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The title compound, [Zn(C7H5N2)(C2H3O2)]n, was obtained unintentionally as the product of an attempted synthesis of a polycarboxyl­ate-bridged network complex of zinc(II) using naphthalene-1,4,5,8-tetra­carboxylic acid as the organic acid. The Zn atom is four-coordinated by two O atoms from two acetate (OAc) ligands and two N atoms from two different benzimidazole (bzim) ligands, resulting in a ZnN2O2 tetra­hedron. The OAc and bzim ligands bridge the Zn atoms to form an infinite three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030309/hb2445sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030309/hb2445Isup2.hkl
Contains datablock I

CCDC reference: 654813

Key indicators

  • Single-crystal X-ray study
  • T = 292 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.023
  • wR factor = 0.063
  • Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C9
Alert level G PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 1.91
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 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 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

Coordination polymers with a variety of supramolecular structures have been studied extensively because of their novel topologies and potential applications as functional materials (Eddaoudi et al., 2002). However, such compounds containing deprotonated benzimidazole (C7H5N2-, bzim) ligands have been rarely studied (Huang et al.,2003). We now report the title compound, (I), which is a new coordination polymer containing Zn2+ cations, bzim anions, and acetate (C2H3O2-) anions. These species combine in a 1:1:1 ratio, to esnsure charge balance.

In compond (I), the Zn atom is coordinated by two N atoms of two different bzim ligands and two O atoms from two different acetate anions, in a slightly distorted tetrahedral geometry (Fig. 1). The bond lengths (Table 1) are normal (Orpen et al., 1989). The C—O bond lengths of the acetate ion imply charge delocalization.

The acetic acid anion serves to link two Zn2+ ions together and the bzim species also acts as a bridge between two zinc ions. This connectivity results the coordination plymer in a three-dimensional network framwork structure (Fig. 2).

Related literature top

For a related structure, see: Huang et al. (2003). For background, see: Eddaoudi et al. (2002); Allen et al. (1987).

Experimental top

Naphthalene-1,4,5,8-tetracarboxylic acid, benzimidazole and zinc acetate dihydrate were reacted in a molar ratio of 1:2:2. The mixture was stirred for 30 min, then the pH was adjusted to 8.0 with an aqueous solution of KOH (0.1 M). The mixture with a total volume of 21 ml was heated at 393 K for 5 d in a sealed 24 ml Teflon-lined stainless steel vessel under autogenous pressure. After the reaction mixture was slowly cooled to room temperature at a rate of 3 K h-1, pale yellow crystals of (I) were obtained.

Refinement top

The H atoms were positioned geometrically (C—H = 0.93–0.96 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Structure description top

Coordination polymers with a variety of supramolecular structures have been studied extensively because of their novel topologies and potential applications as functional materials (Eddaoudi et al., 2002). However, such compounds containing deprotonated benzimidazole (C7H5N2-, bzim) ligands have been rarely studied (Huang et al.,2003). We now report the title compound, (I), which is a new coordination polymer containing Zn2+ cations, bzim anions, and acetate (C2H3O2-) anions. These species combine in a 1:1:1 ratio, to esnsure charge balance.

In compond (I), the Zn atom is coordinated by two N atoms of two different bzim ligands and two O atoms from two different acetate anions, in a slightly distorted tetrahedral geometry (Fig. 1). The bond lengths (Table 1) are normal (Orpen et al., 1989). The C—O bond lengths of the acetate ion imply charge delocalization.

The acetic acid anion serves to link two Zn2+ ions together and the bzim species also acts as a bridge between two zinc ions. This connectivity results the coordination plymer in a three-dimensional network framwork structure (Fig. 2).

For a related structure, see: Huang et al. (2003). For background, see: Eddaoudi et al. (2002); Allen et al. (1987).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I) expanded to show the Zn coordination sphere. Displacement ellipsoids are drawn at the 30% probability level (arbitrary spheres for the H atoms). Symmetry codes: (i)1 - x, -1/2 + y, 3/2 - z, (ii)x, -1/2 - y, -1/2 + z.
[Figure 2] Fig. 2. The packing diagrame for (I), showing the three-dimentional network structure.
Poly[µ2-acetato-µ2-benzimidazolato-zinc(II)] top
Crystal data top
[Zn(C7H5N2)(C2H3O2)]F(000) = 488
Mr = 241.54Dx = 1.730 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1655 reflections
a = 10.8177 (8) Åθ = 6.0–26.1°
b = 9.8371 (7) ŵ = 2.62 mm1
c = 8.8206 (6) ÅT = 292 K
β = 98.938 (1)°Block, pale yellow
V = 927.24 (11) Å30.47 × 0.35 × 0.12 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer
1825 independent reflections
Radiation source: fine-focus sealed tube1646 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
ω scansθmax = 26.0°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1313
Tmin = 0.344, Tmax = 0.728k = 1212
7653 measured reflectionsl = 1010
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)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.063H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0373P)2 + 0.3915P]
where P = (Fo2 + 2Fc2)/3
1825 reflections(Δ/σ)max = 0.001
127 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
[Zn(C7H5N2)(C2H3O2)]V = 927.24 (11) Å3
Mr = 241.54Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.8177 (8) ŵ = 2.62 mm1
b = 9.8371 (7) ÅT = 292 K
c = 8.8206 (6) Å0.47 × 0.35 × 0.12 mm
β = 98.938 (1)°
Data collection top
Bruker SMART CCD
diffractometer
1825 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
1646 reflections with I > 2σ(I)
Tmin = 0.344, Tmax = 0.728Rint = 0.020
7653 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0230 restraints
wR(F2) = 0.063H-atom parameters constrained
S = 1.04Δρmax = 0.33 e Å3
1825 reflectionsΔρmin = 0.35 e Å3
127 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
Zn10.35482 (2)0.27314 (2)0.65710 (2)0.02707 (10)
O20.19757 (15)0.19050 (17)0.70465 (16)0.0377 (4)
O10.31062 (14)0.18521 (17)0.93276 (16)0.0343 (3)
N20.60329 (16)0.04848 (17)0.74407 (19)0.0291 (4)
N10.48884 (16)0.13627 (18)0.66275 (19)0.0305 (4)
C10.49555 (19)0.0187 (2)0.7378 (2)0.0306 (5)
H1A0.42950.01450.78300.037*
C30.6497 (2)0.2471 (2)0.5230 (3)0.0402 (5)
H3A0.60230.32310.48890.048*
C70.67473 (19)0.0327 (2)0.6622 (2)0.0285 (4)
C60.7953 (2)0.0167 (2)0.6286 (3)0.0401 (5)
H6A0.84390.05810.66420.048*
C40.7678 (3)0.2287 (3)0.4880 (3)0.0506 (7)
H4A0.80060.29300.42790.061*
C20.60357 (19)0.1473 (2)0.6118 (2)0.0284 (4)
C50.8401 (3)0.1151 (3)0.5410 (3)0.0533 (7)
H5A0.92020.10620.51630.064*
C80.2094 (2)0.1628 (2)0.8459 (2)0.0316 (5)
C90.1003 (3)0.1018 (3)0.9057 (3)0.0608 (8)
H9A0.03160.09230.82330.091*
H9B0.12310.01410.94890.091*
H9C0.07600.15980.98350.091*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02846 (16)0.02436 (15)0.02842 (15)0.00019 (9)0.00446 (10)0.00056 (9)
O20.0378 (9)0.0475 (9)0.0278 (8)0.0105 (7)0.0052 (6)0.0014 (7)
O10.0332 (8)0.0444 (9)0.0260 (7)0.0030 (7)0.0062 (6)0.0027 (6)
N20.0327 (9)0.0243 (9)0.0302 (9)0.0011 (7)0.0050 (7)0.0005 (7)
N10.0335 (10)0.0267 (9)0.0312 (9)0.0039 (7)0.0049 (7)0.0004 (7)
C10.0327 (11)0.0271 (11)0.0332 (11)0.0002 (9)0.0092 (9)0.0017 (8)
C30.0477 (15)0.0337 (12)0.0391 (13)0.0036 (10)0.0069 (11)0.0115 (9)
C70.0336 (11)0.0256 (10)0.0259 (10)0.0018 (8)0.0032 (8)0.0020 (8)
C60.0337 (12)0.0346 (12)0.0529 (14)0.0047 (10)0.0095 (10)0.0047 (10)
C40.0529 (16)0.0459 (15)0.0563 (16)0.0036 (12)0.0191 (13)0.0173 (12)
C20.0308 (11)0.0294 (11)0.0243 (10)0.0003 (8)0.0020 (8)0.0010 (8)
C50.0417 (14)0.0524 (17)0.0708 (18)0.0015 (12)0.0243 (13)0.0114 (14)
C80.0337 (12)0.0308 (11)0.0317 (11)0.0052 (9)0.0091 (9)0.0023 (9)
C90.0490 (16)0.089 (2)0.0461 (15)0.0285 (15)0.0146 (13)0.0058 (14)
Geometric parameters (Å, º) top
Zn1—N11.9735 (17)C3—C21.396 (3)
Zn1—N2i1.9802 (17)C3—H3A0.9300
Zn1—O21.9880 (15)C7—C61.390 (3)
Zn1—O1ii2.0046 (14)C7—C21.398 (3)
C8—O21.262 (3)C6—C51.373 (3)
C8—O11.254 (3)C6—H6A0.9300
O1—Zn1iii2.0046 (14)C4—C51.402 (4)
N2—C11.334 (3)C4—H4A0.9300
N2—C71.389 (3)C5—H5A0.9300
N2—Zn1iv1.9802 (17)C8—C91.492 (3)
N1—C11.329 (3)C9—H9A0.9600
N1—C21.388 (3)C9—H9B0.9600
C1—H1A0.9300C9—H9C0.9600
C3—C41.372 (4)
N1—Zn1—N2i118.46 (7)C6—C7—C2120.78 (19)
N1—Zn1—O2111.41 (7)C5—C6—C7117.7 (2)
N2i—Zn1—O2114.47 (7)C5—C6—H6A121.2
N1—Zn1—O1ii103.06 (7)C7—C6—H6A121.2
N2i—Zn1—O1ii104.87 (7)C3—C4—C5121.3 (2)
O2—Zn1—O1ii102.19 (6)C3—C4—H4A119.3
C8—O2—Zn1109.73 (13)C5—C4—H4A119.3
C8—O1—Zn1iii133.67 (14)N1—C2—C3130.7 (2)
C1—N2—C7104.28 (17)N1—C2—C7108.05 (18)
C1—N2—Zn1iv126.61 (14)C3—C2—C7121.2 (2)
C7—N2—Zn1iv129.08 (14)C6—C5—C4121.5 (2)
C1—N1—C2104.28 (17)C6—C5—H5A119.2
C1—N1—Zn1126.11 (15)C4—C5—H5A119.2
C2—N1—Zn1128.97 (14)O1—C8—O2120.65 (19)
N1—C1—N2115.59 (18)O1—C8—C9121.22 (19)
N1—C1—H1A122.2O2—C8—C9118.1 (2)
N2—C1—H1A122.2C8—C9—H9A109.5
C4—C3—C2117.4 (2)C8—C9—H9B109.5
C4—C3—H3A121.3H9A—C9—H9B109.5
C2—C3—H3A121.3C8—C9—H9C109.5
N2—C7—C6131.4 (2)H9A—C9—H9C109.5
N2—C7—C2107.79 (18)H9B—C9—H9C109.5
Symmetry codes: (i) x+1, y1/2, z+3/2; (ii) x, y1/2, z1/2; (iii) x, y1/2, z+1/2; (iv) x+1, y+1/2, z+3/2.

Experimental details

Crystal data
Chemical formula[Zn(C7H5N2)(C2H3O2)]
Mr241.54
Crystal system, space groupMonoclinic, P21/c
Temperature (K)292
a, b, c (Å)10.8177 (8), 9.8371 (7), 8.8206 (6)
β (°) 98.938 (1)
V3)927.24 (11)
Z4
Radiation typeMo Kα
µ (mm1)2.62
Crystal size (mm)0.47 × 0.35 × 0.12
Data collection
DiffractometerBruker SMART CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.344, 0.728
No. of measured, independent and
observed [I > 2σ(I)] reflections
7653, 1825, 1646
Rint0.020
(sin θ/λ)max1)0.618
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.063, 1.04
No. of reflections1825
No. of parameters127
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.33, 0.35

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXL97.

Selected bond lengths (Å) top
Zn1—N11.9735 (17)Zn1—O21.9880 (15)
Zn1—N2i1.9802 (17)Zn1—O1ii2.0046 (14)
Symmetry codes: (i) x+1, y1/2, z+3/2; (ii) x, y1/2, z1/2.
 

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