Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105028751/hj1069sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105028751/hj1069Isup2.hkl |
CCDC reference: 290557
H4L was purchased from TCI and used without further purification. Compound (I) was synthesized hydrothermally under autogenous pressure. A mixture of Cd(CH3COO)2·3H2O (0.303 g, 1 mmol), H4L (0.330 g, 1 mmol), 4,4'-bpy (0.312 g, 2 mmol) and NaOH (0.080 g, 2 mmol) was stirred for 20 min and then sealed in a Parr Teflon-lined stainless steel vessel, which was heated to 443 K for 72 h. After slow cooling to ambient temperature, colorless block-shaped crystals of (I) were separated mechanically from the powder and washed with distilled water (yield ca 70% based on Cd). The compound is insoluble in common organic solvents and water. Analysis found: C 57.3, H 3.3, N 7.5%; C36H24.70CdN4O8.35 requires: C 56.9, H 3.28, N 7.38%.
All H atoms on C and O atoms were positioned geometrically and refined as riding atoms [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C); O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O)]. The water molecule O9W was refined freely with a site occupancy of 0.35, and the attached H atoms were not located.
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).
[Cd(C16H8O8)(C10H8N2)2]·0.35H2O | F(000) = 1534 |
Mr = 759.34 | Dx = 1.661 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
a = 12.101 (5) Å | Cell parameters from 18569 reflections |
b = 24.379 (5) Å | θ = 1.7–28.2° |
c = 10.679 (5) Å | µ = 0.79 mm−1 |
β = 105.413 (5)° | T = 298 K |
V = 3037 (2) Å3 | BLOCK, colorless |
Z = 4 | 0.35 × 0.26 × 0.25 mm |
Rigaku R-AXIS RAPID diffractometer | 7162 independent reflections |
Radiation source: fine-focus sealed tube | 3097 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.084 |
Detector resolution: 10.0 pixels mm-1 | θmax = 28.3°, θmin = 1.7° |
ω scans | h = −7→15 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −32→32 |
Tmin = 0.784, Tmax = 0.828 | l = −14→14 |
18797 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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 0.96 | w = 1/[σ2(Fo2) + (0.036P)2] where P = (Fo2 + 2Fc2)/3 |
7162 reflections | (Δ/σ)max = 0.074 |
454 parameters | Δρmax = 0.62 e Å−3 |
0 restraints | Δρmin = −0.64 e Å−3 |
[Cd(C16H8O8)(C10H8N2)2]·0.35H2O | V = 3037 (2) Å3 |
Mr = 759.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.101 (5) Å | µ = 0.79 mm−1 |
b = 24.379 (5) Å | T = 298 K |
c = 10.679 (5) Å | 0.35 × 0.26 × 0.25 mm |
β = 105.413 (5)° |
Rigaku R-AXIS RAPID diffractometer | 7162 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 3097 reflections with I > 2σ(I) |
Tmin = 0.784, Tmax = 0.828 | Rint = 0.084 |
18797 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.62 e Å−3 |
7162 reflections | Δρmin = −0.64 e Å−3 |
454 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 | Occ. (<1) | |
Cd1 | 0.90990 (4) | 0.548869 (16) | 0.60887 (4) | 0.03137 (14) | |
C1 | 1.0949 (5) | 0.6760 (2) | 1.4369 (5) | 0.0304 (14) | |
C2 | 1.0549 (5) | 0.7268 (2) | 1.3886 (5) | 0.0448 (18) | |
H2 | 1.0795 | 0.7578 | 1.4392 | 0.054* | |
C3 | 0.9787 (5) | 0.7331 (2) | 1.2663 (5) | 0.0422 (17) | |
H3 | 0.9539 | 0.7680 | 1.2366 | 0.051* | |
C4 | 0.9392 (5) | 0.6878 (2) | 1.1881 (5) | 0.0291 (14) | |
C5 | 0.9756 (5) | 0.6367 (2) | 1.2385 (5) | 0.0324 (15) | |
H5 | 0.9482 | 0.6059 | 1.1884 | 0.039* | |
C6 | 1.0511 (4) | 0.6291 (2) | 1.3603 (5) | 0.0274 (13) | |
C7 | 0.8585 (5) | 0.6924 (2) | 1.0572 (5) | 0.0283 (14) | |
C8 | 0.7753 (5) | 0.7341 (2) | 1.0308 (5) | 0.0327 (14) | |
H8 | 0.7734 | 0.7605 | 1.0932 | 0.039* | |
C9 | 0.6961 (5) | 0.7353 (2) | 0.9099 (5) | 0.0333 (14) | |
H9 | 0.6398 | 0.7623 | 0.8931 | 0.040* | |
C10 | 0.6981 (4) | 0.69732 (19) | 0.8129 (4) | 0.0221 (13) | |
C11 | 0.7827 (4) | 0.65735 (19) | 0.8388 (4) | 0.0220 (12) | |
C12 | 0.8607 (4) | 0.6557 (2) | 0.9592 (5) | 0.0268 (13) | |
H12 | 0.9171 | 0.6287 | 0.9752 | 0.032* | |
C13 | 1.1896 (5) | 0.6733 (2) | 1.5605 (6) | 0.0377 (16) | |
C14 | 1.0722 (4) | 0.5717 (2) | 1.4110 (5) | 0.0270 (14) | |
C15 | 0.8039 (5) | 0.6169 (2) | 0.7439 (5) | 0.0270 (13) | |
C16 | 0.6056 (5) | 0.7008 (2) | 0.6875 (5) | 0.0321 (14) | |
C17 | 0.7529 (5) | 0.6151 (2) | 0.3680 (5) | 0.0369 (15) | |
H17 | 0.7763 | 0.6435 | 0.4274 | 0.044* | |
C18 | 0.6844 (5) | 0.6275 (2) | 0.2476 (5) | 0.0356 (15) | |
H18 | 0.6615 | 0.6636 | 0.2276 | 0.043* | |
C19 | 0.6489 (4) | 0.5873 (2) | 0.1559 (5) | 0.0296 (14) | |
C20 | 0.6880 (5) | 0.5345 (2) | 0.1924 (5) | 0.0410 (16) | |
H20 | 0.6682 | 0.5058 | 0.1332 | 0.049* | |
C21 | 0.7553 (5) | 0.5245 (2) | 0.3145 (5) | 0.0429 (17) | |
H21 | 0.7797 | 0.4888 | 0.3364 | 0.051* | |
C22 | 0.4290 (5) | 0.6514 (2) | −0.1220 (6) | 0.0413 (16) | |
H22 | 0.3800 | 0.6815 | −0.1356 | 0.050* | |
C23 | 0.5006 (5) | 0.6435 (2) | 0.0005 (5) | 0.0369 (15) | |
H23 | 0.4994 | 0.6680 | 0.0668 | 0.044* | |
C24 | 0.5742 (4) | 0.5991 (2) | 0.0249 (5) | 0.0307 (14) | |
C25 | 0.5737 (5) | 0.5661 (2) | −0.0790 (5) | 0.0468 (18) | |
H25 | 0.6236 | 0.5365 | −0.0686 | 0.056* | |
C26 | 0.4990 (6) | 0.5767 (3) | −0.2002 (5) | 0.0531 (19) | |
H26 | 0.5004 | 0.5536 | −0.2690 | 0.064* | |
C27 | 1.1061 (5) | 0.6123 (2) | 0.8243 (5) | 0.0387 (16) | |
H27 | 1.0912 | 0.6367 | 0.7550 | 0.046* | |
C28 | 1.1770 (5) | 0.6288 (2) | 0.9425 (5) | 0.0404 (16) | |
H28 | 1.2088 | 0.6638 | 0.9508 | 0.049* | |
C29 | 1.2016 (5) | 0.5933 (2) | 1.0503 (5) | 0.0346 (15) | |
C30 | 1.1529 (5) | 0.5417 (2) | 1.0296 (5) | 0.0358 (15) | |
H30 | 1.1682 | 0.5162 | 1.0967 | 0.043* | |
C31 | 1.0820 (5) | 0.5281 (2) | 0.9106 (5) | 0.0399 (16) | |
H31 | 1.0482 | 0.4935 | 0.9004 | 0.048* | |
C32 | 1.3739 (6) | 0.6798 (3) | 1.3239 (6) | 0.0543 (19) | |
H32 | 1.3801 | 0.7167 | 1.3471 | 0.065* | |
C33 | 1.2930 (5) | 0.6650 (2) | 1.2125 (6) | 0.0471 (18) | |
H33 | 1.2460 | 0.6915 | 1.1625 | 0.056* | |
C34 | 1.2818 (5) | 0.6106 (2) | 1.1748 (5) | 0.0336 (15) | |
C35 | 1.3503 (5) | 0.5734 (3) | 1.2578 (6) | 0.056 (2) | |
H35 | 1.3427 | 0.5360 | 1.2407 | 0.067* | |
C36 | 1.4301 (6) | 0.5924 (3) | 1.3663 (6) | 0.064 (2) | |
H36 | 1.4776 | 0.5668 | 1.4191 | 0.077* | |
N1 | 0.4260 (4) | 0.6184 (2) | −0.2217 (4) | 0.0401 (13) | |
N2 | 0.7880 (4) | 0.56398 (17) | 0.4049 (4) | 0.0336 (12) | |
N3 | 1.0585 (4) | 0.56275 (19) | 0.8063 (4) | 0.0353 (13) | |
N4 | 1.4438 (4) | 0.6443 (2) | 1.4004 (5) | 0.0520 (15) | |
O1 | 1.2580 (4) | 0.63062 (17) | 1.5593 (3) | 0.0488 (12) | |
H1 | 1.2774 | 0.6169 | 1.6320 | 0.073* | |
O2 | 1.2042 (4) | 0.70631 (16) | 1.6440 (4) | 0.0557 (13) | |
O3 | 1.0579 (3) | 0.55962 (14) | 1.5182 (3) | 0.0407 (10) | |
O4 | 1.0988 (3) | 0.53745 (14) | 1.3326 (3) | 0.0462 (11) | |
O5 | 0.7839 (3) | 0.56738 (14) | 0.7515 (3) | 0.0367 (10) | |
O6 | 0.8586 (3) | 0.63558 (13) | 0.6660 (3) | 0.0330 (9) | |
O7 | 0.6062 (3) | 0.65876 (16) | 0.6114 (4) | 0.0406 (10) | |
H7 | 0.5494 | 0.6599 | 0.5492 | 0.061* | |
O8 | 0.5368 (3) | 0.73779 (15) | 0.6628 (3) | 0.0471 (12) | |
O9W | 0.3789 (16) | 0.4901 (9) | 0.4412 (19) | 0.167 (12) | 0.352 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0390 (3) | 0.0299 (2) | 0.0213 (2) | 0.0065 (3) | 0.00110 (17) | −0.0009 (2) |
C1 | 0.037 (4) | 0.023 (3) | 0.025 (3) | −0.002 (3) | −0.003 (3) | −0.004 (2) |
C2 | 0.057 (5) | 0.028 (3) | 0.037 (4) | −0.002 (3) | −0.009 (4) | −0.005 (3) |
C3 | 0.067 (5) | 0.016 (3) | 0.032 (3) | 0.004 (3) | −0.009 (3) | 0.005 (3) |
C4 | 0.034 (4) | 0.027 (3) | 0.023 (3) | 0.000 (3) | 0.000 (3) | 0.000 (3) |
C5 | 0.039 (4) | 0.029 (3) | 0.025 (3) | 0.001 (3) | 0.001 (3) | −0.007 (3) |
C6 | 0.031 (3) | 0.031 (3) | 0.021 (3) | 0.010 (3) | 0.007 (3) | 0.003 (2) |
C7 | 0.034 (4) | 0.019 (3) | 0.025 (3) | 0.004 (3) | −0.004 (3) | 0.005 (2) |
C8 | 0.047 (4) | 0.030 (3) | 0.021 (3) | 0.004 (3) | 0.009 (3) | −0.007 (2) |
C9 | 0.035 (4) | 0.028 (3) | 0.034 (3) | 0.013 (3) | 0.003 (3) | 0.007 (3) |
C10 | 0.030 (3) | 0.023 (3) | 0.013 (3) | 0.001 (3) | 0.005 (3) | 0.001 (2) |
C11 | 0.029 (3) | 0.018 (3) | 0.020 (3) | 0.001 (3) | 0.010 (3) | −0.001 (2) |
C12 | 0.034 (3) | 0.027 (3) | 0.021 (3) | 0.013 (3) | 0.010 (3) | −0.001 (2) |
C13 | 0.042 (4) | 0.034 (4) | 0.033 (4) | 0.002 (3) | 0.003 (3) | 0.014 (3) |
C14 | 0.020 (3) | 0.025 (3) | 0.030 (3) | 0.003 (2) | −0.002 (3) | 0.001 (3) |
C15 | 0.029 (3) | 0.035 (4) | 0.015 (3) | 0.008 (3) | 0.002 (3) | 0.004 (2) |
C16 | 0.031 (4) | 0.041 (4) | 0.020 (3) | −0.003 (3) | 0.000 (3) | 0.003 (3) |
C17 | 0.046 (4) | 0.034 (4) | 0.027 (3) | −0.001 (3) | 0.002 (3) | −0.002 (3) |
C18 | 0.043 (4) | 0.035 (3) | 0.026 (3) | 0.003 (3) | 0.003 (3) | 0.003 (3) |
C19 | 0.022 (3) | 0.041 (4) | 0.023 (3) | −0.001 (3) | 0.000 (3) | 0.003 (3) |
C20 | 0.046 (4) | 0.037 (4) | 0.031 (3) | 0.005 (3) | −0.005 (3) | −0.009 (3) |
C21 | 0.058 (5) | 0.040 (4) | 0.025 (3) | 0.009 (3) | 0.001 (3) | −0.003 (3) |
C22 | 0.037 (4) | 0.044 (4) | 0.044 (4) | 0.005 (3) | 0.013 (3) | 0.013 (3) |
C23 | 0.033 (4) | 0.042 (4) | 0.033 (3) | −0.003 (3) | 0.003 (3) | 0.002 (3) |
C24 | 0.026 (4) | 0.034 (3) | 0.028 (3) | −0.001 (3) | 0.001 (3) | 0.003 (3) |
C25 | 0.045 (4) | 0.055 (4) | 0.035 (4) | 0.014 (3) | −0.001 (3) | 0.001 (3) |
C26 | 0.069 (5) | 0.054 (4) | 0.024 (3) | −0.002 (4) | −0.009 (3) | −0.004 (3) |
C27 | 0.039 (4) | 0.038 (4) | 0.032 (3) | 0.001 (3) | −0.003 (3) | 0.010 (3) |
C28 | 0.038 (4) | 0.030 (3) | 0.044 (4) | −0.008 (3) | −0.006 (3) | 0.002 (3) |
C29 | 0.028 (4) | 0.042 (4) | 0.028 (3) | 0.000 (3) | −0.003 (3) | −0.006 (3) |
C30 | 0.040 (4) | 0.037 (4) | 0.024 (3) | 0.001 (3) | −0.002 (3) | 0.004 (3) |
C31 | 0.041 (4) | 0.033 (3) | 0.039 (4) | −0.012 (3) | −0.001 (3) | −0.006 (3) |
C32 | 0.058 (5) | 0.056 (4) | 0.045 (4) | −0.012 (4) | 0.006 (4) | −0.024 (4) |
C33 | 0.046 (4) | 0.043 (4) | 0.043 (4) | −0.003 (3) | −0.005 (3) | −0.012 (3) |
C34 | 0.029 (4) | 0.040 (4) | 0.030 (3) | −0.003 (3) | 0.004 (3) | −0.008 (3) |
C35 | 0.063 (5) | 0.046 (4) | 0.042 (4) | 0.010 (4) | −0.015 (4) | −0.016 (3) |
C36 | 0.052 (5) | 0.082 (6) | 0.047 (5) | 0.020 (4) | −0.009 (4) | −0.008 (4) |
N1 | 0.037 (3) | 0.049 (3) | 0.027 (3) | 0.002 (3) | −0.003 (2) | 0.013 (2) |
N2 | 0.040 (3) | 0.030 (3) | 0.026 (3) | 0.009 (2) | 0.002 (2) | 0.004 (2) |
N3 | 0.028 (3) | 0.044 (3) | 0.027 (3) | 0.001 (2) | −0.004 (2) | 0.000 (2) |
N4 | 0.038 (4) | 0.072 (4) | 0.042 (3) | −0.004 (3) | 0.004 (3) | −0.016 (3) |
O1 | 0.051 (3) | 0.056 (3) | 0.027 (2) | 0.005 (2) | −0.013 (2) | −0.001 (2) |
O2 | 0.073 (3) | 0.045 (3) | 0.033 (3) | −0.001 (2) | −0.013 (2) | −0.017 (2) |
O3 | 0.045 (3) | 0.051 (3) | 0.026 (2) | 0.002 (2) | 0.0086 (19) | 0.0175 (19) |
O4 | 0.070 (3) | 0.026 (2) | 0.035 (2) | 0.011 (2) | 0.003 (2) | −0.0014 (18) |
O5 | 0.051 (3) | 0.024 (2) | 0.037 (2) | −0.0006 (19) | 0.016 (2) | −0.0049 (17) |
O6 | 0.040 (2) | 0.030 (2) | 0.028 (2) | 0.0034 (19) | 0.0047 (19) | −0.0062 (17) |
O7 | 0.033 (3) | 0.048 (3) | 0.033 (2) | 0.000 (2) | −0.0053 (19) | −0.008 (2) |
O8 | 0.045 (3) | 0.044 (3) | 0.041 (2) | 0.016 (2) | −0.009 (2) | 0.004 (2) |
O9W | 0.143 (19) | 0.22 (3) | 0.14 (2) | −0.036 (16) | 0.044 (15) | 0.014 (16) |
Cd1—O4i | 2.206 (3) | C19—C20 | 1.392 (7) |
Cd1—O3ii | 2.266 (4) | C19—C24 | 1.477 (6) |
Cd1—N2 | 2.312 (4) | C20—C21 | 1.363 (7) |
Cd1—O6 | 2.330 (3) | C20—H20 | 0.9300 |
Cd1—N3 | 2.404 (4) | C21—N2 | 1.345 (6) |
Cd1—O5 | 2.466 (4) | C21—H21 | 0.9300 |
C1—C2 | 1.378 (7) | C22—N1 | 1.327 (7) |
C1—C6 | 1.424 (6) | C22—C23 | 1.377 (7) |
C1—C13 | 1.503 (7) | C22—H22 | 0.9300 |
C2—C3 | 1.393 (7) | C23—C24 | 1.382 (7) |
C2—H2 | 0.9300 | C23—H23 | 0.9300 |
C3—C4 | 1.390 (6) | C24—C25 | 1.369 (7) |
C3—H3 | 0.9300 | C25—C26 | 1.391 (7) |
C4—C5 | 1.384 (6) | C25—H25 | 0.9300 |
C4—C7 | 1.482 (6) | C26—N1 | 1.325 (7) |
C5—C6 | 1.389 (6) | C26—H26 | 0.9300 |
C5—H5 | 0.9300 | C27—N3 | 1.330 (6) |
C6—C14 | 1.497 (7) | C27—C28 | 1.384 (7) |
C7—C12 | 1.384 (6) | C27—H27 | 0.9300 |
C7—C8 | 1.405 (7) | C28—C29 | 1.407 (7) |
C8—C9 | 1.389 (6) | C28—H28 | 0.9300 |
C8—H8 | 0.9300 | C29—C30 | 1.382 (7) |
C9—C10 | 1.395 (6) | C29—C34 | 1.484 (7) |
C9—H9 | 0.9300 | C30—C31 | 1.372 (6) |
C10—C11 | 1.387 (6) | C30—H30 | 0.9300 |
C10—C16 | 1.502 (6) | C31—N3 | 1.366 (6) |
C11—C12 | 1.378 (6) | C31—H31 | 0.9300 |
C11—C15 | 1.484 (7) | C32—N4 | 1.329 (7) |
C12—H12 | 0.9300 | C32—C33 | 1.373 (7) |
C13—O2 | 1.180 (6) | C32—H32 | 0.9300 |
C13—O1 | 1.330 (6) | C33—C34 | 1.381 (7) |
C14—O3 | 1.238 (6) | C33—H33 | 0.9300 |
C14—O4 | 1.284 (6) | C34—C35 | 1.381 (7) |
C15—O5 | 1.238 (6) | C35—C36 | 1.377 (8) |
C15—O6 | 1.277 (6) | C35—H35 | 0.9300 |
C16—O8 | 1.208 (6) | C36—N4 | 1.313 (8) |
C16—O7 | 1.310 (6) | C36—H36 | 0.9300 |
C17—N2 | 1.343 (6) | O1—H1 | 0.8200 |
C17—C18 | 1.366 (6) | O3—Cd1iii | 2.266 (4) |
C17—H17 | 0.9300 | O4—Cd1i | 2.206 (3) |
C18—C19 | 1.371 (7) | O7—H7 | 0.8200 |
C18—H18 | 0.9300 | ||
O4i—Cd1—O3ii | 109.54 (14) | C18—C19—C20 | 116.3 (5) |
O4i—Cd1—N2 | 110.63 (14) | C18—C19—C24 | 122.3 (5) |
O3ii—Cd1—N2 | 87.58 (15) | C20—C19—C24 | 121.4 (5) |
O4i—Cd1—O6 | 139.04 (14) | C21—C20—C19 | 120.3 (5) |
O3ii—Cd1—O6 | 107.63 (13) | C21—C20—H20 | 119.9 |
N2—Cd1—O6 | 87.38 (13) | C19—C20—H20 | 119.9 |
O4i—Cd1—N3 | 88.09 (15) | N2—C21—C20 | 123.1 (5) |
O3ii—Cd1—N3 | 82.34 (15) | N2—C21—H21 | 118.4 |
N2—Cd1—N3 | 160.90 (15) | C20—C21—H21 | 118.4 |
O6—Cd1—N3 | 80.33 (13) | N1—C22—C23 | 123.6 (6) |
O4i—Cd1—O5 | 85.14 (14) | N1—C22—H22 | 118.2 |
O3ii—Cd1—O5 | 158.62 (12) | C23—C22—H22 | 118.2 |
N2—Cd1—O5 | 102.03 (15) | C24—C23—C22 | 120.0 (6) |
O6—Cd1—O5 | 54.60 (12) | C24—C23—H23 | 120.0 |
N3—Cd1—O5 | 82.73 (14) | C22—C23—H23 | 120.0 |
C2—C1—C6 | 117.8 (5) | C25—C24—C23 | 116.3 (5) |
C2—C1—C13 | 118.7 (5) | C25—C24—C19 | 121.6 (5) |
C6—C1—C13 | 123.3 (5) | C23—C24—C19 | 122.1 (5) |
C1—C2—C3 | 122.0 (5) | C24—C25—C26 | 120.5 (6) |
C1—C2—H2 | 119.0 | C24—C25—H25 | 119.8 |
C3—C2—H2 | 119.0 | C26—C25—H25 | 119.8 |
C4—C3—C2 | 120.8 (5) | N1—C26—C25 | 122.8 (6) |
C4—C3—H3 | 119.6 | N1—C26—H26 | 118.6 |
C2—C3—H3 | 119.6 | C25—C26—H26 | 118.6 |
C5—C4—C3 | 117.4 (5) | N3—C27—C28 | 122.4 (5) |
C5—C4—C7 | 119.8 (5) | N3—C27—H27 | 118.8 |
C3—C4—C7 | 122.8 (5) | C28—C27—H27 | 118.8 |
C4—C5—C6 | 123.1 (5) | C27—C28—C29 | 120.7 (5) |
C4—C5—H5 | 118.5 | C27—C28—H28 | 119.6 |
C6—C5—H5 | 118.5 | C29—C28—H28 | 119.6 |
C5—C6—C1 | 118.9 (5) | C30—C29—C28 | 116.2 (5) |
C5—C6—C14 | 117.9 (5) | C30—C29—C34 | 123.5 (5) |
C1—C6—C14 | 122.8 (4) | C28—C29—C34 | 120.2 (5) |
C12—C7—C8 | 118.3 (5) | C31—C30—C29 | 120.2 (5) |
C12—C7—C4 | 121.6 (5) | C31—C30—H30 | 119.9 |
C8—C7—C4 | 120.1 (5) | C29—C30—H30 | 119.9 |
C9—C8—C7 | 118.8 (5) | N3—C31—C30 | 123.2 (5) |
C9—C8—H8 | 120.6 | N3—C31—H31 | 118.4 |
C7—C8—H8 | 120.6 | C30—C31—H31 | 118.4 |
C8—C9—C10 | 122.2 (5) | N4—C32—C33 | 123.5 (6) |
C8—C9—H9 | 118.9 | N4—C32—H32 | 118.2 |
C10—C9—H9 | 118.9 | C33—C32—H32 | 118.2 |
C9—C10—C11 | 118.4 (4) | C32—C33—C34 | 119.8 (6) |
C9—C10—C16 | 118.0 (5) | C32—C33—H33 | 120.1 |
C11—C10—C16 | 123.6 (5) | C34—C33—H33 | 120.1 |
C12—C11—C10 | 119.6 (4) | C35—C34—C33 | 116.6 (5) |
C12—C11—C15 | 114.6 (4) | C35—C34—C29 | 121.7 (5) |
C10—C11—C15 | 125.6 (4) | C33—C34—C29 | 121.6 (5) |
C11—C12—C7 | 122.7 (5) | C36—C35—C34 | 119.1 (6) |
C11—C12—H12 | 118.7 | C36—C35—H35 | 120.5 |
C7—C12—H12 | 118.7 | C34—C35—H35 | 120.5 |
O2—C13—O1 | 124.9 (6) | N4—C36—C35 | 124.5 (6) |
O2—C13—C1 | 124.0 (6) | N4—C36—H36 | 117.8 |
O1—C13—C1 | 111.0 (5) | C35—C36—H36 | 117.8 |
O3—C14—O4 | 124.7 (5) | C26—N1—C22 | 116.8 (5) |
O3—C14—C6 | 120.3 (5) | C17—N2—C21 | 116.3 (4) |
O4—C14—C6 | 114.9 (5) | C17—N2—Cd1 | 119.8 (3) |
O5—C15—O6 | 122.3 (5) | C21—N2—Cd1 | 123.7 (4) |
O5—C15—C11 | 122.1 (5) | C27—N3—C31 | 117.1 (4) |
O6—C15—C11 | 115.0 (5) | C27—N3—Cd1 | 116.7 (3) |
O8—C16—O7 | 124.5 (5) | C31—N3—Cd1 | 124.9 (4) |
O8—C16—C10 | 123.0 (5) | C36—N4—C32 | 116.4 (5) |
O7—C16—C10 | 112.5 (5) | C13—O1—H1 | 109.5 |
N2—C17—C18 | 123.1 (5) | C14—O3—Cd1iii | 138.0 (3) |
N2—C17—H17 | 118.4 | C14—O4—Cd1i | 113.4 (3) |
C18—C17—H17 | 118.4 | C15—O5—Cd1 | 88.6 (3) |
C17—C18—C19 | 120.8 (5) | C15—O6—Cd1 | 93.9 (3) |
C17—C18—H18 | 119.6 | C16—O7—H7 | 109.5 |
C19—C18—H18 | 119.6 | ||
C6—C1—C2—C3 | −3.2 (9) | C27—C28—C29—C34 | 177.3 (5) |
C13—C1—C2—C3 | 171.1 (6) | C28—C29—C30—C31 | −2.1 (8) |
C1—C2—C3—C4 | 0.4 (10) | C34—C29—C30—C31 | −178.1 (5) |
C2—C3—C4—C5 | 2.1 (9) | C29—C30—C31—N3 | 2.3 (9) |
C2—C3—C4—C7 | −179.8 (6) | N4—C32—C33—C34 | −0.3 (10) |
C3—C4—C5—C6 | −1.9 (9) | C32—C33—C34—C35 | 3.5 (9) |
C7—C4—C5—C6 | −180.0 (5) | C32—C33—C34—C29 | −175.4 (6) |
C4—C5—C6—C1 | −1.0 (9) | C30—C29—C34—C35 | 27.7 (9) |
C4—C5—C6—C14 | 172.2 (5) | C28—C29—C34—C35 | −148.2 (6) |
C2—C1—C6—C5 | 3.5 (8) | C30—C29—C34—C33 | −153.5 (6) |
C13—C1—C6—C5 | −170.6 (5) | C28—C29—C34—C33 | 30.6 (9) |
C2—C1—C6—C14 | −169.4 (5) | C33—C34—C35—C36 | −4.5 (10) |
C13—C1—C6—C14 | 16.5 (9) | C29—C34—C35—C36 | 174.4 (6) |
C5—C4—C7—C12 | −33.1 (8) | C34—C35—C36—N4 | 2.6 (11) |
C3—C4—C7—C12 | 148.8 (6) | C25—C26—N1—C22 | 1.9 (9) |
C5—C4—C7—C8 | 145.4 (6) | C23—C22—N1—C26 | −1.8 (9) |
C3—C4—C7—C8 | −32.6 (8) | C18—C17—N2—C21 | 2.2 (9) |
C12—C7—C8—C9 | 2.7 (8) | C18—C17—N2—Cd1 | 177.5 (4) |
C4—C7—C8—C9 | −175.9 (5) | C20—C21—N2—C17 | −1.4 (9) |
C7—C8—C9—C10 | −1.6 (8) | C20—C21—N2—Cd1 | −176.6 (4) |
C8—C9—C10—C11 | −0.3 (8) | O4i—Cd1—N2—C17 | 159.2 (4) |
C8—C9—C10—C16 | 177.6 (5) | O3ii—Cd1—N2—C17 | −90.9 (4) |
C9—C10—C11—C12 | 1.0 (7) | O6—Cd1—N2—C17 | 16.9 (4) |
C16—C10—C11—C12 | −176.7 (5) | N3—Cd1—N2—C17 | −32.8 (8) |
C9—C10—C11—C15 | −174.4 (5) | O5—Cd1—N2—C17 | 69.9 (4) |
C16—C10—C11—C15 | 8.0 (8) | O4i—Cd1—N2—C21 | −25.8 (5) |
C10—C11—C12—C7 | 0.2 (8) | O3ii—Cd1—N2—C21 | 84.1 (5) |
C15—C11—C12—C7 | 176.0 (5) | O6—Cd1—N2—C21 | −168.1 (5) |
C8—C7—C12—C11 | −2.1 (8) | N3—Cd1—N2—C21 | 142.1 (5) |
C4—C7—C12—C11 | 176.5 (5) | O5—Cd1—N2—C21 | −115.1 (4) |
C2—C1—C13—O2 | 29.8 (9) | C28—C27—N3—C31 | 0.3 (9) |
C6—C1—C13—O2 | −156.2 (6) | C28—C27—N3—Cd1 | 168.1 (4) |
C2—C1—C13—O1 | −146.5 (6) | C30—C31—N3—C27 | −1.3 (9) |
C6—C1—C13—O1 | 27.5 (8) | C30—C31—N3—Cd1 | −168.0 (4) |
C5—C6—C14—O3 | −125.5 (6) | O4i—Cd1—N3—C27 | 177.1 (4) |
C1—C6—C14—O3 | 47.5 (8) | O3ii—Cd1—N3—C27 | 67.1 (4) |
C5—C6—C14—O4 | 50.9 (7) | N2—Cd1—N3—C27 | 8.3 (8) |
C1—C6—C14—O4 | −136.2 (5) | O6—Cd1—N3—C27 | −42.4 (4) |
C12—C11—C15—O5 | 73.8 (7) | O5—Cd1—N3—C27 | −97.6 (4) |
C10—C11—C15—O5 | −110.6 (6) | O4i—Cd1—N3—C31 | −16.2 (5) |
C12—C11—C15—O6 | −96.8 (5) | O3ii—Cd1—N3—C31 | −126.2 (5) |
C10—C11—C15—O6 | 78.8 (7) | N2—Cd1—N3—C31 | 175.1 (4) |
C9—C10—C16—O8 | 7.1 (8) | O6—Cd1—N3—C31 | 124.4 (5) |
C11—C10—C16—O8 | −175.2 (5) | O5—Cd1—N3—C31 | 69.2 (5) |
C9—C10—C16—O7 | −170.8 (5) | C35—C36—N4—C32 | 0.7 (11) |
C11—C10—C16—O7 | 6.9 (7) | C33—C32—N4—C36 | −1.9 (10) |
N2—C17—C18—C19 | −1.0 (9) | O4—C14—O3—Cd1iii | −105.3 (6) |
C17—C18—C19—C20 | −0.9 (8) | C6—C14—O3—Cd1iii | 70.7 (7) |
C17—C18—C19—C24 | 179.6 (5) | O3—C14—O4—Cd1i | 9.4 (7) |
C18—C19—C20—C21 | 1.6 (9) | C6—C14—O4—Cd1i | −166.8 (3) |
C24—C19—C20—C21 | −178.9 (5) | O6—C15—O5—Cd1 | 8.3 (5) |
C19—C20—C21—N2 | −0.5 (10) | C11—C15—O5—Cd1 | −161.6 (4) |
N1—C22—C23—C24 | −0.3 (9) | O4i—Cd1—O5—C15 | 167.3 (3) |
C22—C23—C24—C25 | 2.4 (8) | O3ii—Cd1—O5—C15 | 32.5 (5) |
C22—C23—C24—C19 | −177.1 (5) | N2—Cd1—O5—C15 | −82.6 (3) |
C18—C19—C24—C25 | 154.9 (6) | O6—Cd1—O5—C15 | −4.7 (3) |
C20—C19—C24—C25 | −24.5 (8) | N3—Cd1—O5—C15 | 78.6 (3) |
C18—C19—C24—C23 | −25.7 (8) | O5—C15—O6—Cd1 | −8.8 (5) |
C20—C19—C24—C23 | 154.9 (6) | C11—C15—O6—Cd1 | 161.8 (4) |
C23—C24—C25—C26 | −2.3 (9) | O4i—Cd1—O6—C15 | −7.7 (4) |
C19—C24—C25—C26 | 177.2 (5) | O3ii—Cd1—O6—C15 | −162.1 (3) |
C24—C25—C26—N1 | 0.2 (10) | N2—Cd1—O6—C15 | 111.3 (3) |
N3—C27—C28—C29 | −0.2 (9) | N3—Cd1—O6—C15 | −83.4 (3) |
C27—C28—C29—C30 | 1.1 (9) | O5—Cd1—O6—C15 | 4.6 (3) |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) x, y, z−1; (iii) x, y, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1iv | 0.82 | 2.04 | 2.677 (6) | 134 |
O7—H7···N4v | 0.82 | 1.80 | 2.590 (6) | 163 |
Symmetry codes: (iv) x+1, y, z+2; (v) x−1, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C16H8O8)(C10H8N2)2]·0.35H2O |
Mr | 759.34 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 12.101 (5), 24.379 (5), 10.679 (5) |
β (°) | 105.413 (5) |
V (Å3) | 3037 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.79 |
Crystal size (mm) | 0.35 × 0.26 × 0.25 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.784, 0.828 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18797, 7162, 3097 |
Rint | 0.084 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.115, 0.96 |
No. of reflections | 7162 |
No. of parameters | 454 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.62, −0.64 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1i | 0.82 | 2.04 | 2.677 (6) | 134 |
O7—H7···N4ii | 0.82 | 1.80 | 2.590 (6) | 163 |
Symmetry codes: (i) x+1, y, z+2; (ii) x−1, y, z−1. |
The metal carboxylate coordination polymers have emerged as an important family in the past few years (Rao et al., 2004). It is also well known that the incorporation of carboxylic acid groups into coordination compounds gives interesting supramolecular architectures (Puddephatt et al., 2002). Multifunctional carboxylates and related species provide an effective means of designing novel hybrid structures with porous and other properties (Yaghi et al., 2003; Kitagawa et al., 2004). In some of these structures, the carboxylate acts as a linker between two inorganic units. The biphenyl-3,3',4,4'-tetracarboxylic acid ligand (H4L) has multifunctional possibilities: (a) it has four carboxyl groups that may be completely or partially deprotonated; (b) it can act not only as a hydrogen-bond acceptor but also as a hydrogen-bond donor, depending on the number of deprotonated carboxyl groups; (c) some of the carboxyl groups can be rotated out of the plane of the benzene ring upon complexation as a result of steric effects; thus the ligand may connect metal ions in three dimensions; (d) it is a flexible ligand. To the best of our knowledge, the crystal structure of a metal complex with the H4L ligand has not been reported previously, although there are several crystal structures of complexes with analogous (but rigid) ligands, viz. terephthalic acid (Shi et al., 2005), benzene-1,3,5-tricarboxylic acid (Rosi et al., 2002; Li et al., 1999; Millange et al., 2002; Kepert & Rosseinsky, 1998), benzene-1,2,4,5-tetracarboxylic acid (Shi et al., 2001, 2005; Cao et al., 2002; Hou et al., 2004), biphenyl-4,4'-dicarboxylic acid (Shi et al., 2005; Pan et al., 2003; Dai et al., 2004; Mukherjee et al., 2004; Shiu et al., 2003) and its analogs. However, the H4L coordination geometry is very different from those of the rigid ligands above because of the flexibility of its four carboxyl groups. We report here the preparation and crystal structure of a novel one-dimensional coordination polymer, formulated {[Cd(H2L)(4,4'-bpy)2]·0.35H2O}n (4,4'-bpy is 4,4'-bipyridine), (I).
Single-crystal X-ray diffraction reveals that (I) is an extended broad zonal one-dimensional chain based on ring dimer building blocks constructed from two Cd atoms, two H2L2− ligands and four 4,4'-bpy ligands. Each CdII atom is six-coordinate (Fig. 1), with two O atoms donated by one chelating bidentate H2L2− ligand, two from two separate bridging bidentate H2L2− ligands and two N atoms [Cd1—N2 = 2.312 (4) and Cd1—N3 = 2.404 (4) Å] from two 4,4'-bpy ligands, which, unusualy, act as monodentate (not bridging bidentate) ligands. The four Cd1—Ocarboxyl distances fall in the range 2.206 (3)–2.466 (4) Å and the O—Cd1—O angles vary from 54.6 (1) to 85.1 (1)°. The bond lengths and angles of Cd—Ocarboxyl are similar to those in other cadmium–carboxylate coordination polymers (Shi et al., 2005) with the Cd center displaying the typical distorted octahedral coordination geometry (Table 1). The H2L2− ligands exhibit an interesting connection mode with the metal ions, which is different from those in the other reported analogous ligands (Shi et al., 2001, 2005). As shown in the scheme and Fig. 1, three types of coordination modes of H2L2− ligands are present in the structure, viz. (a) two carboxylate groups (C13 and C16) are not deprotonated and remain free [C13—O2 = 1.180 (6) Å, C13—O1 = 1.330 (6) Å, C16—O8 = 1.208 (6) Å and C16—O7 = 1.310 (6) Å]; (b) one carboxylate group (C15) adopts a bidentate chelating mode, chelating one CdII atom; (c) another carboxylate group (C14) adopts a bidentate bridging mode, connecting two CdII atoms. Each H2L2− ligand acts as a tetradentate ligand coordinating to three CdII atoms. Two Cd atom, two H2L2− and four 4,4'-bpy ligands act as a ring dimer node (see Fig. 2). Nodes are connected through Cd1—O4i and O4—Cd1i bonds [symmetry code: (i) 2 − x, 1 − y, 2 − z] into an extended broad zonal one-dimensional chain along the c axis (see Fig. 3).
In the packing arrangement of (I) (see Fig. 4), adjacent one-dimensional chains are parallel to each other and associate into a two-dimensional supermolecular layer via hydrogen bonds between the N atoms of 4,4'-bpy and the free carboxyl groups of the H2L2− ligands (Table 2). Note that atom H1 bonded to carboxylic atom O1 could not be located in the final difference Fourier map and was instead included in an idealized position. The water molecule O9W was refined with a site occupancy of 0.35 and the H atoms attached to atom O9W were not located.