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Acta Cryst. (2008). E64, m802    [ doi:10.1107/S1600536808013329 ]

Hexaaquahexakis([mu]2-3,5-diamino-4H-1,2,4-triazole)trinickel(II) tris(hexafluoridosilicate) icosahydrate

L.-P. Wu, S.-M. Zhao, G.-F. Zhang and S. W. Ng

Abstract top

The trinuclear cation of the title compound, [Ni3(C2H5N5)6(H2O)6][SiF6]3·20H2O, has the six 3,5-diamino-1,2,4-triazole ligands each bridging two metal atoms; the metal atom in the middle, which lies on a special position (of 32 site symmetry), is connected to six N atoms in an octahedral geometry. The other metal atom, which lies on a special position (of 3 site symmetry), is connected to three N atoms and three O atoms. One hexafluroridosilicate anion lies on a site of 3 symmetry and the other lies on a site of \overline{3} symmetry. The hexacation, dianions and uncoordinated water molecules interact through hydrogen bonds to form a three-dimensional network. One uncoordinated water molecule is disordered, with site occupancy 0.3.

Comment top

A recent study reported the nickel sulfate complex of 3,5-diamino-1,2,4-triazole. The cation is a centrosymmetric trinuclear hexacation [Ni3(C2H5N5)6(H2O)6]6+, whose charge is balanced by the sulfate anions. The N-heterocyclic ligands each bridge two nickel atoms (Zhang et al., 2007). The corresponding synthesis with nickel hexafluoridosilicate in place of nickel sulfate gave the analogous cluster cation (Scheme I, Fig. 1). The cation and anions interact through the coordinated and free water molecules to give rise to a three-dimensional, hydrogen bonded network.

Related literature top

For the structure of the title hexacation as the hydrated sulfate salt, see: Zhang et al. (2007).

Experimental top

Single crystal of the compound were grown by diffusing 3,5-diamino-1,2,4-triazole (0.020 g, 0.2 mmol) dissolved in methanol (5 ml) into nickle(II) hexafluorosilicate (0.027 g, 0.1 mmol) dissolved in water (5 ml).

Refinement top

As one of the five water molecules (O5) lies on a special position of 2 site symmetry, the occupancy would be 0.5. However, the refinement of this atom at the default occupancy lead to a large temperature factor. The refinement of the occupancy factor led to a value of about 0.3; this atom was then allowed to refine off the symmetry element. As the occupancy was nearly 0.3, the occupancy was arbitrarily fixed as 0.3333 so that the formula unit has 20 lattice water molecules.

The N– and O–bound H atoms (other than those of the diordered water molecule) were found in difference maps and were refined with distance restraints of O–H = N–H = O.85±0.01 Å; for the water molecules, an additional H···H = 1.39±0.01 Å restraint was imposed. The Uiso(H) values were tied to those of the parent atoms by a factor of 1.5. The H atoms of the disordered water molecule were placed in chemically sensible positions but were not refined.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot of the title compound. Displacement ellipsoids are drawn at the 25% probability level.
Hexaaquahexakis(µ2-3,5-diamino-4H-1,2,4-triazole)trinickel(II) tris(hexafluoridosilicate) icosahydrate top
Crystal data top
[Ni3(C2H5N5)6(H2O)6][SiF6]3·20H2OZ = 6
Mr = 1665.48F000 = 5160
Trigonal, R3cDx = 1.752 Mg m−3
Hall symbol: -R 3 2"cMo Kα radiation
λ = 0.71073 Å
a = 13.024 (1) ÅCell parameters from 5839 reflections
b = 13.024 Åθ = 3.1–28.2º
c = 64.462 (5) ŵ = 1.09 mm−1
α = 90ºT = 293 (2) K
β = 90ºBlock, blue
γ = 120º0.49 × 0.46 × 0.44 mm
V = 9469.8 (9) Å3
Data collection top
Bruker APEX area-detector
diffractometer		2420 independent reflections
Radiation source: fine-focus sealed tube2093 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.021
T = 293(2) Kθmax = 27.5º
φ and ω scansθmin = 3.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −16→16
Tmin = 0.560, Tmax = 0.646k = −16→16
25347 measured reflectionsl = −79→83
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)] = 0.033H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.106  w = 1/[σ2(Fo2) + (0.0612P)2 + 17.0807P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
2420 reflectionsΔρmax = 0.40 e Å−3
185 parametersΔρmin = −0.42 e Å−3
23 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Ni3(C2H5N5)6(H2O)6][SiF6]3·20H2Oγ = 120º
Mr = 1665.48V = 9469.8 (9) Å3
Trigonal, R3cZ = 6
a = 13.024 (1) ÅMo Kα
b = 13.024 ŵ = 1.09 mm−1
c = 64.462 (5) ÅT = 293 (2) K
α = 90º0.49 × 0.46 × 0.44 mm
β = 90º
Data collection top
Bruker APEX area-detector
diffractometer		2420 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2093 reflections with I > 2σ(I)
Tmin = 0.560, Tmax = 0.646Rint = 0.021
25347 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03323 restraints
wR(F2) = 0.106H atoms treated by a mixture of
independent and constrained refinement
S = 1.06  w = 1/[σ2(Fo2) + (0.0612P)2 + 17.0807P]
where P = (Fo2 + 2Fc2)/3
2420 reflectionsΔρmax = 0.40 e Å−3
185 parametersΔρmin = −0.42 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ni10.66670.33330.140787 (6)0.02689 (14)
Ni20.66670.33330.08330.02377 (16)
Si11.00000.00000.083802 (16)0.0331 (2)
Si20.3333−0.33330.16670.0552 (5)
F10.89685 (14)0.00226 (15)0.09960 (2)0.0623 (4)
F21.00168 (16)0.10635 (14)0.06943 (3)0.0648 (4)
F30.3983 (3)−0.3868 (3)0.15169 (5)0.1399 (12)
O10.72286 (15)0.24063 (14)0.16010 (2)0.0398 (3)
H110.723 (3)0.1843 (18)0.1533 (3)0.060*
H120.699 (3)0.217 (2)0.1724 (2)0.060*
O20.7536 (2)0.0854 (2)0.13625 (4)0.0660 (5)
H210.713 (2)0.0108 (10)0.1358 (6)0.099*
H220.8267 (10)0.108 (3)0.1361 (7)0.099*
O30.65459 (19)0.15616 (17)0.19955 (3)0.0599 (5)
H310.5874 (17)0.094 (2)0.1978 (5)0.090*
H320.650 (3)0.197 (2)0.2092 (4)0.090*
O40.6041 (2)−0.1661 (3)0.12859 (4)0.0796 (6)
H410.576 (3)−0.184 (4)0.1164 (3)0.119*
H420.551 (3)−0.182 (4)0.1374 (4)0.119*
O50.664 (3)−0.1549 (17)0.0893 (3)0.185 (7)0.3333
H510.7382−0.10720.09050.278*0.3333
H520.6338−0.12390.08160.278*0.3333
N10.61588 (14)0.43372 (14)0.12352 (2)0.0290 (3)
N20.59282 (14)0.41343 (14)0.10195 (2)0.0293 (3)
N30.52872 (17)0.53100 (17)0.11289 (3)0.0381 (4)
H30.500 (2)0.576 (2)0.1117 (4)0.057*
N40.5100 (2)0.4865 (2)0.07683 (3)0.0508 (5)
H4A0.514 (3)0.449 (3)0.0663 (4)0.076*
H4B0.468 (2)0.517 (3)0.0744 (6)0.076*
N50.5810 (2)0.5478 (2)0.14862 (3)0.0556 (6)
H5A0.625 (3)0.540 (3)0.1574 (4)0.083*
H5B0.535 (3)0.575 (3)0.1509 (5)0.083*
C10.57611 (18)0.50413 (18)0.12943 (3)0.0343 (4)
C20.54160 (17)0.47436 (17)0.09630 (3)0.0336 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.02997 (17)0.02997 (17)0.0207 (2)0.01499 (9)0.0000.000
Ni20.0253 (2)0.0253 (2)0.0207 (3)0.01265 (10)0.0000.000
Si10.0300 (3)0.0300 (3)0.0394 (5)0.01500 (15)0.0000.000
Si20.0333 (5)0.0333 (5)0.0992 (15)0.0166 (2)0.0000.000
F10.0555 (9)0.0683 (10)0.0701 (10)0.0363 (8)0.0170 (7)0.0016 (8)
F20.0710 (10)0.0574 (9)0.0741 (10)0.0382 (8)−0.0004 (8)0.0199 (8)
F30.146 (3)0.176 (3)0.163 (3)0.129 (3)0.0160 (19)−0.025 (2)
O10.0497 (8)0.0454 (8)0.0292 (7)0.0274 (7)−0.0020 (6)0.0041 (6)
O20.0624 (12)0.0722 (13)0.0750 (13)0.0424 (11)−0.0019 (10)−0.0133 (11)
O30.0764 (13)0.0541 (11)0.0436 (9)0.0283 (10)0.0132 (9)−0.0001 (8)
O40.0709 (15)0.0812 (15)0.0871 (16)0.0383 (13)−0.0030 (12)−0.0025 (14)
O50.119 (7)0.216 (10)0.178 (13)0.051 (7)−0.015 (9)−0.010 (8)
N10.0349 (8)0.0329 (8)0.0226 (7)0.0194 (6)0.0006 (6)−0.0010 (6)
N20.0352 (8)0.0355 (8)0.0219 (7)0.0213 (7)−0.0009 (6)−0.0005 (6)
N30.0476 (10)0.0440 (10)0.0366 (9)0.0334 (8)−0.0010 (7)−0.0015 (7)
N40.0743 (15)0.0720 (14)0.0343 (10)0.0578 (13)−0.0109 (9)−0.0043 (9)
N50.0821 (16)0.0803 (15)0.0348 (10)0.0635 (14)−0.0071 (10)−0.0157 (10)
C10.0390 (10)0.0367 (10)0.0319 (9)0.0224 (9)0.0008 (8)−0.0023 (8)
C20.0377 (10)0.0374 (10)0.0312 (9)0.0229 (9)−0.0009 (7)0.0006 (7)
Geometric parameters (Å, °) top
Ni1—N12.062 (2)Si2—F31.649 (3)
Ni1—N1i2.062 (2)O1—H110.86 (3)
Ni1—N1ii2.062 (2)O1—H120.85 (3)
Ni1—O12.104 (2)O2—H210.84 (3)
Ni1—O1i2.104 (2)O2—H220.84 (3)
Ni1—O1ii2.104 (2)O3—H310.85 (3)
Ni2—N2iii2.111 (2)O3—H320.84 (3)
Ni2—N2iv2.111 (2)O4—H410.85 (3)
Ni2—N2v2.111 (2)O4—H420.84 (3)
Ni2—N2ii2.111 (2)O5—H510.85
Ni2—N2i2.111 (2)O5—H520.85
Ni2—N22.111 (2)N1—C11.315 (2)
Si1—F21.6574 (15)N1—N21.419 (2)
Si1—F2vi1.6574 (15)N2—C21.318 (3)
Si1—F2vii1.6574 (15)N3—C21.356 (3)
Si1—F1vii1.6976 (15)N3—C11.362 (3)
Si1—F1vi1.6976 (15)N3—H30.85 (1)
Si1—F11.6976 (15)N4—C21.354 (3)
Si2—F3viii1.649 (3)N4—H4A0.85 (3)
Si2—F3ix1.649 (3)N4—H4B0.84 (3)
Si2—F3x1.649 (3)N5—C11.350 (3)
Si2—F3xi1.649 (3)N5—H5A0.84 (3)
Si2—F3xii1.649 (3)N5—H5B0.85 (3)
N1ii—Ni1—N1i93.61 (6)F1vi—Si1—F187.74 (9)
N1ii—Ni1—N193.61 (6)F3viii—Si2—F3ix89.21 (17)
N1i—Ni1—N193.61 (6)F3viii—Si2—F3x89.21 (17)
N1ii—Ni1—O187.31 (6)F3ix—Si2—F3x89.21 (17)
N1i—Ni1—O190.45 (6)F3viii—Si2—F3xi90.79 (17)
N1—Ni1—O1175.77 (6)F3ix—Si2—F3xi90.79 (17)
N1ii—Ni1—O1i90.45 (6)F3x—Si2—F3xi179.995 (1)
N1i—Ni1—O1i175.77 (6)F3viii—Si2—F3xii90.79 (17)
N1—Ni1—O1i87.31 (6)F3ix—Si2—F3xii179.995 (1)
O1—Ni1—O1i88.56 (6)F3x—Si2—F3xii90.79 (17)
N1ii—Ni1—O1ii175.78 (6)F3xi—Si2—F3xii89.21 (17)
N1i—Ni1—O1ii87.31 (6)F3viii—Si2—F3179.997 (1)
N1—Ni1—O1ii90.45 (6)F3ix—Si2—F390.79 (17)
O1—Ni1—O1ii88.56 (6)F3x—Si2—F390.79 (17)
O1i—Ni1—O1ii88.56 (6)F3xi—Si2—F389.21 (17)
N2iii—Ni2—N2iv90.87 (6)F3xii—Si2—F389.21 (17)
N2iii—Ni2—N2v90.87 (6)Ni1—O1—H11110 (2)
N2iv—Ni2—N2v90.87 (6)Ni1—O1—H12126 (2)
N2iii—Ni2—N2ii87.57 (8)H11—O1—H12109 (2)
N2iv—Ni2—N2ii177.79 (8)H21—O2—H22111 (2)
N2v—Ni2—N2ii90.72 (8)H31—O3—H32110 (2)
N2iii—Ni2—N2i90.72 (8)H41—O4—H42111 (2)
N2iv—Ni2—N2i87.57 (8)H51—O5—H52109.4
N2v—Ni2—N2i177.79 (8)C1—N1—N2107.04 (15)
N2ii—Ni2—N2i90.88 (6)C1—N1—Ni1130.48 (12)
N2iii—Ni2—N2177.79 (8)N2—N1—Ni1121.05 (11)
N2iv—Ni2—N290.72 (8)C2—N2—N1106.38 (15)
N2v—Ni2—N287.57 (8)C2—N2—Ni2129.31 (13)
N2ii—Ni2—N290.88 (6)N1—N2—Ni2122.87 (12)
N2i—Ni2—N290.88 (6)C2—N3—C1106.38 (16)
F2—Si1—F2vi91.80 (9)C2—N3—H3122 (2)
F2—Si1—F2vii91.80 (9)C1—N3—H3132 (2)
F2vi—Si1—F2vii91.80 (9)C2—N4—H4A125 (2)
F2—Si1—F1vii90.36 (8)C2—N4—H4B122 (3)
F2vi—Si1—F1vii177.12 (10)H4A—N4—H4B111 (3)
F2vii—Si1—F1vii90.03 (8)C1—N5—H5A117 (2)
F2—Si1—F1vi177.12 (10)C1—N5—H5B116 (2)
F2vi—Si1—F1vi90.03 (8)H5A—N5—H5B126 (3)
F2vii—Si1—F1vi90.36 (8)N1—C1—N5127.37 (19)
F1vii—Si1—F1vi87.74 (9)N1—C1—N3109.86 (16)
F2—Si1—F190.03 (8)N5—C1—N3122.76 (18)
F2vi—Si1—F190.36 (8)N2—C2—N4126.92 (19)
F2vii—Si1—F1177.12 (10)N2—C2—N3110.33 (17)
F1vii—Si1—F187.74 (9)N4—C2—N3122.67 (19)
N1ii—Ni1—N1—C1−135.1 (2)N2iv—Ni2—N2—N1146.76 (16)
N1i—Ni1—N1—C1131.1 (2)N2v—Ni2—N2—N1−122.40 (15)
O1i—Ni1—N1—C1−44.81 (19)N2ii—Ni2—N2—N1−31.71 (12)
O1ii—Ni1—N1—C143.72 (19)N2i—Ni2—N2—N159.18 (10)
N1ii—Ni1—N1—N260.39 (10)N2—N1—C1—N5−179.0 (2)
N1i—Ni1—N1—N2−33.46 (12)Ni1—N1—C1—N514.9 (3)
O1i—Ni1—N1—N2150.67 (13)N2—N1—C1—N3−0.1 (2)
O1ii—Ni1—N1—N2−120.79 (13)Ni1—N1—C1—N3−166.30 (14)
C1—N1—N2—C20.6 (2)C2—N3—C1—N1−0.4 (2)
Ni1—N1—N2—C2168.37 (13)C2—N3—C1—N5178.5 (2)
C1—N1—N2—Ni2168.09 (13)N1—N2—C2—N4176.0 (2)
Ni1—N1—N2—Ni2−24.17 (18)Ni2—N2—C2—N49.6 (3)
N2iv—Ni2—N2—C2−48.86 (15)N1—N2—C2—N3−0.9 (2)
N2v—Ni2—N2—C241.98 (14)Ni2—N2—C2—N3−167.25 (14)
N2ii—Ni2—N2—C2132.67 (18)C1—N3—C2—N20.8 (2)
N2i—Ni2—N2—C2−136.44 (18)C1—N3—C2—N4−176.2 (2)
Symmetry codes: (i) −y+1, x−y, z; (ii) −x+y+1, −x+1, z; (iii) y+1/3, x−1/3, −z+1/6; (iv) x−y+1/3, −y+2/3, −z+1/6; (v) −x+4/3, −x+y+2/3, −z+1/6; (vi) −y+1, x−y−1, z; (vii) −x+y+2, −x+1, z; (viii) −x+2/3, −y−2/3, −z+1/3; (ix) x−y−1/3, x−2/3, −z+1/3; (x) y+2/3, −x+y+1/3, −z+1/3; (xi) −y, x−y−1, z; (xii) −x+y+1, −x, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H11···O20.86 (3)1.88 (3)2.724 (3)168 (3)
O1—H12···O30.85 (3)1.89 (3)2.737 (2)174 (3)
O2—H21···O40.84 (3)2.07 (3)2.896 (4)168 (4)
O2—H22···O3xiii0.84 (3)2.12 (3)2.961 (3)175 (4)
O3—H31···O4ix0.85 (3)2.05 (3)2.861 (3)159 (3)
O3—H32···F1ix0.84 (3)2.13 (3)2.904 (2)153 (3)
O4—H41···F2xiv0.85 (3)2.23 (3)2.950 (3)143 (4)
O4—H42···F3xi0.84 (3)2.16 (3)2.973 (4)162 (4)
O4—H41···O50.85 (3)2.03 (3)2.64 (2)128 (4)
O5—H51···F10.851.922.76 (3)167
N3—H3···F2iii0.85 (3)1.97 (3)2.764 (2)157 (3)
N4—H4b···F1iii0.84 (3)2.14 (3)2.974 (3)170 (3)
N5—H5a···O1i0.84 (3)2.23 (3)2.942 (3)142 (3)
N5—H5b···F3xv0.85 (3)2.08 (3)2.909 (3)167 (3)
Symmetry codes: (xiii) −x+5/3, −y+1/3, −z+1/3; (ix) x−y−1/3, x−2/3, −z+1/3; (xiv) y+1/3, x−4/3, −z+1/6; (xi) −y, x−y−1, z; (iii) y+1/3, x−1/3, −z+1/6; (i) −y+1, x−y, z; (xv) x, y+1, z.
Table 1
Selected geometric parameters (Å) top
Ni1—N12.062 (2)Ni2—N22.111 (2)
Ni1—O12.104 (2)
Acknowledgements top

We thank Shaanxi Normal University and the University of Malaya for supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2004). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

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

Westrip, S. P. (2008). publCIF. In preparation.

Zhang, G.-F., Zhao, S.-M., She, J.-B. & Ng, S. W. (2007). Acta Cryst. E63, m1517–m1518.