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In the title compound, [CdCl2(C10H8N2)]n, the CdII ion is six-coordinate and has a distorted octahedral geometry. The basal plane is formed by the two N atoms of the 2,2′-bi­pyridine ligand [Cd—N 2.352 (3) Å] and two Cl atoms [Cd—Cl 2.5519 (8) Å]. The apical sites are occupied by Cl atoms from neighbouring monomeric units [Cd—Cl 2.7517 (9) Å]. All the Cl atoms act as bridging ligands. The adjacent Cd coordination polyhedra share Cl—Cl edges, thus giving rise to a polymeric chain along the c axis. The CdII ion is positioned on a twofold axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803018622/ww6107sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803018622/ww6107Isup2.hkl
Contains datablock I

CCDC reference: 222832

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.025
  • wR factor = 0.065
  • Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low ....... 0.98
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Polynuclear d10 metal complexes have been found to exhibit intriguing structural and photoluminescent properties. Chloride-bridged cadmium(II) polymeric complexes are of considerable interest, because they may act as photoactive materials. Structural studies of chloride-bridged CdII polymeric complexes are common (Bell et al., 1982; Griffith et al., 1982; Bigoli et al., 1983; Huang et al., 1998). However, CdII polymeric complexes with a CdCl2N2 coordination polydedron have rarely been reported (Bonomo et al., 1989). We have introduced 2,2'-bipyridine as a terminal ligand which favours crystal growth of the product. Through a hydrothermal reaction, we have successfully synthesized the title crystalline chloride-bridged Cd complex [CdCl2(bpy)]n (bpy is 2,2'-bipyridine), (I).

Single crystal X-ray diffraction analysis reveals that compound (I) crystallizes in space group C2/c and consists of one-dimensional chains along the c axis. It is isostructural with an analogous bromide-bridged CuII complex (Garland et al., 1988). The CdII ion is positioned on the 21 axis, so the primarily monomeric unit is generated by symmetry (Fig. 1).

The CdII ion in (I) is coordinated by two N atoms from one chelating bpy ligand and by four Cl atoms, to furnish a distorted coordination octahedron, as depicted in Fig. 2. The basal plane is formed by the two cis N atoms from the bpy ligand [Cd—N 2.352 (3) Å] and the two cis Cl atoms [Cd—Cl 2.5519 (8) Å]. The axial positions of the octahedron are occupied by Cl atoms from neighbouring monomeric units [Cd—Cl 2.7517 (9) Å]. Adjacent Cd coordination octahedra share Cl—Cl edges, thus forming a one-dimensional chain along the c axis. All bpy ligands are coordinated in a chelating mode and they lie on alternate sides of the chain. The Cd···Cd distance between neighbouring CdII ions in the chain is 3.931 (9) Å, which is shorter than that of the CuII isomorph [3.974 (1) Å]. The closest distance between the pyridyl rings of two bpy ligands in neighbouring chains is 3.342 (3) Å, indicating the existence of ππ interactions between the adjacent chains. Thus the chains are connected to each other via ππ interactions to form two-dimensional layers parallel to the bc plane.

The packing of (I) (Fig. 3) is determined by van der Waals interactions and possible hydrogen bonds involving the C atoms of the bpy ligand and Cl atoms of the same [C4—H4A···Cli 3.534 (5) Å] or adjacent [C2—H2A···Clii 3.751 (5) Å] chains [symmetry codes: (i) 1 − x, 1 + y, 3/2 − z; (ii) x − 1/2, 1/2 + y, z − 1].

Experimental top

The hydrothermal reaction of cadmium chloride (0.06 g, 0.26 mmol), 2,2'-bipyridine (0.04 g, 0.25 mmol) and water (15.0 ml) was carried out at 433 K for 4 d. After cooling to room temperature at 5 K h−1, the crystalline complex, (I), was isolated in 63% yield (based on Cd). IR (KBr, ν, cm−1): 3417, 1604, 1558, 1439, 1375, 1171, 1016, 771, 735. Elemental analysis, calculated for C10H8N2CdCl2: C 35.38, H 2.38, N 8.25%; found: C 35.16, H 2.17, N 8.23%.

Refinement top

All H atoms were located in a difference Fourier map but were introduced in idealized positions (C—H = 0.93 Å) and treated as riding, with displacement parameters fixed at 120% of those of their parent atoms. The maximum residual electron-density peak is 0.84 Å from the Cd atom.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXTL (Siemens, 1994); program(s) used to refine structure: SHELXTL; molecular graphics: XPREP (Bruker, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick 1997).

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by circles of arbitrary size.
[Figure 2] Fig. 2. A view of the one-dimensional chain of chloride-bridged CdII ions in (I), along the a axis.
[Figure 3] Fig. 3. A packing diagram for (I), viewed down the c axis.
catena-poly[[(2,2'-bipyridine)cadmium(II)]-di-µ-chloro] top
Crystal data top
[CdCl2(C10H8N2)]F(000) = 656
Mr = 339.49Dx = 2.058 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 35 reflections
a = 17.5517 (6) Åθ = 2.5–25.0°
b = 9.3166 (6) ŵ = 2.44 mm1
c = 7.1710 (4) ÅT = 293 K
β = 110.860 (2)°Prism, colourless
V = 1095.76 (10) Å30.56 × 0.22 × 0.20 mm
Z = 4
Data collection top
Siemens SMART CCD area-detector
diffractometer
954 independent reflections
Radiation source: fine-focus sealed tube885 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ω scansθmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 2010
Tmin = 0.494, Tmax = 0.613k = 116
1693 measured reflectionsl = 88
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) = 0.065 w = 1/[σ2(Fo2) + (0.0528P)2 + 0.4415P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max = 0.001
954 reflectionsΔρmax = 0.43 e Å3
70 parametersΔρmin = 0.53 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0037 (4)
Crystal data top
[CdCl2(C10H8N2)]V = 1095.76 (10) Å3
Mr = 339.49Z = 4
Monoclinic, C2/cMo Kα radiation
a = 17.5517 (6) ŵ = 2.44 mm1
b = 9.3166 (6) ÅT = 293 K
c = 7.1710 (4) Å0.56 × 0.22 × 0.20 mm
β = 110.860 (2)°
Data collection top
Siemens SMART CCD area-detector
diffractometer
954 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
885 reflections with I > 2σ(I)
Tmin = 0.494, Tmax = 0.613Rint = 0.019
1693 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.065H-atom parameters constrained
S = 1.12Δρmax = 0.43 e Å3
954 reflectionsΔρmin = 0.53 e Å3
70 parameters
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
Cd0.50000.58652 (3)0.75000.03294 (18)
Cl0.59307 (5)0.41676 (9)1.01188 (13)0.0381 (2)
C10.3487 (2)0.7879 (5)0.4744 (6)0.0440 (9)
H1A0.32630.69890.42640.053*
C20.3018 (2)0.9094 (5)0.4072 (6)0.0504 (11)
H2A0.24860.90230.31720.060*
C30.3354 (3)1.0404 (5)0.4758 (6)0.0526 (11)
H3A0.30511.12380.43190.063*
C40.4139 (3)1.0482 (4)0.6096 (6)0.0427 (9)
H4A0.43771.13660.65600.051*
C50.4574 (2)0.9218 (3)0.6747 (5)0.0309 (7)
N0.42536 (16)0.7934 (3)0.6064 (4)0.0335 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd0.0349 (3)0.0249 (2)0.0302 (2)0.0000.00078 (15)0.000
Cl0.0374 (5)0.0361 (5)0.0362 (5)0.0098 (3)0.0073 (4)0.0075 (3)
C10.0324 (18)0.047 (2)0.046 (2)0.0018 (16)0.0052 (16)0.0092 (17)
C20.031 (2)0.068 (3)0.047 (2)0.0070 (19)0.0070 (17)0.020 (2)
C30.056 (3)0.056 (3)0.050 (2)0.024 (2)0.023 (2)0.021 (2)
C40.055 (2)0.0303 (18)0.046 (2)0.0075 (17)0.0225 (19)0.0080 (16)
C50.0347 (19)0.0278 (17)0.0335 (17)0.0011 (14)0.0162 (15)0.0030 (13)
N0.0283 (14)0.0347 (16)0.0344 (15)0.0014 (12)0.0075 (12)0.0052 (12)
Geometric parameters (Å, º) top
Cd—Ni2.352 (3)C1—H1A0.9300
Cd—N2.352 (3)C2—C31.368 (7)
Cd—Cli2.5519 (8)C2—H2A0.9300
Cd—Cl2.5519 (8)C3—C41.373 (6)
Cd—Clii2.7517 (9)C3—H3A0.9300
Cd—Cliii2.7517 (9)C4—C51.390 (5)
Cl—Cdii2.7517 (9)C4—H4A0.9300
C1—N1.342 (4)C5—N1.338 (4)
C1—C21.381 (6)C5—C5i1.502 (7)
Ni—Cd—N69.93 (14)N—C1—H1A118.7
Ni—Cd—Cli160.22 (7)C2—C1—H1A118.7
N—Cd—Cli94.29 (7)C3—C2—C1118.6 (4)
Ni—Cd—Cl94.29 (7)C3—C2—H2A120.7
N—Cd—Cl160.22 (7)C1—C2—H2A120.7
Cli—Cd—Cl103.40 (4)C2—C3—C4119.7 (4)
Ni—Cd—Clii95.66 (7)C2—C3—H3A120.2
N—Cd—Clii85.39 (7)C4—C3—H3A120.2
Cli—Cd—Clii94.81 (3)C3—C4—C5118.9 (4)
Cl—Cd—Clii84.40 (3)C3—C4—H4A120.5
Ni—Cd—Cliii85.39 (7)C5—C4—H4A120.5
N—Cd—Cliii95.66 (7)N—C5—C4121.7 (4)
Cli—Cd—Cliii84.40 (3)N—C5—C5i116.37 (19)
Cl—Cd—Cliii94.81 (3)C4—C5—C5i121.9 (2)
Clii—Cd—Cliii178.73 (4)C5—N—C1118.5 (3)
Cd—Cl—Cdii95.60 (3)C5—N—Cd118.5 (2)
N—C1—C2122.6 (4)C1—N—Cd122.7 (3)
Ni—Cd—Cl—Cdii95.28 (7)C5i—C5—N—Cd5.7 (5)
N—Cd—Cl—Cdii59.2 (2)C2—C1—N—C50.1 (6)
Cli—Cd—Cl—Cdii93.63 (3)C2—C1—N—Cd172.6 (3)
Clii—Cd—Cl—Cdii0.0Ni—Cd—N—C52.15 (18)
Cliii—Cd—Cl—Cdii179.00 (3)Cli—Cd—N—C5169.9 (2)
N—C1—C2—C31.0 (6)Cl—Cd—N—C536.5 (4)
C1—C2—C3—C40.5 (6)Clii—Cd—N—C595.6 (2)
C2—C3—C4—C50.9 (6)Cliii—Cd—N—C585.1 (2)
C3—C4—C5—N1.8 (5)Ni—Cd—N—C1174.9 (4)
C3—C4—C5—C5i178.3 (4)Cli—Cd—N—C117.4 (3)
C4—C5—N—C11.3 (5)Cl—Cd—N—C1136.2 (3)
C5i—C5—N—C1178.8 (4)Clii—Cd—N—C177.1 (3)
C4—C5—N—Cd174.3 (3)Cliii—Cd—N—C1102.1 (3)
Symmetry codes: (i) x+1, y, z+3/2; (ii) x+1, y+1, z+2; (iii) x, y+1, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···Cliv0.932.833.751 (5)171
C4—H4A···Clv0.932.843.534 (5)132
Symmetry codes: (iv) x1/2, y+1/2, z1; (v) x+1, y+1, z+3/2.

Experimental details

Crystal data
Chemical formula[CdCl2(C10H8N2)]
Mr339.49
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)17.5517 (6), 9.3166 (6), 7.1710 (4)
β (°) 110.860 (2)
V3)1095.76 (10)
Z4
Radiation typeMo Kα
µ (mm1)2.44
Crystal size (mm)0.56 × 0.22 × 0.20
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.494, 0.613
No. of measured, independent and
observed [I > 2σ(I)] reflections
1693, 954, 885
Rint0.019
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.065, 1.12
No. of reflections954
No. of parameters70
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.43, 0.53

Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1994), SHELXTL (Siemens, 1994), SHELXTL, XPREP (Bruker, 1997), SHELXL97 (Sheldrick 1997).

Selected geometric parameters (Å, º) top
Cd—Ni2.352 (3)C2—C31.368 (7)
Cd—Cl2.5519 (8)C3—C41.373 (6)
Cd—Clii2.7517 (9)C4—C51.390 (5)
C1—N1.342 (4)C5—N1.338 (4)
C1—C21.381 (6)C5—C5i1.502 (7)
Ni—Cd—N69.93 (14)Cl—Cd—Clii84.40 (3)
Ni—Cd—Cli160.22 (7)Clii—Cd—Cliii178.73 (4)
N—Cd—Cli94.29 (7)Cd—Cl—Cdii95.60 (3)
N—Cd—Cl160.22 (7)N—C1—C2122.6 (4)
Cli—Cd—Cl103.40 (4)C3—C2—C1118.6 (4)
Ni—Cd—Clii95.66 (7)C2—C3—C4119.7 (4)
N—Cd—Clii85.39 (7)C3—C4—C5118.9 (4)
Cli—Cd—Clii94.81 (3)N—C5—C4121.7 (4)
Symmetry codes: (i) x+1, y, z+3/2; (ii) x+1, y+1, z+2; (iii) x, y+1, z1/2.
 

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