Hexakis(1H-imidazole-κN3)nickel(II) sulfate dihydrate

Sun, X.-C.; Zhou, G.-P.; Liu, Z.-B.; Xu, Y.

doi:10.1107/S1600536807034472

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Hexakis(1H-imidazole-κN³)nickel(II) sulfate dihydrate

X.-C. Sun, G.-P. Zhou, Z.-B. Liu and Y. Xu

The title compound, [Ni(C₃H₄N₂)₆]SO₄·2H₂O, was prepared by hydrothermal synthesis. The Ni^II atom lies on a site of $\overline{3}$ point symmetry and is coordinated by six imidazole ligands in a regular octahedral geometry. The sulfate anion is disordered about a site of 32 point symmetry; water molecules lie on sites of 32 point symmetry and on general positions. The coordinated imidazole molecules make N—H

O hydrogen bonds with the sulfate anions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034472/bi2207sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034472/bi2207Isup2.hkl Contains datablock I

CCDC reference: 657602

checkCIF report

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

Comment top

The title compound was obtained during an attempted synthesis of a metal-organic framework (MOF) incorporating Ni^II 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 Ni^II 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 Ni^II 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.

Related literature top

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).

Experimental top

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.

Structure description top

Computing details top

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.

Figures top

	Fig. 1. The molecular structure of title compound showing displacement ellipsoids at the 70% probability level for non-H atoms.
	Fig. 2. Unit-cell contents for title compound. Dashed lines denote hydrogen bonds.

Hexakis(1H-imidazole-κN³)nickel(II) sulfate dihydrate top

Crystal data top

[Ni(C₃H₄N₂)₆]SO₄·2H₂O	D_x = 1.236 Mg m⁻³
M_r = 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

Data collection top

Bruker APEXII CCD diffractometer	949 independent reflections
Radiation source: fine-focus sealed tube	794 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→9
T_min = 0.913, T_max = 0.919	k = −10→9
7600 measured reflections	l = −15→27

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)] = 0.056	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(F_o²) + (0.13P)² + 0.1485P] where P = (F_o² + 2F_c²)/3
949 reflections	(Δ/σ)_max = 0.032
82 parameters	Δρ_max = 0.49 e Å⁻³
17 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

[Ni(C₃H₄N₂)₆]SO₄·2H₂O	Z = 2
M_r = 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

Data collection top

Bruker APEXII CCD diffractometer	949 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	794 reflections with I > 2σ(I)
T_min = 0.913, T_max = 0.919	R_int = 0.023
7600 measured reflections

Refinement top

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	Δρ_max = 0.49 e Å⁻³
949 reflections	Δρ_min = −0.48 e Å⁻³
82 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq	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

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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—N2^iv	2.1216 (17)	C1—C2	1.328 (3)
Ni1—N2^v	2.1216 (17)	C1—H1A	0.930
S1—O1^vi	1.414 (3)	C2—H4A	0.930
S1—O1	1.414 (3)	C3—H6A	0.930
S1—O2^vii	1.423 (6)	O1—O2^ix	1.400 (7)
S1—O2^viii	1.423 (6)	O1—O2^viii	1.400 (7)
S1—O2^ix	1.423 (6)	O1—O2	1.400 (7)
S1—O2^x	1.423 (6)	O2—O2^vi	1.616 (13)
S1—O2	1.423 (6)	O1W—H1W	0.850 (3)
S1—O2^vi	1.423 (6)	O2W—H2WB	0.855 (18)
N1—C3	1.338 (3)	O2W—H2WA	0.853 (19)

N2ⁱ—Ni1—N2ⁱⁱ	180.00 (11)	O2^ix—S1—O2	96.0 (4)
N2ⁱ—Ni1—N2ⁱⁱⁱ	89.99 (7)	O2^x—S1—O2	103.2 (4)
N2ⁱⁱ—Ni1—N2ⁱⁱⁱ	90.01 (7)	O1^vi—S1—O2^vi	59.1 (3)
N2ⁱ—Ni1—N2	89.99 (7)	O1—S1—O2^vi	120.9 (3)
N2ⁱⁱ—Ni1—N2	90.01 (7)	O2^vii—S1—O2^vi	96.0 (4)
N2ⁱⁱⁱ—Ni1—N2	89.99 (7)	O2^viii—S1—O2^vi	103.2 (4)
N2ⁱ—Ni1—N2^iv	90.01 (7)	O2^ix—S1—O2^vi	156.7 (5)
N2ⁱⁱ—Ni1—N2^iv	89.99 (7)	O2^x—S1—O2^vi	96.0 (4)
N2ⁱⁱⁱ—Ni1—N2^iv	90.01 (7)	O2—S1—O2^vi	69.2 (6)
N2—Ni1—N2^iv	180.00 (9)	C3—N1—C1	108.16 (18)
N2ⁱ—Ni1—N2^v	90.01 (7)	C3—N1—H3A	125.9
N2ⁱⁱ—Ni1—N2^v	89.99 (7)	C1—N1—H3A	125.9
N2ⁱⁱⁱ—Ni1—N2^v	180.00 (10)	C3—N2—C2	104.71 (17)
N2—Ni1—N2^v	90.01 (7)	C3—N2—Ni1	127.15 (12)
N2^iv—Ni1—N2^v	89.99 (7)	C2—N2—Ni1	128.14 (14)
O1^vi—S1—O1	180.0	C2—C1—N1	106.35 (19)
O1^vi—S1—O2^vii	59.1 (3)	C2—C1—H1A	126.8
O1—S1—O2^vii	120.9 (3)	N1—C1—H1A	126.8
O1^vi—S1—O2^viii	120.9 (3)	C1—C2—N2	110.03 (19)
O1—S1—O2^viii	59.1 (3)	C1—C2—H4A	125.0
O2^vii—S1—O2^viii	69.2 (6)	N2—C2—H4A	125.0
O1^vi—S1—O2^ix	120.9 (3)	N2—C3—N1	110.71 (16)
O1—S1—O2^ix	59.1 (3)	N2—C3—H6A	124.6
O2^vii—S1—O2^ix	103.2 (4)	N1—C3—H6A	124.6
O2^viii—S1—O2^ix	96.0 (4)	O2^ix—O1—O2^viii	98.2 (3)
O1^vi—S1—O2^x	59.1 (3)	O2^ix—O1—O2	98.2 (3)
O1—S1—O2^x	120.9 (3)	O2^viii—O1—O2	98.2 (3)
O2^vii—S1—O2^x	96.0 (4)	O2^ix—O1—S1	60.8 (3)
O2^viii—S1—O2^x	156.7 (5)	O2^viii—O1—S1	60.8 (3)
O2^ix—S1—O2^x	69.2 (6)	O2—O1—S1	60.8 (3)
O1^vi—S1—O2	120.9 (3)	O1—O2—S1	60.1 (3)
O1—S1—O2	59.1 (3)	O1—O2—O2^vi	109.6 (3)
O2^vii—S1—O2	156.7 (5)	S1—O2—O2^vi	55.4 (3)
O2^viii—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.

Hydrogen-bond geometry (Å, º) top

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···O2^viii	0.86	2.09	2.908 (7)	159
N1—H3A···O2^ix	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
M_r	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)
T_min, T_max	0.913, 0.919
No. of measured, independent and observed [I > 2σ(I)] reflections	7600, 949, 794
R_int	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
Δρ_max, Δρ_min (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.

Hydrogen-bond geometry (Å, º) top

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.

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