Bis(4-amino-3,5-di-2-pyridyl-1,2,4-triazole-κN,N)diaqua-zinc(II) dinitrate.

The asymmetric unit of the title compound, [Zn(C(12)H(10)N(6))(2)(H(2)O)(2)](NO(3))(2), contains one-half of the complex molecule and one NO(3) (-) anion. The Zn(II) ion displays a distorted tetra-gonal-pyramidal geometry with four N atoms from two chelating 4-amino-3,5-di-2-pyridyl-1,2,4-triazole (2-bpt) lig-ands in the basal plane and one water mol-ecule occupying the apical site. Another water mol-ecule at the opposite of the apical site has a weak inter-action with the Zn(II) ion [Zn-O = 2.852 (5) Å]. The Zn(II) ion and the two water mol-ecules lie on a twofold rotation axis. An extensive system of hydrogen bonds involving the NH(2) groups of the 2-bpt ligands, water mol-ecules and nitrate anions links all residues into a three-dimensional network.

Related literature

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

Crystal data

[Zn(C12H10N6)2(H2O)2](NO3)2

M = 701.94

Monoclinic,

a = 14.856 (3) Å

b = 9.4185 (19) Å

c = 20.230 (4) Å

β = 91.99 (3)°

V = 2829 (1) Å3

Z = 4

Mo Kα radiation

μ = 0.95 mm−1

T = 298 K

0.25 × 0.20 × 0.20 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.797, T max = 0.828

13550 measured reflections

3210 independent reflections

2424 reflections with I > 2σ(I)

R int = 0.067

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.101

S = 1.03

3210 reflections

228 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.64 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809032103/hy2215sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809032103/hy2215Isup2.hkl

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

[Zn(C12H10N6)2(H2O)2](NO3)2	F(000) = 1440
Mr = 701.94	Dx = 1.648 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3210 reflections
a = 14.856 (3) Å	θ = 3.2–27.4°
b = 9.4185 (19) Å	µ = 0.95 mm−1
c = 20.230 (4) Å	T = 298 K
β = 91.99 (3)°	Block, colorless
V = 2829 (1) Å3	0.25 × 0.20 × 0.20 mm
Z = 4

Bruker SMART 1000 CCD diffractometer	3210 independent reflections
Radiation source: sealed tube	2424 reflections with I > 2σ(I)
graphite	Rint = 0.067
φ and ω scans	θmax = 27.4°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→19
Tmin = 0.797, Tmax = 0.828	k = −12→12
13550 measured reflections	l = −22→26

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101	H 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 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.64 e Å−3

	x	y	z	Uiso*/Ueq
Zn1	0.0000	0.04107 (5)	0.7500	0.03188 (15)
O1W	0.0000	−0.1721 (3)	0.7500	0.0441 (8)
O2W	0.0000	0.3439 (5)	0.7500	0.1050 (19)
O1	0.09893 (16)	0.4526 (3)	1.17312 (12)	0.0646 (7)
O2	0.03688 (16)	0.4946 (2)	1.07668 (12)	0.0586 (6)
O3	−0.01516 (15)	0.3294 (2)	1.13778 (10)	0.0511 (6)
N1	0.03975 (14)	0.0690 (2)	0.84865 (10)	0.0298 (5)
N2	0.11637 (14)	0.0466 (2)	0.88711 (10)	0.0304 (5)
N3	0.01446 (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)
N6	0.13761 (15)	0.1407 (2)	1.06063 (10)	0.0335 (5)
N7	0.04037 (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	−0.1720	0.2599	0.9320	0.080*
C4	−0.26341 (18)	0.2426 (3)	0.85559 (15)	0.0409 (7)
H4	−0.3112	0.2859	0.8762	0.080*
C5	−0.27402 (18)	0.1930 (3)	0.79131 (15)	0.0428 (7)
H5	−0.3291	0.2014	0.7684	0.080*
C6	−0.20152 (18)	0.1311 (3)	0.76189 (13)	0.0378 (7)
H6	−0.2087	0.0990	0.7185	0.080*
C7	0.10017 (17)	0.0992 (3)	0.94616 (12)	0.0268 (5)
C8	0.16653 (17)	0.0977 (3)	1.00174 (12)	0.0282 (5)
C9	0.25491 (18)	0.0556 (3)	0.99173 (13)	0.0331 (6)
H9	0.2726	0.0256	0.9503	0.080*
C10	0.31574 (18)	0.0597 (3)	1.04516 (15)	0.0393 (7)
H10	0.3750	0.0306	1.0404	0.080*
C11	0.2877 (2)	0.1073 (3)	1.10541 (15)	0.0416 (7)
H11	0.3279	0.1131	1.1415	0.080*
C12	0.1988 (2)	0.1460 (3)	1.11125 (13)	0.0381 (6)
H12	0.1802	0.1774	1.1522	0.080*
H4A	−0.026 (3)	0.317 (4)	0.9919 (19)	0.080*
H4B	0.004 (3)	0.204 (4)	1.034 (2)	0.080*
H1W	0.001 (2)	−0.214 (3)	0.7165 (14)	0.046 (10)*
H2W	0.040 (3)	0.410 (5)	0.734 (3)	0.13 (2)*

	U11	U22	U33	U12	U13	U23
Zn1	0.0277 (2)	0.0478 (3)	0.0200 (2)	0.000	−0.00160 (16)	0.000
O1W	0.066 (2)	0.0431 (18)	0.0229 (16)	0.000	−0.0029 (15)	0.000
O2W	0.151 (5)	0.057 (3)	0.111 (4)	0.000	0.071 (4)	0.000
O1	0.0634 (15)	0.0664 (16)	0.0616 (16)	−0.0025 (13)	−0.0322 (13)	−0.0026 (13)
O2	0.0622 (15)	0.0615 (15)	0.0514 (14)	−0.0047 (12)	−0.0083 (12)	0.0277 (12)
O3	0.0537 (13)	0.0614 (15)	0.0383 (12)	−0.0128 (12)	0.0016 (10)	0.0083 (10)
N1	0.0270 (11)	0.0368 (13)	0.0253 (11)	0.0028 (9)	−0.0030 (9)	−0.0018 (9)
N2	0.0271 (11)	0.0375 (12)	0.0261 (11)	0.0024 (10)	−0.0054 (9)	−0.0002 (10)
N3	0.0267 (10)	0.0266 (11)	0.0215 (10)	0.0003 (9)	−0.0009 (8)	−0.0023 (8)
N4	0.0344 (12)	0.0418 (13)	0.0273 (12)	0.0038 (11)	0.0018 (10)	−0.0097 (10)
N5	0.0278 (11)	0.0394 (13)	0.0242 (11)	0.0010 (10)	−0.0028 (9)	0.0017 (9)
N6	0.0422 (13)	0.0328 (12)	0.0250 (11)	0.0006 (10)	−0.0047 (10)	0.0003 (9)
N7	0.0366 (13)	0.0393 (14)	0.0350 (13)	0.0044 (11)	−0.0049 (10)	0.0015 (11)
C1	0.0262 (12)	0.0264 (12)	0.0225 (12)	−0.0008 (10)	−0.0026 (10)	0.0001 (10)
C2	0.0278 (12)	0.0245 (12)	0.0275 (13)	0.0000 (10)	−0.0022 (10)	0.0012 (10)
C3	0.0326 (14)	0.0338 (14)	0.0380 (15)	0.0030 (12)	−0.0006 (12)	−0.0029 (12)
C4	0.0293 (14)	0.0428 (16)	0.0505 (18)	0.0073 (12)	−0.0015 (13)	−0.0043 (14)
C5	0.0302 (14)	0.0546 (19)	0.0430 (17)	0.0058 (13)	−0.0079 (13)	0.0075 (14)
C6	0.0300 (14)	0.0540 (18)	0.0288 (14)	0.0012 (13)	−0.0068 (11)	0.0038 (13)
C7	0.0278 (12)	0.0265 (12)	0.0261 (13)	0.0003 (10)	−0.0014 (10)	0.0010 (10)
C8	0.0328 (13)	0.0265 (13)	0.0252 (12)	−0.0028 (11)	−0.0027 (11)	0.0017 (10)
C9	0.0317 (13)	0.0338 (14)	0.0334 (14)	−0.0006 (12)	−0.0040 (11)	−0.0006 (12)
C10	0.0320 (14)	0.0390 (16)	0.0463 (17)	−0.0017 (12)	−0.0092 (13)	0.0050 (13)
C11	0.0438 (17)	0.0413 (16)	0.0384 (16)	−0.0059 (13)	−0.0173 (13)	0.0066 (13)
C12	0.0479 (17)	0.0404 (16)	0.0251 (13)	−0.0030 (13)	−0.0097 (12)	0.0019 (12)

Zn1—O1W	2.008 (3)	N6—C12	1.346 (3)
Zn1—O2W	2.852 (5)	C1—C2	1.469 (3)
Zn1—N1	2.078 (2)	C2—C3	1.382 (4)
Zn1—N5	2.141 (2)	C3—C4	1.387 (4)
O1W—H1W	0.79 (3)	C3—H3	0.9300
O2W—H2W	0.92 (5)	C4—C5	1.386 (4)
O1—N7	1.243 (3)	C4—H4	0.9300
O2—N7	1.238 (3)	C5—C6	1.378 (4)
O3—N7	1.253 (3)	C5—H5	0.9300
N1—C1	1.319 (3)	C6—H6	0.9300
N1—N2	1.373 (3)	C7—C8	1.469 (3)
N2—C7	1.323 (3)	C8—C9	1.393 (4)
N3—C1	1.355 (3)	C9—C10	1.385 (4)
N3—C7	1.372 (3)	C9—H9	0.9300
N3—N4	1.426 (3)	C10—C11	1.377 (4)
N4—H4A	0.94 (4)	C10—H10	0.9300
N4—H4B	0.89 (4)	C11—C12	1.379 (4)
N5—C6	1.340 (3)	C11—H11	0.9300
N5—C2	1.358 (3)	C12—H12	0.9300
N6—C8	1.343 (3)
O1W—Zn1—N1	97.28 (6)	N5—C2—C3	122.7 (2)
O1W—Zn1—N1i	97.28 (6)	N5—C2—C1	111.5 (2)
N1—Zn1—N1i	165.44 (12)	C3—C2—C1	125.9 (2)
O1W—Zn1—N5i	108.96 (6)	C2—C3—C4	118.4 (3)
N1—Zn1—N5i	97.73 (8)	C2—C3—H3	120.8
N1i—Zn1—N5i	77.47 (8)	C4—C3—H3	120.8
O1W—Zn1—N5	108.96 (6)	C5—C4—C3	119.3 (3)
N1—Zn1—N5	77.47 (8)	C5—C4—H4	120.3
N1i—Zn1—N5	97.73 (8)	C3—C4—H4	120.3
N5i—Zn1—N5	142.09 (12)	C6—C5—C4	118.9 (3)
O2W—Zn1—N1	82.73 (5)	C6—C5—H5	120.6
O2W—Zn1—N5	71.05 (5)	C4—C5—H5	120.6
Zn1—O1W—H1W	120 (2)	N5—C6—C5	122.9 (3)
C1—N1—N2	109.2 (2)	N5—C6—H6	118.6
C1—N1—Zn1	114.07 (16)	C5—C6—H6	118.6
N2—N1—Zn1	136.65 (16)	N2—C7—N3	109.8 (2)
C7—N2—N1	106.3 (2)	N2—C7—C8	123.3 (2)
C1—N3—C7	106.0 (2)	N3—C7—C8	126.9 (2)
C1—N3—N4	124.4 (2)	N6—C8—C9	123.1 (2)
C7—N3—N4	129.6 (2)	N6—C8—C7	116.7 (2)
N3—N4—H4A	105 (2)	C9—C8—C7	120.2 (2)
N3—N4—H4B	104 (2)	C10—C9—C8	118.1 (3)
H4A—N4—H4B	102 (3)	C10—C9—H9	120.9
C6—N5—C2	117.9 (2)	C8—C9—H9	120.9
C6—N5—Zn1	126.42 (18)	C11—C10—C9	119.4 (3)
C2—N5—Zn1	115.42 (16)	C11—C10—H10	120.3
C8—N6—C12	117.3 (2)	C9—C10—H10	120.3
O2—N7—O1	121.5 (3)	C10—C11—C12	118.8 (3)
O2—N7—O3	119.0 (2)	C10—C11—H11	120.6
O1—N7—O3	119.4 (2)	C12—C11—H11	120.6
N1—C1—N3	108.7 (2)	N6—C12—C11	123.2 (3)
N1—C1—C2	120.6 (2)	N6—C12—H12	118.4
N3—C1—C2	130.7 (2)	C11—C12—H12	118.4

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O2ii	0.94 (4)	2.25 (4)	3.100 (3)	149 (3)
N4—H4A···O2	0.94 (4)	2.55 (4)	3.192 (4)	126 (3)
N4—H4B···N6	0.89 (4)	2.13 (4)	2.875 (3)	141 (3)
N4—H4B···O3	0.89 (4)	2.43 (4)	3.005 (3)	122 (3)
O1W—H1W···O3iii	0.79 (3)	1.93 (3)	2.714 (3)	170 (3)
O2W—H2W···O1iv	0.92 (5)	2.02 (5)	2.900 (4)	161 (5)

Table 1

Selected bond lengths (Å)

Zn1—O1W	2.008 (3)
Zn1—O2W	2.852 (5)
Zn1—N1	2.078 (2)
Zn1—N5	2.141 (2)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O2i	0.94 (4)	2.25 (4)	3.100 (3)	149 (3)
N4—H4A⋯O2	0.94 (4)	2.55 (4)	3.192 (4)	126 (3)
N4—H4B⋯N6	0.89 (4)	2.13 (4)	2.875 (3)	141 (3)
N4—H4B⋯O3	0.89 (4)	2.43 (4)	3.005 (3)	122 (3)
O1W—H1W⋯O3ii	0.79 (3)	1.93 (3)	2.714 (3)	170 (3)
O2W—H2W⋯O1iii	0.92 (5)	2.02 (5)	2.900 (4)	161 (5)

Symmetry codes: (i) ; (ii) ; (iii) .