Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110004567/sk3355sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110004567/sk3355Isup2.hkl |
CCDC reference: 774881
For related literature, see: Bernstein et al. (1995); Biswas et al. (2008); Cheruzel et al. (2003); Custelcean et al. (2000); Du et al. (2008); Harvey et al. (2000); Kim & Kim (1998); Kim et al. (1999); Liu & Xu (2005); Ludwig (2001); Zhao et al. (2004).
For the preparation of (I), a mixture of Cd(ClO4)2.6H2O (134 mg, 0.32 mmol) and 1,10-phenanthroline (54 mg, 0.30 mmol) in 12 ml distilled water with two drops of 10% HCl was placed in a Parr Teflon-lined autoclave (23 ml) and heated at 423 K for 3 d. Yellow block-shaped crystals were collected in a circa 76% yield based on 1,10-phenanthroline. Analysis calculated for C36H31N6O11.5Cl2Cd1: C 47.26, H 3.41, N 9.18%; found: C 47.32, H 3.51, N 9.23%. IR data (KBr, ν, cm-1): 3535 (m), 3364 (m), 3064 (m), 2925 (m), 1625 (s), 1594 (m), 1579 (m), 1519 (s), 1497 (m), 1429 (s), 1344 (m), 1225 (m), 1147 (s), 1098 (vs), 929 (m), 865 (m), 844 (s), 772 (m), 724 (s), 642 (m), 622 (s), 514 (m), 419 (m).
H atoms linking C were positioned geometrically (C—H = 0.93 Å) and included in the refinement in the riding-model approximation, with Uîso(H) = 1.2Ueq(C). Water H atoms were located in a difference map and refined with Uîso(H) values set at 1.5Ueq(O). The O—H and H···H distances in each water molecule were restrained to be 0.85 (1) and 1.38 (1) Å, respectively. The final difference electron-density Fourier map shows some minor perchlorate disorder.
Data collection: SMART (Bruker, 2008); cell refinement: SMART (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Cd(C12H8N2)3](ClO4)2·3.5H2O | F(000) = 3704 |
Mr = 914.97 | Dx = 1.633 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 5668 reflections |
a = 28.1954 (15) Å | θ = 2.3–22.4° |
b = 19.6534 (11) Å | µ = 0.80 mm−1 |
c = 15.7245 (9) Å | T = 296 K |
β = 121.348 (1)° | Block, yellow |
V = 7441.5 (7) Å3 | 0.32 × 0.12 × 0.06 mm |
Z = 8 |
Bruker SMART CCD area-detector diffractometer | 6960 independent reflections |
Radiation source: fine-focus sealed tube | 5256 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ and ω scans | θmax = 25.8°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −34→33 |
Tmin = 0.642, Tmax = 0.745 | k = −24→24 |
23241 measured reflections | l = −19→19 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0529P)2 + 6.7195P] where P = (Fo2 + 2Fc2)/3 |
6960 reflections | (Δ/σ)max < 0.001 |
532 parameters | Δρmax = 0.61 e Å−3 |
11 restraints | Δρmin = −0.53 e Å−3 |
[Cd(C12H8N2)3](ClO4)2·3.5H2O | V = 7441.5 (7) Å3 |
Mr = 914.97 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 28.1954 (15) Å | µ = 0.80 mm−1 |
b = 19.6534 (11) Å | T = 296 K |
c = 15.7245 (9) Å | 0.32 × 0.12 × 0.06 mm |
β = 121.348 (1)° |
Bruker SMART CCD area-detector diffractometer | 6960 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 5256 reflections with I > 2σ(I) |
Tmin = 0.642, Tmax = 0.745 | Rint = 0.033 |
23241 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 11 restraints |
wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.61 e Å−3 |
6960 reflections | Δρmin = −0.53 e Å−3 |
532 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. |
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 | 0.127101 (10) | 0.228290 (13) | 0.124590 (18) | 0.04709 (11) | |
Cl1 | 0.24764 (4) | 0.46305 (5) | 0.26160 (8) | 0.0665 (3) | |
Cl2 | 0.0000 | 0.25791 (8) | 0.7500 | 0.0639 (4) | |
Cl3 | 0.0000 | 0.16535 (9) | 0.2500 | 0.0823 (5) | |
N1 | 0.14409 (12) | 0.31211 (14) | 0.0383 (2) | 0.0484 (7) | |
N2 | 0.22167 (11) | 0.21882 (14) | 0.1621 (2) | 0.0462 (7) | |
N3 | 0.09694 (12) | 0.12747 (14) | 0.0325 (2) | 0.0501 (7) | |
N4 | 0.03039 (12) | 0.22849 (15) | 0.0332 (2) | 0.0504 (7) | |
N5 | 0.13207 (12) | 0.31042 (15) | 0.2411 (2) | 0.0507 (7) | |
N6 | 0.15441 (12) | 0.17408 (16) | 0.2763 (2) | 0.0545 (7) | |
C1 | 0.10605 (17) | 0.3563 (2) | −0.0245 (3) | 0.0605 (10) | |
H1A | 0.0700 | 0.3526 | −0.0376 | 0.073* | |
C2 | 0.1178 (2) | 0.4077 (2) | −0.0714 (3) | 0.0697 (12) | |
H2A | 0.0901 | 0.4374 | −0.1152 | 0.084* | |
C3 | 0.1701 (2) | 0.4140 (2) | −0.0526 (3) | 0.0683 (11) | |
H3A | 0.1785 | 0.4482 | −0.0835 | 0.082* | |
C4 | 0.21179 (17) | 0.36911 (18) | 0.0135 (3) | 0.0550 (9) | |
C5 | 0.26730 (19) | 0.3725 (2) | 0.0355 (3) | 0.0672 (11) | |
H5A | 0.2773 | 0.4070 | 0.0073 | 0.081* | |
C6 | 0.30582 (18) | 0.3271 (2) | 0.0958 (3) | 0.0638 (11) | |
H6A | 0.3419 | 0.3308 | 0.1091 | 0.077* | |
C7 | 0.29176 (14) | 0.27298 (18) | 0.1401 (3) | 0.0506 (9) | |
C8 | 0.32955 (16) | 0.2224 (2) | 0.1999 (3) | 0.0618 (10) | |
H8A | 0.3658 | 0.2235 | 0.2135 | 0.074* | |
C9 | 0.31324 (15) | 0.1718 (2) | 0.2380 (3) | 0.0622 (10) | |
H9A | 0.3378 | 0.1375 | 0.2767 | 0.075* | |
C10 | 0.25906 (15) | 0.17250 (19) | 0.2179 (3) | 0.0538 (9) | |
H10A | 0.2484 | 0.1382 | 0.2453 | 0.065* | |
C11 | 0.23741 (14) | 0.26869 (16) | 0.1220 (2) | 0.0426 (7) | |
C12 | 0.19643 (14) | 0.31781 (17) | 0.0573 (2) | 0.0446 (8) | |
C13 | 0.12889 (18) | 0.0782 (2) | 0.0321 (3) | 0.0643 (10) | |
H13A | 0.1672 | 0.0838 | 0.0709 | 0.077* | |
C14 | 0.1090 (2) | 0.0196 (2) | −0.0219 (4) | 0.0857 (14) | |
H14A | 0.1332 | −0.0135 | −0.0194 | 0.103* | |
C15 | 0.0531 (3) | 0.0105 (2) | −0.0793 (4) | 0.0951 (16) | |
H15A | 0.0388 | −0.0287 | −0.1174 | 0.114* | |
C16 | 0.01704 (19) | 0.0607 (2) | −0.0808 (3) | 0.0707 (12) | |
C17 | −0.0426 (2) | 0.0548 (3) | −0.1375 (4) | 0.0920 (16) | |
H17A | −0.0589 | 0.0168 | −0.1775 | 0.110* | |
C18 | −0.0748 (2) | 0.1027 (3) | −0.1339 (4) | 0.0874 (15) | |
H18A | −0.1131 | 0.0967 | −0.1693 | 0.105* | |
C19 | −0.05183 (16) | 0.1630 (2) | −0.0769 (3) | 0.0652 (11) | |
C20 | −0.08400 (18) | 0.2150 (3) | −0.0718 (3) | 0.0803 (14) | |
H20A | −0.1224 | 0.2106 | −0.1057 | 0.096* | |
C21 | −0.05956 (19) | 0.2718 (3) | −0.0176 (4) | 0.0805 (14) | |
H21A | −0.0809 | 0.3068 | −0.0149 | 0.097* | |
C22 | −0.00244 (17) | 0.2767 (2) | 0.0336 (3) | 0.0654 (11) | |
H22A | 0.0140 | 0.3159 | 0.0705 | 0.078* | |
C23 | 0.00612 (14) | 0.17196 (19) | −0.0223 (2) | 0.0499 (8) | |
C24 | 0.04121 (15) | 0.11895 (18) | −0.0232 (2) | 0.0495 (8) | |
C25 | 0.12016 (16) | 0.3761 (2) | 0.2246 (3) | 0.0604 (10) | |
H25A | 0.1069 | 0.3930 | 0.1609 | 0.073* | |
C26 | 0.12651 (18) | 0.4208 (2) | 0.2980 (3) | 0.0709 (12) | |
H26A | 0.1170 | 0.4664 | 0.2830 | 0.085* | |
C27 | 0.14660 (17) | 0.3977 (2) | 0.3912 (3) | 0.0691 (11) | |
H27A | 0.1514 | 0.4275 | 0.4411 | 0.083* | |
C28 | 0.16028 (15) | 0.3290 (2) | 0.4130 (3) | 0.0588 (10) | |
C29 | 0.18277 (17) | 0.3013 (3) | 0.5104 (3) | 0.0708 (12) | |
H29A | 0.1886 | 0.3299 | 0.5621 | 0.085* | |
C30 | 0.19570 (17) | 0.2354 (3) | 0.5295 (3) | 0.0698 (12) | |
H30A | 0.2111 | 0.2192 | 0.5941 | 0.084* | |
C31 | 0.18593 (15) | 0.1893 (2) | 0.4506 (3) | 0.0617 (10) | |
C32 | 0.19790 (18) | 0.1200 (3) | 0.4651 (4) | 0.0752 (13) | |
H32A | 0.2130 | 0.1014 | 0.5284 | 0.090* | |
C33 | 0.18769 (19) | 0.0791 (2) | 0.3871 (4) | 0.0786 (13) | |
H33A | 0.1955 | 0.0328 | 0.3964 | 0.094* | |
C34 | 0.16529 (19) | 0.1086 (2) | 0.2933 (3) | 0.0680 (11) | |
H34A | 0.1576 | 0.0806 | 0.2399 | 0.082* | |
C35 | 0.16442 (14) | 0.21519 (19) | 0.3535 (3) | 0.0498 (9) | |
C36 | 0.15206 (14) | 0.28669 (18) | 0.3350 (3) | 0.0488 (8) | |
O1 | 0.24582 (15) | 0.49883 (16) | 0.3388 (2) | 0.0908 (10) | |
O2 | 0.29708 (19) | 0.4772 (2) | 0.2654 (4) | 0.1428 (17) | |
O3 | 0.2459 (2) | 0.39283 (19) | 0.2750 (3) | 0.1343 (17) | |
O4 | 0.2037 (2) | 0.4800 (4) | 0.1712 (3) | 0.192 (3) | |
O5 | 0.01930 (15) | 0.2976 (2) | 0.6997 (3) | 0.1042 (12) | |
O6 | 0.04525 (18) | 0.2184 (2) | 0.8220 (3) | 0.1268 (16) | |
O7 | 0.0179 (3) | 0.1279 (3) | 0.1995 (6) | 0.225 (4) | |
O8 | 0.0428 (2) | 0.2075 (5) | 0.3064 (6) | 0.261 (5) | |
O1W | 0.0478 (3) | 0.5682 (2) | 0.1695 (4) | 0.1402 (17) | |
H1WA | 0.035 (4) | 0.568 (4) | 0.1069 (15) | 0.210* | |
H1WB | 0.038 (4) | 0.605 (2) | 0.185 (5) | 0.210* | |
O2W | 0.1041 (2) | 0.5542 (3) | 0.0732 (4) | 0.1416 (17) | |
H2WA | 0.0746 (19) | 0.542 (4) | 0.019 (4) | 0.212* | |
H2WB | 0.128 (2) | 0.523 (3) | 0.088 (6) | 0.212* | |
O3W | −0.0216 (2) | 0.4588 (3) | 0.1158 (4) | 0.160 (2) | |
H3WA | −0.012 (4) | 0.429 (3) | 0.161 (5) | 0.240* | |
H3WB | 0.000 (3) | 0.493 (3) | 0.140 (6) | 0.240* | |
O4W | 0.0000 | 0.3506 (3) | 0.2500 | 0.1211 (19) | |
H4WA | 0.0282 (7) | 0.3255 (10) | 0.269 (6) | 0.182* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.04305 (16) | 0.04780 (16) | 0.04896 (17) | 0.00097 (11) | 0.02291 (12) | 0.00043 (11) |
Cl1 | 0.0637 (6) | 0.0694 (7) | 0.0631 (6) | −0.0072 (5) | 0.0306 (5) | −0.0049 (5) |
Cl2 | 0.0673 (9) | 0.0694 (9) | 0.0620 (8) | 0.000 | 0.0385 (7) | 0.000 |
Cl3 | 0.0965 (13) | 0.0696 (10) | 0.0809 (11) | 0.000 | 0.0463 (10) | 0.000 |
N1 | 0.0478 (16) | 0.0498 (17) | 0.0422 (15) | 0.0030 (14) | 0.0195 (13) | 0.0021 (13) |
N2 | 0.0435 (15) | 0.0480 (17) | 0.0428 (15) | 0.0018 (13) | 0.0193 (13) | −0.0001 (12) |
N3 | 0.0481 (16) | 0.0493 (17) | 0.0555 (17) | 0.0043 (14) | 0.0288 (14) | 0.0010 (13) |
N4 | 0.0435 (15) | 0.0572 (19) | 0.0524 (17) | 0.0056 (14) | 0.0263 (14) | 0.0033 (14) |
N5 | 0.0483 (16) | 0.0491 (18) | 0.0535 (18) | −0.0045 (14) | 0.0255 (14) | −0.0044 (14) |
N6 | 0.0538 (18) | 0.0582 (19) | 0.0579 (19) | 0.0020 (15) | 0.0337 (15) | 0.0065 (15) |
C1 | 0.058 (2) | 0.063 (2) | 0.053 (2) | 0.010 (2) | 0.0241 (19) | 0.0063 (19) |
C2 | 0.084 (3) | 0.059 (3) | 0.058 (2) | 0.015 (2) | 0.032 (2) | 0.0134 (19) |
C3 | 0.099 (3) | 0.047 (2) | 0.072 (3) | 0.010 (2) | 0.053 (3) | 0.0124 (19) |
C4 | 0.077 (3) | 0.044 (2) | 0.054 (2) | −0.0056 (19) | 0.041 (2) | −0.0057 (16) |
C5 | 0.083 (3) | 0.055 (2) | 0.085 (3) | −0.017 (2) | 0.059 (3) | −0.009 (2) |
C6 | 0.064 (2) | 0.064 (3) | 0.081 (3) | −0.016 (2) | 0.050 (2) | −0.014 (2) |
C7 | 0.0435 (18) | 0.062 (2) | 0.0467 (19) | −0.0070 (17) | 0.0237 (16) | −0.0149 (17) |
C8 | 0.044 (2) | 0.077 (3) | 0.062 (2) | −0.0036 (19) | 0.0257 (19) | −0.012 (2) |
C9 | 0.048 (2) | 0.074 (3) | 0.051 (2) | 0.014 (2) | 0.0172 (18) | 0.0038 (19) |
C10 | 0.053 (2) | 0.057 (2) | 0.046 (2) | 0.0099 (18) | 0.0221 (17) | 0.0082 (16) |
C11 | 0.0457 (18) | 0.0447 (19) | 0.0403 (18) | −0.0047 (15) | 0.0243 (15) | −0.0076 (14) |
C12 | 0.0514 (19) | 0.0430 (18) | 0.0418 (18) | −0.0036 (15) | 0.0260 (16) | −0.0062 (14) |
C13 | 0.067 (2) | 0.059 (2) | 0.075 (3) | 0.007 (2) | 0.043 (2) | −0.003 (2) |
C14 | 0.098 (4) | 0.067 (3) | 0.102 (4) | 0.006 (3) | 0.059 (3) | −0.017 (3) |
C15 | 0.129 (5) | 0.058 (3) | 0.102 (4) | −0.015 (3) | 0.063 (4) | −0.026 (3) |
C16 | 0.077 (3) | 0.063 (3) | 0.064 (3) | −0.015 (2) | 0.031 (2) | −0.006 (2) |
C17 | 0.084 (4) | 0.088 (4) | 0.080 (3) | −0.037 (3) | 0.027 (3) | −0.021 (3) |
C18 | 0.061 (3) | 0.102 (4) | 0.078 (3) | −0.025 (3) | 0.021 (2) | 0.003 (3) |
C19 | 0.044 (2) | 0.088 (3) | 0.058 (2) | −0.005 (2) | 0.0226 (19) | 0.015 (2) |
C20 | 0.041 (2) | 0.125 (4) | 0.071 (3) | 0.013 (3) | 0.027 (2) | 0.023 (3) |
C21 | 0.058 (3) | 0.103 (4) | 0.083 (3) | 0.024 (3) | 0.038 (2) | 0.013 (3) |
C22 | 0.057 (2) | 0.075 (3) | 0.064 (3) | 0.015 (2) | 0.031 (2) | 0.003 (2) |
C23 | 0.0439 (18) | 0.062 (2) | 0.0427 (19) | −0.0020 (17) | 0.0216 (16) | 0.0066 (16) |
C24 | 0.050 (2) | 0.051 (2) | 0.0474 (19) | −0.0046 (17) | 0.0252 (17) | 0.0030 (15) |
C25 | 0.063 (2) | 0.054 (2) | 0.061 (2) | −0.0034 (19) | 0.030 (2) | −0.0064 (18) |
C26 | 0.068 (3) | 0.059 (2) | 0.082 (3) | −0.002 (2) | 0.036 (2) | −0.015 (2) |
C27 | 0.064 (3) | 0.075 (3) | 0.069 (3) | −0.010 (2) | 0.035 (2) | −0.023 (2) |
C28 | 0.046 (2) | 0.080 (3) | 0.053 (2) | −0.0098 (19) | 0.0274 (18) | −0.0136 (19) |
C29 | 0.056 (2) | 0.106 (4) | 0.058 (3) | −0.016 (3) | 0.036 (2) | −0.017 (2) |
C30 | 0.049 (2) | 0.115 (4) | 0.046 (2) | −0.013 (2) | 0.0253 (19) | 0.002 (2) |
C31 | 0.045 (2) | 0.083 (3) | 0.061 (2) | −0.002 (2) | 0.0307 (19) | 0.014 (2) |
C32 | 0.062 (3) | 0.096 (4) | 0.071 (3) | 0.002 (2) | 0.037 (2) | 0.031 (3) |
C33 | 0.084 (3) | 0.071 (3) | 0.094 (3) | 0.007 (2) | 0.055 (3) | 0.027 (3) |
C34 | 0.083 (3) | 0.059 (3) | 0.077 (3) | 0.004 (2) | 0.052 (2) | 0.010 (2) |
C35 | 0.0366 (17) | 0.067 (2) | 0.049 (2) | −0.0054 (16) | 0.0247 (16) | 0.0024 (17) |
C36 | 0.0365 (17) | 0.060 (2) | 0.052 (2) | −0.0072 (16) | 0.0245 (16) | −0.0036 (16) |
O1 | 0.112 (3) | 0.081 (2) | 0.085 (2) | −0.0112 (19) | 0.056 (2) | −0.0254 (18) |
O2 | 0.125 (3) | 0.146 (4) | 0.203 (5) | −0.042 (3) | 0.118 (4) | −0.032 (4) |
O3 | 0.220 (5) | 0.070 (2) | 0.152 (4) | −0.035 (3) | 0.125 (4) | −0.031 (2) |
O4 | 0.153 (4) | 0.287 (7) | 0.074 (3) | 0.123 (5) | 0.016 (3) | 0.005 (3) |
O5 | 0.101 (3) | 0.118 (3) | 0.103 (3) | −0.008 (2) | 0.060 (2) | 0.033 (2) |
O6 | 0.124 (3) | 0.142 (4) | 0.129 (3) | 0.062 (3) | 0.077 (3) | 0.065 (3) |
O7 | 0.323 (9) | 0.179 (5) | 0.298 (8) | −0.115 (6) | 0.249 (8) | −0.139 (6) |
O8 | 0.096 (4) | 0.345 (10) | 0.288 (8) | −0.050 (5) | 0.061 (5) | −0.198 (8) |
O1W | 0.177 (5) | 0.097 (3) | 0.149 (4) | 0.012 (3) | 0.087 (4) | −0.014 (3) |
O2W | 0.118 (4) | 0.134 (4) | 0.139 (4) | 0.029 (3) | 0.043 (3) | −0.011 (3) |
O3W | 0.136 (4) | 0.143 (5) | 0.146 (4) | −0.007 (3) | 0.035 (3) | 0.039 (3) |
O4W | 0.131 (5) | 0.087 (4) | 0.164 (6) | 0.000 | 0.090 (5) | 0.000 |
Cd1—N4 | 2.329 (3) | C11—C12 | 1.442 (5) |
Cd1—N1 | 2.336 (3) | C13—C14 | 1.365 (6) |
Cd1—N3 | 2.338 (3) | C13—H13A | 0.9300 |
Cd1—N6 | 2.347 (3) | C14—C15 | 1.360 (7) |
Cd1—N5 | 2.390 (3) | C14—H14A | 0.9300 |
Cd1—N2 | 2.420 (3) | C15—C16 | 1.407 (7) |
Cl1—O4 | 1.355 (4) | C15—H15A | 0.9300 |
Cl1—O2 | 1.392 (4) | C16—C24 | 1.398 (5) |
Cl1—O3 | 1.401 (4) | C16—C17 | 1.442 (7) |
Cl1—O1 | 1.427 (3) | C17—C18 | 1.330 (7) |
Cl2—O5 | 1.407 (3) | C17—H17A | 0.9300 |
Cl2—O5i | 1.407 (3) | C18—C19 | 1.422 (7) |
Cl2—O6i | 1.417 (4) | C18—H18A | 0.9300 |
Cl2—O6 | 1.417 (4) | C19—C20 | 1.396 (6) |
Cl3—O8ii | 1.347 (6) | C19—C23 | 1.406 (5) |
Cl3—O8 | 1.347 (6) | C20—C21 | 1.355 (7) |
Cl3—O7ii | 1.359 (5) | C20—H20A | 0.9300 |
Cl3—O7 | 1.359 (5) | C21—C22 | 1.379 (6) |
N1—C1 | 1.334 (4) | C21—H21A | 0.9300 |
N1—C12 | 1.350 (4) | C22—H22A | 0.9300 |
N2—C10 | 1.322 (4) | C23—C24 | 1.442 (5) |
N2—C11 | 1.359 (4) | C25—C26 | 1.386 (5) |
N3—C13 | 1.326 (5) | C25—H25A | 0.9300 |
N3—C24 | 1.354 (4) | C26—C27 | 1.346 (6) |
N4—C22 | 1.326 (5) | C26—H26A | 0.9300 |
N4—C23 | 1.358 (4) | C27—C28 | 1.398 (6) |
N5—C25 | 1.325 (5) | C27—H27A | 0.9300 |
N5—C36 | 1.361 (4) | C28—C36 | 1.397 (5) |
N6—C34 | 1.318 (5) | C28—C29 | 1.426 (6) |
N6—C35 | 1.361 (5) | C29—C30 | 1.336 (6) |
C1—C2 | 1.389 (6) | C29—H29A | 0.9300 |
C1—H1A | 0.9300 | C30—C31 | 1.442 (6) |
C2—C3 | 1.349 (6) | C30—H30A | 0.9300 |
C2—H2A | 0.9300 | C31—C32 | 1.392 (6) |
C3—C4 | 1.404 (5) | C31—C35 | 1.412 (5) |
C3—H3A | 0.9300 | C32—C33 | 1.366 (6) |
C4—C12 | 1.409 (5) | C32—H32A | 0.9300 |
C4—C5 | 1.418 (6) | C33—C34 | 1.394 (6) |
C5—C6 | 1.343 (6) | C33—H33A | 0.9300 |
C5—H5A | 0.9300 | C34—H34A | 0.9300 |
C6—C7 | 1.436 (5) | C35—C36 | 1.441 (5) |
C6—H6A | 0.9300 | O1W—H1WA | 0.85 (3) |
C7—C8 | 1.402 (5) | O1W—H1WB | 0.85 (6) |
C7—C11 | 1.407 (5) | O2W—H2WA | 0.86 (6) |
C8—C9 | 1.358 (6) | O2W—H2WB | 0.85 (7) |
C8—H8A | 0.9300 | O3W—H3WA | 0.85 (6) |
C9—C10 | 1.390 (5) | O3W—H3WB | 0.85 (8) |
C9—H9A | 0.9300 | O4W—H4WA | 0.85 (5) |
C10—H10A | 0.9300 | ||
N4—Cd1—N1 | 99.70 (10) | N2—C11—C7 | 122.2 (3) |
N4—Cd1—N3 | 71.79 (10) | N2—C11—C12 | 118.4 (3) |
N1—Cd1—N3 | 110.88 (10) | C7—C11—C12 | 119.4 (3) |
N4—Cd1—N6 | 106.72 (10) | N1—C12—C4 | 122.0 (3) |
N1—Cd1—N6 | 148.46 (10) | N1—C12—C11 | 118.9 (3) |
N3—Cd1—N6 | 93.79 (10) | C4—C12—C11 | 119.1 (3) |
N4—Cd1—N5 | 93.13 (10) | N3—C13—C14 | 124.0 (4) |
N1—Cd1—N5 | 91.19 (10) | N3—C13—H13A | 118.0 |
N3—Cd1—N5 | 154.75 (10) | C14—C13—H13A | 118.0 |
N6—Cd1—N5 | 70.74 (10) | C15—C14—C13 | 118.8 (4) |
N4—Cd1—N2 | 159.81 (10) | C15—C14—H14A | 120.6 |
N1—Cd1—N2 | 70.31 (10) | C13—C14—H14A | 120.6 |
N3—Cd1—N2 | 94.90 (9) | C14—C15—C16 | 119.8 (4) |
N6—Cd1—N2 | 88.85 (10) | C14—C15—H15A | 120.1 |
N5—Cd1—N2 | 104.32 (9) | C16—C15—H15A | 120.1 |
O4—Cl1—O2 | 110.1 (4) | C24—C16—C15 | 117.3 (4) |
O4—Cl1—O3 | 108.4 (4) | C24—C16—C17 | 119.0 (4) |
O2—Cl1—O3 | 107.6 (3) | C15—C16—C17 | 123.7 (5) |
O4—Cl1—O1 | 110.7 (3) | C18—C17—C16 | 121.4 (5) |
O2—Cl1—O1 | 110.1 (3) | C18—C17—H17A | 119.3 |
O3—Cl1—O1 | 109.7 (2) | C16—C17—H17A | 119.3 |
O5—Cl2—O5i | 112.6 (4) | C17—C18—C19 | 121.3 (4) |
O5—Cl2—O6i | 107.7 (2) | C17—C18—H18A | 119.4 |
O5i—Cl2—O6i | 107.6 (2) | C19—C18—H18A | 119.4 |
O5—Cl2—O6 | 107.6 (2) | C20—C19—C23 | 117.2 (4) |
O5i—Cl2—O6 | 107.7 (2) | C20—C19—C18 | 123.3 (4) |
O6i—Cl2—O6 | 113.6 (4) | C23—C19—C18 | 119.6 (4) |
O8ii—Cl3—O8 | 104.1 (8) | C21—C20—C19 | 120.4 (4) |
O8ii—Cl3—O7ii | 103.9 (4) | C21—C20—H20A | 119.8 |
O8—Cl3—O7ii | 115.2 (5) | C19—C20—H20A | 119.8 |
O8ii—Cl3—O7 | 115.2 (5) | C20—C21—C22 | 118.8 (4) |
O8—Cl3—O7 | 103.9 (4) | C20—C21—H21A | 120.6 |
O7ii—Cl3—O7 | 114.4 (6) | C22—C21—H21A | 120.6 |
C1—N1—C12 | 118.3 (3) | N4—C22—C21 | 123.6 (4) |
C1—N1—Cd1 | 124.1 (3) | N4—C22—H22A | 118.2 |
C12—N1—Cd1 | 117.5 (2) | C21—C22—H22A | 118.2 |
C10—N2—C11 | 117.7 (3) | N4—C23—C19 | 122.1 (4) |
C10—N2—Cd1 | 127.7 (2) | N4—C23—C24 | 118.6 (3) |
C11—N2—Cd1 | 114.6 (2) | C19—C23—C24 | 119.3 (4) |
C13—N3—C24 | 118.0 (3) | N3—C24—C16 | 122.1 (4) |
C13—N3—Cd1 | 126.4 (3) | N3—C24—C23 | 118.4 (3) |
C24—N3—Cd1 | 115.6 (2) | C16—C24—C23 | 119.5 (4) |
C22—N4—C23 | 117.9 (3) | N5—C25—C26 | 123.0 (4) |
C22—N4—Cd1 | 126.5 (3) | N5—C25—H25A | 118.5 |
C23—N4—Cd1 | 115.6 (2) | C26—C25—H25A | 118.5 |
C25—N5—C36 | 117.7 (3) | C27—C26—C25 | 119.4 (4) |
C25—N5—Cd1 | 126.9 (3) | C27—C26—H26A | 120.3 |
C36—N5—Cd1 | 115.3 (2) | C25—C26—H26A | 120.3 |
C34—N6—C35 | 118.7 (3) | C26—C27—C28 | 120.0 (4) |
C34—N6—Cd1 | 124.6 (3) | C26—C27—H27A | 120.0 |
C35—N6—Cd1 | 116.4 (2) | C28—C27—H27A | 120.0 |
N1—C1—C2 | 123.0 (4) | C36—C28—C27 | 117.4 (4) |
N1—C1—H1A | 118.5 | C36—C28—C29 | 119.6 (4) |
C2—C1—H1A | 118.5 | C27—C28—C29 | 122.9 (4) |
C3—C2—C1 | 119.0 (4) | C30—C29—C28 | 121.8 (4) |
C3—C2—H2A | 120.5 | C30—C29—H29A | 119.1 |
C1—C2—H2A | 120.5 | C28—C29—H29A | 119.1 |
C2—C3—C4 | 120.2 (4) | C29—C30—C31 | 120.6 (4) |
C2—C3—H3A | 119.9 | C29—C30—H30A | 119.7 |
C4—C3—H3A | 119.9 | C31—C30—H30A | 119.7 |
C3—C4—C12 | 117.4 (4) | C32—C31—C35 | 117.4 (4) |
C3—C4—C5 | 123.0 (4) | C32—C31—C30 | 123.6 (4) |
C12—C4—C5 | 119.7 (4) | C35—C31—C30 | 119.0 (4) |
C6—C5—C4 | 121.7 (4) | C33—C32—C31 | 120.6 (4) |
C6—C5—H5A | 119.1 | C33—C32—H32A | 119.7 |
C4—C5—H5A | 119.1 | C31—C32—H32A | 119.7 |
C5—C6—C7 | 120.6 (4) | C32—C33—C34 | 118.2 (4) |
C5—C6—H6A | 119.7 | C32—C33—H33A | 120.9 |
C7—C6—H6A | 119.7 | C34—C33—H33A | 120.9 |
C8—C7—C11 | 117.5 (3) | N6—C34—C33 | 123.4 (4) |
C8—C7—C6 | 123.1 (4) | N6—C34—H34A | 118.3 |
C11—C7—C6 | 119.5 (3) | C33—C34—H34A | 118.3 |
C9—C8—C7 | 120.1 (4) | N6—C35—C31 | 121.6 (4) |
C9—C8—H8A | 120.0 | N6—C35—C36 | 118.9 (3) |
C7—C8—H8A | 120.0 | C31—C35—C36 | 119.5 (4) |
C8—C9—C10 | 118.5 (4) | N5—C36—C28 | 122.4 (3) |
C8—C9—H9A | 120.8 | N5—C36—C35 | 118.3 (3) |
C10—C9—H9A | 120.8 | C28—C36—C35 | 119.4 (3) |
N2—C10—C9 | 124.1 (4) | H1WA—O1W—H1WB | 109 (7) |
N2—C10—H10A | 118.0 | H2WA—O2W—H2WB | 107 (7) |
C9—C10—H10A | 118.0 | H3WA—O3W—H3WB | 109 (7) |
Symmetry codes: (i) −x, y, −z+3/2; (ii) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O2W | 0.85 (3) | 2.30 (9) | 2.718 (9) | 111 (7) |
O1W—H1WB···O5iii | 0.85 (6) | 2.03 (6) | 2.868 (6) | 167 (8) |
O2W—H2WA···O3Wiv | 0.86 (6) | 1.85 (4) | 2.667 (7) | 158 (10) |
O2W—H2WB···O4 | 0.85 (7) | 2.02 (7) | 2.808 (6) | 155 (7) |
O3W—H3WA···O4W | 0.85 (6) | 1.99 (7) | 2.831 (7) | 170 (9) |
O3W—H3WB···O1W | 0.85 (8) | 1.89 (7) | 2.728 (8) | 168 (10) |
O4W—H4WA···O8 | 0.85 (5) | 2.38 (3) | 3.006 (11) | 131 (2) |
Symmetry codes: (iii) x, −y+1, z−1/2; (iv) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C12H8N2)3](ClO4)2·3.5H2O |
Mr | 914.97 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 296 |
a, b, c (Å) | 28.1954 (15), 19.6534 (11), 15.7245 (9) |
β (°) | 121.348 (1) |
V (Å3) | 7441.5 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.80 |
Crystal size (mm) | 0.32 × 0.12 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.642, 0.745 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23241, 6960, 5256 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.613 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.109, 1.05 |
No. of reflections | 6960 |
No. of parameters | 532 |
No. of restraints | 11 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.61, −0.53 |
Computer programs: SMART (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).
Cd1—N4 | 2.329 (3) | Cd1—N6 | 2.347 (3) |
Cd1—N1 | 2.336 (3) | Cd1—N5 | 2.390 (3) |
Cd1—N3 | 2.338 (3) | Cd1—N2 | 2.420 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O2W | 0.85 (3) | 2.30 (9) | 2.718 (9) | 111 (7) |
O1W—H1WB···O5i | 0.85 (6) | 2.03 (6) | 2.868 (6) | 167 (8) |
O2W—H2WA···O3Wii | 0.86 (6) | 1.85 (4) | 2.667 (7) | 158 (10) |
O2W—H2WB···O4 | 0.85 (7) | 2.02 (7) | 2.808 (6) | 155 (7) |
O3W—H3WA···O4W | 0.85 (6) | 1.99 (7) | 2.831 (7) | 170 (9) |
O3W—H3WB···O1W | 0.85 (8) | 1.89 (7) | 2.728 (8) | 168 (10) |
O4W—H4WA···O8 | 0.85 (5) | 2.38 (3) | 3.006 (11) | 131 (2) |
Symmetry codes: (i) x, −y+1, z−1/2; (ii) −x, −y+1, −z. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
The study of water clusters and water chains in confined environments such as organic and inorganic host matrices is of much interest, in consideration of the essential role of the hydrogen- bonded water aggregates in many biological, chemical and physical processes (Ludwig, 2001). Metal–organic supramolecular structures with suitable organic ligands may provide void spaces where water clusters or chains can exist (Cheruzel et al., 2003; Liu & Xu, 2005; Biswas et al., 2008). However, the water arrays of particular shapes in crystal hosts are still not well understood and much work is required to rationalize the influence of the overall structures on such water aggregations. Previously we have described a cyclic water tetramer stabilized by the host [3-O3S–C6H4–PO3H]2- anions (Du et al., 2008). In the present work, we report a novel water chain stabilized by three types of perchlorate anions, which is observed in the title compound, (I), with the formula of [Cd(C12H8N2)3](ClO4)2.3.5H2O.
Compound (I) crystallizes in the monoclinic C2/c space group. The asymmetric unit contains an isolated [Cd(phen)3]2+cation (phen is 1,10-phenanthroline), one and two half perchlorate anions, and three and a half lattice water molecules (Fig. 1). The Cd1 ion exhibits a slightly distorted octahedral geometry in which the CdII ion is coordinated to six N atoms from three phen ligands. The Cd—N bond lengths (Table 1) are in the expected range (Harvey et al., 2000). The two positive charges of the [Cd(phen)3]2+ cation are compensated by one full and two half perchlorate anions, among which the Cl1 atom occupies a general position while the Cl2 and Cl3 atoms lie on the twofold axis. The discrete [Cd(phen)3]2+ ions are assembled into a two-dimensional layer via π–π packing interactions as well as van der Waals forces (Fig. 2). The overall three-dimensional arrangement of the bulky [Cd(phen)3]2+ ions and the somewhat smaller perchlorate counter-ions leaves out [creates?] crisscross-shaped channels down the c axis, which accommodate a large number of solvent water molecules [residing in them] (Fig. 3).
A closer analysis reveals that an ordered one-dimensional water chain running along the channel is formed via the hydrogen-bonding associations among these water molecules. The geometric parameters of the water morphology are summarized in Table 2. The water chain features a centrosymmetric cyclic water hexameric unit with a chair-like conformation and with neighbouring hexamers linked together by a bridging H2O (Fig. 4). Characterization of such water hexamers has been theoretically and experimentally documented in the literature (Kim et al., 1998, 1999; Custelcean et al., 2000; Zhao et al., 2004). A striking feature of (I) is that the host perchlorate anions recognize and stabilize the guest water chain via three kinds of hydrogen-bond patterns, i.e. the Cl1O4 group acts as a single hydrogen-bond acceptor for one H2O, and the Cl2O4 group serves as double hydrogen-bond acceptors for two H2O, while the Cl3O4 group serves as double hydrogen-bond acceptors for only one H2O. The hydrogen-bonding associations of the one-dimensional water chain and these three types of perchlorate anions lead to the formation of a complicated one-dimensional {[(H2O)7.(ClO4)4]4-}n anion chain. Such an anion chain features three kinds of rings discussed here according to graph-set analysis nomenclature (Bernstein et al., 1995). The cyclic water hexamer can be specified as having an R66(12) pattern. The second ring, including five water molecules and one perchlorate anion, can be specified as having an R65(14) pattern, whereas the third ring, including one water molecule and one perchlorate anion, can be specified as having an R22(6) pattern. Overall, the alternate arrangement of the edge-shared R66(12) and R65(14) rings constitutes the extend[ed] one-dimensional structure, and the R22(6) rings are decorated on one side of the R65(14) rings via [in?] a corner-shared fashion whereas the non-cyclization perchlorate anions dangle on both sides of the R66(12) rings.
In summary, a novel one-dimensional water chain stabilized by three types of perchlorate anions is observed in (I), which provides a good example of how the water aggregations are influenced by the overall structure of their surroundings.