Poly[bis­(μ2-5-{4-[(1H-imidazol-1-yl)meth­yl]phen­yl}tetra­zolato)zinc]

Song, Z.

doi:10.1107/S1600536812050672

metal-organic compounds

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doi:10.1107/S1600536812050672

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Poly[bis(μ₂-5-{4-[(1H-imidazol-1-yl)methyl]phenyl}tetrazolato)zinc]

Zhe Song ^a ^*

^aDepartment of Chemistry, Changchun Normal University, Changchun 130032, People's Republic of China
^*Correspondence e-mail: songzhe@cncnc.edu.cn

(Received 3 December 2012; accepted 13 December 2012; online 9 January 2013)

In the title compound, [Zn(C₁₁H₉N₆)₂]_n, the Zn^II atom lies on an inversion center and is coordinated by four N atoms from four 5-[4-(1H-imidazol-1-ylmethyl)phenyl]tetrazolate ligands in a distorted tetrahedral geometry. The ligands bridge the Zn^II atoms, leading to the formation of a two-dimensional network parallel to (010). The structure is further stabilized by C—H⋯N, C—H⋯π and π–π [centroid–centroid distance = 3.7523 (11) Å] interactions within the network.

Related literature

For background to metal-organic architectures, see: Awaleh et al. (2005 ); Mooibroek & Gamez (2007 ); Su et al. (2009 ). For background to metal–azolate frameworks, see: Darling et al. (2012 ). For related structures, see: Huang et al. (2009 ); Su et al. (2009).

Experimental

Crystal data

[Zn(C₁₁H₉N₆)₂]
M_r = 515.85
Orthorhombic, P b c n
a = 16.1206 (12) Å
b = 9.3720 (7) Å
c = 14.6367 (11) Å
V = 2211.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.15 mm⁻¹
T = 273 K
0.28 × 0.26 × 0.24 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.736, T_max = 0.752
11210 measured reflections
2105 independent reflections
1874 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.081
S = 1.07
2105 reflections
159 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯N4ⁱ	0.93	2.45	3.344 (2)	163
C8—H8A⋯Cg2ⁱⁱ	0.97	2.88	3.692 (2)	142
Symmetry codes: (i) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+1, -y-1, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: XP in SHELXTL and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812050672/zq2192sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812050672/zq2192Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812050672/zq2192Isup3.cdx

checkCIF report

Comment top

Metal–Organic Frameworks (MOFs) continue to receive significant contemporary attention, reflecting their applications to fields as diverse as gas storage, separation, and catalysis (Mooibroek et al., 2007; Awaleh et al., 2005). Transition metal complexes using tetrazole derivatives as ligands are of great interest as many compounds based on these ligands have shown intriguing structures with interesting properties (Su et al., 2009; Darling et al., 2012). Recently, we obtained the title complex by the reaction of zincacetate with 5-(4-imidazol-1-yl-benzyl)-2H-tetrazole using hydrothermal method and its crystal structure is reported here.

In the title compound, the Zn^II atom lies on an inversion center and adopts a distorted tetrahedral coordination geometry, being coordinated by four N atoms from four azolate ligands (Fig. 1). The bridging azolate ligands allow the formation of a two-dimensional network parallel to (010) (Fig. 2), while in a related structure the azolate C₁₁H₉N₆ ligands form one-dimensional chains with the Zn^II atoms (Huang et al., 2009). The crystal structure is further stabilized by C–H···N, C–H···π and and π-π interactions within the network (see Geometric parameters and Table 1: Cg1 and Cg2 corresponding to the centroids of the N1-N2-N3-N4-C7 and C1–C6 rings, respectively).

Related literature top

For background to metal-organic architectures, see: Awaleh et al. (2005); Mooibroek & Gamez (2007); Su et al. (2009). For background to metal–azolate frameworks, see: Darling et al. (2012). For related structures, see: Huang et al. (2009); Su et al. (2009).

Experimental top

A mixture of Zn(OAc)₂.2H₂O (0.2 mmol, 0.043 g), 5-(4-imidazol-1-yl-benzyl)-2H-tetrazole (0.2 mmol, 0.045 g), NH₃.H₂O (2 mL), EtOH (5 ml) and water (5 ml) was sealed in a 15 ml Teflon-lined reactor, which was heated at 100°C for 72 h and then gradually cooled to room temperature. Colourless crystals were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Symmetry codes: (i) -x+1, y, -z+3/2; (ii) -x+3/2, -y-1/2, z+1/2; (iii) x-1/2, -y-1/2, -z+1.
	Fig. 2. View of the two-dimensional network of the title compound.

Poly[bis(µ₂-5-{4-[(1H-imidazol-1-yl)methyl]phenyl}tetrazolato)zinc] top

Crystal data top

[Zn(C₁₁H₉N₆)₂]	F(000) = 1056
M_r = 515.85	D_x = 1.549 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 2105 reflections
a = 16.1206 (12) Å	θ = 2.5–25.7°
b = 9.3720 (7) Å	µ = 1.15 mm⁻¹
c = 14.6367 (11) Å	T = 273 K
V = 2211.3 (3) Å³	Block, colourless
Z = 4	0.28 × 0.26 × 0.24 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2105 independent reflections
Radiation source: fine-focus sealed tube	1874 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
phi and ω scans	θ_max = 25.7°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→19
T_min = 0.736, T_max = 0.752	k = −11→11
11210 measured reflections	l = −17→15

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.045P)² + 1.2542P] where P = (F_o² + 2F_c²)/3
2105 reflections	(Δ/σ)_max < 0.001
159 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

[Zn(C₁₁H₉N₆)₂]	V = 2211.3 (3) Å³
M_r = 515.85	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 16.1206 (12) Å	µ = 1.15 mm⁻¹
b = 9.3720 (7) Å	T = 273 K
c = 14.6367 (11) Å	0.28 × 0.26 × 0.24 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2105 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1874 reflections with I > 2σ(I)
T_min = 0.736, T_max = 0.752	R_int = 0.020
11210 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.081	H-atom parameters constrained
S = 1.07	Δρ_max = 0.29 e Å⁻³
2105 reflections	Δρ_min = −0.27 e Å⁻³
159 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	0.5000	−0.00874 (3)	0.7500	0.02093 (12)
N1	0.56706 (10)	−0.22486 (17)	0.62224 (10)	0.0287 (4)
N2	0.50779 (9)	−0.12643 (17)	0.63732 (11)	0.0250 (3)
N3	0.45760 (9)	−0.11431 (16)	0.56620 (10)	0.0258 (3)
N4	0.48338 (10)	−0.20502 (19)	0.50222 (9)	0.0251 (4)
N5	0.78108 (9)	−0.70455 (15)	0.30116 (10)	0.0227 (3)
N6	0.89739 (10)	−0.60890 (17)	0.25437 (9)	0.0236 (3)
C1	0.59424 (12)	−0.3877 (2)	0.49151 (11)	0.0243 (4)
C2	0.65678 (12)	−0.4625 (2)	0.53566 (13)	0.0294 (4)
H2	0.6729	−0.4359	0.5942	0.080*
C3	0.69536 (13)	−0.5767 (2)	0.49300 (12)	0.0300 (4)
H3	0.7372	−0.6260	0.5232	0.080*
C4	0.67212 (11)	−0.61812 (19)	0.40553 (12)	0.0258 (4)
C5	0.61043 (12)	−0.5417 (2)	0.36076 (13)	0.0277 (4)
H5	0.5949	−0.5677	0.3019	0.080*
C6	0.57190 (11)	−0.4272 (2)	0.40282 (12)	0.0271 (4)
H6	0.5310	−0.3764	0.3719	0.080*
C7	0.54942 (11)	−0.27135 (19)	0.53796 (12)	0.0234 (4)
C8	0.71159 (12)	−0.74616 (19)	0.36103 (13)	0.0299 (4)
H8A	0.7317	−0.8105	0.4079	0.080*
H8B	0.6702	−0.7966	0.3253	0.080*
C9	0.84655 (11)	−0.62443 (18)	0.32411 (12)	0.0233 (4)
H9	0.8550	−0.5850	0.3817	0.080*
C10	0.86280 (13)	−0.6845 (2)	0.18321 (13)	0.0370 (5)
H10	0.8853	−0.6934	0.1250	0.080*
C11	0.79073 (13)	−0.7436 (2)	0.21178 (14)	0.0360 (5)
H11	0.7548	−0.7997	0.1774	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01744 (19)	0.02404 (18)	0.02131 (19)	0.000	−0.00210 (10)	0.000
N1	0.0271 (8)	0.0325 (8)	0.0265 (8)	0.0039 (7)	−0.0012 (6)	−0.0046 (7)
N2	0.0234 (8)	0.0271 (8)	0.0245 (8)	0.0004 (6)	−0.0012 (6)	−0.0019 (7)
N3	0.0253 (8)	0.0272 (8)	0.0249 (8)	−0.0019 (6)	0.0007 (6)	−0.0013 (6)
N4	0.0259 (8)	0.0277 (9)	0.0218 (8)	−0.0003 (7)	0.0010 (6)	−0.0013 (6)
N5	0.0204 (7)	0.0243 (7)	0.0234 (8)	−0.0017 (6)	0.0044 (6)	−0.0008 (6)
N6	0.0203 (8)	0.0265 (8)	0.0239 (8)	−0.0002 (6)	0.0025 (6)	−0.0012 (6)
C1	0.0226 (9)	0.0261 (9)	0.0241 (9)	−0.0036 (7)	0.0054 (7)	0.0004 (7)
C2	0.0286 (10)	0.0357 (10)	0.0241 (10)	0.0017 (8)	0.0021 (8)	−0.0008 (8)
C3	0.0280 (10)	0.0334 (11)	0.0286 (10)	0.0037 (8)	0.0039 (8)	0.0040 (8)
C4	0.0237 (9)	0.0246 (9)	0.0290 (9)	−0.0034 (7)	0.0096 (7)	0.0022 (7)
C5	0.0269 (10)	0.0309 (9)	0.0254 (9)	−0.0039 (8)	0.0037 (8)	−0.0030 (8)
C6	0.0250 (9)	0.0299 (10)	0.0264 (9)	−0.0009 (8)	0.0013 (8)	0.0006 (8)
C7	0.0220 (9)	0.0250 (9)	0.0231 (9)	−0.0031 (7)	0.0026 (7)	0.0008 (7)
C8	0.0276 (10)	0.0259 (9)	0.0361 (10)	−0.0030 (7)	0.0135 (8)	0.0007 (8)
C9	0.0236 (9)	0.0237 (9)	0.0228 (9)	−0.0015 (7)	0.0025 (7)	−0.0009 (7)
C10	0.0322 (11)	0.0568 (13)	0.0221 (9)	−0.0122 (10)	0.0048 (8)	−0.0085 (9)
C11	0.0318 (11)	0.0515 (13)	0.0246 (10)	−0.0116 (9)	0.0022 (8)	−0.0101 (9)

Geometric parameters (Å, º) top

Zn1—N2	1.9880 (16)	C1—C7	1.474 (3)
Zn1—N2ⁱ	1.9880 (16)	C2—C3	1.386 (3)
Zn1—N6ⁱⁱ	1.9889 (16)	C2—H2	0.9300
Zn1—N6ⁱⁱⁱ	1.9889 (16)	C3—C4	1.390 (3)
N1—C7	1.339 (2)	C3—H3	0.9300
N1—N2	1.346 (2)	C4—C5	1.390 (3)
N2—N3	1.323 (2)	C4—C8	1.506 (2)
N3—N4	1.331 (2)	C5—C6	1.384 (3)
N4—C7	1.339 (2)	C5—H5	0.9300
N5—C9	1.338 (2)	C6—H6	0.9300
N5—C11	1.367 (2)	C8—H8A	0.9700
N5—C8	1.475 (2)	C8—H8B	0.9700
N6—C9	1.317 (2)	C9—H9	0.9300
N6—C10	1.377 (2)	C10—C11	1.353 (3)
N6—Zn1^iv	1.9889 (16)	C10—H10	0.9300
C1—C2	1.388 (3)	C11—H11	0.9300
C1—C6	1.397 (2)	Cg1—Cg2^v	3.7523 (11)

N2—Zn1—N2ⁱ	112.61 (9)	C3—C4—C5	118.89 (17)
N2—Zn1—N6ⁱⁱ	106.36 (6)	C3—C4—C8	120.48 (17)
N2ⁱ—Zn1—N6ⁱⁱ	109.48 (6)	C5—C4—C8	120.61 (17)
N2—Zn1—N6ⁱⁱⁱ	109.48 (6)	C6—C5—C4	120.74 (17)
N2ⁱ—Zn1—N6ⁱⁱⁱ	106.36 (6)	C6—C5—H5	119.6
N6ⁱⁱ—Zn1—N6ⁱⁱⁱ	112.67 (9)	C4—C5—H5	119.6
C7—N1—N2	102.90 (15)	C5—C6—C1	120.20 (18)
N3—N2—N1	111.33 (14)	C5—C6—H6	119.9
N3—N2—Zn1	124.49 (12)	C1—C6—H6	119.9
N1—N2—Zn1	124.13 (12)	N1—C7—N4	112.20 (16)
N2—N3—N4	107.92 (14)	N1—C7—C1	124.16 (17)
N3—N4—C7	105.65 (14)	N4—C7—C1	123.56 (16)
C9—N5—C11	107.49 (14)	N5—C8—C4	111.54 (14)
C9—N5—C8	126.75 (15)	N5—C8—H8A	109.3
C11—N5—C8	125.75 (15)	C4—C8—H8A	109.3
C9—N6—C10	106.10 (15)	N5—C8—H8B	109.3
C9—N6—Zn1^iv	127.13 (12)	C4—C8—H8B	109.3
C10—N6—Zn1^iv	126.68 (12)	H8A—C8—H8B	108.0
C2—C1—C6	119.07 (17)	N6—C9—N5	110.99 (15)
C2—C1—C7	121.01 (16)	N6—C9—H9	124.5
C6—C1—C7	119.88 (17)	N5—C9—H9	124.5
C3—C2—C1	120.42 (18)	C11—C10—N6	108.92 (16)
C3—C2—H2	119.8	C11—C10—H10	125.5
C1—C2—H2	119.8	N6—C10—H10	125.5
C2—C3—C4	120.66 (18)	C10—C11—N5	106.49 (16)
C2—C3—H3	119.7	C10—C11—H11	126.8
C4—C3—H3	119.7	N5—C11—H11	126.8

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

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···N4^vi	0.93	2.45	3.344 (2)	163
C8—H8A···Cg2^vii	0.97	2.88	3.692 (2)	142

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

Experimental details

Crystal data
Chemical formula	[Zn(C₁₁H₉N₆)₂]
M_r	515.85
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	273
a, b, c (Å)	16.1206 (12), 9.3720 (7), 14.6367 (11)
V (Å³)	2211.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.15
Crystal size (mm)	0.28 × 0.26 × 0.24

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.736, 0.752
No. of measured, independent and observed [I > 2σ(I)] reflections	11210, 2105, 1874
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.081, 1.07
No. of reflections	2105
No. of parameters	159
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.27

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999).

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···N4ⁱ	0.93	2.45	3.344 (2)	163
C8—H8A···Cg2ⁱⁱ	0.97	2.88	3.692 (2)	142

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

Acknowledgements

This work was supported by the Natural Science Foundation of Changchun Normal University.

References

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