Crystal structure of di­aqua­tris­(1-ethyl-1H-imidazole-κN3)(sulfato-κO)nickel(II)

Holczbauer, T.; Domjan, A.; Fodor, C.

doi:10.1107/S2056989016002863

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Volume 72| Part 3| March 2016| Pages 374-377

doi:10.1107/S2056989016002863

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Crystal structure of diaquatris(1-ethyl-1H-imidazole-κN³)(sulfato-κO)nickel(II)

Tamas Holczbauer,^a ^* Attila Domjan ^b and Csaba Fodor ^c

^aChemical Crystallography Research Group, Institute of Organic Chemistry, Hungarian Academy of Sciences, Magyar Tudosok Korutja 2, Budapest H-1117, Hungary, ^bNMR Research Group, Institute of Organic Chemistry, Hungarian Academy of Sciences, Magyar Tudosok Korutja 2, Budapest H-1117, Hungary, and ^cPolymer Chemistry Research Group, Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, Magyar Tudosok Korutja 2, Budapest H-1117, Hungary
^*Correspondence e-mail: holczbauer.tamas@ttk.mta.hu

Edited by A. J. Lough, University of Toronto, Canada (Received 4 January 2016; accepted 17 February 2016; online 20 February 2016)

In the title complex, [Ni(SO₄)(C₅H₈N₂)₃(H₂O)₂], the Ni^II ion is coordinated by three facial 1-ethyl-1H-imidazole ligands, one monodentate sulfate ligand and two water molecules in a slightly distorted octahedral coordination environment. In the crystal, two pairs of O—H⋯O hydrogen bonds link complex molecules, forming inversion dimers incorporating R₂⁴(8), R₂²(8) and R₂²(12) rings. The dimeric unit also contains two symmetry-unique intramolecular O—H⋯O hydrogen bonds. In addition, weak C—H⋯O hydrogen bonds, weak C—H⋯π interactions and π–π interactions with a centroid–centroid distance of 3.560 (2) Å combine to form a three-dimensional network. One of the ethyl groups is disordered over two sets of sites with occupancies in the ratio 0.586 (7):0.414 (7).

Keywords: crystal structure; nickel(II) complex; hydrogen bonding; disorder; coordination.

CCDC reference: 1454040

1. Chemical context

In spite of efforts in the past decades to synthesize structurally highly varying metal-organic complexes, no structures up to this point have been reported which contain the combination of a hydrophilic sulfate anion, water molecules and hydrophobic 1-ethyl-1H-imidazole molecules as ligands. The title compound was prepared by the reaction of NiSO₄·6H₂O and 1-ethyl-1H-imidazole. The crystal structure of the title compound is presented herein.

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1. The Ni^II ion is coordinated in a slightly distorted octahedral geometry by three facially arranged 1-ethyl-1H-imidazole ligands, one monodentate sulfate ligand and two water molecules. The Ni—N bond lengths are in the range 2.0630 (16)–2.0817 (17)Å and the Ni—O bond lengths are in the range 2.1195 (15)–2.1502 (14). The Niⁱⁱ ion is displaced by 0.1038 (3) Å from the O1/O2/N11/N13 plane. The distances of two water O atoms O1 and O2 from the S1/O3/Ni1/N12 plane are the same within experimental error, with values of 1.520 (2) and −1.504 (2) Å, respectively. The sulfate atom O6 is displaced by only 0.144 (2) Å from the S1/O3/Ni1/N12 plane, while atoms O4 and O5 are displaced by 1.114 (2) and −1.298 (2) Å, respectively, from this plane (see Fig. 2.).

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. Only the major component of disorder is shown.

Figure 2
The distances of the atoms N12, Ni1, O3, S1 and O6 from the least-squares plane defined by S1/O3/Ni1/N12.

3. Supramolecular features

In the crystal, two pairs of O—H⋯O hydrogen bonds (Table 1) link complex molecules, forming inversion dimers incorporating R₂⁴(8), R₂²(8) and R₂²(12) rings. The dimeric unit also contains two symmetry-unique intramolecular O—H⋯O hydrogen bonds (Fig. 3). In addition, weak C—H⋯O hydrogen bonds, weak C—H⋯π interactions and π–π interactions with a centroid–centroid distance of 3.560 (2) Å combine to form a three-dimensional network. The π–π interaction is observed between the N11/C21/N31/C41/C51 ring and the inversion-related ring at (1 − x, −y, 1 − z).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N13–C23–N33–C43–C53 ring and Cg2 is the centroid of the N12–C22–N32–C42–C52 ring

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O4	0.84 (3)	1.88 (3)	2.706 (2)	170 (3)
O1—H1B⋯O5ⁱ	0.77 (3)	2.02 (3)	2.786 (2)	173 (3)
O2—H2B⋯O4ⁱ	0.85 (3)	1.88 (3)	2.720 (2)	171 (3)
O2—H2A⋯O5	0.81 (3)	2.00 (3)	2.791 (2)	165 (3)
C22—H22⋯O5ⁱ	0.95	2.60	3.511 (3)	162
C23—H23⋯O6ⁱⁱ	0.95	2.56	3.409 (3)	150
C52—H52⋯O6ⁱⁱ	0.95	2.42	3.315 (3)	157
C73—H73B⋯O6ⁱⁱⁱ	0.98	2.40	3.347 (3)	163
C61—H61A⋯Cg1^iv	0.99	2.80	3.779 (3)	169
C61—H61B⋯Cg2^v	0.99	2.97	3.816 (3)	144
Symmetry codes: (i) -x, -y, -z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) -x+1, -y, -z+1.

Figure 3
An inversion dimer of the title compound. Hydrogen bonds are shown as dotted blue lines.

4. Database survey

A search of the Cambridge Structural Database (CSD; Groom & Allen, 2014 ) for molecules with two water ligands, a sulfate anion and three nitrogen-containing molecules gave the following hits with Ni: ARUZIW (Ouyang et al., 2004 ), BEDSEJ (Wan et al., 2003 ), FOXRAM (Xu et al., 2009 ), REHKUL (Díaz de Vivar et al., 2006 ), ZAMFUO (Mukherjee et al., 1995 ), and with Cu: ODAHEI, ODAHOS (Adarsh et al., 2011 ), XIHSAI (Gómez-Saiz et al., 2002 ) and QUSJAP (Calatayud et al., 2000 ).

A similar type of hydrogen bonding occurs between the sulfate anion and water molecules in the complex BEDSEJ. In ARUZIW, one of the hydrogen bonds of the sulfate anion involves the protonated hydrogen-acceptor nitrogen atom. Unlike the title compound, one of the water ligands in FOXRAM, REHKUL and ZAMFUO is trans to the sulfate ligand. This also the case in the copper-containing structure QUSJUP, but in ODAHEI, ODAHOS and XIHSAI the two aqua ligands are trans to each other.

Complexes with one Ni^II ion and at least three 1-ethyl-1H-imidazole ligands have already been reported in the literature (DEDLIJ: Huxel et al., 2012 ; IDEJAE: Çetinkaya et al., 2013 ; WENYAK: Liu et al., 2006 ). Complexes have also been reported for Cu (GEVGEV: Hoogerstraete et al., 2012 ; UFOMIM: Liu et al., 2008 ; XIKXEV: Liu et al., 2007 ).

5. Synthesis and crystallization

NiSO₄·6H₂O and 1-ethyl-1H-imidazole in a 1:1 stoichiometric ratio formed an exothermic reaction. The compound was dissolved in methanol and the solution was precipitated with ethyl acetate. After one week, blue crystals suitable for X-ray diffraction grew in the vessel.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Six reflections were found to be shaded by the beamstop and removed from the data set. The hydrogen atoms of the water molecules were located in a difference map and refined freely. Hydrogen atoms bonded to C atoms were placed in calculated positions and refined in a riding-model approximation. One of the ethyl groups is disordered over two sets of sites with occupancies in the ratio 0.586 (7):0.414 (7).

Table 2
Experimental details

Crystal data
Chemical formula	[Ni(SO₄)(C₅H₈N₂)₃(H₂O)₂]
M_r	478.97
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	131
a, b, c (Å)	12.0252 (13), 14.3481 (15), 15.3502 (11)
β (°)	128.980 (5)
V (Å³)	2058.9 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.09
Crystal size (mm)	0.40 × 0.25 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID-S
Absorption correction	Numerical (NUMABS; Higashi, 1999 )
T_min, T_max	0.705, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	28931, 4723, 4284
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.085, 1.07
No. of reflections	4723
No. of parameters	290
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.04, −1.12
Computer programs: CrystalClear (Rigaku, 2008 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1454040

Crystal structure: contains datablock I. DOI: 10.1107/S2056989016002863/lh5802sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989016002863/lh5802Isup2.hkl

checkCIF report

Chemical context top

Structural commentary top

The molecular structure of the title compound is shown in Fig. 1. The Ni^II ion is coordinated in a slightly distorted octahedral geometry by three facial 1-ethyl-1H-imidazole ligands, one sulfate ligand and two water molecules. The Ni—N bond lengths are in the range 2.0630 (16)–2.0817 (17) Å and the Ni—O bond lengths are in the range 2.1195 (15)–2.1502 (14). The Niⁱⁱ ion is displaced by 0.1038 (3) Å from the O1/O2/N11/N13 plane. The distances of two water O atoms O1 and O2 from the S1/O3/Ni1/N12 plane are the same within experimental error, with values of 1.520 (2) and −1.504 (2) Å, respectively. The sulfate atom O6 is displaced by only 0.144 (2) Å from the S1/O3/Ni1/N12 plane, while atoms O4 and O5 are displaced by 1.114 (2) and −1.298 (2) Å, respectively, from this plane (see Fig. 2.).

Supramolecular features top

In the crystal, two pairs of O—H···O hydrogen bonds (Table 1) link complex molecules, forming inversion dimers incorporating R₂⁴(8), R₂²(8) and R₂²(12) rings. The dimeric unit also contains two symmetry-unique intramolecular O—H···O hydrogen bonds (Fig 3). In addition, weak C—H···O hydrogen bonds, weak C—H···π interactions and π–π interactions with a centroid–centroid distance of 3.560 (2) Å combine to form a three-dimensional network. The π–π interaction is observed between the N11/C21/N31/C41/C51 ring and the inversion-related ring at (1 − x, −y, 1 − z).

Database survey top

A search of the Cambridge Structural Database (CSD; Groom & Allen, 2014) for molecules with two water ligands, a sulfate anion and three nitrogen-containing molecules gave the following hits with Ni: ARUZIW (Ouyang et al., 2004), BEDSEJ (Wan et al., 2003), FOXRAM (Xu et al., 2009), REHKUL (Díaz de Vivar et al., 2006), ZAMFUO (Mukherjee et al., 1995), and with Cu: ODAHEI, ODAHOS (Adarsh et al., 2011), XIHSAI (Gómez-Saiz et al., 2002) and QUSJAP (Calatayud et al., 2000).

A similar type of hydrogen bonding occurs between the sulfate anion and water molecules in the complex BEDSEJ. In ARUZIW, one of the hydrogen bonds of the sulfate anion involves the protonated hydrogen-acceptor nitrogen atoms. Unlike the title compound, one of the water ligands in FOXRAM, REHKUL and ZAMFUO is trans to the sulfate ligand. This also the case in the copper-containing structure QUSJUP, but in ODAHEI, ODAHOS and XIHSAI the two aqua ligands are trans to each other.

Complexes with one Ni^II ion and at least three 1-ethyl-1H-imidazole ligands have already been reported in the literature (DEDLIJ: Huxel et al., 2012; IDEJAE: Çetinkaya et al., 2013; WENYAK: Liu et al., 2006). Complexes have also been reported for Cu (GEVGEV: Hoogerstraete et al., 2012; UFOMIM: Liu et al., 2008; XIKXEV: Liu et al., 2007).

Synthesis and crystallization top

Refinement top

Structure description top

A search of the Cambridge Structural Database (CSD; Groom & Allen, 2014) for molecules with two water ligands, a sulfate anion and three nitrogen-containing molecules gave the following hits with Ni: ARUZIW (Ouyang et al., 2004), BEDSEJ (Wan et al., 2003), FOXRAM (Xu et al., 2009), REHKUL (Díaz de Vivar et al., 2006), ZAMFUO (Mukherjee et al., 1995), and with Cu: ODAHEI, ODAHOS (Adarsh et al., 2011), XIHSAI (Gómez-Saiz et al., 2002) and QUSJAP (Calatayud et al., 2000).

A similar type of hydrogen bonding occurs between the sulfate anion and water molecules in the complex BEDSEJ. In ARUZIW, one of the hydrogen bonds of the sulfate anion involves the protonated hydrogen-acceptor nitrogen atoms. Unlike the title compound, one of the water ligands in FOXRAM, REHKUL and ZAMFUO is trans to the sulfate ligand. This also the case in the copper-containing structure QUSJUP, but in ODAHEI, ODAHOS and XIHSAI the two aqua ligands are trans to each other.

Complexes with one Ni^II ion and at least three 1-ethyl-1H-imidazole ligands have already been reported in the literature (DEDLIJ: Huxel et al., 2012; IDEJAE: Çetinkaya et al., 2013; WENYAK: Liu et al., 2006). Complexes have also been reported for Cu (GEVGEV: Hoogerstraete et al., 2012; UFOMIM: Liu et al., 2008; XIKXEV: Liu et al., 2007).

Synthesis and crystallization top

Refinement details top

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. Only the major component of disorder is shown.
	Fig. 2. The distances of the atoms N12, Ni1, O3, S1 and O6 from the least-squares plane defined by S1/O3/Ni1/N12.
	Fig. 3. An inversion dimer of the title compound. Hydrogen bonds are shown as dotted blue lines.

Diaquatris(1-ethyl-1H-imidazole-κN³)(sulfato-κO)nickel(II) top

Crystal data top

[Ni(SO₄)(C₅H₈N₂)₃(H₂O)₂]	F(000) = 1008
M_r = 478.97	D_x = 1.545 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
a = 12.0252 (13) Å	Cell parameters from 24228 reflections
b = 14.3481 (15) Å	θ = 3.0–29.2°
c = 15.3502 (11) Å	µ = 1.09 mm⁻¹
β = 128.980 (5)°	T = 131 K
V = 2058.9 (4) Å³	Prism, blue–green
Z = 4	0.40 × 0.25 × 0.15 mm

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	4723 independent reflections
Radiation source: NORMAL-focus sealed tube	4284 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 10.0000 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
dtprofit.ref scans	h = −15→15
Absorption correction: numerical (NUMABS; Higashi, 1999)	k = −18→18
T_min = 0.705, T_max = 1.000	l = −19→19
28931 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: structure-invariant direct methods
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: mixed
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0358P)² + 2.7059P] where P = (F_o² + 2F_c²)/3
4723 reflections	(Δ/σ)_max = 0.001
290 parameters	Δρ_max = 1.04 e Å⁻³
2 restraints	Δρ_min = −1.12 e Å⁻³

Crystal data top

[Ni(SO₄)(C₅H₈N₂)₃(H₂O)₂]	V = 2058.9 (4) Å³
M_r = 478.97	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.0252 (13) Å	µ = 1.09 mm⁻¹
b = 14.3481 (15) Å	T = 131 K
c = 15.3502 (11) Å	0.40 × 0.25 × 0.15 mm
β = 128.980 (5)°

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	4723 independent reflections
Absorption correction: numerical (NUMABS; Higashi, 1999)	4284 reflections with I > 2σ(I)
T_min = 0.705, T_max = 1.000	R_int = 0.030
28931 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	2 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 1.04 e Å⁻³
4723 reflections	Δρ_min = −1.12 e Å⁻³
290 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.32786 (2)	0.06839 (2)	0.17394 (2)	0.01465 (8)
S1	0.19425 (5)	−0.13289 (3)	0.04041 (4)	0.01533 (11)
O1	0.17269 (16)	0.02378 (11)	0.19192 (12)	0.0184 (3)
O2	0.16244 (15)	0.09393 (11)	0.00106 (12)	0.0194 (3)
O3	0.31939 (14)	−0.07108 (9)	0.11877 (12)	0.0181 (3)
O4	0.10655 (15)	−0.13787 (10)	0.07794 (12)	0.0203 (3)
O5	0.10552 (15)	−0.09040 (10)	−0.07368 (12)	0.0205 (3)
O6	0.24281 (15)	−0.22575 (10)	0.03973 (12)	0.0226 (3)
N11	0.48566 (17)	0.02439 (12)	0.33618 (13)	0.0171 (3)
N12	0.30580 (17)	0.20374 (12)	0.21002 (14)	0.0186 (3)
N13	0.47676 (17)	0.10307 (12)	0.15321 (14)	0.0183 (3)
N31	0.61057 (18)	−0.07752 (12)	0.47365 (15)	0.0205 (3)
N32	0.1943 (2)	0.33190 (13)	0.19606 (18)	0.0293 (4)
N33	0.67307 (18)	0.15163 (12)	0.18436 (15)	0.0203 (3)
C21	0.5071 (2)	−0.06505 (14)	0.36263 (17)	0.0182 (4)
H21	0.4561	−0.1143	0.3101	0.022*
C22	0.1814 (2)	0.24081 (14)	0.17007 (19)	0.0235 (4)
H22	0.0937	0.2074	0.1282	0.028*
C23	0.6062 (2)	0.13902 (14)	0.22810 (17)	0.0200 (4)
H23	0.6465	0.1540	0.3030	0.024*
C41	0.6587 (2)	0.00910 (15)	0.52137 (17)	0.0215 (4)
H41	0.7313	0.0229	0.5985	0.026*
C42	0.3367 (2)	0.35474 (15)	0.2570 (2)	0.0280 (5)
H42	0.3790	0.4141	0.2871	0.034*
C43	0.5818 (2)	0.12208 (15)	0.07504 (18)	0.0239 (4)
H43	0.5989	0.1225	0.0225	0.029*
C51	0.5813 (2)	0.07121 (14)	0.43575 (17)	0.0211 (4)
H51	0.5916	0.1370	0.4434	0.025*
C52	0.4042 (2)	0.27554 (14)	0.26545 (18)	0.0215 (4)
H52	0.5038	0.2701	0.3036	0.026*
C53	0.4619 (2)	0.09216 (15)	0.05751 (17)	0.0209 (4)
H53	0.3798	0.0673	−0.0110	0.025*
C61	0.6605 (3)	−0.16783 (16)	0.5309 (2)	0.0306 (5)
H61A	0.5983	−0.2177	0.4768	0.037*
H61B	0.6524	−0.1688	0.5912	0.037*
C62	0.0740 (3)	0.39212 (18)	0.1578 (3)	0.0462 (7)
H62A	−0.0128	0.3533	0.1216	0.055*	0.586 (7)
H62B	0.0576	0.4354	0.1005	0.055*	0.586 (7)
H62C	0.0944	0.4235	0.2239	0.055*	0.414 (7)
H62D	−0.0116	0.3526	0.1243	0.055*	0.414 (7)
C63	0.8153 (2)	0.19343 (16)	0.24232 (19)	0.0254 (4)
H63A	0.8754	0.1508	0.2368	0.030*
H63B	0.8617	0.2014	0.3227	0.030*
C71	0.8118 (3)	−0.18738 (19)	0.5804 (3)	0.0461 (7)
H71A	0.8749	−0.1414	0.6389	0.069*
H71B	0.8215	−0.1836	0.5217	0.069*
H71C	0.8384	−0.2500	0.6131	0.069*
C72A	0.0951 (4)	0.4480 (3)	0.2497 (3)	0.0344 (11)	0.586 (7)
H72A	0.0106	0.4869	0.2184	0.052*	0.586 (7)
H72B	0.1796	0.4878	0.2850	0.052*	0.586 (7)
H72C	0.1088	0.4057	0.3059	0.052*	0.586 (7)
C72B	0.0385 (8)	0.4659 (5)	0.0733 (6)	0.061 (3)	0.414 (7)
H72D	0.1231	0.5044	0.1042	0.092*	0.414 (7)
H72E	−0.0394	0.5052	0.0568	0.092*	0.414 (7)
H72F	0.0086	0.4358	0.0042	0.092*	0.414 (7)
C73	0.8063 (3)	0.28677 (17)	0.1928 (2)	0.0286 (5)
H73A	0.7374	0.3265	0.1894	0.043*
H73B	0.7752	0.2778	0.1171	0.043*
H73C	0.9006	0.3166	0.2399	0.043*
H2A	0.145 (3)	0.044 (2)	−0.030 (2)	0.030 (7)*
H2B	0.083 (3)	0.112 (2)	−0.017 (2)	0.038 (8)*
H1A	0.152 (3)	−0.029 (2)	0.163 (3)	0.041 (8)*
H1B	0.098 (3)	0.046 (2)	0.159 (3)	0.035 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01215 (12)	0.01505 (13)	0.01544 (13)	−0.00015 (8)	0.00804 (10)	−0.00036 (9)
S1	0.0129 (2)	0.0156 (2)	0.0155 (2)	0.00119 (16)	0.00791 (19)	−0.00091 (16)
O1	0.0150 (7)	0.0182 (7)	0.0209 (7)	−0.0005 (6)	0.0107 (6)	−0.0016 (6)
O2	0.0156 (7)	0.0192 (7)	0.0201 (7)	0.0002 (6)	0.0096 (6)	−0.0001 (6)
O3	0.0135 (6)	0.0186 (7)	0.0189 (7)	−0.0002 (5)	0.0085 (6)	−0.0026 (5)
O4	0.0185 (7)	0.0215 (7)	0.0232 (7)	−0.0017 (5)	0.0143 (6)	−0.0020 (6)
O5	0.0187 (7)	0.0231 (7)	0.0160 (7)	0.0020 (6)	0.0091 (6)	0.0005 (6)
O6	0.0208 (7)	0.0179 (7)	0.0244 (7)	0.0034 (6)	0.0120 (6)	−0.0023 (6)
N11	0.0137 (7)	0.0195 (8)	0.0167 (8)	0.0010 (6)	0.0089 (7)	0.0004 (6)
N12	0.0166 (8)	0.0181 (8)	0.0206 (8)	−0.0013 (6)	0.0114 (7)	−0.0012 (6)
N13	0.0173 (8)	0.0185 (8)	0.0205 (8)	−0.0001 (6)	0.0126 (7)	−0.0002 (6)
N31	0.0182 (8)	0.0211 (8)	0.0199 (8)	0.0007 (6)	0.0109 (7)	0.0025 (7)
N32	0.0258 (9)	0.0194 (9)	0.0452 (12)	0.0010 (7)	0.0236 (9)	−0.0013 (8)
N33	0.0173 (8)	0.0216 (8)	0.0237 (9)	−0.0012 (7)	0.0136 (7)	−0.0013 (7)
C21	0.0145 (9)	0.0201 (9)	0.0180 (9)	−0.0002 (7)	0.0093 (8)	0.0003 (7)
C22	0.0187 (9)	0.0184 (9)	0.0306 (11)	−0.0013 (8)	0.0142 (9)	−0.0021 (8)
C23	0.0178 (9)	0.0227 (10)	0.0206 (9)	−0.0014 (8)	0.0126 (8)	−0.0018 (8)
C41	0.0172 (9)	0.0252 (10)	0.0172 (9)	−0.0006 (8)	0.0084 (8)	−0.0021 (8)
C42	0.0281 (11)	0.0196 (10)	0.0389 (13)	−0.0056 (8)	0.0224 (10)	−0.0052 (9)
C43	0.0219 (10)	0.0301 (11)	0.0227 (10)	−0.0027 (8)	0.0155 (9)	−0.0035 (8)
C51	0.0202 (10)	0.0200 (10)	0.0196 (10)	−0.0003 (7)	0.0109 (8)	−0.0025 (8)
C52	0.0184 (9)	0.0194 (9)	0.0264 (10)	−0.0033 (8)	0.0140 (9)	−0.0017 (8)
C53	0.0182 (9)	0.0237 (10)	0.0203 (9)	−0.0014 (8)	0.0119 (8)	−0.0036 (8)
C61	0.0302 (12)	0.0242 (11)	0.0319 (12)	0.0048 (9)	0.0169 (10)	0.0112 (9)
C62	0.0368 (14)	0.0281 (13)	0.078 (2)	0.0115 (11)	0.0379 (15)	0.0054 (13)
C63	0.0149 (9)	0.0286 (11)	0.0298 (11)	−0.0039 (8)	0.0127 (9)	−0.0026 (9)
C71	0.0353 (14)	0.0302 (13)	0.0618 (18)	0.0143 (11)	0.0252 (14)	0.0112 (12)
C72A	0.025	0.027 (2)	0.048 (3)	0.0004 (15)	0.0218 (14)	−0.0071 (18)
C72B	0.025	0.075 (6)	0.063 (5)	0.022 (3)	0.017 (3)	0.005 (4)
C73	0.0295 (11)	0.0316 (12)	0.0298 (11)	−0.0081 (9)	0.0211 (10)	−0.0042 (9)

Geometric parameters (Å, º) top

Ni1—N11	2.0630 (16)	C41—H41	0.9500
Ni1—N13	2.0667 (16)	C42—C52	1.354 (3)
Ni1—N12	2.0817 (17)	C42—H42	0.9500
Ni1—O2	2.1195 (15)	C43—C53	1.359 (3)
Ni1—O1	2.1485 (15)	C43—H43	0.9500
Ni1—O3	2.1502 (14)	C51—H51	0.9500
S1—O6	1.4574 (14)	C52—H52	0.9500
S1—O4	1.4878 (14)	C53—H53	0.9500
S1—O3	1.4902 (14)	C61—C71	1.492 (3)
S1—O5	1.4920 (14)	C61—H61A	0.9900
O1—H1A	0.84 (3)	C61—H61B	0.9900
O1—H1B	0.77 (3)	C62—C72A	1.499 (3)
O2—H2A	0.81 (3)	C62—C72B	1.512 (3)
O2—H2B	0.85 (3)	C62—H62A	0.9900
N11—C21	1.322 (3)	C62—H62B	0.9900
N11—C51	1.378 (3)	C62—H62C	0.9900
N12—C22	1.320 (3)	C62—H62D	0.9900
N12—C52	1.385 (3)	C63—C73	1.509 (3)
N13—C23	1.326 (3)	C63—H63A	0.9900
N13—C53	1.373 (3)	C63—H63B	0.9900
N31—C21	1.348 (3)	C71—H71A	0.9800
N31—C41	1.372 (3)	C71—H71B	0.9800
N31—C61	1.466 (3)	C71—H71C	0.9800
N32—C22	1.347 (3)	C72A—H72A	0.9800
N32—C42	1.378 (3)	C72A—H72B	0.9800
N32—C62	1.455 (3)	C72A—H72C	0.9800
N33—C23	1.345 (3)	C72B—H72D	0.9800
N33—C43	1.372 (3)	C72B—H72E	0.9800
N33—C63	1.471 (3)	C72B—H72F	0.9800
C21—H21	0.9500	C73—H73A	0.9800
C22—H22	0.9500	C73—H73B	0.9800
C23—H23	0.9500	C73—H73C	0.9800
C41—C51	1.360 (3)

N11—Ni1—N13	91.81 (6)	C53—C43—N33	105.81 (18)
N11—Ni1—N12	97.97 (7)	C53—C43—H43	127.1
N13—Ni1—N12	94.83 (7)	N33—C43—H43	127.1
N11—Ni1—O2	172.09 (6)	C41—C51—N11	109.81 (18)
N13—Ni1—O2	89.27 (6)	C41—C51—H51	125.1
N12—Ni1—O2	89.74 (6)	N11—C51—H51	125.1
N11—Ni1—O1	88.13 (6)	C42—C52—N12	109.66 (18)
N13—Ni1—O1	176.45 (6)	C42—C52—H52	125.2
N12—Ni1—O1	88.70 (6)	N12—C52—H52	125.2
O2—Ni1—O1	90.31 (6)	C43—C53—N13	110.15 (18)
N11—Ni1—O3	88.30 (6)	C43—C53—H53	124.9
N13—Ni1—O3	89.68 (6)	N13—C53—H53	124.9
N12—Ni1—O3	172.14 (6)	N31—C61—C71	112.3 (2)
O2—Ni1—O3	83.87 (6)	N31—C61—H61A	109.1
O1—Ni1—O3	86.76 (6)	C71—C61—H61A	109.1
O6—S1—O4	110.10 (9)	N31—C61—H61B	109.1
O6—S1—O3	110.12 (8)	C71—C61—H61B	109.1
O4—S1—O3	108.54 (8)	H61A—C61—H61B	107.9
O6—S1—O5	111.04 (9)	N32—C62—C72A	113.7 (3)
O4—S1—O5	108.45 (8)	N32—C62—C72B	115.8 (3)
O3—S1—O5	108.52 (8)	N32—C62—H62A	108.8
Ni1—O1—H1A	101 (2)	C72A—C62—H62A	108.8
Ni1—O1—H1B	122 (2)	N32—C62—H62B	108.8
H1A—O1—H1B	101 (3)	C72A—C62—H62B	108.8
Ni1—O2—H2A	106 (2)	H62A—C62—H62B	107.7
Ni1—O2—H2B	116 (2)	N32—C62—H62C	108.3
H2A—O2—H2B	104 (3)	C72B—C62—H62C	108.3
S1—O3—Ni1	130.19 (8)	N32—C62—H62D	108.3
C21—N11—C51	105.50 (17)	C72B—C62—H62D	108.3
C21—N11—Ni1	121.44 (14)	H62C—C62—H62D	107.4
C51—N11—Ni1	133.00 (14)	N33—C63—C73	111.69 (18)
C22—N12—C52	105.42 (17)	N33—C63—H63A	109.3
C22—N12—Ni1	123.31 (14)	C73—C63—H63A	109.3
C52—N12—Ni1	130.90 (13)	N33—C63—H63B	109.3
C23—N13—C53	105.29 (16)	C73—C63—H63B	109.3
C23—N13—Ni1	128.18 (14)	H63A—C63—H63B	107.9
C53—N13—Ni1	126.53 (13)	C61—C71—H71A	109.5
C21—N31—C41	107.37 (17)	C61—C71—H71B	109.5
C21—N31—C61	125.43 (18)	H71A—C71—H71B	109.5
C41—N31—C61	127.20 (18)	C61—C71—H71C	109.5
C22—N32—C42	107.12 (18)	H71A—C71—H71C	109.5
C22—N32—C62	123.8 (2)	H71B—C71—H71C	109.5
C42—N32—C62	128.9 (2)	C62—C72A—H72A	109.5
C23—N33—C43	107.43 (17)	C62—C72A—H72B	109.5
C23—N33—C63	125.87 (18)	H72A—C72A—H72B	109.5
C43—N33—C63	126.65 (18)	C62—C72A—H72C	109.5
N11—C21—N31	111.34 (17)	H72A—C72A—H72C	109.5
N11—C21—H21	124.3	H72B—C72A—H72C	109.5
N31—C21—H21	124.3	C62—C72B—H72D	109.5
N12—C22—N32	111.58 (18)	C62—C72B—H72E	109.5
N12—C22—H22	124.2	H72D—C72B—H72E	109.5
N32—C22—H22	124.2	C62—C72B—H72F	109.5
N13—C23—N33	111.33 (18)	H72D—C72B—H72F	109.5
N13—C23—H23	124.3	H72E—C72B—H72F	109.5
N33—C23—H23	124.3	C63—C73—H73A	109.5
C51—C41—N31	105.98 (18)	C63—C73—H73B	109.5
C51—C41—H41	127.0	H73A—C73—H73B	109.5
N31—C41—H41	127.0	C63—C73—H73C	109.5
C52—C42—N32	106.21 (19)	H73A—C73—H73C	109.5
C52—C42—H42	126.9	H73B—C73—H73C	109.5
N32—C42—H42	126.9

O6—S1—O3—Ni1	−172.84 (10)	C23—N33—C43—C53	−0.2 (2)
O4—S1—O3—Ni1	−52.25 (13)	C63—N33—C43—C53	−177.64 (19)
O5—S1—O3—Ni1	65.42 (13)	N31—C41—C51—N11	0.4 (2)
C51—N11—C21—N31	0.3 (2)	C21—N11—C51—C41	−0.5 (2)
Ni1—N11—C21—N31	−177.08 (12)	Ni1—N11—C51—C41	176.55 (14)
C41—N31—C21—N11	−0.1 (2)	N32—C42—C52—N12	0.3 (3)
C61—N31—C21—N11	179.85 (19)	C22—N12—C52—C42	−0.4 (2)
C52—N12—C22—N32	0.3 (3)	Ni1—N12—C52—C42	172.68 (15)
Ni1—N12—C22—N32	−173.42 (15)	N33—C43—C53—N13	0.4 (2)
C42—N32—C22—N12	−0.1 (3)	C23—N13—C53—C43	−0.4 (2)
C62—N32—C22—N12	176.4 (2)	Ni1—N13—C53—C43	−179.64 (14)
C53—N13—C23—N33	0.3 (2)	C21—N31—C61—C71	114.2 (3)
Ni1—N13—C23—N33	179.50 (13)	C41—N31—C61—C71	−65.9 (3)
C43—N33—C23—N13	−0.1 (2)	C22—N32—C62—C72A	130.5 (3)
C63—N33—C23—N13	177.42 (18)	C42—N32—C62—C72A	−53.8 (4)
C21—N31—C41—C51	−0.2 (2)	C22—N32—C62—C72B	−110.8 (5)
C61—N31—C41—C51	179.9 (2)	C42—N32—C62—C72B	64.9 (5)
C22—N32—C42—C52	−0.1 (3)	C23—N33—C63—C73	−111.6 (2)
C62—N32—C42—C52	−176.4 (2)	C43—N33—C63—C73	65.4 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N13–C23–N33–C43–C53 ring and Cg2 is the centroid of the N12–C22–N32–C42–C52 ring

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4	0.84 (3)	1.88 (3)	2.706 (2)	170 (3)
O1—H1B···O5ⁱ	0.77 (3)	2.02 (3)	2.786 (2)	173 (3)
O2—H2B···O4ⁱ	0.85 (3)	1.88 (3)	2.720 (2)	171 (3)
O2—H2A···O5	0.81 (3)	2.00 (3)	2.791 (2)	165 (3)
C22—H22···O5ⁱ	0.95	2.60	3.511 (3)	162
C23—H23···O6ⁱⁱ	0.95	2.56	3.409 (3)	150
C52—H52···O6ⁱⁱ	0.95	2.42	3.315 (3)	157
C73—H73B···O6ⁱⁱⁱ	0.98	2.40	3.347 (3)	163
C61—H61A···Cg1^iv	0.99	2.80	3.779 (3)	169
C61—H61B···Cg2^v	0.99	2.97	3.816 (3)	144

Symmetry codes: (i) −x, −y, −z; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+1, −y, −z; (iv) −x+1, y−1/2, −z+1/2; (v) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N13–C23–N33–C43–C53 ring and Cg2 is the centroid of the N12–C22–N32–C42–C52 ring

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4	0.84 (3)	1.88 (3)	2.706 (2)	170 (3)
O1—H1B···O5ⁱ	0.77 (3)	2.02 (3)	2.786 (2)	173 (3)
O2—H2B···O4ⁱ	0.85 (3)	1.88 (3)	2.720 (2)	171 (3)
O2—H2A···O5	0.81 (3)	2.00 (3)	2.791 (2)	165 (3)
C22—H22···O5ⁱ	0.95	2.60	3.511 (3)	162
C23—H23···O6ⁱⁱ	0.95	2.56	3.409 (3)	150
C52—H52···O6ⁱⁱ	0.95	2.42	3.315 (3)	157
C73—H73B···O6ⁱⁱⁱ	0.98	2.40	3.347 (3)	163
C61—H61A···Cg1^iv	0.99	2.80	3.779 (3)	169
C61—H61B···Cg2^v	0.99	2.97	3.816 (3)	144

Symmetry codes: (i) −x, −y, −z; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+1, −y, −z; (iv) −x+1, y−1/2, −z+1/2; (v) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Ni(SO₄)(C₅H₈N₂)₃(H₂O)₂]
M_r	478.97
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	131
a, b, c (Å)	12.0252 (13), 14.3481 (15), 15.3502 (11)
β (°)	128.980 (5)
V (Å³)	2058.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.09
Crystal size (mm)	0.40 × 0.25 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID-S
Absorption correction	Numerical (NUMABS; Higashi, 1999)
T_min, T_max	0.705, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	28931, 4723, 4284
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.085, 1.07
No. of reflections	4723
No. of parameters	290
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.04, −1.12

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), Mercury (Macrae et al., 2008), PLATON (Spek, 2009).

Acknowledgements

The above project was supported by the Hungarian Scientific and Research Fund (OTKA 100801).

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Volume 72| Part 3| March 2016| Pages 374-377

doi:10.1107/S2056989016002863

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