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The novel title CdII coordination polymer, poly­[[di­chlorocad­mium(II)]-di-μ-1,1′-(1,4-butane­diyl)­di­imidazole], [CdCl2(C10H14N4)2]n, (I), was obtained by reaction of CdCl2·2.5H2O and 1,1′-(1,4-butane­diyl)diimidazole (hereafter L). In (I), each L molecule coordinates to two CdII cations through its two aromatic N atoms, thus acting as a bridging bidentate ligand. The CdII cations, which lie on the inversion centre, are bridged by four L molecules to form a two-dimensional (4,4)-network. The two-dimensional square-grid sheets are superimposed in an offset fashion.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103022443/av1149sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103022443/av1149Isup2.hkl
Contains datablock I

CCDC reference: 226112

Comment top

In recent years, research into coordination polymers has been expanding rapidly because of their fascinating structural diversity and potential application as functional materials (Batten & Robson, 1998; Moulton & Zaworotko, 2001). To date, a number of one-, two- and three-dimensional infinite frameworks have already been generated with linear N,N'-bidentate spacers (Tong et al., 2002). Much of the work has so far been focused on coordination polymers with rigid ligands, such as 4,4'-bipyridine, pyrazine and their analogues. However, flexible ligands such as 1,1'-(1,4-butanediyl)bis(benzimidazole) (L') and 1,1'-(1,4-butanediyl)bis(imidazole) (L) have not been well explored to date (Ma, Liu, Xing et al., 2000; Ma, Liu, Liu et al., 2000). In the present paper, we report the preparation and crystal structure of a novel two-dimensional coordination polymer, (I), namely [CdL2Cl2]n. \sch

Selected bond lengths and angles for (I) are given in Table 1. As shown in Fig. 1, the CdII cation occupies the inversion centre and is six-coordinated by four N atoms from four L molecules and two Cl anions. Each CdII cation has a slightly distorted [CdN4Cl2] octahedral coordination sphere. The average Cd—N distance of 2.3499 (19) Å is somewhat longer than the value of 2.275 (5) Å found in [CdL1.5(H2O)2(SO4)]·4H2O with a (6,3) network (Ma, Liu, Xing et al., 2000).

As illustrated in Fig. 2, each L molecule in (I) coordinates to two CdII cations through its two aromatic N atoms, thus acting as a bridging bidentate ligand. The CdII cations, which lie on the inversion centre, are bridged by four L molecules to form a two-dimensional neutral (4,4) network. The networks contain square grids (44-membered ring) with a CdII cation at each corner, and an L molecule at each edge connecting two CdII cations. Due to the symmetry of the crystal structure, the edge lengths are equal, and the edge length of 14.167 Å is similar to those of the related compound [CdL1.5(H2O)2(SO4)]·4H2O (Ma, Liu, Xing et al., 2000).

Although large circuits exist in a single net, they are mainly overlapped by other nets. The square-grid sheets superpose in an interesting off-set fashion. The off-set superposition of each pair of adjacent nets by one third of the edges divides the voids into smaller rectangles (Fig. 3), which are similar to those found in A-zeolites and Pentasil zeolites (Tong et al., 1998). In the superposition structure, the sheets are arranged in the sequence ···I—II-III-I—II-III···.

In conclusion, a novel two-dimensional coordination polymer, (I), with off-set superposition has been synthesized and studied by X-ray diffraction. In (I), CdII cations provide the four-connecting nodes of the net, and the L molecules link the nodes to form a two-dimensional (4,4) network.

Experimental top

A mixture of CdCl2·2.5H2O (0.228 g, 1 mmol) and L (0.380 g, 2 mmol) in water (20 ml) was refluxed for 20 min, then filtered whilst hot. Colourless crystals of (I) were obtained by evaporating the filtrate at room temperature for several days. The compound is insoluble in common organic solvents and dissolves in water only very slowly.

Refinement top

All H atoms on C atoms were generated geometrically and refined as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). Analytical expressions of neutral-atom scattering factors were employed and anomalous dispersion corrections incorporated.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990).

Figures top
[Figure 1] Fig. 1. A view of the local coordination of the CdII cation in (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
[Figure 2] Fig. 2. The two-dimensional sheet of the (4,4) network in (I); the Cl anions have been omitted for clarity.
[Figure 3] Fig. 3. A top view showing the off-set superposition of the adjacent nets in (I) along the c axis.
poly[[dichlorocadmium(II)]-di-µ-1,1'-(1,4-butanediyl)diimidazole] top
Crystal data top
[CdCl2(C10H14N4)2]F(000) = 572
Mr = 563.80Dx = 1.628 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 7161 reflections
a = 7.6488 (15) Åθ = 2.2–27.5°
b = 18.732 (4) ŵ = 1.21 mm1
c = 8.6668 (17) ÅT = 293 K
β = 112.11 (3)°Prism, colourless
V = 1150.4 (5) Å30.24 × 0.23 × 0.11 mm
Z = 2
Data collection top
Rigaku R-AXIS Rapid
diffractometer
2554 independent reflections
Radiation source: rotor-target2038 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
Detector resolution: 10.0 pixels mm-1θmax = 27.5°, θmin = 2.2°
ω scansh = 09
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 024
Tmin = 0.703, Tmax = 0.874l = 1010
9903 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.022Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0416P)2]
where P = (Fo2 + 2Fc2)/3
2554 reflections(Δ/σ)max < 0.001
142 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
[CdCl2(C10H14N4)2]V = 1150.4 (5) Å3
Mr = 563.80Z = 2
Monoclinic, P21/nMo Kα radiation
a = 7.6488 (15) ŵ = 1.21 mm1
b = 18.732 (4) ÅT = 293 K
c = 8.6668 (17) Å0.24 × 0.23 × 0.11 mm
β = 112.11 (3)°
Data collection top
Rigaku R-AXIS Rapid
diffractometer
2554 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
2038 reflections with I > 2σ(I)
Tmin = 0.703, Tmax = 0.874Rint = 0.020
9903 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.066H-atom parameters constrained
S = 1.02Δρmax = 0.46 e Å3
2554 reflectionsΔρmin = 0.35 e Å3
142 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
C10.3327 (3)0.12509 (12)0.0672 (3)0.0365 (5)
H10.41360.09180.04990.044*
C20.0910 (4)0.17421 (13)0.0860 (4)0.0555 (8)
H20.03040.18120.08350.067*
C30.2268 (4)0.22421 (13)0.1279 (4)0.0558 (7)
H30.21730.27100.15940.067*
C40.5695 (4)0.22336 (15)0.1569 (4)0.0589 (8)
H4A0.64970.18810.13410.071*
H4B0.62260.23340.27540.071*
C50.5737 (4)0.28992 (13)0.0652 (4)0.0467 (6)
H5A0.49230.32520.08600.056*
H5B0.52450.28000.05330.056*
C60.7703 (3)0.32020 (13)0.1162 (4)0.0461 (6)
H6A0.82550.32250.23690.055*
H6B0.84570.28720.08090.055*
C70.7850 (4)0.39189 (14)0.0497 (4)0.0554 (7)
H7A0.72710.39090.07090.067*
H7B0.71660.42610.08960.067*
C81.0895 (3)0.43827 (13)0.2529 (3)0.0391 (5)
H81.04740.44300.34010.047*
C91.0942 (4)0.41563 (12)0.0090 (3)0.0408 (5)
H91.05960.40200.10170.049*
C101.2638 (3)0.44015 (11)0.1104 (3)0.0374 (5)
H101.36730.44670.08030.045*
N10.1572 (3)0.11152 (10)0.0476 (3)0.0374 (4)
N20.3813 (3)0.19260 (10)0.1149 (3)0.0405 (5)
N31.2615 (2)0.45398 (10)0.2644 (2)0.0339 (4)
N40.9821 (3)0.41468 (10)0.1007 (2)0.0379 (4)
Cd10.00000.00000.00000.02934 (8)
Cl10.19637 (8)0.04189 (4)0.17972 (7)0.04375 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0314 (12)0.0367 (11)0.0435 (12)0.0011 (9)0.0163 (10)0.0052 (10)
C20.0380 (15)0.0359 (13)0.102 (2)0.0000 (11)0.0371 (16)0.0000 (14)
C30.0499 (17)0.0323 (12)0.095 (2)0.0025 (11)0.0387 (16)0.0034 (14)
C40.0301 (14)0.0548 (16)0.080 (2)0.0118 (12)0.0074 (13)0.0210 (15)
C50.0352 (13)0.0378 (13)0.0602 (16)0.0094 (10)0.0100 (12)0.0050 (12)
C60.0294 (13)0.0393 (13)0.0623 (16)0.0059 (10)0.0090 (11)0.0084 (12)
C70.0314 (14)0.0502 (15)0.0646 (17)0.0154 (11)0.0050 (12)0.0120 (13)
C80.0296 (12)0.0516 (14)0.0341 (11)0.0121 (10)0.0098 (9)0.0032 (10)
C90.0510 (16)0.0341 (12)0.0325 (11)0.0050 (11)0.0103 (11)0.0046 (9)
C100.0395 (13)0.0331 (12)0.0447 (12)0.0002 (9)0.0216 (10)0.0029 (10)
N10.0294 (10)0.0337 (10)0.0499 (11)0.0011 (8)0.0160 (9)0.0014 (8)
N20.0290 (10)0.0363 (10)0.0555 (12)0.0034 (8)0.0151 (9)0.0091 (9)
N30.0256 (9)0.0386 (10)0.0345 (9)0.0061 (8)0.0079 (7)0.0032 (8)
N40.0299 (10)0.0352 (10)0.0393 (10)0.0105 (8)0.0025 (8)0.0037 (8)
Cd10.02116 (12)0.02982 (12)0.03409 (12)0.00207 (9)0.00704 (8)0.00272 (9)
Cl10.0361 (3)0.0559 (4)0.0443 (3)0.0085 (3)0.0209 (2)0.0035 (3)
Geometric parameters (Å, º) top
C1—N11.312 (3)C6—H6A0.9700
C1—N21.339 (3)C6—H6B0.9700
C1—H10.9300C7—N41.466 (3)
C2—C31.343 (3)C7—H7A0.9700
C2—N11.369 (3)C7—H7B0.9700
C2—H20.9300C8—N31.315 (3)
C3—N21.364 (3)C8—N41.339 (3)
C3—H30.9300C8—H80.9300
C4—N21.463 (3)C9—C101.345 (3)
C4—C51.485 (3)C9—N41.371 (3)
C4—H4A0.9700C9—H90.9300
C4—H4B0.9700C10—N31.366 (3)
C5—C61.509 (3)C10—H100.9300
C5—H5A0.9700N1—Cd12.3680 (19)
C5—H5B0.9700N3—Cd1i2.3317 (19)
C6—C71.482 (3)Cd1—Cl12.6569 (8)
N1—C1—N2112.0 (2)N4—C8—H8124.0
N1—C1—H1124.0C10—C9—N4106.57 (19)
N2—C1—H1124.0C10—C9—H9126.7
C3—C2—N1110.2 (2)N4—C9—H9126.7
C3—C2—H2124.9C9—C10—N3109.8 (2)
N1—C2—H2124.9C9—C10—H10125.1
C2—C3—N2106.3 (2)N3—C10—H10125.1
C2—C3—H3126.8C1—N1—C2104.9 (2)
N2—C3—H3126.8C1—N1—Cd1128.38 (15)
N2—C4—C5114.5 (2)C2—N1—Cd1126.09 (15)
N2—C4—H4A108.6C1—N2—C3106.65 (19)
C5—C4—H4A108.6C1—N2—C4125.6 (2)
N2—C4—H4B108.6C3—N2—C4127.6 (2)
C5—C4—H4B108.6C8—N3—C10105.34 (18)
H4A—C4—H4B107.6C8—N3—Cd1i125.41 (15)
C4—C5—C6112.2 (2)C10—N3—Cd1i129.20 (15)
C4—C5—H5A109.2C8—N4—C9106.35 (19)
C6—C5—H5A109.2C8—N4—C7124.9 (2)
C4—C5—H5B109.2C9—N4—C7128.7 (2)
C6—C5—H5B109.2N3ii—Cd1—N3iii180.00 (11)
H5A—C5—H5B107.9N3ii—Cd1—N190.29 (7)
C7—C6—C5116.1 (2)N3iii—Cd1—N189.71 (7)
C7—C6—H6A108.3N3ii—Cd1—N1iv89.71 (7)
C5—C6—H6A108.3N3iii—Cd1—N1iv90.29 (7)
C7—C6—H6B108.3N1—Cd1—N1iv180.00 (4)
C5—C6—H6B108.3N3ii—Cd1—Cl188.61 (5)
H6A—C6—H6B107.4N3iii—Cd1—Cl191.39 (5)
N4—C7—C6111.5 (2)N1—Cd1—Cl189.97 (5)
N4—C7—H7A109.3N1iv—Cd1—Cl190.03 (5)
C6—C7—H7A109.3N3ii—Cd1—Cl1iv91.39 (5)
N4—C7—H7B109.3N3iii—Cd1—Cl1iv88.61 (5)
C6—C7—H7B109.3N1—Cd1—Cl1iv90.03 (5)
H7A—C7—H7B108.0N1iv—Cd1—Cl1iv89.97 (5)
N3—C8—N4111.9 (2)Cl1—Cd1—Cl1iv180.00 (3)
N3—C8—H8124.0
N1—C2—C3—N20.3 (4)C9—C10—N3—C80.6 (3)
N2—C4—C5—C6178.7 (3)C9—C10—N3—Cd1i178.29 (15)
C4—C5—C6—C7171.5 (3)N3—C8—N4—C90.1 (3)
C5—C6—C7—N4177.4 (2)N3—C8—N4—C7179.0 (2)
N4—C9—C10—N30.6 (3)C10—C9—N4—C80.3 (3)
N2—C1—N1—C20.3 (3)C10—C9—N4—C7179.4 (2)
N2—C1—N1—Cd1171.22 (15)C6—C7—N4—C875.9 (3)
C3—C2—N1—C10.0 (3)C6—C7—N4—C9103.0 (3)
C3—C2—N1—Cd1171.2 (2)C1—N1—Cd1—N3ii126.2 (2)
N1—C1—N2—C30.5 (3)C2—N1—Cd1—N3ii64.6 (2)
N1—C1—N2—C4176.1 (2)C1—N1—Cd1—N3iii53.8 (2)
C2—C3—N2—C10.4 (3)C2—N1—Cd1—N3iii115.4 (2)
C2—C3—N2—C4176.0 (3)C1—N1—Cd1—Cl1145.2 (2)
C5—C4—N2—C1127.0 (3)C2—N1—Cd1—Cl124.0 (2)
C5—C4—N2—C358.2 (4)C1—N1—Cd1—Cl1iv34.8 (2)
N4—C8—N3—C100.5 (3)C2—N1—Cd1—Cl1iv156.0 (2)
N4—C8—N3—Cd1i178.23 (14)
Symmetry codes: (i) x+3/2, y+1/2, z+1/2; (ii) x3/2, y+1/2, z1/2; (iii) x+3/2, y1/2, z+1/2; (iv) x, y, z.

Experimental details

Crystal data
Chemical formula[CdCl2(C10H14N4)2]
Mr563.80
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)7.6488 (15), 18.732 (4), 8.6668 (17)
β (°) 112.11 (3)
V3)1150.4 (5)
Z2
Radiation typeMo Kα
µ (mm1)1.21
Crystal size (mm)0.24 × 0.23 × 0.11
Data collection
DiffractometerRigaku R-AXIS Rapid
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.703, 0.874
No. of measured, independent and
observed [I > 2σ(I)] reflections
9903, 2554, 2038
Rint0.020
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.066, 1.02
No. of reflections2554
No. of parameters142
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.46, 0.35

Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990).

Selected geometric parameters (Å, º) top
N1—Cd12.3680 (19)Cd1—Cl12.6569 (8)
N3—Cd1i2.3317 (19)
N3ii—Cd1—N190.29 (7)N3iii—Cd1—Cl191.39 (5)
N3iii—Cd1—N189.71 (7)N1—Cd1—Cl189.97 (5)
N3ii—Cd1—Cl188.61 (5)N1iv—Cd1—Cl190.03 (5)
Symmetry codes: (i) x+3/2, y+1/2, z+1/2; (ii) x3/2, y+1/2, z1/2; (iii) x+3/2, y1/2, z+1/2; (iv) x, y, z.
 

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