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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): m913.
Published online 2009 July 11. doi:  10.1107/S1600536809024908
PMCID: PMC2977399

Tetra­aqua­bis(3,5-di-4-pyridyl-1H-1,2,4-triazolido)cadmium(II) dihydrate

Abstract

In the title compound, [Cd(C12H8N5)2(H2O)4]·2H2O, the CdII atom is located on an inversion center and is coordinated by the two N atoms [Cd—N = 2.278 (2) Å] and four O atoms [Cd—O = 2.304 (2)–2.322 (2) Å] in a distorted octa­hedral geometry. Inter­molecular O—H(...)O and O—H(...)N hydrogen bonds link the complex into a three-dimensional supra­molecular framework.

Related literature

For the properties of hydrogen bonds in biological systems, see: Deisenhofer & Michel (1989 [triangle]). For extended supra­molecular structures, see: Beatty (2003 [triangle]); Li et al. (2006 [triangle]); Russell & Ward (1996 [triangle]). For comparitive bond distances, see: Wen et al. (2005 [triangle]); Fu et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0m913-scheme1.jpg

Experimental

Crystal data

  • [Cd(C12H8N5)2(H2O)4]·2H2O
  • M r = 664.97
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m913-efi1.jpg
  • a = 7.5030 (15) Å
  • b = 15.748 (3) Å
  • c = 12.009 (2) Å
  • β = 106.68 (3)°
  • V = 1359.2 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.86 mm−1
  • T = 293 K
  • 0.40 × 0.20 × 0.12 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1998 [triangle]) T min = 0.815, T max = 0.911
  • 9599 measured reflections
  • 3101 independent reflections
  • 2663 reflections with I > 2σ(I)
  • R int = 0.035

Refinement

  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.070
  • S = 1.01
  • 3101 reflections
  • 211 parameters
  • 9 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.30 e Å−3
  • Δρmin = −0.47 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1998 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809024908/bg2273sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809024908/bg2273Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We gratefully acknowledge the Science and Techology Foundation of Shaoyang, Hunan, China and the Foundation of Shaoyang Medical College, China.

supplementary crystallographic information

Comment

The hydrogen bond interaction plays a important role in some biological systems (Deisenhofer & Michel, 1989). Supramolecular assembly through hydrogen bonds has been extensively exploited to generate extended one-, two- and three-dimensional structures (Beatty et al., 2003; Li et al., 2006; Russell & Ward, 1996). As part of this ongoing work, We present here the synthesis and structural characterization of the title cadmium complex, [Cd(C12H8N5)2(H2O)4].2H2O, (I).

The molecule of the title complex, (Fig. 1), is centrosymmetric, so pairs of equivalent ligands lie trans to each other in a slightly distorted octahedral coordination geometry, cis angles deviating from 90° by less than 4°. with Cd—O bond length in the range 2.304 (2)–2.322 (2) Å and a Cd—N bond length of 2.278 (2) Å. These bond distances compare well with those in the literature (Wen et al., 2005; Fu et al., 2007). Molecules are linked by O—H···O and O—H···N hydrogen bonds (Table 1 and Fig. 2).

Experimental

Cd(NO3)2.4H2O (0.5 mmol, 0.154 g), 1H-3,5-di(4-pyridyl)-1,2,4-triazole (0.5 mmol, 0.112 g), and water (12 ml) were placed in a 23-ml Teflon-lined Parr bomb. The bomb was heated at 453 K for 3 d. The colourless block-shapped crystals were filtered off and washed with water and acetone (yield 45%, based on Cd).

Refinement

Hydrogen atoms of water molecules were located in a difference Fourier map and refined with distance restraints of O—H = 0.85 (2) Å and H···H = 1.39 (2) Å, and free isotropic U's. H atoms on C atoms were positoned geometrically and refined using a riding model, with C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
A view of the molecular structure of (I) with the atom-numbering scheme and 30% displacement ellipsoids. Atoms with the suffix A are generated by the symmetry operation (-x, -y + 1, -z + 1).
Fig. 2.
The 3-D network of (I).

Crystal data

[Cd(C12H8N5)2(H2O)4]·2H2OF(000) = 676
Mr = 664.97Dx = 1.625 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2567 reflections
a = 7.5030 (15) Åθ = 2.6–27.3°
b = 15.748 (3) ŵ = 0.86 mm1
c = 12.009 (2) ÅT = 293 K
β = 106.68 (3)°Block, colorless
V = 1359.2 (5) Å30.40 × 0.20 × 0.12 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer3101 independent reflections
Radiation source: fine-focus sealed tube2663 reflections with I > 2σ(I)
graphiteRint = 0.035
[var phi] and ω scansθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 1998)h = −9→9
Tmin = 0.815, Tmax = 0.911k = −20→20
9599 measured reflectionsl = −15→15

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.070H atoms treated by a mixture of independent and constrained refinement
S = 1.01w = 1/[σ2(Fo2) + (0.0271P)2 + P] where P = (Fo2 + 2Fc2)/3
3101 reflections(Δ/σ)max < 0.001
211 parametersΔρmax = 0.30 e Å3
9 restraintsΔρmin = −0.47 e Å3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cd10.00000.50000.50000.02624 (8)
C10.0093 (4)0.67991 (14)0.3780 (2)0.0362 (6)
H1−0.03920.64760.31130.043*
C20.0355 (4)0.76513 (14)0.3660 (2)0.0350 (5)
H20.00380.78940.29230.042*
C30.1089 (3)0.81536 (13)0.46302 (19)0.0260 (5)
C40.1464 (4)0.77542 (14)0.5700 (2)0.0371 (6)
H40.19190.80650.63820.045*
C50.1161 (4)0.68949 (15)0.5749 (2)0.0380 (6)
H50.14300.66380.64760.046*
C60.1502 (3)0.90502 (13)0.45109 (18)0.0265 (5)
C70.2512 (3)1.02895 (14)0.4805 (2)0.0274 (5)
C80.3340 (3)1.10850 (13)0.53511 (19)0.0276 (5)
C90.3496 (4)1.17874 (16)0.4689 (2)0.0472 (7)
H90.31271.17540.38820.057*
C100.4202 (5)1.25321 (16)0.5236 (2)0.0515 (8)
H100.42851.29950.47720.062*
C110.4620 (4)1.19586 (16)0.7006 (2)0.0423 (6)
H110.50121.20100.78110.051*
C120.3919 (4)1.11875 (15)0.6541 (2)0.0376 (6)
H120.38371.07380.70270.045*
H1A0.081 (4)0.4477 (19)0.303 (2)0.065 (11)*
H2A0.251 (5)0.487 (2)0.722 (2)0.076 (12)*
H3A0.333 (4)0.5708 (17)0.2136 (15)0.057 (10)*
H1B0.225 (4)0.5023 (14)0.349 (3)0.050 (9)*
H2B0.371 (3)0.474 (2)0.656 (3)0.071 (11)*
H3B0.419 (4)0.6266 (12)0.301 (2)0.059 (9)*
N10.0504 (3)0.64121 (11)0.48107 (16)0.0309 (4)
N20.1075 (3)0.94209 (12)0.34725 (16)0.0338 (5)
N30.1745 (3)1.02282 (12)0.36636 (17)0.0351 (5)
N40.2401 (3)0.95673 (11)0.53920 (16)0.0269 (4)
N50.4772 (3)1.26344 (13)0.6379 (2)0.0413 (5)
O10.1563 (3)0.46448 (12)0.36541 (15)0.0358 (4)
O20.2657 (3)0.49379 (12)0.65460 (16)0.0416 (4)
O30.3821 (3)0.57563 (10)0.28626 (15)0.0349 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cd10.03522 (14)0.01796 (11)0.02429 (13)−0.00424 (9)0.00655 (10)−0.00067 (8)
C10.0537 (16)0.0256 (11)0.0261 (12)−0.0094 (11)0.0063 (11)−0.0044 (9)
C20.0516 (15)0.0269 (11)0.0240 (11)−0.0059 (11)0.0067 (11)0.0028 (9)
C30.0296 (11)0.0208 (10)0.0275 (11)−0.0013 (8)0.0079 (9)0.0014 (8)
C40.0577 (16)0.0233 (11)0.0255 (12)−0.0090 (11)0.0042 (12)−0.0027 (9)
C50.0596 (17)0.0254 (11)0.0249 (12)−0.0073 (11)0.0057 (12)0.0031 (9)
C60.0331 (12)0.0206 (10)0.0241 (11)−0.0013 (9)0.0056 (9)0.0011 (8)
C70.0333 (12)0.0205 (9)0.0295 (12)−0.0024 (9)0.0106 (10)0.0006 (9)
C80.0302 (12)0.0204 (10)0.0314 (12)−0.0019 (9)0.0075 (10)−0.0006 (9)
C90.078 (2)0.0311 (13)0.0308 (13)−0.0176 (13)0.0137 (14)−0.0018 (10)
C100.084 (2)0.0276 (12)0.0446 (16)−0.0188 (14)0.0214 (16)0.0009 (11)
C110.0532 (16)0.0364 (13)0.0303 (13)−0.0066 (12)0.0010 (12)−0.0046 (10)
C120.0496 (15)0.0260 (11)0.0327 (13)−0.0042 (10)0.0046 (12)0.0042 (9)
N10.0435 (11)0.0199 (9)0.0278 (10)−0.0049 (8)0.0077 (9)0.0005 (7)
N20.0487 (13)0.0241 (9)0.0258 (10)−0.0087 (9)0.0066 (9)0.0016 (7)
N30.0523 (13)0.0239 (9)0.0265 (10)−0.0089 (9)0.0073 (10)0.0020 (8)
N40.0348 (10)0.0192 (9)0.0261 (10)−0.0021 (7)0.0078 (8)0.0005 (7)
N50.0488 (13)0.0280 (10)0.0458 (13)−0.0092 (9)0.0112 (11)−0.0087 (9)
O10.0405 (10)0.0387 (10)0.0295 (9)−0.0055 (8)0.0120 (8)−0.0026 (8)
O20.0349 (10)0.0577 (12)0.0288 (9)0.0058 (9)0.0035 (8)−0.0038 (8)
O30.0458 (10)0.0258 (8)0.0299 (9)−0.0037 (7)0.0060 (8)−0.0015 (7)

Geometric parameters (Å, °)

Cd1—N1i2.278 (2)C7—N41.353 (3)
Cd1—N12.278 (2)C7—C81.467 (3)
Cd1—O22.304 (2)C8—C121.379 (3)
Cd1—O2i2.304 (2)C8—C91.386 (3)
Cd1—O1i2.322 (2)C9—C101.373 (3)
Cd1—O12.322 (2)C9—H90.9300
C1—N11.334 (3)C10—N51.325 (3)
C1—C21.370 (3)C10—H100.9300
C1—H10.9300C11—N51.327 (3)
C2—C31.385 (3)C11—C121.376 (3)
C2—H20.9300C11—H110.9300
C3—C41.385 (3)C12—H120.9300
C3—C61.461 (3)N2—N31.362 (3)
C4—C51.376 (3)O1—H1A0.844 (17)
C4—H40.9300O1—H1B0.845 (17)
C5—N11.331 (3)O2—H2A0.857 (17)
C5—H50.9300O2—H2B0.847 (17)
C6—N21.330 (3)O3—H3A0.848 (16)
C6—N41.352 (3)O3—H3B0.850 (17)
C7—N31.329 (3)
N1i—Cd1—N1180.0N3—C7—N4113.8 (2)
N1i—Cd1—O290.47 (7)N3—C7—C8121.7 (2)
N1—Cd1—O289.53 (7)N4—C7—C8124.5 (2)
N1i—Cd1—O2i89.53 (7)C12—C8—C9116.6 (2)
N1—Cd1—O2i90.47 (7)C12—C8—C7122.1 (2)
O2—Cd1—O2i180.0C9—C8—C7121.3 (2)
N1i—Cd1—O1i91.96 (7)C10—C9—C8119.5 (2)
N1—Cd1—O1i88.04 (7)C10—C9—H9120.3
O2—Cd1—O1i86.71 (7)C8—C9—H9120.3
O2i—Cd1—O1i93.29 (7)N5—C10—C9124.3 (2)
N1i—Cd1—O188.04 (7)N5—C10—H10117.8
N1—Cd1—O191.96 (7)C9—C10—H10117.8
O2—Cd1—O193.29 (7)N5—C11—C12124.3 (2)
O2i—Cd1—O186.71 (7)N5—C11—H11117.9
O1i—Cd1—O1180.0C12—C11—H11117.9
N1—C1—C2122.9 (2)C11—C12—C8119.6 (2)
N1—C1—H1118.5C11—C12—H12120.2
C2—C1—H1118.5C8—C12—H12120.2
C1—C2—C3120.4 (2)C5—N1—C1117.07 (19)
C1—C2—H2119.8C5—N1—Cd1120.33 (15)
C3—C2—H2119.8C1—N1—Cd1122.54 (15)
C2—C3—C4116.5 (2)C6—N2—N3105.89 (18)
C2—C3—C6120.91 (19)C7—N3—N2105.73 (18)
C4—C3—C6122.5 (2)C6—N4—C7100.94 (18)
C5—C4—C3119.6 (2)C10—N5—C11115.8 (2)
C5—C4—H4120.2Cd1—O1—H1A111 (2)
C3—C4—H4120.2Cd1—O1—H1B117 (2)
N1—C5—C4123.5 (2)H1A—O1—H1B108 (2)
N1—C5—H5118.3Cd1—O2—H2A117 (2)
C4—C5—H5118.3Cd1—O2—H2B128 (2)
N2—C6—N4113.65 (19)H2A—O2—H2B108 (2)
N2—C6—C3121.01 (19)H3A—O3—H3B108 (2)
N4—C6—C3125.27 (19)
N1—C1—C2—C30.6 (4)C2—C1—N1—C51.3 (4)
C1—C2—C3—C4−2.3 (4)C2—C1—N1—Cd1178.6 (2)
C1—C2—C3—C6175.5 (2)O2—Cd1—N1—C5−38.2 (2)
C2—C3—C4—C52.2 (4)O2i—Cd1—N1—C5141.8 (2)
C6—C3—C4—C5−175.5 (2)O1i—Cd1—N1—C548.5 (2)
C3—C4—C5—N1−0.4 (4)O1—Cd1—N1—C5−131.5 (2)
C2—C3—C6—N24.4 (3)O2—Cd1—N1—C1144.6 (2)
C4—C3—C6—N2−178.0 (2)O2i—Cd1—N1—C1−35.4 (2)
C2—C3—C6—N4−172.4 (2)O1i—Cd1—N1—C1−128.6 (2)
C4—C3—C6—N45.2 (4)O1—Cd1—N1—C151.4 (2)
N3—C7—C8—C12171.4 (2)N4—C6—N2—N30.9 (3)
N4—C7—C8—C12−6.7 (4)C3—C6—N2—N3−176.3 (2)
N3—C7—C8—C9−5.4 (4)N4—C7—N3—N20.3 (3)
N4—C7—C8—C9176.4 (2)C8—C7—N3—N2−178.0 (2)
C12—C8—C9—C100.0 (4)C6—N2—N3—C7−0.6 (3)
C7—C8—C9—C10177.0 (3)N2—C6—N4—C7−0.7 (3)
C8—C9—C10—N50.4 (5)C3—C6—N4—C7176.3 (2)
N5—C11—C12—C80.6 (4)N3—C7—N4—C60.2 (3)
C9—C8—C12—C11−0.4 (4)C8—C7—N4—C6178.5 (2)
C7—C8—C12—C11−177.5 (2)C9—C10—N5—C11−0.3 (5)
C4—C5—N1—C1−1.4 (4)C12—C11—N5—C10−0.2 (4)
C4—C5—N1—Cd1−178.7 (2)

Symmetry codes: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1A···N2ii0.84 (2)1.95 (3)2.768 (3)164 (3)
O1—H1B···O30.85 (3)1.95 (3)2.786 (3)169 (3)
O2—H2A···N3iii0.85 (3)1.98 (3)2.829 (3)171 (3)
O2—H2B···O3iv0.85 (3)1.95 (3)2.758 (3)161 (3)
O3—H3A···N4v0.85 (3)2.06 (2)2.895 (3)171 (3)
O3—H3B···N5vi0.85 (3)1.95 (2)2.796 (3)170 (3)

Symmetry codes: (ii) −x, y−1/2, −z+1/2; (iii) x, −y+3/2, z+1/2; (iv) −x+1, −y+1, −z+1; (v) x, −y+3/2, z−1/2; (vi) −x+1, −y+2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BG2273).

References

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  • Deisenhofer, J. & Michel, H. (1989). EMBO J.8, 2149–2154. [PubMed]
  • Fu, Z., Gao, S. & Liu, S. (2007). Acta Cryst. C63, m459–m461. [PubMed]
  • Li, F., Su, T.-H., Gao, W. & Cao, R. (2006). Eur. J. Inorg. Chem. pp. 1582–1587.
  • Russell, V. A. & Ward, M. D. (1996). Chem. Mater.8, 1654–1666.
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  • Wen, L.-L., Dang, D.-B., Duan, C.-Y., Li, Y.-Z., Tian, Z.-F. & Meng, Q.-J. (2005). Inorg. Chem.44, 7161–7164. [PubMed]

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