A three-dimensional cadmium coordination polymer based on 1,4-bis­(1,2,4-triazol-1-yl)but-2-ene and benzene-1,3,5-tri­carb­oxy­lic acid

The Cd^II 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 Cd^II 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 Cd^II centres are bridged by 1,3,5-HBTC²⁻ and 1,4-btbe ligands into an overall three-dimensional framework. When the Cd^II 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.

Computing details

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[[[µ₄-1,4-bis(1,2,4-triazol-1-yl)but-2-ene]bis(µ₃-5-carboxybenzene-1,3-dicarboxylato)dicadmium(II)] dihydrate]

Crystal data

[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) Å^3	Block, light-yellow
Z = 4	0.15 × 0.12 × 0.11 mm

Data collection

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

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.020	w = 1/[σ^2(Fo^2) + (0.0141P)^2 + 6.5924P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00264 (10)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Cd1—O1	2.2141 (16)	O7—H1W	0.83 (3)
Cd1—O4^i	2.2406 (14)	O7—H2W	0.79 (4)
Cd1—O3^ii	2.2434 (16)	C1—C6	1.385 (3)
Cd1—N2^iii	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—Cd1^iv	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—C10^vi	1.317 (4)
O3—Cd1^ii	2.2434 (16)	C10—C11	1.496 (3)
O4—C8	1.264 (2)	C10—H10	0.9400
O4—Cd1^v	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—O4^i	105.14 (5)	C3—C4—C5	120.23 (16)
O1—Cd1—O3^ii	126.64 (6)	C3—C4—H4	119.9
O4^i—Cd1—O3^ii	123.92 (6)	C5—C4—H4	119.9
O1—Cd1—N2^iii	107.23 (7)	C4—C5—C6	119.16 (16)
O4^i—Cd1—N2^iii	89.85 (6)	C4—C5—C9	122.85 (17)
O3^ii—Cd1—N2^iii	93.57 (6)	C6—C5—C9	117.98 (16)
O1—Cd1—N1	84.07 (7)	C1—C6—C5	121.03 (17)
O4^i—Cd1—N1	86.75 (5)	C1—C6—H6	119.5
O3^ii—Cd1—N1	79.49 (6)	C5—C6—H6	119.5
N2^iii—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—Cd1^iv	126.19 (13)	O4—C8—C3	117.08 (16)
C13—N2—Cd1^iv	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)	C10^vi—C10—C11	126.4 (2)
C7—O1—Cd1	103.17 (12)	C10^vi—C10—H10	116.8
C8—O3—Cd1^ii	159.61 (14)	C11—C10—H10	116.8
C8—O4—Cd1^v	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)

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···O4^vii	0.83 (3)	2.01 (3)	2.799 (3)	160 (3)
O7—H2W···O2^viii	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.