Poly[chlorido[μ4-2,2′-(2-methyl-1H-benzimidazol-3-ium-1,3-di­yl)diacetato]­zinc]

Liu, J.-Q.; Jiang, Z.-J.; Xu, Z.-H.; Zhang, Y.

doi:10.1107/S1600536812020077

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page m751

doi:10.1107/S1600536812020077

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Poly[chlorido[μ₄-2,2′-(2-methyl-1H-benzimidazol-3-ium-1,3-diyl)diacetato]zinc]

Jia-Qin Liu,^a Zhen-Jü Jiang,^a Zhi-Hong Xu ^a and Yan Zhang ^a ^*

^aSchool of Physics and Chemistry, Xihua University, Chengdu 610039, People's Republic of China
^*Correspondence e-mail: liujq67@yahoo.com.cn

(Received 11 March 2012; accepted 4 May 2012; online 12 May 2012)

The title compound, [Zn(C₁₂H₁₁N₂O₄)Cl]_n, contains a centrosymmetric dimetal tetracarboxylate paddle-wheel moiety in which the Zn^II atom is square-pyramidally coordinated by four carboxylate O atoms at the basal positions and one Cl⁻ anion at the apical position. Each paddle-wheel unit is joined to four such neighbours through bridging dicarboxylate ligands, producing a two-dimensional undulating layer parallel to (-101). Adjacent sheets are stacked in a parallel fashion to form a three-dimensional supramolecular structure which is stabilized by interlayer π–π interactions between benzene rings, with a centroid–centroid distance of 3.722 Å. The range of Zn—O bond lengths is 2.0440 (17)–2.1256 (15) Å and the Zn—Cl bond length is 2.2622 (6) Å.

Related literature

For background to and potential applications of carboxylate-containing coordination polymers, see Bourne et al. (2001 ); Chen et al. (2005 ); Kitagawa et al. (2004 ); Li et al. (2012 ); Xuan et al. (2012 ).

Experimental

Crystal data

[Zn(C₁₂H₁₁N₂O₄)Cl]
M_r = 348.05
Monoclinic, P 2₁ /n
a = 7.1285 (17) Å
b = 13.301 (3) Å
c = 12.804 (3) Å
β = 90.540 (4)°
V = 1214.0 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.26 mm⁻¹
T = 173 K
0.48 × 0.32 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.424, T_max = 0.508
6072 measured reflections
2640 independent reflections
2327 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.078
S = 1.07
2640 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); 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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812020077/bg2452sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020077/bg2452Isup2.hkl

checkCIF report

Comment top

Carboxylate-containing ligands have been intensively investigated to construct metal-organic frameworks with an intriguing variety of topologies and potential applications in gas sorption, separation and/or catalysis (Bourne et al., 2001; Chen et al., 2005; Kitagawa et al., 2004; Li et al., 2012; Xuan et al., 2012). Polycarboxylate ligands with suitable spacers are good choices for such architectures because the topological structures can be adjusted not only by carboxylate groups but also by the organic spacers. Here we use a flexible zwitterionic ligand, 1-acetoxy-2-methylbenzimidazole-3-acetate acid [HL], to prepare the title compound [Zn(L)Cl]_n (I).

The motive consists of a centrosymmetric paddle-wheel dimetal tetracarboxylate moiety [Zn₂(CO₂)₄] (Fig. 1) in which each Zn^II is square-pyramidally coordinated by four carboxylate oxygen atoms at the basal position and one Cl^- anion at the apical position. Each paddle-wheel unit is bridged by four such neighbors through bridging dicarboxylate ligands, producing a two-dimensional undulate layer in which π-π interactions between phenyl rings of benzimidazole moieties (ring-centroid distance: 3.579 (2) Å) cooperate in the 2-D sheet formation (Fig. 2). Adjacent sheets are stacked in a parallel fashion to form a 3-D supramolecular structure stabilized by interlayer π-π interactions between phenyl rings with a ring-centroid distance of 3.722 (2) Å. The Zn—O span is 2.0440 (17)-2.1256 (15) Å and the Zn—Cl distance is 2.2622 (6) Å.

Related literature top

For background to and potential applications of carboxylate-containing coordination polymers, see Bourne et al. (2001); Chen et al. (2005); Kitagawa et al. (2004); Li et al. (2012); Xuan et al. (2012).

Experimental top

After the pH of an ethanol/water mixture solution (10 ml with ratio of 4:1) containing ZnCl₂.2H₂O (0.0408 g, 0.3 mmol) and the HL ligand (0.0498 g,0.2 mmol) was adjusted to 7 by addition of triethylamine, the resulting solution was sealed in a Teflon-lined steel bomb (25 ml) and then heated at 140°C for 2 days. Colorless block crystals were collected. Yield: 16%. Elemental analysis (%) calcd for the title compound: C 41.38, H 3.16, N 8.04; found: C 41.24, H 3.23, N 8.47. IR: 1672(s), 1472(m), 1436(m), 1389(s), 1310(m), 764(s), 721(m), 619(m), 574(m).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP drawing (at 30% probability) of a paddle-wheel unit in the title compound (symmetry codes: A, -x, -y, -z; B, -0.5 + x, 1.5 - y, -0.5 + z; C, 0.5 - x, -0.5 + y, 1.5 - z). Hydrogen atoms are omitted for clarity.
	Fig. 2. The 2-D sheet structure parallel to the (-101) plane, hydrogen atoms are omitted for clarity.

Poly[chlorido[µ₄-2,2'-(2-methyl-1H-benzimidazol-3-ium- 1,3-diyl)diacetato]zinc] top

Crystal data top

[Zn(C₁₂H₁₁N₂O₄)Cl]	Z = 4
M_r = 348.05	F(000) = 704
Monoclinic, P2₁/n	D_x = 1.904 Mg m⁻³
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 7.1285 (17) Å	θ = 2.2–27.1°
b = 13.301 (3) Å	µ = 2.26 mm⁻¹
c = 12.804 (3) Å	T = 173 K
β = 90.540 (4)°	Block, colorless
V = 1214.0 (5) Å³	0.48 × 0.32 × 0.30 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2640 independent reflections
Radiation source: fine-focus sealed tube	2327 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω scans	θ_max = 27.1°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −9→8
T_min = 0.424, T_max = 0.508	k = −11→17
6072 measured reflections	l = −16→9

Refinement top

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0438P)² + 0.6356P] where P = (F_o² + 2F_c²)/3
2640 reflections	(Δ/σ)_max = 0.001
181 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Zn(C₁₂H₁₁N₂O₄)Cl]	V = 1214.0 (5) Å³
M_r = 348.05	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.1285 (17) Å	µ = 2.26 mm⁻¹
b = 13.301 (3) Å	T = 173 K
c = 12.804 (3) Å	0.48 × 0.32 × 0.30 mm
β = 90.540 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2640 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	2327 reflections with I > 2σ(I)
T_min = 0.424, T_max = 0.508	R_int = 0.026
6072 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.078	H-atom parameters constrained
S = 1.07	Δρ_max = 0.45 e Å⁻³
2640 reflections	Δρ_min = −0.45 e Å⁻³
181 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

	x	y	z	U_iso*/U_eq
Zn1	0.13104 (3)	0.553340 (17)	0.417142 (17)	0.01203 (10)
Cl1	0.29440 (7)	0.65999 (4)	0.31470 (4)	0.01697 (13)
O1	0.4360 (2)	0.84000 (11)	0.97522 (12)	0.0181 (3)
O2	0.2502 (2)	0.91230 (12)	1.09352 (13)	0.0217 (4)
O3	0.2669 (2)	0.56544 (13)	0.55787 (12)	0.0241 (4)
O4	0.0830 (2)	0.49535 (12)	0.67900 (12)	0.0203 (3)
N1	0.3143 (2)	0.58092 (13)	0.83280 (13)	0.0122 (3)
N2	0.2081 (2)	0.67202 (13)	0.96116 (14)	0.0131 (4)
C1	0.2938 (3)	0.51606 (15)	0.91696 (16)	0.0123 (4)
C2	0.3314 (3)	0.41392 (16)	0.92770 (17)	0.0164 (4)
H2A	0.3829	0.3755	0.8724	0.020*
C3	0.2899 (3)	0.37134 (16)	1.02313 (18)	0.0190 (5)
H3A	0.3135	0.3018	1.0338	0.023*
C4	0.2140 (3)	0.42806 (17)	1.10429 (18)	0.0190 (5)
H4A	0.1854	0.3957	1.1683	0.023*
C5	0.1792 (3)	0.53041 (16)	1.09412 (16)	0.0157 (4)
H5A	0.1280	0.5689	1.1495	0.019*
C6	0.2235 (3)	0.57346 (15)	0.99858 (16)	0.0133 (4)
C7	0.2610 (3)	0.67345 (15)	0.86146 (16)	0.0128 (4)
C8	0.2578 (3)	0.75932 (16)	0.78819 (17)	0.0197 (5)
H8A	0.2142	0.8196	0.8246	0.030*
H8B	0.1726	0.7443	0.7297	0.030*
H8C	0.3844	0.7709	0.7617	0.030*
C9	0.1487 (3)	0.75902 (15)	1.02331 (17)	0.0159 (4)
H9A	0.1187	0.7357	1.0946	0.019*
H9B	0.0321	0.7867	0.9920	0.019*
C10	0.2944 (3)	0.84401 (15)	1.03157 (16)	0.0136 (4)
C11	0.3852 (3)	0.55606 (16)	0.72945 (16)	0.0142 (4)
H11A	0.4637	0.4948	0.7348	0.017*
H11B	0.4662	0.6116	0.7051	0.017*
C12	0.2295 (3)	0.53811 (15)	0.64823 (17)	0.0138 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01287 (15)	0.01381 (14)	0.00939 (14)	−0.00070 (8)	−0.00114 (9)	0.00073 (8)
Cl1	0.0203 (3)	0.0164 (2)	0.0142 (2)	−0.00402 (19)	0.00246 (19)	−0.00035 (18)
O1	0.0171 (8)	0.0169 (7)	0.0205 (8)	−0.0037 (6)	0.0038 (6)	−0.0020 (6)
O2	0.0251 (9)	0.0166 (7)	0.0235 (8)	−0.0044 (6)	0.0047 (7)	−0.0089 (7)
O3	0.0191 (8)	0.0415 (10)	0.0114 (8)	−0.0005 (7)	−0.0032 (6)	0.0026 (7)
O4	0.0199 (8)	0.0227 (8)	0.0181 (8)	−0.0067 (7)	−0.0050 (6)	−0.0012 (6)
N1	0.0123 (8)	0.0143 (8)	0.0100 (8)	−0.0009 (7)	−0.0026 (6)	−0.0012 (7)
N2	0.0136 (9)	0.0126 (8)	0.0130 (8)	−0.0012 (7)	−0.0004 (7)	−0.0009 (7)
C1	0.0113 (10)	0.0153 (10)	0.0102 (9)	−0.0027 (8)	−0.0039 (7)	−0.0003 (8)
C2	0.0161 (10)	0.0153 (10)	0.0176 (10)	0.0004 (8)	−0.0048 (8)	−0.0025 (8)
C3	0.0172 (11)	0.0136 (10)	0.0261 (12)	−0.0031 (8)	−0.0065 (9)	0.0049 (9)
C4	0.0170 (11)	0.0222 (11)	0.0178 (11)	−0.0050 (9)	−0.0047 (8)	0.0066 (9)
C5	0.0153 (10)	0.0206 (10)	0.0112 (10)	−0.0045 (8)	−0.0019 (8)	−0.0014 (8)
C6	0.0117 (9)	0.0136 (9)	0.0145 (10)	−0.0035 (8)	−0.0032 (8)	−0.0012 (8)
C7	0.0110 (9)	0.0150 (10)	0.0121 (9)	−0.0027 (8)	−0.0038 (7)	−0.0015 (8)
C8	0.0264 (12)	0.0172 (10)	0.0154 (10)	0.0003 (9)	−0.0016 (9)	0.0030 (9)
C9	0.0154 (10)	0.0131 (10)	0.0191 (10)	−0.0007 (8)	0.0028 (8)	−0.0055 (8)
C10	0.0152 (10)	0.0131 (9)	0.0126 (9)	−0.0012 (8)	−0.0025 (8)	−0.0003 (8)
C11	0.0134 (10)	0.0198 (11)	0.0093 (9)	0.0010 (8)	−0.0014 (8)	−0.0014 (8)
C12	0.0142 (10)	0.0150 (10)	0.0121 (9)	0.0045 (8)	−0.0034 (8)	−0.0034 (8)

Geometric parameters (Å, º) top

Zn1—O3	2.0440 (17)	C2—H2A	0.9500
Zn1—O4ⁱ	2.0559 (16)	C3—C4	1.397 (3)
Zn1—O2ⁱⁱ	2.0632 (16)	C3—H3A	0.9500
Zn1—O1ⁱⁱⁱ	2.1256 (15)	C4—C5	1.390 (3)
Zn1—Cl1	2.2622 (6)	C4—H4A	0.9500
O1—C10	1.247 (3)	C5—C6	1.390 (3)
O2—C10	1.248 (3)	C5—H5A	0.9500
O3—C12	1.244 (3)	C7—C8	1.478 (3)
O4—C12	1.256 (3)	C8—H8A	0.9800
N1—C7	1.340 (3)	C8—H8B	0.9800
N1—C1	1.389 (3)	C8—H8C	0.9800
N1—C11	1.459 (3)	C9—C10	1.538 (3)
N2—C7	1.335 (3)	C9—H9A	0.9900
N2—C6	1.400 (3)	C9—H9B	0.9900
N2—C9	1.469 (3)	C11—C12	1.532 (3)
C1—C2	1.391 (3)	C11—H11A	0.9900
C1—C6	1.392 (3)	C11—H11B	0.9900
C2—C3	1.381 (3)

O3—Zn1—O4ⁱ	153.56 (7)	C6—C5—H5A	121.8
O3—Zn1—O2ⁱⁱ	86.48 (7)	C4—C5—H5A	121.8
O4ⁱ—Zn1—O2ⁱⁱ	88.65 (7)	C5—C6—C1	121.4 (2)
O3—Zn1—O1ⁱⁱⁱ	86.86 (7)	C5—C6—N2	132.0 (2)
O4ⁱ—Zn1—O1ⁱⁱⁱ	86.31 (7)	C1—C6—N2	106.52 (18)
O2ⁱⁱ—Zn1—O1ⁱⁱⁱ	154.17 (6)	N2—C7—N1	109.40 (18)
O3—Zn1—Cl1	102.68 (5)	N2—C7—C8	127.98 (19)
O4ⁱ—Zn1—Cl1	103.50 (5)	N1—C7—C8	122.58 (19)
O2ⁱⁱ—Zn1—Cl1	108.55 (5)	C7—C8—H8A	109.5
O1ⁱⁱⁱ—Zn1—Cl1	97.25 (5)	C7—C8—H8B	109.5
C10—O1—Zn1^iv	135.18 (14)	H8A—C8—H8B	109.5
C10—O2—Zn1^v	120.91 (14)	C7—C8—H8C	109.5
C12—O3—Zn1	133.86 (15)	H8A—C8—H8C	109.5
C12—O4—Zn1ⁱ	124.71 (14)	H8B—C8—H8C	109.5
C7—N1—C1	109.00 (17)	N2—C9—C10	114.73 (17)
C7—N1—C11	123.92 (17)	N2—C9—H9A	108.6
C1—N1—C11	127.07 (18)	C10—C9—H9A	108.6
C7—N2—C6	108.60 (17)	N2—C9—H9B	108.6
C7—N2—C9	126.32 (18)	C10—C9—H9B	108.6
C6—N2—C9	125.06 (18)	H9A—C9—H9B	107.6
N1—C1—C2	131.4 (2)	O1—C10—O2	127.5 (2)
N1—C1—C6	106.45 (18)	O1—C10—C9	118.58 (18)
C2—C1—C6	122.14 (19)	O2—C10—C9	113.85 (18)
C3—C2—C1	116.4 (2)	N1—C11—C12	113.33 (17)
C3—C2—H2A	121.8	N1—C11—H11A	108.9
C1—C2—H2A	121.8	C12—C11—H11A	108.9
C2—C3—C4	121.6 (2)	N1—C11—H11B	108.9
C2—C3—H3A	119.2	C12—C11—H11B	108.9
C4—C3—H3A	119.2	H11A—C11—H11B	107.7
C5—C4—C3	122.0 (2)	O3—C12—O4	127.6 (2)
C5—C4—H4A	119.0	O3—C12—C11	115.17 (19)
C3—C4—H4A	119.0	O4—C12—C11	117.18 (19)
C6—C5—C4	116.4 (2)

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

Experimental details

Crystal data
Chemical formula	[Zn(C₁₂H₁₁N₂O₄)Cl]
M_r	348.05
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	7.1285 (17), 13.301 (3), 12.804 (3)
β (°)	90.540 (4)
V (Å³)	1214.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.26
Crystal size (mm)	0.48 × 0.32 × 0.30

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.424, 0.508
No. of measured, independent and observed [I > 2σ(I)] reflections	6072, 2640, 2327
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.642

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.078, 1.07
No. of reflections	2640
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.45

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the Key Program of Xihua University (grant Nos. E0913305, E0913307).

References

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