Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109002674/sk3286sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109002674/sk3286Isup2.hkl |
CCDC reference: 724196
For the synthesis of bis, a mixture of imidazole (3.4 g, 50 mmol) and NaOH (2.0 g, 50 mmol) in dimethyl sulfoxide (10 ml) was stirred at 333 K for 1 h, then 1,4-dichlorobutane (3.2 g, 25 mmol) was added. The mixture was cooled to room temperature after stirring at 333 K for 2 h, then poured into 200 ml of water. A white solid formed immediately, which weighted 3.6 g after drying in air.
For the synthesis of (I), a mixture of CdCl2.2.5H2O (0.114 g, 0.5 mmol), H2chdc (0.086 g, 0.5 mmol) and bis (0.095, 0.5 mmol) was dissolved in 12 ml of distilled water, and then triethylamine was added until the pH value of the system was adjusted to about 5.5. The resulting solution was stirred for about 1 h at room temperature, sealed in a 23 ml Teflon-lined stainless steel autoclave and heated at 425 K for 3 d under autogenous pressure. The reaction system was subsequently cooled slowly to room temperature. Colorless block crystals of (I) suitable for single-crystal X-ray diffraction analysis were collected from the final reaction system by filtration, washed several times with distilled water and dried in air at ambient temperature (yield 57% based on CdII).
C-bound H atoms were positioned geometrically (C—H = 0.93 and 0.97 Å) and refined as riding, with Uiso(H) fixed at 1.2Ueq(C). The water H atoms were located in a difference Fourier map and were refined with O—H and H···H distance restraints of 0.82 (3) and 1.36 (3) Å, respectively; their displacement parameters were tied to those of the parent atoms by a factor of 1.5.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008)); software used to prepare material for publication: publCIF (Westrip, 2009).
[Cd(C8H10O4)(C10H14N4)]·0.5H2O | F(000) = 980 |
Mr = 481.82 | Dx = 1.552 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3999 reflections |
a = 9.468 (4) Å | θ = 1.1–26.0° |
b = 12.339 (5) Å | µ = 1.09 mm−1 |
c = 17.817 (8) Å | T = 293 K |
β = 97.864 (6)° | Block, colorless |
V = 2061.8 (15) Å3 | 0.25 × 0.21 × 0.18 mm |
Z = 4 |
Bruker APEX diffractometer | 3999 independent reflections |
Radiation source: fine-focus sealed tube | 3391 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ϕ and ω scans | θmax = 26.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→11 |
Tmin = 0.755, Tmax = 0.821 | k = −15→14 |
11154 measured reflections | l = −21→16 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0423P)2 + 0.4711P] where P = (Fo2 + 2Fc2)/3 |
3999 reflections | (Δ/σ)max = 0.001 |
259 parameters | Δρmax = 0.57 e Å−3 |
4 restraints | Δρmin = −0.24 e Å−3 |
[Cd(C8H10O4)(C10H14N4)]·0.5H2O | V = 2061.8 (15) Å3 |
Mr = 481.82 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.468 (4) Å | µ = 1.09 mm−1 |
b = 12.339 (5) Å | T = 293 K |
c = 17.817 (8) Å | 0.25 × 0.21 × 0.18 mm |
β = 97.864 (6)° |
Bruker APEX diffractometer | 3999 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3391 reflections with I > 2σ(I) |
Tmin = 0.755, Tmax = 0.821 | Rint = 0.026 |
11154 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 4 restraints |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.57 e Å−3 |
3999 reflections | Δρmin = −0.24 e Å−3 |
259 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 > 2sigma(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) | |
C1 | 1.1390 (3) | −0.0285 (3) | 0.80746 (18) | 0.0399 (7) | |
H1 | 1.1430 | −0.0409 | 0.7563 | 0.048* | |
C2 | 1.0739 (3) | 0.0297 (3) | 0.91085 (18) | 0.0457 (8) | |
H2 | 1.0242 | 0.0659 | 0.9448 | 0.055* | |
C3 | 1.1876 (4) | −0.0359 (3) | 0.93002 (18) | 0.0458 (8) | |
H3 | 1.2296 | −0.0531 | 0.9788 | 0.055* | |
C4 | 1.3434 (3) | −0.1493 (3) | 0.8550 (2) | 0.0428 (8) | |
H4A | 1.3342 | −0.1729 | 0.8026 | 0.051* | |
H4B | 1.3329 | −0.2126 | 0.8861 | 0.051* | |
C5 | 1.4916 (3) | −0.1011 (3) | 0.87738 (19) | 0.0400 (7) | |
H5A | 1.5030 | −0.0793 | 0.9302 | 0.048* | |
H5B | 1.5030 | −0.0375 | 0.8469 | 0.048* | |
C6 | 1.6052 (3) | −0.1858 (3) | 0.86523 (19) | 0.0425 (8) | |
H6A | 1.5865 | −0.2520 | 0.8915 | 0.051* | |
H6B | 1.5984 | −0.2023 | 0.8116 | 0.051* | |
C7 | 1.7524 (4) | −0.1480 (3) | 0.8931 (2) | 0.0519 (9) | |
H7A | 1.7703 | −0.0812 | 0.8673 | 0.062* | |
H7B | 1.7592 | −0.1322 | 0.9468 | 0.062* | |
C8 | 1.9233 (4) | −0.3027 (3) | 0.9316 (2) | 0.0529 (9) | |
H8 | 1.9038 | −0.3130 | 0.9808 | 0.064* | |
C9 | 1.9195 (3) | −0.2421 (3) | 0.81756 (19) | 0.0427 (8) | |
H9 | 1.8949 | −0.2015 | 0.7737 | 0.051* | |
C10 | 2.0164 (4) | −0.3586 (3) | 0.89630 (19) | 0.0495 (9) | |
H10 | 2.0737 | −0.4148 | 0.9178 | 0.059* | |
C11 | 0.7527 (3) | 0.2311 (3) | 0.87430 (18) | 0.0404 (8) | |
C12 | 0.6999 (4) | 0.2971 (3) | 0.93664 (18) | 0.0510 (9) | |
H12 | 0.7580 | 0.2756 | 0.9841 | 0.061* | |
C13 | 0.5454 (4) | 0.2685 (3) | 0.9449 (2) | 0.0655 (11) | |
H13A | 0.5347 | 0.1904 | 0.9443 | 0.079* | |
H13B | 0.5241 | 0.2947 | 0.9935 | 0.079* | |
C14 | 0.4403 (4) | 0.3172 (3) | 0.8824 (2) | 0.0562 (10) | |
H14A | 0.3439 | 0.2988 | 0.8906 | 0.067* | |
H14B | 0.4565 | 0.2872 | 0.8340 | 0.067* | |
C15 | 0.4566 (4) | 0.4401 (3) | 0.88090 (19) | 0.0468 (8) | |
H15 | 0.4447 | 0.4657 | 0.9317 | 0.056* | |
C16 | 0.3455 (3) | 0.4993 (3) | 0.82619 (19) | 0.0433 (8) | |
C17 | 0.6080 (4) | 0.4689 (3) | 0.8693 (2) | 0.0538 (9) | |
H17A | 0.6191 | 0.5470 | 0.8709 | 0.065* | |
H17B | 0.6251 | 0.4442 | 0.8196 | 0.065* | |
C18 | 0.7180 (4) | 0.4180 (3) | 0.9294 (2) | 0.0616 (11) | |
H18A | 0.8126 | 0.4328 | 0.9168 | 0.074* | |
H18B | 0.7108 | 0.4517 | 0.9779 | 0.074* | |
N1 | 1.0436 (3) | 0.0345 (2) | 0.83359 (14) | 0.0391 (6) | |
N2 | 1.2285 (3) | −0.0718 (2) | 0.86376 (14) | 0.0361 (6) | |
N3 | 1.8632 (3) | −0.2279 (2) | 0.88104 (15) | 0.0410 (6) | |
N4 | 2.0147 (3) | −0.3208 (2) | 0.82413 (15) | 0.0402 (6) | |
O1 | 0.8117 (2) | 0.27688 (18) | 0.82333 (13) | 0.0481 (6) | |
O2 | 0.7399 (3) | 0.13002 (19) | 0.87639 (16) | 0.0589 (7) | |
O1W | 1.0816 (5) | 0.3499 (5) | 0.8937 (2) | 0.0533 (13) | 0.50 |
HW11 | 1.119 (7) | 0.375 (6) | 0.858 (3) | 0.080* | 0.50 |
HW12 | 1.003 (4) | 0.324 (6) | 0.875 (3) | 0.080* | 0.50 |
O3 | 0.2411 (3) | 0.4501 (2) | 0.79178 (14) | 0.0594 (7) | |
O4 | 0.3583 (3) | 0.5981 (2) | 0.81789 (19) | 0.0782 (10) | |
Cd1 | 0.85413 (2) | 0.114714 (17) | 0.763790 (12) | 0.03428 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0358 (17) | 0.051 (2) | 0.0328 (17) | 0.0069 (14) | 0.0028 (14) | −0.0048 (14) |
C2 | 0.0441 (19) | 0.055 (2) | 0.0389 (19) | 0.0157 (16) | 0.0077 (15) | −0.0038 (15) |
C3 | 0.049 (2) | 0.053 (2) | 0.0341 (18) | 0.0135 (16) | 0.0009 (15) | −0.0019 (15) |
C4 | 0.0351 (18) | 0.0407 (18) | 0.051 (2) | 0.0112 (14) | 0.0015 (15) | −0.0062 (15) |
C5 | 0.0313 (17) | 0.0393 (18) | 0.049 (2) | 0.0052 (13) | 0.0043 (14) | −0.0042 (14) |
C6 | 0.0355 (18) | 0.0431 (19) | 0.049 (2) | 0.0064 (14) | 0.0059 (15) | −0.0049 (15) |
C7 | 0.0382 (19) | 0.046 (2) | 0.073 (3) | 0.0082 (15) | 0.0099 (17) | −0.0148 (18) |
C8 | 0.053 (2) | 0.066 (2) | 0.041 (2) | 0.0147 (18) | 0.0103 (16) | 0.0046 (17) |
C9 | 0.0413 (18) | 0.0432 (19) | 0.0434 (19) | 0.0099 (15) | 0.0057 (15) | 0.0089 (15) |
C10 | 0.048 (2) | 0.056 (2) | 0.043 (2) | 0.0179 (17) | 0.0012 (16) | 0.0069 (16) |
C11 | 0.0317 (17) | 0.0426 (19) | 0.0449 (19) | 0.0128 (14) | −0.0024 (14) | 0.0015 (15) |
C12 | 0.054 (2) | 0.064 (2) | 0.0330 (18) | 0.0278 (18) | −0.0022 (15) | −0.0006 (16) |
C13 | 0.069 (3) | 0.072 (3) | 0.060 (2) | 0.035 (2) | 0.029 (2) | 0.025 (2) |
C14 | 0.038 (2) | 0.056 (2) | 0.077 (3) | 0.0133 (17) | 0.0176 (18) | 0.0234 (19) |
C15 | 0.049 (2) | 0.049 (2) | 0.0415 (19) | 0.0180 (16) | 0.0002 (15) | −0.0063 (15) |
C16 | 0.0372 (18) | 0.043 (2) | 0.049 (2) | 0.0104 (15) | 0.0020 (15) | −0.0051 (15) |
C17 | 0.043 (2) | 0.039 (2) | 0.075 (3) | 0.0078 (15) | −0.0067 (18) | −0.0062 (17) |
C18 | 0.054 (2) | 0.061 (2) | 0.064 (2) | 0.0221 (19) | −0.0124 (19) | −0.0210 (19) |
N1 | 0.0317 (14) | 0.0458 (16) | 0.0390 (15) | 0.0079 (12) | 0.0018 (11) | −0.0025 (12) |
N2 | 0.0288 (13) | 0.0394 (14) | 0.0394 (15) | 0.0079 (11) | 0.0023 (11) | −0.0030 (12) |
N3 | 0.0305 (14) | 0.0430 (16) | 0.0503 (17) | 0.0058 (11) | 0.0082 (12) | −0.0053 (12) |
N4 | 0.0331 (14) | 0.0445 (16) | 0.0424 (16) | 0.0068 (12) | 0.0032 (11) | 0.0005 (12) |
O1 | 0.0574 (15) | 0.0419 (13) | 0.0465 (14) | 0.0014 (11) | 0.0126 (11) | 0.0010 (10) |
O2 | 0.0667 (18) | 0.0427 (15) | 0.0729 (18) | 0.0092 (12) | 0.0299 (14) | 0.0045 (12) |
O1W | 0.030 (2) | 0.093 (4) | 0.037 (3) | −0.011 (3) | 0.008 (2) | 0.012 (3) |
O3 | 0.0550 (16) | 0.0496 (16) | 0.0669 (17) | −0.0052 (12) | −0.0149 (13) | 0.0098 (12) |
O4 | 0.0578 (17) | 0.0391 (16) | 0.124 (3) | 0.0078 (12) | −0.0364 (17) | 0.0052 (15) |
Cd1 | 0.02753 (14) | 0.03359 (14) | 0.04128 (15) | 0.00105 (9) | 0.00314 (9) | 0.00081 (9) |
C1—N1 | 1.323 (4) | C11—C12 | 1.516 (4) |
C1—N2 | 1.334 (4) | C11—Cd1 | 2.716 (3) |
C1—H1 | 0.9300 | C12—C18 | 1.509 (5) |
C2—C3 | 1.353 (4) | C12—C13 | 1.531 (5) |
C2—N1 | 1.369 (4) | C12—H12 | 0.9800 |
C2—H2 | 0.9300 | C13—C14 | 1.513 (5) |
C3—N2 | 1.366 (4) | C13—H13A | 0.9700 |
C3—H3 | 0.9300 | C13—H13B | 0.9700 |
C4—N2 | 1.473 (4) | C14—C15 | 1.525 (5) |
C4—C5 | 1.526 (4) | C14—H14A | 0.9700 |
C4—H4A | 0.9700 | C14—H14B | 0.9700 |
C4—H4B | 0.9700 | C15—C17 | 1.518 (5) |
C5—C6 | 1.536 (4) | C15—C16 | 1.520 (4) |
C5—H5A | 0.9700 | C15—H15 | 0.9800 |
C5—H5B | 0.9700 | C16—O4 | 1.236 (4) |
C6—C7 | 1.488 (5) | C16—O3 | 1.248 (4) |
C6—H6A | 0.9700 | C16—Cd1i | 2.709 (3) |
C6—H6B | 0.9700 | C17—C18 | 1.523 (5) |
C7—N3 | 1.477 (4) | C17—H17A | 0.9700 |
C7—H7A | 0.9700 | C17—H17B | 0.9700 |
C7—H7B | 0.9700 | C18—H18A | 0.9700 |
C8—C10 | 1.341 (5) | C18—H18B | 0.9700 |
C8—N3 | 1.359 (4) | O1W—HW11 | 0.838 (10) |
C8—H8 | 0.9300 | O1W—HW12 | 0.837 (8) |
C9—N4 | 1.320 (4) | Cd1—N1 | 2.265 (2) |
C9—N3 | 1.326 (4) | Cd1—N4ii | 2.272 (3) |
C9—H9 | 0.9300 | Cd1—O1 | 2.325 (2) |
C10—N4 | 1.365 (4) | Cd1—O2 | 2.414 (3) |
C10—H10 | 0.9300 | Cd1—O4iii | 2.325 (3) |
C11—O2 | 1.255 (4) | Cd1—O3iii | 2.382 (3) |
C11—O1 | 1.262 (4) | ||
N1—C1—N2 | 111.4 (3) | C13—C14—H14A | 109.6 |
N1—C1—H1 | 124.3 | C15—C14—H14A | 109.6 |
N2—C1—H1 | 124.3 | C13—C14—H14B | 109.6 |
C3—C2—N1 | 109.3 (3) | C15—C14—H14B | 109.6 |
C3—C2—H2 | 125.4 | H14A—C14—H14B | 108.1 |
N1—C2—H2 | 125.4 | C17—C15—C16 | 112.6 (3) |
C2—C3—N2 | 106.6 (3) | C17—C15—C14 | 109.6 (3) |
C2—C3—H3 | 126.7 | C16—C15—C14 | 115.3 (3) |
N2—C3—H3 | 126.7 | C17—C15—H15 | 106.3 |
N2—C4—C5 | 112.7 (3) | C16—C15—H15 | 106.3 |
N2—C4—H4A | 109.1 | C14—C15—H15 | 106.3 |
C5—C4—H4A | 109.1 | O4—C16—O3 | 120.4 (3) |
N2—C4—H4B | 109.1 | O4—C16—C15 | 118.7 (3) |
C5—C4—H4B | 109.1 | O3—C16—C15 | 120.9 (3) |
H4A—C4—H4B | 107.8 | O4—C16—Cd1i | 58.86 (18) |
C4—C5—C6 | 109.6 (3) | O3—C16—Cd1i | 61.54 (17) |
C4—C5—H5A | 109.8 | C15—C16—Cd1i | 176.1 (2) |
C6—C5—H5A | 109.8 | C15—C17—C18 | 112.1 (3) |
C4—C5—H5B | 109.8 | C15—C17—H17A | 109.2 |
C6—C5—H5B | 109.8 | C18—C17—H17A | 109.2 |
H5A—C5—H5B | 108.2 | C15—C17—H17B | 109.2 |
C7—C6—C5 | 112.4 (3) | C18—C17—H17B | 109.2 |
C7—C6—H6A | 109.1 | H17A—C17—H17B | 107.9 |
C5—C6—H6A | 109.1 | C12—C18—C17 | 113.1 (3) |
C7—C6—H6B | 109.1 | C12—C18—H18A | 109.0 |
C5—C6—H6B | 109.1 | C17—C18—H18A | 109.0 |
H6A—C6—H6B | 107.9 | C12—C18—H18B | 109.0 |
N3—C7—C6 | 113.2 (3) | C17—C18—H18B | 109.0 |
N3—C7—H7A | 108.9 | H18A—C18—H18B | 107.8 |
C6—C7—H7A | 108.9 | C1—N1—C2 | 105.6 (3) |
N3—C7—H7B | 108.9 | C1—N1—Cd1 | 126.2 (2) |
C6—C7—H7B | 108.9 | C2—N1—Cd1 | 127.8 (2) |
H7A—C7—H7B | 107.8 | C1—N2—C3 | 107.1 (3) |
C10—C8—N3 | 106.3 (3) | C1—N2—C4 | 125.7 (3) |
C10—C8—H8 | 126.8 | C3—N2—C4 | 127.1 (3) |
N3—C8—H8 | 126.8 | C9—N3—C8 | 107.1 (3) |
N4—C9—N3 | 111.8 (3) | C9—N3—C7 | 126.1 (3) |
N4—C9—H9 | 124.1 | C8—N3—C7 | 126.8 (3) |
N3—C9—H9 | 124.1 | C9—N4—C10 | 104.7 (3) |
C8—C10—N4 | 110.0 (3) | C9—N4—Cd1iv | 128.9 (2) |
C8—C10—H10 | 125.0 | C10—N4—Cd1iv | 126.3 (2) |
N4—C10—H10 | 125.0 | C11—O1—Cd1 | 93.70 (19) |
O2—C11—O1 | 121.3 (3) | C11—O2—Cd1 | 89.8 (2) |
O2—C11—C12 | 118.0 (3) | HW11—O1W—HW12 | 107 (3) |
O1—C11—C12 | 120.6 (3) | C16—O3—Cd1i | 91.0 (2) |
O2—C11—Cd1 | 62.68 (18) | C16—O4—Cd1i | 94.1 (2) |
O1—C11—Cd1 | 58.67 (17) | N1—Cd1—N4ii | 93.72 (10) |
C12—C11—Cd1 | 178.5 (2) | N1—Cd1—O4iii | 149.02 (9) |
C18—C12—C11 | 114.5 (3) | N4ii—Cd1—O4iii | 96.15 (11) |
C18—C12—C13 | 110.9 (3) | N1—Cd1—O1 | 107.38 (9) |
C11—C12—C13 | 111.2 (3) | N4ii—Cd1—O1 | 99.10 (9) |
C18—C12—H12 | 106.5 | O4iii—Cd1—O1 | 99.95 (9) |
C11—C12—H12 | 106.5 | N1—Cd1—O3iii | 94.69 (9) |
C13—C12—H12 | 106.5 | N4ii—Cd1—O3iii | 102.91 (10) |
C14—C13—C12 | 112.3 (3) | O4iii—Cd1—O3iii | 54.48 (9) |
C14—C13—H13A | 109.2 | O1—Cd1—O3iii | 147.59 (9) |
C12—C13—H13A | 109.2 | N1—Cd1—O2 | 89.38 (9) |
C14—C13—H13B | 109.2 | N4ii—Cd1—O2 | 153.55 (9) |
C12—C13—H13B | 109.2 | O4iii—Cd1—O2 | 94.55 (12) |
H13A—C13—H13B | 107.9 | O1—Cd1—O2 | 55.14 (8) |
C13—C14—C15 | 110.4 (3) | O3iii—Cd1—O2 | 103.00 (9) |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+3, y+1/2, −z+3/2; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+3, y−1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—HW11···O3v | 0.84 (1) | 1.98 (2) | 2.803 (5) | 166 (6) |
O1W—HW12···O1 | 0.84 (1) | 2.00 (1) | 2.835 (5) | 173 (6) |
Symmetry code: (v) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C8H10O4)(C10H14N4)]·0.5H2O |
Mr | 481.82 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.468 (4), 12.339 (5), 17.817 (8) |
β (°) | 97.864 (6) |
V (Å3) | 2061.8 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.09 |
Crystal size (mm) | 0.25 × 0.21 × 0.18 |
Data collection | |
Diffractometer | Bruker APEX diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.755, 0.821 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11154, 3999, 3391 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.081, 1.04 |
No. of reflections | 3999 |
No. of parameters | 259 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.57, −0.24 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008)), publCIF (Westrip, 2009).
Cd1—N1 | 2.265 (2) | Cd1—O2 | 2.414 (3) |
Cd1—N4i | 2.272 (3) | Cd1—O4ii | 2.325 (3) |
Cd1—O1 | 2.325 (2) | Cd1—O3ii | 2.382 (3) |
N1—Cd1—N4i | 93.72 (10) | O4ii—Cd1—O3ii | 54.48 (9) |
N1—Cd1—O4ii | 149.02 (9) | O1—Cd1—O3ii | 147.59 (9) |
N4i—Cd1—O4ii | 96.15 (11) | N1—Cd1—O2 | 89.38 (9) |
N1—Cd1—O1 | 107.38 (9) | N4i—Cd1—O2 | 153.55 (9) |
N4i—Cd1—O1 | 99.10 (9) | O4ii—Cd1—O2 | 94.55 (12) |
O4ii—Cd1—O1 | 99.95 (9) | O1—Cd1—O2 | 55.14 (8) |
N1—Cd1—O3ii | 94.69 (9) | O3ii—Cd1—O2 | 103.00 (9) |
N4i—Cd1—O3ii | 102.91 (10) |
Symmetry codes: (i) −x+3, y+1/2, −z+3/2; (ii) −x+1, y−1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—HW11···O3iii | 0.838 (10) | 1.982 (18) | 2.803 (5) | 166 (6) |
O1W—HW12···O1 | 0.837 (8) | 2.001 (9) | 2.835 (5) | 173 (6) |
Symmetry code: (iii) x+1, y, z. |
The design and synthesis of coordination polymers with infinite two- and three-dimensional networks have been an area of rapid growth in recent years because of the potential of these polymers in various applications, such as catalysis, electrical conductivity, host–guest chemistry and magnetism (Eddaoudi et al., 2001; Moulton et al., 2003). Generally, the topology of a coordination polymer can often be controlled and modified by selecting the coordination geometry preferred by the metal ion and the chemical structure of the organic ligand chosen (Carlucci et al., 2003; Hsu et al., 2008). It is well known that long ligands will lead to larger voids that may result in interpenetrated structures (Yang et al., 2008). Therefore, flexible dicarboxylate and long bidentate N-donor ligands with these characteristics are excellent candidates for the construction of interpenetrating networks (Batten, 2001). The cyclohexane-1,4-dicarboxylate dianion (chdc2-) is an example of a dianion with a flexible conformation (Yang et al., 2007). The H2chdc ligand has three possible conformations: a,a-trans-, e,e-trans-, and e,a-cis-H2chdc. Usually, the e,e-trans form is thermodynamically more stable than the e,a-cis form because of the presence of two equatorial substituents in the latter, and the a,a-trans form is the least stable owing to 1,3-diaxial hindrance. So far, the coordination polymers resulting from adduct formation with a rigid bidentate N-donor ligand, such as, for example, 2,5-bis(4-pyridyl)-1,3,4-oxadiazole, adopt layer structures, as observed for the copper (Du et al., 2005) adduct. On the other hand, flexible bidentate N-donor ligands in place of rigid spacers have been known to yield three-dimensional network structures, particularly if the spacer ligands are both flexible and long (Ockwig et al., 2005). In the present study, 1,1'-(butane-1,4-diyl)diimidazole (bis) assembles with cadmium cyclohexane-1,4-dicarboxylate (chdc2-) to furnish a 1:1 adduct, [Cd(bis)(cis-chdc)].0.5H2O, (I), which exists as an unusual twofold interpenetrating (4,4)-network.
Selected bond lengths and angles for (I) are given in Table 1. As shown in Fig. 1, the asymmetric unit of (I) contains one CdII atom, one cis-chdc2- anion, one bis ligand and half a free water molecule. Each CdII atom lies on a center of symmetry and is six-coordinated in a distorted octahedral environment surrounded by four carboxylate O atoms from two different chdc2- anions and two N atoms from two distinct bis ligands. The average Cd—O and Cd—N distances in (I) (Table 1) are comparable to those observed for [Cd4(1,4-bix)4(bpea)4].4H2O [1,4-bix is 1,4-bis(imidazol-1-ylmethyl)benzene and H2bpea is biphenylethene-4,4'-dicarboxylic acid; Yang et al., 2008]. As depicted in Fig. 2, each CdII center is bridged by the chdc2- dianions and bis ligands to give a two-dimensional four-connected (4,4)-network (Ma, Liu, Liu et al., 2000). The networks are parallel with the (001) plane. The two (4,4)-networks are further interpenetrated in an unusual parallel mode. It should be pointed out that the driving force for the formation of this unusual topology becomes apparent when the structure of (I) is examined in detail. The O1W molecule, as the donor, forms a hydrogen bond with carboxylate atom O3iii [symmetry code: (iii) x + 1, y, z; Table 2]. The O—Hwater···Ocarboxylate hydrogen bonds observed in the network consolidate the interpenetrating nets of (I).
It is noteworthy that the structure of (I) is entirely different from that of the related structure [Mn(bis)(BF4)2] (Duncan et al., 1996). This reported complex is composed of two equivalent, mutually interpenetrating three-dimensional networks. The structure of (I) is also entirely different from that of the related polymer [Zn(bis)1.5(H2O)(SO4)].6H2O (Ma, Liu, Xing et al., 2000). In that structure, the networks are interpenetrated in an inclined mode by symmetry-related, identical networks to give an interlocked three-dimensional structure.
Over the past decade, interpenetrating structures have received much attention in coordination chemistry and materials chemistry because of their importantance in advanced materials (Batten & Robson, 1998). Consequently, many interpenetrating structures have been generated by self-assembly processes. To the best of our knowledge, the reported (4,4)-networks interpenetrated in parallel mode are usually constructed by only one type of ligand. Compound (I) is the first two-dimensional parallel interpenetrating (4,4)-network structure based on flexible dicarboxylate and long bidentate N-donor ligands.