Hexaaqua­hexa­kis(μ₂-3,5-diamino-4H-1,2,4-triazole)trinickel(II) tris­(hexa­fluoridosilicate) icosa­hydrate

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 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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](Si-F) = 0.003 Å
• Disorder in solvent or counterion
• R factor = 0.033
• wR factor = 0.107
• Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.96
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Si1
PLAT731_ALERT_1_C Bond    Calc   0.843(12), Rep     0.84(3) ......       2.50 su-Ra
              O2   -H21     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(3), Rep   0.850(10) ......       3.00 su-Ra
              N3   -H3      1.555   1.555
PLAT735_ALERT_1_C D-H     Calc   0.843(12), Rep     0.84(3) ......       2.50 su-Ra
              O2   -H21     1.555   1.555
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              F6 Si
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          4
              H4 O2
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          7
              H2 O

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         23
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT302_ALERT_4_G Anion/Solvent Disorder .........................       4.00 Perc.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  10 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

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

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

S2. Experimental

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).

S3. Refinement

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 U_iso(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

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

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

Crystal data

[Ni3(C2H5N5)6(H2O)6][SiF6]3·20H2O	Dx = 1.752 Mg m^−3
Mr = 1665.48	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c	Cell parameters from 5839 reflections
Hall symbol: -R 3 2"c	θ = 3.1–28.2°
a = 13.024 (1) Å	µ = 1.09 mm^−1
c = 64.462 (5) Å	T = 293 K
V = 9469.8 (9) Å^3	Block, blue
Z = 6	0.49 × 0.46 × 0.44 mm
F(000) = 5160

Data collection

Bruker APEX area-detector diffractometer	2420 independent reflections
Radiation source: fine-focus sealed tube	2093 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ϕ and ω scans	θmax = 27.5°, θmin = 3.1°
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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0612P)^2 + 17.0807P] where P = (Fo^2 + 2Fc^2)/3
2420 reflections	(Δ/σ)max = 0.001
185 parameters	Δρmax = 0.40 e Å^−3
23 restraints	Δρmin = −0.43 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Ni1—N1	2.062 (2)	Si2—F3	1.649 (3)
Ni1—N1^i	2.062 (2)	O1—H11	0.86 (3)
Ni1—N1^ii	2.062 (2)	O1—H12	0.85 (3)
Ni1—O1	2.104 (2)	O2—H21	0.84 (3)
Ni1—O1^i	2.104 (2)	O2—H22	0.84 (3)
Ni1—O1^ii	2.104 (2)	O3—H31	0.85 (3)
Ni2—N2^iii	2.111 (2)	O3—H32	0.84 (3)
Ni2—N2^iv	2.111 (2)	O4—H41	0.85 (3)
Ni2—N2^v	2.111 (2)	O4—H42	0.84 (3)
Ni2—N2^ii	2.111 (2)	O5—H51	0.85
Ni2—N2^i	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—F2^vi	1.6574 (15)	N2—C2	1.318 (3)
Si1—F2^vii	1.6574 (15)	N3—C2	1.356 (3)
Si1—F1^vii	1.6976 (15)	N3—C1	1.362 (3)
Si1—F1^vi	1.6976 (15)	N3—H3	0.85 (1)
Si1—F1	1.6976 (15)	N4—C2	1.354 (3)
Si2—F3^viii	1.649 (3)	N4—H4A	0.85 (3)
Si2—F3^ix	1.649 (3)	N4—H4B	0.84 (3)
Si2—F3^x	1.649 (3)	N5—C1	1.350 (3)
Si2—F3^xi	1.649 (3)	N5—H5A	0.84 (3)
Si2—F3^xii	1.649 (3)	N5—H5B	0.85 (3)
N1^ii—Ni1—N1^i	93.61 (6)	F1^vi—Si1—F1	87.74 (9)
N1^ii—Ni1—N1	93.61 (6)	F3^viii—Si2—F3^ix	89.21 (17)
N1^i—Ni1—N1	93.61 (6)	F3^viii—Si2—F3^x	89.21 (17)
N1^ii—Ni1—O1	87.31 (6)	F3^ix—Si2—F3^x	89.21 (17)
N1^i—Ni1—O1	90.45 (6)	F3^viii—Si2—F3^xi	90.79 (17)
N1—Ni1—O1	175.77 (6)	F3^ix—Si2—F3^xi	90.79 (17)
N1^ii—Ni1—O1^i	90.45 (6)	F3^x—Si2—F3^xi	179.995 (1)
N1^i—Ni1—O1^i	175.77 (6)	F3^viii—Si2—F3^xii	90.79 (17)
N1—Ni1—O1^i	87.31 (6)	F3^ix—Si2—F3^xii	179.995 (1)
O1—Ni1—O1^i	88.56 (6)	F3^x—Si2—F3^xii	90.79 (17)
N1^ii—Ni1—O1^ii	175.78 (6)	F3^xi—Si2—F3^xii	89.21 (17)
N1^i—Ni1—O1^ii	87.31 (6)	F3^viii—Si2—F3	179.997 (1)
N1—Ni1—O1^ii	90.45 (6)	F3^ix—Si2—F3	90.79 (17)
O1—Ni1—O1^ii	88.56 (6)	F3^x—Si2—F3	90.79 (17)
O1^i—Ni1—O1^ii	88.56 (6)	F3^xi—Si2—F3	89.21 (17)
N2^iii—Ni2—N2^iv	90.87 (6)	F3^xii—Si2—F3	89.21 (17)
N2^iii—Ni2—N2^v	90.87 (6)	Ni1—O1—H11	110 (2)
N2^iv—Ni2—N2^v	90.87 (6)	Ni1—O1—H12	126 (2)
N2^iii—Ni2—N2^ii	87.57 (8)	H11—O1—H12	109 (2)
N2^iv—Ni2—N2^ii	177.79 (8)	H21—O2—H22	111 (2)
N2^v—Ni2—N2^ii	90.72 (8)	H31—O3—H32	110 (2)
N2^iii—Ni2—N2^i	90.72 (8)	H41—O4—H42	111 (2)
N2^iv—Ni2—N2^i	87.57 (8)	H51—O5—H52	109.4
N2^v—Ni2—N2^i	177.79 (8)	C1—N1—N2	107.04 (15)
N2^ii—Ni2—N2^i	90.88 (6)	C1—N1—Ni1	130.48 (12)
N2^iii—Ni2—N2	177.79 (8)	N2—N1—Ni1	121.05 (11)
N2^iv—Ni2—N2	90.72 (8)	C2—N2—N1	106.38 (15)
N2^v—Ni2—N2	87.57 (8)	C2—N2—Ni2	129.31 (13)
N2^ii—Ni2—N2	90.88 (6)	N1—N2—Ni2	122.87 (12)
N2^i—Ni2—N2	90.88 (6)	C2—N3—C1	106.38 (16)
F2—Si1—F2^vi	91.80 (9)	C2—N3—H3	122 (2)
F2—Si1—F2^vii	91.80 (9)	C1—N3—H3	132 (2)
F2^vi—Si1—F2^vii	91.80 (9)	C2—N4—H4A	125 (2)
F2—Si1—F1^vii	90.36 (8)	C2—N4—H4B	122 (3)
F2^vi—Si1—F1^vii	177.12 (10)	H4A—N4—H4B	111 (3)
F2^vii—Si1—F1^vii	90.03 (8)	C1—N5—H5A	117 (2)
F2—Si1—F1^vi	177.12 (10)	C1—N5—H5B	116 (2)
F2^vi—Si1—F1^vi	90.03 (8)	H5A—N5—H5B	126 (3)
F2^vii—Si1—F1^vi	90.36 (8)	N1—C1—N5	127.37 (19)
F1^vii—Si1—F1^vi	87.74 (9)	N1—C1—N3	109.86 (16)
F2—Si1—F1	90.03 (8)	N5—C1—N3	122.76 (18)
F2^vi—Si1—F1	90.36 (8)	N2—C2—N4	126.92 (19)
F2^vii—Si1—F1	177.12 (10)	N2—C2—N3	110.33 (17)
F1^vii—Si1—F1	87.74 (9)	N4—C2—N3	122.67 (19)
N1^ii—Ni1—N1—C1	−135.1 (2)	N2^iv—Ni2—N2—N1	146.76 (16)
N1^i—Ni1—N1—C1	131.1 (2)	N2^v—Ni2—N2—N1	−122.40 (15)
O1^i—Ni1—N1—C1	−44.81 (19)	N2^ii—Ni2—N2—N1	−31.71 (12)
O1^ii—Ni1—N1—C1	43.72 (19)	N2^i—Ni2—N2—N1	59.18 (10)
N1^ii—Ni1—N1—N2	60.39 (10)	N2—N1—C1—N5	−179.0 (2)
N1^i—Ni1—N1—N2	−33.46 (12)	Ni1—N1—C1—N5	14.9 (3)
O1^i—Ni1—N1—N2	150.67 (13)	N2—N1—C1—N3	−0.1 (2)
O1^ii—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)
N2^iv—Ni2—N2—C2	−48.86 (15)	N1—N2—C2—N3	−0.9 (2)
N2^v—Ni2—N2—C2	41.98 (14)	Ni2—N2—C2—N3	−167.25 (14)
N2^ii—Ni2—N2—C2	132.67 (18)	C1—N3—C2—N2	0.8 (2)
N2^i—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, º)

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···O3^xiii	0.84 (3)	2.12 (3)	2.961 (3)	175 (4)
O3—H31···O4^ix	0.85 (3)	2.05 (3)	2.861 (3)	159 (3)
O3—H32···F1^ix	0.84 (3)	2.13 (3)	2.904 (2)	153 (3)
O4—H41···F2^xiv	0.85 (3)	2.23 (3)	2.950 (3)	143 (4)
O4—H42···F3^xi	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···F2^iii	0.85 (3)	1.97 (3)	2.764 (2)	157 (3)
N4—H4b···F1^iii	0.84 (3)	2.14 (3)	2.974 (3)	170 (3)
N5—H5a···O1^i	0.84 (3)	2.23 (3)	2.942 (3)	142 (3)
N5—H5b···F3^xv	0.85 (3)	2.08 (3)	2.909 (3)	167 (3)

Symmetry codes: (i) −y+1, x−y, z; (iii) y+1/3, x−1/3, −z+1/6; (ix) x−y−1/3, x−2/3, −z+1/3; (xi) −y, x−y−1, z; (xiii) −x+5/3, −y+1/3, −z+1/3; (xiv) y+1/3, x−4/3, −z+1/6; (xv) x, y+1, z.