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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): m1033.
Published online 2008 July 16. doi:  10.1107/S1600536808021946
PMCID: PMC2962247

catena-Poly[zinc(II)-bis­[μ-5-(2-amino­phenyl)tetra­zolato]-κ3 N 1,N 5:N 23 N 2:N 1,N 5]

Abstract

The polymeric title compound, [Zn(C7H6N5)2]n, was synthesized by the hydro­thermal reaction of Zn(NO3)2 with 2-amino­benzonitrile in the presence of NaN3. The zinc(II) metal centre displays a distorted octa­hedral coordination environment provided by N atoms of two bidentate chelating and two monodentate 5-(2-amino­phen­yl)tetra­zolate ligands. These ligands act as bridges, linking adjacent Zn atoms into polymeric criss-crossed chains parallel to the [110] and [An external file that holds a picture, illustration, etc.
Object name is e-64-m1033-efi3.jpg10] directions. Intra­chain N—H(...)N hydrogen-bonding inter­actions are observed.

Related literature

For the applications of tetra­zole compounds, see: Arp et al. (2000 [triangle]); Dunica et al. (1991 [triangle]); Wang et al. (2004 [triangle], 2005 [triangle]); Wittenberger & Donner (1993 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1033-scheme1.jpg

Experimental

Crystal data

  • [Zn(C7H6N5)2]
  • M r = 385.71
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1033-efi4.jpg
  • a = 10.6751 (16) Å
  • b = 10.9051 (14) Å
  • c = 25.321 (5) Å
  • β = 94.972 (13)°
  • V = 2936.6 (8) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 1.70 mm−1
  • T = 298 (2) K
  • 0.28 × 0.12 × 0.10 mm

Data collection

  • Rigaku Mercury2 diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.783, T max = 0.844
  • 14618 measured reflections
  • 3343 independent reflections
  • 2859 reflections with I > 2σ(I)
  • R int = 0.044

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.092
  • S = 1.09
  • 3343 reflections
  • 226 parameters
  • H-atom parameters constrained
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.70 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL/PC (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL/PC.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808021946/rz2234sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808021946/rz2234Isup2.hkl

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

Acknowledgments

This work was supported by a Start-up Grant from Southeast University to Professor Ren-Gen Xiong.

supplementary crystallographic information

Comment

The tetrazole functional group has found a wide range of applications in coordination chemistry as polydentate ligand, in medicinal chemistry as a metabolically stable surrogate of the carboxylic group, and in materials science as the field of high density energy materials (Wang et al., 2005; Dunica et al., 1991; Wittenberger & Donner, 1993). The crystal structure of the polymeric title compound is reported here.

The compound is isostructural with the corresponding cadmium(II) derivative (Wang et al., 2004). The asymmetric unit of the title compound consists of one zinc(II) atom and two 5-(2-aminobenzyl)tetrazolato ligands. The benzene and tetrazole rings are twisted from each other at dihedral angles of 27.39(14 ) and 21.59(14 )°. Bond distances and angles within the tetrazole rings fall in the usual ranges (Wang et al., 2005; Arp et al., 2000). The metal centre exhibits a distorted octahedral coordination environment (Fig. 1) provided by N atoms of two bidentate-chelating and two monodentate ligands. Both independent ligands act as bridges linking adjacent zinc(II) atoms into polymeric criss-crossed chains parallel to the [110] and [-110] directions (Fig. 2). Intrachain N—H···N hydrogen bonding interactions (Table 1) are present.

Experimental

A mixture of 2-aminobenzonitrile (0.2 mmol), NaN3 (0.4 mmol), Zn(NO3)2(0.15 mmol) ethanol (1 ml) and a few drops of water was sealed in a glass tube and maintained at 120 °C. Colourless block crystals suitable for X-ray analysis were obtained after 3 days.

Refinement

All H atoms attached to C and N atoms were fixed geometrically and treated as riding with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C), N—H = 0.90 Å and Uiso(H) = 1.5Ueq(N).

Figures

Fig. 1.
View of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (A) 1/2-x, 1/2-y,-z; (B) -x, 1-y, -z; (C) 1/2+x, y-1/2, z].
Fig. 2.
Crystal packing of the title compound viewed along the viewed along the [-110] direction. Intrachain hydrogen bonds are shwn as dashed lines. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity.

Crystal data

[Zn(C7H6N5)2]F000 = 1568
Mr = 385.71Dx = 1.745 Mg m3
Monoclinic, C2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3668 reflections
a = 10.6751 (16) Åθ = 3.0–27.5º
b = 10.9051 (14) ŵ = 1.70 mm1
c = 25.321 (5) ÅT = 298 (2) K
β = 94.972 (13)ºBlock, colourless
V = 2936.6 (8) Å30.28 × 0.12 × 0.10 mm
Z = 8

Data collection

Rigaku Mercury2 diffractometer3343 independent reflections
Radiation source: fine-focus sealed tube2859 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.044
Detector resolution: 13.6612 pixels mm-1θmax = 27.5º
T = 298(2) Kθmin = 3.0º
ω scansh = −13→13
Absorption correction: multi-scan(CrystalClear; Rigaku, 2005)k = −14→14
Tmin = 0.783, Tmax = 0.844l = −32→32
14618 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.092  w = 1/[σ2(Fo2) + (0.0386P)2 + 3.3164P] where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max = 0.001
3343 reflectionsΔρmax = 0.37 e Å3
226 parametersΔρmin = −0.70 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)

xyzUiso*/Ueq
Zn10.16630 (3)0.40663 (2)0.032125 (11)0.02512 (10)
N40.11712 (19)0.60243 (17)0.02478 (8)0.0249 (4)
N100.0847 (2)0.4084 (2)0.10837 (9)0.0323 (5)
H10A0.02850.46960.10970.048*
H10B0.04380.33650.10380.048*
C100.1638 (2)0.4052 (2)0.15692 (10)0.0288 (5)
N90.3503 (2)0.49221 (19)0.04291 (9)0.0310 (5)
H9A0.41050.43430.04450.046*
H9B0.35210.53480.01250.046*
C90.2582 (2)0.3162 (2)0.16320 (9)0.0272 (5)
N80.24495 (18)0.23775 (18)0.06944 (8)0.0245 (4)
C10.1781 (2)0.6906 (2)0.05410 (10)0.0252 (5)
C20.2884 (2)0.6711 (2)0.09210 (10)0.0283 (5)
C140.3353 (3)0.3134 (3)0.21067 (10)0.0346 (6)
H14A0.39830.25450.21540.041*
C30.3720 (2)0.5736 (2)0.08704 (11)0.0291 (5)
C130.3197 (3)0.3964 (3)0.25076 (12)0.0438 (7)
H13A0.37180.39340.28210.053*
C40.4704 (3)0.5554 (3)0.12574 (13)0.0404 (7)
H4A0.52650.49130.12220.048*
C70.3079 (3)0.7491 (3)0.13564 (11)0.0360 (6)
H7A0.25530.81630.13850.043*
C60.4044 (3)0.7281 (3)0.17470 (12)0.0437 (7)
H6A0.41420.77880.20430.052*
C50.4859 (3)0.6316 (3)0.16940 (13)0.0451 (7)
H5A0.55150.61770.19530.054*
C110.1483 (3)0.4882 (3)0.19728 (12)0.0414 (7)
H11A0.08520.54700.19310.050*
C120.2265 (3)0.4838 (3)0.24397 (12)0.0473 (8)
H12A0.21600.54020.27080.057*
C80.2794 (2)0.2265 (2)0.12170 (9)0.0250 (5)
N60.3457 (2)0.0666 (2)0.08495 (9)0.0380 (6)
N50.3411 (2)0.1218 (2)0.13199 (9)0.0368 (5)
N70.2890 (2)0.13536 (19)0.04763 (8)0.0280 (4)
N10.1206 (2)0.79890 (19)0.04653 (9)0.0330 (5)
N20.0204 (2)0.77701 (19)0.01204 (9)0.0334 (5)
N30.01805 (19)0.65985 (19)−0.00074 (9)0.0282 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.02992 (17)0.02214 (16)0.02306 (16)0.00230 (11)0.00100 (11)0.00016 (11)
N40.0276 (10)0.0202 (10)0.0265 (10)0.0028 (8)0.0004 (8)0.0011 (8)
N100.0334 (12)0.0362 (12)0.0277 (11)0.0113 (9)0.0041 (9)0.0050 (9)
C100.0350 (14)0.0262 (12)0.0257 (12)0.0023 (10)0.0051 (10)0.0031 (10)
N90.0311 (11)0.0215 (10)0.0408 (13)0.0045 (9)0.0056 (9)0.0009 (9)
C90.0312 (13)0.0276 (12)0.0230 (12)−0.0015 (10)0.0028 (10)0.0027 (10)
N80.0295 (10)0.0217 (10)0.0221 (10)0.0045 (8)0.0017 (8)0.0006 (8)
C10.0270 (12)0.0208 (11)0.0284 (12)0.0000 (9)0.0056 (9)0.0001 (10)
C20.0278 (12)0.0253 (12)0.0317 (13)−0.0025 (10)0.0016 (10)0.0010 (10)
C140.0381 (15)0.0354 (14)0.0292 (13)−0.0008 (12)−0.0025 (11)0.0022 (11)
C30.0292 (13)0.0240 (12)0.0343 (14)−0.0020 (10)0.0029 (10)0.0024 (10)
C130.0549 (19)0.0487 (18)0.0266 (14)−0.0089 (15)−0.0029 (13)−0.0062 (13)
C40.0330 (14)0.0339 (14)0.0528 (18)0.0008 (12)−0.0044 (13)0.0080 (13)
C70.0381 (15)0.0323 (14)0.0371 (15)−0.0016 (12)0.0011 (12)−0.0038 (12)
C60.0459 (17)0.0455 (17)0.0382 (16)−0.0079 (14)−0.0051 (13)−0.0047 (14)
C50.0386 (16)0.0472 (17)0.0467 (18)−0.0071 (14)−0.0130 (13)0.0094 (14)
C110.0539 (18)0.0321 (14)0.0396 (16)0.0081 (13)0.0128 (13)−0.0022 (12)
C120.068 (2)0.0427 (17)0.0322 (15)−0.0033 (16)0.0106 (14)−0.0131 (13)
C80.0256 (12)0.0245 (12)0.0248 (12)0.0030 (10)0.0019 (9)0.0042 (10)
N60.0532 (15)0.0346 (12)0.0270 (12)0.0154 (11)0.0081 (10)0.0042 (10)
N50.0485 (14)0.0376 (12)0.0245 (11)0.0164 (11)0.0034 (10)0.0034 (10)
N70.0353 (11)0.0245 (10)0.0248 (11)0.0062 (9)0.0063 (9)0.0007 (8)
N10.0308 (11)0.0243 (11)0.0426 (13)0.0009 (9)−0.0042 (10)−0.0014 (10)
N20.0309 (11)0.0233 (11)0.0453 (14)0.0024 (9)−0.0012 (10)0.0013 (10)
N30.0283 (11)0.0243 (11)0.0318 (11)0.0027 (8)0.0006 (9)0.0029 (9)

Geometric parameters (Å, °)

Zn1—N7i2.164 (2)C2—C31.401 (4)
Zn1—N92.170 (2)C14—C131.381 (4)
Zn1—N3ii2.181 (2)C14—H14A0.9300
Zn1—N102.186 (2)C3—C41.387 (4)
Zn1—N82.2027 (19)C13—C121.377 (4)
Zn1—N42.2028 (19)C13—H13A0.9300
N4—N31.345 (3)C4—C51.381 (5)
N4—C11.348 (3)C4—H4A0.9300
N10—C101.430 (3)C7—C61.384 (4)
N10—H10A0.9000C7—H7A0.9300
N10—H10B0.9001C6—C51.380 (4)
C10—C111.386 (4)C6—H6A0.9300
C10—C91.397 (3)C5—H5A0.9300
N9—C31.430 (3)C11—C121.388 (4)
N9—H9A0.9000C11—H11A0.9300
N9—H9B0.9001C12—H12A0.9300
C9—C141.398 (3)C8—N51.333 (3)
C9—C81.467 (3)N6—N71.312 (3)
N8—C81.348 (3)N6—N51.339 (3)
N8—N71.348 (3)N7—Zn1i2.164 (2)
C1—N11.337 (3)N1—N21.342 (3)
C1—C21.470 (3)N2—N31.318 (3)
C2—C71.394 (4)N3—Zn1ii2.181 (2)
N7i—Zn1—N986.46 (8)C7—C2—C1119.1 (2)
N7i—Zn1—N3ii81.63 (8)C3—C2—C1122.0 (2)
N9—Zn1—N3ii165.18 (8)C13—C14—C9121.2 (3)
N7i—Zn1—N10164.38 (9)C13—C14—H14A119.4
N9—Zn1—N10108.10 (9)C9—C14—H14A119.4
N3ii—Zn1—N1084.76 (9)C4—C3—C2119.5 (3)
N7i—Zn1—N896.71 (7)C4—C3—N9121.7 (2)
N9—Zn1—N889.91 (8)C2—C3—N9118.8 (2)
N3ii—Zn1—N8100.18 (8)C12—C13—C14119.6 (3)
N10—Zn1—N878.16 (8)C12—C13—H13A120.2
N7i—Zn1—N4101.33 (8)C14—C13—H13A120.2
N9—Zn1—N478.48 (8)C5—C4—C3120.7 (3)
N3ii—Zn1—N495.19 (8)C5—C4—H4A119.6
N10—Zn1—N487.46 (8)C3—C4—H4A119.6
N8—Zn1—N4157.80 (8)C6—C7—C2121.0 (3)
N3—N4—C1104.77 (18)C6—C7—H7A119.5
N3—N4—Zn1131.56 (16)C2—C7—H7A119.5
C1—N4—Zn1123.01 (16)C5—C6—C7119.6 (3)
C10—N10—Zn1120.53 (17)C5—C6—H6A120.2
C10—N10—H10A109.5C7—C6—H6A120.2
Zn1—N10—H10A110.9C6—C5—C4120.2 (3)
C10—N10—H10B109.5C6—C5—H5A119.9
Zn1—N10—H10B96.0C4—C5—H5A119.9
H10A—N10—H10B109.5C10—C11—C12120.3 (3)
C11—C10—C9120.0 (2)C10—C11—H11A119.9
C11—C10—N10121.2 (2)C12—C11—H11A119.9
C9—C10—N10118.8 (2)C13—C12—C11120.3 (3)
C3—N9—Zn1116.66 (16)C13—C12—H12A119.8
C3—N9—H9A109.5C11—C12—H12A119.8
Zn1—N9—H9A109.8N5—C8—N8111.0 (2)
C3—N9—H9B109.5N5—C8—C9122.4 (2)
Zn1—N9—H9B101.6N8—C8—C9126.6 (2)
H9A—N9—H9B109.5N7—N6—N5109.5 (2)
C10—C9—C14118.6 (2)C8—N5—N6105.5 (2)
C10—C9—C8122.4 (2)N6—N7—N8109.5 (2)
C14—C9—C8119.0 (2)N6—N7—Zn1i115.23 (16)
C8—N8—N7104.58 (19)N8—N7—Zn1i132.09 (16)
C8—N8—Zn1123.94 (16)C1—N1—N2105.5 (2)
N7—N8—Zn1130.57 (15)N3—N2—N1109.2 (2)
N1—C1—N4110.9 (2)N2—N3—N4109.6 (2)
N1—C1—C2123.6 (2)N2—N3—Zn1ii114.14 (16)
N4—C1—C2125.4 (2)N4—N3—Zn1ii131.85 (16)
C7—C2—C3118.9 (2)

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N10—H10A···N6iii0.902.263.095 (3)154
N9—H9A···N2iv0.902.273.108 (3)155
N9—H9B···N1v0.902.383.246 (3)160
N9—H9B···N2v0.902.573.242 (3)132

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2234).

References

  • Arp, H. P. H., Decken, A., Passmore, J. & Wood, D. J. (2000). Inorg. Chem.39, 1840–1848. [PubMed]
  • Dunica, J. V., Pierce, M. E. & Santella, J. B. III (1991). J. Org. Chem.56, 2395–2400.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, X.-S., Tang, Y.-Z., Huang, X.-F., Qu, Z.-R., Che, C.-M., Chan, C. W. H. & Xiong, R.-G. (2005). Inorg. Chem.44, 5278–5285. [PubMed]
  • Wang, Y.-C., Zhao, H., Song, Y.-M., Wang, X.-S. & Xiong, R.-G. (2004). Appl. Organomet. Chem.18, 494–495.
  • Wittenberger, S. J. & Donner, B. G. (1993). J. Org. Chem.58, 4139–4141.

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