Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101013890/da1194sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101013890/da1194Isup2.hkl |
CCDC reference: 179248
For related literature, see: Bakir & Abdur-Rashid (1999); Bakir et al. (2000); Batchelor et al. (2000); Bosshard et al. (1995); Czerney & Grummt (1997); Drain et al. (2001); Gerber et al. (1993, 1995); Gibson et al. (1998); Glusker et al. (1994); Horn & Snow (1980); Luo et al. (2001); Pan et al. (1997); Prasad & Williams (1991); Sherrington & Taskinen (2001); Uppadine et al. (2001); Vishweshwar et al. (2001); Williams (1993); Xue et al. (1998); Yam et al. (1995, 1998).
fac-[ReCl(dpknph)(CO)3] was synthesized as described previously (Bakir & Abdur-Rashid, 1999). Reagent grade DMSO used for the crystallization was thoroughly deoxygenated prior to use. When fac-[ReCl(dpknph)(CO)3] was allowed to stand in DMSO for several days at room temperature, yellow–green crystals of (I) were obtained. A single-crystal was selected and mounted on a glass fiber with epoxy cement and used for data collection.
The H atom involved in the amine-H to solvent O hydrogen bond was refined without contraints. All other H-atom positions were assigned by assuming idealized geometry with C—H distances of 0.96 and 0.93 Å for aliphatic and aromatic H atoms, respectively. The DMSO molecule is slightly disordered such that the S atom exists in two different positions; the major orientation has an occupancy of 0.847 (4).
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[ReCl(C17H13N5O2)(CO)3]·C2H6OS | Dx = 1.799 Mg m−3 |
Mr = 703.13 | Melting point: not measured K |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 21.104 (2) Å | Cell parameters from 30 reflections |
b = 14.486 (2) Å | θ = 10.7–22.4° |
c = 18.962 (2) Å | µ = 4.91 mm−1 |
β = 116.408 (7)° | T = 298 K |
V = 5192.0 (10) Å3 | Irregular, yellow-green |
Z = 8 | 0.42 × 0.38 × 0.34 mm |
F(000) = 2736 |
Bruker P4 diffractometer | 3969 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
Graphite monochromator | θmax = 25.0°, θmin = 1.8° |
2θ/ω scans | h = −1→25 |
Absorption correction: ψ scan (XSCANS; Bruker, 1996) | k = −1→17 |
Tmin = 0.157, Tmax = 0.188 | l = −22→20 |
5397 measured reflections | 3 standard reflections every 97 reflections |
4562 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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.026P)2 + 8.P] where P = (Fo2 + 2Fc2)/3 |
4562 reflections | (Δ/σ)max = 0.002 |
339 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.85 e Å−3 |
[ReCl(C17H13N5O2)(CO)3]·C2H6OS | V = 5192.0 (10) Å3 |
Mr = 703.13 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.104 (2) Å | µ = 4.91 mm−1 |
b = 14.486 (2) Å | T = 298 K |
c = 18.962 (2) Å | 0.42 × 0.38 × 0.34 mm |
β = 116.408 (7)° |
Bruker P4 diffractometer | 3969 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XSCANS; Bruker, 1996) | Rint = 0.027 |
Tmin = 0.157, Tmax = 0.188 | 3 standard reflections every 97 reflections |
5397 measured reflections | intensity decay: none |
4562 independent reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.37 e Å−3 |
4562 reflections | Δρmin = −0.85 e Å−3 |
339 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 | Occ. (<1) | |
Re1 | 0.264771 (8) | 0.534013 (12) | 0.880100 (9) | 0.04002 (7) | |
Cl1 | 0.29956 (7) | 0.39331 (9) | 0.96173 (8) | 0.0638 (3) | |
N1 | 0.37510 (17) | 0.5386 (2) | 0.89800 (19) | 0.0369 (7) | |
N2 | 0.30833 (19) | 0.6044 (3) | 0.9944 (2) | 0.0465 (8) | |
C1 | 0.1708 (3) | 0.5319 (4) | 0.8690 (3) | 0.0616 (13) | |
C2 | 0.2359 (2) | 0.4629 (4) | 0.7857 (3) | 0.0542 (11) | |
C3 | 0.2420 (2) | 0.6436 (4) | 0.8184 (3) | 0.0534 (11) | |
O1 | 0.1137 (2) | 0.5325 (3) | 0.8630 (3) | 0.0916 (14) | |
O2 | 0.2222 (2) | 0.4193 (4) | 0.7311 (2) | 0.0897 (14) | |
O3 | 0.2270 (2) | 0.7070 (3) | 0.7778 (2) | 0.0802 (12) | |
C11 | 0.4016 (2) | 0.4659 (3) | 0.8744 (3) | 0.0446 (9) | |
H11A | 0.3737 | 0.4135 | 0.8548 | 0.053* | |
C12 | 0.4682 (2) | 0.4672 (3) | 0.8785 (3) | 0.0488 (10) | |
H12A | 0.4845 | 0.4168 | 0.8609 | 0.059* | |
C13 | 0.5105 (2) | 0.5431 (3) | 0.9086 (3) | 0.0494 (11) | |
H13A | 0.5559 | 0.5448 | 0.9123 | 0.059* | |
C14 | 0.4842 (2) | 0.6167 (3) | 0.9332 (2) | 0.0441 (10) | |
H14A | 0.5123 | 0.6687 | 0.9543 | 0.053* | |
C15 | 0.4159 (2) | 0.6138 (3) | 0.9268 (2) | 0.0379 (8) | |
C | 0.3890 (2) | 0.6892 (3) | 0.9588 (2) | 0.0400 (9) | |
C21 | 0.2816 (3) | 0.5859 (4) | 1.0454 (3) | 0.0676 (15) | |
H21A | 0.2458 | 0.5422 | 1.0314 | 0.081* | |
C22 | 0.3048 (3) | 0.6287 (5) | 1.1175 (3) | 0.0772 (17) | |
H22A | 0.2856 | 0.6135 | 1.1516 | 0.093* | |
C23 | 0.3570 (3) | 0.6940 (5) | 1.1379 (3) | 0.0737 (16) | |
H23A | 0.3733 | 0.7249 | 1.1858 | 0.088* | |
C24 | 0.3848 (3) | 0.7131 (4) | 1.0864 (3) | 0.0576 (12) | |
H24A | 0.4207 | 0.7566 | 1.0996 | 0.069* | |
C25 | 0.3595 (2) | 0.6677 (3) | 1.0149 (2) | 0.0433 (9) | |
N3 | 0.39610 (19) | 0.7769 (2) | 0.9520 (2) | 0.0444 (8) | |
N4 | 0.4223 (2) | 0.8112 (3) | 0.9045 (2) | 0.0474 (9) | |
H4 | 0.422 (2) | 0.777 (3) | 0.863 (3) | 0.055 (14)* | |
C31 | 0.4247 (2) | 0.9072 (3) | 0.9001 (2) | 0.0433 (9) | |
C32 | 0.4070 (2) | 0.9644 (3) | 0.9472 (3) | 0.0498 (10) | |
H32A | 0.3942 | 0.9393 | 0.9841 | 0.060* | |
C33 | 0.4086 (3) | 1.0587 (3) | 0.9388 (3) | 0.0574 (12) | |
H33A | 0.3963 | 1.0977 | 0.9698 | 0.069* | |
C34 | 0.4284 (2) | 1.0951 (3) | 0.8845 (3) | 0.0548 (12) | |
C35 | 0.4475 (2) | 1.0403 (3) | 0.8391 (3) | 0.0568 (12) | |
H35A | 0.4616 | 1.0665 | 0.8036 | 0.068* | |
C36 | 0.4459 (2) | 0.9442 (3) | 0.8461 (3) | 0.0525 (11) | |
H36A | 0.4587 | 0.9058 | 0.8153 | 0.063* | |
N5 | 0.4294 (2) | 1.1951 (3) | 0.8765 (3) | 0.0723 (14) | |
O4 | 0.4130 (3) | 1.2433 (3) | 0.9193 (3) | 0.118 (2) | |
O5 | 0.4466 (2) | 1.2259 (3) | 0.8276 (3) | 0.0939 (14) | |
O6 | 0.4230 (3) | 0.7309 (4) | 0.7719 (2) | 0.1154 (19) | |
S1 | 0.39660 (12) | 0.68617 (13) | 0.69270 (10) | 0.0793 (7) | 0.847 (4) |
C4 | 0.3052 (5) | 0.6638 (7) | 0.6605 (5) | 0.140 (4) | 0.847 (4) |
H4A | 0.2996 | 0.6156 | 0.6921 | 0.210* | 0.847 (4) |
H4B | 0.2842 | 0.6449 | 0.6064 | 0.210* | 0.847 (4) |
H4C | 0.2822 | 0.7188 | 0.6657 | 0.210* | 0.847 (4) |
C5 | 0.3868 (4) | 0.7737 (5) | 0.6256 (4) | 0.095 (2) | 0.847 (4) |
H5A | 0.4326 | 0.7956 | 0.6341 | 0.143* | 0.847 (4) |
H5B | 0.3603 | 0.8237 | 0.6327 | 0.143* | 0.847 (4) |
H5C | 0.3620 | 0.7502 | 0.5729 | 0.143* | 0.847 (4) |
S1' | 0.3543 (7) | 0.7550 (8) | 0.6972 (6) | 0.083 (4) | 0.153 (4) |
C4' | 0.3052 (5) | 0.6638 (7) | 0.6605 (5) | 0.140 (4) | 0.153 (4) |
H4'A | 0.2838 | 0.6459 | 0.6938 | 0.210* | 0.153 (4) |
H4'B | 0.3339 | 0.6141 | 0.6574 | 0.210* | 0.153 (4) |
H4'C | 0.2688 | 0.6777 | 0.6088 | 0.210* | 0.153 (4) |
C5' | 0.3868 (4) | 0.7737 (5) | 0.6256 (4) | 0.095 (2) | 0.153 (4) |
H5'A | 0.4182 | 0.8258 | 0.6410 | 0.143* | 0.153 (4) |
H5'B | 0.3477 | 0.7856 | 0.5752 | 0.143* | 0.153 (4) |
H5'C | 0.4117 | 0.7198 | 0.6222 | 0.143* | 0.153 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Re1 | 0.03414 (10) | 0.04760 (11) | 0.04102 (10) | −0.00310 (8) | 0.01916 (7) | −0.00309 (8) |
Cl1 | 0.0682 (8) | 0.0559 (7) | 0.0678 (7) | −0.0105 (6) | 0.0306 (6) | 0.0110 (6) |
N1 | 0.0338 (16) | 0.0377 (18) | 0.0405 (17) | −0.0018 (14) | 0.0176 (14) | 0.0007 (15) |
N2 | 0.048 (2) | 0.053 (2) | 0.0458 (19) | −0.0042 (18) | 0.0276 (17) | −0.0036 (18) |
C1 | 0.047 (3) | 0.083 (4) | 0.062 (3) | −0.005 (3) | 0.031 (2) | −0.008 (3) |
C2 | 0.039 (2) | 0.070 (3) | 0.055 (3) | 0.002 (2) | 0.022 (2) | −0.008 (3) |
C3 | 0.048 (3) | 0.064 (3) | 0.055 (3) | 0.009 (2) | 0.029 (2) | 0.001 (2) |
O1 | 0.050 (2) | 0.132 (4) | 0.108 (3) | −0.012 (2) | 0.049 (2) | −0.012 (3) |
O2 | 0.055 (2) | 0.135 (4) | 0.072 (2) | 0.001 (2) | 0.021 (2) | −0.049 (3) |
O3 | 0.085 (3) | 0.081 (3) | 0.086 (3) | 0.029 (2) | 0.048 (2) | 0.028 (2) |
C11 | 0.046 (2) | 0.039 (2) | 0.050 (2) | −0.0053 (19) | 0.021 (2) | −0.008 (2) |
C12 | 0.048 (2) | 0.046 (2) | 0.058 (3) | 0.009 (2) | 0.029 (2) | 0.002 (2) |
C13 | 0.041 (2) | 0.053 (3) | 0.062 (3) | 0.005 (2) | 0.030 (2) | 0.008 (2) |
C14 | 0.036 (2) | 0.043 (2) | 0.053 (2) | −0.0044 (18) | 0.0207 (19) | −0.001 (2) |
C15 | 0.039 (2) | 0.042 (2) | 0.0353 (19) | 0.0004 (17) | 0.0184 (17) | 0.0025 (17) |
C | 0.037 (2) | 0.039 (2) | 0.044 (2) | −0.0058 (17) | 0.0186 (18) | −0.0060 (18) |
C21 | 0.069 (3) | 0.087 (4) | 0.065 (3) | −0.024 (3) | 0.047 (3) | −0.015 (3) |
C22 | 0.089 (4) | 0.102 (5) | 0.064 (3) | −0.021 (4) | 0.055 (3) | −0.020 (3) |
C23 | 0.075 (4) | 0.100 (5) | 0.056 (3) | −0.008 (3) | 0.039 (3) | −0.029 (3) |
C24 | 0.057 (3) | 0.065 (3) | 0.058 (3) | −0.010 (2) | 0.033 (2) | −0.016 (2) |
C25 | 0.045 (2) | 0.046 (2) | 0.044 (2) | 0.0003 (19) | 0.0249 (19) | −0.0031 (19) |
N3 | 0.0446 (19) | 0.042 (2) | 0.048 (2) | −0.0036 (16) | 0.0227 (17) | 0.0004 (16) |
N4 | 0.054 (2) | 0.043 (2) | 0.053 (2) | −0.0005 (17) | 0.0305 (19) | −0.0019 (18) |
C31 | 0.037 (2) | 0.040 (2) | 0.047 (2) | −0.0016 (18) | 0.0123 (18) | 0.0015 (19) |
C32 | 0.051 (2) | 0.046 (3) | 0.050 (2) | 0.000 (2) | 0.020 (2) | −0.002 (2) |
C33 | 0.059 (3) | 0.043 (3) | 0.060 (3) | 0.001 (2) | 0.018 (2) | −0.009 (2) |
C34 | 0.049 (3) | 0.041 (3) | 0.057 (3) | −0.005 (2) | 0.008 (2) | 0.001 (2) |
C35 | 0.044 (2) | 0.058 (3) | 0.061 (3) | −0.002 (2) | 0.017 (2) | 0.019 (3) |
C36 | 0.049 (3) | 0.058 (3) | 0.055 (3) | −0.002 (2) | 0.026 (2) | 0.001 (2) |
N5 | 0.062 (3) | 0.045 (3) | 0.076 (3) | −0.005 (2) | 0.001 (2) | 0.012 (2) |
O4 | 0.184 (6) | 0.043 (2) | 0.118 (4) | 0.004 (3) | 0.058 (4) | −0.009 (3) |
O5 | 0.079 (3) | 0.068 (3) | 0.106 (3) | −0.019 (2) | 0.015 (3) | 0.029 (3) |
O6 | 0.154 (5) | 0.133 (4) | 0.051 (2) | 0.042 (4) | 0.038 (3) | −0.012 (3) |
S1 | 0.1192 (16) | 0.0656 (11) | 0.0626 (10) | 0.0243 (10) | 0.0489 (11) | −0.0037 (8) |
C4 | 0.180 (10) | 0.163 (9) | 0.124 (7) | −0.066 (8) | 0.109 (7) | −0.043 (7) |
C5 | 0.106 (5) | 0.099 (5) | 0.073 (4) | −0.008 (4) | 0.034 (4) | 0.009 (4) |
S1' | 0.105 (8) | 0.087 (8) | 0.066 (6) | −0.003 (6) | 0.046 (6) | −0.015 (5) |
C4' | 0.180 (10) | 0.163 (9) | 0.124 (7) | −0.066 (8) | 0.109 (7) | −0.043 (7) |
C5' | 0.106 (5) | 0.099 (5) | 0.073 (4) | −0.008 (4) | 0.034 (4) | 0.009 (4) |
Re1—C1 | 1.900 (5) | C21—C22 | 1.377 (7) |
Re1—C3 | 1.902 (5) | C22—C23 | 1.371 (8) |
Re1—C2 | 1.914 (5) | C23—C24 | 1.372 (7) |
Re1—N2 | 2.193 (4) | C24—C25 | 1.383 (6) |
Re1—N1 | 2.200 (3) | N3—N4 | 1.345 (5) |
Re1—Cl1 | 2.4654 (13) | N4—C31 | 1.394 (6) |
N1—C15 | 1.344 (5) | N4—H4 | 0.93 (5) |
N1—C11 | 1.359 (5) | C31—C32 | 1.385 (6) |
N2—C25 | 1.335 (6) | C31—C36 | 1.395 (6) |
N2—C21 | 1.346 (6) | C32—C33 | 1.377 (7) |
C1—O1 | 1.158 (6) | C33—C34 | 1.378 (7) |
C2—O2 | 1.135 (6) | C34—C35 | 1.358 (7) |
C3—O3 | 1.150 (6) | C34—N5 | 1.458 (7) |
C11—C12 | 1.373 (6) | C35—C36 | 1.400 (7) |
C12—C13 | 1.370 (6) | N5—O5 | 1.220 (6) |
C13—C14 | 1.376 (6) | N5—O4 | 1.232 (7) |
C14—C15 | 1.394 (5) | O6—S1 | 1.498 (4) |
C15—C | 1.478 (6) | O6—S1' | 1.550 (13) |
C—N3 | 1.293 (5) | S1—C5 | 1.743 (7) |
C—C25 | 1.487 (6) | S1—C4 | 1.776 (9) |
C1—Re1—C3 | 88.8 (2) | N3—C—C15 | 127.1 (4) |
C1—Re1—C2 | 90.3 (2) | N3—C—C25 | 112.4 (4) |
C3—Re1—C2 | 89.2 (2) | C15—C—C25 | 119.9 (4) |
C1—Re1—N2 | 94.29 (18) | N2—C21—C22 | 123.2 (5) |
C3—Re1—N2 | 95.75 (17) | C23—C22—C21 | 118.5 (5) |
C2—Re1—N2 | 173.34 (17) | C22—C23—C24 | 118.8 (5) |
C1—Re1—N1 | 177.59 (17) | C23—C24—C25 | 120.0 (5) |
C3—Re1—N1 | 91.75 (16) | N2—C25—C24 | 121.5 (4) |
C2—Re1—N1 | 92.06 (16) | N2—C25—C | 118.5 (4) |
N2—Re1—N1 | 83.32 (12) | C24—C25—C | 120.0 (4) |
C1—Re1—Cl1 | 93.50 (17) | C—N3—N4 | 122.0 (4) |
C3—Re1—Cl1 | 177.63 (15) | H4—N4—N3 | 121 (3) |
C2—Re1—Cl1 | 91.40 (16) | H4—N4—C31 | 118 (3) |
N2—Re1—Cl1 | 83.52 (10) | N3—N4—C31 | 116.4 (4) |
N1—Re1—Cl1 | 85.93 (9) | C32—C31—N4 | 122.1 (4) |
C15—N1—C11 | 118.6 (3) | C32—C31—C36 | 120.6 (4) |
C15—N1—Re1 | 122.0 (3) | N4—C31—C36 | 117.3 (4) |
C11—N1—Re1 | 119.2 (3) | C33—C32—C31 | 119.5 (5) |
C25—N2—C21 | 118.0 (4) | C32—C33—C34 | 119.8 (5) |
C25—N2—Re1 | 122.4 (3) | C35—C34—C33 | 121.7 (4) |
C21—N2—Re1 | 119.5 (3) | C35—C34—N5 | 119.5 (5) |
O1—C1—Re1 | 178.5 (5) | C33—C34—N5 | 118.9 (5) |
O2—C2—Re1 | 176.5 (4) | C34—C35—C36 | 119.6 (5) |
O3—C3—Re1 | 176.6 (4) | C31—C36—C35 | 118.8 (5) |
N1—C11—C12 | 122.1 (4) | O5—N5—O4 | 124.0 (5) |
C13—C12—C11 | 119.7 (4) | O5—N5—C34 | 117.8 (6) |
C12—C13—C14 | 118.5 (4) | O4—N5—C34 | 118.1 (5) |
C13—C14—C15 | 120.3 (4) | S1—O6—S1' | 53.2 (4) |
N1—C15—C14 | 120.7 (4) | O6—S1—C5 | 106.8 (3) |
N1—C15—C | 118.2 (3) | O6—S1—C4 | 106.6 (4) |
C14—C15—C | 120.8 (4) | C5—S1—C4 | 97.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O6 | 0.93 (5) | 1.85 (5) | 2.775 (5) | 169 (4) |
C5—H5C···Cl1i | 0.96 | 2.83 | 3.716 (7) | 153 |
C4—H4C···O3 | 0.96 | 2.85 | 3.364 (8) | 115 |
C14—H14A···O4ii | 0.93 | 2.55 | 3.353 (7) | 145 |
C24—H24A···O5ii | 0.93 | 2.53 | 3.308 (7) | 142 |
C22—H22A···O2iii | 0.93 | 2.47 | 3.393 (6) | 174 |
C23—H23A···O5iv | 0.93 | 2.54 | 3.436 (7) | 163 |
Symmetry codes: (i) x, −y+1, z−1/2; (ii) −x+1, −y+2, −z+2; (iii) x, −y+1, z+1/2; (iv) x, −y+2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [ReCl(C17H13N5O2)(CO)3]·C2H6OS |
Mr | 703.13 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 21.104 (2), 14.486 (2), 18.962 (2) |
β (°) | 116.408 (7) |
V (Å3) | 5192.0 (10) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 4.91 |
Crystal size (mm) | 0.42 × 0.38 × 0.34 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ scan (XSCANS; Bruker, 1996) |
Tmin, Tmax | 0.157, 0.188 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5397, 4562, 3969 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.064, 1.08 |
No. of reflections | 4562 |
No. of parameters | 339 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.37, −0.85 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL.
Re1—C1 | 1.900 (5) | N3—N4 | 1.345 (5) |
Re1—C3 | 1.902 (5) | N4—C31 | 1.394 (6) |
Re1—C2 | 1.914 (5) | N4—H4 | 0.93 (5) |
Re1—N2 | 2.193 (4) | C34—N5 | 1.458 (7) |
Re1—N1 | 2.200 (3) | N5—O5 | 1.220 (6) |
Re1—Cl1 | 2.4654 (13) | N5—O4 | 1.232 (7) |
C—N3 | 1.293 (5) | ||
C1—Re1—C3 | 88.8 (2) | N2—Re1—N1 | 83.32 (12) |
C1—Re1—C2 | 90.3 (2) | C3—Re1—Cl1 | 177.63 (15) |
C3—Re1—C2 | 89.2 (2) | C—N3—N4 | 122.0 (4) |
C3—Re1—N2 | 95.75 (17) | N3—N4—C31 | 116.4 (4) |
C2—Re1—N2 | 173.34 (17) | O5—N5—O4 | 124.0 (5) |
C2—Re1—N1 | 92.06 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O6 | 0.93 (5) | 1.85 (5) | 2.775 (5) | 169 (4) |
C5—H5C···Cl1i | 0.96 | 2.83 | 3.716 (7) | 153 |
C4—H4C···O3 | 0.96 | 2.85 | 3.364 (8) | 115 |
C14—H14A···O4ii | 0.93 | 2.55 | 3.353 (7) | 145 |
C24—H24A···O5ii | 0.93 | 2.53 | 3.308 (7) | 142 |
C22—H22A···O2iii | 0.93 | 2.47 | 3.393 (6) | 174 |
C23—H23A···O5iv | 0.93 | 2.54 | 3.436 (7) | 163 |
Symmetry codes: (i) x, −y+1, z−1/2; (ii) −x+1, −y+2, −z+2; (iii) x, −y+1, z+1/2; (iv) x, −y+2, z+1/2. |
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The development of molecular systems sensitive to their surroundings is of interest for their rich physicochemical properties, reactivity patterns and applications in devices employed in photonic, electronic and sensing techniques (Drain et al., 2001; Luo et al., 2001; Prasad et al., 1991; Bosshard et al., 1995; Czerney & Grummt, 1997). The synthesis of di-2-pyridylmethanone p-nitrophenylhydrazone (dpknph) and its rhenium tricarbonyl compound, fac-[ReCl(dpknph)(CO)3], have been reported (Bakir & Abdur-Rashid, 1999). Optical and thermodynamic measurements on fac-[ReCl(dpknph)(CO)3] in polar solvents have revealed strong solvent–solute and solute–solute interactions, and facile interconversion between two charge–transfer bands (Bakir et al., 2000). Manipulation of the charge-transfer bands in fac-[ReCl(dpknph)(CO)3]·DMSO, (I), led to the use of these systems {fac-[ReCl(dpknph)(CO)3] and surrounding solvent molecules} as spectrophotometric sensors for a variety of substrates that include metal ions. The structure of (I) is reported here and compared to the structures of tricabonylrhenium compounds containing α-diimine ligands, e.g. di-2-pyridylketoneoxime (dpk.oxime) and hydroxyd(2-pyridyl)methoxide (dpkO,OH).
An ORTEP view of (I) is shown in Fig. 1, and Table 1 contains selected bond distances and angles. Two N atoms of the bidentate chelating dpknph ligand and two C atoms from two carbonyl groups occupy the equatorial positions in fac-[ReCl(dpknph)(CO)3] and the two axial positions are occupied by a carbonyl C atom and a Cl atom. The N,N-chelating dpknph molecule forms a six-membered (Re1—N1—C15—C—C25—N2) metallocyclic ring in a boat conformation. The N,N-bite angle of 83.32 (12)° is of the same order as those reported for tricabonylrhenium compounds of N,N-bidentate polypyridyl-like ligands containing six-membered rings (Bakir, 2001; Gerber et al., 1993, 1995). For example, an N,N-bite angle of 84.6 (4)° was reported for dpkO,OH in [ReOCl2(dpkO,OH)] (Gerber et al., 1995, 1993) and a bite angle of 80.27 (19)° was observed for dpk.oxime in fac-[ReCl(dpk.oxime)(CO)3]·DMSO (Bakir, 2001). The carbonyl groups are in facial positions, with an average C—Re—C bond angle of 89.4 (3)°. The Re—C, Re—N and Re—Cl bonds distances are normal and similar to those reported for fac-[ReCl(dpk.oxime)(CO)3]·DMSO (Bakir, 2001) and a variety of tricarbonylrhenium compounds of the type fac-[ReCl(L—L)(CO)3], where L—L is an α-diimine ligand (Horn & Snow, 1980; Xue et al., 1998; Yam et al., 1995, 1998; Gibson et al., 1998). For example, in fac-[ReCl(tBu2bpy)(CO)3], the Re—C, Re—N and Re—Cl bond distances are 1.935 (9)/1.935 (9)/1.896 (3), 2.169 (6)/2.170 (5) and 2.476 (2) Å, respectively (Yam et al., 1995). The p-nitrophenylhydrazone moiety in (I) is planar with all C and N atoms in sp2-hybridized forms.
The packing of molecules (Fig. 2) shows antiparallel stacks of (I) having the p-nitrophenylhydrazone (P—NO2—C6H4—NH—N) moieties from adjacent stacks face-to-face. The interplanar distance between the phenyl rings of approximately 3.45 Å is of the same order as the π-stacking in aromatic and charge-transfer compounds and is shorter than the interplanar distance of 4.97 Å reported for the pure benzene dimer (Glusker et al., 1994; Batchelor et al., 2000; Williams, 1993). The antiparallel arrangement of the p-nitrophenylhydrazone moieties facilitates the formation of intermolecular non-classical C—H···O hydrogen bonds between the nitro O4 and O5 atoms and the pyridine H14 and H24 atoms. A classical intramolecular N—H···O hydrogen bond, a non-classical intramolecular C—H···O hydrogen bond and a non-classical intermolecular C—H···Cl hydrogen bonds were observed between DMSO and fac-[ReCl(dpknph)(CO)3] (Fig. 3). In addition, side-to-side intermolecular hydrogen bonds were observed between adjacent carbonyl groups, nitro groups and pyridine rings, i.e. C22—H22A···O2 and C23—H23A···O5. The bond distances and angles (Table 2) of the classical hydrogen bonds between the DMSO O6 atom and the amino N4—H4 group of the hydrazone moiety are similar to those reported for a variety of N—H···O hydrogen bonds (Bakir, 2001; Sherrington & Taskinen, 2001; Uppadine et al., 2001; Glusker et al., 1994; Pan et al., 1997). For example, in 5-nitro-2-thiophenecarboxaldehyde-4-methylphenylhydrazone form I (NTMPH-I), two different N—H···O hydrogen bonds, with O—H = 2.0–2.3 Å, N—O = 3.01–3.18 Å and N—H···O = 161–160° were observed (Pan et al., 1997). The non-classical hydrogen bonds are of the same order as the sum of their van der Waals radii; for example, the van der Waals O—H distance is about 2.8 Å (Glusker et al., 1994; Pan et al., 1997). The non-covalent interactions observed in this interlocking system (solute–solute and solvent–solute) may account for the optical and molecular sensing behavior of (I), as any slight interaction between this system and its surroundings may disrupt the weak non-covalent interactions present. This is consistent with the low values of the activation parameters reported for the interconversion between the charge-transfer bands in fac-[ReCl(dpknph)(CO)3] (Bakir et al., 2000) and the low values for the bond energies of non-covalent interactions (Vishweshwar et al., 2001). The layer arrangement of (I) and the planar hydrazone moiety may also account for the observed fast electronic transfer in fac-[ReCl(dpknph)(CO)3] compared with dpknph (Bakir & Abdur-Rashid, 1999). Studies are in progress to grow single crystals of the uncoordinated dpknph molecule and compare its structure with the structure of (I).
In conclusion, structural studies on (I) revealed the presence of weak non-covalent interactions that include solvent–solute, solute–solute and π-stacking interactions, which may account for the interlocked charge-transfer bands and molecular sensitivity of fac-[ReCl(dpknph)(CO)3] in polar solvents.