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Acta Cryst. (2007). E63, m1517-m1518    [ doi:10.1107/S160053680702051X ]

Hexaaquahexakis([mu]2-3,5-diamino-1,2,4-triazole)trinickel(II) trisulfate octadecahydrate

G.-F. Zhang, S.-M. Zhao, J.-B. She and S. W. Ng

Abstract top

In the centrosymmetric trinuclear cation of the title compound, [Ni3(C2H5N5)6(H2O)6](SO4)3·18H2O, the six 3,5-diamino-1,2,4-triazole ligands each bridge two metal atoms; the Ni atom in the centre (site symmetry 3 2) of the cluster is coordinated by six N atoms in an octahedral geometry. The other metal atom (site symmetry 3) is connected to three N atoms and three O atoms. The sulfate anion on the \overline{3} site is heavily disordered whereas that on the 3 site is ordered. The hexacation, dianions and uncoordinated water molecules interact through numerous O-H...O and N-H...O hydrogen bonds, forming a three-dimensional network.

Comment top

3,5-Diamino-1,2,4-triazole (C2H5N5) binds to cobalt to yield a centrosymmetric mixed-valence compound in which six of the ligands function as a bridge to a chain of three cobalt centers. The central metal atom is connected to six N-donor sites whereas the other two are each connected to three N atoms as well as to three water molecules. The charge of the cation is balanced by chloride ions, and the structure of the salt is stabilized by extensive hydrogen bonds (Antolini et al., 1991).

The title nickel analog displays a similar structure (Fig. 1, Table 1), but the charge of the trinuclear cation is balanced by three sulfate dianions. The cations and anions interact through uncoordinated water molecules to give rise to a three-dimensional, hydrogen bonded network (Table 2).

Related literature top

For the structure of a related cobalt-containing complex, see: Antolini et al. (1991).

Experimental top

Single crystals of (I) were grown by slowly diffusing 3,5-diamino-1,2,4-triazole (0.020 g, 0.2 mmol) dissolved in methanol (5 ml) into nickel(II) sulfate hexahydrate (0.027 g, 0.1 mmol) dissolved in water (5 ml).

Refinement top

The N– and O-bound H atoms were found in difference maps and refined with distance restraints of O–H = N–H = 0.85 (1) Å; for the water molecules, an additional H···H = 1.39±0.01 Å restraint was imposed. The Uiso values of the H atoms were tied to those of the parent atoms by a factor of 1.2.

The O atoms of one of the sulfate ions are diordered. For the ordered and disordered sulfate ions, the S–O distance was restrained to 1.45±0.01 Å and the O···O distance to 2.35±0.01 Å; the vibration of the oxygen atoms was restrained to be nearly isotropic.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. View of the trinuclear cation in (I) at the 50% ellipsoid probability level. Hydrogen atoms are shown as spheres of arbitrary radius. Symmetry codes: (i) 1 - y, x-y, z; (ii) 1 - x + y, 1 - x, z; (iii) x-y + 1/3, 2/3 - y, 1/6 - z; (iv) 4/3 - x, 2/3 - x + y,1/6 - z; (v) 1/3 + y,x - 1/3,1/6 - z.
Hexaaquahexakis(µ2-3,5-diamino-1,2,4-triazole)trinickel(II) trisulfate octadecahydrate top
Crystal data top
[Ni3(C2H5N5)6(H2O)6](SO4)3·18H2ODx = 1.681 Mg m−3
Mr = 1491.35Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3cCell parameters from 7201 reflections
Hall symbol: -R 3 2"cθ = 3.2–28.2°
a = 12.664 (2) ŵ = 1.17 mm−1
c = 63.653 (6) ÅT = 295 K
V = 8841 (2) Å3Block, blue
Z = 60.43 × 0.32 × 0.23 mm
F(000) = 4680
Data collection top
Bruker APEX CCD
diffractometer		2269 independent reflections
Radiation source: fine-focus sealed tube1868 reflections with I > 2σ(I)
graphiteRint = 0.026
φ and ω scansθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −16→15
Tmin = 0.676, Tmax = 0.775k = −16→16
24396 measured reflectionsl = −82→81
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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.180All H-atom parameters refined
S = 1.33 w = 1/[σ2(Fo2) + (0.1P)2 + 1P]
where P = (Fo2 + 2Fc2)/3
2269 reflections(Δ/σ)max = 0.001
197 parametersΔρmax = 0.91 e Å−3
66 restraintsΔρmin = −0.64 e Å−3
Crystal data top
[Ni3(C2H5N5)6(H2O)6](SO4)3·18H2OZ = 6
Mr = 1491.35Mo Kα radiation
Trigonal, R3cµ = 1.17 mm−1
a = 12.664 (2) ÅT = 295 K
c = 63.653 (6) Å0.43 × 0.32 × 0.23 mm
V = 8841 (2) Å3
Data collection top
Bruker APEX CCD
diffractometer		2269 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1868 reflections with I > 2σ(I)
Tmin = 0.676, Tmax = 0.775Rint = 0.026
24396 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.047All H-atom parameters refined
wR(F2) = 0.180Δρmax = 0.91 e Å−3
S = 1.33Δρmin = −0.64 e Å−3
2269 reflectionsAbsolute structure: ?
197 parametersFlack parameter: ?
66 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ni10.66670.33330.08330.0208 (3)
Ni20.66670.33330.025169 (9)0.0238 (2)
S11.00000.00000.00000.0730 (9)
S20.66670.3333−0.08615 (2)0.0328 (3)
O11.0719 (19)0.068 (2)0.0183 (3)0.118 (14)0.1666667
O20.8739 (9)−0.0434 (17)0.0039 (3)0.071 (7)0.1666667
O31.040 (2)0.0874 (19)−0.0174 (3)0.098 (11)0.1666667
O41.0253 (16)−0.0949 (13)−0.0048 (3)0.065 (6)0.1666667
O50.66670.3333−0.06391 (8)0.107 (3)
O60.6948 (4)0.4519 (3)−0.09445 (7)0.0967 (12)
O1w0.8185 (2)0.3878 (2)0.00548 (3)0.0359 (5)
H1w10.875 (2)0.390 (3)0.0128 (4)0.043*
H1w20.812 (3)0.352 (3)−0.0060 (3)0.043*
O2W1.0048 (2)0.4140 (3)0.03031 (5)0.0591 (8)
H2w11.060 (3)0.4875 (15)0.0326 (8)0.071*
H2w21.038 (3)0.370 (3)0.0293 (8)0.071*
O3w0.8269 (3)0.3208 (3)−0.03537 (4)0.0596 (7)
H3w10.781 (4)0.314 (3)−0.0456 (5)0.072*
H3w20.818 (4)0.251 (2)−0.0324 (6)0.072*
O4w1.1016 (4)0.2587 (4)0.03766 (9)0.0919 (12)
H4w11.099 (6)0.229 (6)0.0495 (4)0.110*
H4w21.111 (7)0.220 (5)0.0278 (6)0.110*
N10.3477 (3)0.1713 (3)0.08987 (5)0.0489 (9)
H1n10.394 (3)0.157 (4)0.0974 (6)0.059*
H1n20.2696 (11)0.134 (3)0.0909 (8)0.059*
N20.5086 (2)0.2574 (2)0.06450 (3)0.0265 (5)
N30.5114 (2)0.2826 (2)0.04272 (3)0.0255 (5)
N40.3585 (3)0.2501 (3)0.01736 (4)0.0492 (8)
H4n10.404 (3)0.290 (3)0.0070 (4)0.059*
H4n20.292 (2)0.194 (3)0.0123 (6)0.059*
N50.3218 (2)0.1958 (3)0.05358 (4)0.0348 (6)
H5n0.2477 (13)0.177 (3)0.0544 (6)0.042*
C10.3940 (3)0.2063 (3)0.07033 (5)0.0307 (6)
C20.3987 (2)0.2440 (3)0.03683 (4)0.0308 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0225 (3)0.0225 (3)0.0173 (5)0.01127 (16)0.0000.000
Ni20.0269 (3)0.0269 (3)0.0177 (4)0.01346 (15)0.0000.000
S10.0772 (13)0.0772 (13)0.0646 (19)0.0386 (7)0.0000.000
S20.0295 (4)0.0295 (4)0.0392 (7)0.0148 (2)0.0000.000
O10.118 (17)0.127 (16)0.108 (17)0.061 (11)−0.007 (9)0.000 (10)
O20.059 (10)0.080 (10)0.080 (10)0.039 (8)−0.015 (7)0.016 (8)
O30.108 (13)0.096 (14)0.083 (13)0.045 (9)0.012 (8)0.011 (9)
O40.069 (9)0.051 (8)0.098 (10)0.047 (7)−0.024 (8)−0.001 (7)
O50.131 (4)0.131 (4)0.058 (4)0.065 (2)0.0000.000
O60.092 (3)0.062 (2)0.134 (3)0.037 (2)−0.002 (3)0.023 (2)
O1w0.0364 (12)0.0448 (12)0.0269 (10)0.0205 (10)0.0055 (9)0.0021 (9)
O2W0.0448 (15)0.0558 (16)0.0683 (18)0.0187 (12)−0.0077 (13)0.0059 (14)
O3w0.0704 (19)0.0721 (18)0.0478 (14)0.0442 (16)−0.0095 (13)−0.0148 (13)
O4w0.065 (2)0.074 (2)0.139 (3)0.0363 (19)0.018 (3)0.031 (3)
N10.0305 (15)0.077 (2)0.0313 (15)0.0208 (14)0.0076 (12)0.0115 (13)
N20.0267 (12)0.0321 (12)0.0191 (11)0.0135 (9)0.0011 (9)0.0009 (8)
N30.0267 (11)0.0309 (11)0.0199 (10)0.0153 (9)−0.0014 (8)−0.0008 (9)
N40.0322 (14)0.073 (2)0.0317 (14)0.0182 (14)−0.0094 (11)0.0048 (13)
N50.0228 (11)0.0443 (14)0.0337 (13)0.0141 (11)−0.0003 (10)0.0005 (11)
C10.0249 (14)0.0370 (15)0.0267 (14)0.0128 (11)0.0016 (11)0.0001 (10)
C20.0293 (14)0.0344 (15)0.0287 (13)0.0159 (12)−0.0040 (10)−0.0023 (11)
Geometric parameters (Å, °) top
Ni1—N22.108 (2)S2—O51.415 (5)
Ni1—N2i2.108 (2)S2—O6ii1.458 (3)
Ni1—N2ii2.108 (2)S2—O6i1.458 (3)
Ni1—N2iii2.108 (2)S2—O61.458 (3)
Ni1—N2iv2.108 (2)O1w—H1w10.838 (10)
Ni1—N2v2.108 (2)O1w—H1w20.841 (10)
Ni2—N32.065 (2)O2W—H2w10.853 (10)
Ni2—N3i2.065 (2)O2W—H2w20.852 (10)
Ni2—N3ii2.065 (2)O3w—H3w10.848 (10)
Ni2—O1w2.101 (2)O3w—H3w20.852 (10)
Ni2—O1wi2.101 (2)O4w—H4w10.838 (10)
Ni2—O1wii2.101 (2)O4w—H4w20.845 (10)
S1—O4vi1.422 (8)N1—C11.352 (4)
S1—O4vii1.422 (8)N1—H1n10.846 (10)
S1—O4viii1.422 (8)N1—H1n20.859 (11)
S1—O41.422 (8)N2—C11.313 (4)
S1—O4ix1.422 (8)N2—N31.419 (3)
S1—O4x1.422 (8)N3—C21.311 (3)
S1—O2vii1.427 (9)N4—C21.357 (4)
S1—O2x1.427 (9)N4—H4n10.855 (10)
S1—O21.427 (9)N4—H4n20.846 (10)
S1—O2viii1.427 (9)N5—C21.365 (4)
S1—O2vi1.427 (9)N5—C11.367 (4)
S1—O2ix1.427 (9)N5—H5n0.847 (10)
N2iii—Ni1—N2iv90.85 (8)O2vii—S1—O2viii117.0 (4)
N2iii—Ni1—N2v90.85 (8)O4vi—S1—O2vi113.1 (8)
N2iv—Ni1—N2v90.85 (8)O2vii—S1—O2vi117.0 (4)
N2iii—Ni1—N2i177.85 (11)O2viii—S1—O2vi117.0 (4)
N2iv—Ni1—N2i90.70 (12)O4ix—S1—O2ix113.1 (8)
N2v—Ni1—N2i87.63 (12)O2x—S1—O2ix117.0 (4)
N2iii—Ni1—N287.64 (12)O2—S1—O2ix117.0 (4)
N2iv—Ni1—N2177.85 (11)O5—S2—O6ii111.26 (18)
N2v—Ni1—N290.70 (12)O5—S2—O6i111.26 (19)
N2i—Ni1—N290.85 (8)O6ii—S2—O6i107.6 (2)
N2iii—Ni1—N2ii90.70 (12)O5—S2—O6111.26 (18)
N2iv—Ni1—N2ii87.64 (12)O6ii—S2—O6107.6 (2)
N2v—Ni1—N2ii177.85 (11)O6i—S2—O6107.6 (2)
N2i—Ni1—N2ii90.85 (8)Ni2—O1w—H1w1108 (2)
N2—Ni1—N2ii90.85 (8)Ni2—O1w—H1w2121 (2)
N3i—Ni2—N3ii93.50 (8)H1w1—O1w—H1w2110.9 (17)
N3i—Ni2—N393.50 (8)H2w1—O2W—H2w2108.3 (17)
N3ii—Ni2—N393.50 (8)H3w1—O3w—H3w2109.4 (18)
N3i—Ni2—O1w90.39 (9)H4w1—O4w—H4w2113 (2)
N3ii—Ni2—O1w87.94 (9)C1—N1—H1n1111 (3)
N3—Ni2—O1w175.77 (8)C1—N1—H1n2116 (3)
N3i—Ni2—O1wii87.94 (9)H1n1—N1—H1n2125 (4)
N3ii—Ni2—O1wii175.77 (8)C1—N2—N3106.5 (2)
N3—Ni2—O1wii90.39 (9)C1—N2—Ni1128.87 (19)
O1w—Ni2—O1wii88.07 (9)N3—N2—Ni1122.82 (17)
N3i—Ni2—O1wi175.77 (8)C2—N3—N2107.2 (2)
N3ii—Ni2—O1wi90.39 (9)C2—N3—Ni2130.62 (18)
N3—Ni2—O1wi87.94 (9)N2—N3—Ni2120.73 (16)
O1w—Ni2—O1wi88.07 (9)C2—N4—H4n1125 (3)
O1wii—Ni2—O1wi88.07 (9)C2—N4—H4n2123 (3)
O4vi—S1—O4vii115.6 (5)H4n1—N4—H4n2107 (4)
O4vi—S1—O4viii115.6 (5)C2—N5—C1105.8 (2)
O4—S1—O4ix115.6 (5)C2—N5—H5n128 (2)
O4—S1—O4x115.6 (5)C1—N5—H5n125 (2)
O4ix—S1—O4x115.6 (5)N2—C1—N1127.9 (3)
O4vii—S1—O2vii113.1 (8)N2—C1—N5110.4 (3)
O4x—S1—O2x113.1 (8)N1—C1—N5121.7 (3)
O4—S1—O2113.1 (8)N3—C2—N4127.6 (3)
O2x—S1—O2117.0 (4)N3—C2—N5110.1 (2)
O4viii—S1—O2viii113.1 (8)N4—C2—N5122.3 (3)
N2iii—Ni1—N2—C1−41.1 (2)N3i—Ni2—N3—N232.54 (16)
N2v—Ni1—N2—C149.7 (2)N3ii—Ni2—N3—N2−61.19 (14)
N2i—Ni1—N2—C1137.3 (3)O1wii—Ni2—N3—N2120.50 (19)
N2ii—Ni1—N2—C1−131.8 (3)O1wi—Ni2—N3—N2−151.45 (19)
N2iii—Ni1—N2—N3121.4 (2)N3—N2—C1—N1−176.9 (3)
N2v—Ni1—N2—N3−147.8 (2)Ni1—N2—C1—N1−12.1 (4)
N2i—Ni1—N2—N3−60.12 (14)N3—N2—C1—N50.5 (3)
N2ii—Ni1—N2—N330.75 (16)Ni1—N2—C1—N5165.2 (2)
C1—N2—N3—C2−0.7 (3)C2—N5—C1—N2−0.1 (3)
Ni1—N2—N3—C2−166.61 (18)C2—N5—C1—N1177.4 (3)
C1—N2—N3—Ni2−168.31 (18)N2—N3—C2—N4179.5 (3)
Ni1—N2—N3—Ni225.8 (3)Ni2—N3—C2—N4−14.5 (5)
N3i—Ni2—N3—C2−131.8 (3)N2—N3—C2—N50.7 (3)
N3ii—Ni2—N3—C2134.5 (3)Ni2—N3—C2—N5166.6 (2)
O1wii—Ni2—N3—C2−43.8 (3)C1—N5—C2—N3−0.4 (3)
O1wi—Ni2—N3—C244.2 (3)C1—N5—C2—N4−179.3 (3)
Symmetry codes: (i) −y+1, x−y, z; (ii) −x+y+1, −x+1, z; (iii) x−y+1/3, −y+2/3, −z+1/6; (iv) −x+4/3, −x+y+2/3, −z+1/6; (v) y+1/3, x−1/3, −z+1/6; (vi) y+1, −x+y+1, −z; (vii) x−y, x−1, −z; (viii) −x+2, −y, −z; (ix) −y+1, x−y−1, z; (x) −x+y+2, −x+1, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1w—H1w1···O2w0.84 (1)1.89 (1)2.719 (4)173 (3)
O1w—H1w2···O3w0.84 (1)1.94 (2)2.754 (3)162 (4)
N4—H4n1···O1wi0.86 (1)2.33 (3)2.962 (4)131 (4)
N4—H4n2···O2ii0.85 (1)2.41 (3)3.15 (2)147 (4)
N5—H5n···O6xi0.85 (1)2.08 (2)2.843 (5)150 (3)
O2W—H2w1···O3wxii0.85 (1)2.12 (1)2.962 (4)168 (4)
O2W—H2w2···O4w0.85 (1)2.01 (2)2.828 (5)160 (5)
O3w—H3w1···O50.85 (1)1.97 (2)2.787 (5)162 (4)
O3w—H3w2···O4wvii0.85 (1)2.10 (2)2.885 (5)154 (5)
O4w—H4w1···O6xiii0.84 (1)1.98 (2)2.786 (6)163 (6)
O4w—H4w2···O10.85 (1)1.83 (4)2.57 (2)145 (6)
Symmetry codes: (i) −y+1, x−y, z; (ii) −x+y+1, −x+1, z; (xi) −x+y+1/3, y−1/3, z+1/6; (xii) −x+2, −y+1, −z; (vii) x−y, x−1, −z; (xiii) −x+y+4/3, y−1/3, z+1/6.
Table 1
Selected geometric parameters (Å) top
Ni1—N22.108 (2)Ni2—O1w2.101 (2)
Ni2—N32.065 (2)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1w—H1w1···O2w0.84 (1)1.89 (1)2.719 (4)173 (3)
O1w—H1w2···O3w0.84 (1)1.94 (2)2.754 (3)162 (4)
N4—H4n1···O1wi0.86 (1)2.33 (3)2.962 (4)131 (4)
N4—H4n2···O2ii0.85 (1)2.41 (3)3.15 (2)147 (4)
N5—H5n···O6iii0.85 (1)2.08 (2)2.843 (5)150 (3)
O2W—H2w1···O3wiv0.85 (1)2.12 (1)2.962 (4)168 (4)
O2W—H2w2···O4w0.85 (1)2.01 (2)2.828 (5)160 (5)
O3w—H3w1···O50.85 (1)1.97 (2)2.787 (5)162 (4)
O3w—H3w2···O4wv0.85 (1)2.10 (2)2.885 (5)154 (5)
O4w—H4w1···O6vi0.84 (1)1.98 (2)2.786 (6)163 (6)
O4w—H4w2···O10.85 (1)1.83 (4)2.57 (2)145 (6)
Symmetry codes: (i) −y+1, x−y, z; (ii) −x+y+1, −x+1, z; (iii) −x+y+1/3, y−1/3, z+1/6; (iv) −x+2, −y+1, −z; (v) x−y, x−1, −z; (vi) −x+y+4/3, y−1/3, z+1/6.
Acknowledgements top

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

references
References top

Antolini, L., Fabretti, A. C., Gatteschi, D., Giusti, A. & Sessoli, R. (1991). Inorg. Chem. 30, 4858–4860.

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

Bruker (2004). SAINT (Version 7.06A) and SMART (Version 7.06A). Bruker AXS Inc., Madison, Winsonsin, USA.

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

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Westrip, S. P. (2007). publCIF. In preparation.