catena-Poly[[bis­[2-(2-pyrid­yl)-1-H-imidazole-κ² N ²,N ³]cadmium]-μ-benzene-1,3-dicarboxyl­ato-κ² O ¹:O ³]

Abstract

In the title coordinaltion polymer, [Cd(C₈H₄O₄)(C₈H₇N₃)₂]_n, the Cd^II atom, lying on a twofold rotation axis, is six-coordinated by two carboxyl­ate O atoms from two benzene-1,3-dicarboxyl­ate (m-BDC) ligands and four N atoms from two chelating 2-(2-pyrid­yl)imidazole mol­ecules, forming a slightly distorted octa­hedral geometry. The m-BDC ligand is located over a twofold rotation axis. The Cd^II atoms are bridged by the m-BDC ligands, leading to a wave-shaped chain structure along [010]. N—H⋯O hydrogen bonds connect the chains.

Related literature

For general background to metal-organic frameworks, see: Chen et al. (2009 ▶); Rosi et al. (2003 ▶); Su et al. (2004 ▶); Xiao et al. (2006 ▶). For compounds based on benzene-1,3-dicarboxylate ligands, see: Banerjee et al. (2008 ▶); Che et al. (2009 ▶); Clegg & Russo (2009 ▶); Li et al. (2008 ▶); Su et al. (2009 ▶); Zhao (2008 ▶).

Experimental

Crystal data

• [Cd(C₈H₄O₄)(C₈H₇N₃)₂]

• M _r = 566.85

• Orthorhombic,

• a = 8.720 (5) Å

• b = 20.102 (4) Å

• c = 13.483 (5) Å

• V = 2363.4 (17) ų

• Z = 4

• Mo Kα radiation

• μ = 0.97 mm⁻¹

• T = 293 K

• 0.10 × 0.08 × 0.06 mm

Data collection

• Bruker APEX CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.911, T _max = 0.944

• 11996 measured reflections

• 2330 independent reflections

• 1298 reflections with I > 2σ(I)

• R _int = 0.060

Refinement

• R[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 0.100

• S = 1.00

• 2330 reflections

• 164 parameters

• 75 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.39 e Å⁻³

• Δρ_min = −0.69 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Cd1—O1	2.257 (3)
Cd1—N1	2.288 (4)
Cd1—N3	2.461 (4)

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N⋯O2i	0.95 (5)	1.80 (5)	2.741 (5)	166 (5)

Symmetry code: (i) .

supplementary crystallographic information

Comment

Currently, the design and synthesis of metal-organic frameworks (MOFs) are of great interest owing to their intriguing variety of architectures and their tremendous potential applications in many fields (Chen et al., 2009; Rosi et al., 2003; Su et al., 2004; Xiao et al., 2006). As a multidentate ligand, benzene-1,3-dicarboxylic acid (m-H₂BDC) has two carboxyl groups and, therefore, has been widely reported as a good candidate not only in the construction of various coordination polymers but also in the construction of MOFs with multi-dimension (Banerjee et al., 2008; Che et al., 2009; Clegg & Russo, 2009; Li et al., 2008; Su et al., 2009; Zhao, 2008).

In the title coordinaltion polymer (Fig. 1), the central Cd^II ion is six-coordinated by two carboxylate O atoms from two m-BDC ligands and four N atoms from two 2-(2-pyridyl)imidazole (2-PyIM) molecules (Table 1), forming a slightly distorted octahedral geometry. The Cd^II ions are bridged by the m-BDC ligands, leading to a wave-shaped chain structure, as shown in Fig. 2. N—H···O hydrogen bonds connect the chains (Table 2).

Experimental

All chemicals were purchased from commercial sources and used without further purification. CdSO₄.8H₂O (0.033 mmol), m-H₂BDC (0.1 mmol) and 2-PyIM (0.2 mmol) were dissolved in 15 ml of water. The mixture was stirred for 2 h at room temperature and then heated in a 30 ml Teflon-lined stainless steel autoclave for 3 d at 323 K. After the autoclave was cooled to room temperature, colorless block crystals were harvested.

Refinement

C-bound H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The H atom on imidazole N2 was located from a difference Fourier map and refined isotropically.

Figures

Fig. 1.

The structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) -x+5/2, -y+1, z; (ii) x, -y+1/2, -z+3/2.]

Fig. 2.

View of the one-dimensional chain structure of the title compound.

Crystal data

[Cd(C8H4O4)(C8H7N3)2]	F(000) = 1136
Mr = 566.85	Dx = 1.593 Mg m−3Dm = 1.593 Mg m−3Dm measured by not measured
Orthorhombic, Pnna	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2bc	Cell parameters from 2329 reflections
a = 8.720 (5) Å	θ = 2.0–52.0°
b = 20.102 (4) Å	µ = 0.97 mm−1
c = 13.483 (5) Å	T = 293 K
V = 2363.4 (17) Å3	Block, colorless
Z = 4	0.10 × 0.08 × 0.06 mm

Data collection

Bruker APEX CCD diffractometer	2330 independent reflections
Radiation source: fine-focus sealed tube	1298 reflections with I > 2σ(I)
graphite	Rint = 0.060
φ and ω scans	θmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.911, Tmax = 0.944	k = −21→24
11996 measured reflections	l = −16→16

Refinement

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.051P)2] where P = (Fo2 + 2Fc2)/3
2330 reflections	(Δ/σ)max < 0.001
164 parameters	Δρmax = 0.39 e Å−3
75 restraints	Δρmin = −0.69 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cd1	0.96428 (5)	0.2500	0.7500	0.05598 (19)
O1	1.1284 (4)	0.33138 (14)	0.7049 (2)	0.0738 (8)
C2	1.2020 (5)	0.44358 (18)	0.6952 (3)	0.0589 (10)
O2	1.1291 (4)	0.39000 (15)	0.8440 (2)	0.0883 (10)
C9	0.7428 (5)	0.1504 (2)	0.6230 (4)	0.0691 (12)
C3	1.2500	0.5000	0.7444 (4)	0.0549 (13)
H3	1.2500	0.5000	0.8133	0.066*
N3	0.7725 (5)	0.16257 (19)	0.7191 (3)	0.0692 (10)
N2	0.7945 (5)	0.1991 (2)	0.4546 (3)	0.0759 (12)
C13	0.7096 (7)	0.1223 (3)	0.7857 (4)	0.0919 (16)
H13	0.7293	0.1300	0.8525	0.110*
N1	0.9098 (5)	0.24430 (17)	0.5842 (3)	0.0673 (10)
C8	0.8139 (5)	0.1966 (2)	0.5556 (3)	0.0621 (11)
C6	0.9516 (6)	0.2781 (3)	0.4998 (4)	0.0769 (15)
H6	1.0177	0.3144	0.4980	0.092*
C1	1.1489 (6)	0.3835 (2)	0.7533 (3)	0.0630 (9)
C4	1.2024 (6)	0.4443 (2)	0.5936 (3)	0.0934 (15)
H4	1.1702	0.4070	0.5587	0.112*
C10	0.6521 (6)	0.0978 (3)	0.5917 (4)	0.0947 (16)
H10	0.6344	0.0903	0.5246	0.114*
C11	0.5901 (6)	0.0577 (3)	0.6615 (5)	0.1110 (17)
H11	0.5292	0.0218	0.6429	0.133*
C12	0.6178 (8)	0.0702 (3)	0.7606 (4)	0.1049 (17)
H12	0.5744	0.0435	0.8094	0.126*
C7	0.8821 (8)	0.2507 (3)	0.4193 (4)	0.0852 (15)
H7	0.8919	0.2642	0.3537	0.102*
C5	1.2500	0.5000	0.5431 (5)	0.158 (5)
H5	1.2500	0.5000	0.4741	0.189*
H1N	0.735 (6)	0.174 (3)	0.409 (4)	0.14 (2)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cd1	0.0763 (3)	0.0434 (3)	0.0482 (3)	0.000	0.000	0.0039 (2)
O1	0.0959 (19)	0.0469 (15)	0.0786 (16)	−0.0127 (15)	0.0124 (16)	−0.0040 (14)
C2	0.086 (3)	0.041 (2)	0.0496 (19)	−0.006 (2)	0.000 (2)	−0.0011 (18)
O2	0.139 (3)	0.064 (2)	0.061 (2)	−0.016 (2)	0.000 (2)	0.0127 (16)
C9	0.062 (3)	0.063 (3)	0.083 (3)	0.002 (2)	0.001 (3)	−0.001 (3)
C3	0.075 (3)	0.046 (3)	0.045 (3)	0.000 (3)	0.000	0.000
N3	0.076 (3)	0.066 (2)	0.066 (2)	−0.011 (2)	0.007 (2)	0.0065 (19)
N2	0.094 (3)	0.072 (3)	0.062 (3)	0.005 (2)	−0.018 (2)	−0.010 (2)
C13	0.101 (4)	0.100 (4)	0.075 (3)	−0.020 (4)	0.006 (3)	0.007 (3)
N1	0.088 (3)	0.060 (2)	0.054 (2)	−0.007 (2)	−0.008 (2)	0.0039 (19)
C8	0.074 (3)	0.056 (3)	0.057 (3)	0.006 (2)	−0.009 (2)	−0.002 (2)
C6	0.106 (4)	0.061 (3)	0.064 (3)	−0.011 (3)	−0.004 (3)	0.012 (3)
C1	0.083 (2)	0.0461 (18)	0.0602 (19)	−0.0035 (17)	0.000 (2)	−0.0019 (19)
C4	0.152 (4)	0.071 (3)	0.057 (2)	−0.041 (3)	0.001 (3)	−0.010 (2)
C10	0.090 (4)	0.099 (4)	0.095 (4)	−0.028 (3)	0.000 (3)	−0.003 (3)
C11	0.100 (4)	0.125 (4)	0.108 (3)	−0.033 (3)	0.004 (3)	−0.001 (3)
C12	0.105 (4)	0.114 (4)	0.096 (3)	−0.033 (4)	0.005 (3)	0.009 (3)
C7	0.121 (4)	0.082 (4)	0.052 (3)	0.004 (4)	−0.007 (3)	0.014 (3)
C5	0.319 (13)	0.108 (6)	0.046 (4)	−0.116 (8)	0.000	0.000

Geometric parameters (Å, °)

Cd1—O1	2.257 (3)	C13—C12	1.360 (8)
Cd1—N1	2.288 (4)	C13—H13	0.9300
Cd1—N3	2.461 (4)	N1—C8	1.330 (5)
O1—C1	1.246 (5)	N1—C6	1.376 (6)
C2—C4	1.370 (5)	C6—C7	1.359 (7)
C2—C3	1.378 (4)	C6—H6	0.9300
C2—C1	1.512 (6)	C4—C5	1.374 (5)
O2—C1	1.243 (4)	C4—H4	0.9300
C9—N3	1.343 (5)	C10—C11	1.352 (7)
C9—C10	1.388 (6)	C10—H10	0.9300
C9—C8	1.439 (6)	C11—C12	1.380 (6)
C3—C2i	1.378 (4)	C11—H11	0.9300
C3—H3	0.9300	C12—H12	0.9300
N3—C13	1.328 (6)	C7—H7	0.9300
N2—C7	1.373 (6)	C5—C4i	1.374 (5)
N2—C8	1.374 (5)	C5—H5	0.9300
N2—H1N	0.95 (5)
O1ii—Cd1—O1	101.29 (17)	N3—C13—H13	118.5
O1ii—Cd1—N1ii	84.54 (13)	C12—C13—H13	118.5
O1—Cd1—N1ii	111.01 (12)	C8—N1—C6	106.5 (4)
O1ii—Cd1—N1	111.01 (12)	C8—N1—Cd1	116.8 (3)
O1—Cd1—N1	84.54 (13)	C6—N1—Cd1	136.8 (3)
N1ii—Cd1—N1	156.0 (2)	N1—C8—N2	109.7 (4)
O1ii—Cd1—N3	87.64 (13)	N1—C8—C9	123.5 (4)
O1—Cd1—N3	154.52 (13)	N2—C8—C9	126.7 (5)
N1ii—Cd1—N3	93.45 (13)	C7—C6—N1	110.0 (4)
N1—Cd1—N3	69.99 (13)	C7—C6—H6	125.0
O1ii—Cd1—N3ii	154.52 (13)	N1—C6—H6	125.0
O1—Cd1—N3ii	87.64 (13)	O2—C1—O1	125.7 (4)
N1ii—Cd1—N3ii	69.99 (13)	O2—C1—C2	117.9 (4)
N1—Cd1—N3ii	93.45 (13)	O1—C1—C2	116.4 (4)
N3—Cd1—N3ii	94.41 (19)	C2—C4—C5	120.4 (5)
C1—O1—Cd1	124.0 (3)	C2—C4—H4	119.8
C4—C2—C3	118.1 (4)	C5—C4—H4	119.8
C4—C2—C1	121.8 (4)	C11—C10—C9	118.1 (5)
C3—C2—C1	120.1 (4)	C11—C10—H10	121.0
N3—C9—C10	122.9 (4)	C9—C10—H10	121.0
N3—C9—C8	114.1 (4)	C10—C11—C12	119.7 (6)
C10—C9—C8	123.0 (5)	C10—C11—H11	120.2
C2—C3—C2i	122.6 (5)	C12—C11—H11	120.2
C2—C3—H3	118.7	C13—C12—C11	119.0 (5)
C2i—C3—H3	118.7	C13—C12—H12	120.5
C13—N3—C9	117.5 (4)	C11—C12—H12	120.5
C13—N3—Cd1	127.0 (4)	C6—C7—N2	106.2 (4)
C9—N3—Cd1	115.1 (3)	C6—C7—H7	126.9
C7—N2—C8	107.7 (4)	N2—C7—H7	126.9
C7—N2—H1N	119 (3)	C4i—C5—C4	120.5 (6)
C8—N2—H1N	133 (3)	C4i—C5—H5	119.7
N3—C13—C12	123.0 (5)	C4—C5—H5	119.7
O1ii—Cd1—O1—C1	−109.2 (4)	N3—Cd1—N1—C6	177.0 (5)
N1ii—Cd1—O1—C1	−20.8 (4)	N3ii—Cd1—N1—C6	83.6 (5)
N1—Cd1—O1—C1	140.4 (4)	C6—N1—C8—N2	0.4 (5)
N3—Cd1—O1—C1	142.1 (4)	Cd1—N1—C8—N2	−179.2 (3)
N3ii—Cd1—O1—C1	46.7 (4)	C6—N1—C8—C9	−179.4 (4)
C4—C2—C3—C2i	−0.1 (3)	Cd1—N1—C8—C9	1.1 (6)
C1—C2—C3—C2i	−179.3 (4)	C7—N2—C8—N1	−0.1 (6)
C10—C9—N3—C13	−0.8 (7)	C7—N2—C8—C9	179.6 (4)
C8—C9—N3—C13	179.5 (4)	N3—C9—C8—N1	4.8 (6)
C10—C9—N3—Cd1	172.1 (4)	C10—C9—C8—N1	−175.0 (4)
C8—C9—N3—Cd1	−7.6 (5)	N3—C9—C8—N2	−174.9 (4)
O1ii—Cd1—N3—C13	64.9 (4)	C10—C9—C8—N2	5.3 (7)
O1—Cd1—N3—C13	176.6 (4)	C8—N1—C6—C7	−0.5 (6)
N1ii—Cd1—N3—C13	−19.4 (4)	Cd1—N1—C6—C7	178.9 (4)
N1—Cd1—N3—C13	178.3 (4)	Cd1—O1—C1—O2	26.3 (7)
N3ii—Cd1—N3—C13	−89.6 (4)	Cd1—O1—C1—C2	−153.4 (3)
O1ii—Cd1—N3—C9	−107.2 (3)	C4—C2—C1—O2	−168.9 (5)
O1—Cd1—N3—C9	4.5 (5)	C3—C2—C1—O2	10.2 (6)
N1ii—Cd1—N3—C9	168.4 (3)	C4—C2—C1—O1	10.9 (7)
N1—Cd1—N3—C9	6.2 (3)	C3—C2—C1—O1	−170.0 (4)
N3ii—Cd1—N3—C9	98.2 (3)	C3—C2—C4—C5	0.3 (7)
C9—N3—C13—C12	−0.1 (8)	C1—C2—C4—C5	179.4 (4)
Cd1—N3—C13—C12	−172.1 (5)	N3—C9—C10—C11	0.7 (8)
O1ii—Cd1—N1—C8	75.6 (3)	C8—C9—C10—C11	−179.6 (5)
O1—Cd1—N1—C8	175.6 (3)	C9—C10—C11—C12	0.3 (9)
N1ii—Cd1—N1—C8	−52.2 (3)	N3—C13—C12—C11	1.1 (10)
N3—Cd1—N1—C8	−3.6 (3)	C10—C11—C12—C13	−1.2 (9)
N3ii—Cd1—N1—C8	−97.1 (3)	N1—C6—C7—N2	0.4 (6)
O1ii—Cd1—N1—C6	−103.8 (5)	C8—N2—C7—C6	−0.2 (6)
O1—Cd1—N1—C6	−3.7 (5)	C2—C4—C5—C4i	−0.1 (3)
N1ii—Cd1—N1—C6	128.4 (5)

Symmetry codes: (i) −x+5/2, −y+1, z; (ii) x, −y+1/2, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···O2iii	0.95 (5)	1.80 (5)	2.741 (5)	166 (5)

Symmetry codes: (iii) x−1/2, −y+1/2, z−1/2.