Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702051X/hb2392sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680702051X/hb2392Isup2.hkl |
CCDC reference: 648073
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
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).
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.
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).
For the structure of a related cobalt-containing complex, see: Antolini et al. (1991).
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).
[Ni3(C2H5N5)6(H2O)6](SO4)3·18H2O | Dx = 1.681 Mg m−3 |
Mr = 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 |
Bruker APEX CCD diffractometer | 2269 independent reflections |
Radiation source: fine-focus sealed tube | 1868 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
φ and ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −16→15 |
Tmin = 0.676, Tmax = 0.775 | k = −16→16 |
24396 measured reflections | l = −82→81 |
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(Fo2) + (0.1P)2 + 1P] where P = (Fo2 + 2Fc2)/3 |
2269 reflections | (Δ/σ)max = 0.001 |
197 parameters | Δρmax = 0.91 e Å−3 |
66 restraints | Δρmin = −0.64 e Å−3 |
[Ni3(C2H5N5)6(H2O)6](SO4)3·18H2O | Z = 6 |
Mr = 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 |
Bruker APEX CCD diffractometer | 2269 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1868 reflections with I > 2σ(I) |
Tmin = 0.676, Tmax = 0.775 | Rint = 0.026 |
24396 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 66 restraints |
wR(F2) = 0.180 | All H-atom parameters refined |
S = 1.33 | Δρmax = 0.91 e Å−3 |
2269 reflections | Δρmin = −0.64 e Å−3 |
197 parameters |
x | y | z | Uiso*/Ueq | 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) |
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) |
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—N2iv | 2.108 (2) | O1w—H1w1 | 0.838 (10) |
Ni1—N2v | 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—O4vi | 1.422 (8) | N1—C1 | 1.352 (4) |
S1—O4vii | 1.422 (8) | N1—H1n1 | 0.846 (10) |
S1—O4viii | 1.422 (8) | N1—H1n2 | 0.859 (11) |
S1—O4 | 1.422 (8) | N2—C1 | 1.313 (4) |
S1—O4ix | 1.422 (8) | N2—N3 | 1.419 (3) |
S1—O4x | 1.422 (8) | N3—C2 | 1.311 (3) |
S1—O2vii | 1.427 (9) | N4—C2 | 1.357 (4) |
S1—O2x | 1.427 (9) | N4—H4n1 | 0.855 (10) |
S1—O2 | 1.427 (9) | N4—H4n2 | 0.846 (10) |
S1—O2viii | 1.427 (9) | N5—C2 | 1.365 (4) |
S1—O2vi | 1.427 (9) | N5—C1 | 1.367 (4) |
S1—O2ix | 1.427 (9) | N5—H5n | 0.847 (10) |
N2iii—Ni1—N2iv | 90.85 (8) | O2vii—S1—O2viii | 117.0 (4) |
N2iii—Ni1—N2v | 90.85 (8) | O4vi—S1—O2vi | 113.1 (8) |
N2iv—Ni1—N2v | 90.85 (8) | O2vii—S1—O2vi | 117.0 (4) |
N2iii—Ni1—N2i | 177.85 (11) | O2viii—S1—O2vi | 117.0 (4) |
N2iv—Ni1—N2i | 90.70 (12) | O4ix—S1—O2ix | 113.1 (8) |
N2v—Ni1—N2i | 87.63 (12) | O2x—S1—O2ix | 117.0 (4) |
N2iii—Ni1—N2 | 87.64 (12) | O2—S1—O2ix | 117.0 (4) |
N2iv—Ni1—N2 | 177.85 (11) | O5—S2—O6ii | 111.26 (18) |
N2v—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) |
N2iv—Ni1—N2ii | 87.64 (12) | O6ii—S2—O6 | 107.6 (2) |
N2v—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) |
O4vi—S1—O4vii | 115.6 (5) | H4n1—N4—H4n2 | 107 (4) |
O4vi—S1—O4viii | 115.6 (5) | C2—N5—C1 | 105.8 (2) |
O4—S1—O4ix | 115.6 (5) | C2—N5—H5n | 128 (2) |
O4—S1—O4x | 115.6 (5) | C1—N5—H5n | 125 (2) |
O4ix—S1—O4x | 115.6 (5) | N2—C1—N1 | 127.9 (3) |
O4vii—S1—O2vii | 113.1 (8) | N2—C1—N5 | 110.4 (3) |
O4x—S1—O2x | 113.1 (8) | N1—C1—N5 | 121.7 (3) |
O4—S1—O2 | 113.1 (8) | N3—C2—N4 | 127.6 (3) |
O2x—S1—O2 | 117.0 (4) | N3—C2—N5 | 110.1 (2) |
O4viii—S1—O2viii | 113.1 (8) | N4—C2—N5 | 122.3 (3) |
N2iii—Ni1—N2—C1 | −41.1 (2) | N3i—Ni2—N3—N2 | 32.54 (16) |
N2v—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) |
N2v—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. |
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···O6xi | 0.85 (1) | 2.08 (2) | 2.843 (5) | 150 (3) |
O2W—H2w1···O3wxii | 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···O4wvii | 0.85 (1) | 2.10 (2) | 2.885 (5) | 154 (5) |
O4w—H4w1···O6xiii | 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 |
Mr | 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) |
Tmin, Tmax | 0.676, 0.775 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24396, 2269, 1868 |
Rint | 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 |
Δρmax, Δρmin (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).
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···O6iii | 0.85 (1) | 2.08 (2) | 2.843 (5) | 150 (3) |
O2W—H2w1···O3wiv | 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···O4wv | 0.85 (1) | 2.10 (2) | 2.885 (5) | 154 (5) |
O4w—H4w1···O6vi | 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; (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. |
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).