Bis(4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole)diaquanickel(II) bis(perchlorate).

In the mol-ecular structure of the centrosymmetric mononuclear complex [Ni(2-bpt)(2)(H(2)O)(2)](ClO(4))(2) [2-bpt = 4-amino-3,5-di-2-pyridyl-1,2,4-triazole, (C(12)H(10)N(6))], the central Ni(II) atom is six-coordinated by a pair of chelating 2-bpt ligands and two water mol-ecules. Inter-molecular O-H⋯N inter-actions link the monomeric units into a two-dimensional hydrogen-bonded (4,4) network, which is extended to a three-dimensional supra-molecular aggregate via π⋯π stacking inter-actions [centroid-centroid distances 3.809 (3) and 3.499 (3)  Å].

Related literature

Diverse coordination architectures can be constructed by coordinative bonds using metal ions to combine with multifunctional ligands, see: Moulton & Zaworotko (2001 ▶). Supra­molecular inter­actions such as hydrogen bonding and aromatic stacking are usually used to extend or sustain the resultant structures, see: Roesky & Andruh (2003 ▶); Ye et al. (2005 ▶); Du et al. (2007 ▶). For polypyrid­yl–transition metal complexes, see: Haasnoot (2000 ▶). For the potential ability of 4-amino-3,5-di-2-pyridyl-1,2,4-triazole (2-bpt) to provide multi-coordination modes and generate hydrogen-bonding and/or aromatic stacking inter­actions, see: Van Koningsbruggen et al. (1998 ▶); Moliner et al. (2001 ▶); García-Couceiro et al. (2004 ▶); Peng et al. (2006 ▶). For NiII–2-bpt complexes, see: Keij et al. (1984 ▶); Tong et al. (2007 ▶). For the (4,4) topology, see: Batten & Robson (1998 ▶).

Experimental

Crystal data

[Ni(C12H10N6)2(H2O)2](ClO4)2

M = 770.16

Monoclinic,

a = 9.9219 (15) Å

b = 14.359 (2) Å

c = 10.9220 (18) Å

β = 100.560 (3)°

V = 1529.7 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.89 mm−1

T = 296 K

0.20 × 0.18 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.840, T max = 0.870

7639 measured reflections

2686 independent reflections

2171 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.154

S = 1.07

2686 reflections

223 parameters

H-atom parameters constrained

Δρmax = 1.12 e Å−3

Δρmin = −0.40 e Å−3

Data collection: APEX2 (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 & Berndt, 1999 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809012598/hg2489sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809012598/hg2489Isup2.hkl

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

[Ni(C12H10N6)2(H2O)2](ClO4)2	F(000) = 788
Mr = 770.16	Dx = 1.672 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2386 reflections
a = 9.9219 (15) Å	θ = 2.4–24.5°
b = 14.359 (2) Å	µ = 0.89 mm−1
c = 10.9220 (18) Å	T = 296 K
β = 100.560 (3)°	Block, pale green
V = 1529.7 (4) Å3	0.20 × 0.18 × 0.16 mm
Z = 2

Bruker SMART CCD area-detector diffractometer	2686 independent reflections
Radiation source: fine-focus sealed tube	2171 reflections with I > 2σ(I)
graphite	Rint = 0.028
phi and ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→11
Tmin = 0.840, Tmax = 0.870	k = −17→16
7639 measured reflections	l = −11→13

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.090P)2 + 1.5989P] where P = (Fo2 + 2Fc2)/3
2686 reflections	(Δ/σ)max < 0.001
223 parameters	Δρmax = 1.12 e Å−3
0 restraints	Δρmin = −0.40 e Å−3

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.

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.0000	0.5000	0.0297 (2)
Cl1	0.37983 (11)	0.36054 (8)	0.32882 (10)	0.0472 (3)
O1	0.5877 (3)	0.12860 (19)	0.5625 (3)	0.0416 (7)
H1A	0.6502	0.1302	0.6271	0.062*
H1B	0.5281	0.1717	0.5556	0.062*
O2	0.4370 (5)	0.2802 (3)	0.3892 (4)	0.0890 (14)
O3	0.4030 (7)	0.3637 (7)	0.2091 (6)	0.184 (4)
O4	0.2372 (5)	0.3650 (5)	0.3186 (6)	0.130 (2)
O5	0.4382 (8)	0.4351 (3)	0.3942 (8)	0.203 (5)
N1	0.5588 (3)	0.0213 (2)	0.3259 (3)	0.0330 (7)
N2	0.3327 (3)	0.0682 (2)	0.4056 (3)	0.0328 (7)
N3	0.2087 (3)	0.0979 (2)	0.4288 (3)	0.0365 (7)
N4	0.2168 (3)	0.1192 (2)	0.2312 (3)	0.0318 (7)
N5	0.1787 (4)	0.1333 (3)	0.1001 (3)	0.0424 (8)
H5A	0.1399	0.0796	0.0693	0.064*
H5B	0.1170	0.1795	0.0974	0.064*
N6	−0.0420 (3)	0.2165 (3)	0.2012 (3)	0.0440 (8)
C1	0.6805 (4)	0.0015 (3)	0.2978 (4)	0.0396 (9)
H1	0.7459	−0.0283	0.3566	0.047*
C2	0.7126 (4)	0.0244 (3)	0.1820 (4)	0.0456 (10)
H2	0.7975	0.0085	0.1635	0.055*
C3	0.6174 (5)	0.0706 (3)	0.0954 (4)	0.0468 (11)
H3	0.6380	0.0884	0.0190	0.056*
C4	0.4893 (4)	0.0901 (3)	0.1251 (4)	0.0414 (10)
H4	0.4221	0.1200	0.0681	0.050*
C5	0.4640 (4)	0.0642 (2)	0.2404 (3)	0.0324 (8)
C6	0.3373 (4)	0.0829 (2)	0.2869 (3)	0.0305 (8)
C7	0.1398 (4)	0.1292 (3)	0.3220 (4)	0.0332 (8)
C8	0.0045 (4)	0.1734 (3)	0.3089 (4)	0.0353 (9)
C9	−0.1653 (5)	0.2580 (3)	0.1895 (5)	0.0524 (11)
H9	−0.2008	0.2869	0.1142	0.063*
C10	−0.2413 (5)	0.2603 (3)	0.2819 (5)	0.0542 (12)
H10	−0.3253	0.2908	0.2703	0.065*
C11	−0.1904 (5)	0.2166 (3)	0.3918 (5)	0.0563 (12)
H11	−0.2397	0.2174	0.4565	0.068*
C12	−0.0655 (4)	0.1712 (3)	0.4068 (4)	0.0472 (11)
H12	−0.0301	0.1402	0.4804	0.057*

	U11	U22	U33	U12	U13	U23
Ni1	0.0277 (4)	0.0354 (4)	0.0254 (4)	0.0013 (3)	0.0039 (3)	0.0021 (3)
Cl1	0.0438 (6)	0.0497 (6)	0.0437 (6)	0.0050 (5)	−0.0036 (5)	0.0001 (5)
O1	0.0389 (16)	0.0406 (15)	0.0433 (17)	−0.0022 (12)	0.0021 (13)	0.0004 (12)
O2	0.108 (3)	0.058 (2)	0.087 (3)	0.013 (2)	−0.018 (3)	0.014 (2)
O3	0.150 (6)	0.339 (11)	0.077 (4)	0.078 (6)	0.055 (4)	0.074 (5)
O4	0.061 (3)	0.203 (6)	0.129 (5)	0.035 (3)	0.028 (3)	0.020 (4)
O5	0.230 (8)	0.055 (3)	0.247 (8)	0.012 (4)	−0.159 (7)	−0.024 (4)
N1	0.0329 (17)	0.0362 (16)	0.0301 (17)	0.0002 (13)	0.0064 (14)	−0.0015 (13)
N2	0.0325 (17)	0.0390 (17)	0.0269 (16)	0.0028 (13)	0.0051 (13)	0.0010 (13)
N3	0.0338 (18)	0.0441 (18)	0.0308 (17)	0.0025 (14)	0.0038 (14)	0.0006 (14)
N4	0.0336 (17)	0.0352 (16)	0.0256 (16)	0.0004 (13)	0.0029 (13)	0.0006 (13)
N5	0.044 (2)	0.055 (2)	0.0268 (17)	0.0075 (16)	0.0039 (15)	0.0078 (15)
N6	0.0336 (18)	0.056 (2)	0.042 (2)	0.0059 (16)	0.0061 (15)	0.0106 (17)
C1	0.033 (2)	0.036 (2)	0.048 (2)	0.0017 (16)	0.0034 (18)	−0.0033 (18)
C2	0.036 (2)	0.055 (3)	0.049 (3)	−0.0033 (19)	0.016 (2)	−0.010 (2)
C3	0.053 (3)	0.056 (3)	0.036 (2)	−0.006 (2)	0.020 (2)	−0.002 (2)
C4	0.044 (2)	0.050 (2)	0.031 (2)	0.0007 (19)	0.0095 (18)	0.0035 (18)
C5	0.036 (2)	0.0314 (19)	0.0306 (19)	−0.0021 (15)	0.0085 (16)	−0.0006 (15)
C6	0.033 (2)	0.0306 (18)	0.0283 (19)	−0.0012 (15)	0.0056 (16)	0.0000 (15)
C7	0.031 (2)	0.0362 (19)	0.031 (2)	−0.0004 (15)	0.0037 (16)	−0.0015 (16)
C8	0.0298 (19)	0.037 (2)	0.039 (2)	−0.0018 (16)	0.0063 (16)	−0.0005 (17)
C9	0.041 (2)	0.053 (3)	0.061 (3)	0.009 (2)	0.004 (2)	0.014 (2)
C10	0.038 (2)	0.049 (3)	0.077 (4)	0.009 (2)	0.015 (2)	0.002 (2)
C11	0.045 (3)	0.065 (3)	0.066 (3)	0.001 (2)	0.029 (2)	−0.006 (3)
C12	0.043 (2)	0.059 (3)	0.042 (2)	0.002 (2)	0.012 (2)	0.003 (2)

Ni1—N2i	2.037 (3)	N5—H5B	0.9000
Ni1—N2	2.037 (3)	N6—C8	1.334 (5)
Ni1—O1	2.101 (3)	N6—C9	1.346 (5)
Ni1—O1i	2.101 (3)	C1—C2	1.399 (6)
Ni1—N1	2.111 (3)	C1—H1	0.9300
Ni1—N1i	2.111 (3)	C2—C3	1.378 (7)
Cl1—O5	1.357 (5)	C2—H2	0.9300
Cl1—O3	1.369 (6)	C3—C4	1.397 (6)
Cl1—O2	1.396 (4)	C3—H3	0.9300
Cl1—O4	1.401 (5)	C4—C5	1.379 (5)
O1—H1A	0.8499	C4—H4	0.9300
O1—H1B	0.8500	C5—C6	1.465 (5)
N1—C1	1.330 (5)	C7—C8	1.468 (5)
N1—C5	1.348 (5)	C8—C12	1.378 (6)
N2—C6	1.323 (5)	C9—C10	1.367 (7)
N2—N3	1.369 (4)	C9—H9	0.9300
N3—C7	1.318 (5)	C10—C11	1.367 (7)
N4—C6	1.343 (5)	C10—H10	0.9300
N4—C7	1.366 (5)	C11—C12	1.383 (6)
N4—N5	1.426 (4)	C11—H11	0.9300
N5—H5A	0.9000	C12—H12	0.9300
N2i—Ni1—N2	180.00 (16)	C8—N6—C9	116.8 (4)
N2i—Ni1—O1	90.42 (11)	N1—C1—C2	121.7 (4)
N2—Ni1—O1	89.58 (11)	N1—C1—H1	119.1
N2i—Ni1—O1i	89.58 (11)	C2—C1—H1	119.1
N2—Ni1—O1i	90.42 (11)	C3—C2—C1	119.5 (4)
O1—Ni1—O1i	180.00 (7)	C3—C2—H2	120.2
N2i—Ni1—N1	101.04 (12)	C1—C2—H2	120.2
N2—Ni1—N1	78.96 (12)	C2—C3—C4	118.4 (4)
O1—Ni1—N1	89.94 (11)	C2—C3—H3	120.8
O1i—Ni1—N1	90.06 (11)	C4—C3—H3	120.8
N2i—Ni1—N1i	78.96 (12)	C5—C4—C3	118.9 (4)
N2—Ni1—N1i	101.04 (12)	C5—C4—H4	120.5
O1—Ni1—N1i	90.06 (11)	C3—C4—H4	120.5
O1i—Ni1—N1i	89.94 (11)	N1—C5—C4	122.4 (4)
N1—Ni1—N1i	180.000 (1)	N1—C5—C6	112.2 (3)
O5—Cl1—O3	110.3 (6)	C4—C5—C6	125.3 (4)
O5—Cl1—O2	107.8 (3)	N2—C6—N4	108.5 (3)
O3—Cl1—O2	110.8 (4)	N2—C6—C5	119.8 (3)
O5—Cl1—O4	109.5 (5)	N4—C6—C5	131.6 (3)
O3—Cl1—O4	105.5 (4)	N3—C7—N4	109.8 (3)
O2—Cl1—O4	113.1 (4)	N3—C7—C8	123.4 (3)
Ni1—O1—H1A	119.3	N4—C7—C8	126.7 (3)
Ni1—O1—H1B	111.7	N6—C8—C12	123.5 (4)
H1A—O1—H1B	116.3	N6—C8—C7	116.6 (3)
C1—N1—C5	119.0 (4)	C12—C8—C7	119.8 (4)
C1—N1—Ni1	126.2 (3)	N6—C9—C10	123.7 (4)
C5—N1—Ni1	114.7 (2)	N6—C9—H9	118.2
C6—N2—N3	109.0 (3)	C10—C9—H9	118.2
C6—N2—Ni1	113.7 (2)	C9—C10—C11	118.2 (4)
N3—N2—Ni1	137.1 (2)	C9—C10—H10	120.9
C7—N3—N2	106.3 (3)	C11—C10—H10	120.9
C6—N4—C7	106.4 (3)	C10—C11—C12	119.9 (4)
C6—N4—N5	124.0 (3)	C10—C11—H11	120.0
C7—N4—N5	129.3 (3)	C12—C11—H11	120.0
N4—N5—H5A	105.7	C8—C12—C11	117.8 (4)
N4—N5—H5B	101.1	C8—C12—H12	121.1
H5A—N5—H5B	112.2	C11—C12—H12	121.1
N2i—Ni1—N1—C1	−5.8 (3)	Ni1—N2—C6—N4	173.7 (2)
N2—Ni1—N1—C1	174.2 (3)	N3—N2—C6—C5	174.9 (3)
O1—Ni1—N1—C1	84.6 (3)	Ni1—N2—C6—C5	−9.6 (4)
O1i—Ni1—N1—C1	−95.4 (3)	C7—N4—C6—N2	2.2 (4)
N2i—Ni1—N1—C5	178.4 (2)	N5—N4—C6—N2	−172.0 (3)
N2—Ni1—N1—C5	−1.6 (2)	C7—N4—C6—C5	−174.1 (4)
O1—Ni1—N1—C5	−91.2 (3)	N5—N4—C6—C5	11.8 (6)
O1i—Ni1—N1—C5	88.8 (3)	N1—C5—C6—N2	8.2 (5)
O1—Ni1—N2—C6	95.9 (3)	C4—C5—C6—N2	−169.2 (4)
O1i—Ni1—N2—C6	−84.1 (3)	N1—C5—C6—N4	−175.9 (4)
N1—Ni1—N2—C6	5.9 (3)	C4—C5—C6—N4	6.7 (7)
N1i—Ni1—N2—C6	−174.1 (3)	N2—N3—C7—N4	0.6 (4)
O1—Ni1—N2—N3	−90.3 (4)	N2—N3—C7—C8	−175.7 (3)
O1i—Ni1—N2—N3	89.7 (4)	C6—N4—C7—N3	−1.7 (4)
N1—Ni1—N2—N3	179.7 (4)	N5—N4—C7—N3	172.1 (3)
N1i—Ni1—N2—N3	−0.3 (4)	C6—N4—C7—C8	174.4 (4)
C6—N2—N3—C7	0.8 (4)	N5—N4—C7—C8	−11.8 (6)
Ni1—N2—N3—C7	−173.2 (3)	C9—N6—C8—C12	−1.1 (6)
C5—N1—C1—C2	0.2 (6)	C9—N6—C8—C7	−179.2 (4)
Ni1—N1—C1—C2	−175.4 (3)	N3—C7—C8—N6	168.3 (4)
N1—C1—C2—C3	1.6 (6)	N4—C7—C8—N6	−7.3 (6)
C1—C2—C3—C4	−2.3 (6)	N3—C7—C8—C12	−9.9 (6)
C2—C3—C4—C5	1.4 (6)	N4—C7—C8—C12	174.5 (4)
C1—N1—C5—C4	−1.2 (6)	C8—N6—C9—C10	1.9 (7)
Ni1—N1—C5—C4	174.9 (3)	N6—C9—C10—C11	−1.1 (7)
C1—N1—C5—C6	−178.6 (3)	C9—C10—C11—C12	−0.4 (7)
Ni1—N1—C5—C6	−2.6 (4)	N6—C8—C12—C11	−0.3 (7)
C3—C4—C5—N1	0.4 (6)	C7—C8—C12—C11	177.7 (4)
C3—C4—C5—C6	177.5 (4)	C10—C11—C12—C8	1.1 (7)
N3—N2—C6—N4	−1.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3ii	0.85	2.51	3.245 (8)	146
O1—H1A···O4ii	0.85	2.11	2.918 (7)	158
O1—H1B···O2	0.85	2.44	3.085 (5)	134
O1—H1B···N6ii	0.85	2.45	3.100 (5)	134
N5—H5A···O5iii	0.90	2.28	3.078 (7)	148
N5—H5B···N6	0.90	2.17	2.886 (5)	136

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O3i	0.85	2.51	3.245 (8)	146
O1—H1A⋯O4i	0.85	2.11	2.918 (7)	158
O1—H1B⋯O2	0.85	2.44	3.085 (5)	134
O1—H1B⋯N6i	0.85	2.45	3.100 (5)	134
N5—H5A⋯O5ii	0.90	2.28	3.078 (7)	148
N5—H5B⋯N6	0.90	2.17	2.886 (5)	136

Symmetry codes: (i) ; (ii) .