Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100009756/bk1540sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100009756/bk1540Isup2.hkl |
CCDC reference: 152592
To prepare the p-hydroxybenzoate molecule, [Rh2(C7H5O3)4], RhCl3·3H2O (0.25 g, 0.95 mmol) and 4-hydroxybenzoic acid (0.52 g, 3.8 mmol) were dissolved in ethanol-water (10 ml; 1:1) and heated at 333–343 K for 1 h. The mixture was cooled to room temperature and evaporated to dryness using a rotary evaporator. Excess 4-hydroxybenzoic acid and unreacted rhodium chloride were removed by washing with three hot 10 ml portions of water-ethanol (10:1). The green product was dried in a vacuum oven at 313 K for 24 h (yield 0.11 g, 28%, based on Rh). The purity of the compound obtained was checked by 1H and 13C NMR methods, using 5 mm tubes in a Bruker AM 300 NMR spectrometer operating at 300.13 and 75.47 MHz, respectively. 1H NMR (CD3OD, d, p.p.m., AA'BB' system): 6.60–6.63 (m), 7.45–7.77 (m); 13C NMR (CD3OD, d, p.p.m.): 115.65 (d, CH), 125.39 (s, CCOO), 132.23 (d, CH), 162.39 (s, COH), 186.26 (s, COO). Tetra-µ-butyrate dirhodium(II), [Rh2(C4H7O2)4], was prepared using literature methods (Behrens et al., 1985; Drago et al., 1979; Cotton & Shiu, 1986). Slow evaporation of an ethanol solution of a mixture of [Rh2(C7H5O3)4] and [Rh2(C4H7O2)4] with addition of some drops of dimethyl sulfoxide adventitiously generated crystals of (I) in a recycling container. Crystals of the pure tetrabenzoate dimer were also obtained and X-ray data were collected. However, after partial refinement it became clear that the axial ligands, water and ethanol were disordered. Poor data quality prevented further refinement (R1 > 10%) and the structure was abandoned.
H atoms connected to C were placed in calculated positions using a riding model. H atoms connected to O were refined isotropically in observed positions, subject to a restraint of 0.82 (3) Å on the O—H distance. The rotations of the dmso methyl groups were varied. One of the butyrate chains showed slight disorder. Atom C19 occupies an alternative position C19A. In order to model the disordered H atoms on C18 and C20, atoms C18A and C20A were utilized. Their coordinates and displacement parameters were constrained to be identical to those of C18 and C20.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SHELXTL (Sheldrick, 1997a); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: DIAMOND.
[Rh2(C7H5O3)4(C2H6OS)2]·[Rh2(C4H7O2)4(C2H6OS)2]·2C2H6O | F(000) = 1744 |
Mr = 1713.12 | Dx = 1.638 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.9418 (6) Å | Cell parameters from 6450 reflections |
b = 15.2880 (8) Å | θ = 4.8–56.5° |
c = 19.0307 (10) Å | µ = 1.13 mm−1 |
β = 90.915 (1)° | T = 173 K |
V = 3473.9 (3) Å3 | Block, red |
Z = 2 | 0.22 × 0.20 × 0.14 mm |
SMART CCD area-detector diffractometer | 7201 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.052 |
Graphite monochromator | θmax = 28.3°, θmin = 1.7° |
ω scans | h = −15→15 |
38253 measured reflections | k = −20→20 |
8473 independent reflections | l = −24→24 |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.035P)2 + 3.15P] where P = (Fo2 + 2Fc2)/3 |
8473 reflections | (Δ/σ)max = 0.001 |
433 parameters | Δρmax = 0.54 e Å−3 |
3 restraints | Δρmin = −0.97 e Å−3 |
[Rh2(C7H5O3)4(C2H6OS)2]·[Rh2(C4H7O2)4(C2H6OS)2]·2C2H6O | V = 3473.9 (3) Å3 |
Mr = 1713.12 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.9418 (6) Å | µ = 1.13 mm−1 |
b = 15.2880 (8) Å | T = 173 K |
c = 19.0307 (10) Å | 0.22 × 0.20 × 0.14 mm |
β = 90.915 (1)° |
SMART CCD area-detector diffractometer | 7201 reflections with I > 2σ(I) |
38253 measured reflections | Rint = 0.052 |
8473 independent reflections |
R[F2 > 2σ(F2)] = 0.030 | 3 restraints |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.54 e Å−3 |
8473 reflections | Δρmin = −0.97 e Å−3 |
433 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. Crystal stability was monitored by re-collection of the first 50 frames (395 reflections) after data collection was complete. No significant decay was observed. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Rh1 | 0.100678 (14) | 0.005528 (11) | 0.001162 (9) | 0.01307 (5) | |
Rh2 | 0.054096 (17) | 0.066295 (13) | −0.499505 (11) | 0.02311 (6) | |
S1 | 0.30491 (5) | 0.01462 (4) | 0.00847 (3) | 0.01631 (12) | |
S2 | 0.15621 (6) | 0.20343 (4) | −0.49344 (4) | 0.02477 (14) | |
O1 | 0.10233 (14) | −0.09530 (11) | 0.07042 (9) | 0.0198 (4) | |
O2 | −0.08636 (13) | −0.10590 (11) | 0.06930 (9) | 0.0191 (3) | |
O3 | 0.05008 (19) | −0.42358 (17) | 0.26575 (14) | 0.0508 (7) | |
O4 | 0.10156 (14) | −0.08141 (11) | −0.07970 (9) | 0.0201 (4) | |
O5 | −0.08718 (14) | −0.09147 (11) | −0.08273 (9) | 0.0195 (4) | |
O6 | 0.04274 (17) | −0.28154 (15) | −0.36579 (10) | 0.0314 (5) | |
O7 | 0.37429 (14) | −0.03176 (12) | −0.04481 (9) | 0.0241 (4) | |
O8 | −0.03579 (17) | −0.07098 (13) | −0.60592 (10) | 0.0307 (4) | |
O9 | −0.09256 (16) | 0.13256 (13) | −0.51254 (10) | 0.0311 (4) | |
O10 | 0.06733 (17) | 0.05271 (13) | −0.60602 (10) | 0.0301 (4) | |
O11 | 0.14268 (16) | 0.26783 (13) | −0.55202 (10) | 0.0290 (4) | |
O12 | −0.14880 (18) | −0.46942 (14) | 0.31493 (11) | 0.0306 (4) | |
O13 | −0.19390 (17) | 0.00855 (13) | −0.51556 (11) | 0.0332 (5) | |
C1 | 0.01081 (19) | −0.12983 (15) | 0.08933 (12) | 0.0170 (5) | |
C2 | 0.0196 (2) | −0.20528 (16) | 0.13781 (12) | 0.0189 (5) | |
C3 | −0.0732 (2) | −0.23637 (17) | 0.17333 (13) | 0.0222 (5) | |
H3 | −0.1434 | −0.2078 | 0.1674 | 0.027* | |
C4 | −0.0645 (2) | −0.30812 (19) | 0.21701 (14) | 0.0289 (6) | |
H4 | −0.1282 | −0.3279 | 0.2417 | 0.035* | |
C5 | 0.0368 (2) | −0.3514 (2) | 0.22493 (15) | 0.0315 (6) | |
C6 | 0.1305 (2) | −0.3214 (2) | 0.18945 (17) | 0.0389 (8) | |
H6 | 0.2000 | −0.3513 | 0.1942 | 0.047* | |
C7 | 0.1220 (2) | −0.24779 (19) | 0.14733 (15) | 0.0285 (6) | |
H7 | 0.1866 | −0.2260 | 0.1247 | 0.034* | |
C8 | 0.00949 (19) | −0.10839 (15) | −0.10639 (12) | 0.0170 (5) | |
C9 | 0.0169 (2) | −0.16140 (16) | −0.17127 (12) | 0.0180 (5) | |
C10 | 0.1201 (2) | −0.17232 (18) | −0.20336 (14) | 0.0246 (5) | |
H10 | 0.1864 | −0.1514 | −0.1808 | 0.030* | |
C11 | 0.1265 (2) | −0.2136 (2) | −0.26803 (14) | 0.0291 (6) | |
H11 | 0.1973 | −0.2213 | −0.2893 | 0.035* | |
C12 | 0.0306 (2) | −0.24372 (17) | −0.30184 (13) | 0.0234 (5) | |
C13 | −0.0723 (2) | −0.23536 (18) | −0.26947 (14) | 0.0255 (6) | |
H13 | −0.1380 | −0.2580 | −0.2916 | 0.031* | |
C14 | −0.0790 (2) | −0.19411 (17) | −0.20500 (13) | 0.0232 (5) | |
H14 | −0.1498 | −0.1880 | −0.1834 | 0.028* | |
C15 | 0.3522 (2) | 0.12465 (18) | 0.01076 (16) | 0.0310 (6) | |
H15A | 0.4325 | 0.1259 | 0.0220 | 0.047* | |
H15B | 0.3114 | 0.1569 | 0.0468 | 0.047* | |
H15C | 0.3386 | 0.1519 | −0.0352 | 0.047* | |
C16 | 0.3522 (2) | −0.02245 (19) | 0.09234 (13) | 0.0249 (5) | |
H16A | 0.3321 | −0.0842 | 0.0981 | 0.037* | |
H16B | 0.3168 | 0.0124 | 0.1291 | 0.037* | |
H16C | 0.4337 | −0.0160 | 0.0960 | 0.037* | |
C17 | −0.1838 (2) | 0.09052 (19) | −0.51952 (15) | 0.0305 (6) | |
C18 | −0.2872 (3) | 0.1442 (2) | −0.5348 (2) | 0.0493 (9) | 0.50 |
H18A | −0.2858 | 0.1624 | −0.5847 | 0.059* | 0.50 |
H18B | −0.2833 | 0.1979 | −0.5059 | 0.059* | 0.50 |
C19 | −0.3982 (5) | 0.1000 (5) | −0.5217 (4) | 0.0415 (15) | 0.50 |
H19A | −0.3989 | 0.0415 | −0.5440 | 0.050* | 0.50 |
H19B | −0.4594 | 0.1350 | −0.5433 | 0.050* | 0.50 |
C20 | −0.4185 (4) | 0.0904 (4) | −0.4415 (3) | 0.0981 (19) | 0.50 |
H20A | −0.4912 | 0.0623 | −0.4342 | 0.147* | 0.50 |
H20B | −0.4182 | 0.1483 | −0.4195 | 0.147* | 0.50 |
H20C | −0.3590 | 0.0544 | −0.4204 | 0.147* | 0.50 |
C18A | −0.2872 (3) | 0.1442 (2) | −0.5348 (2) | 0.0493 (9) | 0.50 |
H18C | −0.3388 | 0.1093 | −0.5650 | 0.059* | 0.50 |
H18D | −0.2654 | 0.1967 | −0.5618 | 0.059* | 0.50 |
C19A | −0.3498 (7) | 0.1734 (5) | −0.4701 (4) | 0.0552 (19) | 0.50 |
H19C | −0.4018 | 0.2217 | −0.4822 | 0.066* | 0.50 |
H19D | −0.2963 | 0.1944 | −0.4335 | 0.066* | 0.50 |
C20A | −0.4185 (4) | 0.0904 (4) | −0.4415 (3) | 0.0981 (19) | 0.50 |
H20D | −0.4580 | 0.1067 | −0.3987 | 0.147* | 0.50 |
H20E | −0.3665 | 0.0424 | −0.4310 | 0.147* | 0.50 |
H20F | −0.4729 | 0.0714 | −0.4775 | 0.147* | 0.50 |
C21 | 0.3020 (3) | 0.1901 (2) | −0.4778 (2) | 0.0473 (9) | |
H21A | 0.3353 | 0.1597 | −0.5177 | 0.071* | |
H21B | 0.3141 | 0.1556 | −0.4349 | 0.071* | |
H21C | 0.3372 | 0.2476 | −0.4720 | 0.071* | |
C22 | 0.1200 (3) | 0.2581 (2) | −0.41420 (15) | 0.0412 (8) | |
H22A | 0.1602 | 0.3139 | −0.4111 | 0.062* | |
H22B | 0.1408 | 0.2214 | −0.3738 | 0.062* | |
H22C | 0.0391 | 0.2690 | −0.4141 | 0.062* | |
C23 | −0.2090 (4) | −0.5441 (3) | 0.2115 (2) | 0.0710 (13) | |
H23A | −0.2368 | −0.4887 | 0.1922 | 0.106* | |
H23B | −0.2557 | −0.5923 | 0.1938 | 0.106* | |
H23C | −0.1314 | −0.5531 | 0.1972 | 0.106* | |
C24 | −0.2138 (3) | −0.5414 (2) | 0.28980 (17) | 0.0375 (7) | |
H24A | −0.2925 | −0.5349 | 0.3047 | 0.045* | |
H24B | −0.1840 | −0.5967 | 0.3097 | 0.045* | |
C25 | 0.0210 (2) | −0.01212 (18) | −0.63610 (15) | 0.0280 (6) | |
C26 | 0.0357 (3) | −0.0220 (2) | −0.71426 (15) | 0.0348 (7) | |
H26A | −0.0063 | −0.0743 | −0.7304 | 0.042* | |
H26B | 0.0024 | 0.0296 | −0.7382 | 0.042* | |
C27 | 0.1530 (3) | −0.0306 (3) | −0.7356 (2) | 0.0704 (14) | |
H27A | 0.1943 | 0.0231 | −0.7220 | 0.084* | |
H27B | 0.1556 | −0.0360 | −0.7874 | 0.084* | |
C28 | 0.2094 (6) | −0.1070 (5) | −0.7033 (3) | 0.160 (4) | |
H28A | 0.2193 | −0.0971 | −0.6527 | 0.240* | |
H28B | 0.2827 | −0.1152 | −0.7247 | 0.240* | |
H28C | 0.1635 | −0.1594 | −0.7111 | 0.240* | |
H3O | −0.009 (2) | −0.435 (3) | 0.278 (2) | 0.064 (14)* | |
H6O | −0.010 (2) | −0.277 (2) | −0.3865 (15) | 0.029 (9)* | |
H12O | −0.146 (3) | −0.470 (2) | 0.3534 (12) | 0.040 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh1 | 0.01132 (9) | 0.01500 (10) | 0.01289 (9) | −0.00033 (7) | 0.00035 (7) | 0.00025 (7) |
Rh2 | 0.02344 (11) | 0.02204 (12) | 0.02382 (11) | −0.00281 (8) | −0.00077 (8) | 0.00200 (8) |
S1 | 0.0131 (3) | 0.0190 (3) | 0.0169 (3) | −0.0004 (2) | 0.0008 (2) | −0.0009 (2) |
S2 | 0.0240 (3) | 0.0232 (3) | 0.0270 (3) | −0.0029 (3) | −0.0043 (3) | 0.0015 (3) |
O1 | 0.0148 (8) | 0.0220 (9) | 0.0226 (9) | −0.0016 (7) | −0.0008 (7) | 0.0086 (7) |
O2 | 0.0149 (8) | 0.0212 (9) | 0.0212 (8) | 0.0011 (7) | 0.0001 (7) | 0.0073 (7) |
O3 | 0.0258 (11) | 0.0555 (16) | 0.0709 (17) | 0.0009 (11) | −0.0005 (12) | 0.0485 (13) |
O4 | 0.0160 (8) | 0.0259 (9) | 0.0183 (8) | 0.0014 (7) | 0.0001 (7) | −0.0078 (7) |
O5 | 0.0151 (8) | 0.0245 (9) | 0.0189 (8) | −0.0005 (7) | 0.0015 (7) | −0.0063 (7) |
O6 | 0.0256 (10) | 0.0469 (13) | 0.0218 (10) | 0.0059 (9) | −0.0026 (8) | −0.0145 (9) |
O7 | 0.0201 (9) | 0.0316 (10) | 0.0208 (9) | 0.0048 (8) | 0.0034 (7) | −0.0046 (8) |
O8 | 0.0366 (11) | 0.0316 (11) | 0.0240 (9) | −0.0082 (9) | −0.0016 (8) | 0.0014 (8) |
O9 | 0.0274 (10) | 0.0259 (10) | 0.0400 (11) | 0.0009 (8) | −0.0030 (9) | 0.0027 (9) |
O10 | 0.0371 (11) | 0.0282 (10) | 0.0252 (10) | −0.0067 (9) | 0.0028 (8) | 0.0008 (8) |
O11 | 0.0288 (10) | 0.0299 (10) | 0.0280 (10) | −0.0051 (8) | −0.0029 (8) | 0.0061 (8) |
O12 | 0.0354 (11) | 0.0352 (11) | 0.0210 (10) | −0.0105 (9) | −0.0003 (9) | 0.0049 (9) |
O13 | 0.0273 (11) | 0.0280 (11) | 0.0441 (12) | 0.0000 (8) | −0.0040 (9) | 0.0035 (9) |
C1 | 0.0180 (11) | 0.0181 (12) | 0.0149 (11) | −0.0002 (9) | 0.0008 (9) | 0.0000 (9) |
C2 | 0.0176 (11) | 0.0210 (12) | 0.0182 (11) | −0.0021 (9) | −0.0005 (9) | 0.0026 (9) |
C3 | 0.0180 (12) | 0.0235 (13) | 0.0253 (13) | 0.0022 (10) | 0.0027 (10) | 0.0053 (10) |
C4 | 0.0224 (13) | 0.0343 (16) | 0.0301 (14) | −0.0029 (11) | 0.0031 (11) | 0.0138 (12) |
C5 | 0.0232 (13) | 0.0349 (16) | 0.0362 (15) | −0.0010 (12) | −0.0044 (12) | 0.0208 (13) |
C6 | 0.0193 (13) | 0.0437 (18) | 0.054 (2) | 0.0046 (12) | −0.0006 (13) | 0.0261 (15) |
C7 | 0.0182 (12) | 0.0331 (15) | 0.0342 (15) | −0.0001 (11) | 0.0018 (11) | 0.0142 (12) |
C8 | 0.0176 (11) | 0.0161 (11) | 0.0173 (11) | −0.0003 (9) | −0.0004 (9) | 0.0014 (9) |
C9 | 0.0181 (11) | 0.0182 (12) | 0.0177 (11) | −0.0010 (9) | 0.0002 (9) | −0.0010 (9) |
C10 | 0.0173 (12) | 0.0303 (14) | 0.0261 (13) | 0.0012 (10) | −0.0036 (10) | −0.0091 (11) |
C11 | 0.0190 (12) | 0.0401 (16) | 0.0282 (14) | 0.0051 (11) | 0.0018 (11) | −0.0115 (12) |
C12 | 0.0241 (13) | 0.0258 (14) | 0.0203 (12) | 0.0036 (11) | −0.0013 (10) | −0.0055 (10) |
C13 | 0.0197 (12) | 0.0316 (15) | 0.0252 (13) | −0.0030 (11) | −0.0025 (10) | −0.0087 (11) |
C14 | 0.0179 (12) | 0.0281 (14) | 0.0237 (13) | −0.0025 (10) | 0.0024 (10) | −0.0059 (10) |
C15 | 0.0301 (14) | 0.0214 (13) | 0.0416 (16) | −0.0074 (11) | 0.0027 (12) | −0.0008 (12) |
C16 | 0.0215 (12) | 0.0325 (15) | 0.0205 (12) | 0.0003 (11) | −0.0041 (10) | 0.0005 (11) |
C17 | 0.0283 (14) | 0.0293 (15) | 0.0339 (15) | 0.0010 (12) | −0.0019 (12) | 0.0032 (12) |
C18 | 0.0341 (17) | 0.0379 (19) | 0.075 (3) | 0.0039 (15) | −0.0096 (17) | 0.0110 (18) |
C19 | 0.018 (3) | 0.047 (4) | 0.060 (4) | 0.004 (3) | 0.000 (3) | 0.002 (3) |
C20 | 0.060 (3) | 0.142 (5) | 0.093 (4) | 0.026 (3) | 0.028 (3) | 0.024 (4) |
C18A | 0.0341 (17) | 0.0379 (19) | 0.075 (3) | 0.0039 (15) | −0.0096 (17) | 0.0110 (18) |
C19A | 0.060 (5) | 0.040 (4) | 0.066 (5) | 0.013 (4) | −0.008 (4) | −0.001 (4) |
C20A | 0.060 (3) | 0.142 (5) | 0.093 (4) | 0.026 (3) | 0.028 (3) | 0.024 (4) |
C21 | 0.0265 (16) | 0.052 (2) | 0.063 (2) | −0.0017 (15) | −0.0083 (15) | 0.0129 (18) |
C22 | 0.065 (2) | 0.0291 (16) | 0.0291 (15) | 0.0019 (15) | −0.0048 (15) | −0.0016 (12) |
C23 | 0.081 (3) | 0.091 (3) | 0.041 (2) | −0.026 (3) | −0.004 (2) | −0.022 (2) |
C24 | 0.0372 (17) | 0.0328 (16) | 0.0424 (18) | −0.0074 (14) | −0.0016 (14) | −0.0017 (14) |
C25 | 0.0311 (15) | 0.0283 (15) | 0.0246 (14) | 0.0018 (12) | −0.0007 (11) | 0.0039 (11) |
C26 | 0.0462 (18) | 0.0331 (16) | 0.0252 (14) | −0.0022 (14) | 0.0008 (13) | 0.0038 (12) |
C27 | 0.049 (2) | 0.114 (4) | 0.049 (2) | −0.020 (2) | 0.0122 (19) | −0.043 (2) |
C28 | 0.141 (6) | 0.247 (9) | 0.090 (4) | 0.148 (7) | −0.049 (4) | −0.083 (5) |
Rh1—O1 | 2.0280 (16) | C9—C14 | 1.397 (3) |
Rh1—O4 | 2.0335 (16) | C10—C11 | 1.386 (3) |
Rh1—O5i | 2.0421 (16) | C10—H10 | 0.9500 |
Rh1—O2i | 2.0431 (16) | C11—C12 | 1.384 (4) |
Rh1—Rh1i | 2.4102 (4) | C11—H11 | 0.9500 |
Rh1—S1 | 2.4445 (6) | C12—C13 | 1.389 (4) |
Rh2—O8ii | 2.0230 (19) | C13—C14 | 1.383 (3) |
Rh2—O9 | 2.0350 (19) | C13—H13 | 0.9500 |
Rh2—O13ii | 2.040 (2) | C14—H14 | 0.9500 |
Rh2—O10 | 2.0462 (19) | C15—H15A | 0.9800 |
Rh2—Rh2ii | 2.4037 (4) | C15—H15B | 0.9800 |
Rh2—S2 | 2.4272 (7) | C15—H15C | 0.9800 |
S1—O7 | 1.4980 (17) | C16—H16A | 0.9800 |
S1—C15 | 1.775 (3) | C16—H16B | 0.9800 |
S1—C16 | 1.777 (3) | C16—H16C | 0.9800 |
S2—O11 | 1.4941 (19) | C17—C18 | 1.507 (4) |
S2—C21 | 1.773 (3) | C18—C19 | 1.512 (7) |
S2—C22 | 1.783 (3) | C18—H18A | 0.9900 |
O1—C1 | 1.271 (3) | C18—H18B | 0.9900 |
O2—C1 | 1.270 (3) | C19—C20 | 1.556 (9) |
O2—Rh1i | 2.0431 (16) | C19—H19A | 0.9900 |
O3—C5 | 1.357 (3) | C19—H19B | 0.9900 |
O3—H3O | 0.77 (3) | C20—H20A | 0.9800 |
O4—C8 | 1.272 (3) | C20—H20B | 0.9800 |
O5—C8 | 1.272 (3) | C20—H20C | 0.9800 |
O5—Rh1i | 2.0421 (16) | C19A—H19C | 0.9900 |
O6—C12 | 1.357 (3) | C19A—H19D | 0.9900 |
O6—H6O | 0.75 (2) | C21—H21A | 0.9800 |
O8—C25 | 1.270 (3) | C21—H21B | 0.9800 |
O8—Rh2ii | 2.0230 (19) | C21—H21C | 0.9800 |
O9—C17 | 1.270 (3) | C22—H22A | 0.9800 |
O10—C25 | 1.267 (3) | C22—H22B | 0.9800 |
O12—C24 | 1.426 (4) | C22—H22C | 0.9800 |
O12—H12O | 0.73 (2) | C23—C24 | 1.492 (5) |
O13—C17 | 1.261 (3) | C23—H23A | 0.9800 |
O13—Rh2ii | 2.040 (2) | C23—H23B | 0.9800 |
C1—C2 | 1.480 (3) | C23—H23C | 0.9800 |
C2—C3 | 1.391 (3) | C24—H24A | 0.9900 |
C2—C7 | 1.394 (3) | C24—H24B | 0.9900 |
C3—C4 | 1.379 (4) | C25—C26 | 1.508 (4) |
C3—H3 | 0.9500 | C26—C27 | 1.471 (5) |
C4—C5 | 1.385 (4) | C26—H26A | 0.9900 |
C4—H4 | 0.9500 | C26—H26B | 0.9900 |
C5—C6 | 1.394 (4) | C27—C28 | 1.477 (8) |
C6—C7 | 1.384 (4) | C27—H27A | 0.9900 |
C6—H6 | 0.9500 | C27—H27B | 0.9900 |
C7—H7 | 0.9500 | C28—H28A | 0.9800 |
C8—C9 | 1.481 (3) | C28—H28B | 0.9800 |
C9—C10 | 1.394 (3) | C28—H28C | 0.9800 |
O1—Rh1—O4 | 89.71 (7) | O6—C12—C13 | 123.0 (2) |
O1—Rh1—O5i | 89.72 (7) | C11—C12—C13 | 119.7 (2) |
O4—Rh1—O5i | 175.73 (6) | C14—C13—C12 | 120.0 (2) |
O1—Rh1—O2i | 175.72 (6) | C14—C13—H13 | 120.0 |
O4—Rh1—O2i | 89.75 (7) | C12—C13—H13 | 120.0 |
O5i—Rh1—O2i | 90.51 (7) | C13—C14—C9 | 120.8 (2) |
O1—Rh1—Rh1i | 87.59 (5) | C13—C14—H14 | 119.6 |
O4—Rh1—Rh1i | 87.57 (5) | C9—C14—H14 | 119.6 |
O5i—Rh1—Rh1i | 88.18 (5) | S1—C15—H15A | 109.5 |
O2i—Rh1—Rh1i | 88.14 (5) | S1—C15—H15B | 109.5 |
O1—Rh1—S1 | 90.39 (5) | H15A—C15—H15B | 109.5 |
O4—Rh1—S1 | 93.61 (5) | S1—C15—H15C | 109.5 |
O5i—Rh1—S1 | 90.63 (5) | H15A—C15—H15C | 109.5 |
O2i—Rh1—S1 | 93.88 (5) | H15B—C15—H15C | 109.5 |
Rh1i—Rh1—S1 | 177.664 (18) | S1—C16—H16A | 109.5 |
O8ii—Rh2—O9 | 89.82 (8) | S1—C16—H16B | 109.5 |
O8ii—Rh2—O13ii | 88.95 (9) | H16A—C16—H16B | 109.5 |
O9—Rh2—O13ii | 175.51 (8) | S1—C16—H16C | 109.5 |
O8ii—Rh2—O10 | 175.82 (8) | H16A—C16—H16C | 109.5 |
O9—Rh2—O10 | 90.55 (8) | H16B—C16—H16C | 109.5 |
O13ii—Rh2—O10 | 90.36 (8) | O13—C17—O9 | 125.4 (3) |
O8ii—Rh2—Rh2ii | 88.34 (6) | O13—C17—C18 | 118.2 (3) |
O9—Rh2—Rh2ii | 87.56 (6) | O9—C17—C18 | 116.4 (3) |
O13ii—Rh2—Rh2ii | 88.09 (6) | C17—C18—C19 | 116.3 (4) |
O10—Rh2—Rh2ii | 87.52 (5) | C17—C18—H18A | 108.2 |
O8ii—Rh2—S2 | 89.11 (6) | C19—C18—H18A | 108.2 |
O9—Rh2—S2 | 90.38 (6) | C17—C18—H18B | 108.2 |
O13ii—Rh2—S2 | 93.92 (6) | C19—C18—H18B | 108.2 |
O10—Rh2—S2 | 95.05 (6) | H18A—C18—H18B | 107.4 |
Rh2ii—Rh2—S2 | 176.72 (2) | C18—C19—C20 | 110.8 (5) |
O7—S1—C15 | 106.63 (13) | C18—C19—H19A | 109.5 |
O7—S1—C16 | 106.60 (12) | C20—C19—H19A | 109.5 |
C15—S1—C16 | 100.59 (14) | C18—C19—H19B | 109.5 |
O7—S1—Rh1 | 119.78 (8) | C20—C19—H19B | 109.5 |
C15—S1—Rh1 | 111.83 (10) | H19A—C19—H19B | 108.1 |
C16—S1—Rh1 | 109.59 (9) | C19—C20—H20A | 109.5 |
O11—S2—C21 | 107.19 (14) | C19—C20—H20B | 109.5 |
O11—S2—C22 | 107.30 (13) | H20A—C20—H20B | 109.5 |
C21—S2—C22 | 99.34 (18) | C19—C20—H20C | 109.5 |
O11—S2—Rh2 | 119.04 (8) | H20A—C20—H20C | 109.5 |
C21—S2—Rh2 | 113.57 (12) | H20B—C20—H20C | 109.5 |
C22—S2—Rh2 | 108.45 (12) | H19C—C19A—H19D | 108.5 |
C1—O1—Rh1 | 120.02 (15) | S2—C21—H21A | 109.5 |
C1—O2—Rh1i | 118.69 (15) | S2—C21—H21B | 109.5 |
C5—O3—H3O | 105 (3) | H21A—C21—H21B | 109.5 |
C8—O4—Rh1 | 119.94 (15) | S2—C21—H21C | 109.5 |
C8—O5—Rh1i | 118.87 (15) | H21A—C21—H21C | 109.5 |
C12—O6—H6O | 109 (2) | H21B—C21—H21C | 109.5 |
C25—O8—Rh2ii | 119.38 (18) | S2—C22—H22A | 109.5 |
C17—O9—Rh2 | 119.74 (18) | S2—C22—H22B | 109.5 |
C25—O10—Rh2 | 119.13 (17) | H22A—C22—H22B | 109.5 |
C24—O12—H12O | 111 (3) | S2—C22—H22C | 109.5 |
C17—O13—Rh2ii | 119.12 (19) | H22A—C22—H22C | 109.5 |
O2—C1—O1 | 125.5 (2) | H22B—C22—H22C | 109.5 |
O2—C1—C2 | 117.8 (2) | C24—C23—H23A | 109.5 |
O1—C1—C2 | 116.6 (2) | C24—C23—H23B | 109.5 |
C3—C2—C7 | 118.8 (2) | H23A—C23—H23B | 109.5 |
C3—C2—C1 | 121.4 (2) | C24—C23—H23C | 109.5 |
C7—C2—C1 | 119.8 (2) | H23A—C23—H23C | 109.5 |
C4—C3—C2 | 120.8 (2) | H23B—C23—H23C | 109.5 |
C4—C3—H3 | 119.6 | O12—C24—C23 | 109.1 (3) |
C2—C3—H3 | 119.6 | O12—C24—H24A | 109.9 |
C3—C4—C5 | 120.2 (2) | C23—C24—H24A | 109.9 |
C3—C4—H4 | 119.9 | O12—C24—H24B | 109.9 |
C5—C4—H4 | 119.9 | C23—C24—H24B | 109.9 |
O3—C5—C4 | 123.0 (2) | H24A—C24—H24B | 108.3 |
O3—C5—C6 | 117.2 (3) | O10—C25—O8 | 125.6 (3) |
C4—C5—C6 | 119.8 (2) | O10—C25—C26 | 117.9 (3) |
C7—C6—C5 | 119.7 (3) | O8—C25—C26 | 116.5 (3) |
C7—C6—H6 | 120.1 | C27—C26—C25 | 114.0 (3) |
C5—C6—H6 | 120.1 | C27—C26—H26A | 108.7 |
C6—C7—C2 | 120.7 (2) | C25—C26—H26A | 108.7 |
C6—C7—H7 | 119.6 | C27—C26—H26B | 108.7 |
C2—C7—H7 | 119.6 | C25—C26—H26B | 108.7 |
O5—C8—O4 | 125.2 (2) | H26A—C26—H26B | 107.6 |
O5—C8—C9 | 118.2 (2) | C26—C27—C28 | 112.7 (5) |
O4—C8—C9 | 116.6 (2) | C26—C27—H27A | 109.0 |
C10—C9—C14 | 118.7 (2) | C28—C27—H27A | 109.0 |
C10—C9—C8 | 119.8 (2) | C26—C27—H27B | 109.0 |
C14—C9—C8 | 121.3 (2) | C28—C27—H27B | 109.0 |
C11—C10—C9 | 120.4 (2) | H27A—C27—H27B | 107.8 |
C11—C10—H10 | 119.8 | C27—C28—H28A | 109.5 |
C9—C10—H10 | 119.8 | C27—C28—H28B | 109.5 |
C12—C11—C10 | 120.5 (2) | H28A—C28—H28B | 109.5 |
C12—C11—H11 | 119.8 | C27—C28—H28C | 109.5 |
C10—C11—H11 | 119.8 | H28A—C28—H28C | 109.5 |
O6—C12—C11 | 117.3 (2) | H28B—C28—H28C | 109.5 |
O1—Rh1—S1—O7 | 95.09 (10) | Rh1i—O2—C1—O1 | 1.6 (3) |
O4—Rh1—S1—O7 | 5.36 (10) | Rh1i—O2—C1—C2 | −177.22 (16) |
O5i—Rh1—S1—O7 | −175.19 (10) | Rh1—O1—C1—O2 | −1.2 (3) |
O2i—Rh1—S1—O7 | −84.64 (10) | Rh1—O1—C1—C2 | 177.65 (15) |
Rh1i—Rh1—S1—O7 | 125.5 (4) | O2—C1—C2—C3 | −14.8 (4) |
O1—Rh1—S1—C15 | −139.15 (12) | O1—C1—C2—C3 | 166.3 (2) |
O4—Rh1—S1—C15 | 131.12 (12) | O2—C1—C2—C7 | 163.8 (2) |
O5i—Rh1—S1—C15 | −49.43 (12) | O1—C1—C2—C7 | −15.1 (3) |
O2i—Rh1—S1—C15 | 41.12 (12) | C7—C2—C3—C4 | −0.3 (4) |
Rh1i—Rh1—S1—C15 | −108.7 (5) | C1—C2—C3—C4 | 178.4 (2) |
O1—Rh1—S1—C16 | −28.49 (11) | C2—C3—C4—C5 | −1.3 (4) |
O4—Rh1—S1—C16 | −118.23 (11) | C3—C4—C5—O3 | −178.4 (3) |
O5i—Rh1—S1—C16 | 61.23 (11) | C3—C4—C5—C6 | 1.0 (5) |
O2i—Rh1—S1—C16 | 151.78 (11) | O3—C5—C6—C7 | −179.7 (3) |
Rh1i—Rh1—S1—C16 | 1.9 (5) | C4—C5—C6—C7 | 0.9 (5) |
O8ii—Rh2—S2—O11 | −144.55 (11) | C5—C6—C7—C2 | −2.5 (5) |
O9—Rh2—S2—O11 | −54.73 (11) | C3—C2—C7—C6 | 2.2 (4) |
O13ii—Rh2—S2—O11 | 126.57 (11) | C1—C2—C7—C6 | −176.5 (3) |
O10—Rh2—S2—O11 | 35.86 (11) | Rh1i—O5—C8—O4 | 6.0 (3) |
Rh2ii—Rh2—S2—O11 | −105.7 (4) | Rh1i—O5—C8—C9 | −172.05 (16) |
O8ii—Rh2—S2—C21 | 87.80 (15) | Rh1—O4—C8—O5 | −6.6 (3) |
O9—Rh2—S2—C21 | 177.61 (15) | Rh1—O4—C8—C9 | 171.53 (15) |
O13ii—Rh2—S2—C21 | −1.09 (15) | O5—C8—C9—C10 | 172.3 (2) |
O10—Rh2—S2—C21 | −91.80 (15) | O4—C8—C9—C10 | −6.0 (3) |
Rh2ii—Rh2—S2—C21 | 126.6 (4) | O5—C8—C9—C14 | −1.6 (4) |
O8ii—Rh2—S2—C22 | −21.60 (13) | O4—C8—C9—C14 | −179.8 (2) |
O9—Rh2—S2—C22 | 68.21 (13) | C14—C9—C10—C11 | 1.0 (4) |
O13ii—Rh2—S2—C22 | −110.49 (13) | C8—C9—C10—C11 | −173.0 (2) |
O10—Rh2—S2—C22 | 158.80 (13) | C9—C10—C11—C12 | 0.6 (4) |
Rh2ii—Rh2—S2—C22 | 17.2 (4) | C10—C11—C12—O6 | 178.4 (3) |
O4—Rh1—O1—C1 | −87.36 (18) | C10—C11—C12—C13 | −2.4 (4) |
O5i—R1—O1—C1 | 88.40 (18) | O6—C12—C13—C14 | −178.4 (3) |
O2i—Rh1—O1—C1 | −4.6 (10) | C11—C12—C13—C14 | 2.5 (4) |
Rh1i—Rh1—O1—C1 | 0.21 (17) | C12—C13—C14—C9 | −0.8 (4) |
S1—Rh1—O1—C1 | 179.03 (17) | C10—C9—C14—C13 | −1.0 (4) |
O1—Rh1—O4—C8 | 90.99 (18) | C8—C9—C14—C13 | 172.9 (2) |
O5i—Rh1—O4—C8 | 8.7 (10) | Rh2ii—O13—C17—O9 | −2.5 (4) |
O2i—Rh1—O4—C8 | −84.76 (18) | Rh2ii—O13—C17—C18 | 176.5 (2) |
Rh1i—Rh1—O4—C8 | 3.39 (17) | Rh2—O9—C17—O13 | 3.9 (4) |
S1—Rh1—O4—C8 | −178.63 (17) | Rh2—O9—C17—C18 | −175.2 (2) |
O8ii—Rh2—O9—C17 | −91.1 (2) | O13—C17—C18—C19 | 18.7 (6) |
O13ii—Rh2—O9—C17 | −17.0 (12) | O9—C17—C18—C19 | −162.2 (4) |
O10—Rh2—O9—C17 | 84.7 (2) | C17—C18—C19—C20 | 72.0 (6) |
Rh2ii—Rh2—O9—C17 | −2.8 (2) | Rh2—O10—C25—O8 | 0.9 (4) |
S2—Rh2—O9—C17 | 179.8 (2) | Rh2—O10—C25—C26 | −177.9 (2) |
O8ii—Rh2—O10—C25 | 7.7 (13) | Rh2ii—O8—C25—O10 | −1.5 (4) |
O9—Rh2—O10—C25 | −87.4 (2) | Rh2ii—O8—C25—C26 | 177.25 (19) |
O13ii—Rh2—O10—C25 | 88.2 (2) | O10—C25—C26—C27 | 59.8 (4) |
Rh2ii—Rh2—O10—C25 | 0.1 (2) | O8—C25—C26—C27 | −119.1 (4) |
S2—Rh2—O10—C25 | −177.9 (2) | C25—C26—C27—C28 | 59.4 (5) |
Symmetry codes: (i) −x, −y, −z; (ii) −x, −y, −z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3O···O12 | 0.77 (3) | 1.90 (3) | 2.661 (3) | 175 (5) |
O6—H6O···O11ii | 0.75 (2) | 1.95 (2) | 2.699 (3) | 175 (3) |
O12—H12O···O7iii | 0.73 (2) | 1.95 (2) | 2.679 (3) | 176 (4) |
Symmetry codes: (ii) −x, −y, −z−1; (iii) x−1/2, −y−1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Rh2(C7H5O3)4(C2H6OS)2]·[Rh2(C4H7O2)4(C2H6OS)2]·2C2H6O |
Mr | 1713.12 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 11.9418 (6), 15.2880 (8), 19.0307 (10) |
β (°) | 90.915 (1) |
V (Å3) | 3473.9 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.13 |
Crystal size (mm) | 0.22 × 0.20 × 0.14 |
Data collection | |
Diffractometer | SMART CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 38253, 8473, 7201 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.079, 1.02 |
No. of reflections | 8473 |
No. of parameters | 433 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.54, −0.97 |
Computer programs: SMART (Bruker, 1998), SMART, SHELXTL (Sheldrick, 1997a), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997b), DIAMOND (Bergerhoff, 1996), DIAMOND.
Rh1—O1 | 2.0280 (16) | Rh2—O8ii | 2.0230 (19) |
Rh1—O4 | 2.0335 (16) | Rh2—O9 | 2.0350 (19) |
Rh1—O5i | 2.0421 (16) | Rh2—O13ii | 2.040 (2) |
Rh1—O2i | 2.0431 (16) | Rh2—O10 | 2.0462 (19) |
Rh1—Rh1i | 2.4102 (4) | Rh2—Rh2ii | 2.4037 (4) |
Rh1—S1 | 2.4445 (6) | Rh2—S2 | 2.4272 (7) |
Symmetry codes: (i) −x, −y, −z; (ii) −x, −y, −z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3O···O12 | 0.77 (3) | 1.90 (3) | 2.661 (3) | 175 (5) |
O6—H6O···O11ii | 0.75 (2) | 1.95 (2) | 2.699 (3) | 175 (3) |
O12—H12O···O7iii | 0.73 (2) | 1.95 (2) | 2.679 (3) | 176 (4) |
Symmetry codes: (ii) −x, −y, −z−1; (iii) x−1/2, −y−1/2, z+1/2. |
Dirhodium(II) tetracarboxylate complexes have been extensively studied (Boyar & Robinson, 1983; Cotton & Walton, 1993). Our interest in the preparation of dirhodium(II) tetracarboxylates with functional organic groups is directed towards incorporation of these complexes into polyoxometalates. Recent success with incorporation of dirhodium(II) tetraacetate into PW11O397− and SiW11O398− via hydrothermal techniques (Wei et al., 1997; Wei, 1997) prompted us to investigate this reaction using other known dirhodium(II) carboxylates, as well as to synthesize novel dirhodium complexes. As part of this research, we have prepared tetrakis(p-hydroxybenzoate)dirhodium(II), [Rh2(C7H5O3)4]. Several dirhodium(II) tetracarboxylate crystal structures containing aromatic carboxylates have been reported (Li & Sun, 1981; Bancroft et al., 1984; Cotton & Thompson, 1984; Simmons et al., 1986; Callot et al., 1989; Mehmet & Tocher, 1991). Here, we report the X-ray structure determination of an adventitiously obtained single-crystal of [Rh2(C7H5O3)4(dmso)2] (dmso is dimethyl sulfoxide) co-crystallized with [Rh2(C4H7O2)4(dmso)2] as the ethanol disolvate, (I). \sch
The Rh—Rh distances of 2.4102 (4) Å for the p-hydroxybenzoate molecule in (I) and 2.4037 (4) Å for the butyrate molecule are similar to those of the related compounds tetrakis(benzoato)bis(dmso)dirhodium [2.405 (1) Å; Simmons et al., 1986] and tetrakis(propionato)bis(dmso)dirhodium [2.419 (1) Å; Cotton & Felthouse, 1980). The Rh—S distances are also similar, with values of 2.4445 (6) and 2.4272 (7) Å, respectively, for the present compound, compared with averages of 2.449 (8) and 2.449 (6) Å, respectively, for the literature compounds. Angles around Rh in (I) are within 5° of 90 or 180°.
Two of the hydroxyl groups on the benzoate ligands donate protons to the O atoms of the dmso ligands on the butyrate molecule, and the other two hydroxyl groups form hydrogen bonds through ethanol molecules to the O atoms of the dmso ligands on neighbouring benzoate molecules (Table 2).