Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034472/bi2207sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034472/bi2207Isup2.hkl |
CCDC reference: 657602
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- Disorder in solvent or counterion
- R factor = 0.056
- wR factor = 0.183
- Data-to-parameter ratio = 11.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.50 Ratio PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for O2 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for S1 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for O1 PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 43.00 Perc. PLAT395_ALERT_2_C Deviating X-O-Y Angle from 120 Deg for <O2W 141.00 Deg. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 2 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.15 Ratio PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 O4 S PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 3 H2.04 O PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 4 H2 O
Alert level G FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C18 H28 N12 Ni1 O6 S1 Atom count from the _atom_site data: C18 H28.02 N12 Ni1 O6 S1 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 17
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 13 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 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 9 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Light purple block crystals were synthesized hydrothermally from a complex reaction mixture. In a typical synthesis, GeO2 (0.1054 g), NH4VO3 (0.1079) and NiSO4 (0.5278 g) were dissolved in the mixed solvent of dimethyl formamide (0.5162 g) and water (1.8388 g) followed by addition of imidazole (0.4551 g) with constant stirring. The mixture was kept in a 25 ml Teflon-lined steel autoclave at 443 K for 7 days then slowly cooled to room temperature. The product was filtered, washed with distilled water, and dried at room temperature.
H atoms bound to C or N atoms were placed geometrically and allowed to ride with C—H = 0.93 Å or N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C/N). H atoms of the water molecules were located in difference Fourier maps and refined with O—H distances restrained to be 0.85 (1)Å and with Uiso(H) = 1.2Ueq(O). The displacement parameters of the O atoms of the water molecules were restrained to approximate isotropic behaviour and the S—O distances in the disordered sulfate anion were restrained to be 1.420 (2) Å.
The title compound was obtained during an attempted synthesis of a metal-organic framework (MOF) incorporating NiII and imidazole. The unit cell has been reported previously (Phung et al., 1976), although complete space group information and atomic coordinates were not given.
The structure comprises discrete [Ni(C3N2H4)6]2+ cations (Figure 1). The NiII atom lies on a site of 3 point symmetry and is coordinated by six N atoms from six imidazole molecules in a regular octahedral geometry with Ni—N = 2.1216 (17) Å. The Ni—N bond lengths and angles are comparable to those in similar reported NiII compounds (for example, Fu et al., 2007). The sulfate anion is disordered about a site of 32 point symmetry. As shown in Figure 2, the non-coordinated N atoms of imidazole are involved in hydrogen-bonding interactions with O atoms of the sulfate groups.
The unit-cell dimensions of this compound have been reported previously (Phung et al., 1976), although complete space-group information and atomic coordinates were not given. For examples of other structures containing [Ni(C3N2H4)6]2+ cations, see: Fu et al. (2007); Gao et al. (2004); Wang et al. (2000).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
[Ni(C3H4N2)6]SO4·2H2O | Dx = 1.236 Mg m−3 |
Mr = 599.29 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, P31c | Cell parameters from 7600 reflections |
Hall symbol: -P 3 2c | θ = 2.6–25.0° |
a = 9.0029 (9) Å | µ = 0.72 mm−1 |
c = 22.937 (4) Å | T = 293 K |
V = 1610.0 (4) Å3 | Block, blue |
Z = 2 | 0.13 × 0.12 × 0.12 mm |
F(000) = 624 |
Bruker APEXII CCD diffractometer | 949 independent reflections |
Radiation source: fine-focus sealed tube | 794 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ω scans | θmax = 25.0°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −10→9 |
Tmin = 0.913, Tmax = 0.919 | k = −10→9 |
7600 measured reflections | l = −15→27 |
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.183 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.16 | w = 1/[σ2(Fo2) + (0.13P)2 + 0.1485P] where P = (Fo2 + 2Fc2)/3 |
949 reflections | (Δ/σ)max = 0.032 |
82 parameters | Δρmax = 0.49 e Å−3 |
17 restraints | Δρmin = −0.48 e Å−3 |
[Ni(C3H4N2)6]SO4·2H2O | Z = 2 |
Mr = 599.29 | Mo Kα radiation |
Trigonal, P31c | µ = 0.72 mm−1 |
a = 9.0029 (9) Å | T = 293 K |
c = 22.937 (4) Å | 0.13 × 0.12 × 0.12 mm |
V = 1610.0 (4) Å3 |
Bruker APEXII CCD diffractometer | 949 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 794 reflections with I > 2σ(I) |
Tmin = 0.913, Tmax = 0.919 | Rint = 0.023 |
7600 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 17 restraints |
wR(F2) = 0.183 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.16 | Δρmax = 0.49 e Å−3 |
949 reflections | Δρmin = −0.48 e Å−3 |
82 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.0000 | 0.0000 | 0.0000 | 0.04666 (14) | |
S1 | 0.3333 | −0.3333 | −0.2500 | 0.0660 (3) | |
N1 | 0.3116 (2) | −0.0743 (2) | −0.12231 (8) | 0.0878 (5) | |
H3A | 0.3235 | −0.1243 | −0.1524 | 0.105* | |
N2 | 0.18871 (19) | −0.00718 (14) | −0.05341 (7) | 0.0557 (4) | |
C1 | 0.4392 (3) | 0.0428 (3) | −0.08892 (12) | 0.0901 (8) | |
H1A | 0.5562 | 0.0872 | −0.0945 | 0.108* | |
C2 | 0.3650 (2) | 0.0825 (3) | −0.04641 (10) | 0.0746 (6) | |
H4A | 0.4229 | 0.1592 | −0.0163 | 0.090* | |
C3 | 0.1628 (2) | −0.0995 (2) | −0.10058 (8) | 0.0693 (5) | |
H6A | 0.0557 | −0.1725 | −0.1167 | 0.083* | |
O1 | 0.3333 | −0.3333 | −0.18837 (15) | 0.108 (2) | 0.50 |
O2 | 0.3702 (8) | −0.4468 (6) | −0.2181 (3) | 0.211 (2) | 0.50 |
O1W | 0.0000 | −1.0000 | −0.2500 | 0.313 (5) | 0.50 |
H1W | 0.0255 (4) | −1.0713 (3) | −0.2645 (3) | 0.375* | 0.17 |
O2W | 0.3549 (10) | −0.7269 (11) | −0.2078 (5) | 0.137 (3) | 0.25 |
H2WB | 0.460 (2) | −0.647 (6) | −0.211 (6) | 0.165* | 0.25 |
H2WA | 0.271 (3) | −0.799 (6) | −0.2284 (17) | 0.165* | 0.25 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.05113 (18) | 0.05113 (18) | 0.0377 (3) | 0.02556 (9) | 0.000 | 0.000 |
S1 | 0.0785 (4) | 0.0785 (4) | 0.0412 (5) | 0.0392 (2) | 0.000 | 0.000 |
N1 | 0.1061 (8) | 0.1020 (9) | 0.0739 (10) | 0.0660 (7) | 0.0246 (9) | −0.0081 (8) |
N2 | 0.0600 (7) | 0.0609 (6) | 0.0504 (8) | 0.0334 (5) | 0.0035 (7) | −0.0022 (5) |
C1 | 0.0703 (9) | 0.1121 (11) | 0.0945 (17) | 0.0506 (9) | 0.0056 (11) | −0.0219 (12) |
C2 | 0.0606 (7) | 0.0906 (11) | 0.0753 (12) | 0.0398 (7) | 0.0016 (9) | −0.0088 (10) |
C3 | 0.0742 (8) | 0.0729 (9) | 0.0624 (11) | 0.0380 (6) | 0.0110 (8) | −0.0046 (8) |
O1 | 0.135 (3) | 0.135 (3) | 0.054 (3) | 0.0674 (15) | 0.000 | 0.000 |
O2 | 0.317 (4) | 0.165 (3) | 0.196 (5) | 0.155 (2) | −0.079 (4) | 0.024 (3) |
O1W | 0.315 (6) | 0.315 (6) | 0.307 (8) | 0.158 (3) | 0.000 | 0.000 |
O2W | 0.155 (4) | 0.141 (4) | 0.143 (5) | 0.095 (3) | 0.018 (4) | 0.003 (4) |
Ni1—N2i | 2.1216 (17) | N1—C1 | 1.344 (3) |
Ni1—N2ii | 2.1216 (17) | N1—H3A | 0.860 |
Ni1—N2iii | 2.1216 (17) | N2—C3 | 1.312 (2) |
Ni1—N2 | 2.1216 (17) | N2—C2 | 1.384 (2) |
Ni1—N2iv | 2.1216 (17) | C1—C2 | 1.328 (3) |
Ni1—N2v | 2.1216 (17) | C1—H1A | 0.930 |
S1—O1vi | 1.414 (3) | C2—H4A | 0.930 |
S1—O1 | 1.414 (3) | C3—H6A | 0.930 |
S1—O2vii | 1.423 (6) | O1—O2ix | 1.400 (7) |
S1—O2viii | 1.423 (6) | O1—O2viii | 1.400 (7) |
S1—O2ix | 1.423 (6) | O1—O2 | 1.400 (7) |
S1—O2x | 1.423 (6) | O2—O2vi | 1.616 (13) |
S1—O2 | 1.423 (6) | O1W—H1W | 0.850 (3) |
S1—O2vi | 1.423 (6) | O2W—H2WB | 0.855 (18) |
N1—C3 | 1.338 (3) | O2W—H2WA | 0.853 (19) |
N2i—Ni1—N2ii | 180.00 (11) | O2ix—S1—O2 | 96.0 (4) |
N2i—Ni1—N2iii | 89.99 (7) | O2x—S1—O2 | 103.2 (4) |
N2ii—Ni1—N2iii | 90.01 (7) | O1vi—S1—O2vi | 59.1 (3) |
N2i—Ni1—N2 | 89.99 (7) | O1—S1—O2vi | 120.9 (3) |
N2ii—Ni1—N2 | 90.01 (7) | O2vii—S1—O2vi | 96.0 (4) |
N2iii—Ni1—N2 | 89.99 (7) | O2viii—S1—O2vi | 103.2 (4) |
N2i—Ni1—N2iv | 90.01 (7) | O2ix—S1—O2vi | 156.7 (5) |
N2ii—Ni1—N2iv | 89.99 (7) | O2x—S1—O2vi | 96.0 (4) |
N2iii—Ni1—N2iv | 90.01 (7) | O2—S1—O2vi | 69.2 (6) |
N2—Ni1—N2iv | 180.00 (9) | C3—N1—C1 | 108.16 (18) |
N2i—Ni1—N2v | 90.01 (7) | C3—N1—H3A | 125.9 |
N2ii—Ni1—N2v | 89.99 (7) | C1—N1—H3A | 125.9 |
N2iii—Ni1—N2v | 180.00 (10) | C3—N2—C2 | 104.71 (17) |
N2—Ni1—N2v | 90.01 (7) | C3—N2—Ni1 | 127.15 (12) |
N2iv—Ni1—N2v | 89.99 (7) | C2—N2—Ni1 | 128.14 (14) |
O1vi—S1—O1 | 180.0 | C2—C1—N1 | 106.35 (19) |
O1vi—S1—O2vii | 59.1 (3) | C2—C1—H1A | 126.8 |
O1—S1—O2vii | 120.9 (3) | N1—C1—H1A | 126.8 |
O1vi—S1—O2viii | 120.9 (3) | C1—C2—N2 | 110.03 (19) |
O1—S1—O2viii | 59.1 (3) | C1—C2—H4A | 125.0 |
O2vii—S1—O2viii | 69.2 (6) | N2—C2—H4A | 125.0 |
O1vi—S1—O2ix | 120.9 (3) | N2—C3—N1 | 110.71 (16) |
O1—S1—O2ix | 59.1 (3) | N2—C3—H6A | 124.6 |
O2vii—S1—O2ix | 103.2 (4) | N1—C3—H6A | 124.6 |
O2viii—S1—O2ix | 96.0 (4) | O2ix—O1—O2viii | 98.2 (3) |
O1vi—S1—O2x | 59.1 (3) | O2ix—O1—O2 | 98.2 (3) |
O1—S1—O2x | 120.9 (3) | O2viii—O1—O2 | 98.2 (3) |
O2vii—S1—O2x | 96.0 (4) | O2ix—O1—S1 | 60.8 (3) |
O2viii—S1—O2x | 156.7 (5) | O2viii—O1—S1 | 60.8 (3) |
O2ix—S1—O2x | 69.2 (6) | O2—O1—S1 | 60.8 (3) |
O1vi—S1—O2 | 120.9 (3) | O1—O2—S1 | 60.1 (3) |
O1—S1—O2 | 59.1 (3) | O1—O2—O2vi | 109.6 (3) |
O2vii—S1—O2 | 156.7 (5) | S1—O2—O2vi | 55.4 (3) |
O2viii—S1—O2 | 96.0 (4) | H2WB—O2W—H2WA | 141 (10) |
Symmetry codes: (i) −x+y, −x, z; (ii) x−y, x, −z; (iii) −y, x−y, z; (iv) −x, −y, −z; (v) y, −x+y, −z; (vi) −y, −x, −z−1/2; (vii) x, x−y−1, −z−1/2; (viii) −y, x−y−1, z; (ix) −x+y+1, −x, z; (x) −x+y+1, y, −z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H3A···O1 | 0.86 | 2.10 | 2.868 (3) | 149 |
N1—H3A···O2viii | 0.86 | 2.09 | 2.908 (7) | 159 |
N1—H3A···O2ix | 0.86 | 2.44 | 3.191 (7) | 146 |
Symmetry codes: (viii) −y, x−y−1, z; (ix) −x+y+1, −x, z. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C3H4N2)6]SO4·2H2O |
Mr | 599.29 |
Crystal system, space group | Trigonal, P31c |
Temperature (K) | 293 |
a, c (Å) | 9.0029 (9), 22.937 (4) |
V (Å3) | 1610.0 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.72 |
Crystal size (mm) | 0.13 × 0.12 × 0.12 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.913, 0.919 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7600, 949, 794 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.183, 1.16 |
No. of reflections | 949 |
No. of parameters | 82 |
No. of restraints | 17 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.49, −0.48 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H3A···O1 | 0.86 | 2.096 | 2.868 (3) | 149 |
N1—H3A···O2i | 0.86 | 2.090 | 2.908 (7) | 159 |
N1—H3A···O2ii | 0.86 | 2.444 | 3.191 (7) | 146 |
Symmetry codes: (i) −y, x−y−1, z; (ii) −x+y+1, −x, z. |
The title compound was obtained during an attempted synthesis of a metal-organic framework (MOF) incorporating NiII and imidazole. The unit cell has been reported previously (Phung et al., 1976), although complete space group information and atomic coordinates were not given.
The structure comprises discrete [Ni(C3N2H4)6]2+ cations (Figure 1). The NiII atom lies on a site of 3 point symmetry and is coordinated by six N atoms from six imidazole molecules in a regular octahedral geometry with Ni—N = 2.1216 (17) Å. The Ni—N bond lengths and angles are comparable to those in similar reported NiII compounds (for example, Fu et al., 2007). The sulfate anion is disordered about a site of 32 point symmetry. As shown in Figure 2, the non-coordinated N atoms of imidazole are involved in hydrogen-bonding interactions with O atoms of the sulfate groups.