Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112044587/em3052sup1.cif | |
MDL mol file https://doi.org/10.1107/S0108270112044587/em3052Isup2.mol | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112044587/em3052Isup3.hkl |
CCDC reference: 915088
For related literature, see: Blatov (2007); Chen et al. (2010); Dai et al. (2010); Forster & Cheetham (2002); He et al. (2010); Kong et al. (2008); Li et al. (2010, 2011); Liu et al. (2010); Ma et al. (2011); Sun et al. (2010); Sun, Liu, Huang & Zheng (2011); Sun, Luo, Zhang, Huang & Zheng (2011); Sun, Wang, Han, Zhang, Huang & Zheng (2011); Tao et al. (2012); Wang et al. (2011); Yin et al. (2012); Zhang et al. (2011); Zhao et al. (2011); Zheng et al. (2011).
A solution of H2TMBDC (4 mg, 0.010 mmol) in cyclohexanol and toluene (0.5 ml, 1:1 v:v) was layered onto an aqueous solution (0.5 ml) of Cd(NO3)2.4H2O (6 mg, 0.020 mmol) and 18-crown-6 (1 mg, 0.004 mmol), and 2 drops of pyridine were added. The solution was sealed in a glass tube and heated to 403 K for 5 h, kept at 403 K for 72 h, then slowly cooled to 303 K over 10 h. Colourless block-shaped crystals of (I) were collected (yield 48%).
C-bound H atoms were placed geometrically and treated as riding on their parent atoms, with C—H = 0.96 (methyl), 0.97 (methenyl) or 0.93 Å (aromatic), and with Uiso(H) = 1.2Ueq(C). The H atoms of the water molecule were located in a difference map and then included in the model as riding, with O—H = 0.85 Å and Uiso(H) = 1.2Ueq(O).
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
[Cd(C25H22O4)(C5H5N)(H2O)] | F(000) = 2432 |
Mr = 595.94 | Dx = 1.491 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 40.058 (4) Å | Cell parameters from 4106 reflections |
b = 5.9102 (5) Å | θ = 4.5–53.6° |
c = 24.142 (2) Å | µ = 0.86 mm−1 |
β = 111.723 (1)° | T = 298 K |
V = 5309.8 (8) Å3 | Block, colourless |
Z = 8 | 0.10 × 0.10 × 0.08 mm |
Bruker SMART APEXII CCD area-detector diffractometer | 6029 independent reflections |
Radiation source: fine-focus sealed tube | 4415 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ω and ϕ scans | θmax = 27.5°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −50→51 |
Tmin = 0.919, Tmax = 0.934 | k = −7→7 |
14990 measured reflections | l = −31→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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0287P)2 + 1.6485P] where P = (Fo2 + 2Fc2)/3 |
6029 reflections | (Δ/σ)max = 0.003 |
337 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
[Cd(C25H22O4)(C5H5N)(H2O)] | V = 5309.8 (8) Å3 |
Mr = 595.94 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 40.058 (4) Å | µ = 0.86 mm−1 |
b = 5.9102 (5) Å | T = 298 K |
c = 24.142 (2) Å | 0.10 × 0.10 × 0.08 mm |
β = 111.723 (1)° |
Bruker SMART APEXII CCD area-detector diffractometer | 6029 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 4415 reflections with I > 2σ(I) |
Tmin = 0.919, Tmax = 0.934 | Rint = 0.031 |
14990 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.48 e Å−3 |
6029 reflections | Δρmin = −0.29 e Å−3 |
337 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 | ||
Cd1 | 0.712203 (5) | 0.41631 (3) | 1.028794 (8) | 0.03501 (7) | |
C1 | 0.71592 (6) | 0.2840 (5) | 0.90723 (11) | 0.0394 (6) | |
C2 | 0.68222 (6) | 0.3377 (4) | 0.85560 (10) | 0.0350 (6) | |
C3 | 0.66517 (7) | 0.5452 (5) | 0.85087 (11) | 0.0433 (7) | |
H3 | 0.6738 | 0.6502 | 0.8816 | 0.052* | |
C4 | 0.63537 (7) | 0.5963 (5) | 0.80056 (12) | 0.0462 (7) | |
H4 | 0.6239 | 0.7350 | 0.7981 | 0.055* | |
C5 | 0.62239 (7) | 0.4438 (5) | 0.75390 (11) | 0.0407 (6) | |
C6 | 0.63862 (7) | 0.2353 (5) | 0.76003 (12) | 0.0490 (7) | |
H6 | 0.6295 | 0.1279 | 0.7300 | 0.059* | |
C7 | 0.66839 (7) | 0.1832 (5) | 0.81039 (12) | 0.0463 (7) | |
H7 | 0.6791 | 0.0417 | 0.8136 | 0.056* | |
C8 | 0.59218 (8) | 0.5106 (5) | 0.69607 (13) | 0.0549 (8) | |
H8A | 0.5749 | 0.6018 | 0.7056 | 0.066* | |
H8B | 0.6021 | 0.6037 | 0.6728 | 0.066* | |
C9 | 0.57273 (7) | 0.3103 (5) | 0.65829 (11) | 0.0445 (7) | |
C10 | 0.58113 (7) | 0.2381 (6) | 0.61010 (12) | 0.0499 (7) | |
C11 | 0.56298 (8) | 0.0547 (6) | 0.57769 (12) | 0.0576 (8) | |
H11 | 0.5688 | 0.0053 | 0.5458 | 0.069* | |
C12 | 0.53656 (8) | −0.0595 (5) | 0.59015 (12) | 0.0512 (7) | |
C13 | 0.52838 (7) | 0.0098 (5) | 0.63866 (12) | 0.0467 (7) | |
C14 | 0.54686 (7) | 0.1937 (5) | 0.67331 (12) | 0.0453 (7) | |
C15 | 0.53877 (8) | 0.2679 (6) | 0.72702 (13) | 0.0680 (9) | |
H15A | 0.5414 | 0.1413 | 0.7532 | 0.102* | |
H15B | 0.5146 | 0.3241 | 0.7142 | 0.102* | |
H15C | 0.5552 | 0.3853 | 0.7478 | 0.102* | |
C16 | 0.60921 (9) | 0.3562 (7) | 0.59200 (16) | 0.0812 (12) | |
H16A | 0.6011 | 0.5060 | 0.5781 | 0.122* | |
H16B | 0.6128 | 0.2721 | 0.5607 | 0.122* | |
H16C | 0.6314 | 0.3650 | 0.6257 | 0.122* | |
C17 | 0.51738 (9) | −0.2554 (6) | 0.55088 (15) | 0.0763 (11) | |
H17A | 0.5230 | −0.3930 | 0.5736 | 0.114* | |
H17B | 0.5251 | −0.2673 | 0.5177 | 0.114* | |
H17C | 0.4919 | −0.2300 | 0.5364 | 0.114* | |
C18 | 0.49866 (7) | −0.1080 (5) | 0.65219 (14) | 0.0576 (8) | |
H18A | 0.5044 | −0.1028 | 0.6949 | 0.069* | |
H18B | 0.4981 | −0.2658 | 0.6409 | 0.069* | |
C19 | 0.46135 (7) | −0.0082 (5) | 0.62091 (12) | 0.0439 (7) | |
C20 | 0.43140 (7) | −0.1317 (5) | 0.61823 (14) | 0.0527 (8) | |
H20 | 0.4344 | −0.2732 | 0.6363 | 0.063* | |
C21 | 0.39694 (7) | −0.0480 (5) | 0.58901 (13) | 0.0512 (7) | |
H21 | 0.3772 | −0.1354 | 0.5867 | 0.061* | |
C22 | 0.39184 (6) | 0.1647 (4) | 0.56331 (11) | 0.0372 (6) | |
C23 | 0.42143 (7) | 0.2881 (5) | 0.56611 (12) | 0.0470 (7) | |
H23 | 0.4184 | 0.4312 | 0.5489 | 0.056* | |
C24 | 0.45580 (7) | 0.2023 (5) | 0.59427 (13) | 0.0520 (8) | |
H24 | 0.4755 | 0.2881 | 0.5952 | 0.062* | |
C25 | 0.35503 (7) | 0.2602 (5) | 0.53201 (11) | 0.0388 (6) | |
C26 | 0.71673 (10) | 0.5108 (7) | 1.16252 (15) | 0.0721 (10) | |
H26 | 0.7287 | 0.6354 | 1.1552 | 0.087* | |
C27 | 0.71442 (11) | 0.4934 (8) | 1.21776 (17) | 0.0815 (11) | |
H27 | 0.7241 | 0.6047 | 1.2465 | 0.098* | |
C28 | 0.69805 (13) | 0.3143 (9) | 1.22914 (19) | 0.0921 (13) | |
H28 | 0.6968 | 0.2951 | 1.2666 | 0.111* | |
C29 | 0.68310 (14) | 0.1588 (8) | 1.1853 (2) | 0.1049 (15) | |
H29 | 0.6709 | 0.0343 | 1.1920 | 0.126* | |
C30 | 0.68627 (11) | 0.1886 (6) | 1.13040 (17) | 0.0766 (11) | |
H30 | 0.6761 | 0.0818 | 1.1006 | 0.092* | |
N1 | 0.70310 (7) | 0.3622 (4) | 1.11923 (11) | 0.0536 (6) | |
O1 | 0.72884 (5) | 0.4313 (3) | 0.94771 (8) | 0.0491 (5) | |
O1W | 0.71470 (5) | 0.7930 (3) | 1.04106 (8) | 0.0523 (5) | |
H1WA | 0.7335 | 0.8425 | 1.0367 | 0.063* | |
H1WB | 0.6962 | 0.8524 | 1.0150 | 0.063* | |
O2 | 0.73032 (5) | 0.0959 (4) | 0.90692 (8) | 0.0566 (6) | |
O3 | 0.35118 (5) | 0.4644 (3) | 0.51865 (9) | 0.0511 (5) | |
O4 | 0.32799 (5) | 0.1295 (3) | 0.51925 (9) | 0.0490 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.02656 (10) | 0.03547 (11) | 0.03684 (11) | −0.00178 (9) | 0.00455 (7) | 0.00330 (9) |
C1 | 0.0254 (13) | 0.0599 (19) | 0.0297 (13) | −0.0040 (13) | 0.0064 (10) | 0.0067 (13) |
C2 | 0.0256 (12) | 0.0459 (15) | 0.0294 (13) | −0.0022 (11) | 0.0054 (10) | 0.0020 (11) |
C3 | 0.0432 (16) | 0.0453 (17) | 0.0357 (14) | 0.0006 (13) | 0.0078 (12) | −0.0033 (12) |
C4 | 0.0421 (15) | 0.0416 (16) | 0.0482 (16) | 0.0109 (13) | 0.0090 (13) | 0.0025 (13) |
C5 | 0.0295 (13) | 0.0468 (17) | 0.0372 (14) | 0.0018 (12) | 0.0025 (11) | 0.0064 (12) |
C6 | 0.0425 (16) | 0.0475 (17) | 0.0402 (15) | 0.0059 (14) | −0.0042 (12) | −0.0071 (13) |
C7 | 0.0397 (15) | 0.0411 (16) | 0.0446 (16) | 0.0116 (13) | −0.0003 (12) | −0.0027 (13) |
C8 | 0.0418 (17) | 0.0608 (19) | 0.0476 (17) | 0.0080 (14) | −0.0005 (14) | 0.0133 (15) |
C9 | 0.0249 (13) | 0.0616 (18) | 0.0338 (14) | 0.0071 (13) | −0.0047 (11) | 0.0083 (13) |
C10 | 0.0273 (14) | 0.077 (2) | 0.0372 (15) | 0.0051 (15) | 0.0024 (12) | 0.0143 (15) |
C11 | 0.0432 (17) | 0.089 (3) | 0.0342 (15) | 0.0190 (18) | 0.0069 (13) | 0.0062 (16) |
C12 | 0.0372 (15) | 0.0577 (19) | 0.0437 (16) | 0.0123 (15) | −0.0025 (12) | 0.0052 (14) |
C13 | 0.0243 (13) | 0.0602 (18) | 0.0453 (16) | 0.0127 (12) | 0.0007 (12) | 0.0163 (14) |
C14 | 0.0274 (14) | 0.0647 (19) | 0.0369 (15) | 0.0114 (13) | 0.0038 (11) | 0.0077 (14) |
C15 | 0.0530 (19) | 0.097 (3) | 0.058 (2) | 0.003 (2) | 0.0242 (16) | −0.002 (2) |
C16 | 0.059 (2) | 0.121 (3) | 0.066 (2) | −0.003 (2) | 0.0268 (18) | 0.022 (2) |
C17 | 0.069 (2) | 0.069 (2) | 0.065 (2) | 0.009 (2) | −0.0048 (18) | −0.0049 (19) |
C18 | 0.0349 (15) | 0.061 (2) | 0.067 (2) | 0.0097 (14) | 0.0069 (14) | 0.0207 (16) |
C19 | 0.0279 (14) | 0.0470 (16) | 0.0505 (17) | 0.0028 (12) | 0.0069 (12) | 0.0056 (13) |
C20 | 0.0361 (15) | 0.0425 (17) | 0.070 (2) | 0.0010 (13) | 0.0087 (14) | 0.0143 (14) |
C21 | 0.0294 (14) | 0.0479 (18) | 0.071 (2) | −0.0051 (13) | 0.0120 (13) | 0.0076 (15) |
C22 | 0.0250 (13) | 0.0388 (14) | 0.0416 (15) | 0.0006 (11) | 0.0050 (11) | −0.0036 (11) |
C23 | 0.0313 (14) | 0.0430 (17) | 0.0590 (18) | 0.0007 (13) | 0.0077 (13) | 0.0099 (14) |
C24 | 0.0256 (14) | 0.0537 (19) | 0.068 (2) | −0.0054 (13) | 0.0080 (13) | 0.0127 (15) |
C25 | 0.0296 (13) | 0.0435 (16) | 0.0395 (14) | 0.0002 (12) | 0.0083 (11) | −0.0063 (12) |
C26 | 0.078 (3) | 0.082 (3) | 0.061 (2) | −0.012 (2) | 0.031 (2) | 0.001 (2) |
C27 | 0.088 (3) | 0.102 (3) | 0.061 (2) | 0.001 (2) | 0.035 (2) | −0.005 (2) |
C28 | 0.111 (3) | 0.112 (4) | 0.079 (3) | 0.017 (3) | 0.065 (3) | 0.013 (3) |
C29 | 0.141 (4) | 0.100 (3) | 0.110 (4) | −0.016 (3) | 0.088 (3) | 0.018 (3) |
C30 | 0.098 (3) | 0.068 (2) | 0.084 (3) | −0.012 (2) | 0.057 (2) | 0.003 (2) |
N1 | 0.0551 (16) | 0.0588 (17) | 0.0503 (15) | −0.0023 (13) | 0.0236 (12) | 0.0066 (12) |
O1 | 0.0406 (11) | 0.0654 (13) | 0.0322 (10) | −0.0227 (10) | 0.0029 (8) | 0.0012 (9) |
O1W | 0.0306 (10) | 0.0381 (11) | 0.0775 (14) | −0.0007 (9) | 0.0076 (9) | 0.0106 (10) |
O2 | 0.0352 (10) | 0.0798 (16) | 0.0429 (11) | 0.0201 (11) | 0.0007 (8) | 0.0016 (10) |
O3 | 0.0306 (10) | 0.0409 (12) | 0.0698 (13) | 0.0028 (8) | 0.0047 (9) | 0.0016 (10) |
O4 | 0.0260 (9) | 0.0425 (11) | 0.0675 (13) | −0.0023 (8) | 0.0044 (9) | −0.0065 (9) |
Cd1—O1W | 2.2431 (19) | C16—H16B | 0.9600 |
Cd1—O2i | 2.2516 (18) | C16—H16C | 0.9600 |
Cd1—O1 | 2.2913 (18) | C17—H17A | 0.9600 |
Cd1—O4ii | 2.3302 (18) | C17—H17B | 0.9600 |
Cd1—N1 | 2.365 (2) | C17—H17C | 0.9600 |
Cd1—O3ii | 2.3846 (18) | C18—C19 | 1.522 (4) |
C1—O2 | 1.254 (3) | C18—H18A | 0.9700 |
C1—O1 | 1.267 (3) | C18—H18B | 0.9700 |
C1—C2 | 1.494 (3) | C19—C24 | 1.380 (4) |
C2—C7 | 1.373 (3) | C19—C20 | 1.385 (4) |
C2—C3 | 1.387 (4) | C20—C21 | 1.388 (4) |
C3—C4 | 1.385 (4) | C20—H20 | 0.9300 |
C3—H3 | 0.9300 | C21—C22 | 1.383 (4) |
C4—C5 | 1.385 (4) | C21—H21 | 0.9300 |
C4—H4 | 0.9300 | C22—C23 | 1.372 (3) |
C5—C6 | 1.376 (4) | C22—C25 | 1.496 (3) |
C5—C8 | 1.523 (3) | C23—C24 | 1.386 (4) |
C6—C7 | 1.386 (3) | C23—H23 | 0.9300 |
C6—H6 | 0.9300 | C24—H24 | 0.9300 |
C7—H7 | 0.9300 | C25—O3 | 1.244 (3) |
C8—C9 | 1.521 (4) | C25—O4 | 1.272 (3) |
C8—H8A | 0.9700 | C25—Cd1ii | 2.708 (3) |
C8—H8B | 0.9700 | C26—N1 | 1.319 (4) |
C9—C10 | 1.393 (4) | C26—C27 | 1.375 (5) |
C9—C14 | 1.400 (4) | C26—H26 | 0.9300 |
C10—C11 | 1.377 (4) | C27—C28 | 1.326 (6) |
C10—C16 | 1.519 (4) | C27—H27 | 0.9300 |
C11—C12 | 1.379 (4) | C28—C29 | 1.362 (6) |
C11—H11 | 0.9300 | C28—H28 | 0.9300 |
C12—C13 | 1.390 (4) | C29—C30 | 1.388 (5) |
C12—C17 | 1.513 (4) | C29—H29 | 0.9300 |
C13—C14 | 1.403 (4) | C30—N1 | 1.309 (4) |
C13—C18 | 1.516 (4) | C30—H30 | 0.9300 |
C14—C15 | 1.513 (4) | O1W—H1WA | 0.8501 |
C15—H15A | 0.9600 | O1W—H1WB | 0.8498 |
C15—H15B | 0.9600 | O2—Cd1i | 2.2516 (18) |
C15—H15C | 0.9600 | O3—Cd1ii | 2.3846 (18) |
C16—H16A | 0.9600 | O4—Cd1ii | 2.3302 (17) |
O1W—Cd1—O2i | 87.51 (7) | H15B—C15—H15C | 109.5 |
O1W—Cd1—O1 | 93.53 (7) | C10—C16—H16A | 109.5 |
O2i—Cd1—O1 | 92.50 (7) | C10—C16—H16B | 109.5 |
O1W—Cd1—O4ii | 140.95 (6) | H16A—C16—H16B | 109.5 |
O2i—Cd1—O4ii | 131.43 (7) | C10—C16—H16C | 109.5 |
O1—Cd1—O4ii | 88.21 (7) | H16A—C16—H16C | 109.5 |
O1W—Cd1—N1 | 91.54 (8) | H16B—C16—H16C | 109.5 |
O2i—Cd1—N1 | 80.04 (8) | C12—C17—H17A | 109.5 |
O1—Cd1—N1 | 170.79 (8) | C12—C17—H17B | 109.5 |
O4ii—Cd1—N1 | 92.69 (8) | H17A—C17—H17B | 109.5 |
O1W—Cd1—O3ii | 86.14 (6) | C12—C17—H17C | 109.5 |
O2i—Cd1—O3ii | 165.98 (7) | H17A—C17—H17C | 109.5 |
O1—Cd1—O3ii | 100.35 (7) | H17B—C17—H17C | 109.5 |
O4ii—Cd1—O3ii | 55.31 (6) | C13—C18—C19 | 114.9 (2) |
N1—Cd1—O3ii | 87.65 (8) | C13—C18—H18A | 108.5 |
O2—C1—O1 | 123.8 (2) | C19—C18—H18A | 108.5 |
O2—C1—C2 | 117.3 (2) | C13—C18—H18B | 108.5 |
O1—C1—C2 | 118.9 (3) | C19—C18—H18B | 108.5 |
C7—C2—C3 | 118.7 (2) | H18A—C18—H18B | 107.5 |
C7—C2—C1 | 119.8 (2) | C24—C19—C20 | 117.8 (2) |
C3—C2—C1 | 121.4 (2) | C24—C19—C18 | 122.6 (2) |
C4—C3—C2 | 120.2 (3) | C20—C19—C18 | 119.6 (2) |
C4—C3—H3 | 119.9 | C19—C20—C21 | 121.1 (3) |
C2—C3—H3 | 119.9 | C19—C20—H20 | 119.4 |
C3—C4—C5 | 120.9 (3) | C21—C20—H20 | 119.4 |
C3—C4—H4 | 119.6 | C22—C21—C20 | 120.4 (3) |
C5—C4—H4 | 119.6 | C22—C21—H21 | 119.8 |
C6—C5—C4 | 118.4 (2) | C20—C21—H21 | 119.8 |
C6—C5—C8 | 121.0 (3) | C23—C22—C21 | 118.7 (2) |
C4—C5—C8 | 120.6 (2) | C23—C22—C25 | 119.8 (2) |
C5—C6—C7 | 120.8 (3) | C21—C22—C25 | 121.6 (2) |
C5—C6—H6 | 119.6 | C22—C23—C24 | 120.8 (3) |
C7—C6—H6 | 119.6 | C22—C23—H23 | 119.6 |
C2—C7—C6 | 120.8 (3) | C24—C23—H23 | 119.6 |
C2—C7—H7 | 119.6 | C19—C24—C23 | 121.2 (3) |
C6—C7—H7 | 119.6 | C19—C24—H24 | 119.4 |
C9—C8—C5 | 113.9 (2) | C23—C24—H24 | 119.4 |
C9—C8—H8A | 108.8 | O3—C25—O4 | 120.9 (2) |
C5—C8—H8A | 108.8 | O3—C25—C22 | 120.1 (2) |
C9—C8—H8B | 108.8 | O4—C25—C22 | 119.0 (2) |
C5—C8—H8B | 108.8 | O3—C25—Cd1ii | 61.70 (13) |
H8A—C8—H8B | 107.7 | O4—C25—Cd1ii | 59.26 (13) |
C10—C9—C14 | 119.8 (3) | C22—C25—Cd1ii | 177.11 (18) |
C10—C9—C8 | 120.7 (3) | N1—C26—C27 | 124.2 (4) |
C14—C9—C8 | 119.5 (3) | N1—C26—H26 | 117.9 |
C11—C10—C9 | 118.4 (3) | C27—C26—H26 | 117.9 |
C11—C10—C16 | 119.3 (3) | C28—C27—C26 | 118.5 (4) |
C9—C10—C16 | 122.2 (3) | C28—C27—H27 | 120.8 |
C10—C11—C12 | 123.2 (3) | C26—C27—H27 | 120.8 |
C10—C11—H11 | 118.4 | C27—C28—C29 | 119.1 (4) |
C12—C11—H11 | 118.4 | C27—C28—H28 | 120.5 |
C11—C12—C13 | 118.6 (3) | C29—C28—H28 | 120.5 |
C11—C12—C17 | 119.4 (3) | C28—C29—C30 | 119.2 (4) |
C13—C12—C17 | 122.0 (3) | C28—C29—H29 | 120.4 |
C12—C13—C14 | 119.6 (3) | C30—C29—H29 | 120.4 |
C12—C13—C18 | 119.7 (3) | N1—C30—C29 | 122.1 (4) |
C14—C13—C18 | 120.7 (3) | N1—C30—H30 | 118.9 |
C9—C14—C13 | 120.3 (3) | C29—C30—H30 | 118.9 |
C9—C14—C15 | 119.6 (3) | C30—N1—C26 | 116.9 (3) |
C13—C14—C15 | 120.1 (3) | C30—N1—Cd1 | 124.3 (2) |
C14—C15—H15A | 109.5 | C26—N1—Cd1 | 118.8 (2) |
C14—C15—H15B | 109.5 | C1—O1—Cd1 | 117.87 (16) |
H15A—C15—H15B | 109.5 | Cd1—O1W—H1WA | 108.9 |
C14—C15—H15C | 109.5 | Cd1—O1W—H1WB | 109.2 |
H15A—C15—H15C | 109.5 | H1WA—O1W—H1WB | 109.5 |
Symmetry codes: (i) −x+3/2, −y+1/2, −z+2; (ii) −x+1, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O1iii | 0.85 | 1.95 | 2.719 (2) | 151 |
O1W—H1WB···O4iv | 0.85 | 1.93 | 2.675 (2) | 146 |
Symmetry codes: (iii) −x+3/2, −y+3/2, −z+2; (iv) −x+1, y+1, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C25H22O4)(C5H5N)(H2O)] |
Mr | 595.94 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 40.058 (4), 5.9102 (5), 24.142 (2) |
β (°) | 111.723 (1) |
V (Å3) | 5309.8 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.86 |
Crystal size (mm) | 0.10 × 0.10 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.919, 0.934 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14990, 6029, 4415 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.071, 1.00 |
No. of reflections | 6029 |
No. of parameters | 337 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.29 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2008), publCIF (Westrip, 2010).
Cd1—O1W | 2.2431 (19) | Cd1—O4ii | 2.3302 (18) |
Cd1—O2i | 2.2516 (18) | Cd1—N1 | 2.365 (2) |
Cd1—O1 | 2.2913 (18) | Cd1—O3ii | 2.3846 (18) |
O1W—Cd1—O2i | 87.51 (7) | O1—Cd1—N1 | 170.79 (8) |
O1W—Cd1—O1 | 93.53 (7) | O4ii—Cd1—N1 | 92.69 (8) |
O2i—Cd1—O1 | 92.50 (7) | O1W—Cd1—O3ii | 86.14 (6) |
O1W—Cd1—O4ii | 140.95 (6) | O2i—Cd1—O3ii | 165.98 (7) |
O2i—Cd1—O4ii | 131.43 (7) | O1—Cd1—O3ii | 100.35 (7) |
O1—Cd1—O4ii | 88.21 (7) | O4ii—Cd1—O3ii | 55.31 (6) |
O1W—Cd1—N1 | 91.54 (8) | N1—Cd1—O3ii | 87.65 (8) |
O2i—Cd1—N1 | 80.04 (8) |
Symmetry codes: (i) −x+3/2, −y+1/2, −z+2; (ii) −x+1, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O1iii | 0.85 | 1.95 | 2.719 (2) | 150.7 |
O1W—H1WB···O4iv | 0.85 | 1.93 | 2.675 (2) | 146.2 |
Symmetry codes: (iii) −x+3/2, −y+3/2, −z+2; (iv) −x+1, y+1, −z+3/2. |
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The search for new coordination polymers (CPs) remains at the forefront of synthetic materials science, as their networks continue to be of interest for many potential applications such as luminescence, gas adsorption, catalysis, magnetism, molecular recognition etc. (Chen et al., 2010; Liu et al., 2010; Kong et al., 2008; Tao et al., 2012; Li et al., 2010; Sun, Liu et al., 2011). One of the main synthetic strategies for CPs is based on the diversity of polynuclear metallic units known as secondary building units (SBUs), as well as predesigned organic spacers (Zhao et al., 2011). Current studies of CPs have suggested that choosing a suitable ligand is very important for the achievement of CPs possessing the required properties, not only because the structure of the ligands has a significant influence on the topology, but also because the functionality of the ligand can be embedded into the whole framework (Blatov, 2007; Sun, Luo et al., 2011; Sun, Wang et al., 2011; Sun et al., 2010). The widely used carboxylic acids, such as aromatic carboxylic acids, often participate in coordination with transition metals, rare earth metal ions or mixed metal ions, exhibiting diverse coordination modes such as monodentate bridging, bidentate chelating or bridging (Wang et al., 2011; Ma et al., 2011; Zheng et al., 2011; Yin et al., 2012; Zhang et al., 2011; Li et al., 2011). Despite CPs constructed from a range of carboxylates having been widely reported, to the best of our knowledge CPs based on H2TMBDC {4,4'-[(2,4,6-trimethyl-1,3-phenylene)bis(methylene)]dibenzoic acid} have not yet been reported. The presence of methyl groups on the central phenyl ring and methylene groups as connectors between the central phenyl ring and the benzoic acid units could give both steric hindance and flexiblility, giving the H2TMBDC ligand very interesting structural and functional features. Based on all these points, we have here chosen the semirigid H2TMBDC ligand and pyridine (py) as mixed ligands and CdII as the metal centre to build an infinite one-dimensional ribbon incorporating [Cd2(COO)4] SBUs, namely catena-poly[[aquapyridinecadmium(II)]µ3-{4,4'-[(2,4,6-trimethyl- 1,3-phenylene)bis(methylene)]dibenzoato}], (I).
The asymmetric unit of (I) contains one crystallographically independent CdII centre, one TMBDC ligand, one py ligand and one coordinated water ligand. As shown in Fig. 1, atom Cd1 is six-coordinated by the py N atom, four carboxylate O atoms from three different TMBDC ligands and a water molecule, giving a distorted octahedral coordination geometry. The Cd—N and Cd—O distances, in the range 2.2431 (19)–2.3846 (18) Å (Table 1), are comparable with those reported for Cd-based CPs (He et al., 2010; Dai et al., 2010). Interestingly, the terminal coordinated water and pyridine molecules form the shortest and the second longest bond distances to CdII, respectively. One carboxylate group of the TMBDC ligand adopts the syn–anti bridging mode and the other adopts a chelating mode.
Two inversion-related CdII cations are bridged by four carboxylate groups to form a dinuclear [Cd2(COO)4] SBU with a Cd···Cd distance of 5.4568 (5) Å. The two benzoate units are not coplanar with the central benzene ring but distributed on either side of the central benzene ring, generating an anti conformation.
The [Cd2(COO)4] SBUs are joined by TMBDC ligands to form an infinite one-dimensional ribbon (Fig. 2). The py ligand acts as a terminal group occupying the remaining coordination site, which prevents the structure from attaining a higher dimensionality. Adjacent one-dimensional ribbons are extended into a two-dimensional supramolecular sheet by interribbon water–TMBDC O—H···O hydrogen bonds (Fig. 3 and Table 2). No π–π interactions are observed in the crystal structure.
The effect of the synthetic method on the structure of this system was investigated by running the reaction in biphasic solvothermal (cyclohexanol–toluene = 1:1) and traditional single-phase solvothermal methods (N,N'-dimethylformamide). Under biphasic solvothermal conditions, we obtained large well shaped single crystals, but only intractable precipitates were obtained by the traditional single-phase solvothermal method. The difference between the two methods confirms that biphasic solvothermal conditions could reduce reaction times and avoid the formation of precipitates (Forster & Cheetham, 2002), thus favouring the growth of single crystals at the interface of the two immiscible solvents.