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The title structure, [Rh2(C7H5O3)4(C2H6OS)2]·[Rh2(C4H7­O2)4(C2H6OS)2]·2C2H6O, contains two discrete neutral Rh–Rh dimers cocrystallized as the ethanol disolvate. Each dimer is situated on an inversion center. The butyrate chain displays disorder in one C-atom position. In each dimer, the di­methyl sulfoxide ligand (dmso) is bound via S, as expected. The ethanol is a hydrogen-bond acceptor for one p-hydroxy­benzoate hydroxyl group and acts as a hydrogen-bond donor to the dmso O atom of a neighboring p-hydroxy­benzoate dirhodium complex. A third hydrogen bond is formed from the other p-hydroxy­benzoate hydroxyl group to the dmso O atom of a butyrate–dirhodium complex.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100009756/bk1540sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100009756/bk1540Isup2.hkl
Contains datablock I

CCDC reference: 152592

Comment top

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).

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A view of the [Rh2(C7H5O3)4(dmso)2] molecule in (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms bonded to C have been omitted for clarity. One ethanol solvate molecule is shown.
[Figure 2] Fig. 2. A view of the [Rh2(C4H7O2)4(dmso)2] molecule in (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. The disordered atom C19A is not shown.
[Figure 3] Fig. 3. The stereopacking diagram for (I) viewed down the a axis.
Tetrakis(µ-p-hydroxybenzoato-O,O')bis(dimethyl sulfoxide-S)dirhodium(II)- tetrakis(µ-butyrato-O,O')bis(dimethyl sulfoxide-S)dirhodium(II) cocrystal ethanol disolvate top
Crystal data top
[Rh2(C7H5O3)4(C2H6OS)2]·[Rh2(C4H7O2)4(C2H6OS)2]·2C2H6OF(000) = 1744
Mr = 1713.12Dx = 1.638 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 11.9418 (6) ÅCell parameters from 6450 reflections
b = 15.2880 (8) Åθ = 4.8–56.5°
c = 19.0307 (10) ŵ = 1.13 mm1
β = 90.915 (1)°T = 173 K
V = 3473.9 (3) Å3Block, red
Z = 20.22 × 0.20 × 0.14 mm
Data collection top
SMART CCD area-detector
diffractometer
7201 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tubeRint = 0.052
Graphite monochromatorθmax = 28.3°, θmin = 1.7°
ω scansh = 1515
38253 measured reflectionsk = 2020
8473 independent reflectionsl = 2424
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079H 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 parametersΔρmax = 0.54 e Å3
3 restraintsΔρmin = 0.97 e Å3
Crystal data top
[Rh2(C7H5O3)4(C2H6OS)2]·[Rh2(C4H7O2)4(C2H6OS)2]·2C2H6OV = 3473.9 (3) Å3
Mr = 1713.12Z = 2
Monoclinic, P21/nMo Kα radiation
a = 11.9418 (6) ŵ = 1.13 mm1
b = 15.2880 (8) ÅT = 173 K
c = 19.0307 (10) Å0.22 × 0.20 × 0.14 mm
β = 90.915 (1)°
Data collection top
SMART CCD area-detector
diffractometer
7201 reflections with I > 2σ(I)
38253 measured reflectionsRint = 0.052
8473 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0303 restraints
wR(F2) = 0.079H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.54 e Å3
8473 reflectionsΔρmin = 0.97 e Å3
433 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Rh10.100678 (14)0.005528 (11)0.001162 (9)0.01307 (5)
Rh20.054096 (17)0.066295 (13)0.499505 (11)0.02311 (6)
S10.30491 (5)0.01462 (4)0.00847 (3)0.01631 (12)
S20.15621 (6)0.20343 (4)0.49344 (4)0.02477 (14)
O10.10233 (14)0.09530 (11)0.07042 (9)0.0198 (4)
O20.08636 (13)0.10590 (11)0.06930 (9)0.0191 (3)
O30.05008 (19)0.42358 (17)0.26575 (14)0.0508 (7)
O40.10156 (14)0.08141 (11)0.07970 (9)0.0201 (4)
O50.08718 (14)0.09147 (11)0.08273 (9)0.0195 (4)
O60.04274 (17)0.28154 (15)0.36579 (10)0.0314 (5)
O70.37429 (14)0.03176 (12)0.04481 (9)0.0241 (4)
O80.03579 (17)0.07098 (13)0.60592 (10)0.0307 (4)
O90.09256 (16)0.13256 (13)0.51254 (10)0.0311 (4)
O100.06733 (17)0.05271 (13)0.60602 (10)0.0301 (4)
O110.14268 (16)0.26783 (13)0.55202 (10)0.0290 (4)
O120.14880 (18)0.46942 (14)0.31493 (11)0.0306 (4)
O130.19390 (17)0.00855 (13)0.51556 (11)0.0332 (5)
C10.01081 (19)0.12983 (15)0.08933 (12)0.0170 (5)
C20.0196 (2)0.20528 (16)0.13781 (12)0.0189 (5)
C30.0732 (2)0.23637 (17)0.17333 (13)0.0222 (5)
H30.14340.20780.16740.027*
C40.0645 (2)0.30812 (19)0.21701 (14)0.0289 (6)
H40.12820.32790.24170.035*
C50.0368 (2)0.3514 (2)0.22493 (15)0.0315 (6)
C60.1305 (2)0.3214 (2)0.18945 (17)0.0389 (8)
H60.20000.35130.19420.047*
C70.1220 (2)0.24779 (19)0.14733 (15)0.0285 (6)
H70.18660.22600.12470.034*
C80.00949 (19)0.10839 (15)0.10639 (12)0.0170 (5)
C90.0169 (2)0.16140 (16)0.17127 (12)0.0180 (5)
C100.1201 (2)0.17232 (18)0.20336 (14)0.0246 (5)
H100.18640.15140.18080.030*
C110.1265 (2)0.2136 (2)0.26803 (14)0.0291 (6)
H110.19730.22130.28930.035*
C120.0306 (2)0.24372 (17)0.30184 (13)0.0234 (5)
C130.0723 (2)0.23536 (18)0.26947 (14)0.0255 (6)
H130.13800.25800.29160.031*
C140.0790 (2)0.19411 (17)0.20500 (13)0.0232 (5)
H140.14980.18800.18340.028*
C150.3522 (2)0.12465 (18)0.01076 (16)0.0310 (6)
H15A0.43250.12590.02200.047*
H15B0.31140.15690.04680.047*
H15C0.33860.15190.03520.047*
C160.3522 (2)0.02245 (19)0.09234 (13)0.0249 (5)
H16A0.33210.08420.09810.037*
H16B0.31680.01240.12910.037*
H16C0.43370.01600.09600.037*
C170.1838 (2)0.09052 (19)0.51952 (15)0.0305 (6)
C180.2872 (3)0.1442 (2)0.5348 (2)0.0493 (9)0.50
H18A0.28580.16240.58470.059*0.50
H18B0.28330.19790.50590.059*0.50
C190.3982 (5)0.1000 (5)0.5217 (4)0.0415 (15)0.50
H19A0.39890.04150.54400.050*0.50
H19B0.45940.13500.54330.050*0.50
C200.4185 (4)0.0904 (4)0.4415 (3)0.0981 (19)0.50
H20A0.49120.06230.43420.147*0.50
H20B0.41820.14830.41950.147*0.50
H20C0.35900.05440.42040.147*0.50
C18A0.2872 (3)0.1442 (2)0.5348 (2)0.0493 (9)0.50
H18C0.33880.10930.56500.059*0.50
H18D0.26540.19670.56180.059*0.50
C19A0.3498 (7)0.1734 (5)0.4701 (4)0.0552 (19)0.50
H19C0.40180.22170.48220.066*0.50
H19D0.29630.19440.43350.066*0.50
C20A0.4185 (4)0.0904 (4)0.4415 (3)0.0981 (19)0.50
H20D0.45800.10670.39870.147*0.50
H20E0.36650.04240.43100.147*0.50
H20F0.47290.07140.47750.147*0.50
C210.3020 (3)0.1901 (2)0.4778 (2)0.0473 (9)
H21A0.33530.15970.51770.071*
H21B0.31410.15560.43490.071*
H21C0.33720.24760.47200.071*
C220.1200 (3)0.2581 (2)0.41420 (15)0.0412 (8)
H22A0.16020.31390.41110.062*
H22B0.14080.22140.37380.062*
H22C0.03910.26900.41410.062*
C230.2090 (4)0.5441 (3)0.2115 (2)0.0710 (13)
H23A0.23680.48870.19220.106*
H23B0.25570.59230.19380.106*
H23C0.13140.55310.19720.106*
C240.2138 (3)0.5414 (2)0.28980 (17)0.0375 (7)
H24A0.29250.53490.30470.045*
H24B0.18400.59670.30970.045*
C250.0210 (2)0.01212 (18)0.63610 (15)0.0280 (6)
C260.0357 (3)0.0220 (2)0.71426 (15)0.0348 (7)
H26A0.00630.07430.73040.042*
H26B0.00240.02960.73820.042*
C270.1530 (3)0.0306 (3)0.7356 (2)0.0704 (14)
H27A0.19430.02310.72200.084*
H27B0.15560.03600.78740.084*
C280.2094 (6)0.1070 (5)0.7033 (3)0.160 (4)
H28A0.21930.09710.65270.240*
H28B0.28270.11520.72470.240*
H28C0.16350.15940.71110.240*
H3O0.009 (2)0.435 (3)0.278 (2)0.064 (14)*
H6O0.010 (2)0.277 (2)0.3865 (15)0.029 (9)*
H12O0.146 (3)0.470 (2)0.3534 (12)0.040 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Rh10.01132 (9)0.01500 (10)0.01289 (9)0.00033 (7)0.00035 (7)0.00025 (7)
Rh20.02344 (11)0.02204 (12)0.02382 (11)0.00281 (8)0.00077 (8)0.00200 (8)
S10.0131 (3)0.0190 (3)0.0169 (3)0.0004 (2)0.0008 (2)0.0009 (2)
S20.0240 (3)0.0232 (3)0.0270 (3)0.0029 (3)0.0043 (3)0.0015 (3)
O10.0148 (8)0.0220 (9)0.0226 (9)0.0016 (7)0.0008 (7)0.0086 (7)
O20.0149 (8)0.0212 (9)0.0212 (8)0.0011 (7)0.0001 (7)0.0073 (7)
O30.0258 (11)0.0555 (16)0.0709 (17)0.0009 (11)0.0005 (12)0.0485 (13)
O40.0160 (8)0.0259 (9)0.0183 (8)0.0014 (7)0.0001 (7)0.0078 (7)
O50.0151 (8)0.0245 (9)0.0189 (8)0.0005 (7)0.0015 (7)0.0063 (7)
O60.0256 (10)0.0469 (13)0.0218 (10)0.0059 (9)0.0026 (8)0.0145 (9)
O70.0201 (9)0.0316 (10)0.0208 (9)0.0048 (8)0.0034 (7)0.0046 (8)
O80.0366 (11)0.0316 (11)0.0240 (9)0.0082 (9)0.0016 (8)0.0014 (8)
O90.0274 (10)0.0259 (10)0.0400 (11)0.0009 (8)0.0030 (9)0.0027 (9)
O100.0371 (11)0.0282 (10)0.0252 (10)0.0067 (9)0.0028 (8)0.0008 (8)
O110.0288 (10)0.0299 (10)0.0280 (10)0.0051 (8)0.0029 (8)0.0061 (8)
O120.0354 (11)0.0352 (11)0.0210 (10)0.0105 (9)0.0003 (9)0.0049 (9)
O130.0273 (11)0.0280 (11)0.0441 (12)0.0000 (8)0.0040 (9)0.0035 (9)
C10.0180 (11)0.0181 (12)0.0149 (11)0.0002 (9)0.0008 (9)0.0000 (9)
C20.0176 (11)0.0210 (12)0.0182 (11)0.0021 (9)0.0005 (9)0.0026 (9)
C30.0180 (12)0.0235 (13)0.0253 (13)0.0022 (10)0.0027 (10)0.0053 (10)
C40.0224 (13)0.0343 (16)0.0301 (14)0.0029 (11)0.0031 (11)0.0138 (12)
C50.0232 (13)0.0349 (16)0.0362 (15)0.0010 (12)0.0044 (12)0.0208 (13)
C60.0193 (13)0.0437 (18)0.054 (2)0.0046 (12)0.0006 (13)0.0261 (15)
C70.0182 (12)0.0331 (15)0.0342 (15)0.0001 (11)0.0018 (11)0.0142 (12)
C80.0176 (11)0.0161 (11)0.0173 (11)0.0003 (9)0.0004 (9)0.0014 (9)
C90.0181 (11)0.0182 (12)0.0177 (11)0.0010 (9)0.0002 (9)0.0010 (9)
C100.0173 (12)0.0303 (14)0.0261 (13)0.0012 (10)0.0036 (10)0.0091 (11)
C110.0190 (12)0.0401 (16)0.0282 (14)0.0051 (11)0.0018 (11)0.0115 (12)
C120.0241 (13)0.0258 (14)0.0203 (12)0.0036 (11)0.0013 (10)0.0055 (10)
C130.0197 (12)0.0316 (15)0.0252 (13)0.0030 (11)0.0025 (10)0.0087 (11)
C140.0179 (12)0.0281 (14)0.0237 (13)0.0025 (10)0.0024 (10)0.0059 (10)
C150.0301 (14)0.0214 (13)0.0416 (16)0.0074 (11)0.0027 (12)0.0008 (12)
C160.0215 (12)0.0325 (15)0.0205 (12)0.0003 (11)0.0041 (10)0.0005 (11)
C170.0283 (14)0.0293 (15)0.0339 (15)0.0010 (12)0.0019 (12)0.0032 (12)
C180.0341 (17)0.0379 (19)0.075 (3)0.0039 (15)0.0096 (17)0.0110 (18)
C190.018 (3)0.047 (4)0.060 (4)0.004 (3)0.000 (3)0.002 (3)
C200.060 (3)0.142 (5)0.093 (4)0.026 (3)0.028 (3)0.024 (4)
C18A0.0341 (17)0.0379 (19)0.075 (3)0.0039 (15)0.0096 (17)0.0110 (18)
C19A0.060 (5)0.040 (4)0.066 (5)0.013 (4)0.008 (4)0.001 (4)
C20A0.060 (3)0.142 (5)0.093 (4)0.026 (3)0.028 (3)0.024 (4)
C210.0265 (16)0.052 (2)0.063 (2)0.0017 (15)0.0083 (15)0.0129 (18)
C220.065 (2)0.0291 (16)0.0291 (15)0.0019 (15)0.0048 (15)0.0016 (12)
C230.081 (3)0.091 (3)0.041 (2)0.026 (3)0.004 (2)0.022 (2)
C240.0372 (17)0.0328 (16)0.0424 (18)0.0074 (14)0.0016 (14)0.0017 (14)
C250.0311 (15)0.0283 (15)0.0246 (14)0.0018 (12)0.0007 (11)0.0039 (11)
C260.0462 (18)0.0331 (16)0.0252 (14)0.0022 (14)0.0008 (13)0.0038 (12)
C270.049 (2)0.114 (4)0.049 (2)0.020 (2)0.0122 (19)0.043 (2)
C280.141 (6)0.247 (9)0.090 (4)0.148 (7)0.049 (4)0.083 (5)
Geometric parameters (Å, º) top
Rh1—O12.0280 (16)C9—C141.397 (3)
Rh1—O42.0335 (16)C10—C111.386 (3)
Rh1—O5i2.0421 (16)C10—H100.9500
Rh1—O2i2.0431 (16)C11—C121.384 (4)
Rh1—Rh1i2.4102 (4)C11—H110.9500
Rh1—S12.4445 (6)C12—C131.389 (4)
Rh2—O8ii2.0230 (19)C13—C141.383 (3)
Rh2—O92.0350 (19)C13—H130.9500
Rh2—O13ii2.040 (2)C14—H140.9500
Rh2—O102.0462 (19)C15—H15A0.9800
Rh2—Rh2ii2.4037 (4)C15—H15B0.9800
Rh2—S22.4272 (7)C15—H15C0.9800
S1—O71.4980 (17)C16—H16A0.9800
S1—C151.775 (3)C16—H16B0.9800
S1—C161.777 (3)C16—H16C0.9800
S2—O111.4941 (19)C17—C181.507 (4)
S2—C211.773 (3)C18—C191.512 (7)
S2—C221.783 (3)C18—H18A0.9900
O1—C11.271 (3)C18—H18B0.9900
O2—C11.270 (3)C19—C201.556 (9)
O2—Rh1i2.0431 (16)C19—H19A0.9900
O3—C51.357 (3)C19—H19B0.9900
O3—H3O0.77 (3)C20—H20A0.9800
O4—C81.272 (3)C20—H20B0.9800
O5—C81.272 (3)C20—H20C0.9800
O5—Rh1i2.0421 (16)C19A—H19C0.9900
O6—C121.357 (3)C19A—H19D0.9900
O6—H6O0.75 (2)C21—H21A0.9800
O8—C251.270 (3)C21—H21B0.9800
O8—Rh2ii2.0230 (19)C21—H21C0.9800
O9—C171.270 (3)C22—H22A0.9800
O10—C251.267 (3)C22—H22B0.9800
O12—C241.426 (4)C22—H22C0.9800
O12—H12O0.73 (2)C23—C241.492 (5)
O13—C171.261 (3)C23—H23A0.9800
O13—Rh2ii2.040 (2)C23—H23B0.9800
C1—C21.480 (3)C23—H23C0.9800
C2—C31.391 (3)C24—H24A0.9900
C2—C71.394 (3)C24—H24B0.9900
C3—C41.379 (4)C25—C261.508 (4)
C3—H30.9500C26—C271.471 (5)
C4—C51.385 (4)C26—H26A0.9900
C4—H40.9500C26—H26B0.9900
C5—C61.394 (4)C27—C281.477 (8)
C6—C71.384 (4)C27—H27A0.9900
C6—H60.9500C27—H27B0.9900
C7—H70.9500C28—H28A0.9800
C8—C91.481 (3)C28—H28B0.9800
C9—C101.394 (3)C28—H28C0.9800
O1—Rh1—O489.71 (7)O6—C12—C13123.0 (2)
O1—Rh1—O5i89.72 (7)C11—C12—C13119.7 (2)
O4—Rh1—O5i175.73 (6)C14—C13—C12120.0 (2)
O1—Rh1—O2i175.72 (6)C14—C13—H13120.0
O4—Rh1—O2i89.75 (7)C12—C13—H13120.0
O5i—Rh1—O2i90.51 (7)C13—C14—C9120.8 (2)
O1—Rh1—Rh1i87.59 (5)C13—C14—H14119.6
O4—Rh1—Rh1i87.57 (5)C9—C14—H14119.6
O5i—Rh1—Rh1i88.18 (5)S1—C15—H15A109.5
O2i—Rh1—Rh1i88.14 (5)S1—C15—H15B109.5
O1—Rh1—S190.39 (5)H15A—C15—H15B109.5
O4—Rh1—S193.61 (5)S1—C15—H15C109.5
O5i—Rh1—S190.63 (5)H15A—C15—H15C109.5
O2i—Rh1—S193.88 (5)H15B—C15—H15C109.5
Rh1i—Rh1—S1177.664 (18)S1—C16—H16A109.5
O8ii—Rh2—O989.82 (8)S1—C16—H16B109.5
O8ii—Rh2—O13ii88.95 (9)H16A—C16—H16B109.5
O9—Rh2—O13ii175.51 (8)S1—C16—H16C109.5
O8ii—Rh2—O10175.82 (8)H16A—C16—H16C109.5
O9—Rh2—O1090.55 (8)H16B—C16—H16C109.5
O13ii—Rh2—O1090.36 (8)O13—C17—O9125.4 (3)
O8ii—Rh2—Rh2ii88.34 (6)O13—C17—C18118.2 (3)
O9—Rh2—Rh2ii87.56 (6)O9—C17—C18116.4 (3)
O13ii—Rh2—Rh2ii88.09 (6)C17—C18—C19116.3 (4)
O10—Rh2—Rh2ii87.52 (5)C17—C18—H18A108.2
O8ii—Rh2—S289.11 (6)C19—C18—H18A108.2
O9—Rh2—S290.38 (6)C17—C18—H18B108.2
O13ii—Rh2—S293.92 (6)C19—C18—H18B108.2
O10—Rh2—S295.05 (6)H18A—C18—H18B107.4
Rh2ii—Rh2—S2176.72 (2)C18—C19—C20110.8 (5)
O7—S1—C15106.63 (13)C18—C19—H19A109.5
O7—S1—C16106.60 (12)C20—C19—H19A109.5
C15—S1—C16100.59 (14)C18—C19—H19B109.5
O7—S1—Rh1119.78 (8)C20—C19—H19B109.5
C15—S1—Rh1111.83 (10)H19A—C19—H19B108.1
C16—S1—Rh1109.59 (9)C19—C20—H20A109.5
O11—S2—C21107.19 (14)C19—C20—H20B109.5
O11—S2—C22107.30 (13)H20A—C20—H20B109.5
C21—S2—C2299.34 (18)C19—C20—H20C109.5
O11—S2—Rh2119.04 (8)H20A—C20—H20C109.5
C21—S2—Rh2113.57 (12)H20B—C20—H20C109.5
C22—S2—Rh2108.45 (12)H19C—C19A—H19D108.5
C1—O1—Rh1120.02 (15)S2—C21—H21A109.5
C1—O2—Rh1i118.69 (15)S2—C21—H21B109.5
C5—O3—H3O105 (3)H21A—C21—H21B109.5
C8—O4—Rh1119.94 (15)S2—C21—H21C109.5
C8—O5—Rh1i118.87 (15)H21A—C21—H21C109.5
C12—O6—H6O109 (2)H21B—C21—H21C109.5
C25—O8—Rh2ii119.38 (18)S2—C22—H22A109.5
C17—O9—Rh2119.74 (18)S2—C22—H22B109.5
C25—O10—Rh2119.13 (17)H22A—C22—H22B109.5
C24—O12—H12O111 (3)S2—C22—H22C109.5
C17—O13—Rh2ii119.12 (19)H22A—C22—H22C109.5
O2—C1—O1125.5 (2)H22B—C22—H22C109.5
O2—C1—C2117.8 (2)C24—C23—H23A109.5
O1—C1—C2116.6 (2)C24—C23—H23B109.5
C3—C2—C7118.8 (2)H23A—C23—H23B109.5
C3—C2—C1121.4 (2)C24—C23—H23C109.5
C7—C2—C1119.8 (2)H23A—C23—H23C109.5
C4—C3—C2120.8 (2)H23B—C23—H23C109.5
C4—C3—H3119.6O12—C24—C23109.1 (3)
C2—C3—H3119.6O12—C24—H24A109.9
C3—C4—C5120.2 (2)C23—C24—H24A109.9
C3—C4—H4119.9O12—C24—H24B109.9
C5—C4—H4119.9C23—C24—H24B109.9
O3—C5—C4123.0 (2)H24A—C24—H24B108.3
O3—C5—C6117.2 (3)O10—C25—O8125.6 (3)
C4—C5—C6119.8 (2)O10—C25—C26117.9 (3)
C7—C6—C5119.7 (3)O8—C25—C26116.5 (3)
C7—C6—H6120.1C27—C26—C25114.0 (3)
C5—C6—H6120.1C27—C26—H26A108.7
C6—C7—C2120.7 (2)C25—C26—H26A108.7
C6—C7—H7119.6C27—C26—H26B108.7
C2—C7—H7119.6C25—C26—H26B108.7
O5—C8—O4125.2 (2)H26A—C26—H26B107.6
O5—C8—C9118.2 (2)C26—C27—C28112.7 (5)
O4—C8—C9116.6 (2)C26—C27—H27A109.0
C10—C9—C14118.7 (2)C28—C27—H27A109.0
C10—C9—C8119.8 (2)C26—C27—H27B109.0
C14—C9—C8121.3 (2)C28—C27—H27B109.0
C11—C10—C9120.4 (2)H27A—C27—H27B107.8
C11—C10—H10119.8C27—C28—H28A109.5
C9—C10—H10119.8C27—C28—H28B109.5
C12—C11—C10120.5 (2)H28A—C28—H28B109.5
C12—C11—H11119.8C27—C28—H28C109.5
C10—C11—H11119.8H28A—C28—H28C109.5
O6—C12—C11117.3 (2)H28B—C28—H28C109.5
O1—Rh1—S1—O795.09 (10)Rh1i—O2—C1—O11.6 (3)
O4—Rh1—S1—O75.36 (10)Rh1i—O2—C1—C2177.22 (16)
O5i—Rh1—S1—O7175.19 (10)Rh1—O1—C1—O21.2 (3)
O2i—Rh1—S1—O784.64 (10)Rh1—O1—C1—C2177.65 (15)
Rh1i—Rh1—S1—O7125.5 (4)O2—C1—C2—C314.8 (4)
O1—Rh1—S1—C15139.15 (12)O1—C1—C2—C3166.3 (2)
O4—Rh1—S1—C15131.12 (12)O2—C1—C2—C7163.8 (2)
O5i—Rh1—S1—C1549.43 (12)O1—C1—C2—C715.1 (3)
O2i—Rh1—S1—C1541.12 (12)C7—C2—C3—C40.3 (4)
Rh1i—Rh1—S1—C15108.7 (5)C1—C2—C3—C4178.4 (2)
O1—Rh1—S1—C1628.49 (11)C2—C3—C4—C51.3 (4)
O4—Rh1—S1—C16118.23 (11)C3—C4—C5—O3178.4 (3)
O5i—Rh1—S1—C1661.23 (11)C3—C4—C5—C61.0 (5)
O2i—Rh1—S1—C16151.78 (11)O3—C5—C6—C7179.7 (3)
Rh1i—Rh1—S1—C161.9 (5)C4—C5—C6—C70.9 (5)
O8ii—Rh2—S2—O11144.55 (11)C5—C6—C7—C22.5 (5)
O9—Rh2—S2—O1154.73 (11)C3—C2—C7—C62.2 (4)
O13ii—Rh2—S2—O11126.57 (11)C1—C2—C7—C6176.5 (3)
O10—Rh2—S2—O1135.86 (11)Rh1i—O5—C8—O46.0 (3)
Rh2ii—Rh2—S2—O11105.7 (4)Rh1i—O5—C8—C9172.05 (16)
O8ii—Rh2—S2—C2187.80 (15)Rh1—O4—C8—O56.6 (3)
O9—Rh2—S2—C21177.61 (15)Rh1—O4—C8—C9171.53 (15)
O13ii—Rh2—S2—C211.09 (15)O5—C8—C9—C10172.3 (2)
O10—Rh2—S2—C2191.80 (15)O4—C8—C9—C106.0 (3)
Rh2ii—Rh2—S2—C21126.6 (4)O5—C8—C9—C141.6 (4)
O8ii—Rh2—S2—C2221.60 (13)O4—C8—C9—C14179.8 (2)
O9—Rh2—S2—C2268.21 (13)C14—C9—C10—C111.0 (4)
O13ii—Rh2—S2—C22110.49 (13)C8—C9—C10—C11173.0 (2)
O10—Rh2—S2—C22158.80 (13)C9—C10—C11—C120.6 (4)
Rh2ii—Rh2—S2—C2217.2 (4)C10—C11—C12—O6178.4 (3)
O4—Rh1—O1—C187.36 (18)C10—C11—C12—C132.4 (4)
O5i—R1—O1—C188.40 (18)O6—C12—C13—C14178.4 (3)
O2i—Rh1—O1—C14.6 (10)C11—C12—C13—C142.5 (4)
Rh1i—Rh1—O1—C10.21 (17)C12—C13—C14—C90.8 (4)
S1—Rh1—O1—C1179.03 (17)C10—C9—C14—C131.0 (4)
O1—Rh1—O4—C890.99 (18)C8—C9—C14—C13172.9 (2)
O5i—Rh1—O4—C88.7 (10)Rh2ii—O13—C17—O92.5 (4)
O2i—Rh1—O4—C884.76 (18)Rh2ii—O13—C17—C18176.5 (2)
Rh1i—Rh1—O4—C83.39 (17)Rh2—O9—C17—O133.9 (4)
S1—Rh1—O4—C8178.63 (17)Rh2—O9—C17—C18175.2 (2)
O8ii—Rh2—O9—C1791.1 (2)O13—C17—C18—C1918.7 (6)
O13ii—Rh2—O9—C1717.0 (12)O9—C17—C18—C19162.2 (4)
O10—Rh2—O9—C1784.7 (2)C17—C18—C19—C2072.0 (6)
Rh2ii—Rh2—O9—C172.8 (2)Rh2—O10—C25—O80.9 (4)
S2—Rh2—O9—C17179.8 (2)Rh2—O10—C25—C26177.9 (2)
O8ii—Rh2—O10—C257.7 (13)Rh2ii—O8—C25—O101.5 (4)
O9—Rh2—O10—C2587.4 (2)Rh2ii—O8—C25—C26177.25 (19)
O13ii—Rh2—O10—C2588.2 (2)O10—C25—C26—C2759.8 (4)
Rh2ii—Rh2—O10—C250.1 (2)O8—C25—C26—C27119.1 (4)
S2—Rh2—O10—C25177.9 (2)C25—C26—C27—C2859.4 (5)
Symmetry codes: (i) x, y, z; (ii) x, y, z1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3O···O120.77 (3)1.90 (3)2.661 (3)175 (5)
O6—H6O···O11ii0.75 (2)1.95 (2)2.699 (3)175 (3)
O12—H12O···O7iii0.73 (2)1.95 (2)2.679 (3)176 (4)
Symmetry codes: (ii) x, y, z1; (iii) x1/2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Rh2(C7H5O3)4(C2H6OS)2]·[Rh2(C4H7O2)4(C2H6OS)2]·2C2H6O
Mr1713.12
Crystal system, space groupMonoclinic, P21/n
Temperature (K)173
a, b, c (Å)11.9418 (6), 15.2880 (8), 19.0307 (10)
β (°) 90.915 (1)
V3)3473.9 (3)
Z2
Radiation typeMo Kα
µ (mm1)1.13
Crystal size (mm)0.22 × 0.20 × 0.14
Data collection
DiffractometerSMART CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
38253, 8473, 7201
Rint0.052
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.079, 1.02
No. of reflections8473
No. of parameters433
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.54, 0.97

Computer programs: SMART (Bruker, 1998), SMART, SHELXTL (Sheldrick, 1997a), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997b), DIAMOND (Bergerhoff, 1996), DIAMOND.

Selected bond lengths (Å) top
Rh1—O12.0280 (16)Rh2—O8ii2.0230 (19)
Rh1—O42.0335 (16)Rh2—O92.0350 (19)
Rh1—O5i2.0421 (16)Rh2—O13ii2.040 (2)
Rh1—O2i2.0431 (16)Rh2—O102.0462 (19)
Rh1—Rh1i2.4102 (4)Rh2—Rh2ii2.4037 (4)
Rh1—S12.4445 (6)Rh2—S22.4272 (7)
Symmetry codes: (i) x, y, z; (ii) x, y, z1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3O···O120.77 (3)1.90 (3)2.661 (3)175 (5)
O6—H6O···O11ii0.75 (2)1.95 (2)2.699 (3)175 (3)
O12—H12O···O7iii0.73 (2)1.95 (2)2.679 (3)176 (4)
Symmetry codes: (ii) x, y, z1; (iii) x1/2, y1/2, z+1/2.
 

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