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Acta Cryst. (2009). E65, m622    [ doi:10.1107/S1600536809016055 ]

Diazidobis[2,4-diamino-6-(2-pyridyl)-1,3,5-triazine-[kappa]2N1,N6]zinc(II)

Q.-H. Zhao, A.-L. Fan, L.-N. Li and M.-J. Xie

Abstract top

In the title mononuclear complex, [Zn(N3)2(C8H8N6)2], the ZnII atom, lying on a twofold rotation axis, is six-coordinated in a distorted octahedral environment by four N atoms from two 2,4-diamino-6-(2-pyridyl)-1,3,5-triazine ligands and two N atoms from two end-on-coordinated azide ions. N-H...N hydrogen bonds between the ligand and azide ion link the complex molecules into a three-dimensional network.

Comment top

At present, the design and synthesis of organic–inorganic hybrid compounds have drawn considerable attention. It was reported that 1H-1,3,5-triazole derivatives are a type of heterocyclic compounds with widely biological activity and outstanding capability. Meanwhile, a large number of complexes with azide ligands have been structurally and magnetically characterized (Carranza et al., 2008; Gadad et al., 2000, 2004; Sun & Du, 2005). Herein we report the synthesis and crystal structure of the title compound.

As shown in Fig. 1, the central ZnII atom is coordinated by six N atoms and assumes a distorted octahedral geometry. The Zn—N(amide) bond [2.166 (2) Å] and the Zn—N(azide) bond [2.153 (3) Å] are significantly shorter than the Zn—N(pyridine) bond [2.202 (2) Å] (Table 1). The pyridyl and triazine rings of the ligand are essentially planar. The C3 atom shows an evident deviation of 0.1264 (3)Å from the mean plane through all atoms of the ligand. The two ligands coordinated to the Zn atom form a dihedral angle of 74.80 (7)°. The molecules are connected into a three-dimensional network through N—H···N hydrogen bonds (Table 2 and Fig. 2).

Related literature top

For general background to organic–inorganic hybrid complexes with azide ligands, see: Carranza et al. (2008); Gadad et al. (2000, 2004); Sun & Du (2005).

Experimental top

All chemicals used (reagent grade) were commercially available. The compound was synthesized by heating a mixture of Zn(CH3COO)2 (30 mg, 0.15 mmol), 2,4-diamino-6-pyridyl-l,3,5-triazine (17.6 mg, 0.1 mmol), CH3OH (5 ml) and H2O (15 ml) at 338 K in stirring condition. After a few minutes, an aqueous solution (2 ml) of sodium azide (6.5 mg, 0.1 mmol) was added to it and stirred for 30 min. Colourless single crystals suitable for X-ray analysis were obtained by slow evaporation at room temperature for three weeks.

Refinement top

H atoms were positioned geometrically and treated as riding on their parent atoms, with N—H = 0.86 and C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(C,N).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) -x+1, y, -z+3/2.]
[Figure 2] Fig. 2. The crystal packing diagram of the title compound, showing hydrogen bonds (dashed lines).
Diazidobis[2,4-diamino-6-(2-pyridyl)-1,3,5-triazine-κ2N1,N6]zinc(II) top
Crystal data top
[Zn(N3)2(C8H8N6)2]F000 = 1072
Mr = 525.86Dx = 1.624 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2266 reflections
a = 18.288 (9) Åθ = 1.9–28.6º
b = 14.231 (7) ŵ = 1.19 mm−1
c = 9.144 (4) ÅT = 293 K
β = 115.382 (5)ºBlock, colourless
V = 2150.2 (18) Å30.20 × 0.18 × 0.08 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer		2569 independent reflections
Radiation source: fine-focus sealed tube1766 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.056
T = 293 Kθmax = 28.6º
φ and ω scansθmin = 1.9º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −24→24
Tmin = 0.588, Tmax = 0.841k = −18→19
9145 measured reflectionsl = −12→12
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.111  w = 1/[σ2(Fo2) + (0.0537P)2 + 0.3944P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2569 reflectionsΔρmax = 0.51 e Å−3
159 parametersΔρmin = −0.41 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Zn(N3)2(C8H8N6)2]V = 2150.2 (18) Å3
Mr = 525.86Z = 4
Monoclinic, C2/cMo Kα
a = 18.288 (9) ŵ = 1.19 mm−1
b = 14.231 (7) ÅT = 293 K
c = 9.144 (4) Å0.20 × 0.18 × 0.08 mm
β = 115.382 (5)º
Data collection top
Bruker APEXII CCD
diffractometer		2569 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1766 reflections with I > 2σ(I)
Tmin = 0.588, Tmax = 0.841Rint = 0.056
9145 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.045159 parameters
wR(F2) = 0.111H-atom parameters constrained
S = 1.00Δρmax = 0.51 e Å−3
2569 reflectionsΔρmin = −0.41 e Å−3
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.50000.26762 (3)0.75000.03110 (17)
N10.57688 (14)0.16446 (17)0.7022 (3)0.0345 (6)
N20.72454 (13)0.16338 (16)1.1155 (3)0.0317 (6)
N30.67379 (15)0.25546 (16)1.2722 (3)0.0335 (6)
N40.59865 (13)0.24286 (16)0.9857 (3)0.0295 (6)
N50.79367 (15)0.17410 (19)1.3913 (3)0.0466 (7)
H5A0.79940.19401.48450.056*
H5B0.82970.13801.38420.056*
N60.55659 (15)0.33821 (19)1.1393 (3)0.0463 (7)
H6A0.56220.36081.23080.056*
H6B0.51570.35421.05170.056*
N70.56565 (14)0.37551 (19)0.6915 (3)0.0370 (6)
N80.58831 (15)0.43984 (19)0.7856 (3)0.0372 (6)
N90.61108 (18)0.5009 (2)0.8783 (4)0.0554 (8)
C10.5666 (2)0.1303 (2)0.5574 (4)0.0486 (9)
H1A0.51780.14210.46820.058*
C20.6245 (2)0.0791 (3)0.5352 (4)0.0536 (10)
H2A0.61490.05720.43270.064*
C30.6968 (2)0.0602 (2)0.6659 (4)0.0452 (8)
H3A0.73700.02570.65370.054*
C40.70815 (19)0.0941 (2)0.8161 (4)0.0375 (7)
H4A0.75600.08180.90710.045*
C50.64771 (17)0.14623 (19)0.8293 (3)0.0294 (6)
C60.65790 (16)0.18691 (19)0.9882 (3)0.0276 (6)
C70.72914 (17)0.1992 (2)1.2585 (3)0.0320 (7)
C80.61087 (17)0.2789 (2)1.1335 (3)0.0311 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0264 (3)0.0377 (3)0.0228 (3)0.0000.00450 (19)0.000
N10.0326 (13)0.0405 (15)0.0225 (13)0.0043 (11)0.0043 (11)−0.0033 (10)
N20.0282 (13)0.0402 (15)0.0218 (13)0.0042 (10)0.0060 (10)0.0004 (10)
N30.0307 (13)0.0454 (16)0.0206 (12)0.0050 (11)0.0075 (10)0.0004 (10)
N40.0244 (12)0.0399 (15)0.0198 (12)0.0021 (10)0.0052 (10)−0.0012 (10)
N50.0393 (15)0.070 (2)0.0202 (13)0.0202 (14)0.0027 (11)−0.0020 (13)
N60.0393 (15)0.070 (2)0.0212 (13)0.0195 (14)0.0050 (12)−0.0045 (12)
N70.0326 (14)0.0448 (16)0.0321 (14)−0.0050 (12)0.0123 (11)−0.0025 (12)
N80.0285 (14)0.0446 (17)0.0338 (15)−0.0006 (12)0.0089 (11)0.0082 (13)
N90.061 (2)0.0489 (18)0.0433 (17)−0.0132 (15)0.0104 (15)−0.0083 (15)
C10.0435 (19)0.063 (2)0.0272 (17)0.0092 (17)0.0041 (15)−0.0105 (16)
C20.059 (2)0.065 (2)0.0317 (18)0.0114 (19)0.0149 (17)−0.0161 (16)
C30.051 (2)0.046 (2)0.042 (2)0.0076 (16)0.0222 (17)−0.0088 (15)
C40.0379 (17)0.0382 (18)0.0335 (17)0.0037 (14)0.0125 (14)−0.0006 (14)
C50.0316 (15)0.0283 (15)0.0265 (15)−0.0020 (12)0.0108 (12)−0.0022 (12)
C60.0265 (14)0.0303 (15)0.0244 (15)−0.0014 (12)0.0094 (12)0.0012 (12)
C70.0291 (15)0.0372 (17)0.0246 (15)0.0008 (13)0.0066 (12)0.0047 (12)
C80.0284 (15)0.0384 (17)0.0231 (15)0.0021 (13)0.0078 (12)0.0020 (12)
Geometric parameters (Å, °) top
Zn1—N72.153 (3)N5—H5B0.8600
Zn1—N7i2.153 (3)N6—C81.322 (4)
Zn1—N4i2.166 (2)N6—H6A0.8600
Zn1—N42.166 (2)N6—H6B0.8600
Zn1—N12.202 (2)N7—N81.202 (4)
Zn1—N1i2.202 (2)N8—N91.159 (4)
N1—C51.343 (3)C1—C21.371 (5)
N1—C11.346 (4)C1—H1A0.9300
N2—C61.318 (3)C2—C31.377 (5)
N2—C71.372 (4)C2—H2A0.9300
N3—C71.338 (4)C3—C41.385 (4)
N3—C81.339 (4)C3—H3A0.9300
N4—C61.337 (3)C4—C51.379 (4)
N4—C81.371 (4)C4—H4A0.9300
N5—C71.329 (3)C5—C61.500 (4)
N5—H5A0.8600
N7—Zn1—N7i89.01 (14)H6A—N6—H6B120.0
N7—Zn1—N4i100.61 (9)N8—N7—Zn1115.1 (2)
N7i—Zn1—N4i92.75 (9)N9—N8—N7178.8 (3)
N7—Zn1—N492.75 (9)N1—C1—C2123.1 (3)
N7i—Zn1—N4100.61 (9)N1—C1—H1A118.4
N4i—Zn1—N4161.28 (13)C2—C1—H1A118.4
N7—Zn1—N187.41 (10)C1—C2—C3119.4 (3)
N7i—Zn1—N1174.96 (9)C1—C2—H2A120.3
N4i—Zn1—N191.39 (9)C3—C2—H2A120.3
N4—Zn1—N176.04 (9)C2—C3—C4118.2 (3)
N7—Zn1—N1i174.96 (9)C2—C3—H3A120.9
N7i—Zn1—N1i87.41 (10)C4—C3—H3A120.9
N4i—Zn1—N1i76.04 (9)C5—C4—C3119.3 (3)
N4—Zn1—N1i91.39 (9)C5—C4—H4A120.4
N1—Zn1—N1i96.38 (14)C3—C4—H4A120.4
C5—N1—C1117.3 (3)N1—C5—C4122.7 (3)
C5—N1—Zn1114.71 (18)N1—C5—C6115.9 (2)
C1—N1—Zn1127.1 (2)C4—C5—C6121.4 (3)
C6—N2—C7113.8 (2)N2—C6—N4127.0 (2)
C7—N3—C8115.9 (2)N2—C6—C5116.2 (2)
C6—N4—C8114.7 (2)N4—C6—C5116.8 (2)
C6—N4—Zn1115.90 (17)N5—C7—N3119.1 (3)
C8—N4—Zn1129.38 (19)N5—C7—N2116.0 (3)
C7—N5—H5A120.0N3—C7—N2124.9 (2)
C7—N5—H5B120.0N6—C8—N3118.4 (3)
H5A—N5—H5B120.0N6—C8—N4118.1 (2)
C8—N6—H6A120.0N3—C8—N4123.5 (3)
C8—N6—H6B120.0
Symmetry codes: (i) −x+1, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N5—H5A···N3ii0.862.193.042 (4)175
N5—H5B···N7iii0.862.313.060 (4)147
N6—H6A···N9iv0.862.343.025 (4)137
N6—H6B···N7i0.862.102.939 (4)164
Symmetry codes: (ii) −x+3/2, −y+1/2, −z+3; (iii) −x+3/2, −y+1/2, −z+2; (iv) x, −y+1, z+1/2; (i) −x+1, y, −z+3/2.
Table 1
Selected geometric parameters (Å) top
Zn1—N72.153 (3)Zn1—N12.202 (2)
Zn1—N42.166 (2)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N5—H5A···N3i0.862.193.042 (4)175
N5—H5B···N7ii0.862.313.060 (4)147
N6—H6A···N9iii0.862.343.025 (4)137
N6—H6B···N7iv0.862.102.939 (4)164
Symmetry codes: (i) −x+3/2, −y+1/2, −z+3; (ii) −x+3/2, −y+1/2, −z+2; (iii) x, −y+1, z+1/2; (iv) −x+1, y, −z+3/2.
Acknowledgements top

We acknowledge the National Natural Science Foundation of China (grant No. 20761005) for financial support.

references
References top

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Gadad, A. K., Noolvi, M. N. & Karpoormath, R. V. (2004). Bioorg. Med. Chem. 12, 5651–5659.

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

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