supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2008). E64, m1254    [ doi:10.1107/S1600536808027980 ]

catena-Poly[cadmium(II)-[mu]-benzene-1,2-diamine-[kappa]2N:N'-di-[mu]-chlorido]

W.-X. Liang and Z.-R. Qu

Abstract top

The title compound, [CdCl2(C6H8N2)]n, is a coordination polymer prepared by the hydrothermal reaction of cadmium chloride and o-diaminobenzene. The cadmium cation, located on an inversion center, is octahedrally coordinated by four Cl atoms at equatorial sites and two N atoms from two ligands at the axial sites. Cd atoms are bridged by Cl atoms, forming extended chains parallel to [010]. Neighboring chains are connected by N-H...Cl hydrogen bonds.

Comment top

Coordination frameworks have received much attention over the past decade due to their potential applications. Scientists have dedicated much attention to coordination compounds which constructed by ligands with diamino coordination sites (Choi et al., 1999; Fu et al., 2007), since cis-diamminedichloroplatium(II) received Food and Drug Administration's approval in 1979 for use as an anticancer drug (Spingler et al., 2001). The title compound, [CdCl2(C6H8N2)]n, is a coordination polymer prepared by the hydrothermal reaction of cadmium chloride and o-diaminobenzene.The Cd cation is located on the inversion center and octahedrally coordinated by four Cl atoms at equatorial sites and two N atoms from two ligands at the axial sites. Cd cations are bridged by Cl atoms to form a one-dimensional extended chain. The neighboring chains are binded by N—H···Cl hydrogen bonds.(Table 1) to form a two-dimensional network (Fig. 2).

Related literature top

For related literature, see: Choi et al. (1999); Spingler et al. (2001); Fu et al. (2007).

Experimental top

A mixture of CdCl2 (0.0366 g, 0.2 mmol) and benzene-1,2-diamine (0.0216 g, 0.2 mmol) in H2O (4 ml) was heated in Pyrex tube at 100°C for two days. After slowly cooling down to room temperature over a period of 10 h, colorless crystals of the title compound suitable for diffraction were isolated.

Refinement top

Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C, N atoms to which they are bonded, with C—H = 0.93 Å, N—H = 0.90 Å and with Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. A partial packing diagram of the title compound, with the displacement ellipsoids were drawn at the 30% probability level. [Symmetry codes: (A) 1-x, -y, 1-z; (B) 1-x, -12+y, 1-z; (C) +x, 1/2-y, +z.]
[Figure 2] Fig. 2. Part of the structure of (I), showing two-dimensional extended polymeric network. Dotted lines show intermolecular hydrogen bonding.
catena-Poly[cadmium(II)-µ-benzene-1,2-diamine-κ2N:N'-di-µ-chlorido] top
Crystal data top
[CdCl2(C6H8N2)]F(000) = 280
Mr = 291.44Dx = 2.147 Mg m−3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 4460 reflections
a = 6.1235 (6) Åθ = 3.1–27.5°
b = 7.5473 (5) ŵ = 2.95 mm−1
c = 10.1081 (6) ÅT = 293 K
β = 105.230 (1)°Prism, colourless
V = 450.75 (6) Å30.18 × 0.15 × 0.14 mm
Z = 2
Data collection top
Rigaku SCXmini
diffractometer		1109 independent reflections
Radiation source: fine-focus sealed tube1020 reflections with I > 2σ(I)
graphiteRint = 0.029
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.4°
CCD profile fitting scansh = −7→7
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −9→9
Tmin = 0.595, Tmax = 0.660l = −13→13
4700 measured reflections
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)] = 0.018H-atom parameters constrained
wR(F2) = 0.040 w = 1/[σ2(Fo2) + (0.0114P)2 + 0.0467P]
where P = (Fo2 + 2Fc2)/3
S = 1.22(Δ/σ)max < 0.001
1109 reflectionsΔρmax = 0.25 e Å−3
56 parametersΔρmin = −0.35 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.115 (2)
Crystal data top
[CdCl2(C6H8N2)]V = 450.75 (6) Å3
Mr = 291.44Z = 2
Monoclinic, P21/mMo Kα radiation
a = 6.1235 (6) ŵ = 2.95 mm−1
b = 7.5473 (5) ÅT = 293 K
c = 10.1081 (6) Å0.18 × 0.15 × 0.14 mm
β = 105.230 (1)°
Data collection top
Rigaku SCXmini
diffractometer		1109 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		1020 reflections with I > 2σ(I)
Tmin = 0.595, Tmax = 0.660Rint = 0.029
4700 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.018H-atom parameters constrained
wR(F2) = 0.040Δρmax = 0.25 e Å−3
S = 1.22Δρmin = −0.35 e Å−3
1109 reflectionsAbsolute structure: ?
56 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Cd10.50000.00000.50000.02699 (11)
Cl10.26524 (11)0.25000.58281 (8)0.03186 (18)
Cl20.62145 (13)0.25000.35295 (7)0.03336 (19)
N10.8292 (3)0.0596 (2)0.67983 (17)0.0290 (4)
H1A0.8687−0.05460.70420.043*
H1B0.93410.10800.64390.043*
C20.7996 (3)0.1574 (2)0.79569 (18)0.0249 (4)
C30.7561 (3)0.0677 (3)0.9058 (2)0.0348 (5)
H30.7530−0.05550.90560.042*
C40.7174 (3)0.1588 (3)1.0153 (2)0.0411 (5)
H40.69130.09711.08930.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.03100 (15)0.02342 (14)0.02722 (15)−0.00010 (7)0.00882 (10)−0.00260 (7)
Cl10.0293 (4)0.0263 (4)0.0466 (4)0.0000.0218 (3)0.000
Cl20.0499 (4)0.0270 (4)0.0289 (4)0.0000.0205 (3)0.000
N10.0290 (9)0.0270 (8)0.0324 (9)−0.0003 (7)0.0108 (8)−0.0011 (7)
C20.0180 (8)0.0319 (10)0.0234 (9)−0.0015 (7)0.0031 (7)−0.0008 (8)
C30.0284 (10)0.0391 (12)0.0348 (11)−0.0017 (9)0.0045 (9)0.0089 (10)
C40.0308 (11)0.0662 (15)0.0271 (10)−0.0034 (10)0.0093 (9)0.0071 (10)
Geometric parameters (Å, °) top
Cd1—N1i2.3758 (17)N1—H1A0.9113
Cd1—N12.3758 (17)N1—H1B0.8946
Cd1—Cl22.6274 (5)C2—C31.387 (3)
Cd1—Cl2i2.6274 (5)C2—C2iii1.398 (4)
Cd1—Cl1i2.6381 (5)C3—C41.375 (3)
Cd1—Cl12.6381 (5)C3—H30.9300
Cl1—Cd1ii2.6381 (5)C4—C4iii1.377 (5)
Cl2—Cd1ii2.6274 (5)C4—H40.9300
N1—C21.436 (2)
N1i—Cd1—N1180.00 (7)Cd1—Cl2—Cd1ii91.80 (2)
N1i—Cd1—Cl290.71 (4)C2—N1—Cd1117.26 (11)
N1—Cd1—Cl289.29 (4)C2—N1—H1A110.3
N1i—Cd1—Cl2i89.29 (4)Cd1—N1—H1A98.0
N1—Cd1—Cl2i90.71 (4)C2—N1—H1B112.2
Cl2—Cd1—Cl2i180.0Cd1—N1—H1B108.8
N1i—Cd1—Cl1i92.61 (4)H1A—N1—H1B109.2
N1—Cd1—Cl1i87.39 (4)C3—C2—C2iii119.20 (13)
Cl2—Cd1—Cl1i94.319 (17)C3—C2—N1119.72 (18)
Cl2i—Cd1—Cl1i85.682 (17)C2iii—C2—N1120.96 (10)
N1i—Cd1—Cl187.39 (4)C4—C3—C2120.8 (2)
N1—Cd1—Cl192.61 (4)C4—C3—H3119.6
Cl2—Cd1—Cl185.682 (17)C2—C3—H3119.6
Cl2i—Cd1—Cl194.318 (17)C3—C4—C4iii119.98 (13)
Cl1i—Cd1—Cl1180.00 (3)C3—C4—H4120.0
Cd1ii—Cl1—Cd191.32 (2)C4iii—C4—H4120.0
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, y+1/2, −z+1; (iii) x, −y+1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···Cl1iv0.892.513.3960 (18)171.
Symmetry codes: (iv) x+1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···Cl1i0.892.513.3960 (18)171.
Symmetry codes: (i) x+1, y, z.
Acknowledgements top

This work was supported by a Start-up Grant from Southeast University to ZRQ.

references
References top

Choi, K. Y., Kim, Y. J., Ryu, H. & Suh, I. H. (1999). Inorg. Chem. Commun. 2, 176–180.

Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.

Fu, D.-W. & Zhao, H. (2007). Acta Cryst. E63, m1630.

Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spingler, B., Whittington, D. A. & Lippard, S. J. (2001). Inorg. Chem. 40, 5596–5602.