Hexaaqua­hexa­kis(μ2-3,5-diamino-1,2,4-triazole)trinickel(II) tris­ulfate octa­deca­hydrate

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

doi:10.1107/S160053680702051X

Hexaaquahexakis(μ₂-3,5-diamino-1,2,4-triazole)trinickel(II) trisulfate octadecahydrate

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

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.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702051X/hb2392sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680702051X/hb2392Isup2.hkl Contains datablock I

CCDC reference: 648073

checkCIF report

Key indicators

Single-crystal X-ray study
T = 295 K
Mean (S-O) = 0.005 Å
Disorder in solvent or counterion
R factor = 0.047
wR factor = 0.180
Data-to-parameter ratio = 11.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT731_ALERT_1_B Bond    Calc     0.84(6), Rep   0.845(10) ......       6.00 su-Ra
              O4W  -H4W2    1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.84(6), Rep   0.850(10) ......       6.00 su-Ra
              O4W  -H8#     1.555   1.555

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.99
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         S2
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      12.00 Perc.
PLAT417_ALERT_2_C Short Inter D-H..H-D       H1W2   ..  H3W2    ..       2.14 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         12
PLAT731_ALERT_1_C Bond    Calc     0.84(3), Rep   0.838(10) ......       3.00 su-Ra
              O1W  -H1W1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(4), Rep   0.852(10) ......       4.00 su-Ra
              O2W  -H2W2    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(4), Rep   0.848(10) ......       4.00 su-Ra
              O3W  -H3W1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.86(3), Rep   0.852(10) ......       3.00 su-Ra
              O3W  -H3W2    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(4), Rep   0.838(10) ......       4.00 su-Ra
              O4W  -H4W1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(4), Rep   0.846(10) ......       4.00 su-Ra
              N1   -H1N1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.86(3), Rep   0.859(11) ......       2.73 su-Ra
              N1   -H1N2    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.86(3), Rep   0.855(10) ......       3.00 su-Ra
              N4   -H4N1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(3), Rep   0.846(10) ......       3.00 su-Ra
              N4   -H4N2    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(3), Rep   0.847(10) ......       3.00 su-Ra
              N5   -H5N     1.555   1.555
PLAT732_ALERT_1_C Angle   Calc      109(4), Rep   108.3(17) ......       2.35 su-Ra
              H2W1 -O2W  -H2W2    1.555   1.555   1.555
PLAT732_ALERT_1_C Angle   Calc      110(4), Rep   109.4(18) ......       2.22 su-Ra
              H3W1 -O3W  -H3W2    1.555   1.555   1.555
PLAT732_ALERT_1_C Angle   Calc      113(6), Rep      113(2) ......       3.00 su-Ra
              H4W1 -O4W  -H4W2    1.555   1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(3), Rep   0.840(10) ......       3.00 su-Ra
              O1W  -H1#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.86(3), Rep   0.860(10) ......       3.00 su-Ra
              N4   -H11#    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Ra
              N4   -H12#    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Ra
              N5   -H5N     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Ra
              O2W  -H4#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Ra
              O3W  -H5#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.86(3), Rep   0.850(10) ......       3.00 su-Ra
              O3W  -H6#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(4), Rep   0.840(10) ......       4.00 su-Ra
              O4W  -H7#     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.88(3), Rep   1.890(10) ......       3.00 su-Ra
              H1#  -O2W     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.97(5), Rep     1.97(2) ......       2.50 su-Ra
              H5#  -O5      1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.98(5), Rep     1.98(2) ......       2.50 su-Ra
              H7#  -O6      1.555  16.644
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          6
              H2 O

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C12 H78 N30 Ni3 O36 S3
            Atom count from _chemical_formula_moiety:
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         66

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

  30 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   5 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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).

Structure description top

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

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

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)₃·18H₂O	D_x = 1.681 Mg m⁻³
M_r = 1491.35	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c	Cell parameters from 7201 reflections
Hall symbol: -R 3 2"c	θ = 3.2–28.2°
a = 12.664 (2) Å	µ = 1.17 mm⁻¹
c = 63.653 (6) Å	T = 295 K
V = 8841 (2) Å³	Block, blue
Z = 6	0.43 × 0.32 × 0.23 mm
F(000) = 4680

Data collection top

Bruker APEX CCD diffractometer	2269 independent reflections
Radiation source: fine-focus sealed tube	1868 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
φ and ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→15
T_min = 0.676, T_max = 0.775	k = −16→16
24396 measured reflections	l = −82→81

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.180	All H-atom parameters refined
S = 1.33	w = 1/[σ²(F_o²) + (0.1P)² + 1P] where P = (F_o² + 2F_c²)/3
2269 reflections	(Δ/σ)_max = 0.001
197 parameters	Δρ_max = 0.91 e Å⁻³
66 restraints	Δρ_min = −0.64 e Å⁻³

Crystal data top

[Ni₃(C₂H₅N₅)₆(H₂O)₆](SO₄)₃·18H₂O	Z = 6
M_r = 1491.35	Mo Kα radiation
Trigonal, R3c	µ = 1.17 mm⁻¹
a = 12.664 (2) Å	T = 295 K
c = 63.653 (6) Å	0.43 × 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)
T_min = 0.676, T_max = 0.775	R_int = 0.026
24396 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	66 restraints
wR(F²) = 0.180	All H-atom parameters refined
S = 1.33	Δρ_max = 0.91 e Å⁻³
2269 reflections	Δρ_min = −0.64 e Å⁻³
197 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.6667	0.3333	0.0833	0.0208 (3)
Ni2	0.6667	0.3333	0.025169 (9)	0.0238 (2)
S1	1.0000	0.0000	0.0000	0.0730 (9)
S2	0.6667	0.3333	−0.08615 (2)	0.0328 (3)
O1	1.0719 (19)	0.068 (2)	0.0183 (3)	0.118 (14)	0.1666667
O2	0.8739 (9)	−0.0434 (17)	0.0039 (3)	0.071 (7)	0.1666667
O3	1.040 (2)	0.0874 (19)	−0.0174 (3)	0.098 (11)	0.1666667
O4	1.0253 (16)	−0.0949 (13)	−0.0048 (3)	0.065 (6)	0.1666667
O5	0.6667	0.3333	−0.06391 (8)	0.107 (3)
O6	0.6948 (4)	0.4519 (3)	−0.09445 (7)	0.0967 (12)
O1w	0.8185 (2)	0.3878 (2)	0.00548 (3)	0.0359 (5)
H1w1	0.875 (2)	0.390 (3)	0.0128 (4)	0.043*
H1w2	0.812 (3)	0.352 (3)	−0.0060 (3)	0.043*
O2W	1.0048 (2)	0.4140 (3)	0.03031 (5)	0.0591 (8)
H2w1	1.060 (3)	0.4875 (15)	0.0326 (8)	0.071*
H2w2	1.038 (3)	0.370 (3)	0.0293 (8)	0.071*
O3w	0.8269 (3)	0.3208 (3)	−0.03537 (4)	0.0596 (7)
H3w1	0.781 (4)	0.314 (3)	−0.0456 (5)	0.072*
H3w2	0.818 (4)	0.251 (2)	−0.0324 (6)	0.072*
O4w	1.1016 (4)	0.2587 (4)	0.03766 (9)	0.0919 (12)
H4w1	1.099 (6)	0.229 (6)	0.0495 (4)	0.110*
H4w2	1.111 (7)	0.220 (5)	0.0278 (6)	0.110*
N1	0.3477 (3)	0.1713 (3)	0.08987 (5)	0.0489 (9)
H1n1	0.394 (3)	0.157 (4)	0.0974 (6)	0.059*
H1n2	0.2696 (11)	0.134 (3)	0.0909 (8)	0.059*
N2	0.5086 (2)	0.2574 (2)	0.06450 (3)	0.0265 (5)
N3	0.5114 (2)	0.2826 (2)	0.04272 (3)	0.0255 (5)
N4	0.3585 (3)	0.2501 (3)	0.01736 (4)	0.0492 (8)
H4n1	0.404 (3)	0.290 (3)	0.0070 (4)	0.059*
H4n2	0.292 (2)	0.194 (3)	0.0123 (6)	0.059*
N5	0.3218 (2)	0.1958 (3)	0.05358 (4)	0.0348 (6)
H5n	0.2477 (13)	0.177 (3)	0.0544 (6)	0.042*
C1	0.3940 (3)	0.2063 (3)	0.07033 (5)	0.0307 (6)
C2	0.3987 (2)	0.2440 (3)	0.03683 (4)	0.0308 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0225 (3)	0.0225 (3)	0.0173 (5)	0.01127 (16)	0.000	0.000
Ni2	0.0269 (3)	0.0269 (3)	0.0177 (4)	0.01346 (15)	0.000	0.000
S1	0.0772 (13)	0.0772 (13)	0.0646 (19)	0.0386 (7)	0.000	0.000
S2	0.0295 (4)	0.0295 (4)	0.0392 (7)	0.0148 (2)	0.000	0.000
O1	0.118 (17)	0.127 (16)	0.108 (17)	0.061 (11)	−0.007 (9)	0.000 (10)
O2	0.059 (10)	0.080 (10)	0.080 (10)	0.039 (8)	−0.015 (7)	0.016 (8)
O3	0.108 (13)	0.096 (14)	0.083 (13)	0.045 (9)	0.012 (8)	0.011 (9)
O4	0.069 (9)	0.051 (8)	0.098 (10)	0.047 (7)	−0.024 (8)	−0.001 (7)
O5	0.131 (4)	0.131 (4)	0.058 (4)	0.065 (2)	0.000	0.000
O6	0.092 (3)	0.062 (2)	0.134 (3)	0.037 (2)	−0.002 (3)	0.023 (2)
O1w	0.0364 (12)	0.0448 (12)	0.0269 (10)	0.0205 (10)	0.0055 (9)	0.0021 (9)
O2W	0.0448 (15)	0.0558 (16)	0.0683 (18)	0.0187 (12)	−0.0077 (13)	0.0059 (14)
O3w	0.0704 (19)	0.0721 (18)	0.0478 (14)	0.0442 (16)	−0.0095 (13)	−0.0148 (13)
O4w	0.065 (2)	0.074 (2)	0.139 (3)	0.0363 (19)	0.018 (3)	0.031 (3)
N1	0.0305 (15)	0.077 (2)	0.0313 (15)	0.0208 (14)	0.0076 (12)	0.0115 (13)
N2	0.0267 (12)	0.0321 (12)	0.0191 (11)	0.0135 (9)	0.0011 (9)	0.0009 (8)
N3	0.0267 (11)	0.0309 (11)	0.0199 (10)	0.0153 (9)	−0.0014 (8)	−0.0008 (9)
N4	0.0322 (14)	0.073 (2)	0.0317 (14)	0.0182 (14)	−0.0094 (11)	0.0048 (13)
N5	0.0228 (11)	0.0443 (14)	0.0337 (13)	0.0141 (11)	−0.0003 (10)	0.0005 (11)
C1	0.0249 (14)	0.0370 (15)	0.0267 (14)	0.0128 (11)	0.0016 (11)	0.0001 (10)
C2	0.0293 (14)	0.0344 (15)	0.0287 (13)	0.0159 (12)	−0.0040 (10)	−0.0023 (11)

Geometric parameters (Å, º) top

Ni1—N2	2.108 (2)	S2—O5	1.415 (5)
Ni1—N2ⁱ	2.108 (2)	S2—O6ⁱⁱ	1.458 (3)
Ni1—N2ⁱⁱ	2.108 (2)	S2—O6ⁱ	1.458 (3)
Ni1—N2ⁱⁱⁱ	2.108 (2)	S2—O6	1.458 (3)
Ni1—N2^iv	2.108 (2)	O1w—H1w1	0.838 (10)
Ni1—N2^v	2.108 (2)	O1w—H1w2	0.841 (10)
Ni2—N3	2.065 (2)	O2W—H2w1	0.853 (10)
Ni2—N3ⁱ	2.065 (2)	O2W—H2w2	0.852 (10)
Ni2—N3ⁱⁱ	2.065 (2)	O3w—H3w1	0.848 (10)
Ni2—O1w	2.101 (2)	O3w—H3w2	0.852 (10)
Ni2—O1wⁱ	2.101 (2)	O4w—H4w1	0.838 (10)
Ni2—O1wⁱⁱ	2.101 (2)	O4w—H4w2	0.845 (10)
S1—O4^vi	1.422 (8)	N1—C1	1.352 (4)
S1—O4^vii	1.422 (8)	N1—H1n1	0.846 (10)
S1—O4^viii	1.422 (8)	N1—H1n2	0.859 (11)
S1—O4	1.422 (8)	N2—C1	1.313 (4)
S1—O4^ix	1.422 (8)	N2—N3	1.419 (3)
S1—O4^x	1.422 (8)	N3—C2	1.311 (3)
S1—O2^vii	1.427 (9)	N4—C2	1.357 (4)
S1—O2^x	1.427 (9)	N4—H4n1	0.855 (10)
S1—O2	1.427 (9)	N4—H4n2	0.846 (10)
S1—O2^viii	1.427 (9)	N5—C2	1.365 (4)
S1—O2^vi	1.427 (9)	N5—C1	1.367 (4)
S1—O2^ix	1.427 (9)	N5—H5n	0.847 (10)

N2ⁱⁱⁱ—Ni1—N2^iv	90.85 (8)	O2^vii—S1—O2^viii	117.0 (4)
N2ⁱⁱⁱ—Ni1—N2^v	90.85 (8)	O4^vi—S1—O2^vi	113.1 (8)
N2^iv—Ni1—N2^v	90.85 (8)	O2^vii—S1—O2^vi	117.0 (4)
N2ⁱⁱⁱ—Ni1—N2ⁱ	177.85 (11)	O2^viii—S1—O2^vi	117.0 (4)
N2^iv—Ni1—N2ⁱ	90.70 (12)	O4^ix—S1—O2^ix	113.1 (8)
N2^v—Ni1—N2ⁱ	87.63 (12)	O2^x—S1—O2^ix	117.0 (4)
N2ⁱⁱⁱ—Ni1—N2	87.64 (12)	O2—S1—O2^ix	117.0 (4)
N2^iv—Ni1—N2	177.85 (11)	O5—S2—O6ⁱⁱ	111.26 (18)
N2^v—Ni1—N2	90.70 (12)	O5—S2—O6ⁱ	111.26 (19)
N2ⁱ—Ni1—N2	90.85 (8)	O6ⁱⁱ—S2—O6ⁱ	107.6 (2)
N2ⁱⁱⁱ—Ni1—N2ⁱⁱ	90.70 (12)	O5—S2—O6	111.26 (18)
N2^iv—Ni1—N2ⁱⁱ	87.64 (12)	O6ⁱⁱ—S2—O6	107.6 (2)
N2^v—Ni1—N2ⁱⁱ	177.85 (11)	O6ⁱ—S2—O6	107.6 (2)
N2ⁱ—Ni1—N2ⁱⁱ	90.85 (8)	Ni2—O1w—H1w1	108 (2)
N2—Ni1—N2ⁱⁱ	90.85 (8)	Ni2—O1w—H1w2	121 (2)
N3ⁱ—Ni2—N3ⁱⁱ	93.50 (8)	H1w1—O1w—H1w2	110.9 (17)
N3ⁱ—Ni2—N3	93.50 (8)	H2w1—O2W—H2w2	108.3 (17)
N3ⁱⁱ—Ni2—N3	93.50 (8)	H3w1—O3w—H3w2	109.4 (18)
N3ⁱ—Ni2—O1w	90.39 (9)	H4w1—O4w—H4w2	113 (2)
N3ⁱⁱ—Ni2—O1w	87.94 (9)	C1—N1—H1n1	111 (3)
N3—Ni2—O1w	175.77 (8)	C1—N1—H1n2	116 (3)
N3ⁱ—Ni2—O1wⁱⁱ	87.94 (9)	H1n1—N1—H1n2	125 (4)
N3ⁱⁱ—Ni2—O1wⁱⁱ	175.77 (8)	C1—N2—N3	106.5 (2)
N3—Ni2—O1wⁱⁱ	90.39 (9)	C1—N2—Ni1	128.87 (19)
O1w—Ni2—O1wⁱⁱ	88.07 (9)	N3—N2—Ni1	122.82 (17)
N3ⁱ—Ni2—O1wⁱ	175.77 (8)	C2—N3—N2	107.2 (2)
N3ⁱⁱ—Ni2—O1wⁱ	90.39 (9)	C2—N3—Ni2	130.62 (18)
N3—Ni2—O1wⁱ	87.94 (9)	N2—N3—Ni2	120.73 (16)
O1w—Ni2—O1wⁱ	88.07 (9)	C2—N4—H4n1	125 (3)
O1wⁱⁱ—Ni2—O1wⁱ	88.07 (9)	C2—N4—H4n2	123 (3)
O4^vi—S1—O4^vii	115.6 (5)	H4n1—N4—H4n2	107 (4)
O4^vi—S1—O4^viii	115.6 (5)	C2—N5—C1	105.8 (2)
O4—S1—O4^ix	115.6 (5)	C2—N5—H5n	128 (2)
O4—S1—O4^x	115.6 (5)	C1—N5—H5n	125 (2)
O4^ix—S1—O4^x	115.6 (5)	N2—C1—N1	127.9 (3)
O4^vii—S1—O2^vii	113.1 (8)	N2—C1—N5	110.4 (3)
O4^x—S1—O2^x	113.1 (8)	N1—C1—N5	121.7 (3)
O4—S1—O2	113.1 (8)	N3—C2—N4	127.6 (3)
O2^x—S1—O2	117.0 (4)	N3—C2—N5	110.1 (2)
O4^viii—S1—O2^viii	113.1 (8)	N4—C2—N5	122.3 (3)

N2ⁱⁱⁱ—Ni1—N2—C1	−41.1 (2)	N3ⁱ—Ni2—N3—N2	32.54 (16)
N2^v—Ni1—N2—C1	49.7 (2)	N3ⁱⁱ—Ni2—N3—N2	−61.19 (14)
N2ⁱ—Ni1—N2—C1	137.3 (3)	O1wⁱⁱ—Ni2—N3—N2	120.50 (19)
N2ⁱⁱ—Ni1—N2—C1	−131.8 (3)	O1wⁱ—Ni2—N3—N2	−151.45 (19)
N2ⁱⁱⁱ—Ni1—N2—N3	121.4 (2)	N3—N2—C1—N1	−176.9 (3)
N2^v—Ni1—N2—N3	−147.8 (2)	Ni1—N2—C1—N1	−12.1 (4)
N2ⁱ—Ni1—N2—N3	−60.12 (14)	N3—N2—C1—N5	0.5 (3)
N2ⁱⁱ—Ni1—N2—N3	30.75 (16)	Ni1—N2—C1—N5	165.2 (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—N1	177.4 (3)
C1—N2—N3—Ni2	−168.31 (18)	N2—N3—C2—N4	179.5 (3)
Ni1—N2—N3—Ni2	25.8 (3)	Ni2—N3—C2—N4	−14.5 (5)
N3ⁱ—Ni2—N3—C2	−131.8 (3)	N2—N3—C2—N5	0.7 (3)
N3ⁱⁱ—Ni2—N3—C2	134.5 (3)	Ni2—N3—C2—N5	166.6 (2)
O1wⁱⁱ—Ni2—N3—C2	−43.8 (3)	C1—N5—C2—N3	−0.4 (3)
O1wⁱ—Ni2—N3—C2	44.2 (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, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w1···O2w	0.84 (1)	1.89 (1)	2.719 (4)	173 (3)
O1w—H1w2···O3w	0.84 (1)	1.94 (2)	2.754 (3)	162 (4)
N4—H4n1···O1wⁱ	0.86 (1)	2.33 (3)	2.962 (4)	131 (4)
N4—H4n2···O2ⁱⁱ	0.85 (1)	2.41 (3)	3.15 (2)	147 (4)
N5—H5n···O6^xi	0.85 (1)	2.08 (2)	2.843 (5)	150 (3)
O2W—H2w1···O3w^xii	0.85 (1)	2.12 (1)	2.962 (4)	168 (4)
O2W—H2w2···O4w	0.85 (1)	2.01 (2)	2.828 (5)	160 (5)
O3w—H3w1···O5	0.85 (1)	1.97 (2)	2.787 (5)	162 (4)
O3w—H3w2···O4w^vii	0.85 (1)	2.10 (2)	2.885 (5)	154 (5)
O4w—H4w1···O6^xiii	0.84 (1)	1.98 (2)	2.786 (6)	163 (6)
O4w—H4w2···O1	0.85 (1)	1.83 (4)	2.57 (2)	145 (6)

Symmetry codes: (i) −y+1, x−y, z; (ii) −x+y+1, −x+1, z; (vii) x−y, x−1, −z; (xi) −x+y+1/3, y−1/3, z+1/6; (xii) −x+2, −y+1, −z; (xiii) −x+y+4/3, y−1/3, z+1/6.

Experimental details

Crystal data
Chemical formula	[Ni₃(C₂H₅N₅)₆(H₂O)₆](SO₄)₃·18H₂O
M_r	1491.35
Crystal system, space group	Trigonal, R3c
Temperature (K)	295
a, c (Å)	12.664 (2), 63.653 (6)
V (Å³)	8841 (2)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	1.17
Crystal size (mm)	0.43 × 0.32 × 0.23

Data collection
Diffractometer	Bruker APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.676, 0.775
No. of measured, independent and observed [I > 2σ(I)] reflections	24396, 2269, 1868
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.180, 1.33
No. of reflections	2269
No. of parameters	197
No. of restraints	66
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.91, −0.64

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).

Selected bond lengths (Å) top

Ni1—N2	2.108 (2)	Ni2—O1w	2.101 (2)
Ni2—N3	2.065 (2)