Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103022443/av1149sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103022443/av1149Isup2.hkl |
CCDC reference: 226112
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.
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.
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).
[CdCl2(C10H14N4)2] | F(000) = 572 |
Mr = 563.80 | Dx = 1.628 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7161 reflections |
a = 7.6488 (15) Å | θ = 2.2–27.5° |
b = 18.732 (4) Å | µ = 1.21 mm−1 |
c = 8.6668 (17) Å | T = 293 K |
β = 112.11 (3)° | Prism, colourless |
V = 1150.4 (5) Å3 | 0.24 × 0.23 × 0.11 mm |
Z = 2 |
Rigaku R-AXIS Rapid diffractometer | 2554 independent reflections |
Radiation source: rotor-target | 2038 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
Detector resolution: 10.0 pixels mm-1 | θmax = 27.5°, θmin = 2.2° |
ω scans | h = 0→9 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = 0→24 |
Tmin = 0.703, Tmax = 0.874 | l = −10→10 |
9903 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.066 | H-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 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
[CdCl2(C10H14N4)2] | V = 1150.4 (5) Å3 |
Mr = 563.80 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.6488 (15) Å | µ = 1.21 mm−1 |
b = 18.732 (4) Å | T = 293 K |
c = 8.6668 (17) Å | 0.24 × 0.23 × 0.11 mm |
β = 112.11 (3)° |
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 = 0.874 | Rint = 0.020 |
9903 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.46 e Å−3 |
2554 reflections | Δρmin = −0.35 e Å−3 |
142 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.3327 (3) | 0.12509 (12) | 0.0672 (3) | 0.0365 (5) | |
H1 | 0.4136 | 0.0918 | 0.0499 | 0.044* | |
C2 | 0.0910 (4) | 0.17421 (13) | 0.0860 (4) | 0.0555 (8) | |
H2 | −0.0304 | 0.1812 | 0.0835 | 0.067* | |
C3 | 0.2268 (4) | 0.22421 (13) | 0.1279 (4) | 0.0558 (7) | |
H3 | 0.2173 | 0.2710 | 0.1594 | 0.067* | |
C4 | 0.5695 (4) | 0.22336 (15) | 0.1569 (4) | 0.0589 (8) | |
H4A | 0.6497 | 0.1881 | 0.1341 | 0.071* | |
H4B | 0.6226 | 0.2334 | 0.2754 | 0.071* | |
C5 | 0.5737 (4) | 0.28992 (13) | 0.0652 (4) | 0.0467 (6) | |
H5A | 0.4923 | 0.3252 | 0.0860 | 0.056* | |
H5B | 0.5245 | 0.2800 | −0.0533 | 0.056* | |
C6 | 0.7703 (3) | 0.32020 (13) | 0.1162 (4) | 0.0461 (6) | |
H6A | 0.8255 | 0.3225 | 0.2369 | 0.055* | |
H6B | 0.8457 | 0.2872 | 0.0809 | 0.055* | |
C7 | 0.7850 (4) | 0.39189 (14) | 0.0497 (4) | 0.0554 (7) | |
H7A | 0.7271 | 0.3909 | −0.0709 | 0.067* | |
H7B | 0.7166 | 0.4261 | 0.0896 | 0.067* | |
C8 | 1.0895 (3) | 0.43827 (13) | 0.2529 (3) | 0.0391 (5) | |
H8 | 1.0474 | 0.4430 | 0.3401 | 0.047* | |
C9 | 1.0942 (4) | 0.41563 (12) | 0.0090 (3) | 0.0408 (5) | |
H9 | 1.0596 | 0.4020 | −0.1017 | 0.049* | |
C10 | 1.2638 (3) | 0.44015 (11) | 0.1104 (3) | 0.0374 (5) | |
H10 | 1.3673 | 0.4467 | 0.0803 | 0.045* | |
N1 | 0.1572 (3) | 0.11152 (10) | 0.0476 (3) | 0.0374 (4) | |
N2 | 0.3813 (3) | 0.19260 (10) | 0.1149 (3) | 0.0405 (5) | |
N3 | 1.2615 (2) | 0.45398 (10) | 0.2644 (2) | 0.0339 (4) | |
N4 | 0.9821 (3) | 0.41468 (10) | 0.1007 (2) | 0.0379 (4) | |
Cd1 | 0.0000 | 0.0000 | 0.0000 | 0.02934 (8) | |
Cl1 | −0.19637 (8) | 0.04189 (4) | 0.17972 (7) | 0.04375 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0314 (12) | 0.0367 (11) | 0.0435 (12) | 0.0011 (9) | 0.0163 (10) | 0.0052 (10) |
C2 | 0.0380 (15) | 0.0359 (13) | 0.102 (2) | 0.0000 (11) | 0.0371 (16) | 0.0000 (14) |
C3 | 0.0499 (17) | 0.0323 (12) | 0.095 (2) | −0.0025 (11) | 0.0387 (16) | −0.0034 (14) |
C4 | 0.0301 (14) | 0.0548 (16) | 0.080 (2) | −0.0118 (12) | 0.0074 (13) | 0.0210 (15) |
C5 | 0.0352 (13) | 0.0378 (13) | 0.0602 (16) | −0.0094 (10) | 0.0100 (12) | 0.0050 (12) |
C6 | 0.0294 (13) | 0.0393 (13) | 0.0623 (16) | −0.0059 (10) | 0.0090 (11) | 0.0084 (12) |
C7 | 0.0314 (14) | 0.0502 (15) | 0.0646 (17) | −0.0154 (11) | −0.0050 (12) | 0.0120 (13) |
C8 | 0.0296 (12) | 0.0516 (14) | 0.0341 (11) | −0.0121 (10) | 0.0098 (9) | −0.0032 (10) |
C9 | 0.0510 (16) | 0.0341 (12) | 0.0325 (11) | −0.0050 (11) | 0.0103 (11) | −0.0046 (9) |
C10 | 0.0395 (13) | 0.0331 (12) | 0.0447 (12) | −0.0002 (9) | 0.0216 (10) | −0.0029 (10) |
N1 | 0.0294 (10) | 0.0337 (10) | 0.0499 (11) | −0.0011 (8) | 0.0160 (9) | 0.0014 (8) |
N2 | 0.0290 (10) | 0.0363 (10) | 0.0555 (12) | −0.0034 (8) | 0.0151 (9) | 0.0091 (9) |
N3 | 0.0256 (9) | 0.0386 (10) | 0.0345 (9) | −0.0061 (8) | 0.0079 (7) | −0.0032 (8) |
N4 | 0.0299 (10) | 0.0352 (10) | 0.0393 (10) | −0.0105 (8) | 0.0025 (8) | 0.0037 (8) |
Cd1 | 0.02116 (12) | 0.02982 (12) | 0.03409 (12) | 0.00207 (9) | 0.00704 (8) | 0.00272 (9) |
Cl1 | 0.0361 (3) | 0.0559 (4) | 0.0443 (3) | 0.0085 (3) | 0.0209 (2) | 0.0035 (3) |
C1—N1 | 1.312 (3) | C6—H6A | 0.9700 |
C1—N2 | 1.339 (3) | C6—H6B | 0.9700 |
C1—H1 | 0.9300 | C7—N4 | 1.466 (3) |
C2—C3 | 1.343 (3) | C7—H7A | 0.9700 |
C2—N1 | 1.369 (3) | C7—H7B | 0.9700 |
C2—H2 | 0.9300 | C8—N3 | 1.315 (3) |
C3—N2 | 1.364 (3) | C8—N4 | 1.339 (3) |
C3—H3 | 0.9300 | C8—H8 | 0.9300 |
C4—N2 | 1.463 (3) | C9—C10 | 1.345 (3) |
C4—C5 | 1.485 (3) | C9—N4 | 1.371 (3) |
C4—H4A | 0.9700 | C9—H9 | 0.9300 |
C4—H4B | 0.9700 | C10—N3 | 1.366 (3) |
C5—C6 | 1.509 (3) | C10—H10 | 0.9300 |
C5—H5A | 0.9700 | N1—Cd1 | 2.3680 (19) |
C5—H5B | 0.9700 | N3—Cd1i | 2.3317 (19) |
C6—C7 | 1.482 (3) | Cd1—Cl1 | 2.6569 (8) |
N1—C1—N2 | 112.0 (2) | N4—C8—H8 | 124.0 |
N1—C1—H1 | 124.0 | C10—C9—N4 | 106.57 (19) |
N2—C1—H1 | 124.0 | C10—C9—H9 | 126.7 |
C3—C2—N1 | 110.2 (2) | N4—C9—H9 | 126.7 |
C3—C2—H2 | 124.9 | C9—C10—N3 | 109.8 (2) |
N1—C2—H2 | 124.9 | C9—C10—H10 | 125.1 |
C2—C3—N2 | 106.3 (2) | N3—C10—H10 | 125.1 |
C2—C3—H3 | 126.8 | C1—N1—C2 | 104.9 (2) |
N2—C3—H3 | 126.8 | C1—N1—Cd1 | 128.38 (15) |
N2—C4—C5 | 114.5 (2) | C2—N1—Cd1 | 126.09 (15) |
N2—C4—H4A | 108.6 | C1—N2—C3 | 106.65 (19) |
C5—C4—H4A | 108.6 | C1—N2—C4 | 125.6 (2) |
N2—C4—H4B | 108.6 | C3—N2—C4 | 127.6 (2) |
C5—C4—H4B | 108.6 | C8—N3—C10 | 105.34 (18) |
H4A—C4—H4B | 107.6 | C8—N3—Cd1i | 125.41 (15) |
C4—C5—C6 | 112.2 (2) | C10—N3—Cd1i | 129.20 (15) |
C4—C5—H5A | 109.2 | C8—N4—C9 | 106.35 (19) |
C6—C5—H5A | 109.2 | C8—N4—C7 | 124.9 (2) |
C4—C5—H5B | 109.2 | C9—N4—C7 | 128.7 (2) |
C6—C5—H5B | 109.2 | N3ii—Cd1—N3iii | 180.00 (11) |
H5A—C5—H5B | 107.9 | N3ii—Cd1—N1 | 90.29 (7) |
C7—C6—C5 | 116.1 (2) | N3iii—Cd1—N1 | 89.71 (7) |
C7—C6—H6A | 108.3 | N3ii—Cd1—N1iv | 89.71 (7) |
C5—C6—H6A | 108.3 | N3iii—Cd1—N1iv | 90.29 (7) |
C7—C6—H6B | 108.3 | N1—Cd1—N1iv | 180.00 (4) |
C5—C6—H6B | 108.3 | N3ii—Cd1—Cl1 | 88.61 (5) |
H6A—C6—H6B | 107.4 | N3iii—Cd1—Cl1 | 91.39 (5) |
N4—C7—C6 | 111.5 (2) | N1—Cd1—Cl1 | 89.97 (5) |
N4—C7—H7A | 109.3 | N1iv—Cd1—Cl1 | 90.03 (5) |
C6—C7—H7A | 109.3 | N3ii—Cd1—Cl1iv | 91.39 (5) |
N4—C7—H7B | 109.3 | N3iii—Cd1—Cl1iv | 88.61 (5) |
C6—C7—H7B | 109.3 | N1—Cd1—Cl1iv | 90.03 (5) |
H7A—C7—H7B | 108.0 | N1iv—Cd1—Cl1iv | 89.97 (5) |
N3—C8—N4 | 111.9 (2) | Cl1—Cd1—Cl1iv | 180.00 (3) |
N3—C8—H8 | 124.0 | ||
N1—C2—C3—N2 | 0.3 (4) | C9—C10—N3—C8 | −0.6 (3) |
N2—C4—C5—C6 | 178.7 (3) | C9—C10—N3—Cd1i | −178.29 (15) |
C4—C5—C6—C7 | −171.5 (3) | N3—C8—N4—C9 | −0.1 (3) |
C5—C6—C7—N4 | −177.4 (2) | N3—C8—N4—C7 | 179.0 (2) |
N4—C9—C10—N3 | 0.6 (3) | C10—C9—N4—C8 | −0.3 (3) |
N2—C1—N1—C2 | −0.3 (3) | C10—C9—N4—C7 | −179.4 (2) |
N2—C1—N1—Cd1 | −171.22 (15) | C6—C7—N4—C8 | −75.9 (3) |
C3—C2—N1—C1 | 0.0 (3) | C6—C7—N4—C9 | 103.0 (3) |
C3—C2—N1—Cd1 | 171.2 (2) | C1—N1—Cd1—N3ii | −126.2 (2) |
N1—C1—N2—C3 | 0.5 (3) | C2—N1—Cd1—N3ii | 64.6 (2) |
N1—C1—N2—C4 | 176.1 (2) | C1—N1—Cd1—N3iii | 53.8 (2) |
C2—C3—N2—C1 | −0.4 (3) | C2—N1—Cd1—N3iii | −115.4 (2) |
C2—C3—N2—C4 | −176.0 (3) | C1—N1—Cd1—Cl1 | 145.2 (2) |
C5—C4—N2—C1 | 127.0 (3) | C2—N1—Cd1—Cl1 | −24.0 (2) |
C5—C4—N2—C3 | −58.2 (4) | C1—N1—Cd1—Cl1iv | −34.8 (2) |
N4—C8—N3—C10 | 0.5 (3) | C2—N1—Cd1—Cl1iv | 156.0 (2) |
N4—C8—N3—Cd1i | 178.23 (14) |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x−3/2, −y+1/2, z−1/2; (iii) −x+3/2, y−1/2, −z+1/2; (iv) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [CdCl2(C10H14N4)2] |
Mr | 563.80 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 7.6488 (15), 18.732 (4), 8.6668 (17) |
β (°) | 112.11 (3) |
V (Å3) | 1150.4 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.21 |
Crystal size (mm) | 0.24 × 0.23 × 0.11 |
Data collection | |
Diffractometer | Rigaku R-AXIS Rapid diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.703, 0.874 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9903, 2554, 2038 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.066, 1.02 |
No. of reflections | 2554 |
No. of parameters | 142 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.35 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990).
N1—Cd1 | 2.3680 (19) | Cd1—Cl1 | 2.6569 (8) |
N3—Cd1i | 2.3317 (19) | ||
N3ii—Cd1—N1 | 90.29 (7) | N3iii—Cd1—Cl1 | 91.39 (5) |
N3iii—Cd1—N1 | 89.71 (7) | N1—Cd1—Cl1 | 89.97 (5) |
N3ii—Cd1—Cl1 | 88.61 (5) | N1iv—Cd1—Cl1 | 90.03 (5) |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x−3/2, −y+1/2, z−1/2; (iii) −x+3/2, y−1/2, −z+1/2; (iv) −x, −y, −z. |
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.