Hexaaqua-hexa-kis(μ(2)-3,5-diamino-4H-1,2,4-triazole)trinickel(II) tris-(hexa-fluoridosilicate) icosa-hydrate.

The trinuclear cation of the title compound, [Ni(3)(C(2)H(5)N(5))(6)(H(2)O)(6)][SiF(6)](3)·20H(2)O, 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 octa-hedral 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 hexa-fluroridosilicate anion lies on a site of 3 symmetry and the other lies on a site of symmetry. The hexa-cation, dianions and uncoordinated water mol-ecules inter-act through hydrogen bonds to form a three-dimensional network. One uncoordinated water molecule is disordered, with site occupancy 0.3.

Related literature

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

Experimental

Crystal data

[Ni3(C2H5N5)6(H2O)6][SiF6]3·20H2O

M = 1665.48

Trigonal,

a = 13.024 (1) Å

c = 64.462 (5) Å

V = 9469.8 (9) Å3

Z = 6

Mo Kα radiation

μ = 1.09 mm−1

T = 293 (2) K

0.49 × 0.46 × 0.44 mm

Data collection

Bruker APEX area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.560, T max = 0.646

25347 measured reflections

2420 independent reflections

2093 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.106

S = 1.06

2420 reflections

185 parameters

23 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.40 e Å−3

Δρmin = −0.42 e Å−3

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; 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 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808013329/si2084sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808013329/si2084Isup2.hkl

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

[Ni3(C2H5N5)6(H2O)6][SiF6]3·20H2O	Z = 6
Mr = 1665.48	F000 = 5160
Trigonal, R3c	Dx = 1.752 Mg m−3
Hall symbol: -R 3 2"c	Mo Kα radiation λ = 0.71073 Å
a = 13.024 (1) Å	Cell parameters from 5839 reflections
b = 13.024 Å	θ = 3.1–28.2º
c = 64.462 (5) Å	µ = 1.09 mm−1
α = 90º	T = 293 (2) K
β = 90º	Block, blue
γ = 120º	0.49 × 0.46 × 0.44 mm
V = 9469.8 (9) Å3

Bruker APEX area-detector diffractometer	2420 independent reflections
Radiation source: fine-focus sealed tube	2093 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.021
T = 293(2) K	θmax = 27.5º
φ and ω scans	θmin = 3.1º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −16→16
Tmin = 0.560, Tmax = 0.646	k = −16→16
25347 measured reflections	l = −79→83

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033	H 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 reflections	Δρmax = 0.40 e Å−3
185 parameters	Δρmin = −0.42 e Å−3
23 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.6667	0.3333	0.140787 (6)	0.02689 (14)
Ni2	0.6667	0.3333	0.0833	0.02377 (16)
Si1	1.0000	0.0000	0.083802 (16)	0.0331 (2)
Si2	0.3333	−0.3333	0.1667	0.0552 (5)
F1	0.89685 (14)	0.00226 (15)	0.09960 (2)	0.0623 (4)
F2	1.00168 (16)	0.10635 (14)	0.06943 (3)	0.0648 (4)
F3	0.3983 (3)	−0.3868 (3)	0.15169 (5)	0.1399 (12)
O1	0.72286 (15)	0.24063 (14)	0.16010 (2)	0.0398 (3)
H11	0.723 (3)	0.1843 (18)	0.1533 (3)	0.060*
H12	0.699 (3)	0.217 (2)	0.1724 (2)	0.060*
O2	0.7536 (2)	0.0854 (2)	0.13625 (4)	0.0660 (5)
H21	0.713 (2)	0.0108 (10)	0.1358 (6)	0.099*
H22	0.8267 (10)	0.108 (3)	0.1361 (7)	0.099*
O3	0.65459 (19)	0.15616 (17)	0.19955 (3)	0.0599 (5)
H31	0.5874 (17)	0.094 (2)	0.1978 (5)	0.090*
H32	0.650 (3)	0.197 (2)	0.2092 (4)	0.090*
O4	0.6041 (2)	−0.1661 (3)	0.12859 (4)	0.0796 (6)
H41	0.576 (3)	−0.184 (4)	0.1164 (3)	0.119*
H42	0.551 (3)	−0.182 (4)	0.1374 (4)	0.119*
O5	0.664 (3)	−0.1549 (17)	0.0893 (3)	0.185 (7)	0.3333
H51	0.7382	−0.1072	0.0905	0.278*	0.3333
H52	0.6338	−0.1239	0.0816	0.278*	0.3333
N1	0.61588 (14)	0.43372 (14)	0.12352 (2)	0.0290 (3)
N2	0.59282 (14)	0.41343 (14)	0.10195 (2)	0.0293 (3)
N3	0.52872 (17)	0.53100 (17)	0.11289 (3)	0.0381 (4)
H3	0.500 (2)	0.576 (2)	0.1117 (4)	0.057*
N4	0.5100 (2)	0.4865 (2)	0.07683 (3)	0.0508 (5)
H4A	0.514 (3)	0.449 (3)	0.0663 (4)	0.076*
H4B	0.468 (2)	0.517 (3)	0.0744 (6)	0.076*
N5	0.5810 (2)	0.5478 (2)	0.14862 (3)	0.0556 (6)
H5A	0.625 (3)	0.540 (3)	0.1574 (4)	0.083*
H5B	0.535 (3)	0.575 (3)	0.1509 (5)	0.083*
C1	0.57611 (18)	0.50413 (18)	0.12943 (3)	0.0343 (4)
C2	0.54160 (17)	0.47436 (17)	0.09630 (3)	0.0336 (4)

	U11	U22	U33	U12	U13	U23
Ni1	0.02997 (17)	0.02997 (17)	0.0207 (2)	0.01499 (9)	0.000	0.000
Ni2	0.0253 (2)	0.0253 (2)	0.0207 (3)	0.01265 (10)	0.000	0.000
Si1	0.0300 (3)	0.0300 (3)	0.0394 (5)	0.01500 (15)	0.000	0.000
Si2	0.0333 (5)	0.0333 (5)	0.0992 (15)	0.0166 (2)	0.000	0.000
F1	0.0555 (9)	0.0683 (10)	0.0701 (10)	0.0363 (8)	0.0170 (7)	0.0016 (8)
F2	0.0710 (10)	0.0574 (9)	0.0741 (10)	0.0382 (8)	−0.0004 (8)	0.0199 (8)
F3	0.146 (3)	0.176 (3)	0.163 (3)	0.129 (3)	0.0160 (19)	−0.025 (2)
O1	0.0497 (8)	0.0454 (8)	0.0292 (7)	0.0274 (7)	−0.0020 (6)	0.0041 (6)
O2	0.0624 (12)	0.0722 (13)	0.0750 (13)	0.0424 (11)	−0.0019 (10)	−0.0133 (11)
O3	0.0764 (13)	0.0541 (11)	0.0436 (9)	0.0283 (10)	0.0132 (9)	−0.0001 (8)
O4	0.0709 (15)	0.0812 (15)	0.0871 (16)	0.0383 (13)	−0.0030 (12)	−0.0025 (14)
O5	0.119 (7)	0.216 (10)	0.178 (13)	0.051 (7)	−0.015 (9)	−0.010 (8)
N1	0.0349 (8)	0.0329 (8)	0.0226 (7)	0.0194 (6)	0.0006 (6)	−0.0010 (6)
N2	0.0352 (8)	0.0355 (8)	0.0219 (7)	0.0213 (7)	−0.0009 (6)	−0.0005 (6)
N3	0.0476 (10)	0.0440 (10)	0.0366 (9)	0.0334 (8)	−0.0010 (7)	−0.0015 (7)
N4	0.0743 (15)	0.0720 (14)	0.0343 (10)	0.0578 (13)	−0.0109 (9)	−0.0043 (9)
N5	0.0821 (16)	0.0803 (15)	0.0348 (10)	0.0635 (14)	−0.0071 (10)	−0.0157 (10)
C1	0.0390 (10)	0.0367 (10)	0.0319 (9)	0.0224 (9)	0.0008 (8)	−0.0023 (8)
C2	0.0377 (10)	0.0374 (10)	0.0312 (9)	0.0229 (9)	−0.0009 (7)	0.0006 (7)

Ni1—N1	2.062 (2)	Si2—F3	1.649 (3)
Ni1—N1i	2.062 (2)	O1—H11	0.86 (3)
Ni1—N1ii	2.062 (2)	O1—H12	0.85 (3)
Ni1—O1	2.104 (2)	O2—H21	0.84 (3)
Ni1—O1i	2.104 (2)	O2—H22	0.84 (3)
Ni1—O1ii	2.104 (2)	O3—H31	0.85 (3)
Ni2—N2iii	2.111 (2)	O3—H32	0.84 (3)
Ni2—N2iv	2.111 (2)	O4—H41	0.85 (3)
Ni2—N2v	2.111 (2)	O4—H42	0.84 (3)
Ni2—N2ii	2.111 (2)	O5—H51	0.85
Ni2—N2i	2.111 (2)	O5—H52	0.85
Ni2—N2	2.111 (2)	N1—C1	1.315 (2)
Si1—F2	1.6574 (15)	N1—N2	1.419 (2)
Si1—F2vi	1.6574 (15)	N2—C2	1.318 (3)
Si1—F2vii	1.6574 (15)	N3—C2	1.356 (3)
Si1—F1vii	1.6976 (15)	N3—C1	1.362 (3)
Si1—F1vi	1.6976 (15)	N3—H3	0.85 (1)
Si1—F1	1.6976 (15)	N4—C2	1.354 (3)
Si2—F3viii	1.649 (3)	N4—H4A	0.85 (3)
Si2—F3ix	1.649 (3)	N4—H4B	0.84 (3)
Si2—F3x	1.649 (3)	N5—C1	1.350 (3)
Si2—F3xi	1.649 (3)	N5—H5A	0.84 (3)
Si2—F3xii	1.649 (3)	N5—H5B	0.85 (3)
N1ii—Ni1—N1i	93.61 (6)	F1vi—Si1—F1	87.74 (9)
N1ii—Ni1—N1	93.61 (6)	F3viii—Si2—F3ix	89.21 (17)
N1i—Ni1—N1	93.61 (6)	F3viii—Si2—F3x	89.21 (17)
N1ii—Ni1—O1	87.31 (6)	F3ix—Si2—F3x	89.21 (17)
N1i—Ni1—O1	90.45 (6)	F3viii—Si2—F3xi	90.79 (17)
N1—Ni1—O1	175.77 (6)	F3ix—Si2—F3xi	90.79 (17)
N1ii—Ni1—O1i	90.45 (6)	F3x—Si2—F3xi	179.995 (1)
N1i—Ni1—O1i	175.77 (6)	F3viii—Si2—F3xii	90.79 (17)
N1—Ni1—O1i	87.31 (6)	F3ix—Si2—F3xii	179.995 (1)
O1—Ni1—O1i	88.56 (6)	F3x—Si2—F3xii	90.79 (17)
N1ii—Ni1—O1ii	175.78 (6)	F3xi—Si2—F3xii	89.21 (17)
N1i—Ni1—O1ii	87.31 (6)	F3viii—Si2—F3	179.997 (1)
N1—Ni1—O1ii	90.45 (6)	F3ix—Si2—F3	90.79 (17)
O1—Ni1—O1ii	88.56 (6)	F3x—Si2—F3	90.79 (17)
O1i—Ni1—O1ii	88.56 (6)	F3xi—Si2—F3	89.21 (17)
N2iii—Ni2—N2iv	90.87 (6)	F3xii—Si2—F3	89.21 (17)
N2iii—Ni2—N2v	90.87 (6)	Ni1—O1—H11	110 (2)
N2iv—Ni2—N2v	90.87 (6)	Ni1—O1—H12	126 (2)
N2iii—Ni2—N2ii	87.57 (8)	H11—O1—H12	109 (2)
N2iv—Ni2—N2ii	177.79 (8)	H21—O2—H22	111 (2)
N2v—Ni2—N2ii	90.72 (8)	H31—O3—H32	110 (2)
N2iii—Ni2—N2i	90.72 (8)	H41—O4—H42	111 (2)
N2iv—Ni2—N2i	87.57 (8)	H51—O5—H52	109.4
N2v—Ni2—N2i	177.79 (8)	C1—N1—N2	107.04 (15)
N2ii—Ni2—N2i	90.88 (6)	C1—N1—Ni1	130.48 (12)
N2iii—Ni2—N2	177.79 (8)	N2—N1—Ni1	121.05 (11)
N2iv—Ni2—N2	90.72 (8)	C2—N2—N1	106.38 (15)
N2v—Ni2—N2	87.57 (8)	C2—N2—Ni2	129.31 (13)
N2ii—Ni2—N2	90.88 (6)	N1—N2—Ni2	122.87 (12)
N2i—Ni2—N2	90.88 (6)	C2—N3—C1	106.38 (16)
F2—Si1—F2vi	91.80 (9)	C2—N3—H3	122 (2)
F2—Si1—F2vii	91.80 (9)	C1—N3—H3	132 (2)
F2vi—Si1—F2vii	91.80 (9)	C2—N4—H4A	125 (2)
F2—Si1—F1vii	90.36 (8)	C2—N4—H4B	122 (3)
F2vi—Si1—F1vii	177.12 (10)	H4A—N4—H4B	111 (3)
F2vii—Si1—F1vii	90.03 (8)	C1—N5—H5A	117 (2)
F2—Si1—F1vi	177.12 (10)	C1—N5—H5B	116 (2)
F2vi—Si1—F1vi	90.03 (8)	H5A—N5—H5B	126 (3)
F2vii—Si1—F1vi	90.36 (8)	N1—C1—N5	127.37 (19)
F1vii—Si1—F1vi	87.74 (9)	N1—C1—N3	109.86 (16)
F2—Si1—F1	90.03 (8)	N5—C1—N3	122.76 (18)
F2vi—Si1—F1	90.36 (8)	N2—C2—N4	126.92 (19)
F2vii—Si1—F1	177.12 (10)	N2—C2—N3	110.33 (17)
F1vii—Si1—F1	87.74 (9)	N4—C2—N3	122.67 (19)
N1ii—Ni1—N1—C1	−135.1 (2)	N2iv—Ni2—N2—N1	146.76 (16)
N1i—Ni1—N1—C1	131.1 (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—C1	43.72 (19)	N2i—Ni2—N2—N1	59.18 (10)
N1ii—Ni1—N1—N2	60.39 (10)	N2—N1—C1—N5	−179.0 (2)
N1i—Ni1—N1—N2	−33.46 (12)	Ni1—N1—C1—N5	14.9 (3)
O1i—Ni1—N1—N2	150.67 (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—C2	0.6 (2)	C2—N3—C1—N1	−0.4 (2)
Ni1—N1—N2—C2	168.37 (13)	C2—N3—C1—N5	178.5 (2)
C1—N1—N2—Ni2	168.09 (13)	N1—N2—C2—N4	176.0 (2)
Ni1—N1—N2—Ni2	−24.17 (18)	Ni2—N2—C2—N4	9.6 (3)
N2iv—Ni2—N2—C2	−48.86 (15)	N1—N2—C2—N3	−0.9 (2)
N2v—Ni2—N2—C2	41.98 (14)	Ni2—N2—C2—N3	−167.25 (14)
N2ii—Ni2—N2—C2	132.67 (18)	C1—N3—C2—N2	0.8 (2)
N2i—Ni2—N2—C2	−136.44 (18)	C1—N3—C2—N4	−176.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···O2	0.86 (3)	1.88 (3)	2.724 (3)	168 (3)
O1—H12···O3	0.85 (3)	1.89 (3)	2.737 (2)	174 (3)
O2—H21···O4	0.84 (3)	2.07 (3)	2.896 (4)	168 (4)
O2—H22···O3xiii	0.84 (3)	2.12 (3)	2.961 (3)	175 (4)
O3—H31···O4ix	0.85 (3)	2.05 (3)	2.861 (3)	159 (3)
O3—H32···F1ix	0.84 (3)	2.13 (3)	2.904 (2)	153 (3)
O4—H41···F2xiv	0.85 (3)	2.23 (3)	2.950 (3)	143 (4)
O4—H42···F3xi	0.84 (3)	2.16 (3)	2.973 (4)	162 (4)
O4—H41···O5	0.85 (3)	2.03 (3)	2.64 (2)	128 (4)
O5—H51···F1	0.85	1.92	2.76 (3)	167
N3—H3···F2iii	0.85 (3)	1.97 (3)	2.764 (2)	157 (3)
N4—H4b···F1iii	0.84 (3)	2.14 (3)	2.974 (3)	170 (3)
N5—H5a···O1i	0.84 (3)	2.23 (3)	2.942 (3)	142 (3)
N5—H5b···F3xv	0.85 (3)	2.08 (3)	2.909 (3)	167 (3)

Table 1

Selected bond lengths (Å)

Ni1—N1	2.062 (2)
Ni1—O1	2.104 (2)
Ni2—N2	2.111 (2)