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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): m132.
Published online 2007 December 6. doi:  10.1107/S160053680706518X
PMCID: PMC2915080

Poly[bis­(μ2-5-n-butyl­tetra­zolato-κ2 N 1:N 4)zinc(II)]

Abstract

In the title complex, [Zn(C5H9N4)2]n, the ZnII center is coordinated by four N atoms of different tetra­zolate ligands with a slightly distorted tetra­hedral geometry [Zn—N distances and N—Zn—N angles are in the ranges 1.991 (2)–2.007 (2) Å and 104.22 (8)–116.13 (8)°, respectively]. Each ligand links two ZnII atoms through its 1- and 4-position tetra­zole N atoms, forming a single, fully connected three-dimensional framework with a diamond-like topology. In the crystal structure, the Zn(...)Zn separations across each tetra­zole unit are 6.115 (2) and 6.134 (2) Å and the Zn(...)Zn(...)Zn angles are in the range 107.77 (8)–116.83 (8)°.

Related literature

For related literature, see: Li et al. (2007 [triangle]) and references therein; Wang et al. (2005 [triangle]); Ye et al. (2005 [triangle]).

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Object name is e-64-0m132-scheme1.jpg

Experimental

Crystal data

  • [Zn(C5H9N4)2]
  • M r = 315.69
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m132-efi9.jpg
  • a = 9.6534 (19) Å
  • b = 10.096 (2) Å
  • c = 14.359 (3) Å
  • V = 1399.4 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.76 mm−1
  • T = 113 (2) K
  • 0.24 × 0.22 × 0.22 mm

Data collection

  • Bruker SMART 1000 CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1998 [triangle]) T min = 0.978, T max = 1.000 (expected range = 0.665–0.680)
  • 17371 measured reflections
  • 3325 independent reflections
  • 3068 reflections with I > 2σ(I)
  • R int = 0.032

Refinement

  • R[F 2 > 2σ(F 2)] = 0.022
  • wR(F 2) = 0.050
  • S = 1.02
  • 3325 reflections
  • 172 parameters
  • H-atom parameters constrained
  • Δρmax = 0.50 e Å−3
  • Δρmin = −0.35 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1405 Friedel pairs
  • Flack parameter: −0.012 (9)

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1998 [triangle]); data reduction: SHELXTL (Bruker, 1998 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680706518X/sf2013sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680706518X/sf2013Isup2.hkl

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

Acknowledgments

The authors thank Nankai University for supporting this work.

supplementary crystallographic information

Comment

As the analogue of carboxylic acid, it has been realised that 5-substituted tetrazolate-based organic ligands have great potential in generating coordination polymers with novel network topologies and interesting properties [Li et al., 2007 and references therein]. Recently, three ZnII tetrazolate-based complexes having similar diamondoid structure to the title complex, [Zn(C5H9N4)2]n: catena-[bis(µ2-5-phenyltetrazolato-N,N''')-zinc(II)], catena-[bis(µ2-5-(4'-amino-6'-pyridyl)tetrazolato-N,N''')-zinc(II)] (Ye et al., 2005) and catena-[bis(µ2tetrazolato-N,N''')-zinc(II)] (Wang et al., 2005) were reported.

As shown in Fig. 1, in the title complex the ZnII center locates at the crystallographically general position and is coordinated by four N atoms of distinct tetrazolate ligands. The coordination geometry is of slightly distorted tetrahedron with Zn—N distances and N—Zn—N angles being in the range of 1.991 (2)–2.007 (2) Å and 104.22 (8)–116.13 (8) °, respectively. Each ligand links two ZnII atoms through its 1- and 4-position tetrazole N atoms to form a single three-dimensional diamond-like framework (Fig. 2). In the structure, the Zn—Zn separations across each tetrazole moiety are 6.115 (2) and 6.134 (2) Å and the Zn—Zn—Zn angles are revealed to range from 107.77 (8) to 116.83 (8) °.

Experimental

A mixture of ZnCl2 (27 mg, 0.2 mmol), NaN3 (33 mg, 0.5 mmol) and valeronitrile (33 mg, 0.4 mmol) in 10 ml of water was sealed in a Teflon-lined stainless-steel Parr bomb that was heated at 373 K for 48 h. Colorless crystals of the title compound were collected after the bomb was allowed to cool to room temperature spontaneously. Yield, 30% with respect to ZnII. Caution: Metal azides may be explosive. Although we have met no problems in this work, only a small amount of them should be prepared and handled with great caution.

Refinement

H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C—H = 0.97 and 0.96 Å and Uiso(H) = 1.2 Ueq(C, N).

Figures

Fig. 1.
View of coordination environments of ZnII and ligand in the title complex with 40% displacement probability. [Herein, labelled atoms A—D correspond to symmetry oprations i-iv, respectively. (i) = 1/2 + x, -3/2 - y, -z; (ii) = -x, 1/2 + y, -1/2 ...
Fig. 2.
three-dimensional structure of the title compound with butyl groups omitted for clarity.

Crystal data

[Zn(C5H9N4)2]F000 = 656
Mr = 315.69Dx = 1.498 Mg m3
Orthorhombic, P212121Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 5045 reflections
a = 9.6534 (19) Åθ = 2.8–27.9º
b = 10.096 (2) ŵ = 1.76 mm1
c = 14.359 (3) ÅT = 113 (2) K
V = 1399.4 (5) Å3Block, colorless
Z = 40.24 × 0.22 × 0.22 mm

Data collection

Bruker Smart 1000 CCD area-detector diffractometer3325 independent reflections
Radiation source: fine-focus sealed tube3068 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.032
T = 113(2) Kθmax = 27.9º
[var phi] and ω scanθmin = 2.8º
Absorption correction: multi-scan(SADABS; Bruker, 1998)h = −11→12
Tmin = 0.978, Tmax = 1.000k = −13→13
17371 measured reflectionsl = −18→18

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.022  w = 1/[σ2(Fo2) + (0.0274P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.050(Δ/σ)max = 0.001
S = 1.02Δρmax = 0.50 e Å3
3325 reflectionsΔρmin = −0.35 e Å3
172 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1405 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: −0.012 (9)

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 (Å2)

xyzUiso*/Ueq
Zn1−0.029407 (19)−0.736890 (17)−0.131493 (12)0.01072 (6)
C1−0.26406 (18)−0.79890 (17)0.00726 (12)0.0128 (4)
C2−0.2305 (2)−0.94018 (19)0.02652 (15)0.0211 (4)
H2A−0.2072−0.94980.09190.025*
H2B−0.1497−0.9653−0.00960.025*
C3−0.3495 (2)−1.03381 (19)0.00312 (17)0.0294 (5)
H3A−0.3606−1.0382−0.06390.035*
H3B−0.4347−0.99930.02940.035*
C4−0.3233 (3)−1.1747 (2)0.0416 (2)0.0495 (7)
H4A−0.2441−1.21330.01010.059*
H4B−0.3018−1.16930.10750.059*
C5−0.4459 (3)−1.2612 (2)0.0281 (2)0.0636 (8)
H5A−0.4274−1.34720.05380.085*
H5B−0.4652−1.2695−0.03730.085*
H5C−0.5245−1.22300.05900.085*
C60.04569 (18)−0.97174 (16)−0.25457 (11)0.0131 (4)
C70.19069 (19)−0.92793 (18)−0.27100 (14)0.0168 (4)
H7A0.2021−0.8392−0.24630.020*
H7B0.2073−0.9240−0.33760.020*
C80.29893 (19)−1.01919 (19)−0.22630 (15)0.0226 (4)
H8A0.2883−1.1079−0.25120.027*
H8B0.2828−1.0232−0.15970.027*
C90.4475 (2)−0.9711 (2)−0.24428 (16)0.0313 (5)
H9A0.5121−1.0369−0.22100.038*
H9B0.4619−0.9629−0.31090.038*
C100.4783 (2)−0.8388 (2)−0.1982 (2)0.0468 (7)
H10A0.5718−0.8128−0.21200.070*
H10B0.4673−0.8470−0.13200.070*
H10C0.4154−0.7729−0.22140.070*
N1−0.19539 (15)−0.71806 (14)−0.05010 (10)0.0135 (3)
N2−0.25827 (17)−0.59748 (15)−0.04447 (12)0.0188 (4)
N3−0.36058 (17)−0.60558 (15)0.01261 (11)0.0177 (3)
N4−0.36690 (14)−0.73163 (15)0.04700 (10)0.0137 (3)
N5−0.04611 (16)−0.90468 (13)−0.20430 (10)0.0131 (3)
N6−0.16579 (16)−0.97651 (15)−0.20460 (11)0.0162 (3)
N7−0.14673 (16)−1.08254 (16)−0.25271 (11)0.0162 (3)
N8−0.01317 (16)−1.08258 (14)−0.28558 (10)0.0136 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.01061 (9)0.01059 (9)0.01096 (9)−0.00005 (7)0.00044 (8)0.00010 (7)
C10.0115 (8)0.0141 (9)0.0126 (8)0.0008 (6)−0.0007 (7)−0.0011 (7)
C20.0235 (11)0.0146 (10)0.0250 (10)0.0049 (8)0.0080 (9)0.0031 (8)
C30.0306 (12)0.0158 (11)0.0418 (14)−0.0035 (9)0.0143 (10)−0.0064 (9)
C40.0491 (16)0.0252 (13)0.074 (2)0.0053 (12)0.0047 (16)−0.0033 (13)
C50.066 (2)0.0236 (13)0.071 (2)−0.0005 (14)0.0079 (17)0.0005 (14)
C60.0151 (9)0.0116 (8)0.0126 (8)0.0030 (7)−0.0003 (8)0.0003 (6)
C70.0139 (9)0.0140 (9)0.0223 (10)−0.0017 (7)0.0028 (8)−0.0055 (8)
C80.0185 (10)0.0204 (10)0.0288 (11)0.0016 (8)−0.0013 (9)−0.0045 (8)
C90.0156 (11)0.0356 (12)0.0425 (13)0.0034 (9)−0.0011 (10)−0.0062 (10)
C100.0216 (12)0.0350 (13)0.074 (2)−0.0046 (11)−0.0066 (15)−0.0078 (13)
N10.0142 (7)0.0127 (8)0.0136 (7)0.0004 (6)0.0014 (6)−0.0001 (6)
N20.0200 (8)0.0135 (8)0.0229 (9)0.0030 (6)0.0073 (7)0.0021 (7)
N30.0213 (9)0.0119 (8)0.0200 (8)0.0004 (6)0.0064 (7)0.0032 (6)
N40.0166 (7)0.0105 (7)0.0140 (7)0.0007 (6)0.0007 (6)0.0014 (6)
N50.0123 (8)0.0124 (7)0.0146 (7)−0.0003 (6)0.0014 (6)−0.0006 (6)
N60.0132 (8)0.0161 (8)0.0195 (8)−0.0045 (6)0.0017 (7)−0.0047 (7)
N70.0129 (8)0.0194 (8)0.0162 (8)−0.0011 (6)0.0027 (7)−0.0027 (6)
N80.0124 (8)0.0141 (7)0.0143 (7)−0.0016 (6)0.0015 (6)−0.0024 (6)

Geometric parameters (Å, °)

Zn1—N11.9923 (15)C6—C71.487 (2)
Zn1—N51.9971 (14)C7—C81.534 (3)
Zn1—N8i2.0035 (14)C7—H7A0.9700
Zn1—N4ii2.0085 (14)C7—H7B0.9700
C1—N41.331 (2)C8—C91.536 (3)
C1—N11.336 (2)C8—H8A0.9700
C1—C21.489 (3)C8—H8B0.9700
C2—C31.525 (3)C9—C101.521 (3)
C2—H2A0.9700C9—H9A0.9700
C2—H2B0.9700C9—H9B0.9700
C3—C41.547 (3)C10—H10A0.9600
C3—H3A0.9700C10—H10B0.9600
C3—H3B0.9700C10—H10C0.9600
C4—C51.484 (3)N1—N21.363 (2)
C4—H4A0.9700N2—N31.286 (2)
C4—H4B0.9700N3—N41.366 (2)
C5—H5A0.9600N4—Zn1iii2.0085 (14)
C5—H5B0.9600N5—N61.364 (2)
C5—H5C0.9600N6—N71.287 (2)
C6—N51.329 (2)N7—N81.373 (2)
C6—N81.332 (2)N8—Zn1iv2.0035 (14)
N1—Zn1—N5108.85 (6)C8—C7—H7A108.9
N1—Zn1—N8i116.07 (6)C6—C7—H7B108.9
N5—Zn1—N8i111.41 (6)C8—C7—H7B108.9
N1—Zn1—N4ii106.79 (6)H7A—C7—H7B107.7
N5—Zn1—N4ii104.18 (6)C7—C8—C9112.09 (17)
N8i—Zn1—N4ii108.77 (6)C7—C8—H8A109.2
N4—C1—N1108.82 (16)C9—C8—H8A109.2
N4—C1—C2124.86 (16)C7—C8—H8B109.2
N1—C1—C2126.30 (16)C9—C8—H8B109.2
C1—C2—C3112.90 (17)H8A—C8—H8B107.9
C1—C2—H2A109.0C10—C9—C8112.78 (18)
C3—C2—H2A109.0C10—C9—H9A109.0
C1—C2—H2B109.0C8—C9—H9A109.0
C3—C2—H2B109.0C10—C9—H9B109.0
H2A—C2—H2B107.8C8—C9—H9B109.0
C2—C3—C4111.6 (2)H9A—C9—H9B107.8
C2—C3—H3A109.3C9—C10—H10A109.5
C4—C3—H3A109.3C9—C10—H10B109.5
C2—C3—H3B109.3H10A—C10—H10B109.5
C4—C3—H3B109.3C9—C10—H10C109.5
H3A—C3—H3B108.0H10A—C10—H10C109.5
C5—C4—C3111.4 (2)H10B—C10—H10C109.5
C5—C4—H4A109.4C1—N1—N2106.75 (14)
C3—C4—H4A109.4C1—N1—Zn1134.64 (12)
C5—C4—H4B109.4N2—N1—Zn1118.57 (11)
C3—C4—H4B109.4N3—N2—N1108.85 (14)
H4A—C4—H4B108.0N2—N3—N4108.89 (14)
C4—C5—H5A109.5C1—N4—N3106.68 (14)
C4—C5—H5B109.5C1—N4—Zn1iii139.52 (13)
H5A—C5—H5B109.5N3—N4—Zn1iii113.61 (11)
C4—C5—H5C109.5C6—N5—N6106.99 (14)
H5A—C5—H5C109.5C6—N5—Zn1131.52 (12)
H5B—C5—H5C109.5N6—N5—Zn1121.40 (11)
N5—C6—N8108.99 (15)N7—N6—N5108.83 (14)
N5—C6—C7124.24 (15)N6—N7—N8108.60 (14)
N8—C6—C7126.77 (16)C6—N8—N7106.59 (14)
C6—C7—C8113.35 (16)C6—N8—Zn1iv139.87 (13)
C6—C7—H7A108.9N7—N8—Zn1iv113.40 (11)
N4—C1—C2—C360.4 (3)N1—C1—N4—Zn1iii174.28 (14)
N1—C1—C2—C3−121.4 (2)C2—C1—N4—Zn1iii−7.2 (3)
C1—C2—C3—C4−168.7 (2)N2—N3—N4—C1−0.44 (19)
C2—C3—C4—C5173.6 (2)N2—N3—N4—Zn1iii−176.38 (12)
N5—C6—C7—C8114.1 (2)N8—C6—N5—N6−0.20 (19)
N8—C6—C7—C8−64.9 (2)C7—C6—N5—N6−179.41 (16)
C6—C7—C8—C9−179.85 (16)N8—C6—N5—Zn1176.40 (12)
C7—C8—C9—C1065.2 (2)C7—C6—N5—Zn1−2.8 (3)
N4—C1—N1—N20.4 (2)N1—Zn1—N5—C6−166.75 (15)
C2—C1—N1—N2−178.09 (17)N8i—Zn1—N5—C664.01 (17)
N4—C1—N1—Zn1177.93 (12)N4ii—Zn1—N5—C6−53.10 (16)
C2—C1—N1—Zn1−0.5 (3)N1—Zn1—N5—N69.43 (14)
N5—Zn1—N1—C146.63 (19)N8i—Zn1—N5—N6−119.81 (13)
N8i—Zn1—N1—C1173.24 (16)N4ii—Zn1—N5—N6123.08 (13)
N4ii—Zn1—N1—C1−65.30 (18)C6—N5—N6—N70.2 (2)
N5—Zn1—N1—N2−136.05 (13)Zn1—N5—N6—N7−176.78 (11)
N8i—Zn1—N1—N2−9.44 (15)N5—N6—N7—N8−0.18 (19)
N4ii—Zn1—N1—N2112.02 (13)N5—C6—N8—N70.09 (18)
C1—N1—N2—N3−0.7 (2)C7—C6—N8—N7179.28 (17)
Zn1—N1—N2—N3−178.68 (12)N5—C6—N8—Zn1iv175.30 (14)
N1—N2—N3—N40.7 (2)C7—C6—N8—Zn1iv−5.5 (3)
N1—C1—N4—N30.01 (19)N6—N7—N8—C60.06 (18)
C2—C1—N4—N3178.52 (17)N6—N7—N8—Zn1iv−176.58 (12)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SF2013).

References

  • Bruker (1998). SMART (Version 5.051), SAINT (Version 5.01), SADABS (Version 2.03) and SHELXTL (Version 6.1). Bruker AXS Inc., Madison, Wisconsin, USA.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Li, J.-R., Tao, Y., Yu, Q. & Bu, X.-H. (2007). Chem. Commun. pp. 1527–1529. [PubMed]
  • Sheldrick, G. M. (1997). SHELXL97 and SHELXS97 University of Göttingen, Germany.
  • Wang, X.-S., Tang, Y.-Z., Huang, X.-F., Qu, Z.-R., Che, C.-M., Chan, P. W. H. & Xiong, R.-G. (2005). Inorg. Chem.44, 5278–5285. [PubMed]
  • Ye, Q., Li, Y.-H., Song, Y.-M., Huang, X.-F., Xiong, R.-G. & Xue, Z. (2005). Inorg. Chem.44, 3618–3625. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography