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Acta Cryst. (2009). E65, m1590    [ doi:10.1107/S1600536809047102 ]

Tetraaquabis[3-(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazolido]nickel(II) dihydrate

Y.-L. Zhang, T.-L. Liu and S.-J. Sun

Abstract top

In the title compound, [Ni(C12H8N5)2(H2O)4]·2H2O, the NiII atom is coordinated by the two N atoms [Ni-N = 2.094 (3) Å] and four O atoms [Ni-O = 2.063 (3)-2.083 (2) Å] in a distorted octahedral geometry. The molecule is centrosymmetric and the NiII atom is located on an inversion center. Intermolecular O-H...N and O-H...O hydrogen bonds link the complex into a three-dimensional supramolecular framework.

Comment top

The hydrogen bond interaction plays a important role in some biological systems (Deisenhofer & Michel, 1989). Supramolecular assembly through hydrogen bonds has been extensively exploited to generate extended one-, two- and three-dimensional structures (Beatty et al., 2003; Li et al., 2006; Russell & Ward, 1996). As part of this ongoing work (Liu et al., 2009), We present here the synthesis and structural characterization of the title nickel complex, [Ni(C12H8N5)2(H2O)4].2H2O, (I).

The molecule of the title complex, (Fig. 1), is centrosymmetric, so pairs of equivalent ligands lie trans to each other in a slightly distorted octahedral coordination geometry, cis angles deviating from 90° by less than 2°. with Ni—O bond length in the range 2.063–2.083 Å and Ni—N bond length 2.094 Å. These bond distances compare well with those in the literature (Liu et al., 2008; Rarig et al., 2001). Molecules are linked by O—H···O and O—H···N hydrogen bonds (Fig. 2, Table 1).

Related literature top

For hydrogen-bond interactions in biological systems, see: Deisenhofer & Michel (1989). For supramolecular assembly through hydrogen bonds, see: Beatty et al. (2003); Li et al. (2006); Russell & Ward (1996). For related structures, see: Liu et al. (2008); Liu & Zhang (2009); Rarig et al. (2001).

Experimental top

Ni(NO3)2.4H2O (0.5 mmol, 0.145 g), 1H-3-(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazole (0.5 mmol, 0.112 g), and water (12 ml) were placed in a 23-ml Teflon-lined Parr bomb. The bomb was heated at 453 K for 3 d. The green block-shapped crystals were filtered off and washed with water and acetone (yield 33%, based on Ni).

Refinement top

Hydrogen atoms of water molecules were located in a difference Fourier map and refined with distance restraints of O—H = 0.82 (2) Å and H···H = 1.35 (2) Å. H atoms on C atom were positoned geometrically and refined using a riding model, with C—H = 0.93 Å, in all cases with U(H)= 1.2/1.5× Ueqiv(Host)

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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. A view of the molecular structure of (I) with the atom-numbering scheme and 50% displacement ellipsoids (arbitrary spheres for the H atoms). Atoms with the suffix A are generated by the symmetry operation (-x, -y + 1, -z + 1).
[Figure 2] Fig. 2. The 3-D network of (I).
Tetraaquabis[3-(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazolido]nickel(II) dihydrate top
Crystal data top
[Ni(C12H8N5)2(H2O)4]·2H2OZ = 1
Mr = 611.25F(000) = 318
Triclinic, P1Dx = 1.491 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.2240 (16) ÅCell parameters from 2567 reflections
b = 9.1990 (18) Åθ = 1.5–25.3°
c = 9.3850 (19) ŵ = 0.77 mm−1
α = 90.70 (3)°T = 293 K
β = 104.96 (3)°Block, green
γ = 96.47 (3)°0.20 × 0.12 × 0.08 mm
V = 680.9 (2) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		2437 independent reflections
Radiation source: fine-focus sealed tube2258 reflections with I > 2σ(I)
graphiteRint = 0.040
φ and ω scansθmax = 25.2°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)'		h = −9→9
Tmin = 0.866, Tmax = 0.943k = −9→11
4042 measured reflectionsl = −11→11
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)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.150H atoms treated by a mixture of independent and constrained refinement
S = 0.99 w = 1/[σ2(Fo2) + (0.0912P)2 + 0.8P]
where P = (Fo2 + 2Fc2)/3
2437 reflections(Δ/σ)max < 0.001
211 parametersΔρmax = 0.55 e Å−3
9 restraintsΔρmin = −0.85 e Å−3
Crystal data top
[Ni(C12H8N5)2(H2O)4]·2H2Oγ = 96.47 (3)°
Mr = 611.25V = 680.9 (2) Å3
Triclinic, P1Z = 1
a = 8.2240 (16) ÅMo Kα radiation
b = 9.1990 (18) ŵ = 0.77 mm−1
c = 9.3850 (19) ÅT = 293 K
α = 90.70 (3)°0.20 × 0.12 × 0.08 mm
β = 104.96 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		2437 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)'		2258 reflections with I > 2σ(I)
Tmin = 0.866, Tmax = 0.943Rint = 0.040
4042 measured reflectionsθmax = 25.2°
Refinement top
R[F2 > 2σ(F2)] = 0.052H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.150Δρmax = 0.55 e Å−3
S = 0.99Δρmin = −0.85 e Å−3
2437 reflectionsAbsolute structure: ?
211 parametersFlack parameter: ?
9 restraintsRogers parameter: ?
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.

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) top
xyzUiso*/Ueq
Ni10.00000.50000.50000.0217 (2)
C10.2767 (4)0.3042 (4)0.6004 (4)0.0291 (7)
H10.32560.38140.66830.035*
C20.3637 (5)0.1847 (4)0.5989 (4)0.0347 (8)
H20.46790.18060.66630.042*
C30.2938 (4)0.0712 (4)0.4959 (4)0.0299 (8)
H30.3508−0.01000.49280.036*
C40.1385 (4)0.0799 (3)0.3976 (3)0.0211 (6)
C50.0578 (4)0.2022 (3)0.4086 (3)0.0235 (7)
H5A−0.04800.20780.34400.028*
C60.0580 (4)−0.0361 (3)0.2837 (3)0.0214 (6)
C7−0.1047 (4)−0.1550 (3)0.1011 (3)0.0231 (7)
C8−0.2408 (4)−0.2007 (4)−0.0305 (4)0.0270 (7)
C9−0.2480 (5)−0.3324 (4)−0.1091 (4)0.0382 (9)
H9A−0.1643−0.3938−0.07850.046*
C10−0.3798 (6)−0.3703 (5)−0.2319 (5)0.0480 (11)
H10A−0.3804−0.4570−0.28410.058*
C11−0.4989 (5)−0.1649 (5)−0.2061 (4)0.0428 (10)
H11A−0.5863−0.1074−0.23790.051*
C12−0.3699 (5)−0.1149 (4)−0.0848 (4)0.0363 (8)
H12A−0.3689−0.0242−0.03950.044*
N10.1255 (4)0.3132 (3)0.5083 (3)0.0253 (6)
N2−0.0797 (3)−0.0233 (3)0.1726 (3)0.0243 (6)
N30.1159 (4)−0.1651 (3)0.2840 (3)0.0263 (6)
N40.0088 (4)−0.2439 (3)0.1640 (3)0.0276 (6)
N5−0.5067 (4)−0.2906 (4)−0.2810 (4)0.0442 (9)
O10.2181 (3)0.6258 (3)0.4839 (3)0.0321 (6)
O20.0796 (4)0.5155 (3)0.7297 (3)0.0353 (6)
O30.8076 (4)0.2539 (3)0.0662 (3)0.0405 (7)
H1A0.302 (4)0.650 (5)0.555 (3)0.059 (15)*
H2A0.122 (5)0.580 (3)0.796 (4)0.043 (12)*
H3A0.850 (8)0.182 (5)0.103 (6)0.12 (3)*
H1B0.210 (5)0.695 (3)0.427 (4)0.043 (12)*
H2B0.051 (6)0.440 (3)0.771 (4)0.049 (13)*
H3B0.836 (7)0.274 (5)−0.009 (4)0.069 (17)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0260 (4)0.0160 (3)0.0190 (3)0.0037 (2)−0.0020 (2)−0.0023 (2)
C10.0293 (18)0.0210 (17)0.0308 (18)0.0002 (13)−0.0018 (15)−0.0049 (13)
C20.0247 (18)0.031 (2)0.040 (2)0.0061 (14)−0.0065 (15)−0.0046 (15)
C30.0285 (18)0.0260 (18)0.0344 (19)0.0079 (14)0.0048 (15)−0.0010 (14)
C40.0249 (16)0.0183 (16)0.0203 (15)0.0011 (12)0.0068 (13)0.0007 (12)
C50.0241 (17)0.0199 (16)0.0223 (16)0.0026 (12)−0.0016 (13)−0.0007 (12)
C60.0260 (16)0.0171 (15)0.0211 (15)0.0023 (12)0.0062 (13)0.0001 (12)
C70.0277 (17)0.0209 (16)0.0197 (16)0.0004 (12)0.0054 (13)0.0008 (12)
C80.0285 (18)0.0289 (18)0.0218 (16)−0.0021 (14)0.0057 (14)0.0005 (13)
C90.038 (2)0.032 (2)0.036 (2)0.0010 (16)−0.0030 (17)−0.0087 (16)
C100.049 (3)0.051 (3)0.035 (2)−0.005 (2)0.0004 (19)−0.0144 (18)
C110.031 (2)0.052 (3)0.039 (2)−0.0002 (17)−0.0001 (17)0.0073 (18)
C120.033 (2)0.038 (2)0.034 (2)0.0034 (16)0.0022 (16)−0.0022 (16)
N10.0311 (15)0.0184 (14)0.0242 (14)0.0033 (11)0.0031 (12)−0.0016 (11)
N20.0275 (15)0.0193 (14)0.0239 (14)0.0022 (11)0.0030 (12)−0.0017 (11)
N30.0363 (16)0.0175 (14)0.0217 (14)0.0035 (11)0.0015 (12)−0.0013 (10)
N40.0356 (16)0.0224 (15)0.0203 (14)0.0040 (12)−0.0009 (12)−0.0031 (11)
N50.0390 (19)0.054 (2)0.0289 (17)−0.0109 (16)−0.0033 (14)0.0008 (15)
O10.0298 (13)0.0263 (13)0.0320 (14)0.0000 (10)−0.0057 (11)0.0068 (11)
O20.0554 (17)0.0220 (14)0.0216 (12)−0.0001 (12)−0.0001 (12)0.0005 (10)
O30.0514 (18)0.0363 (16)0.0345 (15)0.0052 (13)0.0128 (14)−0.0034 (12)
Geometric parameters (Å, °) top
Ni1—O1i2.063 (3)C7—N21.347 (4)
Ni1—O12.063 (3)C7—C81.456 (5)
Ni1—O22.083 (2)C8—C121.389 (5)
Ni1—O2i2.083 (2)C8—C91.398 (5)
Ni1—N12.094 (3)C9—C101.373 (6)
Ni1—N1i2.094 (3)C9—H9A0.9300
C1—N11.330 (4)C10—N51.331 (6)
C1—C21.379 (5)C10—H10A0.9300
C1—H10.9300C11—N51.333 (5)
C2—C31.381 (5)C11—C121.373 (5)
C2—H20.9300C11—H11A0.9300
C3—C41.380 (5)C12—H12A0.9300
C3—H30.9300N3—N41.376 (4)
C4—C51.385 (4)O1—H1A0.836 (19)
C4—C61.472 (4)O1—H1B0.830 (18)
C5—N11.345 (4)O2—H2A0.828 (18)
C5—H5A0.9300O2—H2B0.836 (19)
C6—N31.327 (4)O3—H3A0.82 (5)
C6—N21.344 (4)O3—H3B0.81 (4)
C7—N41.337 (4)
O1i—Ni1—O1180.00 (15)N4—C7—N2113.1 (3)
O1i—Ni1—O288.62 (11)N4—C7—C8121.9 (3)
O1—Ni1—O291.38 (11)N2—C7—C8125.0 (3)
O1i—Ni1—O2i91.38 (11)C12—C8—C9116.5 (3)
O1—Ni1—O2i88.62 (11)C12—C8—C7121.6 (3)
O2—Ni1—O2i180.0C9—C8—C7121.9 (3)
O1i—Ni1—N190.86 (11)C10—C9—C8119.4 (4)
O1—Ni1—N189.14 (11)C10—C9—H9A120.3
O2—Ni1—N187.82 (11)C8—C9—H9A120.3
O2i—Ni1—N192.18 (11)N5—C10—C9124.1 (4)
O1i—Ni1—N1i89.14 (11)N5—C10—H10A118.0
O1—Ni1—N1i90.86 (11)C9—C10—H10A118.0
O2—Ni1—N1i92.18 (11)N5—C11—C12124.1 (4)
O2i—Ni1—N1i87.82 (11)N5—C11—H11A117.9
N1—Ni1—N1i180.000 (1)C12—C11—H11A117.9
N1—C1—C2122.5 (3)C11—C12—C8119.5 (4)
N1—C1—H1118.7C11—C12—H12A120.2
C2—C1—H1118.7C8—C12—H12A120.2
C1—C2—C3119.1 (3)C1—N1—C5118.1 (3)
C1—C2—H2120.5C1—N1—Ni1122.7 (2)
C3—C2—H2120.5C5—N1—Ni1118.9 (2)
C4—C3—C2119.2 (3)C6—N2—C7101.9 (3)
C4—C3—H3120.4C6—N3—N4105.3 (3)
C2—C3—H3120.4C7—N4—N3105.8 (3)
C3—C4—C5118.1 (3)C10—N5—C11116.3 (3)
C3—C4—C6122.0 (3)Ni1—O1—H1A125 (3)
C5—C4—C6119.9 (3)Ni1—O1—H1B119 (3)
N1—C5—C4122.9 (3)H1A—O1—H1B107 (3)
N1—C5—H5A118.5Ni1—O2—H2A138 (3)
C4—C5—H5A118.5Ni1—O2—H2B114 (3)
N3—C6—N2114.0 (3)H2A—O2—H2B107 (3)
N3—C6—C4121.9 (3)H3A—O3—H3B111 (3)
N2—C6—C4124.1 (3)
N1—C1—C2—C31.6 (6)C4—C5—N1—C1−0.1 (5)
C1—C2—C3—C4−0.3 (5)C4—C5—N1—Ni1174.5 (2)
C2—C3—C4—C5−1.0 (5)O1i—Ni1—N1—C1−129.6 (3)
C2—C3—C4—C6179.1 (3)O1—Ni1—N1—C150.4 (3)
C3—C4—C5—N11.3 (5)O2—Ni1—N1—C1−41.0 (3)
C6—C4—C5—N1−178.8 (3)O2i—Ni1—N1—C1139.0 (3)
C3—C4—C6—N311.2 (5)O1i—Ni1—N1—C556.0 (2)
C5—C4—C6—N3−168.7 (3)O1—Ni1—N1—C5−124.0 (2)
C3—C4—C6—N2−169.8 (3)O2—Ni1—N1—C5144.6 (2)
C5—C4—C6—N210.3 (5)O2i—Ni1—N1—C5−35.4 (2)
N4—C7—C8—C12172.1 (3)N3—C6—N2—C7−0.4 (4)
N2—C7—C8—C12−7.2 (5)C4—C6—N2—C7−179.4 (3)
N4—C7—C8—C9−8.3 (5)N4—C7—N2—C60.5 (4)
N2—C7—C8—C9172.4 (3)C8—C7—N2—C6179.8 (3)
C12—C8—C9—C10−0.7 (6)N2—C6—N3—N40.1 (4)
C7—C8—C9—C10179.7 (4)C4—C6—N3—N4179.2 (3)
C8—C9—C10—N5−1.7 (7)N2—C7—N4—N3−0.5 (4)
N5—C11—C12—C8−2.7 (6)C8—C7—N4—N3−179.8 (3)
C9—C8—C12—C112.8 (5)C6—N3—N4—C70.2 (3)
C7—C8—C12—C11−177.6 (3)C9—C10—N5—C112.0 (6)
C2—C1—N1—C5−1.3 (5)C12—C11—N5—C100.2 (6)
C2—C1—N1—Ni1−175.7 (3)
Symmetry codes: (i) −x, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N5ii0.83 (2)1.92 (3)2.751 (4)179 (3)
O1—H1B···N3iii0.83 (3)1.95 (3)2.750 (4)162 (3)
O2—H2A···O3iv0.83 (3)1.93 (3)2.751 (4)171 (3)
O2—H2B···N4v0.84 (3)1.96 (3)2.791 (4)169 (3)
O3—H3A···N2vi0.82 (5)2.10 (5)2.911 (4)170 (3)
O3—H3B···N4vii0.82 (4)2.20 (5)2.944 (4)151 (3)
Symmetry codes: (ii) x+1, y+1, z+1; (iii) x, y+1, z; (iv) −x+1, −y+1, −z+1; (v) −x, −y, −z+1; (vi) x+1, y, z; (vii) −x+1, −y, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N5i0.83 (2)1.92 (3)2.751 (4)179 (3)
O1—H1B···N3ii0.83 (3)1.95 (3)2.750 (4)162 (3)
O2—H2A···O3iii0.83 (3)1.93 (3)2.751 (4)171 (3)
O2—H2B···N4iv0.84 (3)1.96 (3)2.791 (4)169 (3)
O3—H3A···N2v0.82 (5)2.10 (5)2.911 (4)170 (3)
O3—H3B···N4vi0.82 (4)2.20 (5)2.944 (4)151 (3)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z; (iii) −x+1, −y+1, −z+1; (iv) −x, −y, −z+1; (v) x+1, y, z; (vi) −x+1, −y, −z.
Acknowledgements top

We acknowledge financial support from the Foundation of Shaoyang Medical College (grant No. XK200804) and the Science & Technology Foundation of Shaoyang (grant Nos. 56 J08 & J0966)

references
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