Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106007189/gz3002sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106007189/gz3002Isup2.hkl |
CCDC reference: 605667
InCl3·6H2O (0.38 g, 1.0 mmol) and H2pdc (0.246 g, 1.5 mmol) were dissolved in distilled water (20 ml) and the pH value was adjusted to 5.5 with dilute aqueous NaOH solution. The solution was heated in a 25 ml Teflon-lined reaction vessel at 433 K for 90 h and then cooled to room temperature over a period of 12 h. Colorless crystals of (I) were collected with a yield of 75%.
All H atoms on C atoms were positioned geometrically and refined as riding atoms with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). H atoms of water molecules were located from difference Fourier maps and refined freely.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXTL-Plus.
[In(C6H4NO2)(C7H3NO4)(H2O)2]·3H2O | Z = 2 |
Mr = 492.11 | F(000) = 492 |
Triclinic, P1 | Dx = 1.827 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0818 (16) Å | Cell parameters from 8707 reflections |
b = 11.129 (2) Å | θ = 3.1–27.5° |
c = 11.626 (2) Å | µ = 1.38 mm−1 |
α = 67.56 (3)° | T = 292 K |
β = 74.48 (3)° | Block, colorless |
γ = 69.55 (3)° | 0.39 × 0.33 × 0.28 mm |
V = 894.6 (4) Å3 |
Rigaku R-AXIS RAPID diffractometer | 4000 independent reflections |
Radiation source: rotor-target | 3457 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
Detector resolution: 10.0 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scan | h = −10→10 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −14→14 |
Tmin = 0.528, Tmax = 0.670 | l = −15→15 |
8707 measured reflections |
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.057 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0254P)2] where P = (Fo2 + 2Fc2)/3 |
4000 reflections | (Δ/σ)max = 0.001 |
280 parameters | Δρmax = 0.60 e Å−3 |
14 restraints | Δρmin = −0.44 e Å−3 |
[In(C6H4NO2)(C7H3NO4)(H2O)2]·3H2O | γ = 69.55 (3)° |
Mr = 492.11 | V = 894.6 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.0818 (16) Å | Mo Kα radiation |
b = 11.129 (2) Å | µ = 1.38 mm−1 |
c = 11.626 (2) Å | T = 292 K |
α = 67.56 (3)° | 0.39 × 0.33 × 0.28 mm |
β = 74.48 (3)° |
Rigaku R-AXIS RAPID diffractometer | 4000 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 3457 reflections with I > 2σ(I) |
Tmin = 0.528, Tmax = 0.670 | Rint = 0.035 |
8707 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 14 restraints |
wR(F2) = 0.057 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.60 e Å−3 |
4000 reflections | Δρmin = −0.44 e Å−3 |
280 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 | ||
C1 | 0.6112 (3) | 0.7708 (3) | 0.3402 (2) | 0.0287 (6) | |
C2 | 0.6446 (3) | 0.8138 (2) | 0.1983 (2) | 0.0269 (5) | |
C3 | 0.6193 (4) | 0.7425 (3) | 0.1327 (3) | 0.0399 (7) | |
H3 | 0.5766 | 0.6670 | 0.1756 | 0.048* | |
C4 | 0.6582 (4) | 0.7848 (3) | 0.0029 (3) | 0.0464 (8) | |
H4 | 0.6413 | 0.7384 | −0.0428 | 0.056* | |
C5 | 0.7223 (4) | 0.8967 (3) | −0.0582 (3) | 0.0401 (7) | |
H5 | 0.7499 | 0.9267 | −0.1456 | 0.048* | |
C6 | 0.7447 (4) | 0.9630 (3) | 0.0126 (2) | 0.0350 (6) | |
H6 | 0.7894 | 1.0378 | −0.0287 | 0.042* | |
C7 | 0.8131 (4) | 1.2836 (3) | 0.0699 (2) | 0.0317 (6) | |
C8 | 0.8440 (3) | 1.2933 (3) | 0.1880 (2) | 0.0289 (6) | |
C9 | 0.9006 (4) | 1.3944 (3) | 0.1940 (3) | 0.0406 (7) | |
H9 | 0.9259 | 1.4633 | 0.1214 | 0.049* | |
C10 | 0.9186 (4) | 1.3905 (3) | 0.3100 (3) | 0.0465 (8) | |
H10 | 0.9554 | 1.4579 | 0.3163 | 0.056* | |
C11 | 0.8817 (4) | 1.2861 (3) | 0.4179 (3) | 0.0392 (7) | |
H11 | 0.8928 | 1.2831 | 0.4966 | 0.047* | |
C12 | 0.8283 (3) | 1.1873 (2) | 0.4051 (2) | 0.0262 (5) | |
C13 | 0.7850 (3) | 1.0672 (3) | 0.5134 (2) | 0.0243 (5) | |
N1 | 0.7047 (3) | 0.9243 (2) | 0.13962 (18) | 0.0262 (5) | |
N2 | 0.8097 (3) | 1.1917 (2) | 0.29297 (18) | 0.0236 (4) | |
O1 | 0.7636 (2) | 1.18133 (18) | 0.08325 (16) | 0.0329 (4) | |
O2 | 0.8395 (3) | 1.3754 (2) | −0.03180 (17) | 0.0435 (5) | |
O3 | 0.5622 (3) | 0.66632 (19) | 0.39969 (17) | 0.0456 (5) | |
O4 | 0.6382 (2) | 0.84340 (17) | 0.39065 (15) | 0.0303 (4) | |
O5 | 0.7351 (2) | 0.98725 (16) | 0.48387 (15) | 0.0263 (4) | |
O6 | 0.8019 (2) | 1.05038 (19) | 0.62137 (16) | 0.0342 (4) | |
O1W | 1.0025 (2) | 0.91200 (19) | 0.25742 (18) | 0.0299 (4) | |
O2W | 0.4499 (2) | 1.13989 (19) | 0.29456 (18) | 0.0322 (4) | |
O3W | 0.0761 (3) | 0.6636 (2) | 0.2627 (2) | 0.0510 (6) | |
O5W | 0.4143 (4) | 0.4041 (2) | 0.1825 (2) | 0.0605 (6) | |
In1 | 0.72576 (2) | 1.024842 (16) | 0.275845 (15) | 0.02134 (6) | |
O4W | 0.3866 (4) | 0.5110 (2) | 0.3684 (2) | 0.0561 (6) | |
HW11 | 1.034 (4) | 0.828 (2) | 0.265 (3) | 0.063 (11)* | |
HW12 | 1.069 (4) | 0.911 (3) | 0.305 (2) | 0.048 (9)* | |
HW21 | 0.418 (4) | 1.2262 (18) | 0.275 (3) | 0.054 (10)* | |
HW22 | 0.393 (5) | 1.105 (3) | 0.367 (2) | 0.098 (15)* | |
HW31 | 0.170 (4) | 0.614 (4) | 0.302 (5) | 0.147* | |
HW32 | 0.114 (6) | 0.667 (5) | 0.181 (2) | 0.100 (16)* | |
HW51 | 0.402 (7) | 0.438 (5) | 0.243 (3) | 0.150* | |
HW52 | 0.355 (7) | 0.472 (4) | 0.122 (3) | 0.150* | |
HW41 | 0.385 (7) | 0.448 (4) | 0.443 (3) | 0.150* | |
HW42 | 0.443 (5) | 0.565 (3) | 0.377 (3) | 0.078 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0390 (14) | 0.0255 (13) | 0.0249 (13) | −0.0132 (12) | −0.0075 (11) | −0.0061 (11) |
C2 | 0.0356 (13) | 0.0233 (13) | 0.0242 (13) | −0.0111 (11) | −0.0088 (10) | −0.0046 (10) |
C3 | 0.0622 (19) | 0.0364 (16) | 0.0285 (14) | −0.0246 (15) | −0.0082 (13) | −0.0076 (12) |
C4 | 0.067 (2) | 0.0523 (19) | 0.0356 (16) | −0.0266 (17) | −0.0095 (15) | −0.0201 (14) |
C5 | 0.0486 (16) | 0.0503 (18) | 0.0248 (14) | −0.0187 (15) | −0.0036 (12) | −0.0125 (13) |
C6 | 0.0414 (15) | 0.0365 (15) | 0.0267 (14) | −0.0199 (13) | 0.0002 (11) | −0.0052 (12) |
C7 | 0.0376 (14) | 0.0291 (14) | 0.0265 (14) | −0.0123 (12) | −0.0035 (11) | −0.0053 (11) |
C8 | 0.0356 (13) | 0.0246 (13) | 0.0246 (13) | −0.0121 (12) | −0.0019 (11) | −0.0043 (10) |
C9 | 0.0593 (18) | 0.0327 (15) | 0.0339 (15) | −0.0259 (15) | −0.0026 (13) | −0.0064 (12) |
C10 | 0.069 (2) | 0.0397 (17) | 0.0457 (18) | −0.0350 (17) | −0.0081 (15) | −0.0121 (14) |
C11 | 0.0560 (17) | 0.0378 (16) | 0.0363 (16) | −0.0251 (15) | −0.0075 (13) | −0.0140 (13) |
C12 | 0.0306 (12) | 0.0257 (13) | 0.0248 (13) | −0.0113 (11) | −0.0050 (10) | −0.0073 (10) |
C13 | 0.0215 (11) | 0.0313 (14) | 0.0215 (12) | −0.0102 (11) | −0.0011 (9) | −0.0086 (10) |
N1 | 0.0321 (11) | 0.0257 (11) | 0.0236 (11) | −0.0124 (10) | −0.0049 (9) | −0.0064 (9) |
N2 | 0.0277 (10) | 0.0237 (11) | 0.0210 (10) | −0.0103 (9) | −0.0031 (8) | −0.0064 (8) |
O1 | 0.0493 (11) | 0.0308 (10) | 0.0239 (9) | −0.0201 (9) | −0.0060 (8) | −0.0062 (8) |
O2 | 0.0696 (13) | 0.0351 (11) | 0.0244 (10) | −0.0259 (11) | −0.0093 (9) | 0.0036 (8) |
O3 | 0.0849 (15) | 0.0373 (11) | 0.0265 (10) | −0.0420 (12) | −0.0117 (10) | 0.0016 (8) |
O4 | 0.0452 (10) | 0.0317 (10) | 0.0211 (9) | −0.0220 (9) | −0.0039 (8) | −0.0065 (7) |
O5 | 0.0354 (9) | 0.0281 (9) | 0.0205 (8) | −0.0177 (8) | −0.0036 (7) | −0.0055 (7) |
O6 | 0.0444 (11) | 0.0465 (12) | 0.0223 (9) | −0.0251 (10) | −0.0079 (8) | −0.0091 (8) |
O1W | 0.0302 (9) | 0.0310 (11) | 0.0349 (11) | −0.0073 (9) | −0.0099 (8) | −0.0152 (9) |
O2W | 0.0306 (9) | 0.0277 (10) | 0.0328 (11) | −0.0091 (9) | −0.0020 (8) | −0.0047 (8) |
O3W | 0.0631 (14) | 0.0438 (13) | 0.0521 (15) | −0.0093 (11) | −0.0131 (12) | −0.0238 (11) |
O5W | 0.0793 (17) | 0.0348 (13) | 0.0609 (16) | −0.0026 (12) | −0.0187 (14) | −0.0149 (11) |
In1 | 0.02779 (10) | 0.02061 (10) | 0.01840 (9) | −0.01152 (7) | −0.00376 (6) | −0.00473 (6) |
O4W | 0.0901 (17) | 0.0515 (14) | 0.0413 (13) | −0.0393 (14) | −0.0316 (12) | 0.0019 (10) |
C1—O3 | 1.245 (3) | C11—H11 | 0.9300 |
C1—O4 | 1.264 (3) | C12—N2 | 1.333 (3) |
C1—C2 | 1.507 (3) | C12—C13 | 1.516 (3) |
C2—N1 | 1.346 (3) | C13—O6 | 1.235 (3) |
C2—C3 | 1.382 (4) | C13—O5 | 1.276 (3) |
C3—C4 | 1.381 (4) | N1—In1 | 2.328 (2) |
C3—H3 | 0.9300 | N2—In1 | 2.277 (2) |
C4—C5 | 1.379 (4) | O1—In1 | 2.2734 (19) |
C4—H4 | 0.9300 | O4—In1 | 2.1897 (17) |
C5—C6 | 1.376 (4) | O5—In1 | 2.3093 (17) |
C5—H5 | 0.9300 | O1W—In1 | 2.147 (2) |
C6—N1 | 1.351 (3) | O1W—HW11 | 0.855 (18) |
C6—H6 | 0.9300 | O1W—HW12 | 0.863 (18) |
C7—O2 | 1.258 (3) | O2W—In1 | 2.1484 (19) |
C7—O1 | 1.277 (3) | O2W—HW21 | 0.855 (17) |
C7—C8 | 1.508 (4) | O2W—HW22 | 0.858 (18) |
C8—N2 | 1.352 (3) | O3W—HW31 | 0.89 (4) |
C8—C9 | 1.384 (4) | O3W—HW32 | 0.903 (19) |
C9—C10 | 1.378 (4) | O5W—HW51 | 0.89 (5) |
C9—H9 | 0.9300 | O5W—HW52 | 0.90 (4) |
C10—C11 | 1.393 (4) | O4W—HW41 | 0.882 (19) |
C10—H10 | 0.9300 | O4W—HW42 | 0.92 (4) |
C11—C12 | 1.382 (3) | ||
O3—C1—O4 | 124.4 (2) | C2—N1—C6 | 117.9 (2) |
O3—C1—C2 | 118.6 (2) | C2—N1—In1 | 113.87 (15) |
O4—C1—C2 | 117.0 (2) | C6—N1—In1 | 128.28 (16) |
N1—C2—C3 | 122.2 (2) | C12—N2—C8 | 120.6 (2) |
N1—C2—C1 | 115.7 (2) | C12—N2—In1 | 120.08 (15) |
C3—C2—C1 | 122.2 (2) | C8—N2—In1 | 119.28 (16) |
C4—C3—C2 | 119.2 (2) | C7—O1—In1 | 120.85 (16) |
C4—C3—H3 | 120.4 | C1—O4—In1 | 121.10 (15) |
C2—C3—H3 | 120.4 | C13—O5—In1 | 120.29 (14) |
C5—C4—C3 | 119.2 (3) | In1—O1W—HW11 | 121.2 (19) |
C5—C4—H4 | 120.4 | In1—O1W—HW12 | 119 (2) |
C3—C4—H4 | 120.4 | HW11—O1W—HW12 | 100 (3) |
C6—C5—C4 | 118.7 (3) | In1—O2W—HW21 | 122 (2) |
C6—C5—H5 | 120.6 | In1—O2W—HW22 | 111 (3) |
C4—C5—H5 | 120.6 | HW21—O2W—HW22 | 110 (3) |
N1—C6—C5 | 122.9 (2) | HW31—O3W—HW32 | 106 (5) |
N1—C6—H6 | 118.6 | HW51—O5W—HW52 | 106 (3) |
C5—C6—H6 | 118.6 | O1W—In1—O2W | 179.22 (7) |
O2—C7—O1 | 126.2 (3) | O1W—In1—O4 | 92.87 (8) |
O2—C7—C8 | 117.6 (2) | O2W—In1—O4 | 87.73 (8) |
O1—C7—C8 | 116.2 (2) | O1W—In1—O1 | 92.62 (8) |
N2—C8—C9 | 121.0 (2) | O2W—In1—O1 | 87.13 (8) |
N2—C8—C7 | 113.5 (2) | O4—In1—O1 | 147.99 (7) |
C9—C8—C7 | 125.5 (2) | O1W—In1—N2 | 88.48 (7) |
C10—C9—C8 | 118.4 (2) | O2W—In1—N2 | 90.74 (8) |
C10—C9—H9 | 120.8 | O4—In1—N2 | 141.55 (7) |
C8—C9—H9 | 120.8 | O1—In1—N2 | 70.10 (7) |
C9—C10—C11 | 120.2 (2) | O1W—In1—O5 | 88.45 (8) |
C9—C10—H10 | 119.9 | O2W—In1—O5 | 91.26 (8) |
C11—C10—H10 | 119.9 | O4—In1—O5 | 72.02 (6) |
C12—C11—C10 | 118.4 (3) | O1—In1—O5 | 139.66 (6) |
C12—C11—H11 | 120.8 | N2—In1—O5 | 69.61 (7) |
C10—C11—H11 | 120.8 | O1W—In1—N1 | 84.52 (7) |
N2—C12—C11 | 121.3 (2) | O2W—In1—N1 | 96.14 (8) |
N2—C12—C13 | 114.2 (2) | O4—In1—N1 | 72.27 (7) |
C11—C12—C13 | 124.5 (2) | O1—In1—N1 | 76.91 (7) |
O6—C13—O5 | 124.2 (2) | N2—In1—N1 | 145.90 (7) |
O6—C13—C12 | 120.1 (2) | O5—In1—N1 | 143.15 (6) |
O5—C13—C12 | 115.7 (2) | HW41—O4W—HW42 | 103 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—HW12···O6i | 0.86 (2) | 1.76 (2) | 2.601 (2) | 166 (3) |
O1W—HW11···O3Wii | 0.86 (2) | 1.75 (2) | 2.596 (3) | 171 (3) |
O2W—HW22···O5iii | 0.86 (2) | 1.89 (2) | 2.740 (3) | 173 (4) |
O2W—HW21···O5Wiv | 0.86 (2) | 1.85 (2) | 2.667 (3) | 159 (3) |
O3W—HW32···O2v | 0.90 (2) | 1.88 (2) | 2.750 (3) | 160 (4) |
O3W—HW31···O4W | 0.89 (4) | 1.90 (2) | 2.788 (4) | 174 (5) |
O4W—HW42···O3 | 0.92 (4) | 1.84 (4) | 2.758 (3) | 177 (3) |
O4W—HW41···O3vi | 0.88 (2) | 1.85 (3) | 2.701 (3) | 162 (4) |
O5W—HW52···O2v | 0.90 (4) | 2.03 (3) | 2.902 (3) | 162 (5) |
O5W—HW51···O4W | 0.89 (5) | 1.88 (4) | 2.766 (4) | 177 (5) |
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) x+1, y, z; (iii) −x+1, −y+2, −z+1; (iv) x, y+1, z; (v) −x+1, −y+2, −z; (vi) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [In(C6H4NO2)(C7H3NO4)(H2O)2]·3H2O |
Mr | 492.11 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 292 |
a, b, c (Å) | 8.0818 (16), 11.129 (2), 11.626 (2) |
α, β, γ (°) | 67.56 (3), 74.48 (3), 69.55 (3) |
V (Å3) | 894.6 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.38 |
Crystal size (mm) | 0.39 × 0.33 × 0.28 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.528, 0.670 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8707, 4000, 3457 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.057, 1.01 |
No. of reflections | 4000 |
No. of parameters | 280 |
No. of restraints | 14 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.60, −0.44 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990), SHELXTL-Plus.
N1—In1 | 2.328 (2) | O5—In1 | 2.3093 (17) |
N2—In1 | 2.277 (2) | O1W—In1 | 2.147 (2) |
O1—In1 | 2.2734 (19) | O2W—In1 | 2.1484 (19) |
O4—In1 | 2.1897 (17) | ||
O1W—In1—O2W | 179.22 (7) | O2W—In1—O5 | 91.26 (8) |
O1W—In1—O4 | 92.87 (8) | O4—In1—O5 | 72.02 (6) |
O2W—In1—O4 | 87.73 (8) | O1—In1—O5 | 139.66 (6) |
O1W—In1—O1 | 92.62 (8) | N2—In1—O5 | 69.61 (7) |
O2W—In1—O1 | 87.13 (8) | O1W—In1—N1 | 84.52 (7) |
O4—In1—O1 | 147.99 (7) | O2W—In1—N1 | 96.14 (8) |
O1W—In1—N2 | 88.48 (7) | O4—In1—N1 | 72.27 (7) |
O2W—In1—N2 | 90.74 (8) | O1—In1—N1 | 76.91 (7) |
O4—In1—N2 | 141.55 (7) | N2—In1—N1 | 145.90 (7) |
O1—In1—N2 | 70.10 (7) | O5—In1—N1 | 143.15 (6) |
O1W—In1—O5 | 88.45 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—HW12···O6i | 0.863 (18) | 1.755 (19) | 2.601 (2) | 166 (3) |
O1W—HW11···O3Wii | 0.855 (18) | 1.748 (19) | 2.596 (3) | 171 (3) |
O2W—HW22···O5iii | 0.858 (18) | 1.887 (18) | 2.740 (3) | 173 (4) |
O2W—HW21···O5Wiv | 0.855 (17) | 1.852 (18) | 2.667 (3) | 159 (3) |
O3W—HW32···O2v | 0.903 (19) | 1.88 (2) | 2.750 (3) | 160 (4) |
O3W—HW31···O4W | 0.89 (4) | 1.90 (2) | 2.788 (4) | 174 (5) |
O4W—HW42···O3 | 0.92 (4) | 1.84 (4) | 2.758 (3) | 177 (3) |
O4W—HW41···O3vi | 0.882 (19) | 1.85 (3) | 2.701 (3) | 162 (4) |
O5W—HW52···O2v | 0.90 (4) | 2.03 (3) | 2.902 (3) | 162 (5) |
O5W—HW51···O4W | 0.89 (5) | 1.88 (4) | 2.766 (4) | 177 (5) |
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) x+1, y, z; (iii) −x+1, −y+2, −z+1; (iv) x, y+1, z; (v) −x+1, −y+2, −z; (vi) −x+1, −y+1, −z+1. |
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The study of water clusters is important to an understanding of the structures and characteristics of liquid water and ice (Ludwig, 2001). Thus, the search for the experimental models of small water clusters is very important to improve our studies of liquid water and ice (Ye et al., 2004). So far, a variety of water clusters, including tetramers, hexamers, octamers and decamers, found in a number of crystalline hosts have been structurally characterized and display different configurations (Ghosh & Bharadwaj, 2004). Curiously, odd-membered water clusters are known to occur very rarely (Infantes & Motherwell, 2002). Few reports of structural characterization of the cyclic water pentamer are relatively recent (Naskar et al., 2005). Theoretically, the cyclic water pentamer is much more stable than the acyclic version because of cooperative hydrogen bonding in the cyclic moiety (Cruzan et al., 1996). To the best of our knowledge, no organic or metallo-organic compound is known in which an isolated acyclic water pentamer has been detected (Infantes & Motherwell, 2002). We report here for the first time the formation and structure of an acyclic water pentamer in the title compound, [In(pdc)(pc)(H2O)2]·3H2O, (I), where pdc is pyridine-2,6-dicarboxylate and pc is pyridine-2-carboxylate.
Selected bond lengths and angles for (I) are given in Table 1. Compound (I) was obtained under hydrothermal conditions at 433 K. The compound once formed is insoluble in most solvents, including water. The structure of (I) can be described as a three-dimensional hydrogen-bonding superamolecular structure. The asymmetric unit for (I) is shown in Fig. 1. The central InIII atom is seven-coordinated by one pdc ligand, one pc ligand and two water molecules in a pentagonal bipyramidal coordination environment, in which the three carboxylate O atoms (O1, O4 and O5) and two N atoms (N1 and N2) from the pdc and pc anions make up the basal plane, while the axial positions are occupied by two water molecules (O1W and O2W). The In—O (carboxylate) bond lengths range from 2.1897 (17) to 2.3093 (17) Å, and the In—O1W and In—O2W distances are 2.147 (2) and 2.1484 (19) Å, respectively.
A new in situ reaction occurs in the InCl3·6H2O/H2pdc system under hydrothermal conditions. In the reaction process, some of the pdc is transformed into pc via decarboxylation. A similar reaction process, in which quinolinic acid is transformed into pc via decarboxylation, has been observed recently (Yu et al., 2003). So far, a few novel in situ reactions, such as ligand oxidative coupling, hydrolysis and substitution, have been uncovered during the hydrothermal process (Zheng et al., 2004), in which many factors, including the nature of the metal ion and the temperature, pressure and pH, have been found to influence significantly the reaction outcome. As far as our system is concerned, the pH value may play a key role in the decarboxylation of pdc. When the pH value was adjusted to higher or lower than 5.5, no crystals of (I) were obtained under hydrothermal conditions at 433 K. To the best of our knowledge, the in situ transformation from pdc to pc has not been observed before.
An interesting feature of (I) is the presence of an InIII—water chain based on an unusual acyclic water pentamer (Figs. 2 and 3; Li et al., 2005). Within the water pentamer, three water molecules (O3W, O4W and O5W) act as both hydrogen-bond donors and acceptors, while another two water molecules (O1W and O2W) act only as hydrogen-bond acceptors. The hydrogen-bond parameters are given in Table 2. The average hydrogen-bond distance is 2.73 (5) Å, which is slightly shorter than the average hydrogen-bond distance of the liquid water pentamer (2.78 Å; Naskar et al., 2005). Interestingly, the water molecules of the pentamer are hydrogen bonded to the carboxylate O atoms (O2v, O3, O3vi, O5vi and O6i) from the pdc and pc ligands. Meanwhile, two water molecules (O1Wvii and O2Wviii; symmetry codes as in Fig. 2) bind to the InIII atoms in the water pentamer, resulting in three-dimensional supramolecular structure. This observation indicates that the water pentamer is stabilized not only by hydrogen bonds but also by coordination interactions. The water molecule, the pdc and pc ligands, and the InIII atom play a crucial role in the formation of the water clusters.
In summary, a new InIII compound with three-dimensional supramolecular structure was synthesized through the hydrothermal method at 4333 K. In this compound, an InIII–water chain based on an unusual acyclic water pentamer was observed. In addition, a new in situ reaction under hydrothermal conditions leads to the formation of (I).