Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802015775/ci6156sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802015775/ci6156Isup2.hkl |
CCDC reference: 198292
Potassium methylxanthate (2.0 g) and hexaaquachromium(III) chloride (4.0 g) were each dissolved in pure water (40 ml and 80 ml, respectively), and powder of (I) was precipitated by combining the two solutions. Recrystallization from an ether solution at room temperature gave dark-blue plate-shaped crystals of (I).
H atoms were placed in geometrically calculated positions and allowed to ride on their parent atoms, with Uiso parameters equal to 1.2 times the Ueq parameters of their parent atoms.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: CrystalStructure (Molecular Structure Corporation and Rigaku Corporation, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CrystalStructure; molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: CrystalStructure.
Fig. 1. ORTEPIII (Burnett & Johnson, 1996) drawing of the title chromium methylxanthate complex. Displacement ellipsoids are drawn at the 50% probability level. |
[Cr(C2H3OS2)3] | F(000) = 756 |
Mr = 373.55 | Dx = 1.720 Mg m−3 Dm = 1.715 Mg m−3 Dm measured by flotation in zinc iodide (aq) |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2yn | Cell parameters from 23 reflections |
a = 9.633 (4) Å | θ = 15.2–16.3° |
b = 13.852 (4) Å | µ = 1.65 mm−1 |
c = 11.301 (3) Å | T = 296 K |
β = 106.94 (2)° | Plate, dark blue |
V = 1442.5 (8) Å3 | 0.45 × 0.35 × 0.10 mm |
Z = 4 |
Rigaku AFC-5S diffractometer | Rint = 0.029 |
ω–2θ scans | θmax = 27.5° |
Absorption correction: ψ (North, Phillips & Mathews, 1968) | h = 0→12 |
Tmin = 0.510, Tmax = 0.848 | k = 0→17 |
3640 measured reflections | l = −14→14 |
3311 independent reflections | 3 standard reflections every 150 reflections |
2041 reflections with I > 3σ(I) | intensity decay: 0.1% |
Refinement on F | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.033 | Weighting scheme based on measured s.u.'s w = 1/σ2(Fo) |
wR(F2) = 0.022 | (Δ/σ)max < 0.001 |
S = 1.66 | Δρmax = 0.26 e Å−3 |
2041 reflections | Δρmin = −0.29 e Å−3 |
145 parameters |
[Cr(C2H3OS2)3] | V = 1442.5 (8) Å3 |
Mr = 373.55 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.633 (4) Å | µ = 1.65 mm−1 |
b = 13.852 (4) Å | T = 296 K |
c = 11.301 (3) Å | 0.45 × 0.35 × 0.10 mm |
β = 106.94 (2)° |
Rigaku AFC-5S diffractometer | 2041 reflections with I > 3σ(I) |
Absorption correction: ψ (North, Phillips & Mathews, 1968) | Rint = 0.029 |
Tmin = 0.510, Tmax = 0.848 | 3 standard reflections every 150 reflections |
3640 measured reflections | intensity decay: 0.1% |
3311 independent reflections |
R[F2 > 2σ(F2)] = 0.033 | 145 parameters |
wR(F2) = 0.022 | H-atom parameters constrained |
S = 1.66 | Δρmax = 0.26 e Å−3 |
2041 reflections | Δρmin = −0.29 e Å−3 |
x | y | z | Uiso*/Ueq | ||
Cr | 0.67719 (6) | 0.48456 (4) | 0.26848 (6) | 0.0396 (2) | |
S1 | 0.9122 (1) | 0.56029 (8) | 0.3246 (1) | 0.0481 (3) | |
S2 | 0.8025 (1) | 0.41613 (8) | 0.1341 (1) | 0.0517 (3) | |
S3 | 0.7465 (1) | 0.36479 (8) | 0.4272 (1) | 0.0514 (3) | |
S4 | 0.4827 (1) | 0.37002 (8) | 0.2228 (1) | 0.0539 (3) | |
S5 | 0.5738 (1) | 0.59631 (8) | 0.3819 (1) | 0.0515 (3) | |
S6 | 0.5521 (1) | 0.60248 (7) | 0.1208 (1) | 0.0490 (3) | |
O1 | 1.0596 (3) | 0.4870 (2) | 0.1784 (2) | 0.057 (1) | |
O2 | 0.5307 (3) | 0.2378 (2) | 0.3902 (3) | 0.057 (1) | |
O3 | 0.4285 (3) | 0.7281 (2) | 0.2368 (3) | 0.060 (1) | |
C1 | 0.9391 (4) | 0.4892 (3) | 0.2119 (4) | 0.043 (1) | |
C2 | 0.5844 (4) | 0.3159 (3) | 0.3537 (4) | 0.044 (1) | |
C3 | 0.5103 (4) | 0.6512 (3) | 0.2419 (4) | 0.044 (1) | |
C4 | 1.1805 (4) | 0.5471 (3) | 0.2428 (4) | 0.070 (2) | |
C5 | 0.6188 (5) | 0.1880 (3) | 0.4984 (4) | 0.073 (2) | |
C6 | 0.3702 (5) | 0.7760 (3) | 0.1188 (4) | 0.078 (2) | |
H1 | 1.2579 | 0.5389 | 0.2074 | 0.085* | |
H2 | 1.2118 | 0.5285 | 0.3274 | 0.085* | |
H3 | 1.1516 | 0.6129 | 0.2367 | 0.085* | |
H4 | 0.5682 | 0.1342 | 0.5178 | 0.092* | |
H5 | 0.6429 | 0.2316 | 0.5662 | 0.092* | |
H6 | 0.7052 | 0.1663 | 0.4824 | 0.092* | |
H7 | 0.3110 | 0.8291 | 0.1265 | 0.087* | |
H8 | 0.4493 | 0.7985 | 0.0921 | 0.087* | |
H9 | 0.3143 | 0.7316 | 0.0600 | 0.087* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cr | 0.0312 (3) | 0.0473 (4) | 0.0404 (4) | −0.0037 (3) | 0.0103 (3) | −0.0043 (3) |
S1 | 0.0384 (6) | 0.0572 (7) | 0.0502 (7) | −0.0109 (5) | 0.0151 (5) | −0.0180 (6) |
S2 | 0.0403 (6) | 0.0599 (7) | 0.0554 (7) | −0.0085 (5) | 0.0149 (5) | −0.0232 (6) |
S3 | 0.0389 (6) | 0.0621 (8) | 0.0476 (7) | −0.0027 (5) | 0.0037 (5) | 0.0047 (6) |
S4 | 0.0370 (6) | 0.0624 (8) | 0.0544 (7) | −0.0118 (5) | 0.0009 (5) | 0.0034 (6) |
S5 | 0.0457 (6) | 0.0688 (8) | 0.0421 (7) | 0.0035 (6) | 0.0160 (5) | −0.0085 (6) |
S6 | 0.0501 (7) | 0.0571 (7) | 0.0412 (6) | 0.0017 (6) | 0.0152 (5) | 0.0010 (6) |
O1 | 0.038 (2) | 0.068 (2) | 0.074 (2) | −0.008 (2) | 0.027 (2) | −0.022 (2) |
O2 | 0.062 (2) | 0.054 (2) | 0.060 (2) | −0.010 (2) | 0.026 (2) | 0.003 (2) |
O3 | 0.054 (2) | 0.056 (2) | 0.065 (2) | 0.012 (2) | 0.010 (2) | −0.011 (2) |
C1 | 0.034 (2) | 0.047 (2) | 0.049 (3) | −0.000 (2) | 0.013 (2) | −0.001 (2) |
C2 | 0.041 (2) | 0.048 (3) | 0.050 (3) | −0.000 (2) | 0.023 (2) | −0.005 (2) |
C3 | 0.032 (2) | 0.048 (3) | 0.052 (3) | −0.008 (2) | 0.010 (2) | −0.008 (2) |
C4 | 0.031 (2) | 0.080 (3) | 0.101 (4) | −0.014 (2) | 0.024 (2) | −0.020 (3) |
C5 | 0.104 (4) | 0.062 (3) | 0.063 (3) | 0.007 (3) | 0.041 (3) | 0.014 (3) |
C6 | 0.078 (4) | 0.053 (3) | 0.086 (4) | 0.014 (3) | −0.003 (3) | −0.001 (3) |
Cr—S1 | 2.406 (1) | O2—C2 | 1.316 (4) |
Cr—S2 | 2.394 (1) | O2—C5 | 1.445 (4) |
Cr—S3 | 2.391 (1) | O3—C3 | 1.317 (4) |
Cr—S4 | 2.394 (1) | O3—C6 | 1.448 (4) |
Cr—S5 | 2.403 (1) | C4—H1 | 0.95 |
Cr—S6 | 2.394 (1) | C4—H2 | 0.95 |
S1—C1 | 1.688 (4) | C4—H3 | 0.95 |
S2—C1 | 1.690 (4) | C5—H4 | 0.95 |
S3—C2 | 1.682 (4) | C5—H5 | 0.95 |
S4—C2 | 1.693 (4) | C5—H6 | 0.95 |
S5—C3 | 1.700 (4) | C6—H7 | 0.95 |
S6—C3 | 1.676 (4) | C6—H8 | 0.95 |
O1—C1 | 1.322 (4) | C6—H9 | 0.95 |
O1—C4 | 1.444 (4) | ||
O1···C5i | 3.563 (5) | O3···C5v | 3.363 (5) |
O1···C5ii | 3.318 (5) | C1···C5i | 3.573 (5) |
O2···C4iii | 3.405 (5) | C3···C4iv | 3.491 (5) |
O3···C4iv | 3.478 (4) | ||
S1—Cr—S2 | 74.35 (4) | S2—C1—O1 | 116.9 (3) |
S1—Cr—S3 | 93.98 (5) | S3—C2—S4 | 118.1 (2) |
S1—Cr—S4 | 164.34 (5) | S3—C2—O2 | 124.7 (3) |
S1—Cr—S5 | 94.76 (5) | S4—C2—O2 | 117.2 (3) |
S1—Cr—S6 | 97.47 (5) | S5—C3—S6 | 118.2 (2) |
S2—Cr—S3 | 96.85 (5) | S5—C3—O3 | 116.8 (3) |
S2—Cr—S4 | 96.23 (5) | S6—C3—O3 | 124.9 (3) |
S2—Cr—S5 | 163.21 (5) | O1—C4—H1 | 109.6 |
S2—Cr—S6 | 94.15 (5) | O1—C4—H2 | 108.9 |
S3—Cr—S4 | 74.44 (4) | H1—C4—H2 | 109.5 |
S3—Cr—S5 | 96.62 (5) | O1—C4—H3 | 109.9 |
S3—Cr—S6 | 165.89 (4) | H1—C4—H3 | 109.5 |
S4—Cr—S5 | 97.01 (5) | H2—C4—H3 | 109.5 |
S4—Cr—S6 | 95.64 (5) | O2—C5—H4 | 110.8 |
S5—Cr—S6 | 74.31 (4) | O2—C5—H5 | 108.9 |
Cr—S1—C1 | 83.5 (1) | H4—C5—H5 | 109.5 |
Cr—S2—C1 | 83.8 (1) | O2—C5—H6 | 108.7 |
Cr—S3—C2 | 83.9 (1) | H4—C5—H6 | 109.5 |
Cr—S4—C2 | 83.6 (1) | H5—C5—H6 | 109.5 |
Cr—S5—C3 | 83.4 (1) | O3—C6—H7 | 110.7 |
Cr—S6—C3 | 84.1 (1) | O3—C6—H8 | 108.1 |
C1—O1—C4 | 119.3 (3) | H7—C6—H8 | 109.5 |
C2—O2—C5 | 118.0 (3) | O3—C6—H9 | 109.6 |
C3—O3—C6 | 118.6 (3) | H7—C6—H9 | 109.5 |
S1—C1—S2 | 118.3 (2) | H8—C6—H9 | 109.5 |
S1—C1—O1 | 124.8 (3) |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x+1/2, −y+1/2, z−1/2; (iii) −x+3/2, y−1/2, −z+1/2; (iv) x−1, y, z; (v) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cr(C2H3OS2)3] |
Mr | 373.55 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 9.633 (4), 13.852 (4), 11.301 (3) |
β (°) | 106.94 (2) |
V (Å3) | 1442.5 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.65 |
Crystal size (mm) | 0.45 × 0.35 × 0.10 |
Data collection | |
Diffractometer | Rigaku AFC-5S diffractometer |
Absorption correction | ψ (North, Phillips & Mathews, 1968) |
Tmin, Tmax | 0.510, 0.848 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 3640, 3311, 2041 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.022, 1.66 |
No. of reflections | 2041 |
No. of parameters | 145 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.29 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), MSC/AFC Diffractometer Control Software, CrystalStructure (Molecular Structure Corporation and Rigaku Corporation, 2001), SIR92 (Altomare et al., 1994), CrystalStructure, ORTEPIII (Burnett & Johnson, 1996).
Cr—S1 | 2.406 (1) | S4—C2 | 1.693 (4) |
Cr—S2 | 2.394 (1) | S5—C3 | 1.700 (4) |
Cr—S3 | 2.391 (1) | S6—C3 | 1.676 (4) |
Cr—S4 | 2.394 (1) | O1—C1 | 1.322 (4) |
Cr—S5 | 2.403 (1) | O1—C4 | 1.444 (4) |
Cr—S6 | 2.394 (1) | O2—C2 | 1.316 (4) |
S1—C1 | 1.688 (4) | O2—C5 | 1.445 (4) |
S2—C1 | 1.690 (4) | O3—C3 | 1.317 (4) |
S3—C2 | 1.682 (4) | O3—C6 | 1.448 (4) |
S1—Cr—S2 | 74.35 (4) | S2—Cr—S6 | 94.15 (5) |
S1—Cr—S3 | 93.98 (5) | S3—Cr—S4 | 74.44 (4) |
S1—Cr—S4 | 164.34 (5) | S3—Cr—S5 | 96.62 (5) |
S1—Cr—S5 | 94.76 (5) | S3—Cr—S6 | 165.89 (4) |
S1—Cr—S6 | 97.47 (5) | S4—Cr—S5 | 97.01 (5) |
S2—Cr—S3 | 96.85 (5) | S4—Cr—S6 | 95.64 (5) |
S2—Cr—S4 | 96.23 (5) | S5—Cr—S6 | 74.31 (4) |
S2—Cr—S5 | 163.21 (5) |
As part of the study of metal xanthates and dialkyl dithiophosphates (Ito, 2002a,b), the crystal and molecular structure of the title complex, (I), has been determined. A displacement ellipsoid plot of (I) is shown in Fig.1. The average Cr—S distance of 2.397 (2) Å is 0.032 (7) Å shorter than that in tris(O,O'-dimethyldithiophosphato)chromium(III), (II), (Ito, 2002b), which shows that the Cr—S bonds in (I) are stronger than those in (II). On the other hand, distortions of S atoms around the Cr atom from the octahedral coordination in (I) are larger than those in (II). For example, average S—Cr—S chelate angles in (I) and (II) are 74.5 (2)° and 81.8°, respectively.
The structures of xanthic ligands in (I) are very similar to those in iron methylxanthate, (III), (Ito, 2002a). Average S—C, S2C—O and O—CH3 bond distances of 1.688 (4), 1.318 (4) and 1.446 (4) Å, respectively, are in agreement with the corresponding distances in (III) within standard uncertainties.