Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100004728/qa0259sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100004728/qa0259Isup2.hkl |
CCDC reference: 145629
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.
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.
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.
[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) Å3 | Block, green yellow |
Z = 4 | 0.52 × 0.26 × 0.26 mm |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.082 | Calculated w = 1/[σ2(Fo2) + (0.0367P)2 + 0.3862P] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: heavy-atom method | Extinction coefficient: 0.0038 (2) |
[W(C10H9N3)(CO)5] | V = 1619 (3) Å3 |
Mr = 495.10 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.812 (11) Å | µ = 7.17 mm−1 |
b = 7.185 (7) Å | T = 298 K |
c = 17.835 (15) Å | 0.52 × 0.26 × 0.26 mm |
β = 99.61 (7)° |
Nicolet P3 diffractometer | 2799 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.041 |
Tmin = 0.071, Tmax = 0.151 | 2 standard reflections every 50 reflections |
3904 measured reflections | intensity decay: random variation +−2% |
3748 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.99 e Å−3 |
3748 reflections | Δρmin = −0.60 e Å−3 |
222 parameters |
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 Uiso 1.2 x Uequ of the C to which they were attached whereas the amino H (H1) was refined isotropically in the normal manner. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
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) |
Experimental details
Crystal data | |
Chemical formula | [W(C10H9N3)(CO)5] |
Mr | 495.10 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 12.812 (11), 7.185 (7), 17.835 (15) |
β (°) | 99.61 (7) |
V (Å3) | 1619 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.17 |
Crystal size (mm) | 0.52 × 0.26 × 0.26 |
Data collection | |
Diffractometer | Nicolet P3 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.071, 0.151 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3904, 3748, 2799 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.082, 1.02 |
No. of reflections | 3748 |
No. of parameters | 222 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.99, −0.60 |
Computer programs: Nicolet P3 Software (Nicolet, 1980), RDNIC (Howie, 1980), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXL97.
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) |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
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.