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The CdII three-dimensional coordination poly[[[μ4-1,4-bis(1,2,4-triazol-1-yl)but-2-ene]bis(μ3-5-carboxybenzene-1,3-dicarboxylato)dicadmium(II)] dihydrate], {[Cd2(C9H4O6)2(C8H10N6)]·2H2O}n, (I), has been synthesized by the hydrothermal reaction of Cd(NO3)2·4H2O, benzene-1,3,5-tricarboxylic acid (1,3,5-H3BTC) and 1,4-bis(1,2,4-triazol-1-yl)but-2-ene (1,4-btbe). The IR spectrum suggests the presence of protonated carboxylic acid, deprotonated carboxylate and triazolyl groups. The purity of the bulk sample was confirmed by elemental analysis and X-ray powder diffraction. Single-crystal X-ray diffraction analysis reveals that the CdII ions adopt a five-coordinated distorted trigonal–bipyramidal geometry, coordinated by three O atoms from three different 1,3,5-HBTC2− ligands and two N atoms from two different 1,4-btbe ligands; the latter are situated on centres of inversion. The CdII centres are bridged by 1,3,5-HBTC2− and 1,4-btbe ligands into an overall three-dimensional framework. When the CdII centres and the tetradentate 1,4-btbe ligands are regarded as nodes, the three-dimensional topology can be simplified as a binodal 4,6-connected network. Thermogravimetric analysis confirms the presence of lattice water in (I). Photoluminescence studies imply that the emission of (I) may be ascribed to intraligand fluorescence.
Supporting information
CCDC reference: 1562434
Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: publCIF (Westrip, 2010).
Poly[[[µ
4-1,4-bis(1,2,4-triazol-1-yl)but-2-ene]bis(µ
3-5-carboxybenzene-1,3-dicarboxylato)dicadmium(II)] dihydrate]
top
Crystal data top
[Cd2(C9H4O6)2(C8H10N6)]·2H2O | F(000) = 1712 |
Mr = 867.32 | Dx = 2.100 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 16.560 (3) Å | Cell parameters from 16412 reflections |
b = 13.383 (3) Å | θ = 2.9–27.5° |
c = 13.302 (3) Å | µ = 1.64 mm−1 |
β = 111.47 (3)° | T = 223 K |
V = 2743.5 (12) Å3 | Block, light-yellow |
Z = 4 | 0.15 × 0.12 × 0.11 mm |
Data collection top
Bruker D8 goniometer with an APEX CCD detector diffractometer | 3022 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
phi and ω scans | θmax = 27.5°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −19→21 |
Tmin = 0.783, Tmax = 0.822 | k = −17→17 |
16412 measured reflections | l = −17→17 |
3144 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.020 | w = 1/[σ2(Fo2) + (0.0141P)2 + 6.5924P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.047 | (Δ/σ)max = 0.002 |
S = 1.16 | Δρmax = 0.49 e Å−3 |
3144 reflections | Δρmin = −0.30 e Å−3 |
230 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.00264 (10) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cd1 | 0.86746 (2) | 0.50263 (2) | 0.44418 (2) | 0.01539 (7) | |
N1 | 0.88685 (11) | 0.57657 (12) | 0.62511 (13) | 0.0212 (3) | |
N2 | 0.87896 (11) | 0.56249 (12) | 0.78951 (13) | 0.0204 (3) | |
N3 | 0.87461 (11) | 0.66821 (12) | 0.66277 (13) | 0.0189 (3) | |
O1 | 0.72767 (10) | 0.50682 (11) | 0.41868 (15) | 0.0307 (4) | |
O2 | 0.76010 (9) | 0.34741 (12) | 0.41863 (14) | 0.0306 (3) | |
O3 | 0.53260 (10) | 0.10140 (11) | 0.44638 (13) | 0.0311 (3) | |
O4 | 0.39765 (9) | 0.15500 (10) | 0.39758 (12) | 0.0236 (3) | |
O5 | 0.33089 (10) | 0.51091 (12) | 0.34630 (14) | 0.0277 (3) | |
H5 | 0.306 (2) | 0.560 (3) | 0.338 (2) | 0.046 (9)* | |
O6 | 0.43188 (10) | 0.61969 (11) | 0.34219 (14) | 0.0301 (3) | |
O7 | 0.23181 (12) | 0.67140 (14) | 0.30808 (18) | 0.0430 (5) | |
H1W | 0.196 (2) | 0.681 (2) | 0.246 (3) | 0.045 (9)* | |
H2W | 0.237 (2) | 0.721 (3) | 0.342 (3) | 0.052 (10)* | |
C1 | 0.61619 (11) | 0.39091 (14) | 0.40510 (14) | 0.0164 (3) | |
C2 | 0.59066 (12) | 0.29353 (13) | 0.41525 (14) | 0.0165 (3) | |
H2 | 0.6311 | 0.2411 | 0.4297 | 0.020* | |
C3 | 0.50509 (11) | 0.27378 (13) | 0.40397 (14) | 0.0149 (3) | |
C4 | 0.44527 (12) | 0.35112 (13) | 0.38259 (14) | 0.0165 (3) | |
H4 | 0.3874 | 0.3374 | 0.3736 | 0.020* | |
C5 | 0.47074 (12) | 0.44897 (13) | 0.37438 (14) | 0.0156 (3) | |
C6 | 0.55646 (12) | 0.46785 (14) | 0.38600 (15) | 0.0176 (3) | |
H6 | 0.5740 | 0.5338 | 0.3808 | 0.021* | |
C7 | 0.70748 (12) | 0.41558 (15) | 0.41468 (14) | 0.0186 (4) | |
C8 | 0.47748 (12) | 0.16917 (13) | 0.41734 (14) | 0.0156 (3) | |
C9 | 0.40998 (12) | 0.53533 (14) | 0.35267 (14) | 0.0184 (4) | |
C10 | 0.78489 (14) | 0.77818 (14) | 0.51233 (16) | 0.0219 (4) | |
H10 | 0.7811 | 0.8345 | 0.4686 | 0.026* | |
C11 | 0.86965 (14) | 0.76134 (14) | 0.60314 (16) | 0.0230 (4) | |
H11A | 0.9160 | 0.7614 | 0.5739 | 0.028* | |
H11B | 0.8803 | 0.8174 | 0.6538 | 0.028* | |
C12 | 0.87012 (13) | 0.65794 (15) | 0.76006 (16) | 0.0220 (4) | |
H12 | 0.8619 | 0.7107 | 0.8020 | 0.026* | |
C13 | 0.88905 (14) | 0.51632 (15) | 0.70434 (16) | 0.0219 (4) | |
H13 | 0.8970 | 0.4469 | 0.7019 | 0.026* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cd1 | 0.01644 (9) | 0.01344 (8) | 0.01795 (9) | −0.00174 (5) | 0.00827 (6) | 0.00063 (4) |
N1 | 0.0288 (9) | 0.0152 (7) | 0.0219 (8) | 0.0038 (6) | 0.0120 (7) | 0.0006 (6) |
N2 | 0.0251 (8) | 0.0173 (8) | 0.0210 (8) | 0.0033 (6) | 0.0113 (6) | 0.0025 (6) |
N3 | 0.0237 (8) | 0.0132 (7) | 0.0205 (7) | 0.0012 (6) | 0.0090 (6) | 0.0011 (6) |
O1 | 0.0228 (8) | 0.0229 (8) | 0.0528 (10) | −0.0108 (6) | 0.0215 (7) | −0.0105 (6) |
O2 | 0.0178 (7) | 0.0274 (8) | 0.0479 (9) | 0.0036 (6) | 0.0137 (6) | 0.0091 (7) |
O3 | 0.0289 (8) | 0.0147 (7) | 0.0422 (9) | 0.0050 (6) | 0.0042 (7) | 0.0062 (6) |
O4 | 0.0227 (7) | 0.0150 (6) | 0.0368 (8) | −0.0049 (5) | 0.0152 (6) | 0.0019 (6) |
O5 | 0.0188 (7) | 0.0192 (7) | 0.0439 (9) | 0.0047 (6) | 0.0103 (7) | 0.0042 (6) |
O6 | 0.0297 (8) | 0.0146 (7) | 0.0462 (9) | 0.0037 (6) | 0.0140 (7) | 0.0076 (6) |
O7 | 0.0332 (9) | 0.0289 (9) | 0.0535 (12) | 0.0101 (8) | 0.0002 (9) | −0.0078 (9) |
C1 | 0.0145 (8) | 0.0183 (8) | 0.0170 (8) | −0.0033 (7) | 0.0064 (6) | 0.0000 (7) |
C2 | 0.0151 (8) | 0.0153 (8) | 0.0197 (8) | 0.0009 (7) | 0.0071 (7) | 0.0012 (6) |
C3 | 0.0176 (8) | 0.0110 (8) | 0.0162 (8) | −0.0017 (7) | 0.0065 (6) | 0.0009 (6) |
C4 | 0.0152 (8) | 0.0153 (8) | 0.0193 (8) | −0.0019 (7) | 0.0066 (7) | 0.0011 (6) |
C5 | 0.0169 (8) | 0.0130 (8) | 0.0166 (8) | 0.0007 (7) | 0.0057 (7) | 0.0015 (6) |
C6 | 0.0199 (9) | 0.0123 (8) | 0.0207 (8) | −0.0039 (7) | 0.0076 (7) | 0.0003 (7) |
C7 | 0.0157 (8) | 0.0226 (9) | 0.0180 (8) | −0.0052 (7) | 0.0066 (7) | −0.0011 (7) |
C8 | 0.0212 (8) | 0.0115 (8) | 0.0148 (8) | −0.0016 (7) | 0.0075 (7) | −0.0005 (6) |
C9 | 0.0191 (9) | 0.0156 (8) | 0.0180 (8) | 0.0023 (7) | 0.0039 (7) | 0.0021 (7) |
C10 | 0.0324 (10) | 0.0128 (8) | 0.0244 (9) | 0.0035 (7) | 0.0148 (8) | 0.0042 (7) |
C11 | 0.0311 (10) | 0.0134 (8) | 0.0250 (9) | −0.0022 (8) | 0.0110 (8) | 0.0030 (7) |
C12 | 0.0278 (10) | 0.0173 (9) | 0.0226 (9) | 0.0022 (8) | 0.0111 (8) | −0.0008 (7) |
C13 | 0.0290 (10) | 0.0148 (8) | 0.0240 (9) | 0.0045 (8) | 0.0123 (8) | 0.0024 (7) |
Geometric parameters (Å, º) top
Cd1—O1 | 2.2141 (16) | O7—H1W | 0.83 (3) |
Cd1—O4i | 2.2406 (14) | O7—H2W | 0.79 (4) |
Cd1—O3ii | 2.2434 (16) | C1—C6 | 1.385 (3) |
Cd1—N2iii | 2.3054 (16) | C1—C2 | 1.392 (2) |
Cd1—N1 | 2.5117 (17) | C1—C7 | 1.507 (2) |
N1—C13 | 1.317 (2) | C2—C3 | 1.394 (2) |
N1—N3 | 1.368 (2) | C2—H2 | 0.9400 |
N2—C12 | 1.328 (2) | C3—C4 | 1.388 (2) |
N2—C13 | 1.353 (2) | C3—C8 | 1.503 (2) |
N2—Cd1iv | 2.3054 (16) | C4—C5 | 1.392 (2) |
N3—C12 | 1.330 (2) | C4—H4 | 0.9400 |
N3—C11 | 1.463 (2) | C5—C6 | 1.394 (3) |
O1—C7 | 1.262 (2) | C5—C9 | 1.490 (3) |
O2—C7 | 1.249 (2) | C6—H6 | 0.9400 |
O3—C8 | 1.244 (2) | C10—C10vi | 1.317 (4) |
O3—Cd1ii | 2.2434 (16) | C10—C11 | 1.496 (3) |
O4—C8 | 1.264 (2) | C10—H10 | 0.9400 |
O4—Cd1v | 2.2405 (14) | C11—H11A | 0.9800 |
O5—C9 | 1.322 (2) | C11—H11B | 0.9800 |
O5—H5 | 0.77 (3) | C12—H12 | 0.9400 |
O6—C9 | 1.209 (2) | C13—H13 | 0.9400 |
| | | |
O1—Cd1—O4i | 105.14 (5) | C3—C4—C5 | 120.23 (16) |
O1—Cd1—O3ii | 126.64 (6) | C3—C4—H4 | 119.9 |
O4i—Cd1—O3ii | 123.92 (6) | C5—C4—H4 | 119.9 |
O1—Cd1—N2iii | 107.23 (7) | C4—C5—C6 | 119.16 (16) |
O4i—Cd1—N2iii | 89.85 (6) | C4—C5—C9 | 122.85 (17) |
O3ii—Cd1—N2iii | 93.57 (6) | C6—C5—C9 | 117.98 (16) |
O1—Cd1—N1 | 84.07 (7) | C1—C6—C5 | 121.03 (17) |
O4i—Cd1—N1 | 86.75 (5) | C1—C6—H6 | 119.5 |
O3ii—Cd1—N1 | 79.49 (6) | C5—C6—H6 | 119.5 |
N2iii—Cd1—N1 | 168.70 (6) | O2—C7—O1 | 122.34 (17) |
C13—N1—N3 | 102.72 (15) | O2—C7—C1 | 120.43 (17) |
C13—N1—Cd1 | 118.82 (13) | O1—C7—C1 | 117.23 (17) |
N3—N1—Cd1 | 136.07 (12) | O3—C8—O4 | 123.22 (17) |
C12—N2—C13 | 103.07 (16) | O3—C8—C3 | 119.70 (17) |
C12—N2—Cd1iv | 126.19 (13) | O4—C8—C3 | 117.08 (16) |
C13—N2—Cd1iv | 130.56 (13) | O6—C9—O5 | 123.72 (18) |
C12—N3—N1 | 109.40 (15) | O6—C9—C5 | 122.47 (18) |
C12—N3—C11 | 127.10 (16) | O5—C9—C5 | 113.80 (16) |
N1—N3—C11 | 123.48 (15) | C10vi—C10—C11 | 126.4 (2) |
C7—O1—Cd1 | 103.17 (12) | C10vi—C10—H10 | 116.8 |
C8—O3—Cd1ii | 159.61 (14) | C11—C10—H10 | 116.8 |
C8—O4—Cd1v | 113.66 (12) | N3—C11—C10 | 114.58 (16) |
C9—O5—H5 | 106 (2) | N3—C11—H11A | 108.6 |
H1W—O7—H2W | 109 (3) | C10—C11—H11A | 108.6 |
C6—C1—C2 | 119.47 (16) | N3—C11—H11B | 108.6 |
C6—C1—C7 | 118.66 (16) | C10—C11—H11B | 108.6 |
C2—C1—C7 | 121.87 (16) | H11A—C11—H11B | 107.6 |
C1—C2—C3 | 119.99 (16) | N2—C12—N3 | 110.30 (17) |
C1—C2—H2 | 120.0 | N2—C12—H12 | 124.9 |
C3—C2—H2 | 120.0 | N3—C12—H12 | 124.8 |
C4—C3—C2 | 120.10 (16) | N1—C13—N2 | 114.50 (17) |
C4—C3—C8 | 119.56 (16) | N1—C13—H13 | 122.7 |
C2—C3—C8 | 120.32 (16) | N2—C13—H13 | 122.7 |
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) −x+3/2, −y+1/2, −z+1; (iii) x, −y+1, z−1/2; (iv) x, −y+1, z+1/2; (v) x−1/2, y−1/2, z; (vi) −x+3/2, −y+3/2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O7 | 0.77 (3) | 1.87 (3) | 2.637 (2) | 173 (3) |
O7—H1W···O4vii | 0.83 (3) | 2.01 (3) | 2.799 (3) | 160 (3) |
O7—H2W···O2viii | 0.79 (4) | 1.94 (4) | 2.725 (3) | 174 (3) |
Symmetry codes: (vii) −x+1/2, y+1/2, −z+1/2; (viii) x−1/2, y+1/2, z. |
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