Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111001065/lg3047sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111001065/lg3047Isup2.hkl |
CCDC reference: 817036
For related literature, see: Allen (2002); Bernstein et al. (1995); Chagas et al. (2008); Huang et al. (2009); Kido & Okamoto (2002); Li & Yang (2004); Li et al. (2006, 2008); Manna et al. (2006); Onoda et al. (2001); Song et al. (2004); Su et al. (2005); Tsukube & Shinoda (2002); Wan et al. (2009); Xiao et al. (2005); Zhao et al. (2008).
A mixture of 2-sulfobenzoate (30.6 mg, 0.16 mmol), Gd(NO3)3.6H2O (72.5 mg, 0.16 mmol), oxalate (7.3 mg, 0.08 mmol) and KOH aqueous solution (0.6 ml, 1 M) was added to H2O (10 ml). After stirring, the reaction mixture was sealed in a 23 ml Teflon-lined stainless steel reactor and heated at 393 K for 72 h, then cooled slowly to room temperature. Yellow block-shaped crystals of the title coordination polymer were obtained with a yield of 32% (based on Gd).
The ΔF2/s.u. values of the reflections -1 6 6, 1 1 0 and 1 1 1 are 18.32, 16.90 and 13.35, respectively, and Fo2 << Fc2, which may be caused by an inappropriate beam stop mask file (used in data reduction). They are omitted in the refinement. The H atoms bonded to C atoms were refined in idealized positions using the riding-model approximation, with C—H = 0.93 Å, and Uiso(H) = 1.2Ueq(C). The H atoms of the coordinated water molecules were located in difference maps and refined with an O—H distance restraint of 0.85 (2) Å and H···H distance restraint of 1.34 (2) Å, with Uiso(H) = 1.5Ueq(O).
Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: SHELXL (Sheldrick, 2008).
[Gd2(C7H4O5S)2(C2O4)(H2O)6] | Z = 1 |
Mr = 910.94 | F(000) = 436 |
Triclinic, P1 | Dx = 2.429 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.7597 (16) Å | Cell parameters from 2008 reflections |
b = 8.4998 (17) Å | θ = 3.3–25.7° |
c = 10.641 (2) Å | µ = 5.54 mm−1 |
α = 70.98 (3)° | T = 293 K |
β = 87.90 (3)° | Block, yellow |
γ = 70.32 (3)° | 0.26 × 0.15 × 0.09 mm |
V = 622.7 (2) Å3 |
Rigaku Saturn 724 CCD area-detector diffractometer | 2308 independent reflections |
Radiation source: fine-focus sealed tube | 2290 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ω scans | θmax = 25.7°, θmin = 3.3° |
Absorption correction: numerical (RAPID-AUTO; Rigaku, 1998) | h = −9→9 |
Tmin = 0.20, Tmax = 0.47 | k = −10→9 |
4598 measured reflections | l = −12→12 |
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)] = 0.021 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.050 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0186P)2 + 1.4132P] where P = (Fo2 + 2Fc2)/3 |
2308 reflections | (Δ/σ)max = 0.001 |
199 parameters | Δρmax = 0.79 e Å−3 |
9 restraints | Δρmin = −0.85 e Å−3 |
[Gd2(C7H4O5S)2(C2O4)(H2O)6] | γ = 70.32 (3)° |
Mr = 910.94 | V = 622.7 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.7597 (16) Å | Mo Kα radiation |
b = 8.4998 (17) Å | µ = 5.54 mm−1 |
c = 10.641 (2) Å | T = 293 K |
α = 70.98 (3)° | 0.26 × 0.15 × 0.09 mm |
β = 87.90 (3)° |
Rigaku Saturn 724 CCD area-detector diffractometer | 2308 independent reflections |
Absorption correction: numerical (RAPID-AUTO; Rigaku, 1998) | 2290 reflections with I > 2σ(I) |
Tmin = 0.20, Tmax = 0.47 | Rint = 0.034 |
4598 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 9 restraints |
wR(F2) = 0.050 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.79 e Å−3 |
2308 reflections | Δρmin = −0.85 e Å−3 |
199 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. 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 | ||
Gd1 | 0.66614 (2) | 0.22407 (2) | 0.109705 (15) | 0.01674 (7) | |
S1 | 0.28821 (12) | 0.19343 (12) | 0.30992 (9) | 0.02198 (19) | |
O3 | 0.1660 (4) | 0.2985 (4) | 0.1893 (3) | 0.0335 (6) | |
O4 | 0.2243 (4) | 0.0586 (4) | 0.4002 (3) | 0.0355 (7) | |
O2 | 0.4356 (3) | 0.4811 (3) | 0.1272 (3) | 0.0226 (5) | |
O5 | 0.4775 (3) | 0.1175 (3) | 0.2785 (3) | 0.0239 (5) | |
O6 | 0.4167 (3) | 0.2256 (3) | −0.0225 (3) | 0.0220 (5) | |
C6 | 0.2501 (8) | 0.4105 (7) | 0.5982 (5) | 0.0520 (14) | |
H6 | 0.2378 | 0.3755 | 0.6895 | 0.062* | |
C1 | 0.4154 (5) | 0.0836 (4) | −0.0341 (3) | 0.0181 (7) | |
C3 | 0.2906 (5) | 0.5137 (5) | 0.3255 (4) | 0.0242 (8) | |
C8 | 0.2862 (5) | 0.3444 (5) | 0.3935 (4) | 0.0242 (8) | |
C2 | 0.3201 (5) | 0.5788 (5) | 0.1808 (4) | 0.0205 (7) | |
C4 | 0.2708 (7) | 0.6300 (6) | 0.3961 (4) | 0.0407 (11) | |
H4 | 0.2708 | 0.7441 | 0.3516 | 0.049* | |
C7 | 0.2674 (7) | 0.2938 (6) | 0.5296 (4) | 0.0379 (10) | |
H7 | 0.2663 | 0.1803 | 0.5751 | 0.045* | |
C5 | 0.2511 (9) | 0.5780 (7) | 0.5315 (5) | 0.0539 (14) | |
H5 | 0.2386 | 0.6568 | 0.5776 | 0.065* | |
O1W | 0.8132 (4) | 0.4267 (3) | 0.1107 (3) | 0.0323 (7) | |
H1WA | 0.924 (3) | 0.405 (6) | 0.131 (5) | 0.048* | |
H1WB | 0.763 (5) | 0.536 (3) | 0.082 (5) | 0.048* | |
O2W | 0.9997 (4) | 0.0655 (4) | 0.1193 (3) | 0.0293 (6) | |
H2WA | 1.060 (6) | −0.041 (3) | 0.124 (5) | 0.044* | |
H2WB | 1.066 (6) | 0.124 (5) | 0.080 (5) | 0.044* | |
O3W | 0.8250 (4) | 0.1000 (4) | 0.3335 (3) | 0.0341 (7) | |
H3WA | 0.941 (3) | 0.065 (7) | 0.347 (5) | 0.051* | |
H3WB | 0.789 (6) | 0.057 (7) | 0.409 (3) | 0.051* | |
O1 | 0.2318 (4) | 0.7378 (3) | 0.1138 (3) | 0.0289 (6) | |
O7 | 0.2925 (3) | 0.0631 (3) | −0.0929 (3) | 0.0234 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Gd1 | 0.01559 (10) | 0.01520 (10) | 0.02063 (11) | −0.00513 (7) | 0.00239 (7) | −0.00778 (7) |
S1 | 0.0204 (4) | 0.0256 (5) | 0.0225 (4) | −0.0113 (4) | 0.0050 (3) | −0.0081 (4) |
O3 | 0.0213 (14) | 0.0469 (17) | 0.0302 (15) | −0.0113 (13) | −0.0019 (11) | −0.0101 (13) |
O4 | 0.0445 (18) | 0.0367 (16) | 0.0357 (16) | −0.0272 (15) | 0.0173 (13) | −0.0133 (13) |
O2 | 0.0193 (13) | 0.0212 (13) | 0.0273 (13) | −0.0040 (11) | 0.0077 (10) | −0.0117 (11) |
O5 | 0.0215 (13) | 0.0213 (13) | 0.0263 (13) | −0.0066 (11) | 0.0040 (10) | −0.0053 (11) |
O6 | 0.0234 (13) | 0.0151 (12) | 0.0291 (13) | −0.0062 (10) | −0.0015 (10) | −0.0092 (10) |
C6 | 0.091 (4) | 0.043 (3) | 0.021 (2) | −0.021 (3) | 0.009 (2) | −0.011 (2) |
C1 | 0.0200 (17) | 0.0149 (16) | 0.0188 (16) | −0.0064 (15) | 0.0021 (13) | −0.0045 (13) |
C3 | 0.0254 (19) | 0.0210 (18) | 0.0225 (19) | −0.0034 (15) | 0.0049 (15) | −0.0076 (15) |
C8 | 0.0270 (19) | 0.0244 (19) | 0.0211 (18) | −0.0079 (16) | 0.0035 (14) | −0.0087 (15) |
C2 | 0.0188 (17) | 0.0199 (17) | 0.0219 (17) | −0.0054 (14) | 0.0013 (13) | −0.0068 (14) |
C4 | 0.065 (3) | 0.025 (2) | 0.032 (2) | −0.013 (2) | 0.011 (2) | −0.0107 (18) |
C7 | 0.059 (3) | 0.028 (2) | 0.025 (2) | −0.016 (2) | 0.0085 (19) | −0.0051 (17) |
C5 | 0.096 (4) | 0.038 (3) | 0.031 (3) | −0.020 (3) | 0.012 (3) | −0.020 (2) |
O1W | 0.0195 (13) | 0.0161 (13) | 0.0554 (19) | −0.0040 (11) | −0.0114 (13) | −0.0050 (13) |
O2W | 0.0211 (14) | 0.0263 (14) | 0.0389 (16) | −0.0032 (11) | 0.0050 (11) | −0.0143 (13) |
O3W | 0.0291 (15) | 0.0485 (18) | 0.0226 (14) | −0.0186 (14) | 0.0010 (11) | −0.0033 (13) |
O1 | 0.0321 (15) | 0.0197 (13) | 0.0226 (13) | 0.0008 (11) | 0.0062 (11) | −0.0018 (11) |
O7 | 0.0204 (13) | 0.0176 (12) | 0.0320 (14) | −0.0037 (10) | −0.0047 (10) | −0.0100 (11) |
Gd1—O1W | 2.368 (3) | C1—O7 | 1.248 (4) |
Gd1—O2 | 2.370 (3) | C1—C1i | 1.554 (7) |
Gd1—O5 | 2.415 (3) | C3—C4 | 1.392 (6) |
Gd1—O7i | 2.418 (2) | C3—C8 | 1.396 (5) |
Gd1—O6 | 2.429 (2) | C3—C2 | 1.495 (5) |
Gd1—O1ii | 2.433 (3) | C8—C7 | 1.388 (5) |
Gd1—O3W | 2.451 (3) | C2—O1 | 1.260 (4) |
Gd1—O2W | 2.471 (3) | C2—Gd1ii | 3.015 (4) |
Gd1—O2ii | 2.820 (3) | C4—C5 | 1.382 (6) |
Gd1—C2ii | 3.015 (4) | C4—H4 | 0.9300 |
S1—O4 | 1.454 (3) | C7—H7 | 0.9300 |
S1—O3 | 1.454 (3) | C5—H5 | 0.9300 |
S1—O5 | 1.467 (3) | O1W—H1WA | 0.840 (19) |
S1—C8 | 1.779 (4) | O1W—H1WB | 0.831 (19) |
O2—C2 | 1.260 (4) | O2W—H2WA | 0.855 (19) |
O2—Gd1ii | 2.820 (3) | O2W—H2WB | 0.842 (19) |
O6—C1 | 1.255 (4) | O3W—H3WA | 0.851 (19) |
C6—C5 | 1.371 (7) | O3W—H3WB | 0.846 (19) |
C6—C7 | 1.383 (7) | O1—Gd1ii | 2.433 (3) |
C6—H6 | 0.9300 | O7—Gd1i | 2.418 (2) |
O1W—Gd1—O2 | 72.97 (9) | O3—S1—O5 | 111.38 (16) |
O1W—Gd1—O5 | 125.62 (10) | O4—S1—C8 | 107.18 (17) |
O2—Gd1—O5 | 74.39 (9) | O3—S1—C8 | 105.74 (18) |
O1W—Gd1—O7i | 145.33 (9) | O5—S1—C8 | 107.58 (17) |
O2—Gd1—O7i | 141.66 (9) | C2—O2—Gd1 | 158.4 (2) |
O5—Gd1—O7i | 78.34 (9) | C2—O2—Gd1ii | 86.4 (2) |
O1W—Gd1—O6 | 136.48 (9) | Gd1—O2—Gd1ii | 115.17 (10) |
O2—Gd1—O6 | 81.26 (9) | S1—O5—Gd1 | 133.99 (15) |
O5—Gd1—O6 | 77.70 (9) | C1—O6—Gd1 | 120.0 (2) |
O7i—Gd1—O6 | 66.86 (9) | C5—C6—C7 | 119.9 (4) |
O1W—Gd1—O1ii | 84.13 (11) | C5—C6—H6 | 120.0 |
O2—Gd1—O1ii | 113.26 (9) | C7—C6—H6 | 120.0 |
O5—Gd1—O1ii | 149.37 (10) | O7—C1—O6 | 127.0 (3) |
O7i—Gd1—O1ii | 79.11 (9) | O7—C1—C1i | 117.2 (4) |
O6—Gd1—O1ii | 74.51 (10) | O6—C1—C1i | 115.8 (4) |
O1W—Gd1—O3W | 76.45 (10) | C4—C3—C8 | 118.8 (3) |
O2—Gd1—O3W | 100.30 (11) | C4—C3—C2 | 117.0 (3) |
O5—Gd1—O3W | 68.12 (9) | C8—C3—C2 | 124.3 (3) |
O7i—Gd1—O3W | 93.85 (10) | C7—C8—C3 | 119.8 (4) |
O6—Gd1—O3W | 143.70 (9) | C7—C8—S1 | 117.8 (3) |
O1ii—Gd1—O3W | 134.03 (10) | C3—C8—S1 | 122.3 (3) |
O1W—Gd1—O2W | 73.36 (10) | O2—C2—O1 | 120.2 (3) |
O2—Gd1—O2W | 145.70 (9) | O2—C2—C3 | 121.5 (3) |
O5—Gd1—O2W | 122.03 (10) | O1—C2—C3 | 118.2 (3) |
O7i—Gd1—O2W | 72.37 (9) | O2—C2—Gd1ii | 68.98 (19) |
O6—Gd1—O2W | 129.33 (9) | O1—C2—Gd1ii | 51.22 (18) |
O1ii—Gd1—O2W | 69.29 (10) | C3—C2—Gd1ii | 169.4 (3) |
O3W—Gd1—O2W | 65.35 (10) | C5—C4—C3 | 120.8 (4) |
O1W—Gd1—O2ii | 69.10 (9) | C5—C4—H4 | 119.6 |
O2—Gd1—O2ii | 64.83 (10) | C3—C4—H4 | 119.6 |
O5—Gd1—O2ii | 129.63 (8) | C6—C7—C8 | 120.6 (4) |
O7i—Gd1—O2ii | 117.65 (8) | C6—C7—H7 | 119.7 |
O6—Gd1—O2ii | 68.33 (8) | C8—C7—H7 | 119.7 |
O1ii—Gd1—O2ii | 48.45 (8) | C6—C5—C4 | 120.2 (4) |
O3W—Gd1—O2ii | 145.11 (9) | C6—C5—H5 | 119.9 |
O2W—Gd1—O2ii | 108.28 (9) | C4—C5—H5 | 119.9 |
O1W—Gd1—C2ii | 75.22 (11) | Gd1—O1W—H1WA | 128 (3) |
O2—Gd1—C2ii | 89.47 (10) | Gd1—O1W—H1WB | 125 (3) |
O5—Gd1—C2ii | 145.75 (9) | H1WA—O1W—H1WB | 107 (3) |
O7i—Gd1—C2ii | 98.55 (10) | Gd1—O2W—H2WA | 131 (3) |
O6—Gd1—C2ii | 70.00 (9) | Gd1—O2W—H2WB | 118 (3) |
O1ii—Gd1—C2ii | 23.81 (9) | H2WA—O2W—H2WB | 105 (3) |
O3W—Gd1—C2ii | 145.72 (9) | Gd1—O3W—H3WA | 123 (3) |
O2W—Gd1—C2ii | 88.19 (10) | Gd1—O3W—H3WB | 131 (3) |
O2ii—Gd1—C2ii | 24.64 (9) | H3WA—O3W—H3WB | 105 (3) |
O4—S1—O3 | 112.83 (18) | C2—O1—Gd1ii | 105.0 (2) |
O4—S1—O5 | 111.72 (17) | C1—O7—Gd1i | 119.9 (2) |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O3iii | 0.84 (2) | 1.82 (2) | 2.636 (4) | 165 (4) |
O1W—H1WB···O6ii | 0.83 (2) | 1.94 (2) | 2.750 (4) | 163 (4) |
O2W—H2WA···O1iv | 0.86 (2) | 1.94 (2) | 2.779 (4) | 168 (4) |
O2W—H2WB···O3iii | 0.84 (2) | 2.47 (4) | 2.983 (4) | 120 (4) |
O3W—H3WA···O4iii | 0.85 (2) | 2.27 (3) | 3.080 (4) | 160 (5) |
O3W—H3WB···O4v | 0.85 (2) | 1.96 (2) | 2.787 (4) | 164 (4) |
Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x+1, y, z; (iv) x+1, y−1, z; (v) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Gd2(C7H4O5S)2(C2O4)(H2O)6] |
Mr | 910.94 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.7597 (16), 8.4998 (17), 10.641 (2) |
α, β, γ (°) | 70.98 (3), 87.90 (3), 70.32 (3) |
V (Å3) | 622.7 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 5.54 |
Crystal size (mm) | 0.26 × 0.15 × 0.09 |
Data collection | |
Diffractometer | Rigaku Saturn 724 CCD area-detector diffractometer |
Absorption correction | Numerical (RAPID-AUTO; Rigaku, 1998) |
Tmin, Tmax | 0.20, 0.47 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4598, 2308, 2290 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.609 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.050, 1.04 |
No. of reflections | 2308 |
No. of parameters | 199 |
No. of restraints | 9 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.79, −0.85 |
Computer programs: CrystalClear (Rigaku, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2004), SHELXL (Sheldrick, 2008).
Gd1—O1W | 2.368 (3) | Gd1—O3W | 2.451 (3) |
Gd1—O2 | 2.370 (3) | Gd1—O2W | 2.471 (3) |
Gd1—O5 | 2.415 (3) | Gd1—O2ii | 2.820 (3) |
Gd1—O7i | 2.418 (2) | S1—O4 | 1.454 (3) |
Gd1—O6 | 2.429 (2) | S1—O3 | 1.454 (3) |
Gd1—O1ii | 2.433 (3) | S1—O5 | 1.467 (3) |
O1W—Gd1—O2 | 72.97 (9) | O7i—Gd1—O3W | 93.85 (10) |
O1W—Gd1—O5 | 125.62 (10) | O6—Gd1—O3W | 143.70 (9) |
O2—Gd1—O5 | 74.39 (9) | O1ii—Gd1—O3W | 134.03 (10) |
O1W—Gd1—O7i | 145.33 (9) | O1W—Gd1—O2W | 73.36 (10) |
O2—Gd1—O7i | 141.66 (9) | O2—Gd1—O2W | 145.70 (9) |
O5—Gd1—O7i | 78.34 (9) | O5—Gd1—O2W | 122.03 (10) |
O1W—Gd1—O6 | 136.48 (9) | O7i—Gd1—O2W | 72.37 (9) |
O2—Gd1—O6 | 81.26 (9) | O6—Gd1—O2W | 129.33 (9) |
O5—Gd1—O6 | 77.70 (9) | O1ii—Gd1—O2W | 69.29 (10) |
O7i—Gd1—O6 | 66.86 (9) | O3W—Gd1—O2W | 65.35 (10) |
O1W—Gd1—O1ii | 84.13 (11) | O1W—Gd1—O2ii | 69.10 (9) |
O2—Gd1—O1ii | 113.26 (9) | O2—Gd1—O2ii | 64.83 (10) |
O5—Gd1—O1ii | 149.37 (10) | O5—Gd1—O2ii | 129.63 (8) |
O7i—Gd1—O1ii | 79.11 (9) | O7i—Gd1—O2ii | 117.65 (8) |
O6—Gd1—O1ii | 74.51 (10) | O6—Gd1—O2ii | 68.33 (8) |
O1W—Gd1—O3W | 76.45 (10) | O1ii—Gd1—O2ii | 48.45 (8) |
O2—Gd1—O3W | 100.30 (11) | O3W—Gd1—O2ii | 145.11 (9) |
O5—Gd1—O3W | 68.12 (9) | O2W—Gd1—O2ii | 108.28 (9) |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O3iii | 0.840 (19) | 1.82 (2) | 2.636 (4) | 165 (4) |
O1W—H1WB···O6ii | 0.831 (19) | 1.94 (2) | 2.750 (4) | 163 (4) |
O2W—H2WA···O1iv | 0.855 (19) | 1.94 (2) | 2.779 (4) | 168 (4) |
O2W—H2WB···O3iii | 0.842 (19) | 2.47 (4) | 2.983 (4) | 120 (4) |
O3W—H3WA···O4iii | 0.851 (19) | 2.27 (3) | 3.080 (4) | 160 (5) |
O3W—H3WB···O4v | 0.846 (19) | 1.96 (2) | 2.787 (4) | 164 (4) |
Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x+1, y, z; (iv) x+1, y−1, z; (v) −x+1, −y, −z+1. |
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During the past decades, metal–organic coordination polymers (MOCPs) containing lanthanide ions have attracted considerable attention, not only for their novel topologies but also for their potential in the areas of magnetic and fluorescence applications, molecular recognition and photovoltaic conversion (Kido & Okamoto, 2002; Tsukube & Shinoda, 2002; Li et al., 2006; Manna et al., 2006; Zhao et al., 2008; Huang et al., 2009). A key strategy in the construction of MOCPs is to select suitable bi- or multidentate bridging ligands. 2-Sulfonatobenzoate (2-SB) is a prime example of such a ligand for the preparation of MOCPs: its semi-rigidity allows the ligands to accommodate the coordination geometries of different metal centres, and its many O atoms can take part in hydrogen bonds to benefit [leading to] the formation of supramolecular structures. Many transition metal coordination polymers with 2-SB have been prepared and characterized (Li & Yang, 2004; Su et al., 2005; Xiao et al., 2005; Chagas et al., 2008). However, reports of lanthanide coordination compounds with 2-SB are relatively less common: only six lanthanide 2-SB complexes were reported by Li's group, namely, {[Ln2(2-SB)3(phen)3(H2O)2]. nH2O}2 (Ln = Sm, n = 3; Ln = Eu, n = 2; Ln = Tb, n = 2; Ln = Dy, n = 2.5; Ln = Er, Y, n = 4.5) [phen = phenyl?] (Li et al., 2008; Wan et al., 2009). In these compounds, 2-SB works as a bridge and phen as a terminal, and the structures consist of isolated tetranuclear complex molecules, which further assembled into three-dimensional supramolecular architectures through hydrogen-bonding. During our research on coordination polymers containing 2-SB, the oxalate (ox) ligand was selected as a bridge to replace the terminal ligand phen, and the title one-dimensional coordination polymer, (I), was obtained under hydrothermal conditions; this is the first lanthanide metal coordination polymer with 2-SB according to the Cambridge Structural Database (CSD, Version 5.31 of August 2010; Allen, 2002).
The asymmetric unit of the title complex contains one GdIII ion, one 2-SB, three coordinated water molecules and one half of an ox ligand, located on an inversion centre. The GdIII centre is coordinated by nine oxygen atoms from two 2-SB, one ox and three coordinated water molecules with tricapped trigonal–prismatic geometry (Fig. 1). The 2-SB adopts µ2-η1: η2 and µ1-η0: η0: η1 modes to link two GdIII ions, generating a centrosymmetric binuclear [Gd2(2-SB)2(H2O)6]2- subunit. The ox forms a bis-µ1-η1: η1 chelating bridge so that the binuclear [Gd2(2-SB)2(H2O)6]2- subunits form chains parallel to the b axis (Fig. 2). In the structure of the previously reported six lanthanide 2-SB complexes (Li et al., 2008, Wan et al., 2009), the 2-SBs adopt µ2-η1: η1 and µ1-η0: η0: η1 modes or µ1-η0: η1 and µ1-η0: η0: η1 modes. In (I), atoms O2ii, O7i, O3W [symmetry codes: (i) -x + 1, -y, -z; (ii) -x + 1, -y + 1, -z] are situated on the tricapped positions of the coordination polyhedron, atoms O2, O5, O6 and O1W, O2W, O1ii are on the top and bottom of the trigonal prism, and the dihedral angle between these two trigonal prisms is 33.7 (1)°, which indicates that the local coordination geometry around the GdIII centre is seriously distorted. The Gd—O bond lengths are in the range 2.368 (3)–2.820 (3) Å, which is similar to reported values (Song et al., 2004). The S—O bond lengths vary from 1.454 (3) to 1.467 (3) Å, and all fall within the typical range of S—O bond distances in the sulfonate anion (Onoda et al., 2001). The similarity in the three S—O bond lengths indicates that the strong conjugation in the sulfonate group is predominant in the structure of the title polymer. In the chain, GdIII ions adopt a zigzag arrangement, in which the Gd···Gd···Gd angles are 104.202 (8)°. The shortest Gd···Gd distance is 4.389 (2) Å, which is shorter than in the previously reported six lanthanide 2-SB complexes (Li et al., 2008, Wan et al., 2009), namely Ln···Ln = 5.454 (3) Å. The short distance of metal centres can improve the magnetic coupling. The variance may be due to the fact that the bulky co-ligand phen has larger steric hindrance than ox in the structure of (I). The Gd···Gd distance separated by the ox ligand is 6.282 (2) Å.
The hydrogen-bonding and π–π stacking interactions play an important role in the structure of (I). The hydrogen-bond geometry is given in Table 2. Within the one-dimensional chain, a carboxylic O atom of ox, acting as hydrogen-bond acceptor, is involved in an intra-chain hydrogen bond via atom H1WB of one coordinated water molecule with graph set C(6) (Bernstein et al., 1995). The sulfonate coordinates to the GdIII ion only through one O atom, and the uncoordinated sulfonate O atoms form four types of inter-chain hydrogen bonds with coordinated water molecules (via H1WA, H2WB, H3WA and H3WB). Within these hydrogen bonds, one type (via H3WB) connects the neighbouring chains into a two-dimensional layer (Fig. 2), with ring [graph set?] R22(12). Furthermore, a carboxylic O atom of 2-SB forms one type of inter-chain hydrogen bond via atom H2WA of one coordinated water molecule with a C(6) chain; this connects the two-dimensional hydrogen-bond-supported layers into a three-dimensional supramolecular architecture (Fig. 3). In addition, three types of hydrogen bond (via H1WA, H3WA and H2WB) exist between the two-dimensional layers, forming hydrogen-bonded rings R22(8) and R12(6) to promote the stability of the structure. There also exist weak inter-chain π–π stacking interactions between the phenyl rings of 2-SBs, with a centroid–centroid separation of 3.982 (8) Å.