Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107027862/bg3040sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107027862/bg3040Isup2.hkl |
CCDC reference: 659105
For related literature, see: Allen (2002); Bostelaar et al. (1984); Gawronski et al. (1997); González-Silgo, González-Platas, Ruiz-Pérez, López & Torres (1999); Hawthorne et al. (1982); Henisch (1970); Hopwood & Nicol (1972); Ng (2004); Ruiz-Pérez, Hernández-Molina, González-Silgo, López, Yanes & Solans (1996); Templeton et al. (1985); Zhou et al. (2001).
Single crystals of hydrated cadmium sulfate tartrate were grown in a silica-gel medium using the technique described by Henisch (1970). A gel was prepared by adding (R,R)-tartaric acid to sodium metasilicate, with continous stirring to avoid excessive local ion concentration. The final pH of the gel was 5.4 and the mixture was found to set in three days at room temperature. A solution of cadmium sulfate was poured over the set gel. The crystallization was carried out in glass tubes of diameter 1.7 cm. The tubes were kept at 308 K and after seven weeks colorless crystals of suitable size were carefully removed from the gel.
H atoms bonded to C and O atoms of the tartrate anion were positioned geometrically. The C—H bonds were set to 1.00 Å and O—H to 0.84 Å. The positions of the water H atoms were found in difference maps and then the O—Hwater distances were fixed at 0.84 Å. All H atoms were included in the refinement in the riding model approximation, with Uiso(H) values of 1.2Ueq(C) and 1.5 Ueq(O).
Data collection: KM-4 CCD Software (Kuma Diffraction, 2000); cell refinement: KM-4 CCD Software; data reduction: KM-4 CCD Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
[Cd2(C4H4O6)(SO4)(H2O)5]·3H2O | Z = 4 |
Mr = 613.06 | F(000) = 1200 |
Orthorhombic, P212121 | Dx = 2.373 Mg m−3 |
Hall symbol: P 2ac 2ab | Mo Kα radiation, λ = 0.71073 Å |
a = 8.365 (2) Å | µ = 2.69 mm−1 |
b = 9.795 (3) Å | T = 100 K |
c = 20.946 (5) Å | Prism, colourless |
V = 1716.2 (8) Å3 | 0.15 × 0.15 × 0.13 mm |
Kuma KM-4 CCD area-detector diffractometer | 6950 independent reflections |
Radiation source: fine-focus sealed tube | 4968 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
ω scans | θmax = 36.6°, θmin = 2.9° |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2003) | h = −11→13 |
Tmin = 0.689, Tmax = 0.721 | k = −13→15 |
20890 measured reflections | l = −27→35 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.059 | w = 1/[σ2(Fo2) + (0.0221P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.90 | (Δ/σ)max = 0.001 |
6950 reflections | Δρmax = 1.30 e Å−3 |
228 parameters | Δρmin = −1.05 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 2201 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.05 (2) |
[Cd2(C4H4O6)(SO4)(H2O)5]·3H2O | V = 1716.2 (8) Å3 |
Mr = 613.06 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.365 (2) Å | µ = 2.69 mm−1 |
b = 9.795 (3) Å | T = 100 K |
c = 20.946 (5) Å | 0.15 × 0.15 × 0.13 mm |
Kuma KM-4 CCD area-detector diffractometer | 6950 independent reflections |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2003) | 4968 reflections with I > 2σ(I) |
Tmin = 0.689, Tmax = 0.721 | Rint = 0.061 |
20890 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.059 | Δρmax = 1.30 e Å−3 |
S = 0.90 | Δρmin = −1.05 e Å−3 |
6950 reflections | Absolute structure: Flack (1983), 2201 Friedel pairs |
228 parameters | Absolute structure parameter: −0.05 (2) |
0 restraints |
Experimental. crystals grown in silica gel |
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 | ||
Cd1 | 0.49232 (3) | 0.39662 (2) | 0.283235 (11) | 0.01000 (6) | |
Cd2 | 0.69169 (3) | 0.34058 (3) | 0.021338 (12) | 0.00990 (6) | |
S | 0.12883 (12) | 0.23991 (9) | 0.29275 (4) | 0.01068 (19) | |
O1 | 0.2295 (3) | 0.3585 (3) | 0.31206 (11) | 0.0139 (6) | |
O2 | 0.1799 (3) | 0.1176 (2) | 0.32822 (11) | 0.0154 (6) | |
O3 | 0.1502 (3) | 0.2173 (3) | 0.22337 (12) | 0.0157 (6) | |
O4 | −0.0395 (3) | 0.2702 (3) | 0.30747 (12) | 0.0172 (6) | |
O1W | 0.5064 (4) | 0.5054 (2) | 0.38162 (11) | 0.0145 (5) | |
H1W1 | 0.4647 | 0.5831 | 0.3849 | 0.022* | |
H2W1 | 0.5986 | 0.5081 | 0.3974 | 0.022* | |
O2W | 0.6850 (3) | 0.4693 (2) | −0.07107 (11) | 0.0145 (5) | |
H1W2 | 0.6681 | 0.5335 | −0.0453 | 0.022* | |
H2W2 | 0.6010 | 0.4237 | −0.0765 | 0.022* | |
O3W | 0.7323 (3) | 0.3889 (3) | 0.23077 (11) | 0.0137 (6) | |
H1W3 | 0.7568 | 0.4621 | 0.2123 | 0.020* | |
H2W3 | 0.8108 | 0.3580 | 0.2511 | 0.020* | |
O4W | 0.8869 (3) | 0.4853 (3) | 0.05544 (12) | 0.0158 (6) | |
H1W4 | 0.8653 | 0.5282 | 0.0891 | 0.024* | |
H2W4 | 0.9807 | 0.4550 | 0.0574 | 0.024* | |
O5W | 0.6872 (4) | 0.2306 (2) | 0.11741 (11) | 0.0129 (5) | |
H1W5 | 0.7656 | 0.1854 | 0.1308 | 0.019* | |
H2W5 | 0.6613 | 0.2886 | 0.1451 | 0.019* | |
O6W | 0.3350 (4) | 0.2881 (3) | 0.45161 (12) | 0.0186 (6) | |
H1W6 | 0.3783 | 0.2787 | 0.4875 | 0.028* | |
H2W6 | 0.3867 | 0.3448 | 0.4297 | 0.028* | |
O7W | −0.0164 (4) | 0.3001 (2) | 0.43988 (12) | 0.0186 (6) | |
H1W7 | 0.0757 | 0.2711 | 0.4484 | 0.028* | |
H2W7 | −0.0472 | 0.2702 | 0.4044 | 0.028* | |
O8W | −0.0594 (3) | 0.0894 (3) | 0.15001 (11) | 0.0148 (6) | |
H1W8 | −0.0058 | 0.1329 | 0.1771 | 0.022* | |
H2W8 | −0.0908 | 0.0152 | 0.1657 | 0.022* | |
O5 | 0.4186 (3) | 0.3024 (2) | 0.01646 (12) | 0.0121 (5) | |
O6 | 0.1721 (3) | 0.3564 (3) | 0.04455 (12) | 0.0155 (6) | |
O7 | 0.5477 (3) | 0.5176 (3) | 0.07391 (11) | 0.0121 (6) | |
H7 | 0.5752 | 0.5999 | 0.0759 | 0.018* | |
O8 | 0.3843 (3) | 0.3733 (2) | 0.17781 (11) | 0.0117 (6) | |
H8 | 0.3057 | 0.3219 | 0.1844 | 0.018* | |
O9 | 0.4003 (3) | 0.7333 (3) | 0.15598 (12) | 0.0133 (6) | |
O10 | 0.4551 (3) | 0.6092 (3) | 0.24208 (11) | 0.0119 (5) | |
C1 | 0.3216 (5) | 0.3797 (4) | 0.04449 (15) | 0.0113 (7) | |
C2 | 0.3786 (4) | 0.5076 (4) | 0.07983 (16) | 0.0090 (7) | |
H21 | 0.3279 | 0.5900 | 0.0603 | 0.011* | |
C3 | 0.3303 (4) | 0.4985 (3) | 0.15081 (16) | 0.0080 (7) | |
H31 | 0.2112 | 0.5025 | 0.1540 | 0.010* | |
C4 | 0.4011 (4) | 0.6210 (3) | 0.18596 (17) | 0.0098 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.01076 (14) | 0.01013 (11) | 0.00911 (10) | 0.00042 (12) | −0.00034 (11) | 0.00093 (10) |
Cd2 | 0.00970 (14) | 0.01001 (11) | 0.00998 (11) | −0.00011 (12) | 0.00083 (11) | −0.00111 (11) |
S | 0.0103 (5) | 0.0118 (4) | 0.0099 (4) | −0.0002 (4) | −0.0003 (3) | −0.0007 (3) |
O1 | 0.0146 (15) | 0.0150 (14) | 0.0120 (12) | −0.0027 (11) | 0.0015 (10) | −0.0003 (10) |
O2 | 0.0203 (15) | 0.0141 (13) | 0.0118 (11) | 0.0013 (13) | 0.0018 (11) | 0.0008 (10) |
O3 | 0.0193 (16) | 0.0172 (13) | 0.0105 (12) | −0.0040 (11) | 0.0023 (11) | 0.0017 (10) |
O4 | 0.0116 (17) | 0.0197 (14) | 0.0203 (13) | −0.0033 (11) | 0.0000 (11) | −0.0036 (11) |
O1W | 0.0148 (14) | 0.0127 (12) | 0.0159 (12) | 0.0025 (14) | −0.0050 (12) | −0.0044 (10) |
O2W | 0.0144 (15) | 0.0156 (13) | 0.0134 (12) | −0.0010 (13) | 0.0023 (12) | −0.0024 (10) |
O3W | 0.0096 (14) | 0.0151 (13) | 0.0162 (13) | 0.0002 (11) | −0.0010 (9) | 0.0031 (11) |
O4W | 0.0117 (15) | 0.0174 (14) | 0.0182 (14) | 0.0011 (12) | 0.0019 (11) | −0.0068 (11) |
O5W | 0.0154 (15) | 0.0107 (12) | 0.0127 (12) | 0.0049 (12) | 0.0001 (11) | 0.0003 (10) |
O6W | 0.0256 (18) | 0.0214 (14) | 0.0088 (12) | 0.0004 (13) | −0.0025 (11) | 0.0054 (10) |
O7W | 0.0181 (16) | 0.0195 (13) | 0.0183 (13) | 0.0033 (13) | 0.0012 (13) | −0.0006 (10) |
O8W | 0.0179 (15) | 0.0106 (13) | 0.0160 (13) | −0.0021 (11) | −0.0016 (10) | 0.0020 (11) |
O5 | 0.0096 (14) | 0.0125 (12) | 0.0142 (12) | 0.0020 (10) | 0.0012 (10) | −0.0042 (11) |
O6 | 0.0090 (15) | 0.0189 (14) | 0.0187 (12) | −0.0025 (12) | −0.0015 (10) | −0.0058 (11) |
O7 | 0.0110 (15) | 0.0107 (13) | 0.0146 (13) | −0.0044 (11) | 0.0043 (10) | −0.0007 (10) |
O8 | 0.0142 (15) | 0.0078 (13) | 0.0132 (12) | −0.0031 (10) | 0.0012 (10) | 0.0017 (10) |
O9 | 0.0147 (15) | 0.0126 (14) | 0.0126 (12) | −0.0002 (11) | 0.0011 (11) | 0.0015 (10) |
O10 | 0.0140 (15) | 0.0118 (12) | 0.0098 (11) | −0.0001 (11) | −0.0035 (9) | −0.0006 (10) |
C1 | 0.009 (2) | 0.0147 (19) | 0.0102 (14) | −0.0015 (16) | −0.0008 (14) | 0.0025 (13) |
C2 | 0.0070 (18) | 0.0086 (17) | 0.0113 (17) | −0.0027 (15) | 0.0003 (13) | −0.0016 (14) |
C3 | 0.0034 (18) | 0.0068 (16) | 0.0138 (16) | −0.0013 (14) | 0.0028 (13) | −0.0005 (13) |
C4 | 0.0057 (19) | 0.0087 (18) | 0.0148 (17) | 0.0038 (14) | 0.0007 (13) | −0.0016 (14) |
Cd1—O9i | 2.233 (3) | O4W—H1W4 | 0.8399 |
Cd1—O10 | 2.275 (3) | O4W—H2W4 | 0.8400 |
Cd1—O3W | 2.290 (3) | O5W—H1W5 | 0.8400 |
Cd1—O1 | 2.310 (3) | O5W—H2W5 | 0.8401 |
Cd1—O1W | 2.323 (2) | O6W—H1W6 | 0.8399 |
Cd1—O8 | 2.397 (2) | O6W—H2W6 | 0.8401 |
Cd2—O4W | 2.278 (3) | O7W—H1W7 | 0.8400 |
Cd2—O5W | 2.283 (2) | O7W—H2W7 | 0.8400 |
Cd2—O2W | 2.311 (2) | O8W—H1W8 | 0.8400 |
Cd2—O5 | 2.317 (3) | O8W—H2W8 | 0.8400 |
Cd2—O6ii | 2.378 (2) | O5—C1 | 1.255 (4) |
Cd2—O7 | 2.381 (3) | O6—C1 | 1.271 (5) |
Cd2—O5ii | 2.488 (2) | O7—C2 | 1.423 (5) |
S—O4 | 1.472 (3) | O7—H7 | 0.8400 |
S—O2 | 1.473 (3) | O8—C3 | 1.424 (4) |
S—O3 | 1.481 (3) | O8—H8 | 0.8400 |
S—O1 | 1.491 (3) | O9—C4 | 1.267 (4) |
O1W—H1W1 | 0.8400 | O10—C4 | 1.265 (4) |
O1W—H2W1 | 0.8400 | C1—C2 | 1.531 (5) |
O2W—H1W2 | 0.8401 | C2—C3 | 1.543 (5) |
O2W—H2W2 | 0.8400 | C2—H21 | 1.0000 |
O3W—H1W3 | 0.8400 | C3—C4 | 1.527 (5) |
O3W—H2W3 | 0.8399 | C3—H31 | 1.0000 |
O9i—Cd1—O10 | 157.93 (9) | O7—Cd2—O5ii | 160.55 (8) |
O9i—Cd1—O3W | 84.12 (9) | O4—S—O2 | 109.62 (17) |
O10—Cd1—O3W | 88.18 (9) | O4—S—O3 | 110.58 (15) |
O9i—Cd1—O1 | 96.77 (10) | O2—S—O3 | 109.77 (15) |
O10—Cd1—O1 | 96.70 (9) | O4—S—O1 | 109.06 (15) |
O3W—Cd1—O1 | 162.63 (9) | O2—S—O1 | 109.45 (15) |
O9i—Cd1—O1W | 78.60 (9) | O3—S—O1 | 108.34 (14) |
O10—Cd1—O1W | 85.60 (9) | H1W1—O1W—H2W1 | 108.7 |
O3W—Cd1—O1W | 113.35 (10) | H1W2—O2W—H2W2 | 110.1 |
O1—Cd1—O1W | 83.71 (10) | H1W3—O3W—H2W3 | 110.6 |
O9i—Cd1—O8 | 127.49 (8) | H1W4—O4W—H2W4 | 109.7 |
O10—Cd1—O8 | 71.74 (8) | H1W5—O5W—H2W5 | 109.2 |
O3W—Cd1—O8 | 83.40 (9) | H1W6—O6W—H2W6 | 109.8 |
O1—Cd1—O8 | 82.34 (9) | H1W7—O7W—H2W7 | 110.6 |
O1W—Cd1—O8 | 151.66 (9) | H1W8—O8W—H2W8 | 109.9 |
O4W—Cd2—O5W | 91.67 (10) | C2—O7—H7 | 109.5 |
O4W—Cd2—O2W | 86.58 (10) | C3—O8—H8 | 109.5 |
O5W—Cd2—O2W | 174.54 (9) | O5—C1—O6 | 121.9 (3) |
O4W—Cd2—O5 | 145.19 (9) | O5—C1—C2 | 121.2 (3) |
O5W—Cd2—O5 | 86.93 (10) | O6—C1—C2 | 116.9 (3) |
O2W—Cd2—O5 | 91.55 (9) | O7—C2—C1 | 108.9 (3) |
O4W—Cd2—O6ii | 137.44 (9) | O7—C2—C3 | 110.4 (3) |
O5W—Cd2—O6ii | 97.34 (9) | C1—C2—C3 | 109.7 (3) |
O2W—Cd2—O6ii | 87.42 (9) | O7—C2—H21 | 109.3 |
O5—Cd2—O6ii | 77.04 (9) | C1—C2—H21 | 109.3 |
O4W—Cd2—O7 | 76.36 (9) | C3—C2—H21 | 109.3 |
O5W—Cd2—O7 | 85.83 (9) | O8—C3—C4 | 111.2 (3) |
O2W—Cd2—O7 | 88.73 (9) | O8—C3—C2 | 110.4 (3) |
O5—Cd2—O7 | 68.84 (8) | C4—C3—C2 | 108.5 (3) |
O6ii—Cd2—O7 | 145.54 (9) | O8—C3—H31 | 108.9 |
O4W—Cd2—O5ii | 84.46 (9) | C4—C3—H31 | 108.9 |
O5W—Cd2—O5ii | 91.58 (9) | C2—C3—H31 | 108.9 |
O2W—Cd2—O5ii | 93.40 (9) | O10—C4—O9 | 122.8 (3) |
O5—Cd2—O5ii | 130.33 (4) | O10—C4—C3 | 121.0 (3) |
O6ii—Cd2—O5ii | 53.91 (9) | O9—C4—C3 | 116.2 (3) |
O5—C1—C2—O7 | 0.2 (4) | O7—C2—C3—C4 | 55.2 (4) |
O6—C1—C2—O7 | −179.3 (3) | C1—C2—C3—C4 | 175.1 (3) |
O5—C1—C2—C3 | −120.6 (3) | O8—C3—C4—O10 | −20.7 (5) |
O6—C1—C2—C3 | 59.8 (4) | C2—C3—C4—O10 | −142.4 (3) |
O7—C2—C3—O8 | −67.0 (4) | O8—C3—C4—O9 | 160.1 (3) |
C1—C2—C3—O8 | 53.0 (4) | C2—C3—C4—O9 | 38.4 (4) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1/2, −y+1/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O5Wiii | 0.84 | 1.93 | 2.737 (4) | 162 |
O1W—H2W1···O2Wiv | 0.84 | 1.94 | 2.776 (4) | 174 |
O2W—H1W2···O7Wv | 0.84 | 2.09 | 2.673 (4) | 126 |
O2W—H2W2···O8Wii | 0.84 | 2.05 | 2.692 (4) | 133 |
O3W—H1W3···O2iii | 0.84 | 1.82 | 2.661 (4) | 177 |
O3W—H2W3···O4vi | 0.84 | 1.92 | 2.753 (4) | 169 |
O4W—H1W4···O2iii | 0.84 | 1.98 | 2.816 (4) | 176 |
O4W—H2W4···O6vi | 0.84 | 1.89 | 2.709 (4) | 165 |
O5W—H1W5···O8Wvi | 0.84 | 1.78 | 2.621 (4) | 173 |
O5W—H2W5···O3W | 0.84 | 2.13 | 2.861 (4) | 145 |
O6W—H1W6···O7Wvii | 0.84 | 1.92 | 2.731 (4) | 162 |
O6W—H2W6···O1W | 0.84 | 2.12 | 2.956 (4) | 173 |
O7W—H1W7···O6W | 0.84 | 2.18 | 2.952 (4) | 153 |
O7W—H2W7···O4 | 0.84 | 2.03 | 2.796 (4) | 151 |
O8W—H1W8···O3 | 0.84 | 1.82 | 2.647 (4) | 166 |
O8W—H2W8···O1viii | 0.84 | 1.98 | 2.788 (4) | 161 |
O7—H7···O6Wiii | 0.84 | 2.07 | 2.876 (4) | 160 |
O8—H8···O3 | 0.84 | 1.85 | 2.661 (4) | 163 |
Symmetry codes: (ii) x+1/2, −y+1/2, −z; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+3/2, −y+1, z+1/2; (v) −x+1/2, −y+1, z−1/2; (vi) x+1, y, z; (vii) x+1/2, −y+1/2, −z+1; (viii) −x, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cd2(C4H4O6)(SO4)(H2O)5]·3H2O |
Mr | 613.06 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 8.365 (2), 9.795 (3), 20.946 (5) |
V (Å3) | 1716.2 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.69 |
Crystal size (mm) | 0.15 × 0.15 × 0.13 |
Data collection | |
Diffractometer | Kuma KM-4 CCD area-detector diffractometer |
Absorption correction | Analytical (CrysAlis RED; Oxford Diffraction, 2003) |
Tmin, Tmax | 0.689, 0.721 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20890, 6950, 4968 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.839 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.059, 0.90 |
No. of reflections | 6950 |
No. of parameters | 228 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.30, −1.05 |
Absolute structure | Flack (1983), 2201 Friedel pairs |
Absolute structure parameter | −0.05 (2) |
Computer programs: KM-4 CCD Software (Kuma Diffraction, 2000), KM-4 CCD Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1990) and PLATON (Spek, 2003), SHELXL97.
Cd1—O9i | 2.233 (3) | Cd2—O5W | 2.283 (2) |
Cd1—O10 | 2.275 (3) | Cd2—O2W | 2.311 (2) |
Cd1—O3W | 2.290 (3) | Cd2—O5 | 2.317 (3) |
Cd1—O1 | 2.310 (3) | Cd2—O6ii | 2.378 (2) |
Cd1—O1W | 2.323 (2) | Cd2—O7 | 2.381 (3) |
Cd1—O8 | 2.397 (2) | Cd2—O5ii | 2.488 (2) |
Cd2—O4W | 2.278 (3) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1/2, −y+1/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O5Wiii | 0.84 | 1.93 | 2.737 (4) | 162 |
O1W—H2W1···O2Wiv | 0.84 | 1.94 | 2.776 (4) | 174 |
O2W—H1W2···O7Wv | 0.84 | 2.09 | 2.673 (4) | 126 |
O2W—H2W2···O8Wii | 0.84 | 2.05 | 2.692 (4) | 133 |
O3W—H1W3···O2iii | 0.84 | 1.82 | 2.661 (4) | 177 |
O3W—H2W3···O4vi | 0.84 | 1.92 | 2.753 (4) | 169 |
O4W—H1W4···O2iii | 0.84 | 1.98 | 2.816 (4) | 176 |
O4W—H2W4···O6vi | 0.84 | 1.89 | 2.709 (4) | 165 |
O5W—H1W5···O8Wvi | 0.84 | 1.78 | 2.621 (4) | 173 |
O5W—H2W5···O3W | 0.84 | 2.13 | 2.861 (4) | 145 |
O6W—H1W6···O7Wvii | 0.84 | 1.92 | 2.731 (4) | 162 |
O6W—H2W6···O1W | 0.84 | 2.12 | 2.956 (4) | 173 |
O7W—H1W7···O6W | 0.84 | 2.18 | 2.952 (4) | 153 |
O7W—H2W7···O4 | 0.84 | 2.03 | 2.796 (4) | 151 |
O8W—H1W8···O3 | 0.84 | 1.82 | 2.647 (4) | 166 |
O8W—H2W8···O1viii | 0.84 | 1.98 | 2.788 (4) | 161 |
O7—H7···O6Wiii | 0.84 | 2.07 | 2.876 (4) | 160 |
O8—H8···O3 | 0.84 | 1.85 | 2.661 (4) | 163 |
Symmetry codes: (ii) x+1/2, −y+1/2, −z; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+3/2, −y+1, z+1/2; (v) −x+1/2, −y+1, z−1/2; (vi) x+1, y, z; (vii) x+1/2, −y+1/2, −z+1; (viii) −x, y−1/2, −z+1/2. |
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Tartaric acid and its anions are flexible multidentate O-donor ligands, and many salts and complexes with the majority of metal cations have been reported. A search of the Cambridge Structural Database (CSD; Version 5.28; Allen, 2002) for solid phases containing a transition metal cation and a tartrate anion showed over 60 crystal structures. In those crystals, besides the requested contents, accompanying inorganic and/or organic units were present in the form of cations, anions or neutral components. The search, however, showed no examples of structures containing a single type of cation and inorganic anion. To date, only three structures of cadmium tartrates have been published. Two of these complexes contain additional organic ligands, viz. a hydrated complex of cadmium (R,R)-tartrate with hexamethylenetetramine (Ng, 2004), and a cadmium complex with racemic tartrate and tiourea (Zhou et al., 2001). Moreover, two crystal structures of simple cadmium tartrate have been reported, for one of which, of proposed formula Cd(C4H4O6)·5H2O (Hopwood & Nicol, 1972), the structure has not been determined. The second one, [Cd2(C4H4O6)2(H2O)]n.3nH2O, was published by González-Silgo et al. (1999). In this crystal, two symmetry-independent cadmium cations are present, both of then six-coordinated (CdO6). In one of the cations, the coordination sphere includes six tartrate O atoms, while in the other one, one aqua ligand is present. Since three out of four carboxylate groups are bridging bidentate, a three-dimensional polymeric structure is formed.
We have now synthesized the new title cadmium complex [Cd2(C4H406)(SO4)(H2O)5]·3H2O, (I), with mixed organic/inorganic anions (Cd/tartrate/sulfate/water) in a 2:1:1:8 ratio. The present structure also contains two independent cadmium cations, but the two have different coordination numbers and coordinated ligands (Fig. 1). The distorted octahedral geometry for atom Cd1 is completed by three O atoms from tartrate anions, one sulfate O atom and two water molecules. The Cd2 cation exibits sevenfold coordination; the pentagonal bipyramid is formed by four O atoms from tartrate ligands and by three water molecules. Thus, the sulfate anion behaves as a monodentate ligand, while the (R,R)-tartrate dianion is heptadentate. The Cd—O distances range from 2.233 (3) to 2.397 (2) Å for atom Cd1, and from 2.278 (3) to 2.488 (2) Å for atom Cd2 (Table 1). The shortest distances are observed for Cd—Owater bonds, while a longer than normal value is found for the O5—Cd2 bond as a result of the tridentate and chelating-bridging character of the carboxylate group containing the O atom.
The geometry of the tartrate ion is typical and does not differ significantly from those reported in the literature (e.g. tartrates of the divalent cations Cd2+, Mn2+, Ca2+, Ni2+ and Zn2+; González-Silgo et al., 1999; Ruiz-Pérez et al., 1996; Hawthorne et al., 1982; Bostelaar et al., 1984; Templeton et al. 1985). The conformation around the the C2—C3 bond is trans with a planar zigzag carbon chain. The C1—C2—C3—C4 torsion angle is 175.1 (3)°, which is typical for the T-conformer (Gawronski et al., 1997).
The Cd1 and Cd2 coordination spheres form separate linear polymers of different topology. The Cd1 cations are linked through the O9—C4—O10 bridging carboxylate group, forming chains along [010] (shown in projection in Fig. 2, coming out of the plane), whereas within the second type of chains (running along [100], top to bottom in Fig. 2), the neighbouring Cd2 cations share carboxylate atom O5. Fig. 2 also shows the way in which these two columns are interconnected by the whole tartrate backbone, through its carboxylate arms and the hydroxyl group, leading to a three-dimensional architecture that leaves columnar voids along a which are filled by the solvent water molecules. The very complex hydrogen-bonding scheme arising from the superabundance of donors and acceptors is shown in Fig. 2. Full details are given in Table 2.
A comparison with the reported cadmium tartrate tetrahydrate (González-Silgo et al., 1999) reveals that the inclusion of an SO42- anion in (I) forces an increased number of (coordinated) water molecules in the structure, with the corresponding environment change around the Cd cations.