Poly[[(μ-1H-benzimidazole-5,6-dicarboxyl­ato)zinc(II)] monohydrate]

Abstract

The three-dimensional polymeric title compound, {[Zn(C₉H₄N₂O₄)]·H₂O}_n, contains one crystallographically independent Zn^II atom, one fully deprotonated 1H-benzimid­azole-5,6-dicarboxyl­ate (bdc) ligand and one uncoordinated water mol­ecule. The Zn^II atom is four-coordinated by three O atoms and one N atom from the bdc ligands, giving a distorted tetra­hedral coordination geometry. The uncoordinated water mol­ecule is bound to the main structure through a strong bdc–water N—H⋯O hydrogen bond, and two much weaker water–bdc O—H⋯O inter­actions.

Related literature

For structures of other bdc complexes, see: Gao et al. (2008 ▶); Lo et al. (2007 ▶); Wei et al. (2008 ▶); Yao et al. (2008 ▶).

Experimental

Crystal data

• [Zn(C₉H₄N₂O₄)]·H₂O

• M _r = 287.55

• Monoclinic,

• a = 6.4735 (5) Å

• b = 8.1836 (6) Å

• c = 18.4407 (12) Å

• β = 104.397 (2)°

• V = 946.25 (12) ų

• Z = 4

• Mo Kα radiation

• μ = 2.61 mm⁻¹

• T = 298 K

• 0.35 × 0.26 × 0.18 mm

Data collection

• Bruker APEXII area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.444, T _max = 0.625

• 4613 measured reflections

• 1665 independent reflections

• 1513 reflections with I > 2σ(I)

• R _int = 0.019

Refinement

• R[F ² > 2σ(F ²)] = 0.026

• wR(F ²) = 0.072

• S = 1.06

• 1665 reflections

• 154 parameters

• H-atom parameters constrained

• Δρ_max = 0.54 e Å⁻³

• Δρ_min = −0.32 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1W	0.86	2.02	2.809 (3)	152
O1W—H1W⋯O1i	0.93	2.45	3.211 (5)	139
O1W—H2W⋯O4ii	0.91	2.29	3.095 (3)	146

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

N-Heterocyclic carboxylic acids have atracted attention not only because their versatile coordination modes but also owing to their forming high-dimensional polymers through H-bonding interactions. 1H-benzimidazole-5,6-dicarboxylic acid (bdc), having six coordination points, is a good candidate for the generation of three-dimensional coordination polymers. However, up to now the complexes based on the bdc ligand are rare (Lo et al., 2007; Gao et al., 2008; Wei et al., 2008; Yao et al., 2008). Here we report the first three-dimensional Zn coordination polymer connected by bdc ligands, [Zn(C₉H₄N₂O₂)].H₂O.

As is shown in Figure 1, the asymmetric unit consists of one Zn²⁺ cation, a fully deprotonated bdc^2- ligand, and a free water moelcule. The cation has a tetrahedral coordination environment, and is surrounded by three oxygen and one nitrogen atoms from the bdc ligands. A packing diagram showing the 3D structure coming out from the tetradentate character of the bdc ligand is shown in Figure 2. To the best of our knowledge, the title compound is the first 3D transition metal coordination polymer based on the 1H-benzimidazole-5,6-dicarboxylic acid ligand.

Experimental

A mixture of bdc (0.0415 g, 0.20 mmol), Zn(NO₃)₂.6H₂O (0.0594 g, 0.20 mmol) and water (10 ml) was heated up to 430 K for 72 h in a 23 ml Teflon-lined stainless-steel autoclave and then cooled down to room temperature in a 278 K/hour rate. Colourless prismatic crystals were collected and dried in air.

Refinement

H atoms attached to carbon and nitrogen were placed at calculated positions and treated as riding on their parent atoms with C—H = 0.93Å, C—N = 0.86Å. Those attached to oxygen were found from the Fourier maps, and allowed to ride without further refinement. In all cases Uĩso~(H) = 1.2 or 1.5 U~eq~(C, O).

Figures

Fig. 1.

Displacement ellipsoid plot (50% probability level) of the title compound, with atom numbering. Symmetry codes: (i) -x, -y+2, -z+2; (ii) -x, y+1/2, -z+3/2; (iii) x-1, y, z.

Fig. 2.

The packing diagram of the title compound, with H atoms omitted for clarity. Hydrogen bonds are shown as dashed lines.

Crystal data

[Zn(C9H4N2O4)]·H2O	F(000) = 576
Mr = 287.55	Dx = 2.018 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2639 reflections
a = 6.4735 (5) Å	θ = 2.3–27.6°
b = 8.1836 (6) Å	µ = 2.61 mm−1
c = 18.4407 (12) Å	T = 298 K
β = 104.397 (2)°	Block, colorless
V = 946.25 (12) Å3	0.35 × 0.26 × 0.18 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer	1665 independent reflections
Radiation source: fine-focus sealed tube	1513 reflections with I > 2σ(I)
graphite	Rint = 0.019
φ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −7→7
Tmin = 0.444, Tmax = 0.625	k = −9→8
4613 measured reflections	l = −21→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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0407P)2 + 0.8076P] where P = (Fo2 + 2Fc2)/3
1665 reflections	(Δ/σ)max = 0.001
154 parameters	Δρmax = 0.54 e Å−3
0 restraints	Δρmin = −0.32 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.6805 (4)	0.7618 (3)	1.14674 (15)	0.0244 (6)
H1	0.7562	0.7565	1.1967	0.029*
C2	0.4362 (4)	0.8133 (3)	1.04587 (14)	0.0210 (6)
C3	0.5993 (4)	0.7274 (3)	1.02485 (14)	0.0209 (6)
C4	0.5896 (4)	0.6922 (3)	0.95017 (14)	0.0232 (6)
H4	0.6986	0.6358	0.9364	0.028*
C5	0.2433 (4)	0.8286 (3)	0.91858 (14)	0.0210 (6)
C6	0.2567 (4)	0.8630 (3)	0.99290 (14)	0.0225 (6)
H6	0.1474	0.9184	1.0070	0.027*
C7	0.4108 (4)	0.7447 (3)	0.89738 (14)	0.0198 (5)
C8	0.0478 (4)	0.8790 (3)	0.85989 (15)	0.0244 (6)
C9	0.4056 (4)	0.7163 (3)	0.81632 (14)	0.0200 (6)
N1	0.4937 (3)	0.8337 (3)	1.12397 (12)	0.0223 (5)
N2	0.7500 (3)	0.6973 (3)	1.09061 (12)	0.0255 (5)
H2	0.8682	0.6459	1.0948	0.031*
O1	0.0221 (4)	0.8307 (4)	0.79625 (13)	0.0700 (10)
O2	−0.0815 (3)	0.9719 (3)	0.88154 (11)	0.0371 (5)
O3	0.3461 (3)	0.5800 (3)	0.78853 (10)	0.0317 (5)
O4	0.4720 (4)	0.8254 (3)	0.78041 (11)	0.0360 (5)
Zn1	−0.35253 (5)	1.02462 (4)	0.814219 (16)	0.02108 (13)
O1W	1.1216 (4)	0.5187 (3)	1.15400 (15)	0.0533 (7)
H1W	1.0604	0.4556	1.1853	0.080*
H2W	1.1968	0.6024	1.1810	0.080*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0238 (14)	0.0330 (16)	0.0141 (13)	0.0009 (12)	0.0004 (11)	0.0029 (11)
C2	0.0226 (13)	0.0263 (14)	0.0138 (13)	0.0008 (11)	0.0037 (11)	−0.0001 (10)
C3	0.0189 (13)	0.0270 (15)	0.0153 (13)	0.0023 (11)	0.0013 (11)	0.0010 (11)
C4	0.0215 (13)	0.0306 (15)	0.0177 (14)	0.0056 (11)	0.0053 (11)	−0.0025 (11)
C5	0.0212 (13)	0.0264 (15)	0.0146 (13)	0.0006 (11)	0.0029 (11)	−0.0019 (10)
C6	0.0206 (13)	0.0310 (15)	0.0159 (13)	0.0052 (11)	0.0046 (11)	−0.0016 (11)
C7	0.0222 (13)	0.0220 (14)	0.0151 (13)	−0.0006 (11)	0.0043 (10)	−0.0015 (10)
C8	0.0230 (14)	0.0329 (16)	0.0160 (14)	0.0016 (12)	0.0025 (11)	−0.0013 (11)
C9	0.0174 (12)	0.0266 (15)	0.0152 (12)	0.0018 (10)	0.0025 (10)	−0.0009 (11)
N1	0.0239 (12)	0.0313 (13)	0.0107 (11)	0.0047 (10)	0.0026 (9)	0.0001 (9)
N2	0.0208 (12)	0.0352 (14)	0.0189 (12)	0.0083 (10)	0.0017 (9)	0.0002 (10)
O1	0.0496 (15)	0.125 (3)	0.0230 (13)	0.0460 (16)	−0.0143 (11)	−0.0294 (14)
O2	0.0285 (11)	0.0578 (15)	0.0209 (11)	0.0200 (10)	−0.0012 (9)	−0.0072 (9)
O3	0.0511 (13)	0.0269 (11)	0.0190 (10)	−0.0077 (10)	0.0125 (9)	−0.0057 (8)
O4	0.0532 (14)	0.0376 (13)	0.0185 (10)	−0.0200 (10)	0.0117 (10)	−0.0050 (9)
Zn1	0.0221 (2)	0.0270 (2)	0.01325 (19)	0.00140 (12)	0.00268 (13)	−0.00017 (12)
O1W	0.0410 (14)	0.0652 (18)	0.0468 (16)	0.0148 (12)	−0.0022 (12)	−0.0085 (12)

Geometric parameters (Å, °)

C1—N1	1.316 (3)	C6—H6	0.9300
C1—N2	1.336 (3)	C7—C9	1.505 (4)
C1—H1	0.9300	C8—O1	1.210 (3)
C2—C6	1.380 (4)	C8—O2	1.266 (3)
C2—C3	1.401 (4)	C9—O3	1.247 (3)
C2—N1	1.405 (3)	C9—O4	1.250 (3)
C3—N2	1.376 (3)	N2—H2	0.8600
C3—C4	1.393 (4)	Zn1—O2	1.929 (2)
C4—C7	1.383 (4)	Zn1—N1i	1.999 (2)
C4—H4	0.9300	Zn1—O3ii	1.9587 (19)
C5—C6	1.381 (4)	Zn1—O4iii	1.996 (2)
C5—C7	1.418 (4)	O1W—H1W	0.9333
C5—C8	1.504 (4)	O1W—H2W	0.9127
N1—C1—N2	112.9 (2)	O1—C8—C5	119.8 (3)
N1—C1—H1	123.6	O2—C8—C5	116.2 (2)
N2—C1—H1	123.6	O3—C9—O4	122.2 (2)
C6—C2—C3	120.8 (2)	O3—C9—C7	118.3 (2)
C6—C2—N1	130.8 (2)	O4—C9—C7	119.3 (2)
C3—C2—N1	108.5 (2)	C1—N1—C2	105.2 (2)
N2—C3—C4	133.0 (2)	C1—N1—Zn1i	126.26 (18)
N2—C3—C2	105.3 (2)	C2—N1—Zn1i	127.64 (17)
C4—C3—C2	121.7 (2)	C1—N2—C3	108.1 (2)
C7—C4—C3	117.1 (2)	C1—N2—H2	125.9
C7—C4—H4	121.4	C3—N2—H2	125.9
C3—C4—H4	121.4	C8—O2—Zn1	119.85 (18)
C6—C5—C7	120.6 (2)	C9—O3—Zn1iv	121.73 (18)
C6—C5—C8	119.5 (2)	C9—O4—Zn1v	131.46 (18)
C7—C5—C8	119.9 (2)	O2—Zn1—O3ii	116.08 (9)
C2—C6—C5	118.5 (2)	O2—Zn1—O4iii	111.99 (10)
C2—C6—H6	120.8	O3ii—Zn1—O4iii	91.96 (9)
C5—C6—H6	120.8	O2—Zn1—N1i	103.56 (9)
C4—C7—C5	121.3 (2)	O3ii—Zn1—N1i	122.67 (9)
C4—C7—C9	117.4 (2)	O4iii—Zn1—N1i	110.27 (9)
C5—C7—C9	121.3 (2)	H1W—O1W—H2W	109.2
O1—C8—O2	124.0 (3)
C6—C2—C3—N2	−179.7 (3)	C5—C7—C9—O3	−99.2 (3)
N1—C2—C3—N2	0.4 (3)	C4—C7—C9—O4	−92.4 (3)
C6—C2—C3—C4	1.5 (4)	C5—C7—C9—O4	84.8 (3)
N1—C2—C3—C4	−178.4 (3)	N2—C1—N1—C2	0.3 (3)
N2—C3—C4—C7	−178.8 (3)	N2—C1—N1—Zn1i	−169.63 (19)
C2—C3—C4—C7	−0.5 (4)	C6—C2—N1—C1	179.7 (3)
C3—C2—C6—C5	−1.1 (4)	C3—C2—N1—C1	−0.4 (3)
N1—C2—C6—C5	178.8 (3)	C6—C2—N1—Zn1i	−10.6 (4)
C7—C5—C6—C2	−0.2 (4)	C3—C2—N1—Zn1i	169.32 (18)
C8—C5—C6—C2	179.0 (3)	N1—C1—N2—C3	0.0 (3)
C3—C4—C7—C5	−0.9 (4)	C4—C3—N2—C1	178.4 (3)
C3—C4—C7—C9	176.3 (2)	C2—C3—N2—C1	−0.2 (3)
C6—C5—C7—C4	1.3 (4)	O1—C8—O2—Zn1	7.0 (5)
C8—C5—C7—C4	−178.0 (3)	C5—C8—O2—Zn1	−173.02 (19)
C6—C5—C7—C9	−175.8 (3)	O4—C9—O3—Zn1iv	0.2 (4)
C8—C5—C7—C9	4.9 (4)	C7—C9—O3—Zn1iv	−175.59 (17)
C6—C5—C8—O1	−170.2 (3)	O3—C9—O4—Zn1v	−160.8 (2)
C7—C5—C8—O1	9.1 (5)	C7—C9—O4—Zn1v	14.9 (4)
C6—C5—C8—O2	9.8 (4)	C8—O2—Zn1—O3ii	−44.1 (3)
C7—C5—C8—O2	−170.9 (3)	C8—O2—Zn1—O4iii	59.7 (2)
C4—C7—C9—O3	83.6 (3)	C8—O2—Zn1—N1i	178.5 (2)

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

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1W	0.86	2.02	2.809 (3)	152
O1W—H1W···O1vi	0.93	2.45	3.211 (5)	139
O1W—H2W···O4vii	0.91	2.29	3.095 (3)	146

Symmetry codes: (vi) −x+1, −y+1, −z+2; (vii) x+1, −y+3/2, z+1/2.