Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101009593/fg1636sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009593/fg1636Isup2.hkl |
CCDC reference: 174802
fac-Re(CO)3(dpk.oxime)Cl was synthesized as described earlier by Bakir (1999). The dimethyl sulfoxide used for the crystallization was reagent grade and thoroughly deoxygenated prior to use. When fac-Re(CO)3(dpk.oxime)Cl was allowed to stand in dimethyl sulfoxide for several days at room temperature, yellow crystals of (I) were obtained.
H atoms were assigned by assuming idealized geometry, with C—H = 0.96 and 0.93 Å for the aliphatic and aromatic H atoms, respectively, and O—H = 0.82 Å. In the final refinement, seven peaks with residual electron density greater than 1 e Å-3 were seen. Six are ghosts of the Re atom and one is due to the non-bonding pair of electrons on atom N3 of the oxime moiety. The deepest hole, with an electron density of -1.767 e Å-3, was observed 0.91 Å from Re.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[ReCl(C11H9N3O)(CO)3]·C2H6OS | Z = 2 |
Mr = 583.02 | F(000) = 560 |
Triclinic, P1 | Dx = 1.986 Mg m−3 |
a = 9.257 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.483 (2) Å | Cell parameters from 21 reflections |
c = 10.6838 (17) Å | θ = 4.9–22.0° |
α = 103.807 (12)° | µ = 6.51 mm−1 |
β = 92.84 (3)° | T = 298 K |
γ = 103.09 (5)° | Irregular, yellow |
V = 974.7 (7) Å3 | 0.22 × 0.21 × 0.20 mm |
Bruker P4 diffractometer | 3207 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
2θ/ω scans | h = −10→1 |
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968) | k = −11→12 |
Tmin = 0.213, Tmax = 0.272 | l = −12→12 |
4089 measured reflections | 3 standard reflections every 97 reflections |
3399 independent reflections | intensity decay: none |
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) = 0.096 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.08P)2] where P = (Fo2 + 2Fc2)/3 |
3399 reflections | (Δ/σ)max = 0.002 |
244 parameters | Δρmax = 1.57 e Å−3 |
0 restraints | Δρmin = −1.77 e Å−3 |
[ReCl(C11H9N3O)(CO)3]·C2H6OS | γ = 103.09 (5)° |
Mr = 583.02 | V = 974.7 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.257 (6) Å | Mo Kα radiation |
b = 10.483 (2) Å | µ = 6.51 mm−1 |
c = 10.6838 (17) Å | T = 298 K |
α = 103.807 (12)° | 0.22 × 0.21 × 0.20 mm |
β = 92.84 (3)° |
Bruker P4 diffractometer | 3207 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968) | Rint = 0.026 |
Tmin = 0.213, Tmax = 0.272 | 3 standard reflections every 97 reflections |
4089 measured reflections | intensity decay: none |
3399 independent reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.57 e Å−3 |
3399 reflections | Δρmin = −1.77 e Å−3 |
244 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Re1 | 0.63015 (2) | 0.742833 (18) | 0.738902 (17) | 0.03219 (12) | |
Cl1 | 0.6008 (2) | 0.97255 (17) | 0.83720 (18) | 0.0510 (4) | |
C1 | 0.6381 (8) | 0.7808 (7) | 0.5712 (7) | 0.0496 (16) | |
C2 | 0.4177 (7) | 0.6718 (7) | 0.7033 (6) | 0.0432 (14) | |
C3 | 0.6479 (7) | 0.5668 (6) | 0.6589 (6) | 0.0410 (13) | |
N1 | 0.6380 (6) | 0.7077 (5) | 0.9346 (5) | 0.0358 (10) | |
N2 | 0.8713 (5) | 0.8274 (5) | 0.8031 (5) | 0.0355 (10) | |
O1 | 0.6457 (8) | 0.8021 (7) | 0.4711 (5) | 0.0732 (16) | |
O2 | 0.2899 (5) | 0.6249 (6) | 0.6846 (6) | 0.0686 (15) | |
O3 | 0.6528 (7) | 0.4591 (5) | 0.6053 (6) | 0.0673 (15) | |
N3 | 0.9199 (9) | 0.5250 (6) | 0.8431 (7) | 0.076 (2) | |
O4 | 0.8419 (7) | 0.4130 (7) | 0.8718 (6) | 0.0758 (16) | |
H4 | 0.8667 | 0.3466 | 0.8298 | 0.098* | |
C11 | 0.5345 (7) | 0.7358 (7) | 1.0150 (6) | 0.0463 (14) | |
H11 | 0.4662 | 0.7808 | 0.9912 | 0.043* | |
C12 | 0.5268 (9) | 0.6997 (8) | 1.1318 (7) | 0.0565 (17) | |
H12 | 0.4556 | 0.7212 | 1.1861 | 0.078* | |
C13 | 0.6268 (9) | 0.6318 (8) | 1.1652 (7) | 0.0610 (19) | |
H13 | 0.6219 | 0.6043 | 1.2418 | 0.103* | |
C14 | 0.7361 (8) | 0.6038 (6) | 1.0844 (6) | 0.0495 (15) | |
H14 | 0.8052 | 0.5588 | 1.1066 | 0.076* | |
C15 | 0.7388 (6) | 0.6446 (5) | 0.9712 (6) | 0.0372 (12) | |
C4 | 0.8623 (7) | 0.6319 (6) | 0.8878 (6) | 0.0390 (12) | |
C21 | 0.9462 (7) | 0.9455 (6) | 0.7831 (7) | 0.0459 (14) | |
H21 | 0.8926 | 0.9955 | 0.7470 | 0.065* | |
C22 | 1.0989 (8) | 0.9966 (7) | 0.8137 (7) | 0.0543 (17) | |
H22 | 1.1466 | 1.0787 | 0.7984 | 0.064* | |
C23 | 1.1788 (7) | 0.9222 (8) | 0.8676 (7) | 0.0559 (17) | |
H23 | 1.2817 | 0.9523 | 0.8880 | 0.054* | |
C24 | 1.1014 (7) | 0.8019 (7) | 0.8902 (6) | 0.0459 (14) | |
H24 | 1.1526 | 0.7502 | 0.9264 | 0.059* | |
C25 | 0.9485 (6) | 0.7581 (5) | 0.8592 (5) | 0.0358 (11) | |
O5 | 0.9578 (7) | 0.2301 (6) | 0.7159 (6) | 0.0716 (15) | |
S1 | 0.9306 (3) | 0.1820 (2) | 0.5714 (2) | 0.0665 (5) | |
C5 | 0.9896 (11) | 0.3308 (11) | 0.5133 (11) | 0.085 (3) | |
H5A | 1.0965 | 0.3601 | 0.5256 | 0.127* | |
H5B | 0.9482 | 0.4015 | 0.5605 | 0.127* | |
H5C | 0.9556 | 0.3101 | 0.4227 | 0.127* | |
C6 | 0.7327 (11) | 0.1536 (10) | 0.5350 (12) | 0.088 (3) | |
H6A | 0.6827 | 0.0729 | 0.5579 | 0.132* | |
H6B | 0.7094 | 0.1431 | 0.4440 | 0.132* | |
H6C | 0.7001 | 0.2295 | 0.5837 | 0.132* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Re1 | 0.03168 (16) | 0.03600 (17) | 0.02672 (16) | 0.00929 (10) | 0.00011 (10) | 0.00361 (10) |
Cl1 | 0.0540 (9) | 0.0466 (8) | 0.0527 (9) | 0.0220 (7) | 0.0067 (7) | 0.0043 (7) |
C1 | 0.053 (4) | 0.040 (3) | 0.052 (4) | 0.010 (3) | 0.001 (3) | 0.007 (3) |
C2 | 0.033 (3) | 0.057 (4) | 0.038 (3) | 0.015 (3) | 0.000 (2) | 0.007 (3) |
C3 | 0.040 (3) | 0.044 (3) | 0.034 (3) | 0.010 (3) | −0.001 (2) | 0.001 (3) |
N1 | 0.037 (3) | 0.037 (2) | 0.030 (2) | 0.005 (2) | 0.000 (2) | 0.0076 (19) |
N2 | 0.030 (2) | 0.035 (2) | 0.040 (3) | 0.0075 (19) | 0.005 (2) | 0.007 (2) |
O1 | 0.098 (4) | 0.089 (4) | 0.034 (3) | 0.016 (3) | 0.003 (3) | 0.025 (3) |
O2 | 0.036 (3) | 0.090 (4) | 0.071 (4) | 0.003 (3) | −0.003 (2) | 0.018 (3) |
O3 | 0.082 (4) | 0.053 (3) | 0.060 (3) | 0.026 (3) | −0.007 (3) | −0.004 (3) |
N3 | 0.106 (5) | 0.036 (3) | 0.072 (4) | 0.001 (3) | −0.051 (4) | 0.018 (3) |
O4 | 0.073 (4) | 0.079 (4) | 0.079 (4) | 0.023 (3) | 0.010 (3) | 0.024 (3) |
C11 | 0.044 (3) | 0.050 (3) | 0.039 (3) | 0.008 (3) | 0.009 (3) | 0.001 (3) |
C12 | 0.058 (4) | 0.061 (4) | 0.044 (4) | 0.004 (3) | 0.019 (3) | 0.008 (3) |
C13 | 0.079 (5) | 0.057 (4) | 0.041 (4) | 0.001 (4) | 0.005 (4) | 0.018 (3) |
C14 | 0.059 (4) | 0.045 (3) | 0.039 (3) | 0.000 (3) | −0.003 (3) | 0.014 (3) |
C15 | 0.034 (3) | 0.032 (3) | 0.039 (3) | 0.002 (2) | −0.005 (2) | 0.003 (2) |
C4 | 0.044 (3) | 0.038 (3) | 0.038 (3) | 0.018 (2) | 0.000 (2) | 0.007 (2) |
C21 | 0.043 (3) | 0.035 (3) | 0.057 (4) | 0.006 (3) | 0.003 (3) | 0.010 (3) |
C22 | 0.044 (4) | 0.045 (3) | 0.061 (4) | −0.006 (3) | 0.001 (3) | 0.007 (3) |
C23 | 0.033 (3) | 0.066 (4) | 0.058 (4) | 0.003 (3) | −0.004 (3) | 0.007 (3) |
C24 | 0.039 (3) | 0.055 (4) | 0.043 (3) | 0.018 (3) | −0.005 (3) | 0.007 (3) |
C25 | 0.036 (3) | 0.036 (3) | 0.035 (3) | 0.013 (2) | 0.001 (2) | 0.005 (2) |
O5 | 0.098 (4) | 0.059 (3) | 0.066 (3) | 0.036 (3) | 0.004 (3) | 0.018 (3) |
S1 | 0.0816 (13) | 0.0509 (10) | 0.0718 (13) | 0.0333 (10) | 0.0053 (10) | 0.0094 (9) |
C5 | 0.076 (6) | 0.089 (6) | 0.103 (8) | 0.021 (5) | 0.025 (5) | 0.047 (6) |
C6 | 0.085 (7) | 0.060 (5) | 0.112 (9) | 0.007 (5) | −0.010 (6) | 0.023 (5) |
Re1—C3 | 1.888 (6) | C14—C15 | 1.375 (8) |
Re1—C2 | 1.922 (6) | C14—H14 | 0.9300 |
Re1—C1 | 1.927 (8) | C15—C4 | 1.493 (8) |
Re1—N1 | 2.208 (5) | C4—C25 | 1.490 (8) |
Re1—N2 | 2.214 (5) | C21—C22 | 1.386 (9) |
Re1—Cl1 | 2.4685 (17) | C21—H21 | 0.9300 |
C1—O1 | 1.145 (9) | C22—C23 | 1.385 (11) |
C2—O2 | 1.161 (8) | C22—H22 | 0.9300 |
C3—O3 | 1.149 (8) | C23—C24 | 1.384 (10) |
N1—C15 | 1.352 (8) | C23—H23 | 0.9300 |
N1—C11 | 1.354 (8) | C24—C25 | 1.383 (8) |
N2—C25 | 1.340 (7) | C24—H24 | 0.9300 |
N2—C21 | 1.346 (8) | O5—S1 | 1.494 (6) |
N3—O4 | 1.343 (9) | S1—C6 | 1.795 (10) |
N3—C4 | 1.345 (9) | S1—C5 | 1.796 (9) |
O4—H4 | 0.8200 | C6—H6A | 0.9600 |
C11—C12 | 1.388 (10) | C6—H6B | 0.9600 |
C11—H11 | 0.9300 | C6—H6C | 0.9600 |
C12—C13 | 1.370 (12) | C5—H5A | 0.9600 |
C12—H12 | 0.9300 | C5—H5B | 0.9600 |
C13—C14 | 1.399 (11) | C5—H5C | 0.9600 |
C13—H13 | 0.9300 | ||
C3—Re1—C2 | 87.1 (3) | C13—C14—H14 | 120.8 |
C3—Re1—C1 | 87.9 (3) | N1—C15—C14 | 122.3 (6) |
C2—Re1—C1 | 90.4 (3) | N1—C15—C4 | 116.3 (5) |
C3—Re1—N1 | 93.0 (2) | C14—C15—C4 | 121.1 (5) |
C2—Re1—N1 | 93.7 (2) | N3—C4—C25 | 112.7 (6) |
C1—Re1—N1 | 175.9 (2) | N3—C4—C15 | 129.9 (6) |
C3—Re1—N2 | 95.2 (2) | C25—C4—C15 | 117.1 (5) |
C2—Re1—N2 | 173.6 (2) | N2—C21—C22 | 123.4 (6) |
C1—Re1—N2 | 95.6 (3) | N2—C21—H21 | 118.3 |
N1—Re1—N2 | 80.27 (19) | C22—C21—H21 | 118.3 |
C3—Re1—Cl1 | 178.04 (19) | C23—C22—C21 | 118.3 (6) |
C2—Re1—Cl1 | 91.5 (2) | C23—C22—H22 | 120.8 |
C1—Re1—Cl1 | 90.7 (2) | C21—C22—H22 | 120.8 |
N1—Re1—Cl1 | 88.52 (14) | C24—C23—C22 | 118.3 (6) |
N2—Re1—Cl1 | 86.22 (14) | C24—C23—H23 | 120.9 |
O1—C1—Re1 | 178.4 (7) | C22—C23—H23 | 120.9 |
O2—C2—Re1 | 177.1 (6) | C25—C24—C23 | 120.3 (6) |
O3—C3—Re1 | 176.4 (6) | C25—C24—H24 | 119.9 |
C15—N1—C11 | 118.4 (5) | C23—C24—H24 | 119.9 |
C15—N1—Re1 | 119.8 (4) | N2—C25—C24 | 121.7 (5) |
C11—N1—Re1 | 121.4 (4) | N2—C25—C4 | 117.2 (5) |
C25—N2—C21 | 118.0 (5) | C24—C25—C4 | 121.2 (5) |
C25—N2—Re1 | 120.1 (4) | O5—S1—C6 | 104.8 (5) |
C21—N2—Re1 | 121.9 (4) | O5—S1—C5 | 105.5 (5) |
O4—N3—C4 | 111.6 (7) | C6—S1—C5 | 98.6 (5) |
N3—O4—H4 | 109.5 | S1—C6—H6A | 109.5 |
N1—C11—C12 | 122.3 (7) | S1—C6—H6B | 109.5 |
N1—C11—H11 | 118.9 | H6A—C6—H6B | 109.5 |
C12—C11—H11 | 118.9 | S1—C6—H6C | 109.5 |
C13—C12—C11 | 118.4 (7) | H6A—C6—H6C | 109.5 |
C13—C12—H12 | 120.8 | H6B—C6—H6C | 109.5 |
C11—C12—H12 | 120.8 | S1—C5—H5A | 109.5 |
C12—C13—C14 | 120.1 (6) | S1—C5—H5B | 109.5 |
C12—C13—H13 | 120.0 | H5A—C5—H5B | 109.5 |
C14—C13—H13 | 120.0 | S1—C5—H5C | 109.5 |
C15—C14—C13 | 118.3 (7) | H5A—C5—H5C | 109.5 |
C15—C14—H14 | 120.8 | H5B—C5—H5C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O5 | 0.82 | 1.88 | 2.681 (9) | 164 |
C6—H6C···O3 | 0.96 | 2.51 | 3.369 (12) | 150 |
C21—H21···O5i | 0.93 | 2.50 | 3.211 (9) | 133 |
Symmetry code: (i) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [ReCl(C11H9N3O)(CO)3]·C2H6OS |
Mr | 583.02 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 9.257 (6), 10.483 (2), 10.6838 (17) |
α, β, γ (°) | 103.807 (12), 92.84 (3), 103.09 (5) |
V (Å3) | 974.7 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 6.51 |
Crystal size (mm) | 0.22 × 0.21 × 0.20 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | Empirical (using intensity measurements) via ψ scan (North et al., 1968) |
Tmin, Tmax | 0.213, 0.272 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4089, 3399, 3207 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.096, 1.03 |
No. of reflections | 3399 |
No. of parameters | 244 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.57, −1.77 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
Re1—C3 | 1.888 (6) | Re1—N2 | 2.214 (5) |
Re1—C2 | 1.922 (6) | Re1—Cl1 | 2.4685 (17) |
Re1—C1 | 1.927 (8) | N3—O4 | 1.343 (9) |
Re1—N1 | 2.208 (5) | N3—C4 | 1.345 (9) |
C3—Re1—C2 | 87.1 (3) | C1—Re1—N2 | 95.6 (3) |
C3—Re1—C1 | 87.9 (3) | N1—Re1—N2 | 80.27 (19) |
C2—Re1—C1 | 90.4 (3) | C3—Re1—Cl1 | 178.04 (19) |
C3—Re1—N1 | 93.0 (2) | O4—N3—C4 | 111.6 (7) |
C1—Re1—N1 | 175.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O5 | 0.82 | 1.88 | 2.681 (9) | 164 |
C6—H6C···O3 | 0.96 | 2.51 | 3.369 (12) | 150 |
C21—H21···O5i | 0.93 | 2.50 | 3.211 (9) | 133 |
Symmetry code: (i) x, y+1, z. |
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Oximes and their metal complexes have attracted considerable research interest due to their rich physico-chemical properties, reactivity patterns and applications in many important chemical processes (Adams, 2000; Kuznetsov et al., 2000). Although a variety of metal complexes of oximes have been reported, complexes of dipyridyl and dipyridyl-like oximes are scarce (Adams, 2000; Bakir, 1999). Eight structures have been reported for the coordination of di-2-pyridyl ketone oxime (dpk.oxime) (Goher & Mautner, 1999; Jensen et al., 1997; Psomas et al., 1998; Schlemper et al., 1990; Stemmler et al., 1995; Sommerer et al., 1995, 1997). In these reports, dpk.oxime coordinated to the metal centre in a monodentate mode using an N atom of one pyridyl ring, as in [Ag(dpk.oxime)]NO2 (Sommerer et al., 1995), in a bidentate mode using an N atom of one pyridyl ring and the N atom of the oxime moiety, as in [Co(dpkO,OH)(dpk.oxime)]NO2·H2O [dpkO,OH is hydroxy-di-(2-pyridyl)methoxide; Jensen et al., 1997], and in a tridentate mode using combined monodentate and bidentate binding, as in the case of the CuI-dimer [CuCl(dpk.oxime)·H2O]2 (Goher & Mautner, 1999). No evidence for N,N-dipyridyl coordination of dpk.oxime has been noted to date.
The synthesis and optical and electrochemical behaviour of rhenium-tricarbonyl compounds of pyridyl N,N-coordinated di-2-pyridyl ketone (dpk) and its oxime (dpk.oxime) and hydrazone (dpknph), where dpknph is di-2-pyridyl ketone-p-nitrophenyl hydrazone, have previously been reported by us (Bakir, 1997; Bakir & McKenzie, 1997a,b; Bakir, 1999; Bakir & Abdur-Rashid, 1999; Bakir et al., 2000). These compounds exhibit rich electro- and optical properties and their electrochemical and optical sensing properties have been reported. In the case of dpk.oxime, electrochemical mechanisms for the oxidation and reduction of free and rhenium-coordinated dpk.oxime have been reported (Bakir, 1999). In this report, the structure of the dimethyl sulfoxide solvated title complex, (I), is described and compared with the structures of the rhenium compounds of α-diimine ligands and hydroxy-di-(2-pyridyl)methoxide (dpkO,OH). \sch
The molecular structure of (I) is shown in Fig. 1, and selected bond distances and angles are given in Table 1. Two N atoms from the pyridyl rings, three C atoms from the carbonyl groups and one Cl atom occupy the coordinated site. The three carbonyl groups are in facial positions and are orthogonal, with an average C—Re—C angle of 88.47 (3)°. The Re—C bond distances of the carbonyl groups (Table 1), with an average value of 1.91 (7) Å, are normal and are similar to those reported for a variety of rhenium-carbonyl compounds of the type fac-Re(CO)3(L—L)X, where L—L is an α-diimine ligand (Xue et al., 1998; Horn & Snow, 1980). For example, in fac-Re(CO)3(bipy)(OPOF2), the average Re—C distance is 1.91 (2) Å and the average C—Re—C angle is 87.2 (8)° (Horn & Snow, 1980). The distortion from octahedral geometry in (I) is due to the constraints associated with the binding of the dpk.oxime moiety, as apparent from its N—N bite angle of 80.27 (19)°. The coordinated dpk.oxime forms a six-membered Re1/N1/C15/C4/C25/N2 metallocyclic ring, with the pyridine rings in a butterfly formation. This arrangement leaves one pyridine ring in the equatorial plane, the other in the axial plane and the oxime moiety exposed for potential intermolecular interaction. The N—N bite angle of the coordinated dpk.oxime moiety in (I) is smaller than the value of 84.6 (4)° reported for ReOCl2(dpkO,OH) (Gerber et al., 1995, 1993) and larger than the value of 74.3 (2)° in fac-Re(CO)3(bipy)(OPOF2) (Horn & Snow, 1980). These results show that the five-membered Re/N1/C15/C25/N2 rings of α-diimine ligands are more constrained than the six-membered Re1/N1/C15/C4/C25/N2 ring of dpk.oxime.
The packing of the molecules shows stacks of anti-parallel tapes of (I), with a network of hydrogen bonds between the dimethyl sulfoxide solvate and adjacent fac-Re(CO)3(dpk.oxime)Cl molecules (Fig. 2 and Table 2). The bond distances and angles of the hydrogen bonds are of the same order as those observed in a variety of compounds containing such bonds (Gerber et al., 1995, 1997?; Glusker et al., 1994; Batchelor, et al., 2000).
Owing to their rich physico-chemical properties and reactivity patterns, work is in progress to prepare a variety of metal compounds of dpk.oxime, to explore their solid state structures and electro-optical properties.