Poly[aqua­(μ2-4,4′-bipyridine-κ2N:N′)(ethane-1,2-diol-κO)(μ2-sulfato-κ2O:O′)nickel(II)]

Zhong, K.-L.

doi:10.1107/S1600536813003772

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Pages m154-m155

doi:10.1107/S1600536813003772

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Poly[aqua(μ₂-4,4′-bipyridine-κ²N:N′)(ethane-1,2-diol-κO)(μ₂-sulfato-κ²O:O′)nickel(II)]

Kai-Long Zhong ^a ^*

^aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Nanjing 210048, People's Republic of China
^*Correspondence e-mail: zklong@tom.com

(Received 22 January 2013; accepted 7 February 2013; online 16 February 2013)

The title compound, [Ni(SO₄)(C₁₀H₈N₂)(C₂H₆O₂)(H₂O)]_n, contains two crystallographically unique Ni^II atoms, each lying on a twofold rotation axis and having a slightly distorted octahedral environment. It is isotypic with the previously reported Cu^II analog [Zhong et al. (2011 ). Acta Cryst. C67, m62–m64]. One Ni^II atom is coordinated by two N atoms from two bridging 4,4′-bipyridine (4,4′-bipy) ligands, two O atoms from two sulfate ions and two aqua O atoms. The second Ni^II atom is surrounded by two N atoms from 4,4′-bipy ligands and four O atoms, two from bridging sulfate ions and from two ethane-1,2-diol ligands. The sulfate anion acts as a bridging ligand, linking adjacent Ni^II atoms, leading to the formation of linear ⋯Ni1—Ni2—Ni1—Ni2⋯ chains along the a-axis direction. Adjacent chains are further bridged by 4,4′-bipy ligands, resulting in a two-dimensional layered polymer parallel to (001). In the crystal, the polymeric layers are linked by extensive O—H⋯O hydrogen-bonding interactions involving the O atoms of the water molecules and the ethane-1,2-diol molecules, resulting in a three-dimensional supramolecular network.

Related literature

For Ni-(4,4′-bipy) complexes with perchlorate, citraconate or phthalate anions and a water molecule as a second ligand, see: Yang et al. (2003 ); Kopf et al. (2005 ); Wang et al. (2006 ). For an isotypic structure, see: Zhong et al. (2011). For background to coordination polymers, see: Dietzel et al. (2005 ); Robin & Fromm (2006 ); Sarma et al. (2009 ); Zhang et al. (2010 ).

Experimental

Crystal data

[Ni(SO₄)(C₁₀H₈N₂)(C₂H₆O₂)(H₂O)]
M_r = 391.04
Monoclinic, C 2/c
a = 11.022 (2) Å
b = 22.606 (5) Å
c = 12.123 (2) Å
β = 95.65 (3)°
V = 3005.9 (10) Å³
Z = 8
Mo Kα radiation
μ = 1.47 mm⁻¹
T = 223 K
0.40 × 0.35 × 0.10 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.743, T_max = 1.000
8555 measured reflections
3420 independent reflections
2885 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.086
S = 1.06
3420 reflections
214 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—N2	2.072 (2)
Ni1—O1W	2.0809 (15)
Ni1—O1	2.0844 (14)
Ni1—N1	2.101 (2)
Ni2—O5	2.0591 (15)
Ni2—O2	2.0817 (15)
Ni2—N4	2.096 (2)
Ni2—N3	2.101 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6A⋯O4ⁱ	0.82	1.89	2.694 (2)	165
O5—H5B⋯O1	0.82	1.82	2.599 (2)	158
O1W—H1WA⋯O6	0.85	1.86	2.693 (2)	167
O1W—H1WB⋯O3ⁱⁱ	0.85	1.91	2.718 (2)	157
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2007 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813003772/zq2195sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813003772/zq2195Isup2.hkl

checkCIF report

Comment top

Recently, the design and synthesis of metal-organic complexes or polymeric coordination networks belong to a rapidly developing field in coordination and supramolecular chemistry (Dietzel et al., 2005; Robin & Fromm, 2006; Sarma et al., 2009; Zhang et al., 2010). 4,4'-Bipyridine (4,4'-bipy) has been widely used as a bridging ligand to construct interesting complexes. Several Ni-(4,4'-bipy) complexes with perchlorate-anion, citraconate-anion, phthalate-anion and water-molecular ligands have been synthesized and characterized by X-ray diffraction (Yang et al., 2003; Kopf et al., 2005; Wang et al., 2006). The title nickel complex, [Ni₂(SO₄)₂(C₁₀H₈N₂)₂(C₂H₆O₂)₂(H₂O)₂]_n, was obtained via a solvothermal reaction.

The single-crystal X-ray diffraction experiment revealed that the title compound is isostructural to the previously reported Cu^II analog (Zhong et al., 2011). It contains two crystallographically independent Ni^II centres. Atom Ni1 adopts a slightly distorted octahedral geometry. It is coordinated by two N atoms (N1 and N2) from two bridging 4,4'-bipy ligands occupying the axial positions, two O atoms (O1) from two bridging sulfate anions and two O atoms (O1W) from two water molecules occupying the equatorial sites (Fig. 1 & Table 1). The coordination environment of the Ni2 centre is very similar to that of Ni1, with ethane-1,2-diol ligands in place of the water ligands. Both Ni atoms and 4,4'-bipy ligands occupy special positions on crystallographic twofold axes. The Ni—N bond distances [2.072 (2)- 2.101 (2) Å], the Ni—O bond distances [2.0591 (15) - 2.0844 (14) Å] and the cis bond angles around Ni^II centres [87.20 (4) - 92.80 (4) °] are in agreement with those observed in the previously reported Ni-(4,4'-bipy) complex (Yang et al., 2003). The sulfate anion and 4,4'-bipy act as bridging ligands between two different Ni²⁺ ions, giving rise to the formation of linear ···Ni1—O—SO₂—O—Ni2—O— SO₂—O··· chains running along the a direction and ···Ni1-bipy-Ni2-bipy··· chains along the b direction, respectively. The ···M—O—SO₂—O—M··· chains and the ···M—bipy—M··· chains are almost orthogonal, leading to a layered structure (Fig. 2). Intermolecular O1W—H5C···O6 and O5—H6···O1 hydrogen bonds help to further stabilize the layered structure (Table 2). In the crystal structure, extensive O—H···O hydrogen-bonding interactions between the water molecules, sulfate anions and 1,2-ethanediol molecules result in a three-dimensional supramolecular network.

Related literature top

For Ni-(4,4'-bipy) complexes with perchlorate, citraconate or phthalate anions and a water molecule as a second ligand, see: Yang et al. (2003); Kopf et al. (2005); Wang et al. (2006). For an isostructural [isotypic?] compound, see: Zhong et al. (2011). For background to coordination polymers, see: Dietzel et al. (2005); Robin & Fromm (2006); Sarma et al. (2009); Zhang et al. (2010).

Experimental top

Green block-shaped crystals of the title compound were obtained by a procedure similar to that described previously in Zhong et al. (2011) with NiSO₄.7H₂O instead of CuSO₄.5H₂O.

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Part of the structure of the title compound, showing the atom-numbering scheme and with displacement ellipsoids drawn at the 35% probability level. All H atoms have been omitted for clarity. Symmetry codes: (i) -x, y, -z + 3/2; (ii) -x + 1, y, -z + 3/2; (iii) x - 1, y, z; (iv) x + 1, y, z.
	Fig. 2. The crystal structure of the title compound viewed along the c axis. All H atoms have omitted for clarity. Symmetry codes: (v) -x + 1, y - 1, z; (vi) x - 1/2, y - 1/2, z; (viii) x - 1/2, y + 1/2, z.

Poly[aqua(µ₂-4,4'-bipyridine-κ²N:N')(ethane-1,2-diol-κO)(µ₂-sulfato-κ²O:O')nickel(II)] top

Crystal data top

[Ni(SO₄)(C₁₀H₈N₂)(C₂H₆O₂)(H₂O)]	F(000) = 1616
M_r = 391.04	D_x = 1.728 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6950 reflections
a = 11.022 (2) Å	θ = 3.3–27.5°
b = 22.606 (5) Å	µ = 1.47 mm⁻¹
c = 12.123 (2) Å	T = 223 K
β = 95.65 (3)°	Block, green
V = 3005.9 (10) Å³	0.40 × 0.35 × 0.10 mm
Z = 8

Data collection top

Rigaku Mercury CCD diffractometer	3420 independent reflections
Radiation source: fine-focus sealed tube	2885 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.024
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ω scans	h = −14→11
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −23→29
T_min = 0.743, T_max = 1.000	l = −14→15
8555 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.086	w = 1/[σ²(F_o²) + (0.0501P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3420 reflections	Δρ_max = 0.56 e Å⁻³
214 parameters	Δρ_min = −0.41 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0014 (2)

Crystal data top

[Ni(SO₄)(C₁₀H₈N₂)(C₂H₆O₂)(H₂O)]	V = 3005.9 (10) Å³
M_r = 391.04	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 11.022 (2) Å	µ = 1.47 mm⁻¹
b = 22.606 (5) Å	T = 223 K
c = 12.123 (2) Å	0.40 × 0.35 × 0.10 mm
β = 95.65 (3)°

Data collection top

Rigaku Mercury CCD diffractometer	3420 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	2885 reflections with I > 2σ(I)
T_min = 0.743, T_max = 1.000	R_int = 0.024
8555 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.06	Δρ_max = 0.56 e Å⁻³
3420 reflections	Δρ_min = −0.41 e Å⁻³
214 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
Ni1	0.5000	0.379715 (14)	0.2500	0.01501 (11)
Ni2	0.0000	0.378572 (13)	0.2500	0.01544 (11)
S1	0.23450 (4)	0.39830 (2)	0.10920 (4)	0.01777 (13)
O1	0.31124 (12)	0.37951 (6)	0.21319 (12)	0.0197 (3)
O1W	0.47576 (13)	0.37522 (5)	0.41787 (12)	0.0234 (3)
H1WA	0.4323	0.3957	0.4577	0.035*
H1WB	0.5451	0.3772	0.4551	0.035*
O2	0.10883 (12)	0.37748 (5)	0.11907 (11)	0.0194 (3)
O3	0.28195 (13)	0.36860 (7)	0.01488 (13)	0.0289 (4)
O4	0.23754 (14)	0.46204 (6)	0.09809 (14)	0.0360 (4)
O5	0.15466 (13)	0.37609 (6)	0.36000 (12)	0.0233 (3)
H5B	0.2169	0.3765	0.3282	0.028*
O6	0.30832 (13)	0.43173 (6)	0.52663 (13)	0.0329 (4)
H6A	0.2989	0.4663	0.5447	0.049*
N1	0.5000	0.28676 (10)	0.2500	0.0188 (5)
N2	0.5000	0.47137 (10)	0.2500	0.0182 (5)
N3	0.0000	0.28565 (10)	0.2500	0.0213 (5)
N4	0.0000	0.47128 (10)	0.2500	0.0185 (5)
C1	0.5000	0.16183 (12)	0.2500	0.0188 (6)
C2	0.43554 (19)	0.19444 (9)	0.16563 (17)	0.0243 (4)
H2A	0.3912	0.1750	0.1072	0.029*
C3	0.43763 (19)	0.25555 (9)	0.16891 (18)	0.0245 (4)
H3A	0.3935	0.2762	0.1119	0.029*
C4	0.58066 (18)	0.50219 (9)	0.19796 (17)	0.0237 (4)
H4A	0.6383	0.4815	0.1622	0.028*
C5	0.58292 (18)	0.56309 (8)	0.19449 (17)	0.0233 (4)
H5A	0.6395	0.5825	0.1553	0.028*
C6	0.5000	0.59546 (12)	0.2500	0.0200 (6)
C7	0.0000	0.16101 (12)	0.2500	0.0215 (6)
C8	0.0906 (2)	0.19347 (9)	0.2077 (2)	0.0426 (7)
H8A	0.1540	0.1741	0.1774	0.051*
C9	0.0880 (2)	0.25446 (10)	0.2101 (2)	0.0419 (6)
H9A	0.1515	0.2749	0.1821	0.050*
C10	0.0662 (2)	0.50282 (9)	0.32806 (18)	0.0294 (5)
H10A	0.1126	0.4824	0.3839	0.035*
C11	0.0692 (2)	0.56365 (9)	0.33016 (18)	0.0282 (5)
H11A	0.1180	0.5831	0.3857	0.034*
C12	0.0000	0.59610 (12)	0.2500	0.0187 (5)
C13	0.18041 (19)	0.35033 (9)	0.46738 (18)	0.0274 (5)
H13A	0.2502	0.3242	0.4675	0.033*
H13B	0.1111	0.3271	0.4854	0.033*
C14	0.2067 (2)	0.39774 (10)	0.55251 (19)	0.0317 (5)
H14A	0.1360	0.4232	0.5542	0.038*
H14B	0.2239	0.3800	0.6252	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01408 (18)	0.01323 (17)	0.0177 (2)	0.000	0.00165 (14)	0.000
Ni2	0.01432 (18)	0.01335 (18)	0.0185 (2)	0.000	0.00093 (14)	0.000
S1	0.0155 (2)	0.0190 (2)	0.0187 (2)	−0.00140 (18)	0.00098 (17)	0.00331 (18)
O1	0.0152 (7)	0.0260 (7)	0.0178 (7)	0.0001 (5)	0.0010 (6)	0.0034 (5)
O1W	0.0197 (7)	0.0294 (8)	0.0213 (8)	0.0027 (6)	0.0036 (6)	−0.0021 (6)
O2	0.0146 (6)	0.0232 (7)	0.0202 (7)	−0.0016 (5)	0.0009 (6)	−0.0005 (5)
O3	0.0194 (7)	0.0480 (10)	0.0199 (8)	0.0001 (6)	0.0041 (6)	−0.0026 (6)
O4	0.0342 (8)	0.0204 (7)	0.0514 (11)	−0.0054 (6)	−0.0058 (8)	0.0132 (7)
O5	0.0181 (7)	0.0333 (8)	0.0185 (7)	0.0006 (6)	0.0023 (6)	0.0034 (6)
O6	0.0302 (8)	0.0303 (8)	0.0389 (9)	−0.0006 (6)	0.0072 (7)	−0.0136 (7)
N1	0.0188 (11)	0.0154 (11)	0.0217 (12)	0.000	−0.0005 (9)	0.000
N2	0.0180 (11)	0.0151 (10)	0.0213 (12)	0.000	0.0012 (9)	0.000
N3	0.0220 (11)	0.0133 (10)	0.0288 (13)	0.000	0.0041 (10)	0.000
N4	0.0178 (11)	0.0170 (11)	0.0206 (12)	0.000	0.0021 (9)	0.000
C1	0.0193 (13)	0.0183 (13)	0.0193 (14)	0.000	0.0043 (11)	0.000
C2	0.0290 (10)	0.0186 (9)	0.0235 (11)	−0.0018 (8)	−0.0060 (9)	−0.0013 (8)
C3	0.0284 (10)	0.0197 (10)	0.0240 (11)	−0.0003 (9)	−0.0038 (9)	0.0012 (8)
C4	0.0241 (10)	0.0215 (10)	0.0259 (11)	−0.0009 (8)	0.0050 (9)	−0.0019 (8)
C5	0.0241 (10)	0.0202 (9)	0.0268 (11)	−0.0009 (8)	0.0076 (9)	0.0021 (8)
C6	0.0220 (13)	0.0174 (13)	0.0201 (14)	0.000	−0.0003 (11)	0.000
C7	0.0230 (14)	0.0190 (13)	0.0226 (15)	0.000	0.0021 (11)	0.000
C8	0.0407 (13)	0.0191 (10)	0.0735 (19)	0.0030 (10)	0.0328 (14)	−0.0012 (12)
C9	0.0388 (13)	0.0214 (10)	0.0711 (19)	−0.0001 (10)	0.0327 (13)	0.0020 (12)
C10	0.0376 (12)	0.0189 (10)	0.0287 (12)	0.0023 (9)	−0.0120 (10)	−0.0003 (9)
C11	0.0351 (12)	0.0214 (10)	0.0254 (11)	−0.0019 (9)	−0.0106 (9)	−0.0030 (8)
C12	0.0191 (13)	0.0158 (12)	0.0217 (14)	0.000	0.0041 (11)	0.000
C13	0.0284 (11)	0.0268 (11)	0.0265 (11)	−0.0012 (9)	0.0003 (9)	0.0094 (9)
C14	0.0303 (11)	0.0416 (13)	0.0240 (11)	−0.0020 (10)	0.0066 (9)	−0.0008 (10)

Geometric parameters (Å, º) top

Ni1—N2	2.072 (2)	C1—C2ⁱ	1.397 (2)
Ni1—O1W	2.0809 (15)	C1—C2	1.397 (2)
Ni1—O1Wⁱ	2.0809 (15)	C1—C12ⁱⁱⁱ	1.486 (4)
Ni1—O1	2.0844 (14)	C2—C3	1.382 (3)
Ni1—O1ⁱ	2.0844 (14)	C2—H2A	0.9300
Ni1—N1	2.101 (2)	C3—H3A	0.9300
Ni2—O5	2.0591 (15)	C4—C5	1.378 (3)
Ni2—O5ⁱⁱ	2.0591 (15)	C4—H4A	0.9300
Ni2—O2ⁱⁱ	2.0817 (15)	C5—C6	1.395 (2)
Ni2—O2	2.0817 (15)	C5—H5A	0.9300
Ni2—N4	2.096 (2)	C6—C5ⁱ	1.395 (2)
Ni2—N3	2.101 (2)	C6—C7^iv	1.482 (4)
S1—O4	1.4480 (15)	C7—C8	1.378 (3)
S1—O3	1.4660 (16)	C7—C8ⁱⁱ	1.378 (3)
S1—O2	1.4788 (14)	C7—C6^v	1.482 (4)
S1—O1	1.5084 (15)	C8—C9	1.379 (3)
O1W—H1WA	0.8500	C8—H8A	0.9300
O1W—H1WB	0.8500	C9—H9A	0.9300
O5—C13	1.429 (2)	C10—C11	1.376 (3)
O5—H5B	0.8200	C10—H10A	0.9300
O6—C14	1.419 (3)	C11—C12	1.385 (2)
O6—H6A	0.8200	C11—H11A	0.9300
N1—C3	1.343 (2)	C12—C11ⁱⁱ	1.385 (2)
N1—C3ⁱ	1.343 (2)	C12—C1^vi	1.486 (4)
N2—C4ⁱ	1.336 (2)	C13—C14	1.496 (3)
N2—C4	1.336 (2)	C13—H13A	0.9700
N3—C9ⁱⁱ	1.328 (3)	C13—H13B	0.9700
N3—C9	1.328 (3)	C14—H14A	0.9700
N4—C10	1.342 (2)	C14—H14B	0.9700
N4—C10ⁱⁱ	1.342 (2)

N2—Ni1—O1W	92.80 (4)	C9—N3—Ni2	122.06 (13)
N2—Ni1—O1Wⁱ	92.80 (4)	C10—N4—C10ⁱⁱ	115.8 (2)
O1W—Ni1—O1Wⁱ	174.41 (7)	C10—N4—Ni2	122.10 (12)
N2—Ni1—O1	90.13 (4)	C10ⁱⁱ—N4—Ni2	122.10 (12)
O1W—Ni1—O1	89.30 (6)	C2ⁱ—C1—C2	116.3 (2)
O1Wⁱ—Ni1—O1	90.69 (6)	C2ⁱ—C1—C12ⁱⁱⁱ	121.85 (12)
N2—Ni1—O1ⁱ	90.13 (4)	C2—C1—C12ⁱⁱⁱ	121.85 (12)
O1W—Ni1—O1ⁱ	90.69 (6)	C3—C2—C1	120.03 (18)
O1Wⁱ—Ni1—O1ⁱ	89.30 (6)	C3—C2—H2A	120.0
O1—Ni1—O1ⁱ	179.74 (7)	C1—C2—H2A	120.0
N2—Ni1—N1	180.0	N1—C3—C2	123.50 (18)
O1W—Ni1—N1	87.20 (4)	N1—C3—H3A	118.2
O1Wⁱ—Ni1—N1	87.20 (4)	C2—C3—H3A	118.2
O1—Ni1—N1	89.87 (4)	N2—C4—C5	123.4 (2)
O1ⁱ—Ni1—N1	89.87 (4)	N2—C4—H4A	118.3
O5—Ni2—O5ⁱⁱ	176.88 (7)	C5—C4—H4A	118.3
O5—Ni2—O2ⁱⁱ	90.48 (6)	C4—C5—C6	119.7 (2)
O5ⁱⁱ—Ni2—O2ⁱⁱ	89.49 (6)	C4—C5—H5A	120.2
O5—Ni2—O2	89.49 (6)	C6—C5—H5A	120.2
O5ⁱⁱ—Ni2—O2	90.48 (6)	C5ⁱ—C6—C5	116.7 (3)
O2ⁱⁱ—Ni2—O2	178.64 (7)	C5ⁱ—C6—C7^iv	121.66 (13)
O5—Ni2—N4	91.56 (4)	C5—C6—C7^iv	121.66 (13)
O5ⁱⁱ—Ni2—N4	91.56 (4)	C8—C7—C8ⁱⁱ	115.6 (3)
O2ⁱⁱ—Ni2—N4	90.68 (3)	C8—C7—C6^v	122.18 (13)
O2—Ni2—N4	90.68 (3)	C8ⁱⁱ—C7—C6^v	122.18 (13)
O5—Ni2—N3	88.44 (4)	C7—C8—C9	120.5 (2)
O5ⁱⁱ—Ni2—N3	88.44 (4)	C7—C8—H8A	119.8
O2ⁱⁱ—Ni2—N3	89.32 (3)	C9—C8—H8A	119.8
O2—Ni2—N3	89.32 (3)	N3—C9—C8	123.7 (2)
N4—Ni2—N3	180.0	N3—C9—H9A	118.1
O4—S1—O3	111.71 (10)	C8—C9—H9A	118.1
O4—S1—O2	110.77 (8)	N4—C10—C11	123.70 (19)
O3—S1—O2	109.04 (9)	N4—C10—H10A	118.2
O4—S1—O1	109.99 (8)	C11—C10—H10A	118.2
O3—S1—O1	108.01 (8)	C10—C11—C12	120.37 (19)
O2—S1—O1	107.18 (8)	C10—C11—H11A	119.8
S1—O1—Ni1	130.10 (9)	C12—C11—H11A	119.8
Ni1—O1W—H1WA	131.5	C11ⁱⁱ—C12—C11	116.1 (3)
Ni1—O1W—H1WB	108.7	C11ⁱⁱ—C12—C1^vi	121.97 (13)
H1WA—O1W—H1WB	101.4	C11—C12—C1^vi	121.97 (13)
S1—O2—Ni2	132.26 (9)	O5—C13—C14	110.12 (17)
C13—O5—Ni2	132.74 (12)	O5—C13—H13A	109.6
C13—O5—H5B	109.5	C14—C13—H13A	109.6
Ni2—O5—H5B	111.9	O5—C13—H13B	109.6
C14—O6—H6A	109.5	C14—C13—H13B	109.6
C3—N1—C3ⁱ	116.6 (2)	H13A—C13—H13B	108.2
C3—N1—Ni1	121.69 (12)	O6—C14—C13	109.80 (18)
C3ⁱ—N1—Ni1	121.69 (12)	O6—C14—H14A	109.7
C4ⁱ—N2—C4	117.1 (2)	C13—C14—H14A	109.7
C4ⁱ—N2—Ni1	121.44 (12)	O6—C14—H14B	109.7
C4—N2—Ni1	121.44 (12)	C13—C14—H14B	109.7
C9ⁱⁱ—N3—C9	115.9 (3)	H14A—C14—H14B	108.2
C9ⁱⁱ—N3—Ni2	122.06 (13)

O4—S1—O1—Ni1	−70.98 (12)	O2ⁱⁱ—Ni2—N3—C9ⁱⁱ	24.04 (16)
O3—S1—O1—Ni1	51.16 (12)	O2—Ni2—N3—C9ⁱⁱ	−155.96 (16)
O2—S1—O1—Ni1	168.52 (9)	O5—Ni2—N3—C9	−65.47 (16)
N2—Ni1—O1—S1	68.28 (10)	O5ⁱⁱ—Ni2—N3—C9	114.53 (16)
O1W—Ni1—O1—S1	161.08 (10)	O2ⁱⁱ—Ni2—N3—C9	−155.96 (16)
O1Wⁱ—Ni1—O1—S1	−24.52 (10)	O2—Ni2—N3—C9	24.04 (16)
N1—Ni1—O1—S1	−111.72 (10)	O5—Ni2—N4—C10	−15.81 (13)
O4—S1—O2—Ni2	−76.72 (13)	O5ⁱⁱ—Ni2—N4—C10	164.19 (13)
O3—S1—O2—Ni2	159.96 (10)	O2ⁱⁱ—Ni2—N4—C10	74.68 (13)
O1—S1—O2—Ni2	43.28 (12)	O2—Ni2—N4—C10	−105.32 (13)
O5—Ni2—O2—S1	−27.71 (11)	O5—Ni2—N4—C10ⁱⁱ	164.19 (13)
O5ⁱⁱ—Ni2—O2—S1	155.42 (10)	O5ⁱⁱ—Ni2—N4—C10ⁱⁱ	−15.81 (13)
N4—Ni2—O2—S1	63.85 (10)	O2ⁱⁱ—Ni2—N4—C10ⁱⁱ	−105.32 (13)
N3—Ni2—O2—S1	−116.15 (10)	O2—Ni2—N4—C10ⁱⁱ	74.68 (13)
O2ⁱⁱ—Ni2—O5—C13	31.31 (16)	C2ⁱ—C1—C2—C3	−0.18 (15)
O2—Ni2—O5—C13	−147.33 (16)	C12ⁱⁱⁱ—C1—C2—C3	179.82 (15)
N4—Ni2—O5—C13	122.01 (16)	C3ⁱ—N1—C3—C2	−0.20 (16)
N3—Ni2—O5—C13	−57.99 (16)	Ni1—N1—C3—C2	179.80 (16)
O1W—Ni1—N1—C3	135.88 (12)	C1—C2—C3—N1	0.4 (3)
O1Wⁱ—Ni1—N1—C3	−44.12 (12)	C4ⁱ—N2—C4—C5	−0.94 (14)
O1—Ni1—N1—C3	46.58 (12)	Ni1—N2—C4—C5	179.06 (14)
O1ⁱ—Ni1—N1—C3	−133.42 (12)	N2—C4—C5—C6	1.9 (3)
O1W—Ni1—N1—C3ⁱ	−44.12 (12)	C4—C5—C6—C5ⁱ	−0.87 (13)
O1Wⁱ—Ni1—N1—C3ⁱ	135.88 (12)	C4—C5—C6—C7^iv	179.13 (13)
O1—Ni1—N1—C3ⁱ	−133.42 (12)	C8ⁱⁱ—C7—C8—C9	0.6 (2)
O1ⁱ—Ni1—N1—C3ⁱ	46.58 (12)	C6^v—C7—C8—C9	−179.4 (2)
O1W—Ni1—N2—C4ⁱ	−43.57 (11)	C9ⁱⁱ—N3—C9—C8	0.6 (2)
O1Wⁱ—Ni1—N2—C4ⁱ	136.43 (11)	Ni2—N3—C9—C8	−179.4 (2)
O1—Ni1—N2—C4ⁱ	45.73 (11)	C7—C8—C9—N3	−1.2 (4)
O1ⁱ—Ni1—N2—C4ⁱ	−134.27 (11)	C10ⁱⁱ—N4—C10—C11	−0.58 (17)
O1W—Ni1—N2—C4	136.43 (11)	Ni2—N4—C10—C11	179.42 (17)
O1Wⁱ—Ni1—N2—C4	−43.57 (11)	N4—C10—C11—C12	1.2 (3)
O1—Ni1—N2—C4	−134.27 (11)	C10—C11—C12—C11ⁱⁱ	−0.54 (16)
O1ⁱ—Ni1—N2—C4	45.73 (11)	C10—C11—C12—C1^vi	179.46 (16)
O5—Ni2—N3—C9ⁱⁱ	114.53 (16)	Ni2—O5—C13—C14	−114.44 (17)
O5ⁱⁱ—Ni2—N3—C9ⁱⁱ	−65.47 (16)	O5—C13—C14—O6	−59.5 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···O4^vii	0.82	1.89	2.694 (2)	165
O5—H5B···O1	0.82	1.82	2.599 (2)	158
O1W—H1WA···O6	0.85	1.86	2.693 (2)	167
O1W—H1WB···O3ⁱ	0.85	1.91	2.718 (2)	157

Symmetry codes: (i) −x+1, y, −z+1/2; (vii) x, −y+1, z+1/2.

Experimental details

Crystal data
Chemical formula	[Ni(SO₄)(C₁₀H₈N₂)(C₂H₆O₂)(H₂O)]
M_r	391.04
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	223
a, b, c (Å)	11.022 (2), 22.606 (5), 12.123 (2)
β (°)	95.65 (3)
V (Å³)	3005.9 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.47
Crystal size (mm)	0.40 × 0.35 × 0.10

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.743, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8555, 3420, 2885
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.086, 1.06
No. of reflections	3420
No. of parameters	214
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.41

Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ni1—N2	2.072 (2)	Ni2—O5	2.0591 (15)
Ni1—O1W	2.0809 (15)	Ni2—O2	2.0817 (15)
Ni1—O1	2.0844 (14)	Ni2—N4	2.096 (2)
Ni1—N1	2.101 (2)	Ni2—N3	2.101 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···O4ⁱ	0.82	1.89	2.694 (2)	164.6
O5—H5B···O1	0.82	1.82	2.599 (2)	158.2
O1W—H1WA···O6	0.85	1.86	2.693 (2)	167.1
O1W—H1WB···O3ⁱⁱ	0.85	1.91	2.718 (2)	157.3

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

Acknowledgements

This work was supported by the Scientific Research Foundation of Nanjing College of Chemical Technology (grant No. NHKY-2013–10).

References

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