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Acta Cryst. (2009). E65, m1106-m1107    [ doi:10.1107/S1600536809032103 ]

Bis(4-amino-3,5-di-2-pyridyl-1,2,4-triazole-[kappa]2N1,N5)diaquazinc(II) dinitrate

J. Hua, L. Gao and B. Li

Abstract top

The asymmetric unit of the title compound, [Zn(C12H10N6)2(H2O)2](NO3)2, contains one-half of the complex molecule and one NO3- anion. The ZnII ion displays a distorted tetragonal-pyramidal geometry with four N atoms from two chelating 4-amino-3,5-di-2-pyridyl-1,2,4-triazole (2-bpt) ligands in the basal plane and one water molecule occupying the apical site. Another water molecule at the opposite of the apical site has a weak interaction with the ZnII ion [Zn-O = 2.852 (5) Å]. The ZnII ion and the two water molecules lie on a twofold rotation axis. An extensive system of hydrogen bonds involving the NH2 groups of the 2-bpt ligands, water molecules and nitrate anions links all residues into a three-dimensional network.

Comment top

Recently, 4-amino-3,5-di-2-pyridyl-1,2,4-triazole (2-bpt) has been used as ligand because it has potential ability of multi-coordination modes, generating hydrogen-bonding and/or aromatic stacking interactions. The zinc(II) complex of 2-bpt has been reported previously. Hartmann & Vahrenkamp (1995) prepared the complexes based on 2-bpt with Zn(ClO4)2, ZnCl2, Zn(NO3)2 and Zn(BF4)2. But they just obtained the single-crystal structure of Zn(ClO4)2 complex, in which ZnII atom adopts octahedral geometry. Herein, we reported the crystal structure of the title compound obtained by reacting 2-bpt with Zn(NO3)2, in which 2-bpt acts as a chelating ligand and hydrogen-bonding interactions play an important role in stabilizing the solid-state structure.

The structure analysis reveals that the asymmetric unit of the title compund contains half a ZnII atom, one 2-bpt molecule, two half water molecules and one NO3- anion. As depicted in Fig. 1, the distorted tetragonal pyramidal ZnII atom is located on an inversion center. The basal plane is defined by four N atoms from two 2-bpt ligands with a chelating mode, and the apical site is occupied by one water molecule (O1W) with a Zn—O distance of 2.008 (3)Å (Table 1). Another water molecule (O2W) has a weak interaction with the Zn atom [Zn1—O2W = 2.852 (5) Å], which makes the crystal structure differ from the recently reported nickel complex (Shao & Geng, 2009) because of Jahn-Teller effect. The 2-bpt molecule exhibits trans-conformation. The two 2-bpt molecules are not coplanar, with a dihedral angle of 48.54 (5)°. N—H···O, N—H···N and O—H···O hydrogen bonds are observed in the crystal structure (Table 2; Fig. 2).

Related literature top

For transition metal complexes of 4-amino-3,5-di-2-pyridyl-1,2,4-triazole (2-bpt), see: Shao & Geng (2009); Hartmann & Vahrenkamp (1995); Keij et al. (1984); Kitchen et al. (2008); Koningsbruggen et al. (1998); Tong et al. (2007). For rare earth metal complexes of 2-bpt, see: Garcia et al. (1986); Rheingold et al. (1993). For hydrogen-bonding interactions involving 2-bpt in organic compounds, see: Mernari et al. (1998).

Experimental top

To an ethanol solution (20 ml) of 2-bpt (0.012 g, 0.05 mmol) was added an aqueous solution (5 ml) of Zn(NO3)2.6H2O (0.018 g, 0.05 mmol) with stirring. After vigorous stirring for ca 40 min, the resultant solution was filtered and left to stand at room temperature. Colorless block crystals suitable for X-ray analysis were produced by slow evaporation of the solvent for two weeks.

Refinement top

C-bound H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(C). H atoms attached to N atom were found in a difference Fourier map. Their coordinates were refined and Uiso factors were fixed. H atoms of water molecules were found in a difference Fourier map and refined isotropically.

Computing details top

Data collection: SMART (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: DIAMOND (Brandenburg, 1999) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) -x, y, 3/2 - z.]
[Figure 2] Fig. 2. The crystal packing of the title compound. Dashed lines denote hydrogen bonds.
Bis(4-amino-3,5-di-2-pyridyl-1,2,4-triazole- κ2N1,N5)diaquazinc(II) dinitrate top
Crystal data top
[Zn(C12H10N6)2(H2O)2](NO3)2F(000) = 1440
Mr = 701.94Dx = 1.648 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3210 reflections
a = 14.856 (3) Åθ = 3.2–27.4°
b = 9.4185 (19) ŵ = 0.95 mm−1
c = 20.230 (4) ÅT = 298 K
β = 91.99 (3)°Block, colorless
V = 2829 (1) Å30.25 × 0.20 × 0.20 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD
diffractometer		3210 independent reflections
Radiation source: sealed tube2424 reflections with I > 2σ(I)
graphiteRint = 0.067
φ and ω scansθmax = 27.4°, θmin = 3.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −19→19
Tmin = 0.797, Tmax = 0.828k = −12→12
13550 measured reflectionsl = −22→26
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0336P)2 + 4.1918P]
where P = (Fo2 + 2Fc2)/3
3210 reflections(Δ/σ)max < 0.001
228 parametersΔρmax = 0.32 e Å−3
0 restraintsΔρmin = −0.64 e Å−3
Crystal data top
[Zn(C12H10N6)2(H2O)2](NO3)2V = 2829 (1) Å3
Mr = 701.94Z = 4
Monoclinic, C2/cMo Kα radiation
a = 14.856 (3) ŵ = 0.95 mm−1
b = 9.4185 (19) ÅT = 298 K
c = 20.230 (4) Å0.25 × 0.20 × 0.20 mm
β = 91.99 (3)°
Data collection top
Bruker SMART 1000 CCD
diffractometer		3210 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2424 reflections with I > 2σ(I)
Tmin = 0.797, Tmax = 0.828Rint = 0.067
13550 measured reflectionsθmax = 27.4°
Refinement top
R[F2 > 2σ(F2)] = 0.045H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.101Δρmax = 0.32 e Å−3
S = 1.03Δρmin = −0.64 e Å−3
3210 reflectionsAbsolute structure: ?
228 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.00000.04107 (5)0.75000.03188 (15)
O1W0.0000−0.1721 (3)0.75000.0441 (8)
O2W0.00000.3439 (5)0.75000.1050 (19)
O10.09893 (16)0.4526 (3)1.17312 (12)0.0646 (7)
O20.03688 (16)0.4946 (2)1.07668 (12)0.0586 (6)
O3−0.01516 (15)0.3294 (2)1.13778 (10)0.0511 (6)
N10.03975 (14)0.0690 (2)0.84865 (10)0.0298 (5)
N20.11637 (14)0.0466 (2)0.88711 (10)0.0304 (5)
N30.01446 (13)0.1534 (2)0.94627 (9)0.0250 (4)
N4−0.03229 (16)0.2187 (3)0.99862 (11)0.0345 (5)
N5−0.12105 (14)0.1149 (2)0.79303 (10)0.0305 (5)
N60.13761 (15)0.1407 (2)1.06063 (10)0.0335 (5)
N70.04037 (16)0.4274 (2)1.12933 (12)0.0371 (5)
C1−0.02138 (16)0.1310 (3)0.88464 (11)0.0251 (5)
C2−0.11171 (16)0.1616 (3)0.85638 (12)0.0267 (5)
C3−0.18075 (18)0.2271 (3)0.88886 (14)0.0349 (6)
H3−0.17200.25990.93200.080*
C4−0.26341 (18)0.2426 (3)0.85559 (15)0.0409 (7)
H4−0.31120.28590.87620.080*
C5−0.27402 (18)0.1930 (3)0.79131 (15)0.0428 (7)
H5−0.32910.20140.76840.080*
C6−0.20152 (18)0.1311 (3)0.76189 (13)0.0378 (7)
H6−0.20870.09900.71850.080*
C70.10017 (17)0.0992 (3)0.94616 (12)0.0268 (5)
C80.16653 (17)0.0977 (3)1.00174 (12)0.0282 (5)
C90.25491 (18)0.0556 (3)0.99173 (13)0.0331 (6)
H90.27260.02560.95030.080*
C100.31574 (18)0.0597 (3)1.04516 (15)0.0393 (7)
H100.37500.03061.04040.080*
C110.2877 (2)0.1073 (3)1.10541 (15)0.0416 (7)
H110.32790.11311.14150.080*
C120.1988 (2)0.1460 (3)1.11125 (13)0.0381 (6)
H120.18020.17741.15220.080*
H4A−0.026 (3)0.317 (4)0.9919 (19)0.080*
H4B0.004 (3)0.204 (4)1.034 (2)0.080*
H1W0.001 (2)−0.214 (3)0.7165 (14)0.046 (10)*
H2W0.040 (3)0.410 (5)0.734 (3)0.13 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0277 (2)0.0478 (3)0.0200 (2)0.000−0.00160 (16)0.000
O1W0.066 (2)0.0431 (18)0.0229 (16)0.000−0.0029 (15)0.000
O2W0.151 (5)0.057 (3)0.111 (4)0.0000.071 (4)0.000
O10.0634 (15)0.0664 (16)0.0616 (16)−0.0025 (13)−0.0322 (13)−0.0026 (13)
O20.0622 (15)0.0615 (15)0.0514 (14)−0.0047 (12)−0.0083 (12)0.0277 (12)
O30.0537 (13)0.0614 (15)0.0383 (12)−0.0128 (12)0.0016 (10)0.0083 (10)
N10.0270 (11)0.0368 (13)0.0253 (11)0.0028 (9)−0.0030 (9)−0.0018 (9)
N20.0271 (11)0.0375 (12)0.0261 (11)0.0024 (10)−0.0054 (9)−0.0002 (10)
N30.0267 (10)0.0266 (11)0.0215 (10)0.0003 (9)−0.0009 (8)−0.0023 (8)
N40.0344 (12)0.0418 (13)0.0273 (12)0.0038 (11)0.0018 (10)−0.0097 (10)
N50.0278 (11)0.0394 (13)0.0242 (11)0.0010 (10)−0.0028 (9)0.0017 (9)
N60.0422 (13)0.0328 (12)0.0250 (11)0.0006 (10)−0.0047 (10)0.0003 (9)
N70.0366 (13)0.0393 (14)0.0350 (13)0.0044 (11)−0.0049 (10)0.0015 (11)
C10.0262 (12)0.0264 (12)0.0225 (12)−0.0008 (10)−0.0026 (10)0.0001 (10)
C20.0278 (12)0.0245 (12)0.0275 (13)0.0000 (10)−0.0022 (10)0.0012 (10)
C30.0326 (14)0.0338 (14)0.0380 (15)0.0030 (12)−0.0006 (12)−0.0029 (12)
C40.0293 (14)0.0428 (16)0.0505 (18)0.0073 (12)−0.0015 (13)−0.0043 (14)
C50.0302 (14)0.0546 (19)0.0430 (17)0.0058 (13)−0.0079 (13)0.0075 (14)
C60.0300 (14)0.0540 (18)0.0288 (14)0.0012 (13)−0.0068 (11)0.0038 (13)
C70.0278 (12)0.0265 (12)0.0261 (13)0.0003 (10)−0.0014 (10)0.0010 (10)
C80.0328 (13)0.0265 (13)0.0252 (12)−0.0028 (11)−0.0027 (11)0.0017 (10)
C90.0317 (13)0.0338 (14)0.0334 (14)−0.0006 (12)−0.0040 (11)−0.0006 (12)
C100.0320 (14)0.0390 (16)0.0463 (17)−0.0017 (12)−0.0092 (13)0.0050 (13)
C110.0438 (17)0.0413 (16)0.0384 (16)−0.0059 (13)−0.0173 (13)0.0066 (13)
C120.0479 (17)0.0404 (16)0.0251 (13)−0.0030 (13)−0.0097 (12)0.0019 (12)
Geometric parameters (Å, °) top
Zn1—O1W2.008 (3)N6—C121.346 (3)
Zn1—O2W2.852 (5)C1—C21.469 (3)
Zn1—N12.078 (2)C2—C31.382 (4)
Zn1—N52.141 (2)C3—C41.387 (4)
O1W—H1W0.79 (3)C3—H30.9300
O2W—H2W0.92 (5)C4—C51.386 (4)
O1—N71.243 (3)C4—H40.9300
O2—N71.238 (3)C5—C61.378 (4)
O3—N71.253 (3)C5—H50.9300
N1—C11.319 (3)C6—H60.9300
N1—N21.373 (3)C7—C81.469 (3)
N2—C71.323 (3)C8—C91.393 (4)
N3—C11.355 (3)C9—C101.385 (4)
N3—C71.372 (3)C9—H90.9300
N3—N41.426 (3)C10—C111.377 (4)
N4—H4A0.94 (4)C10—H100.9300
N4—H4B0.89 (4)C11—C121.379 (4)
N5—C61.340 (3)C11—H110.9300
N5—C21.358 (3)C12—H120.9300
N6—C81.343 (3)
O1W—Zn1—N197.28 (6)N5—C2—C3122.7 (2)
O1W—Zn1—N1i97.28 (6)N5—C2—C1111.5 (2)
N1—Zn1—N1i165.44 (12)C3—C2—C1125.9 (2)
O1W—Zn1—N5i108.96 (6)C2—C3—C4118.4 (3)
N1—Zn1—N5i97.73 (8)C2—C3—H3120.8
N1i—Zn1—N5i77.47 (8)C4—C3—H3120.8
O1W—Zn1—N5108.96 (6)C5—C4—C3119.3 (3)
N1—Zn1—N577.47 (8)C5—C4—H4120.3
N1i—Zn1—N597.73 (8)C3—C4—H4120.3
N5i—Zn1—N5142.09 (12)C6—C5—C4118.9 (3)
O2W—Zn1—N182.73 (5)C6—C5—H5120.6
O2W—Zn1—N571.05 (5)C4—C5—H5120.6
Zn1—O1W—H1W120 (2)N5—C6—C5122.9 (3)
C1—N1—N2109.2 (2)N5—C6—H6118.6
C1—N1—Zn1114.07 (16)C5—C6—H6118.6
N2—N1—Zn1136.65 (16)N2—C7—N3109.8 (2)
C7—N2—N1106.3 (2)N2—C7—C8123.3 (2)
C1—N3—C7106.0 (2)N3—C7—C8126.9 (2)
C1—N3—N4124.4 (2)N6—C8—C9123.1 (2)
C7—N3—N4129.6 (2)N6—C8—C7116.7 (2)
N3—N4—H4A105 (2)C9—C8—C7120.2 (2)
N3—N4—H4B104 (2)C10—C9—C8118.1 (3)
H4A—N4—H4B102 (3)C10—C9—H9120.9
C6—N5—C2117.9 (2)C8—C9—H9120.9
C6—N5—Zn1126.42 (18)C11—C10—C9119.4 (3)
C2—N5—Zn1115.42 (16)C11—C10—H10120.3
C8—N6—C12117.3 (2)C9—C10—H10120.3
O2—N7—O1121.5 (3)C10—C11—C12118.8 (3)
O2—N7—O3119.0 (2)C10—C11—H11120.6
O1—N7—O3119.4 (2)C12—C11—H11120.6
N1—C1—N3108.7 (2)N6—C12—C11123.2 (3)
N1—C1—C2120.6 (2)N6—C12—H12118.4
N3—C1—C2130.7 (2)C11—C12—H12118.4
Symmetry codes: (i) −x, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···O2ii0.94 (4)2.25 (4)3.100 (3)149 (3)
N4—H4A···O20.94 (4)2.55 (4)3.192 (4)126 (3)
N4—H4B···N60.89 (4)2.13 (4)2.875 (3)141 (3)
N4—H4B···O30.89 (4)2.43 (4)3.005 (3)122 (3)
O1W—H1W···O3iii0.79 (3)1.93 (3)2.714 (3)170 (3)
O2W—H2W···O1iv0.92 (5)2.02 (5)2.900 (4)161 (5)
Symmetry codes: (ii) −x, −y+1, −z+2; (iii) x, −y, z−1/2; (iv) x, −y+1, z−1/2.
Table 1
Selected geometric parameters (Å) top
Zn1—O1W2.008 (3)Zn1—N12.078 (2)
Zn1—O2W2.852 (5)Zn1—N52.141 (2)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4A···O2i0.94 (4)2.25 (4)3.100 (3)149 (3)
N4—H4A···O20.94 (4)2.55 (4)3.192 (4)126 (3)
N4—H4B···N60.89 (4)2.13 (4)2.875 (3)141 (3)
N4—H4B···O30.89 (4)2.43 (4)3.005 (3)122 (3)
O1W—H1W···O3ii0.79 (3)1.93 (3)2.714 (3)170 (3)
O2W—H2W···O1iii0.92 (5)2.02 (5)2.900 (4)161 (5)
Symmetry codes: (i) −x, −y+1, −z+2; (ii) x, −y, z−1/2; (iii) x, −y+1, z−1/2.
Acknowledgements top

We thank the National Natural Science Foundation of China for supporting this work.

references
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