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Acta Cryst. (2007). E63, m3038-m3039    [ doi:10.1107/S1600536807054918 ]

Diaquabis[3-(2-pyridyl)-1H-pyrazole- [kappa]2N2,N3]cadmium(II) dinitrate

C.-S. Liu

Abstract top

In the title centrosymmetric compound, [Cd(C8H7N3)2(H2O)2](NO3)2, the CdII atom lies on a center of symmetry and is six-coordinated by four N donors from two distinct chelating 3-(2-pyridyl)-1H-pyrazole ligands and two O atoms from two water molecules, in a distorted octahedral geometry. The CdII mononuclear units and nitrate ions are linked through intermolecular O-H...O, N-H...O and C-H...O hydrogen-bonding interactions, forming a three-dimensional framework.

Comment top

In recent years, much attention has been focused on the synthetic approach and the structural control of metal-organic coordination architectures with ligands based on pyrazolyl-pyridine chelating units (Steel, 2005; Ward et al., 2001). Many novel functional complexes with 3-(2-pyridyl)-1H-pyrazole (L) and/or 3-(2-pyridyl)pyrazole ligands have been reported (Bell et al., 2003; Paul et al., 2004; Singh et al., 2003; Ward et al., 2001). Recently, we have used 3-(2-pyridyl)-1H-pyrazole and its derivatives to obtain complexes with various structures, including discrete multinuclear molecules, one- and two-dimensional coordination polymers, which exhibit luminescent and magnetic properties (Hu et al., 2006; Liu et al., 2006, 2007; Zou et al., 2004,2005,2006). Now we report here the crystal structure of a cadmium(II) complex of L ligand, [Cd(L)2(H2O)2]2+·2NO32−, the title compound.

In the title centrosymmetric complex, the CdII center is six-coordinated by four N donors from two L ligands and two O atoms from two water molecules (Table 1). The L ligand chelates to the CdII atom, which lies on an inversion center, in a nearly isobidentate manner [Cd1—N2 = 2.3539 (18) Å and Cd1—N3 = 2.2900 (17) Å]. The two other coordination sites are occupied by two water molecules. The coordination geometry around the CdII center can be described as a distorted octahedron (Fig. 1). The distortion from the ideal octahedral geometry is evident from the bond angles given in Table 1.

The CdII mononuclear units are linked to nitrate anions through intermolecular O–H···O, N–H···O and C–H···O (Desiraju & Steiner, 1999) hydrogen-bonding interactions (Table 2) involving the coordinated water molecules and free nitrate anions, forming a three-dimensional framework (Fig. 2).

Related literature top

For related literature, see: Bell et al. (2003); Hu et al. (2006); Liu et al. (2006, 2007); Paul et al. (2004); Steel (2005); Ward et al. (2001); Zou et al. (2004, 2005, 2006). For hydrogen-bond details, see: Desiraju & Steiner (1999).

Experimental top

3-(2-Pyridyl)-1H-pyrazole) (0.1 mmol) and Cd(NO3)2 (0.1 mmol) were added to methanol (15 ml) containing water (5 ml). In few minutes, a white solid appeared which then was filtered. The resulting solution was kept at room temperature. Colourless single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of the solvent after several days (yield: 30%). Analysis calculated for (C16H18CdN8O8): C 34.15, H 3.22, N 19.91%; found: C 34.26, H 3.14, N 18.77%.

Refinement top

H atoms of the water molecule were located in a difference map and were allowed to ride on the parent atom, with Uiso = 1.2Ueq(O). The remaining H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C—H = 0.93 Å, N—H = 0.86 Å and i>Uiso(H) = 1.2Ueq(C,N).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Atoms labelled with the suffix A are generated by the symmetry operation (1 − x, 2 − y, 1 − z).
[Figure 2] Fig. 2. Part of the crystal packing in the title compound. Hydrogen bonds are shown as dashed lines. For clarity only H atoms involved in the interactions are shown.
Diaquabis[3-(2-pyridyl)-1H-pyrazole- κ2N2,N3]cadmium(II) dinitrate top
Crystal data top
[Cd(C8H7N3)2(H2O)2](NO3)2F000 = 564
Mr = 562.78Dx = 1.790 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 666 reflections
a = 8.1283 (16) Åθ = 2.3–22.5º
b = 10.461 (2) ŵ = 1.11 mm−1
c = 12.309 (3) ÅT = 293 (2) K
β = 94.04 (3)ºBlock, colourless
V = 1044.0 (4) Å30.22 × 0.18 × 0.16 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer		2377 independent reflections
Radiation source: fine-focus sealed tube1810 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.032
T = 293(2) Kθmax = 27.5º
φ and ω scansθmin = 2.6º
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		h = −10→10
Tmin = 0.795, Tmax = 0.845k = −14→13
6639 measured reflectionsl = −15→15
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.057  w = 1/[σ2(Fo2) + (0.0278P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.93(Δ/σ)max = 0.001
2377 reflectionsΔρmax = 0.43 e Å−3
151 parametersΔρmin = −0.25 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cd(C8H7N3)2(H2O)2](NO3)2V = 1044.0 (4) Å3
Mr = 562.78Z = 2
Monoclinic, P21/nMo Kα
a = 8.1283 (16) ŵ = 1.11 mm−1
b = 10.461 (2) ÅT = 293 (2) K
c = 12.309 (3) Å0.22 × 0.18 × 0.16 mm
β = 94.04 (3)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		2377 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		1810 reflections with I > 2σ(I)
Tmin = 0.795, Tmax = 0.845Rint = 0.032
6639 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.025151 parameters
wR(F2) = 0.057H-atom parameters constrained
S = 0.93Δρmax = 0.43 e Å−3
2377 reflectionsΔρmin = −0.25 e Å−3
Special details top

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) top
xyzUiso*/Ueq
Cd10.50001.00000.50000.03912 (8)
C10.7329 (3)0.6068 (2)0.5375 (2)0.0564 (6)
H1A0.81480.54500.53530.068*
C20.5940 (3)0.5968 (2)0.5903 (2)0.0559 (6)
H2A0.56050.52830.63150.067*
C30.5102 (3)0.7142 (2)0.56918 (17)0.0423 (5)
C40.3529 (3)0.7578 (2)0.60517 (17)0.0419 (5)
C50.2468 (3)0.6775 (2)0.6560 (2)0.0593 (7)
H5A0.27460.59230.66860.071*
C60.1009 (3)0.7249 (3)0.6875 (2)0.0669 (8)
H6A0.02940.67190.72240.080*
C70.0596 (3)0.8489 (3)0.6681 (2)0.0610 (7)
H7A−0.03980.88160.68900.073*
C80.1675 (3)0.9247 (2)0.6172 (2)0.0536 (6)
H8A0.13931.00950.60300.064*
N10.7326 (2)0.72088 (19)0.48873 (18)0.0529 (5)
H1B0.81020.74790.45060.064*
N20.5972 (2)0.78798 (17)0.50643 (15)0.0444 (4)
N30.3126 (2)0.88119 (17)0.58709 (14)0.0416 (4)
N4−0.4146 (2)0.79729 (19)0.84554 (14)0.0449 (4)
O1−0.4736 (2)0.69650 (17)0.87871 (16)0.0685 (5)
O2−0.2770 (2)0.7968 (2)0.81080 (17)0.0818 (6)
O3−0.4952 (3)0.89658 (17)0.84575 (19)0.0767 (6)
O1W0.3392 (2)0.96843 (16)0.33963 (14)0.0583 (5)
H1WA0.34211.01170.28140.070*
H1WB0.29020.89840.32360.070*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.03983 (12)0.03118 (11)0.04703 (13)−0.00183 (10)0.00790 (8)0.00727 (10)
C10.0514 (14)0.0395 (13)0.0765 (18)0.0158 (11)−0.0076 (13)−0.0038 (12)
C20.0613 (15)0.0411 (12)0.0636 (16)0.0000 (12)−0.0068 (12)0.0072 (12)
C30.0481 (12)0.0337 (10)0.0436 (12)−0.0016 (10)−0.0064 (9)0.0007 (9)
C40.0517 (12)0.0379 (11)0.0353 (11)−0.0125 (10)−0.0017 (9)0.0024 (9)
C50.0677 (17)0.0509 (14)0.0596 (15)−0.0166 (13)0.0075 (13)0.0097 (12)
C60.0603 (16)0.075 (2)0.0674 (17)−0.0231 (15)0.0199 (14)0.0018 (15)
C70.0428 (13)0.0773 (19)0.0655 (16)−0.0073 (13)0.0222 (12)−0.0123 (15)
C80.0530 (13)0.0493 (14)0.0594 (15)−0.0037 (12)0.0100 (12)−0.0038 (12)
N10.0448 (10)0.0454 (11)0.0690 (13)0.0079 (9)0.0072 (9)−0.0014 (10)
N20.0426 (10)0.0353 (9)0.0553 (11)0.0040 (8)0.0036 (8)0.0031 (9)
N30.0402 (9)0.0412 (10)0.0440 (10)−0.0051 (8)0.0069 (8)0.0009 (8)
N40.0498 (11)0.0432 (10)0.0414 (10)−0.0084 (9)0.0017 (8)−0.0012 (8)
O10.0753 (12)0.0446 (10)0.0860 (13)−0.0143 (9)0.0072 (10)0.0178 (10)
O20.0574 (11)0.1002 (16)0.0920 (15)−0.0163 (11)0.0359 (10)−0.0100 (13)
O30.0805 (13)0.0438 (10)0.1049 (16)0.0108 (10)−0.0012 (11)−0.0007 (11)
O1W0.0690 (11)0.0541 (10)0.0504 (9)−0.0187 (8)−0.0056 (8)0.0104 (8)
Geometric parameters (Å, °) top
Cd1—N32.2900 (17)C5—C61.367 (4)
Cd1—N3i2.2900 (17)C5—H5A0.93
Cd1—O1Wi2.3133 (18)C6—C71.357 (4)
Cd1—O1W2.3133 (18)C6—H6A0.93
Cd1—N22.3539 (18)C7—C81.366 (3)
Cd1—N2i2.3539 (18)C7—H7A0.93
C1—N11.336 (3)C8—N31.341 (3)
C1—C21.346 (4)C8—H8A0.93
C1—H1A0.93N1—N21.337 (2)
C2—C31.420 (3)N1—H1B0.86
C2—H2A0.93N4—O21.226 (2)
C3—N21.330 (3)N4—O31.228 (2)
C3—C41.456 (3)N4—O11.239 (2)
C4—N31.346 (3)O1W—H1WA0.85
C4—C51.384 (3)O1W—H1WB0.85
N3—Cd1—N3i180C6—C5—C4119.3 (3)
N3—Cd1—O1Wi91.87 (6)C6—C5—H5A120.4
N3i—Cd1—O1Wi88.13 (6)C4—C5—H5A120.4
N3—Cd1—O1W88.13 (6)C7—C6—C5120.4 (2)
N3i—Cd1—O1W91.87 (6)C7—C6—H6A119.8
O1Wi—Cd1—O1W180C5—C6—H6A119.8
N3—Cd1—N272.87 (6)C6—C7—C8118.4 (2)
N3i—Cd1—N2107.13 (6)C6—C7—H7A120.8
O1Wi—Cd1—N286.43 (7)C8—C7—H7A120.8
O1W—Cd1—N293.57 (7)N3—C8—C7122.4 (2)
N3—Cd1—N2i107.13 (6)N3—C8—H8A118.8
N3i—Cd1—N2i72.87 (6)C7—C8—H8A118.8
O1Wi—Cd1—N2i93.57 (7)C1—N1—N2111.8 (2)
O1W—Cd1—N2i86.43 (7)C1—N1—H1B124.1
N2—Cd1—N2i180N2—N1—H1B124.1
N1—C1—C2108.2 (2)C3—N2—N1105.52 (17)
N1—C1—H1A125.9C3—N2—Cd1112.07 (13)
C2—C1—H1A125.9N1—N2—Cd1140.14 (14)
C1—C2—C3104.6 (2)C8—N3—C4119.2 (2)
C1—C2—H2A127.7C8—N3—Cd1124.93 (16)
C3—C2—H2A127.7C4—N3—Cd1115.83 (14)
N2—C3—C2109.9 (2)O2—N4—O3120.3 (2)
N2—C3—C4120.58 (18)O2—N4—O1119.7 (2)
C2—C3—C4129.5 (2)O3—N4—O1120.0 (2)
N3—C4—C5120.3 (2)Cd1—O1W—H1WA126.6
N3—C4—C3117.32 (18)Cd1—O1W—H1WB123.3
C5—C4—C3122.4 (2)H1WA—O1W—H1WB107.7
N1—C1—C2—C30.1 (3)O1Wi—Cd1—N2—C383.94 (15)
C1—C2—C3—N20.3 (3)O1W—Cd1—N2—C3−96.06 (15)
C1—C2—C3—C4179.9 (2)N3—Cd1—N2—N1−168.5 (2)
N2—C3—C4—N3−10.1 (3)N3i—Cd1—N2—N111.5 (2)
C2—C3—C4—N3170.3 (2)O1Wi—Cd1—N2—N1−75.4 (2)
N2—C3—C4—C5169.8 (2)O1W—Cd1—N2—N1104.6 (2)
C2—C3—C4—C5−9.8 (4)C7—C8—N3—C41.5 (4)
N3—C4—C5—C60.1 (4)C7—C8—N3—Cd1179.34 (19)
C3—C4—C5—C6−179.9 (2)C5—C4—N3—C8−1.1 (3)
C4—C5—C6—C70.7 (4)C3—C4—N3—C8178.82 (19)
C5—C6—C7—C8−0.3 (4)C5—C4—N3—Cd1−179.15 (17)
C6—C7—C8—N3−0.8 (4)C3—C4—N3—Cd10.8 (2)
C2—C1—N1—N2−0.4 (3)O1Wi—Cd1—N3—C8100.70 (18)
C2—C3—N2—N1−0.5 (2)O1W—Cd1—N3—C8−79.30 (18)
C4—C3—N2—N1179.83 (19)N2—Cd1—N3—C8−173.62 (19)
C2—C3—N2—Cd1−166.96 (15)N2i—Cd1—N3—C86.38 (19)
C4—C3—N2—Cd113.4 (2)O1Wi—Cd1—N3—C4−81.39 (16)
C1—N1—N2—C30.6 (3)O1W—Cd1—N3—C498.61 (16)
C1—N1—N2—Cd1160.79 (18)N2—Cd1—N3—C44.29 (14)
N3—Cd1—N2—C3−9.12 (14)N2i—Cd1—N3—C4−175.71 (14)
N3i—Cd1—N2—C3170.88 (14)
Symmetry codes: (i) −x+1, −y+2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O2ii0.852.343.096 (3)148
O1W—H1WA···O3ii0.852.283.036 (3)149
O1W—H1WB···O2iii0.852.122.944 (3)164
N1—H1B···O1iv0.862.102.956 (3)171
N1—H1B···O3iv0.862.603.170 (3)125
O1W—H1WB···O1iii0.852.503.138 (2)133
C1—H1A···O3v0.932.533.319 (3)143
C8—H8A···O1vi0.932.393.253 (3)153
Symmetry codes: (ii) −x, −y+2, −z+1; (iii) x+1/2, −y+3/2, z−1/2; (iv) x+3/2, −y+3/2, z−1/2; (v) −x+1/2, y−1/2, −z+3/2; (vi) −x−1/2, y+1/2, −z+3/2.
Table 1
Selected geometric parameters (Å, °) top
Cd1—N32.2900 (17)Cd1—N22.3539 (18)
Cd1—O1W2.3133 (18)
N3—Cd1—N3i180O1W—Cd1—N293.57 (7)
N3—Cd1—O1Wi91.87 (6)N3—Cd1—N2i107.13 (6)
N3—Cd1—O1W88.13 (6)O1W—Cd1—N2i86.43 (7)
O1Wi—Cd1—O1W180N2—Cd1—N2i180
N3—Cd1—N272.87 (6)
Symmetry codes: (i) −x+1, −y+2, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O2ii0.852.343.096 (3)148
O1W—H1WA···O3ii0.852.283.036 (3)149
O1W—H1WB···O2iii0.852.122.944 (3)164
N1—H1B···O1iv0.862.102.956 (3)171
N1—H1B···O3iv0.862.603.170 (3)125
O1W—H1WB···O1iii0.852.503.138 (2)133
C1—H1A···O3v0.932.533.319 (3)143
C8—H8A···O1vi0.932.393.253 (3)153
Symmetry codes: (ii) −x, −y+2, −z+1; (iii) x+1/2, −y+3/2, z−1/2; (iv) x+3/2, −y+3/2, z−1/2; (v) −x+1/2, y−1/2, −z+3/2; (vi) −x−1/2, y+1/2, −z+3/2.
Acknowledgements top

The authors thank Zhengzhou University of Light Industry, Henan Provincial Key Laboratory of Surface and Interface Science, and Nankai University for supporting this work.

references
References top

Bell, Z. R., Harding, L. P. & Ward, M. D. (2003). Chem. Commun. pp. 2432–2433.

Bruker (1998). SMART (Version 5.051), SAINT (Version 5.01), SADABS (Version 2.03) and SHELXTL (Version 6.1). Bruker AXS Inc., Madison, Wisconsin, USA.

Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural Chemistry and Biology. Oxford University Press.

Hu, T.-L., Li, J.-R., Liu, C.-S., Shi, X.-S., Zhou, J.-N., Bu, X.-H. & Ribas, J. (2006). Inorg. Chem. 45, 162–173.

Liu, C.-S., Li, J.-R., Li, C.-Y., Wang, J.-J. & Bu, X.-H. (2007). Inorg. Chim. Acta, 360, 2532–2540.

Liu, C.-S., Shi, X.-S., Li, J.-R., Wang, J.-J. & Bu, X.-H. (2006). Cryst.Growth Des. 6, 656-663.

Paul, R. L., Argent, S. P., Jeffery, J. C., Harding, L. P., Lynamd, J. M. & Ward, M. D. (2004). J. Chem. Soc. Dalton Trans. pp. 3453–3458.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Steel, P. J. (2005). Acc. Chem. Res. 38, 243–250.

Ward, M. D., McCleverty, J. A. & Jeffery, J. C. (2001). Coord. Chem. Rev. 222, 251–272.

Zou, R.-Q., Bu, X.-H. & Zhang, R.-H. (2004). Inorg. Chem. 43, 5382–5386.

Zou, R.-Q., Liu, C.-S., Huang, Z., Hu, T.-L. & Bu, X.-H. (2006). Cryst. Growth Des. 6, 99–108.

Zou, R.-Q., Liu, C.-S., Shi, X.-S., Bu, X.-H. & Ribas, J. (2005). CrystEngComm, 7, 722–727.