Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110009984/bm3089sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110009984/bm3089Isup2.hkl |
CCDC reference: 774886
A mixture of Cd(OAc)2.2H2O (0.026 g, 0.1 mmol), TCMB (0.030 g, 0.1 mmol), bpe (0.018 g, 0.1 mmol), ethanol (5 ml) and H2O (5 ml) was placed in a Teflon reactor and heated at 353 K for 50 h. After cooling to room temperature, colourless crystals of (I) were obtained (yield 42%, based on TCMB). Elemental analysis for C24H26N2O12Cd (Mr = 646.87): C 44.56, H 4.05, N 4.33%; found: 44.20, H 4.63, N 4.05%. FT–IR (KBr pellet, ν, cm-1): 3422 (s, br), 2928 (w), 1605 (s), 1426 (m), 1337 (w), 1165 (m), 1083 (w), 843 (w).
##AUTHOR: Please check and approve the following revised text.
The H atom on O9 was located from a circular difference Fourier synthesis and thereafter refined as part of a rigid rotating group, with O—H 0.82 Å and Uiso(H) = 1.5Ueq(O). All other H atoms were placed geometrically and treated as riding on their parent atoms, with C—H = 0.93 (aromatic) or 0.97 (methylene) Å, and with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Cd2(C12H10O9)2(C12H10N2)(H2O)4]·C12H10N2·2H2O | Z = 1 |
Mr = 1293.74 | F(000) = 656 |
Triclinic, P1 | Dx = 1.731 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.8627 (9) Å | Cell parameters from 3568 reflections |
b = 11.1883 (9) Å | θ = 2.6–28.0° |
c = 11.3773 (11) Å | µ = 0.95 mm−1 |
α = 69.362 (1)° | T = 298 K |
β = 79.777 (2)° | Block, colourless |
γ = 74.451 (1)° | 0.32 × 0.28 × 0.26 mm |
V = 1241.35 (19) Å3 |
Bruker SMART APEX CCD area-detector diffractometer | 4315 independent reflections |
Radiation source: sealed tube | 3814 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.744, Tmax = 0.785 | k = −13→13 |
6314 measured reflections | l = −10→13 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.034P)2] where P = (Fo2 + 2Fc2)/3 |
4315 reflections | (Δ/σ)max < 0.001 |
353 parameters | Δρmax = 0.59 e Å−3 |
2 restraints | Δρmin = −0.60 e Å−3 |
[Cd2(C12H10O9)2(C12H10N2)(H2O)4]·C12H10N2·2H2O | γ = 74.451 (1)° |
Mr = 1293.74 | V = 1241.35 (19) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.8627 (9) Å | Mo Kα radiation |
b = 11.1883 (9) Å | µ = 0.95 mm−1 |
c = 11.3773 (11) Å | T = 298 K |
α = 69.362 (1)° | 0.32 × 0.28 × 0.26 mm |
β = 79.777 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 4315 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3814 reflections with I > 2σ(I) |
Tmin = 0.744, Tmax = 0.785 | Rint = 0.057 |
6314 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 2 restraints |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.59 e Å−3 |
4315 reflections | Δρmin = −0.60 e Å−3 |
353 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.54365 (2) | 0.41358 (2) | 0.28196 (2) | 0.02636 (9) | |
O1 | 0.3542 (2) | 0.8866 (2) | 0.10268 (19) | 0.0323 (5) | |
O2 | 0.3214 (2) | 1.2522 (2) | −0.28718 (19) | 0.0328 (5) | |
O3 | 0.1420 (2) | 1.3233 (2) | 0.0916 (2) | 0.0390 (6) | |
O4 | 0.4432 (2) | 0.6332 (2) | 0.2357 (2) | 0.0391 (6) | |
O5 | 0.5437 (2) | 0.5865 (2) | 0.0661 (2) | 0.0364 (6) | |
O6 | 0.5431 (3) | 0.2039 (2) | 0.4563 (2) | 0.0458 (7) | |
O7 | 0.4067 (2) | 0.3816 (2) | 0.4773 (2) | 0.0393 (6) | |
O8 | −0.0535 (2) | 1.4391 (3) | 0.3059 (3) | 0.0513 (7) | |
O9 | 0.1493 (2) | 1.4535 (2) | 0.2573 (2) | 0.0432 (6) | |
H9 | 0.1277 | 1.5055 | 0.2969 | 0.065* | |
C1 | 0.3153 (3) | 1.0160 (3) | 0.0337 (3) | 0.0258 (7) | |
C2 | 0.3429 (3) | 1.0643 (3) | −0.0970 (3) | 0.0275 (7) | |
H2 | 0.3902 | 1.0092 | −0.1420 | 0.033* | |
C3 | 0.2977 (3) | 1.1969 (3) | −0.1577 (3) | 0.0262 (7) | |
C4 | 0.2276 (3) | 1.2805 (3) | −0.0947 (3) | 0.0260 (7) | |
H4 | 0.1962 | 1.3685 | −0.1379 | 0.031* | |
C5 | 0.2041 (3) | 1.2307 (3) | 0.0360 (3) | 0.0269 (7) | |
C6 | 0.2464 (3) | 1.0985 (3) | 0.1016 (3) | 0.0286 (7) | |
H6 | 0.2291 | 1.0661 | 0.1886 | 0.034* | |
C7 | 0.4302 (3) | 0.8030 (3) | 0.0343 (3) | 0.0269 (7) | |
H7A | 0.5045 | 0.8377 | −0.0099 | 0.032* | |
H7B | 0.3804 | 0.8023 | −0.0281 | 0.032* | |
C8 | 0.4747 (3) | 0.6645 (3) | 0.1192 (3) | 0.0269 (7) | |
C9 | 0.4244 (3) | 1.1799 (3) | −0.3480 (3) | 0.0339 (8) | |
H9A | 0.4002 | 1.1035 | −0.3505 | 0.041* | |
H9B | 0.4988 | 1.1499 | −0.3004 | 0.041* | |
C10 | 0.4583 (3) | 1.2636 (3) | −0.4811 (3) | 0.0320 (8) | |
C11 | 0.0923 (3) | 1.2835 (3) | 0.2194 (3) | 0.0344 (8) | |
H11A | 0.1563 | 1.2157 | 0.2700 | 0.041* | |
H11B | 0.0174 | 1.2485 | 0.2278 | 0.041* | |
C12 | 0.0562 (3) | 1.4019 (3) | 0.2637 (3) | 0.0310 (8) | |
C13 | 0.7531 (3) | 0.1663 (3) | 0.2358 (3) | 0.0310 (7) | |
H13 | 0.7154 | 0.1270 | 0.3153 | 0.037* | |
C14 | 0.8412 (3) | 0.0875 (3) | 0.1767 (3) | 0.0306 (7) | |
H14 | 0.8612 | −0.0027 | 0.2162 | 0.037* | |
C15 | 0.9007 (3) | 0.1419 (3) | 0.0581 (3) | 0.0254 (7) | |
C16 | 0.8686 (3) | 0.2783 (3) | 0.0088 (3) | 0.0325 (8) | |
H16 | 0.9087 | 0.3208 | −0.0681 | 0.039* | |
C17 | 0.7779 (3) | 0.3505 (3) | 0.0735 (3) | 0.0329 (8) | |
H17 | 0.7573 | 0.4412 | 0.0374 | 0.039* | |
C18 | 0.9902 (3) | 0.0636 (3) | −0.0129 (3) | 0.0283 (7) | |
H18 | 1.0380 | 0.1080 | −0.0830 | 0.034* | |
C19 | 1.0424 (4) | 0.3157 (4) | 0.6064 (3) | 0.0418 (9) | |
H19 | 1.1035 | 0.3583 | 0.6104 | 0.050* | |
C20 | 1.0797 (4) | 0.2125 (3) | 0.5602 (3) | 0.0398 (9) | |
H20 | 1.1652 | 0.1865 | 0.5318 | 0.048* | |
C21 | 0.9897 (4) | 0.1470 (3) | 0.5557 (3) | 0.0376 (8) | |
C22 | 0.8639 (4) | 0.1909 (4) | 0.5974 (4) | 0.0487 (10) | |
H22 | 0.8009 | 0.1496 | 0.5952 | 0.058* | |
C23 | 0.8316 (4) | 0.2955 (4) | 0.6420 (4) | 0.0480 (10) | |
H23 | 0.7468 | 0.3247 | 0.6701 | 0.058* | |
C24 | 1.0359 (4) | 0.0346 (3) | 0.5054 (3) | 0.0443 (9) | |
H24 | 1.1230 | 0.0132 | 0.4800 | 0.053* | |
N1 | 0.7183 (2) | 0.2966 (2) | 0.1854 (2) | 0.0280 (6) | |
N2 | 0.9216 (3) | 0.3558 (3) | 0.6454 (3) | 0.0395 (7) | |
O1W | 0.4035 (2) | 0.3480 (2) | 0.1975 (2) | 0.0419 (6) | |
H1WB | 0.3277 | 0.3919 | 0.2079 | 0.050* | |
H1WC | 0.4254 | 0.3618 | 0.1192 | 0.050* | |
O2W | 0.6901 (2) | 0.4441 (2) | 0.3850 (2) | 0.0430 (6) | |
H2WB | 0.7506 | 0.4707 | 0.3319 | 0.052* | |
H2WC | 0.6534 | 0.5012 | 0.4209 | 0.052* | |
O3W | 0.6588 (3) | 0.9373 (3) | 0.5855 (3) | 0.0756 (10) | |
H3WC | 0.6291 | 1.0182 | 0.5488 | 0.091* | |
H3WD | 0.6087 | 0.8942 | 0.5778 | 0.091* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.02936 (15) | 0.02077 (14) | 0.02383 (14) | −0.00054 (10) | 0.00347 (9) | −0.00757 (10) |
O1 | 0.0427 (14) | 0.0183 (11) | 0.0250 (12) | 0.0015 (10) | 0.0052 (10) | −0.0039 (9) |
O2 | 0.0398 (14) | 0.0282 (12) | 0.0212 (11) | −0.0008 (10) | 0.0043 (9) | −0.0052 (10) |
O3 | 0.0583 (17) | 0.0246 (12) | 0.0283 (13) | −0.0023 (11) | 0.0072 (11) | −0.0119 (10) |
O4 | 0.0456 (15) | 0.0294 (13) | 0.0301 (13) | −0.0015 (11) | 0.0029 (10) | −0.0028 (10) |
O5 | 0.0473 (15) | 0.0214 (11) | 0.0325 (10) | 0.0027 (11) | −0.0007 (10) | −0.0083 (8) |
O6 | 0.0618 (17) | 0.0353 (12) | 0.0273 (12) | −0.0078 (13) | 0.0181 (11) | −0.0074 (8) |
O7 | 0.0526 (16) | 0.0342 (14) | 0.0241 (12) | −0.0072 (12) | 0.0049 (10) | −0.0068 (11) |
O8 | 0.0351 (15) | 0.0548 (17) | 0.0634 (18) | −0.0015 (13) | 0.0105 (13) | −0.0319 (15) |
O9 | 0.0427 (15) | 0.0425 (15) | 0.0563 (17) | −0.0114 (12) | 0.0081 (12) | −0.0349 (13) |
C1 | 0.0298 (18) | 0.0207 (16) | 0.0259 (17) | −0.0055 (13) | −0.0001 (13) | −0.0074 (13) |
C2 | 0.0319 (18) | 0.0273 (17) | 0.0245 (17) | −0.0057 (14) | 0.0021 (13) | −0.0126 (14) |
C3 | 0.0299 (18) | 0.0272 (17) | 0.0198 (16) | −0.0085 (14) | 0.0010 (13) | −0.0054 (13) |
C4 | 0.0310 (18) | 0.0191 (15) | 0.0246 (16) | −0.0043 (13) | 0.0016 (13) | −0.0061 (13) |
C5 | 0.0280 (17) | 0.0242 (16) | 0.0299 (17) | −0.0033 (13) | 0.0011 (13) | −0.0141 (14) |
C6 | 0.0361 (19) | 0.0285 (17) | 0.0198 (16) | −0.0084 (15) | 0.0036 (13) | −0.0081 (14) |
C7 | 0.0297 (18) | 0.0231 (16) | 0.0275 (17) | −0.0036 (14) | 0.0008 (13) | −0.0111 (14) |
C8 | 0.0237 (17) | 0.0221 (16) | 0.0336 (19) | −0.0022 (13) | −0.0039 (13) | −0.0088 (14) |
C9 | 0.040 (2) | 0.0331 (18) | 0.0231 (17) | −0.0047 (15) | 0.0099 (14) | −0.0105 (15) |
C10 | 0.039 (2) | 0.0345 (19) | 0.0262 (18) | −0.0157 (16) | 0.0054 (15) | −0.0124 (15) |
C11 | 0.044 (2) | 0.0317 (18) | 0.0284 (18) | −0.0121 (16) | 0.0076 (15) | −0.0138 (15) |
C12 | 0.037 (2) | 0.0318 (18) | 0.0224 (17) | −0.0039 (16) | 0.0008 (14) | −0.0110 (14) |
C13 | 0.0347 (19) | 0.0287 (17) | 0.0228 (17) | 0.0006 (15) | 0.0024 (13) | −0.0083 (14) |
C14 | 0.0361 (19) | 0.0218 (16) | 0.0279 (18) | 0.0011 (14) | 0.0016 (14) | −0.0084 (14) |
C15 | 0.0224 (16) | 0.0264 (16) | 0.0274 (17) | −0.0002 (13) | −0.0005 (12) | −0.0134 (14) |
C16 | 0.036 (2) | 0.0286 (17) | 0.0300 (18) | −0.0060 (15) | 0.0083 (14) | −0.0126 (15) |
C17 | 0.036 (2) | 0.0230 (17) | 0.0345 (19) | −0.0013 (14) | 0.0043 (15) | −0.0106 (15) |
C18 | 0.0270 (17) | 0.0279 (16) | 0.0280 (17) | −0.0043 (14) | 0.0063 (13) | −0.0123 (14) |
C19 | 0.048 (2) | 0.038 (2) | 0.043 (2) | −0.0090 (18) | −0.0090 (17) | −0.0144 (17) |
C20 | 0.038 (2) | 0.037 (2) | 0.041 (2) | 0.0012 (17) | −0.0021 (16) | −0.0160 (17) |
C21 | 0.053 (2) | 0.0287 (18) | 0.0280 (18) | 0.0001 (17) | −0.0029 (16) | −0.0127 (15) |
C22 | 0.055 (3) | 0.046 (2) | 0.055 (2) | −0.022 (2) | −0.0010 (19) | −0.022 (2) |
C23 | 0.041 (2) | 0.051 (2) | 0.050 (2) | −0.0038 (19) | 0.0084 (17) | −0.026 (2) |
C24 | 0.053 (3) | 0.038 (2) | 0.040 (2) | −0.0088 (17) | −0.0037 (17) | −0.0122 (18) |
N1 | 0.0285 (15) | 0.0280 (14) | 0.0265 (14) | −0.0006 (12) | 0.0014 (11) | −0.0139 (12) |
N2 | 0.051 (2) | 0.0309 (16) | 0.0365 (17) | −0.0029 (14) | 0.0021 (14) | −0.0178 (14) |
O1W | 0.0356 (14) | 0.0540 (16) | 0.0403 (14) | −0.0094 (12) | 0.0012 (11) | −0.0228 (12) |
O2W | 0.0390 (15) | 0.0447 (15) | 0.0503 (15) | −0.0039 (12) | −0.0006 (11) | −0.0271 (13) |
O3W | 0.0492 (19) | 0.067 (2) | 0.116 (3) | −0.0041 (16) | −0.0064 (17) | −0.042 (2) |
Cd1—N1 | 2.338 (2) | C10—O6ii | 1.256 (4) |
Cd1—O4 | 2.315 (2) | C11—C12 | 1.511 (4) |
Cd1—O5 | 2.535 (2) | C11—H11A | 0.9700 |
Cd1—O6 | 2.482 (2) | C11—H11B | 0.9700 |
Cd1—O7 | 2.415 (2) | C13—N1 | 1.337 (4) |
Cd1—O1W | 2.322 (2) | C13—C14 | 1.373 (4) |
Cd1—O2W | 2.293 (2) | C13—H13 | 0.9300 |
O1—C1 | 1.371 (3) | C14—C15 | 1.389 (4) |
O1—C7 | 1.425 (4) | C14—H14 | 0.9300 |
O2—C3 | 1.389 (3) | C15—C16 | 1.395 (4) |
O2—C9 | 1.422 (4) | C15—C18 | 1.459 (4) |
O3—C5 | 1.366 (4) | C16—C17 | 1.378 (4) |
O3—C11 | 1.413 (4) | C16—H16 | 0.9300 |
O4—C8 | 1.254 (4) | C17—N1 | 1.334 (4) |
O5—C8 | 1.245 (4) | C17—H17 | 0.9300 |
O6—C10i | 1.256 (4) | C18—C18iii | 1.312 (6) |
O7—C10i | 1.239 (4) | C18—H18 | 0.9300 |
O8—C12 | 1.223 (4) | C19—N2 | 1.319 (5) |
O9—C12 | 1.272 (4) | C19—C20 | 1.369 (5) |
O9—H9 | 0.8200 | C19—H19 | 0.9300 |
C1—C6 | 1.392 (4) | C20—C21 | 1.388 (5) |
C1—C2 | 1.398 (4) | C20—H20 | 0.9300 |
C2—C3 | 1.389 (4) | C21—C22 | 1.381 (5) |
C2—H2 | 0.9300 | C21—C24 | 1.492 (5) |
C3—C4 | 1.366 (4) | C22—C23 | 1.374 (5) |
C4—C5 | 1.394 (4) | C22—H22 | 0.9300 |
C4—H4 | 0.9300 | C23—N2 | 1.340 (5) |
C5—C6 | 1.391 (4) | C23—H23 | 0.9300 |
C6—H6 | 0.9300 | C24—C24iv | 1.284 (7) |
C7—C8 | 1.508 (4) | C24—H24 | 0.9300 |
C7—H7A | 0.9700 | O1W—H1WB | 0.8500 |
C7—H7B | 0.9700 | O1W—H1WC | 0.8500 |
C9—C10 | 1.514 (4) | O2W—H2WB | 0.8499 |
C9—H9A | 0.9700 | O2W—H2WC | 0.8500 |
C9—H9B | 0.9700 | O3W—H3WC | 0.8500 |
C10—O7ii | 1.239 (4) | O3W—H3WD | 0.8500 |
O2W—Cd1—O4 | 89.90 (9) | H9A—C9—H9B | 108.1 |
O2W—Cd1—O1W | 170.89 (8) | O7ii—C10—O6ii | 123.6 (3) |
O4—Cd1—O1W | 98.45 (9) | O7ii—C10—C9 | 122.1 (3) |
O2W—Cd1—N1 | 86.68 (9) | O6ii—C10—C9 | 114.4 (3) |
O4—Cd1—N1 | 133.85 (8) | O3—C11—C12 | 108.0 (2) |
O1W—Cd1—N1 | 90.11 (9) | O3—C11—H11A | 110.1 |
O2W—Cd1—O7 | 87.25 (9) | C12—C11—H11A | 110.1 |
O4—Cd1—O7 | 85.92 (8) | O3—C11—H11B | 110.1 |
O1W—Cd1—O7 | 89.70 (8) | C12—C11—H11B | 110.1 |
N1—Cd1—O7 | 139.69 (9) | H11A—C11—H11B | 108.4 |
O2W—Cd1—O6 | 86.56 (9) | O8—C12—O9 | 124.6 (3) |
O4—Cd1—O6 | 139.20 (8) | O8—C12—C11 | 121.0 (3) |
O1W—Cd1—O6 | 84.73 (9) | O9—C12—C11 | 114.4 (3) |
N1—Cd1—O6 | 86.53 (8) | N1—C13—C14 | 123.7 (3) |
O7—Cd1—O6 | 53.33 (8) | N1—C13—H13 | 118.2 |
O2W—Cd1—O5 | 105.81 (8) | C14—C13—H13 | 118.2 |
O4—Cd1—O5 | 53.75 (7) | C13—C14—C15 | 120.2 (3) |
O1W—Cd1—O5 | 82.24 (8) | C13—C14—H14 | 119.9 |
N1—Cd1—O5 | 83.14 (8) | C15—C14—H14 | 119.9 |
O7—Cd1—O5 | 136.63 (8) | C14—C15—C16 | 115.7 (3) |
O6—Cd1—O5 | 163.32 (8) | C14—C15—C18 | 123.2 (3) |
C1—O1—C7 | 116.1 (2) | C16—C15—C18 | 121.1 (3) |
C3—O2—C9 | 116.5 (2) | C17—C16—C15 | 120.4 (3) |
C5—O3—C11 | 119.5 (2) | C17—C16—H16 | 119.8 |
C8—O4—Cd1 | 96.34 (19) | C15—C16—H16 | 119.8 |
C8—O5—Cd1 | 86.36 (18) | N1—C17—C16 | 123.1 (3) |
C10i—O6—Cd1 | 89.68 (19) | N1—C17—H17 | 118.4 |
C10i—O7—Cd1 | 93.2 (2) | C16—C17—H17 | 118.4 |
C12—O9—H9 | 109.5 | C18iii—C18—C15 | 126.2 (4) |
O1—C1—C6 | 116.0 (3) | C18iii—C18—H18 | 116.9 |
O1—C1—C2 | 122.9 (3) | C15—C18—H18 | 116.9 |
C6—C1—C2 | 121.1 (3) | N2—C19—C20 | 121.3 (4) |
C3—C2—C1 | 118.1 (3) | N2—C19—H19 | 119.4 |
C3—C2—H2 | 121.0 | C20—C19—H19 | 119.4 |
C1—C2—H2 | 121.0 | C19—C20—C21 | 119.8 (3) |
C4—C3—O2 | 116.0 (3) | C19—C20—H20 | 120.1 |
C4—C3—C2 | 122.5 (3) | C21—C20—H20 | 120.1 |
O2—C3—C2 | 121.4 (3) | C22—C21—C20 | 117.7 (3) |
C3—C4—C5 | 118.3 (3) | C22—C21—C24 | 124.8 (4) |
C3—C4—H4 | 120.8 | C20—C21—C24 | 117.5 (3) |
C5—C4—H4 | 120.8 | C23—C22—C21 | 120.1 (4) |
O3—C5—C6 | 124.3 (3) | C23—C22—H22 | 120.0 |
O3—C5—C4 | 114.1 (3) | C21—C22—H22 | 120.0 |
C6—C5—C4 | 121.6 (3) | N2—C23—C22 | 120.4 (4) |
C5—C6—C1 | 118.3 (3) | N2—C23—H23 | 119.8 |
C5—C6—H6 | 120.8 | C22—C23—H23 | 119.8 |
C1—C6—H6 | 120.8 | C24iv—C24—C21 | 124.6 (5) |
O1—C7—C8 | 112.3 (2) | C24iv—C24—H24 | 117.7 |
O1—C7—H7A | 109.2 | C21—C24—H24 | 117.7 |
C8—C7—H7A | 109.2 | C17—N1—C13 | 116.7 (3) |
O1—C7—H7B | 109.2 | C17—N1—Cd1 | 123.4 (2) |
C8—C7—H7B | 109.2 | C13—N1—Cd1 | 119.5 (2) |
H7A—C7—H7B | 107.9 | C19—N2—C23 | 120.8 (3) |
O5—C8—O4 | 123.5 (3) | Cd1—O1W—H1WB | 109.3 |
O5—C8—C7 | 115.8 (3) | Cd1—O1W—H1WC | 109.3 |
O4—C8—C7 | 120.7 (3) | H1WB—O1W—H1WC | 109.5 |
O2—C9—C10 | 110.7 (3) | Cd1—O2W—H2WB | 109.2 |
O2—C9—H9A | 109.5 | Cd1—O2W—H2WC | 109.3 |
C10—C9—H9A | 109.5 | H2WB—O2W—H2WC | 109.5 |
O2—C9—H9B | 109.5 | H3WC—O3W—H3WD | 108.2 |
C10—C9—H9B | 109.5 |
Symmetry codes: (i) x, y−1, z+1; (ii) x, y+1, z−1; (iii) −x+2, −y, −z; (iv) −x+2, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O9—H9···N2v | 0.82 | 1.81 | 2.619 (4) | 169 |
O1W—H1WB···O9vi | 0.85 | 1.93 | 2.763 (3) | 167 |
O1W—H1WC···O5vii | 0.85 | 1.97 | 2.815 (3) | 172 |
O2W—H2WB···O8viii | 0.85 | 2.05 | 2.763 (4) | 141 |
O2W—H2WC···O7ix | 0.85 | 1.96 | 2.799 (3) | 170 |
O3W—H3WC···O6x | 0.85 | 2.02 | 2.862 (4) | 174 |
O3W—H3WD···O6ix | 0.85 | 2.36 | 3.207 (4) | 174 |
Symmetry codes: (v) −x+1, −y+2, −z+1; (vi) x, y−1, z; (vii) −x+1, −y+1, −z; (viii) x+1, y−1, z; (ix) −x+1, −y+1, −z+1; (x) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cd2(C12H10O9)2(C12H10N2)(H2O)4]·C12H10N2·2H2O |
Mr | 1293.74 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 10.8627 (9), 11.1883 (9), 11.3773 (11) |
α, β, γ (°) | 69.362 (1), 79.777 (2), 74.451 (1) |
V (Å3) | 1241.35 (19) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.95 |
Crystal size (mm) | 0.32 × 0.28 × 0.26 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.744, 0.785 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6314, 4315, 3814 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.078, 1.00 |
No. of reflections | 4315 |
No. of parameters | 353 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.59, −0.60 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Cd1—N1 | 2.338 (2) | Cd1—O7 | 2.415 (2) |
Cd1—O4 | 2.315 (2) | Cd1—O1W | 2.322 (2) |
Cd1—O5 | 2.535 (2) | Cd1—O2W | 2.293 (2) |
Cd1—O6 | 2.482 (2) | ||
O2W—Cd1—O4 | 89.90 (9) | N1—Cd1—O6 | 86.53 (8) |
O2W—Cd1—O1W | 170.89 (8) | O7—Cd1—O6 | 53.33 (8) |
O4—Cd1—O1W | 98.45 (9) | O4—Cd1—O5 | 53.75 (7) |
O4—Cd1—O7 | 85.92 (8) | N1—Cd1—O5 | 83.14 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
O9—H9···N2i | 0.82 | 1.81 | 2.619 (4) | 169 |
O1W—H1WB···O9ii | 0.85 | 1.93 | 2.763 (3) | 167 |
O1W—H1WC···O5iii | 0.85 | 1.97 | 2.815 (3) | 172 |
O2W—H2WB···O8iv | 0.85 | 2.05 | 2.763 (4) | 141 |
O2W—H2WC···O7v | 0.85 | 1.96 | 2.799 (3) | 170 |
O3W—H3WC···O6vi | 0.85 | 2.02 | 2.862 (4) | 174 |
O3W—H3WD···O6v | 0.85 | 2.36 | 3.207 (4) | 174 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, y−1, z; (iii) −x+1, −y+1, −z; (iv) x+1, y−1, z; (v) −x+1, −y+1, −z+1; (vi) x, y+1, z. |
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Recent years have witnessed the rapid development of the construction of metal–organic assemblies, not only for their potential applications but also for their fascinating architectures and topologies (Moulton & Zaworotko, 2001; Kitagawa et al., 2004; Ferey et al., 2005; Murray et al., 2009). Of great interest are interpenetration motifs, which have been classified into more complex types of entanglement involving polycatenation, polythreading and polyknotting, as well as Borromean links, and have been recently reviewed by Batten, Robson and Ciani (Batten & Robson, 1998; Batten, 2001; Carlucci et al., 2003). Polycatenation indicates that entanglement of the lower-dimensional polymeric motifs can generate a structure of overall higher dimensionality, such as 1D → 2D, 1D → 3D and 2D → 3D.
An increase in dimensionality from a two-dimensional layer to a three-dimensional entanglement has been observed for systems interpenetrating in a parallel/inclined fashion. Reports of such examples are still relatively rare (Blatov et al., 2004; Baburin et al., 2005; Chen et al., 2006) since the first 2D → 3D parallel interpenetration was reported by Liu & Tilley (1997). It is even unusual for 2D → 2D parallel → 3D parallel interpenetration, i.e. both 2D → 2D and 2D → 3D parallel interpenetration occurring within the same structure. To the best of our knowledge, there are only a few examples in the field of organic nets (Bényei et al., 1998) and coordination polymers (Banfi et al., 2004; Guo et al., 2009).
Meanwhile, (6,3) nets, one of the most common topologies in two-dimensional coordination polymers, easily interpenetrate with each other when large six-membered rings are formed or the net shows undulating features. Many layers of this type are interlocked into n-fold interpenetrating sheets, or in polycatenated 2D → 3D systems (Tong et al., 1999; Jung et al., 2002). Very recently, Su and co-workers reported a very rare 3D coordination polymer with 11-fold interpenetration and five-fold catenation, which may represent the highest degree of interpenetration yet observed for the (6,3) net (Yang et al., 2009). Herein, we report the title coordination compound, {[Cd2(TCMB)2(bpe)(H2O)4].(bpe).2H2O}n, (I) [TCMB is 1,3,5-tris(carboxymethoxybenzene and bpe is trans-1,2-bis(4-pyridyl)ethene], which features an unusual three-dimensional combination of both 2D → 2D and 2D → 3D parallel interpenetration self-assembled from both coordinative and hydrogen-bonded two-dimensional (6,3) layer motifs.
As shown in Fig. 1, the asymmetric unit of complex (I) is composed of one CdII centre, one TCMB ligand, half a coordinated bpe ligand, two water molecules, half a free bpe ligand and one solvent water molecule. The CdII centre adopts a pentagonal–bipyramidal coordination geometry, with four carboxyl O atoms from two carboxyl groups of different TCMB ligands and one N atom from the bpe ligand in the equatorial plane, and two water O atoms occupying the axial positions. The TCMB ligand is incompletely deprotonated and adopts a bis(chelating bidentate) mode, linking two CdII centres. The two coordinated carboxylate groups (C8 and C10) are almost coplanar with the central benzene ring, with small dihedral angles between the individual groups and the benzene ring of 3.7 (2) and 15.0 (3)°, respectively, while the carboxylic acid group (C12) forms a large dihedral angle of 76.2 (2)°.
The CdII centres of (I) are linked by TCMB ligands and bpe ligands into a ladder structure. These ladders are interlinked through O—H···N hydrogen bonds between the hydroxyl groups (O9—H9) of the TCMB ligands and the N2 atoms of the uncoordinated bpe ligands (Fig. 2). As a result, a two-dimensional undulating layer is formed in the bc plane. Within this layer, there are two kinds of hexagonal ring, A and B. Ring A is situated within the ladder, with four CdII ions and the benzene rings of two TCMB ligands located at its vertices, and four carboxylate groups of two TCMB ligands and two coordinated bpe ligands along its edges. Ring B is formed by hydrogen bonds between the free bpe ligands and two adjacent ladders, the vertices composed of two CdII ions and four benzene rings from different TCMB ligands. The longest opposite sides are situated with two free bpe ligands connected to the carboxylic acid groups of the ladders through hydrogen bonds. The large hexagonal meshes have dimensions of 22.38 (1) × 12.84 (2) Å for ring A and 32.48 (2) × 12.84 (2) Å for ring B, based on the opposite metal···metal or Cg···Cg (Cg is the centre of the benzene ring) distances. If the metal centres and benzene rings of the TCMB ligands are considered as nodes and the hydrogen bonds as actual bonds, the whole layer can be regarded as a (6,3) network.
As expected, the large dimensions and corrugated nature of these layers allow them to interpenetrate in an extensive and unusual fashion. Firstly, pairs of layers interpenetrate in a 2D → 2D parallel fashion and their mean planes are parallel and coincident (Fig. 3). It should be noted that for the doubly interpenetrating layers, each ring A in one layer penetrates a ring B in the other: the two layers are translationally equivalent and are generated by a unique interpenetration vector (Carlucci et al., 2002) Ti = a + 2b with a relative displacement distance of 22.10 (2) Å. Secondly, the resulting two-fold layers interpenetrate further with neighbouring doubly interpenetrating layers that are parallel but offset, in a 2D → 3D parallel fashion. Thus, each individual sheet interpenetrates two others, one in the same layer, the other from the layer above or below (Fig. 4). Repeating this interpenetration in a parallel fashion leads to an overall 2D → 3D increase in dimensionality. Therefore, the generation of the three-dimensional framework in this complex can be considered to occur through interpenetration of the nets via an unusual 2 × 3 parallel polycatenating mode.
To the best of our knowledge, there are only a few examples of this mode in the field of coordination polymers. The first example, namely [Ag(1,3,5-tris(4-cyanophenoxymethyl)-2,4,6-trimethylbenzene) (CF3SO3)].0.5H2O, was reported by Banfi et al. (2004) and exhibits similar entanglement to complex (I). However, in this compound, the undulating (6,3) layer is interlocked with three others, one on the same average plane, plus one of the two layers interpenetrated above and one of the two layers interpenetrated below. In another example, namely [Zn(MFDA)(bpp)] [H2MFDA is 9,9-dimethylfluorene-2,7-dicarboxylic acid and bpp is 1,3-bis(4-pyridyl)propane], each individual (4,4) sheet interpenetrates five others, one in the same layer, two from the layer above and two from the layer below (Guo et al., 2009). The particular arrangement of the hexagons in the case of (I) may explain the unusual polycatenation. On the one hand, the undulating (6,3) layer containing two different kinds of large hexagons is unique; in previous examples, both the (6,3) and (4,4) nets have only one kind of polygon. On the other hand, the coordinated water molecules (O1W and O2W) can form O—H···O hydrogen bonds with the carboxylate O atoms between adjacent layers (Table 2), which may further stabilize the overall packing mode.
Additionally, due to such complex interpenetration, the voids within any single independent two-diemnsional network are almost completely occupied. Only small one-dimensional channels running along the b axis are observed and these contain the guest water molecules (O3W) via hydrogen-bonding interactions with the carboxylate atoms O6. Calculations using PLATON (SOLV routine; Spek, 2009) reveal that these channels occupy 3.4% of the unit-cell volume.
In summary, we have prepared a novel three-dimensional polycatenating motif generated by the 2D → 2D parallel → 3D parallel interpenetration of coordinative and hydrogen-bonded (6,3) layers. The appropriate choice of ligands may lead to more fascinating structures and may further contribute to understanding the assembly processes in coordination chemistry and crystal engineering.