bond trans to the M-N_ligand bond is significantly shorter than the equatorial M-C_carbonyl bonds.

Computing details

For both compounds, data collection: P3/R3 software (Nicolet, 1980); cell refinement: P3/R3 software; data reduction: RDNIC (Howie, 1980); program(s) used to solve structure: MULTAN87 (Debaerdemaeker et al., 1987); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

(I) Pentacarbonyl(4-phenylpyridine)tungsten(0)

Crystal data

[W(CO)5(C11H9N)]	F(000) = 904
Mr = 479.09	Dx = 1.987 Mg m^−3
Orthorhombic, Cmcm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2c 2	Cell parameters from 14 reflections
a = 12.538 (4) Å	θ = 12.5–14.0°
b = 16.239 (6) Å	µ = 7.24 mm^−1
c = 7.866 (5) Å	T = 298 K
V = 1601.6 (13) Å^3	Plate, yellow
Z = 4	0.56 × 0.24 × 0.10 mm

Data collection

Nicolet P3 diffractometer	1136 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 30.1°, θmin = 2.1°
θ/2θ scans	h = 0→17
Absorption correction: ψ-scan (North et al., 1968)	k = 0→22
Tmin = 0.188, Tmax = 0.485	l = 0→11
1251 measured reflections	2 standard reflections every 50 reflections
1251 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0369P)^2 + 0.5806P] where P = (Fo^2 + 2Fc^2)/3
1251 reflections	(Δ/σ)max < 0.001
71 parameters	Δρmax = 0.96 e Å^−3
0 restraints	Δρmin = −1.35 e Å^−3

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 2.8 ° 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.

H in calculated positions and refined with a riding model.

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

	x	y	z	Uiso*/Ueq
W	1/2	−0.35738 (2)	1/4	0.04522 (13)
C1	1/2	−0.4778 (6)	1/4	0.062 (2)
O1	1/2	−0.5492 (4)	1/4	0.090 (3)
C2	0.3847 (4)	−0.3608 (3)	0.4323 (7)	0.0590 (10)
O2	0.3193 (3)	−0.3664 (3)	0.5311 (6)	0.0934 (13)
N	1/2	−0.2174 (5)	1/4	0.0487 (15)
C3	0.5890 (6)	−0.1728 (5)	1/4	0.096 (4)
H3	0.6538	−0.2006	1/4	0.115*
C4	0.5908 (6)	−0.0893 (4)	1/4	0.096 (3)
H4	0.6562	−0.0623	1/4	0.115*
C5	1/2	−0.0445 (5)	1/4	0.0472 (18)
C6	1/2	0.0474 (5)	1/4	0.0499 (19)
C7	0.4091 (7)	0.0907 (5)	1/4	0.117 (5)
H7	0.3443	0.0628	1/4	0.140*
C8	0.4094 (9)	0.1774 (6)	1/4	0.134 (5)
H8	0.3451	0.2059	1/4	0.161*
C9	1/2	0.2185 (8)	1/4	0.070 (3)
H9	1/2	0.2758	1/4	0.084*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
W	0.03341 (17)	0.05072 (19)	0.0515 (2)	0	0	0
C1	0.060 (6)	0.062 (6)	0.063 (6)	0	0	0
O1	0.110 (7)	0.056 (4)	0.105 (6)	0	0	0
C2	0.042 (2)	0.071 (2)	0.064 (3)	0.000 (2)	−0.002 (2)	0.003 (2)
O2	0.055 (2)	0.144 (4)	0.082 (3)	−0.006 (2)	0.021 (2)	0.002 (3)
N	0.034 (3)	0.049 (3)	0.062 (4)	0	0	0
C3	0.033 (3)	0.055 (3)	0.201 (11)	0.004 (3)	0	0
C4	0.034 (3)	0.057 (4)	0.196 (11)	−0.006 (3)	0	0
C5	0.038 (4)	0.052 (4)	0.052 (5)	0	0	0
C6	0.055 (5)	0.048 (4)	0.046 (4)	0	0	0
C7	0.044 (4)	0.060 (4)	0.247 (15)	−0.001 (3)	0	0
C8	0.073 (6)	0.054 (4)	0.275 (17)	0.011 (4)	0	0
C9	0.068 (7)	0.058 (5)	0.085 (7)	0	0	0

Geometric parameters (Å, º)

W—C1	1.955 (10)	C4—C5	1.352 (8)
W—C2	2.037 (5)	C4—H4	0.9300
W—C2^i	2.037 (5)	C5—C4^iii	1.352 (8)
W—C2^ii	2.037 (5)	C5—C6	1.492 (10)
W—C2^iii	2.037 (5)	C6—C7^iii	1.338 (9)
W—N	2.273 (8)	C6—C7	1.338 (9)
C1—O1	1.161 (12)	C7—C8	1.408 (13)
C2—O2	1.134 (6)	C7—H7	0.9300
N—C3	1.330 (9)	C8—C9	1.318 (12)
N—C3^iii	1.330 (9)	C8—H8	0.9300
C3—C4	1.356 (12)	C9—C8^iii	1.318 (12)
C3—H3	0.9300	C9—H9	0.9300
C1—W—C2	88.44 (12)	N—C3—H3	118.0
C1—W—C2^i	88.43 (12)	C4—C3—H3	118.0
C2—W—C2^i	90.4 (3)	C5—C4—C3	121.6 (7)
C1—W—C2^ii	88.43 (12)	C5—C4—H4	119.2
C2—W—C2^ii	89.5 (3)	C3—C4—H4	119.2
C2^i—W—C2^ii	176.9 (2)	C4^iii—C5—C4	114.8 (8)
C1—W—C2^iii	88.43 (12)	C4^iii—C5—C6	122.6 (4)
C2—W—C2^iii	176.9 (2)	C4—C5—C6	122.6 (4)
C2^i—W—C2^iii	89.5 (3)	C7^iii—C6—C7	116.7 (9)
C2^ii—W—C2^iii	90.4 (3)	C7^iii—C6—C5	121.7 (5)
C1—W—N	180.0	C7—C6—C5	121.7 (5)
C2—W—N	91.56 (12)	C6—C7—C8	121.5 (8)
C2^i—W—N	91.57 (12)	C6—C7—H7	119.2
C2^ii—W—N	91.57 (12)	C8—C7—H7	119.2
C2^iii—W—N	91.57 (12)	C9—C8—C7	120.6 (9)
O1—C1—W	180.0	C9—C8—H8	119.7
O2—C2—W	176.7 (4)	C7—C8—H8	119.7
C3—N—C3^iii	114.0 (9)	C8^iii—C9—C8	119.1 (12)
C3—N—W	123.0 (4)	C8^iii—C9—H9	120.5
C3^iii—N—W	123.0 (4)	C8—C9—H9	120.5
N—C3—C4	124.0 (7)

Symmetry codes: (i) −x+1, y, z; (ii) x, y, −z+1/2; (iii) −x+1, y, −z+1/2.

(II) Pentacarbonyl(2-phenylpyridine)chromium(0)

Crystal data

[Cr(CO)5(C11H9N)]	F(000) = 704
Mr = 347.24	Dx = 1.498 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.223 (4) Å	Cell parameters from 14 reflections
b = 13.635 (12) Å	θ = 7.5–10.0°
c = 18.170 (9) Å	µ = 0.77 mm^−1
β = 92.60 (5)°	T = 298 K
V = 1540.1 (18) Å^3	Block, yellow_green
Z = 4	0.56 × 0.50 × 0.20 mm

Data collection

Nicolet P3 diffractometer	1781 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 30.1°, θmin = 1.9°
θ/2θ scans	h = 0→8
Absorption correction: part of the refinement model (ΔF) (XABS 2.0; Parkin et al., 1995)	k = 0→19
Tmin = 0.691, Tmax = 0.858	l = −25→25
4494 measured reflections	2 standard reflections every 50 reflections
4494 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.087	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.157	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.031P)^2 + 1.0286P] where P = (Fo^2 + 2Fc^2)/3
4494 reflections	(Δ/σ)max < 0.001
208 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.42 e Å^−3

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 2.8 ° 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.

H in calculated positions and refined with a riding model.

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

	x	y	z	Uiso*/Ueq
Cr	0.67728 (13)	0.21822 (6)	0.96565 (4)	0.0392 (2)
C1	0.5272 (9)	0.2078 (4)	1.0490 (3)	0.0488 (13)
O1	0.4331 (7)	0.2049 (3)	1.1016 (2)	0.0712 (12)
C2	0.4348 (9)	0.2972 (4)	0.9328 (3)	0.0435 (13)
O2	0.2820 (6)	0.3408 (3)	0.9239 (2)	0.0680 (12)
C3	0.8235 (9)	0.3279 (4)	1.0083 (3)	0.0458 (13)
O3	0.9039 (7)	0.3901 (3)	1.0406 (2)	0.0767 (13)
C4	0.8868 (10)	0.1397 (4)	1.0162 (3)	0.0539 (15)
O4	0.9978 (7)	0.0937 (3)	1.0533 (2)	0.0823 (14)
C5	0.5366 (9)	0.1024 (4)	0.9290 (3)	0.0466 (13)
O5	0.4529 (7)	0.0328 (3)	0.9104 (2)	0.0744 (13)
N	0.8517 (6)	0.2258 (3)	0.86214 (18)	0.0366 (9)
C6	0.9806 (8)	0.1488 (4)	0.8489 (3)	0.0474 (13)
H6	0.9952	0.1009	0.8852	0.057*
C7	1.0911 (9)	0.1358 (4)	0.7866 (3)	0.0554 (15)
H7	1.1795	0.0815	0.7812	0.066*
C8	1.0679 (10)	0.2052 (4)	0.7320 (3)	0.0638 (16)
H8	1.1382	0.1982	0.6882	0.077*
C9	0.9393 (9)	0.2851 (4)	0.7432 (3)	0.0529 (14)
H9	0.9237	0.3335	0.7072	0.063*
C10	0.8331 (7)	0.2935 (3)	0.8081 (2)	0.0369 (11)
C11	0.6975 (8)	0.3824 (3)	0.8168 (2)	0.0388 (11)
C12	0.5166 (9)	0.3941 (4)	0.7709 (3)	0.0548 (15)
H12	0.4799	0.3462	0.7361	0.066*
C13	0.3905 (10)	0.4761 (5)	0.7762 (3)	0.0693 (18)
H13	0.2682	0.4830	0.7453	0.083*
C14	0.4426 (10)	0.5478 (4)	0.8265 (3)	0.0611 (16)
H14	0.3558	0.6029	0.8303	0.073*
C15	0.6250 (10)	0.5374 (4)	0.8716 (3)	0.0560 (15)
H15	0.6617	0.5858	0.9059	0.067*
C16	0.7531 (8)	0.4561 (3)	0.8661 (2)	0.0425 (12)
H16	0.8781	0.4506	0.8959	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cr	0.0399 (5)	0.0402 (4)	0.0374 (4)	−0.0021 (4)	0.0022 (3)	−0.0002 (4)
C1	0.057 (4)	0.047 (3)	0.043 (3)	0.002 (3)	0.007 (3)	0.002 (3)
O1	0.087 (3)	0.073 (3)	0.056 (2)	0.001 (3)	0.028 (2)	0.003 (2)
C2	0.036 (3)	0.050 (3)	0.044 (3)	−0.016 (3)	0.001 (2)	0.004 (2)
O2	0.038 (2)	0.078 (3)	0.088 (3)	0.012 (2)	0.009 (2)	0.013 (2)
C3	0.045 (3)	0.055 (3)	0.038 (3)	−0.001 (3)	0.004 (3)	−0.001 (2)
O3	0.079 (3)	0.081 (3)	0.070 (3)	−0.030 (3)	0.003 (2)	−0.023 (2)
C4	0.057 (4)	0.049 (3)	0.055 (3)	0.004 (3)	−0.004 (3)	0.003 (3)
O4	0.070 (3)	0.085 (3)	0.089 (3)	0.018 (3)	−0.025 (3)	0.012 (3)
C5	0.051 (4)	0.045 (3)	0.044 (3)	0.001 (3)	−0.005 (3)	0.002 (2)
O5	0.084 (3)	0.050 (2)	0.087 (3)	−0.018 (2)	−0.014 (3)	−0.007 (2)
N	0.035 (2)	0.039 (2)	0.0358 (19)	−0.003 (2)	0.0029 (17)	−0.0062 (19)
C6	0.044 (4)	0.040 (3)	0.059 (3)	0.002 (3)	0.007 (3)	−0.001 (3)
C7	0.045 (4)	0.058 (4)	0.064 (3)	0.011 (3)	0.013 (3)	−0.013 (3)
C8	0.062 (4)	0.073 (4)	0.058 (3)	0.002 (4)	0.024 (3)	−0.020 (3)
C9	0.062 (4)	0.056 (3)	0.043 (3)	−0.005 (3)	0.018 (3)	−0.004 (3)
C10	0.028 (3)	0.046 (3)	0.037 (2)	−0.011 (2)	0.001 (2)	−0.006 (2)
C11	0.044 (3)	0.037 (3)	0.035 (2)	−0.001 (3)	0.003 (2)	0.003 (2)
C12	0.052 (4)	0.062 (4)	0.050 (3)	−0.001 (3)	0.000 (3)	−0.003 (3)
C13	0.061 (5)	0.084 (5)	0.061 (4)	0.014 (4)	−0.015 (3)	0.010 (3)
C14	0.056 (4)	0.058 (4)	0.071 (4)	0.016 (3)	0.014 (3)	0.019 (3)
C15	0.066 (4)	0.043 (3)	0.060 (3)	0.000 (3)	0.017 (3)	0.001 (3)
C16	0.046 (3)	0.040 (3)	0.041 (3)	−0.007 (3)	−0.001 (2)	0.004 (2)

Geometric parameters (Å, º)

Cr—C1	1.821 (5)	C8—C9	1.372 (7)
Cr—C4	1.892 (6)	C8—H8	0.9300
Cr—C3	1.897 (6)	C9—C10	1.383 (6)
Cr—C5	1.910 (6)	C9—H9	0.9300
Cr—C2	1.926 (6)	C10—C11	1.489 (6)
Cr—N	2.216 (4)	C11—C12	1.380 (7)
C1—O1	1.143 (5)	C11—C16	1.380 (6)
C2—O2	1.127 (6)	C12—C13	1.372 (7)
C3—O3	1.135 (5)	C12—H12	0.9300
C4—O4	1.133 (6)	C13—C14	1.366 (7)
C5—O5	1.128 (5)	C13—H13	0.9300
N—C10	1.349 (5)	C14—C15	1.376 (7)
N—C6	1.349 (6)	C14—H14	0.9300
C6—C7	1.362 (6)	C15—C16	1.371 (6)
C6—H6	0.9300	C15—H15	0.9300
C7—C8	1.374 (7)	C16—H16	0.9300
C7—H7	0.9300
C1—Cr—C4	85.4 (2)	C8—C7—H7	121.0
C1—Cr—C3	88.7 (2)	C9—C8—C7	118.9 (5)
C4—Cr—C3	86.6 (2)	C9—C8—H8	120.6
C1—Cr—C5	88.9 (2)	C7—C8—H8	120.6
C4—Cr—C5	89.8 (2)	C8—C9—C10	119.8 (5)
C3—Cr—C5	175.8 (2)	C8—C9—H9	120.1
C1—Cr—C2	83.0 (2)	C10—C9—H9	120.1
C4—Cr—C2	168.3 (2)	N—C10—C9	122.4 (5)
C3—Cr—C2	92.3 (2)	N—C10—C11	120.7 (4)
C5—Cr—C2	90.8 (2)	C9—C10—C11	116.9 (4)
C1—Cr—N	177.6 (2)	C12—C11—C16	118.8 (5)
C4—Cr—N	94.9 (2)	C12—C11—C10	118.7 (4)
C3—Cr—N	93.74 (18)	C16—C11—C10	122.3 (5)
C5—Cr—N	88.69 (18)	C13—C12—C11	120.3 (5)
C2—Cr—N	96.75 (18)	C13—C12—H12	119.9
O1—C1—Cr	177.5 (5)	C11—C12—H12	119.9
O2—C2—Cr	169.5 (4)	C14—C13—C12	120.7 (6)
O3—C3—Cr	172.9 (5)	C14—C13—H13	119.6
O4—C4—Cr	172.1 (5)	C12—C13—H13	119.6
O5—C5—Cr	177.0 (5)	C13—C14—C15	119.2 (6)
C10—N—C6	115.8 (4)	C13—C14—H14	120.4
C10—N—Cr	128.3 (3)	C15—C14—H14	120.4
C6—N—Cr	115.7 (3)	C16—C15—C14	120.5 (5)
N—C6—C7	125.2 (5)	C16—C15—H15	119.8
N—C6—H6	117.4	C14—C15—H15	119.8
C7—C6—H6	117.4	C15—C16—C11	120.4 (5)
C6—C7—C8	118.0 (5)	C15—C16—H16	119.8
C6—C7—H7	121.0	C11—C16—H16	119.8
C1—Cr—C2—O2	2 (3)	C6—N—C10—C9	−0.1 (6)
C4—Cr—C2—O2	−2 (3)	Cr—N—C10—C9	−174.5 (3)
C3—Cr—C2—O2	−86 (3)	C6—N—C10—C11	−179.2 (4)
C5—Cr—C2—O2	91 (3)	Cr—N—C10—C11	6.4 (6)
N—Cr—C2—O2	179 (3)	C8—C9—C10—N	0.5 (7)
C4—Cr—N—C10	−157.6 (4)	C8—C9—C10—C11	179.6 (4)
C3—Cr—N—C10	−70.7 (4)	N—C10—C11—C12	−114.7 (5)
C5—Cr—N—C10	112.8 (4)	C9—C10—C11—C12	66.2 (6)
C2—Cr—N—C10	22.1 (4)	N—C10—C11—C16	69.1 (6)
C4—Cr—N—C6	28.1 (4)	C9—C10—C11—C16	−109.9 (5)
C3—Cr—N—C6	114.9 (4)	C16—C11—C12—C13	−2.3 (8)
C5—Cr—N—C6	−61.6 (4)	C10—C11—C12—C13	−178.6 (5)
C2—Cr—N—C6	−152.3 (3)	C11—C12—C13—C14	0.6 (9)
C10—N—C6—C7	0.5 (7)	C12—C13—C14—C15	0.6 (9)
Cr—N—C6—C7	175.6 (4)	C13—C14—C15—C16	0.0 (8)
N—C6—C7—C8	−1.1 (9)	C14—C15—C16—C11	−1.7 (7)
C6—C7—C8—C9	1.4 (8)	C12—C11—C16—C15	2.9 (7)
C7—C8—C9—C10	−1.1 (8)	C10—C11—C16—C15	179.0 (4)