Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802016379/wn6111sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802016379/wn6111Isup2.hkl |
CCDC reference: 198307
Rhenium pentacarbonyl chloride (0.1 mmol, 37 mg) and 1,10-phenanthroline (0.11 mmol, 20 mg) were refluxed in toluene for 1 h under N2. The resulting yellow precipitate was collected by vacuum filtration and chromatographed on a column of silica gel (60–200 mesh), first with CH2Cl2 to elute unreacted starting materials, and then with 5% methanol in CH2Cl2 to elute the desired product. Slow evaporation of the solvent yielded the product as yellow crystals.
H atoms were placed geometrically and refined using a riding model, with Uiso values constrained to be 1.2Ueq of the carrier atom. The largest residual electron density peak is 1.91 e.Å −3 and lies at 1.06 Å from the Re atom.
Data collection: SMART (Bruker, 1997-98); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SHELXTL (Sheldrick, 1998); program(s) used to solve structure: XS in SHELXTL; program(s) used to refine structure: XL in SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: XCIF in SHELXTL.
[Re(C12H8N2)(CO)3Cl] | Z = 2 |
Mr = 485.88 | F(000) = 456 |
Triclinic, P1 | Dx = 2.262 Mg m−3 |
a = 6.4536 (14) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.132 (2) Å | Cell parameters from 950 reflections |
c = 12.841 (3) Å | θ = 2.4–27.4° |
α = 108.264 (3)° | µ = 8.72 mm−1 |
β = 95.935 (3)° | T = 203 K |
γ = 91.440 (3)° | Plate, yellow |
V = 713.5 (3) Å3 | 0.13 × 0.08 × 0.03 mm |
Siemens SMART 1K CCD diffractometer | 2509 independent reflections |
Radiation source: normal-focus sealed tube | 2286 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
Detector resolution: 8.3 pixels mm-1 | θmax = 25.0°, θmin = 2.4° |
ω scans | h = −7→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1999) | k = −10→10 |
Tmin = 0.397, Tmax = 0.780 | l = −15→15 |
7351 measured reflections |
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) = 0.067 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0427P)2] where P = (Fo2 + 2Fc2)/3 |
2509 reflections | (Δ/σ)max < 0.001 |
200 parameters | Δρmax = 1.91 e Å−3 |
0 restraints | Δρmin = −1.38 e Å−3 |
[Re(C12H8N2)(CO)3Cl] | γ = 91.440 (3)° |
Mr = 485.88 | V = 713.5 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.4536 (14) Å | Mo Kα radiation |
b = 9.132 (2) Å | µ = 8.72 mm−1 |
c = 12.841 (3) Å | T = 203 K |
α = 108.264 (3)° | 0.13 × 0.08 × 0.03 mm |
β = 95.935 (3)° |
Siemens SMART 1K CCD diffractometer | 2509 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1999) | 2286 reflections with I > 2σ(I) |
Tmin = 0.397, Tmax = 0.780 | Rint = 0.031 |
7351 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.91 e Å−3 |
2509 reflections | Δρmin = −1.38 e Å−3 |
200 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 | ||
Re | 0.24818 (3) | 0.76085 (2) | 0.293721 (18) | 0.02225 (10) | |
Cl | 0.0123 (2) | 0.71967 (18) | 0.11861 (13) | 0.0311 (3) | |
N1 | 0.3725 (7) | 0.5433 (5) | 0.2014 (4) | 0.0230 (10) | |
C2 | 0.5408 (9) | 0.5258 (7) | 0.1457 (5) | 0.0267 (13) | |
H2 | 0.6262 | 0.6139 | 0.1521 | 0.032* | |
C3 | 0.5935 (9) | 0.3819 (8) | 0.0785 (5) | 0.0299 (14) | |
H3 | 0.7115 | 0.3744 | 0.0404 | 0.036* | |
C4 | 0.4726 (10) | 0.2527 (7) | 0.0689 (5) | 0.0333 (14) | |
H4 | 0.5058 | 0.1557 | 0.0232 | 0.040* | |
C5 | 0.2984 (9) | 0.2654 (7) | 0.1274 (5) | 0.0280 (13) | |
C6 | −0.0411 (8) | 0.3041 (7) | 0.2579 (5) | 0.0247 (12) | |
C7 | −0.1987 (9) | 0.3299 (7) | 0.3287 (5) | 0.0300 (14) | |
H7 | −0.2812 | 0.2463 | 0.3332 | 0.036* | |
C8 | −0.2308 (9) | 0.4775 (7) | 0.3907 (5) | 0.0296 (14) | |
H8 | −0.3365 | 0.4959 | 0.4376 | 0.036* | |
C9 | −0.1063 (9) | 0.6005 (7) | 0.3842 (5) | 0.0264 (13) | |
H9 | −0.1309 | 0.7011 | 0.4273 | 0.032* | |
N10 | 0.0472 (7) | 0.5814 (5) | 0.3190 (4) | 0.0209 (10) | |
C11 | 0.0824 (8) | 0.4331 (6) | 0.2582 (4) | 0.0207 (12) | |
C12 | 0.2551 (8) | 0.4143 (6) | 0.1940 (5) | 0.0212 (12) | |
C13 | 0.1625 (10) | 0.1372 (7) | 0.1248 (5) | 0.0311 (14) | |
H13 | 0.1854 | 0.0383 | 0.0780 | 0.037* | |
C14 | 0.0037 (9) | 0.1530 (7) | 0.1867 (5) | 0.0295 (13) | |
H14 | −0.0792 | 0.0653 | 0.1838 | 0.035* | |
O15 | 0.0104 (7) | 1.0478 (5) | 0.4025 (4) | 0.0393 (11) | |
C15 | 0.1007 (9) | 0.9398 (7) | 0.3634 (5) | 0.0283 (13) | |
C16 | 0.4410 (10) | 0.8945 (7) | 0.2562 (5) | 0.0297 (14) | |
O16 | 0.5550 (7) | 0.9725 (5) | 0.2296 (4) | 0.0440 (12) | |
C17 | 0.4213 (9) | 0.7847 (6) | 0.4354 (5) | 0.0249 (13) | |
O17 | 0.5122 (8) | 0.8039 (6) | 0.5134 (4) | 0.0449 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Re | 0.01975 (13) | 0.02004 (14) | 0.02647 (15) | −0.00248 (9) | 0.00854 (9) | 0.00513 (10) |
Cl | 0.0276 (7) | 0.0327 (8) | 0.0341 (8) | 0.0004 (6) | 0.0087 (6) | 0.0107 (7) |
N1 | 0.020 (2) | 0.026 (3) | 0.024 (3) | 0.003 (2) | 0.0076 (19) | 0.008 (2) |
C2 | 0.020 (3) | 0.032 (3) | 0.029 (3) | 0.001 (2) | 0.007 (2) | 0.010 (3) |
C3 | 0.021 (3) | 0.042 (4) | 0.030 (3) | 0.005 (3) | 0.009 (2) | 0.016 (3) |
C4 | 0.036 (3) | 0.031 (4) | 0.035 (4) | 0.011 (3) | 0.008 (3) | 0.011 (3) |
C5 | 0.031 (3) | 0.026 (3) | 0.028 (3) | 0.006 (3) | 0.006 (2) | 0.007 (3) |
C6 | 0.022 (3) | 0.026 (3) | 0.028 (3) | −0.004 (2) | 0.005 (2) | 0.010 (3) |
C7 | 0.027 (3) | 0.031 (3) | 0.037 (4) | −0.007 (3) | 0.005 (3) | 0.018 (3) |
C8 | 0.023 (3) | 0.037 (4) | 0.034 (3) | 0.003 (3) | 0.012 (2) | 0.016 (3) |
C9 | 0.022 (3) | 0.026 (3) | 0.029 (3) | 0.001 (2) | 0.009 (2) | 0.004 (3) |
N10 | 0.019 (2) | 0.020 (2) | 0.022 (3) | −0.0005 (19) | 0.0049 (19) | 0.005 (2) |
C11 | 0.021 (3) | 0.018 (3) | 0.023 (3) | 0.000 (2) | 0.004 (2) | 0.007 (2) |
C12 | 0.021 (3) | 0.020 (3) | 0.023 (3) | 0.001 (2) | 0.004 (2) | 0.007 (2) |
C13 | 0.038 (3) | 0.022 (3) | 0.032 (4) | 0.006 (3) | 0.007 (3) | 0.006 (3) |
C14 | 0.034 (3) | 0.021 (3) | 0.035 (4) | −0.004 (3) | 0.002 (3) | 0.012 (3) |
O15 | 0.050 (3) | 0.029 (3) | 0.042 (3) | 0.012 (2) | 0.017 (2) | 0.011 (2) |
C15 | 0.029 (3) | 0.027 (3) | 0.030 (3) | −0.002 (3) | 0.006 (3) | 0.011 (3) |
C16 | 0.033 (3) | 0.024 (3) | 0.027 (3) | −0.001 (3) | 0.001 (3) | 0.002 (3) |
O16 | 0.042 (3) | 0.035 (3) | 0.058 (3) | −0.014 (2) | 0.020 (2) | 0.016 (2) |
C17 | 0.020 (3) | 0.017 (3) | 0.029 (3) | −0.004 (2) | 0.016 (3) | −0.008 (2) |
O17 | 0.040 (3) | 0.047 (3) | 0.046 (3) | 0.005 (2) | 0.008 (2) | 0.011 (2) |
Re—C16 | 1.921 (7) | C6—C7 | 1.409 (8) |
Re—C15 | 1.927 (6) | C6—C14 | 1.452 (8) |
Re—C17 | 1.981 (7) | C7—C8 | 1.367 (9) |
Re—N10 | 2.188 (5) | C7—H7 | 0.9400 |
Re—N1 | 2.191 (5) | C8—C9 | 1.393 (8) |
Re—Cl | 2.4996 (16) | C8—H8 | 0.9400 |
N1—C2 | 1.347 (7) | C9—N10 | 1.342 (7) |
N1—C12 | 1.356 (7) | C9—H9 | 0.9400 |
C2—C3 | 1.400 (8) | N10—C11 | 1.373 (7) |
C2—H2 | 0.9400 | C11—C12 | 1.436 (7) |
C3—C4 | 1.363 (9) | C13—C14 | 1.344 (9) |
C3—H3 | 0.9400 | C13—H13 | 0.9400 |
C4—C5 | 1.403 (9) | C14—H14 | 0.9400 |
C4—H4 | 0.9400 | O15—C15 | 1.160 (7) |
C5—C12 | 1.414 (8) | C16—O16 | 1.158 (8) |
C5—C13 | 1.435 (9) | C17—O17 | 1.069 (7) |
C6—C11 | 1.404 (8) | ||
C16—Re—C15 | 88.5 (3) | C11—C6—C7 | 117.6 (5) |
C16—Re—C17 | 91.6 (2) | C11—C6—C14 | 118.3 (5) |
C15—Re—C17 | 90.6 (2) | C7—C6—C14 | 124.2 (5) |
C16—Re—N10 | 171.8 (2) | C8—C7—C6 | 119.5 (5) |
C15—Re—N10 | 99.5 (2) | C8—C7—H7 | 120.3 |
C17—Re—N10 | 90.6 (2) | C6—C7—H7 | 120.3 |
C16—Re—N1 | 96.4 (2) | C7—C8—C9 | 119.8 (5) |
C15—Re—N1 | 171.8 (2) | C7—C8—H8 | 120.1 |
C17—Re—N1 | 95.86 (19) | C9—C8—H8 | 120.1 |
N10—Re—N1 | 75.42 (17) | N10—C9—C8 | 122.8 (5) |
C16—Re—Cl | 92.32 (18) | N10—C9—H9 | 118.6 |
C15—Re—Cl | 89.37 (18) | C8—C9—H9 | 118.6 |
C17—Re—Cl | 176.12 (17) | C9—N10—C11 | 117.5 (5) |
N10—Re—Cl | 85.61 (12) | C9—N10—Re | 127.6 (4) |
N1—Re—Cl | 83.88 (12) | C11—N10—Re | 114.8 (3) |
C2—N1—C12 | 117.8 (5) | N10—C11—C6 | 122.7 (5) |
C2—N1—Re | 127.1 (4) | N10—C11—C12 | 116.7 (5) |
C12—N1—Re | 114.8 (3) | C6—C11—C12 | 120.6 (5) |
N1—C2—C3 | 122.6 (6) | N1—C12—C5 | 122.6 (5) |
N1—C2—H2 | 118.7 | N1—C12—C11 | 117.5 (5) |
C3—C2—H2 | 118.7 | C5—C12—C11 | 119.9 (5) |
C4—C3—C2 | 119.6 (5) | C14—C13—C5 | 122.6 (5) |
C4—C3—H3 | 120.2 | C14—C13—H13 | 118.7 |
C2—C3—H3 | 120.2 | C5—C13—H13 | 118.7 |
C3—C4—C5 | 119.6 (6) | C13—C14—C6 | 120.6 (5) |
C3—C4—H4 | 120.2 | C13—C14—H14 | 119.7 |
C5—C4—H4 | 120.2 | C6—C14—H14 | 119.7 |
C4—C5—C12 | 117.7 (6) | O15—C15—Re | 178.1 (5) |
C4—C5—C13 | 124.4 (5) | O16—C16—Re | 177.6 (5) |
C12—C5—C13 | 117.9 (5) | O17—C17—Re | 176.9 (5) |
C16—Re—N1—C2 | 3.8 (5) | Cl—Re—N10—C11 | 78.0 (4) |
C17—Re—N1—C2 | −88.4 (5) | C9—N10—C11—C6 | 3.1 (8) |
N10—Re—N1—C2 | −177.5 (5) | Re—N10—C11—C6 | −175.5 (4) |
Cl—Re—N1—C2 | 95.5 (5) | C9—N10—C11—C12 | −176.5 (5) |
C16—Re—N1—C12 | −170.9 (4) | Re—N10—C11—C12 | 5.0 (6) |
C17—Re—N1—C12 | 96.9 (4) | C7—C6—C11—N10 | −3.9 (8) |
N10—Re—N1—C12 | 7.8 (4) | C14—C6—C11—N10 | 177.2 (5) |
Cl—Re—N1—C12 | −79.2 (4) | C7—C6—C11—C12 | 175.7 (5) |
C12—N1—C2—C3 | 2.2 (8) | C14—C6—C11—C12 | −3.3 (8) |
Re—N1—C2—C3 | −172.3 (4) | C2—N1—C12—C5 | −2.5 (8) |
N1—C2—C3—C4 | −0.6 (9) | Re—N1—C12—C5 | 172.7 (4) |
C2—C3—C4—C5 | −0.8 (9) | C2—N1—C12—C11 | 176.8 (5) |
C3—C4—C5—C12 | 0.5 (9) | Re—N1—C12—C11 | −8.0 (6) |
C3—C4—C5—C13 | −179.0 (6) | C4—C5—C12—N1 | 1.2 (9) |
C11—C6—C7—C8 | 2.5 (8) | C13—C5—C12—N1 | −179.3 (5) |
C14—C6—C7—C8 | −178.6 (6) | C4—C5—C12—C11 | −178.1 (5) |
C6—C7—C8—C9 | −0.6 (9) | C13—C5—C12—C11 | 1.4 (8) |
C7—C8—C9—N10 | −0.2 (9) | N10—C11—C12—N1 | 2.0 (7) |
C8—C9—N10—C11 | −1.0 (8) | C6—C11—C12—N1 | −177.5 (5) |
C8—C9—N10—Re | 177.3 (4) | N10—C11—C12—C5 | −178.7 (5) |
C15—Re—N10—C9 | −11.7 (5) | C6—C11—C12—C5 | 1.8 (8) |
C17—Re—N10—C9 | 79.0 (5) | C4—C5—C13—C14 | 176.3 (6) |
N1—Re—N10—C9 | 174.9 (5) | C12—C5—C13—C14 | −3.2 (9) |
Cl—Re—N10—C9 | −100.3 (5) | C5—C13—C14—C6 | 1.7 (9) |
C15—Re—N10—C11 | 166.7 (4) | C11—C6—C14—C13 | 1.6 (8) |
C17—Re—N10—C11 | −102.7 (4) | C7—C6—C14—C13 | −177.3 (6) |
N1—Re—N10—C11 | −6.8 (4) |
Experimental details
Crystal data | |
Chemical formula | [Re(C12H8N2)(CO)3Cl] |
Mr | 485.88 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 203 |
a, b, c (Å) | 6.4536 (14), 9.132 (2), 12.841 (3) |
α, β, γ (°) | 108.264 (3), 95.935 (3), 91.440 (3) |
V (Å3) | 713.5 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 8.72 |
Crystal size (mm) | 0.13 × 0.08 × 0.03 |
Data collection | |
Diffractometer | Siemens SMART 1K CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1999) |
Tmin, Tmax | 0.397, 0.780 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7351, 2509, 2286 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.067, 1.04 |
No. of reflections | 2509 |
No. of parameters | 200 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.91, −1.38 |
Computer programs: SMART (Bruker, 1997-98), SAINT-Plus (Bruker, 1999), SHELXTL (Sheldrick, 1998), XS in SHELXTL, XL in SHELXTL, XP in SHELXTL, XCIF in SHELXTL.
Charge-transfer excited states of rhenium(I) diimine complexes result in properties which make these molecules useful as photosensitizers in photochemical and photo-electron transfer reactions (Luong et al., 1978; Richter et al., 1996; Stufkens & Vlcek, 1998), as well as in situ chemical probes (Lees, 1998; Tran et al., 1997). The existence of a Frank-Condon-type barrier between close-lying metal-to-ligand charge transfer (MLCT) and ligand-centered (LC) states for both the singlet states and for the triplet manifolds has been suggested (Striplin & Crosby, 1994; Striplin & Crosby, 2001); also the possibility of preferential loading of the triplet manifolds that is dependent on the nature of the singlet state to which the molecule is excited or of the singlet state to which the excited state initially deactivates through internal conversion (IC). The title compound, (I), is one molecule in a series of rhenium(I) complexes which have been synthesized to examine the validity of the barrier proposal.
The asymmetric unit is shown in Fig. 1. The Re—N distances are 2.181 (5) and 2.186 (5) Å, and the bidentate bite angle N—Re—N is 75.8 (2)°. The Cl—Re—N bond angles are 83.40 (12) and 85.43 (12)°, significantly less than expected for octahedral geometry. There is a noticeable trans influence induced by the Cl− atom on the carbonyl Re—C distance. The Re—C17 distance is ca 0.05 Å longer than the Re—C15 and Re—C16 distances. The bidentate 1,10-phenanthroline deviates slightly from planarity, with a dihedral angle between its two heterocyclic rings of 5.48(0.34)°, and is folded away from the chloride anion. The Re(I) atom lies 0.192 (3) Å from the least-squares plane of 1,10-phenanthroline (Fig. 2).
Some C—H···Cl interactions exist (Neve & Crispini, 2001; Freytag et al., 1999), also C—H···O interactions, as shown in Fig. 3: Cl···C2i 3.584 (6), Cl···C3ii 3.704 (6), O15···C9iii 3.498 (7), O16···C7iv 3.393 (8), O16···C14v 3.473, O17···C7vi 3.460 (8), O17···C9vii 3.378 (7) Å [symmetry codes: (i) −1 + x, y, z; (ii) 1 − x, 1 − y, −z; (iii) −x, 2 − y, 1 − z; (iv) 1 + x, 1 + y, z; (v) 1 + x, 1 + y, z; (vi) −x, 1 − y, 1 − z; (vii) 1 + x, 1 + y, z. These long H contacts with electronegative Cl− and O may account for the folding in the 1,10-phenanthroline moiety. There are no stacking effects between adjacent 1,10-phenanthroline moieties; the closest atomic contact of 3.285 (11) Å is between C2 and C3viii [symmetry code: (viii) 1 − x, 1 − y, z].