Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102004249/ta1364sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102004249/ta1364Isup2.hkl |
CCDC reference: 187909
All synthetic procedures were carried out under a nitrogen atmosphere. Hexachlorobis(methyldiphenylphosphino)dirhenium(III), Re2Cl6(PMePh2)2, (50.1 mg, 0.0508 mmol), 2,2'-dithiobis(benzothiazole) (33.8 mg, 0.102 mmol), and dichloromethane (15 ml) were combined in a 50 ml round-bottomed flask. The mixture was stirred at reflux for 3 h. The resulting deep-purple mixture was filtered through a medium glass frit. Slow evaporation of the filtrate yielded a dark solid. A small amount of this solid was dissolved in dichloromethane (5 ml) and layered with hexanes (20 ml). Thin purple crystals of (I) formed after one week NB red-brown given below. Analysis calculated for Re2Cl4S8N4C29H18: C 29.19, H 1.52, N 4.70%; found: C 28.54, H 1.66, N 4.79%. IR data (KBr, cm-1): 1608 (w), 1465 (m), 1353 (m), 1322 (m), 1288 (w), 1253 (w), 1109 (m-s), 1100 (versus), 1047 (s), 1026 (w), 841 (m), 763 (s), 754 (versus). Visible maxima (nm) in CH2Cl2: 742, 620, 539, 427.
H atoms were treated as riding, with C—H = 0.94–0.98 Å and Uiso(H) = 1.2Ueq(C). Are these the correct constraints? The largest peak in the final difference map is located 0.97 Å from solvent atom Cl3.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXL97.
[Re2(S2NC7H4)4Cl2]·CH2Cl2 | F(000) = 2264 |
Mr = 1193.15 | Dx = 2.250 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.9408 (7) Å | Cell parameters from 9504 reflections |
b = 15.5347 (8) Å | θ = 2.6–27.5° |
c = 17.5303 (9) Å | µ = 7.68 mm−1 |
β = 92.092 (1)° | T = 213 K |
V = 3521.8 (3) Å3 | Plate, red-brown |
Z = 4 | 0.38 × 0.16 × 0.02 mm |
Bruker SMART CCD area-detector diffractometer | 8000 independent reflections |
Radiation source: normal-focus sealed tube | 6368 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
ω scans | θmax = 27.5°, θmin = 1.8° |
Absorption correction: analytical face-indexed (XPREP in SHELXTL; Siemens, 1996) | h = −16→9 |
Tmin = 0.174, Tmax = 0.851 | k = −20→18 |
21991 measured reflections | l = −22→22 |
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.051 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0185P)2] where P = (Fo2 + 2Fc2)/3 |
8000 reflections | (Δ/σ)max = 0.002 |
424 parameters | Δρmax = 1.10 e Å−3 |
0 restraints | Δρmin = −0.71 e Å−3 |
[Re2(S2NC7H4)4Cl2]·CH2Cl2 | V = 3521.8 (3) Å3 |
Mr = 1193.15 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.9408 (7) Å | µ = 7.68 mm−1 |
b = 15.5347 (8) Å | T = 213 K |
c = 17.5303 (9) Å | 0.38 × 0.16 × 0.02 mm |
β = 92.092 (1)° |
Bruker SMART CCD area-detector diffractometer | 8000 independent reflections |
Absorption correction: analytical face-indexed (XPREP in SHELXTL; Siemens, 1996) | 6368 reflections with I > 2σ(I) |
Tmin = 0.174, Tmax = 0.851 | Rint = 0.036 |
21991 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.051 | H-atom parameters constrained |
S = 0.98 | Δρmax = 1.10 e Å−3 |
8000 reflections | Δρmin = −0.71 e Å−3 |
424 parameters |
Experimental. The first 50 frames were measured again at the end of the data collection procedure and used to evaluate any decay. |
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 on 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 | 0.402035 (13) | 0.233553 (9) | 0.636027 (8) | 0.02012 (5) | |
Re2 | 0.570330 (13) | 0.275300 (9) | 0.643519 (8) | 0.01912 (4) | |
Cl1 | 0.24541 (9) | 0.13696 (6) | 0.61028 (6) | 0.0319 (2) | |
Cl2 | 0.73142 (8) | 0.36746 (6) | 0.62748 (6) | 0.0282 (2) | |
S1 | 0.43737 (9) | 0.11491 (6) | 0.71957 (6) | 0.0258 (2) | |
S2 | 0.59375 (9) | 0.08328 (6) | 0.84479 (6) | 0.0296 (2) | |
S3 | 0.44070 (9) | 0.14991 (6) | 0.52467 (6) | 0.0290 (2) | |
S4 | 0.63252 (10) | 0.07321 (7) | 0.46228 (6) | 0.0345 (3) | |
S5 | 0.53868 (9) | 0.35918 (6) | 0.53005 (6) | 0.0278 (2) | |
S6 | 0.35311 (10) | 0.42827 (7) | 0.44396 (7) | 0.0368 (3) | |
S7 | 0.53397 (9) | 0.39333 (6) | 0.72470 (6) | 0.0249 (2) | |
S8 | 0.37442 (10) | 0.42520 (7) | 0.83724 (6) | 0.0323 (3) | |
N1 | 0.6150 (3) | 0.20433 (18) | 0.74394 (17) | 0.0213 (7) | |
N2 | 0.6347 (3) | 0.17647 (19) | 0.57844 (17) | 0.0230 (7) | |
N3 | 0.3410 (3) | 0.32880 (19) | 0.56225 (18) | 0.0241 (7) | |
N4 | 0.3526 (3) | 0.30651 (19) | 0.73294 (17) | 0.0226 (7) | |
C1 | 0.5520 (3) | 0.1392 (2) | 0.7641 (2) | 0.0220 (9) | |
C2 | 0.6958 (3) | 0.2157 (2) | 0.7992 (2) | 0.0228 (9) | |
C3 | 0.7691 (3) | 0.2815 (2) | 0.8013 (2) | 0.0281 (9) | |
H3 | 0.7705 | 0.3230 | 0.7624 | 0.034* | |
C4 | 0.8394 (4) | 0.2838 (3) | 0.8620 (2) | 0.0309 (10) | |
H4 | 0.8896 | 0.3275 | 0.8638 | 0.037* | |
C5 | 0.8389 (4) | 0.2239 (3) | 0.9208 (2) | 0.0333 (10) | |
H5 | 0.8877 | 0.2279 | 0.9617 | 0.040* | |
C6 | 0.7668 (3) | 0.1585 (3) | 0.9191 (2) | 0.0292 (10) | |
H6 | 0.7660 | 0.1173 | 0.9584 | 0.035* | |
C7 | 0.6951 (3) | 0.1550 (2) | 0.8580 (2) | 0.0257 (9) | |
C8 | 0.5709 (3) | 0.1393 (2) | 0.5259 (2) | 0.0254 (9) | |
C9 | 0.7373 (4) | 0.1496 (2) | 0.5716 (2) | 0.0265 (10) | |
C10 | 0.8222 (3) | 0.1720 (2) | 0.6190 (2) | 0.0276 (9) | |
H10 | 0.8137 | 0.2078 | 0.6615 | 0.033* | |
C11 | 0.9184 (4) | 0.1411 (3) | 0.6024 (3) | 0.0371 (11) | |
H11 | 0.9760 | 0.1556 | 0.6341 | 0.044* | |
C12 | 0.9313 (4) | 0.0881 (3) | 0.5386 (3) | 0.0408 (12) | |
H12 | 0.9980 | 0.0694 | 0.5268 | 0.049* | |
C13 | 0.8478 (4) | 0.0630 (3) | 0.4930 (3) | 0.0370 (11) | |
H13 | 0.8563 | 0.0261 | 0.4512 | 0.044* | |
C14 | 0.7503 (4) | 0.0938 (2) | 0.5103 (2) | 0.0315 (10) | |
C15 | 0.4091 (3) | 0.3668 (2) | 0.5167 (2) | 0.0263 (9) | |
C16 | 0.2380 (4) | 0.3521 (2) | 0.5418 (2) | 0.0276 (10) | |
C17 | 0.1496 (4) | 0.3292 (3) | 0.5786 (2) | 0.0299 (10) | |
H17 | 0.1536 | 0.2956 | 0.6233 | 0.036* | |
C18 | 0.0543 (4) | 0.3569 (3) | 0.5483 (3) | 0.0363 (11) | |
H18 | −0.0067 | 0.3411 | 0.5722 | 0.044* | |
C19 | 0.0486 (4) | 0.4080 (3) | 0.4825 (3) | 0.0385 (12) | |
H19 | −0.0164 | 0.4253 | 0.4623 | 0.046* | |
C20 | 0.1364 (4) | 0.4333 (3) | 0.4469 (3) | 0.0358 (11) | |
H20 | 0.1322 | 0.4684 | 0.4033 | 0.043* | |
C21 | 0.2314 (4) | 0.4058 (2) | 0.4769 (2) | 0.0300 (10) | |
C22 | 0.4167 (3) | 0.3693 (2) | 0.7587 (2) | 0.0233 (9) | |
C23 | 0.2680 (3) | 0.2982 (2) | 0.7802 (2) | 0.0231 (9) | |
C24 | 0.1899 (3) | 0.2366 (2) | 0.7754 (2) | 0.0301 (10) | |
H24 | 0.1880 | 0.1956 | 0.7359 | 0.036* | |
C25 | 0.1154 (4) | 0.2367 (3) | 0.8297 (3) | 0.0349 (11) | |
H25 | 0.0614 | 0.1963 | 0.8257 | 0.042* | |
C26 | 0.1175 (4) | 0.2947 (3) | 0.8899 (2) | 0.0365 (11) | |
H26 | 0.0668 | 0.2918 | 0.9268 | 0.044* | |
C27 | 0.1936 (4) | 0.3561 (3) | 0.8958 (2) | 0.0362 (11) | |
H27 | 0.1955 | 0.3960 | 0.9361 | 0.043* | |
C28 | 0.2680 (4) | 0.3577 (2) | 0.8400 (2) | 0.0290 (10) | |
C29 | 0.9784 (7) | −0.0434 (4) | 0.7540 (4) | 0.108 (3) | |
H29A | 0.9957 | −0.0895 | 0.7905 | 0.130* | |
H29B | 0.9433 | −0.0700 | 0.7095 | 0.130* | |
Cl3 | 1.09014 (14) | 0.00144 (9) | 0.72557 (9) | 0.0676 (4) | |
Cl4 | 0.89223 (15) | 0.02667 (11) | 0.79603 (9) | 0.0812 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Re1 | 0.02086 (10) | 0.01914 (8) | 0.02014 (8) | −0.00205 (7) | −0.00233 (6) | −0.00001 (6) |
Re2 | 0.02018 (9) | 0.01788 (7) | 0.01915 (8) | −0.00070 (7) | −0.00144 (6) | 0.00002 (6) |
Cl1 | 0.0280 (6) | 0.0331 (5) | 0.0342 (6) | −0.0082 (5) | −0.0022 (5) | −0.0049 (4) |
Cl2 | 0.0261 (6) | 0.0293 (5) | 0.0289 (5) | −0.0048 (4) | −0.0024 (4) | 0.0049 (4) |
S1 | 0.0285 (6) | 0.0205 (5) | 0.0279 (5) | −0.0049 (4) | −0.0047 (5) | 0.0034 (4) |
S2 | 0.0354 (7) | 0.0283 (5) | 0.0245 (5) | −0.0053 (5) | −0.0055 (5) | 0.0070 (4) |
S3 | 0.0300 (7) | 0.0303 (5) | 0.0264 (5) | −0.0040 (5) | −0.0011 (5) | −0.0074 (4) |
S4 | 0.0402 (8) | 0.0305 (5) | 0.0331 (6) | 0.0001 (5) | 0.0050 (5) | −0.0130 (4) |
S5 | 0.0262 (6) | 0.0304 (5) | 0.0266 (5) | −0.0038 (5) | −0.0031 (5) | 0.0087 (4) |
S6 | 0.0341 (7) | 0.0362 (6) | 0.0393 (6) | −0.0017 (5) | −0.0091 (5) | 0.0166 (5) |
S7 | 0.0244 (6) | 0.0197 (4) | 0.0306 (5) | −0.0026 (4) | 0.0013 (5) | −0.0043 (4) |
S8 | 0.0366 (7) | 0.0319 (5) | 0.0288 (6) | −0.0057 (5) | 0.0065 (5) | −0.0091 (4) |
N1 | 0.028 (2) | 0.0186 (15) | 0.0173 (16) | −0.0007 (14) | −0.0024 (14) | −0.0011 (12) |
N2 | 0.027 (2) | 0.0212 (16) | 0.0207 (17) | 0.0018 (15) | 0.0004 (15) | 0.0010 (13) |
N3 | 0.023 (2) | 0.0233 (16) | 0.0255 (18) | −0.0031 (15) | −0.0052 (15) | −0.0016 (13) |
N4 | 0.0210 (19) | 0.0209 (15) | 0.0257 (18) | 0.0022 (14) | −0.0023 (15) | 0.0025 (13) |
C1 | 0.028 (2) | 0.0202 (18) | 0.0175 (19) | 0.0016 (17) | −0.0027 (17) | −0.0005 (14) |
C2 | 0.021 (2) | 0.0275 (19) | 0.0197 (19) | 0.0017 (17) | 0.0010 (17) | −0.0037 (15) |
C3 | 0.026 (3) | 0.030 (2) | 0.028 (2) | −0.0002 (19) | 0.0001 (19) | 0.0021 (17) |
C4 | 0.025 (3) | 0.035 (2) | 0.033 (2) | −0.005 (2) | −0.001 (2) | −0.0026 (18) |
C5 | 0.028 (3) | 0.044 (2) | 0.027 (2) | 0.002 (2) | −0.0113 (19) | −0.0024 (19) |
C6 | 0.029 (3) | 0.035 (2) | 0.023 (2) | 0.005 (2) | −0.0035 (19) | 0.0023 (17) |
C7 | 0.026 (2) | 0.0252 (19) | 0.026 (2) | −0.0009 (18) | 0.0007 (18) | −0.0013 (16) |
C8 | 0.034 (3) | 0.0230 (19) | 0.020 (2) | −0.0014 (18) | 0.0047 (18) | −0.0018 (15) |
C9 | 0.037 (3) | 0.0205 (19) | 0.023 (2) | 0.0046 (19) | 0.0066 (19) | 0.0027 (15) |
C10 | 0.030 (3) | 0.028 (2) | 0.025 (2) | 0.0068 (19) | −0.0005 (19) | 0.0025 (16) |
C11 | 0.030 (3) | 0.036 (2) | 0.045 (3) | 0.007 (2) | −0.002 (2) | 0.002 (2) |
C12 | 0.036 (3) | 0.033 (2) | 0.053 (3) | 0.014 (2) | 0.009 (2) | −0.001 (2) |
C13 | 0.044 (3) | 0.025 (2) | 0.042 (3) | 0.012 (2) | 0.006 (2) | −0.0049 (18) |
C14 | 0.041 (3) | 0.0179 (19) | 0.036 (2) | 0.0042 (19) | 0.004 (2) | −0.0011 (16) |
C15 | 0.028 (3) | 0.0234 (19) | 0.026 (2) | −0.0006 (18) | −0.0074 (19) | 0.0036 (16) |
C16 | 0.028 (3) | 0.0202 (19) | 0.034 (2) | 0.0033 (18) | −0.008 (2) | −0.0022 (16) |
C17 | 0.029 (3) | 0.033 (2) | 0.027 (2) | 0.005 (2) | −0.002 (2) | −0.0057 (17) |
C18 | 0.029 (3) | 0.038 (2) | 0.042 (3) | 0.002 (2) | 0.000 (2) | −0.011 (2) |
C19 | 0.033 (3) | 0.028 (2) | 0.053 (3) | 0.009 (2) | −0.021 (2) | −0.008 (2) |
C20 | 0.035 (3) | 0.030 (2) | 0.041 (3) | 0.002 (2) | −0.013 (2) | 0.0022 (19) |
C21 | 0.036 (3) | 0.0211 (19) | 0.032 (2) | −0.0004 (19) | −0.007 (2) | −0.0004 (16) |
C22 | 0.026 (2) | 0.0219 (18) | 0.022 (2) | 0.0011 (18) | −0.0022 (18) | 0.0015 (15) |
C23 | 0.024 (2) | 0.0231 (19) | 0.022 (2) | 0.0027 (17) | −0.0012 (17) | 0.0027 (15) |
C24 | 0.029 (3) | 0.031 (2) | 0.031 (2) | −0.003 (2) | 0.0014 (19) | 0.0039 (17) |
C25 | 0.030 (3) | 0.037 (2) | 0.038 (3) | −0.003 (2) | 0.003 (2) | 0.0069 (19) |
C26 | 0.031 (3) | 0.049 (3) | 0.030 (2) | 0.002 (2) | 0.011 (2) | 0.002 (2) |
C27 | 0.037 (3) | 0.043 (3) | 0.029 (2) | 0.004 (2) | 0.011 (2) | −0.0046 (19) |
C28 | 0.032 (3) | 0.031 (2) | 0.024 (2) | −0.001 (2) | −0.0007 (19) | −0.0009 (17) |
C29 | 0.168 (9) | 0.057 (4) | 0.105 (6) | −0.051 (5) | 0.069 (6) | −0.042 (4) |
Cl3 | 0.0685 (12) | 0.0638 (9) | 0.0700 (10) | 0.0075 (8) | −0.0028 (8) | −0.0114 (7) |
Cl4 | 0.0864 (14) | 0.0901 (11) | 0.0683 (11) | 0.0118 (10) | 0.0203 (10) | 0.0025 (9) |
Re1—N3 | 2.100 (3) | C5—H5 | 0.9400 |
Re1—N4 | 2.159 (3) | C6—C7 | 1.393 (6) |
Re1—Re2 | 2.2716 (3) | C6—H6 | 0.9400 |
Re1—S1 | 2.3879 (9) | C9—C14 | 1.395 (5) |
Re1—S3 | 2.4126 (10) | C9—C10 | 1.397 (6) |
Re1—Cl1 | 2.5488 (11) | C10—C11 | 1.376 (6) |
Re2—N2 | 2.103 (3) | C10—H10 | 0.9400 |
Re2—N1 | 2.139 (3) | C11—C12 | 1.405 (6) |
Re2—S7 | 2.3786 (9) | C11—H11 | 0.9400 |
Re2—S5 | 2.4006 (10) | C12—C13 | 1.377 (7) |
Re2—Cl2 | 2.5529 (10) | C12—H12 | 0.9400 |
S1—C1 | 1.694 (4) | C13—C14 | 1.392 (6) |
S2—C1 | 1.729 (4) | C13—H13 | 0.9400 |
S2—C7 | 1.730 (4) | C16—C17 | 1.380 (6) |
S3—C8 | 1.692 (5) | C16—C21 | 1.412 (5) |
S4—C8 | 1.732 (4) | C17—C18 | 1.392 (6) |
S4—C14 | 1.744 (5) | C17—H17 | 0.9400 |
S5—C15 | 1.689 (4) | C18—C19 | 1.401 (6) |
S6—C15 | 1.731 (4) | C18—H18 | 0.9400 |
S6—C21 | 1.733 (5) | C19—C20 | 1.373 (6) |
S7—C22 | 1.692 (4) | C19—H19 | 0.9400 |
S8—C22 | 1.733 (4) | C20—C21 | 1.387 (6) |
S8—C28 | 1.733 (4) | C20—H20 | 0.9400 |
N1—C1 | 1.354 (5) | C23—C24 | 1.392 (6) |
N1—C2 | 1.411 (5) | C23—C28 | 1.398 (5) |
N2—C8 | 1.345 (5) | C24—C25 | 1.379 (6) |
N2—C9 | 1.401 (5) | C24—H24 | 0.9400 |
N3—C15 | 1.346 (5) | C25—C26 | 1.387 (6) |
N3—C16 | 1.415 (5) | C25—H25 | 0.9400 |
N4—C22 | 1.348 (5) | C26—C27 | 1.372 (6) |
N4—C23 | 1.403 (5) | C26—H26 | 0.9400 |
C2—C3 | 1.394 (5) | C27—C28 | 1.397 (6) |
C2—C7 | 1.398 (5) | C27—H27 | 0.9400 |
C3—C4 | 1.375 (6) | C29—Cl3 | 1.696 (7) |
C3—H3 | 0.9400 | C29—Cl4 | 1.742 (7) |
C4—C5 | 1.388 (6) | C29—H29A | 0.9800 |
C4—H4 | 0.9400 | C29—H29B | 0.9800 |
C5—C6 | 1.378 (6) | ||
N3—Re1—N4 | 89.95 (12) | C2—C7—S2 | 111.2 (3) |
N3—Re1—Re2 | 99.94 (9) | N2—C8—S3 | 123.6 (3) |
N4—Re1—Re2 | 96.65 (9) | N2—C8—S4 | 114.2 (3) |
N3—Re1—S1 | 168.74 (10) | S3—C8—S4 | 122.1 (2) |
N4—Re1—S1 | 88.75 (8) | C14—C9—C10 | 119.9 (4) |
Re2—Re1—S1 | 91.33 (3) | C14—C9—N2 | 113.2 (4) |
N3—Re1—S3 | 88.03 (9) | C10—C9—N2 | 127.0 (4) |
N4—Re1—S3 | 174.72 (9) | C11—C10—C9 | 119.1 (4) |
Re2—Re1—S3 | 88.50 (3) | C11—C10—H10 | 120.5 |
S1—Re1—S3 | 92.28 (4) | C9—C10—H10 | 120.5 |
N3—Re1—Cl1 | 91.55 (9) | C10—C11—C12 | 120.5 (5) |
N4—Re1—Cl1 | 101.05 (9) | C10—C11—H11 | 119.7 |
Re2—Re1—Cl1 | 158.88 (3) | C12—C11—H11 | 119.7 |
S1—Re1—Cl1 | 77.73 (4) | C13—C12—C11 | 120.9 (5) |
S3—Re1—Cl1 | 74.14 (4) | C13—C12—H12 | 119.5 |
N2—Re2—N1 | 88.27 (11) | C11—C12—H12 | 119.5 |
N2—Re2—Re1 | 99.09 (9) | C12—C13—C14 | 118.4 (4) |
N1—Re2—Re1 | 97.47 (9) | C12—C13—H13 | 120.8 |
N2—Re2—S7 | 168.07 (10) | C14—C13—H13 | 120.8 |
N1—Re2—S7 | 87.61 (8) | C13—C14—C9 | 121.2 (4) |
Re1—Re2—S7 | 92.55 (3) | C13—C14—S4 | 127.9 (3) |
N2—Re2—S5 | 90.33 (9) | C9—C14—S4 | 110.9 (3) |
N1—Re2—S5 | 174.07 (10) | N3—C15—S5 | 123.7 (3) |
Re1—Re2—S5 | 88.44 (3) | N3—C15—S6 | 114.4 (3) |
S7—Re2—S5 | 92.63 (4) | S5—C15—S6 | 121.8 (2) |
N2—Re2—Cl2 | 90.49 (9) | C17—C16—C21 | 120.2 (4) |
N1—Re2—Cl2 | 100.53 (9) | C17—C16—N3 | 127.2 (4) |
Re1—Re2—Cl2 | 159.85 (2) | C21—C16—N3 | 112.6 (4) |
S7—Re2—Cl2 | 79.27 (3) | C16—C17—C18 | 118.6 (4) |
S5—Re2—Cl2 | 73.72 (3) | C16—C17—H17 | 120.7 |
C1—S1—Re1 | 104.83 (13) | C18—C17—H17 | 120.7 |
C1—S2—C7 | 89.93 (19) | C17—C18—C19 | 120.6 (5) |
C8—S3—Re1 | 106.14 (13) | C17—C18—H18 | 119.7 |
C8—S4—C14 | 89.7 (2) | C19—C18—H18 | 119.7 |
C15—S5—Re2 | 106.92 (14) | C20—C19—C18 | 121.1 (4) |
C15—S6—C21 | 90.3 (2) | C20—C19—H19 | 119.4 |
C22—S7—Re2 | 103.92 (13) | C18—C19—H19 | 119.4 |
C22—S8—C28 | 89.63 (19) | C19—C20—C21 | 118.5 (4) |
C1—N1—C2 | 110.6 (3) | C19—C20—H20 | 120.7 |
C1—N1—Re2 | 117.0 (3) | C21—C20—H20 | 120.7 |
C2—N1—Re2 | 132.2 (2) | C20—C21—C16 | 120.9 (4) |
C8—N2—C9 | 111.9 (3) | C20—C21—S6 | 128.0 (3) |
C8—N2—Re2 | 116.1 (3) | C16—C21—S6 | 111.0 (3) |
C9—N2—Re2 | 131.3 (3) | N4—C22—S7 | 126.2 (3) |
C15—N3—C16 | 111.6 (3) | N4—C22—S8 | 114.9 (3) |
C15—N3—Re1 | 115.8 (3) | S7—C22—S8 | 118.9 (2) |
C16—N3—Re1 | 131.7 (3) | C24—C23—C28 | 118.7 (4) |
C22—N4—C23 | 110.7 (3) | C24—C23—N4 | 127.5 (4) |
C22—N4—Re1 | 116.6 (3) | C28—C23—N4 | 113.8 (4) |
C23—N4—Re1 | 132.6 (3) | C25—C24—C23 | 118.7 (4) |
N1—C1—S1 | 124.8 (3) | C25—C24—H24 | 120.6 |
N1—C1—S2 | 114.6 (3) | C23—C24—H24 | 120.6 |
S1—C1—S2 | 120.5 (2) | C24—C25—C26 | 122.1 (4) |
C3—C2—C7 | 119.9 (4) | C24—C25—H25 | 118.9 |
C3—C2—N1 | 126.7 (3) | C26—C25—H25 | 118.9 |
C7—C2—N1 | 113.4 (3) | C27—C26—C25 | 120.2 (4) |
C4—C3—C2 | 118.0 (4) | C27—C26—H26 | 119.9 |
C4—C3—H3 | 121.0 | C25—C26—H26 | 119.9 |
C2—C3—H3 | 121.0 | C26—C27—C28 | 118.1 (4) |
C3—C4—C5 | 122.4 (4) | C26—C27—H27 | 121.0 |
C3—C4—H4 | 118.8 | C28—C27—H27 | 121.0 |
C5—C4—H4 | 118.8 | C27—C28—C23 | 122.1 (4) |
C6—C5—C4 | 120.0 (4) | C27—C28—S8 | 126.8 (3) |
C6—C5—H5 | 120.0 | C23—C28—S8 | 110.9 (3) |
C4—C5—H5 | 120.0 | Cl3—C29—Cl4 | 115.7 (3) |
C5—C6—C7 | 118.5 (4) | Cl3—C29—H29A | 108.4 |
C5—C6—H6 | 120.8 | Cl4—C29—H29A | 108.4 |
C7—C6—H6 | 120.8 | Cl3—C29—H29B | 108.4 |
C6—C7—C2 | 121.2 (4) | Cl4—C29—H29B | 108.4 |
C6—C7—S2 | 127.5 (3) | H29A—C29—H29B | 107.4 |
S1—Re1—Re2—N1 | −17.44 (8) | N3—Re1—Re2—S5 | −17.91 (9) |
S3—Re1—Re2—N2 | −20.26 (9) | N4—Re1—Re2—S7 | −16.46 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···Cl2 | 0.94 | 2.50 | 3.347 (4) | 150 |
C24—H24···Cl1 | 0.94 | 2.52 | 3.382 (4) | 153 |
Experimental details
Crystal data | |
Chemical formula | [Re2(S2NC7H4)4Cl2]·CH2Cl2 |
Mr | 1193.15 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 213 |
a, b, c (Å) | 12.9408 (7), 15.5347 (8), 17.5303 (9) |
β (°) | 92.092 (1) |
V (Å3) | 3521.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.68 |
Crystal size (mm) | 0.38 × 0.16 × 0.02 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Analytical face-indexed (XPREP in SHELXTL; Siemens, 1996) |
Tmin, Tmax | 0.174, 0.851 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21991, 8000, 6368 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.051, 0.98 |
No. of reflections | 8000 |
No. of parameters | 424 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.10, −0.71 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996), SHELXL97.
Re1—N3 | 2.100 (3) | Re2—N2 | 2.103 (3) |
Re1—N4 | 2.159 (3) | Re2—N1 | 2.139 (3) |
Re1—Re2 | 2.2716 (3) | Re2—S7 | 2.3786 (9) |
Re1—S1 | 2.3879 (9) | Re2—S5 | 2.4006 (10) |
Re1—S3 | 2.4126 (10) | Re2—Cl2 | 2.5529 (10) |
Re1—Cl1 | 2.5488 (11) | ||
Re2—Re1—Cl1 | 158.88 (3) | Re1—Re2—Cl2 | 159.85 (2) |
S1—Re1—Re2—N1 | −17.44 (8) | N3—Re1—Re2—S5 | −17.91 (9) |
S3—Re1—Re2—N2 | −20.26 (9) | N4—Re1—Re2—S7 | −16.46 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···Cl2 | 0.94 | 2.50 | 3.347 (4) | 150 |
C24—H24···Cl1 | 0.94 | 2.52 | 3.382 (4) | 153 |
In the major component, [Re2(S2NC7H4)4Cl2], of the title compound, (I), each one of the four benzothiazole-2-thiolate ligands bridges the dirhenium unit by binding through one S atom and the N atom, rather than through both S atoms. The preference of ReIII to form bonds to N rather than S has been previously documented by the discovery of N-bound thiocyanate ligands in the [Re2(NCS)8]2- ion (Cotton et al., 1967). \sch
The four bridging ligands are arranged so that all N and S atoms are trans to each other. This leads to a cis arrangement of N and S atoms around each Re atom. Two axial Cl- ligands and an Re—Re bond complete the coordination about the dirhenium unit, so that both metal atoms end up in essentially identical pseudo-octahedral environments.
Hydrogen bonding exists between the two Cl- ligands and the H atoms at the 4-positions on two of the benzothiazole-2-thiolate ligands (Table 2). The Cl1—H24 and Cl2—H3 distances are 2.50 and 2.52 Å, respectively, and these are illustrated by dashed lines in Fig. 1. Apparently as a result of this hydrogen bonding, the Re—Re—Cl bond angles are bent away from linearity at 158.88 (3) and 159.85 (2)°.
As illustrated in Fig. 2, the molecule takes on a somewhat staggered conformation, with an average torsion angle about the dirhenium axis of 18 (1)°. This torsional twist is far greater than that in any of the compounds with bridging ligands listed in Cotton and Walton's compilation of structural data for compounds containing Re—Re quadruple bonds (Cotton & Walton, 1993). The Re—Re bond distance of 2.2716 (3) Å is also longer than that in any of the bridged compounds in Cotton and Walton's list. Twisting away from an eclipsed conformation is known to weaken the δ component of the quadruple bond (Campbell et al., 1985). However, another factor seems to be at work in (I).
A search of the Cambridge Structural Database (Version 5.22; Allen & Kennard, 1993) for structures published after Cotton and Walton's book went to press has yielded six molecules with Re—Re quadruple bonds longer than 2.25 Å. In each of these molecules, there is at least one bridging ligand. These bridging ligands are 2,6-bis(diphenylphosphino)pyridine (Cotton et al., 1998) and N,N'-diarylformamidinate, with aryl = p-tolyl (Cotton & Ren, 1992), and p-methoxyphenyl, 3,4-dichlorophenyl and 3,5-dichlorophenyl (Eglin et al., 1999). All torsion angles about the dirhenium units are less than 12°, but the Re—Re bond distances range from 2.270 to 2.304 Å. This elongation of the quadruple bonds has been attributed to the presence of axial Cl- ligands (Cotton et al., 1998).
Molecules of (I) pack in a way that maximizes S—S interactions, as shown in Fig. 3. There are intermolecular contacts involving one Cl- ligand (Cl2) and all S atoms, with the exception of S4. These nonbonding distances range from 3.467 to 3.626 Å.