Bis(2,2′-bipyridyl-κ2N,N′)(sulfato-κ2O,O′)nickel(II) 2.5-hydrate

Iskenderov, T.

doi:10.1107/S1600536813014219

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Pages m347-m348

doi:10.1107/S1600536813014219

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Bis(2,2′-bipyridyl-κ²N,N′)(sulfato-κ²O,O′)nickel(II) 2.5-hydrate

Turganbay Iskenderov ^a ^*

^aDepartment of Chemistry, National Taras Shevchenko University, Volodymyrska Str. 64, 01601 Kiev, Ukraine
^*Correspondence e-mail: tiskenderov@ukr.net

(Received 9 May 2013; accepted 22 May 2013; online 31 May 2013)

The title compound, [Ni(SO₄)(C₁₀H₈N₂)₂]·2.5H₂O, is a nickel(II) complex with a distorted octahedral coordination geometry. The Ni^II atom is bonded by two O atoms of the bidentate chelating sulfate ligand and the four N atoms of two chelating 2,2′-bipyridine ligands. The Ni—N bond lengths range from 2.059 (3) to 2.075 (3) Å and the Ni—O bond lengths are 2.098 (3) and 2.123 (3) Å. The bipyridyl ligands are both close to planar (r.m.s. deviations of 0.254 and 0.0572 Å) and are almost orthogonal, making a dihedral angle of 82.77 (1)°. In the crystal, the complex and water molecules are connected by O—H⋯O hydrogen bonds. Interestingly, six water molecules form a chain linking two complex molecules via sulfate O atoms. There are also stacking interactions between the aromatic rings of neighbouring 2,2′-bipyridine ligands with shortest non-covalent contacts of 3.268 (6), 3.393 (6) and 3.435 (5) Å. One of the three unique water molecules shows half-occupation.

Related literature

For applications of the 2,2′-bipyridyl ligand, see: Fritsky et al. (2004 , 2006 ); Kanderal et al. (2005 ). For related structures, see: Fritsky et al. (1998 , 2000 ); Moroz et al. (2010 , 2012 ); Sliva et al. (1997 ); Świątek-Kozłowska et al. (2000 ); Iskenderov et al. (2009 ).

Experimental

Crystal data

[Ni(SO₄)(C₁₀H₈N₂)₂]·2.5H₂O
M_r = 512.18
Triclinic, $[P \overline 1]$
a = 10.045 (2) Å
b = 10.393 (2) Å
c = 11.028 (2) Å
α = 99.42 (3)°
β = 101.97 (3)°
γ = 98.56 (3)°
V = 1091.0 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.03 mm⁻¹
T = 293 K
0.32 × 0.22 × 0.11 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: multi-scan (North et al., 1968 ) T_min = 0.765, T_max = 0.897
3228 measured reflections
3021 independent reflections
2527 reflections with I > 2σ(I)
R_int = 0.030
3 standard reflections every 100 reflections intensity decay: 2%

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.124
S = 1.07
3021 reflections
301 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 0.76 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O1ⁱ	0.98	1.99	2.925 (5)	160
O1W—H2W1⋯O4ⁱⁱ	0.86	2.04	2.819 (5)	150
O2W—H1W2⋯O3Wⁱⁱⁱ	0.95	2.08	3.03 (2)	174
O2W—H2W2⋯O1W	0.85	1.93	2.774 (11)	170
O3W—H1W3⋯O3W^iv	0.99	1.91	2.86 (4)	163
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x+1, y, z; (iii) x, y-1, z; (iv) -x+1, -y+1, -z.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813014219/sj5321sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813014219/sj5321Isup2.hkl

checkCIF report

Comment top

2,2'-bipyridyl (2,2'-bipy) is a well known neutral bidentate ligand which is widely used in coordination chemistry, in particular, for the preparation of mixed ligand complexes (Fritsky et al., 2004; Kanderal et al., 2005). It is also often used in the synthesis of discrete polynuclear complexes in order to prevent formation of coordination polymers by blocking a certain number of vacant sites in the coordination sphere of a metal ion (Fritsky et al., 2006).

The asymmetric unit of title compound, comprises a neutral monomeric [Ni(SO₄)(C₁₀H₈N₂)₂] complex and three solvent water molecules, one of which is present at half occupancy. The six-coordinate nickel(II) complex adopts a distorted octahedral coordination geometry (Fig. 1).The Ni^II atom is bonded by two O atoms of the bidentate chelating sulfate ligand and four N atoms of the two chelating 2,2'-bipyridine ligands. Each of the bipyridyl ligands is reasonably planar with rms deviations of 0.254Å and 0.0572Å from the best fit meanplanes through the non-hydrogen atoms of the N1,N2 and N3, N4 ligands respectively. The bipyridyl ligands are almost orthogonal [dihedral angle = 82.7 (1)°]. The Ni—N bond distances range from 2.059 (3) to 2.075 (3) Å and the Ni—O bond distances are 2.098 (3) and 2.123 (3) Å and are typical for distorted octahedral Ni^II complexes with the nitrogen and oxygen donors (Fritsky et al., 1998; Świątek-Kozłowska et al., 2000; Sliva et al., 1997). The N—Ni—N bite angles around the central atom deviate significantly from 90°, [N2–Ni1–N1 = 78.94 (13)°, N3–Ni1–N4 = 79.32 (13)°], which is a consequence of the formation of five-membered chelate rings. The O2—Ni1—O1 bite angle is even smaller at 67.56 (10)° due to the formation of a four-membered chelate ring by the bidentate sulfate anion.

The C—N and C—C bond lengths in the pyridine rings are normal for 2-substituted pyridine derivatives (Fritsky et al., 2000; Iskenderov et al., 2009; Moroz et al., 2010; Moroz et al., 2012).

In the crystal structure, the [NiSO₄(C₁₀H₈N₂)₂] and water molecules are connected by intermolecular O—H···O hydrogen bonding, (Fig. 2) in which the water molecules act as donors while the sulfate anions and water oxygen atoms act as acceptors (Fig. 2). Interestingly, six water molecules form a chain O1W···O2W···O3W···O3W'···O2W'···O1W' linking two complex molecules via the O(4) atoms of the sulfate anions. There are also stacking interactions between the aromatic rings of the 2,2'-bipyridine molecules belonging to the neighboring complex molecules with shortest non-covalent contacts C(12)···C(18) (1-x, 1-y, 1-z) = 3.268 (6)Å; C(11)···C(18) = 3.393 (6)Å and N(3)···C(17) (1-x, 1-y, 1-z) = 3.435 (5) Å (Fig. 2).

Related literature top

For applications of the 2,2'-bipyridyl ligand, see: Fritsky et al. (2004, 2006); Kanderal et al. (2005). For related structures, see: Fritsky et al. (1998, 2000); Moroz et al. (2010, 2012); Sliva et al. (1997); Świątek-Kozłowska et al. (2000); Iskenderov et al. (2009).

Experimental top

Nickel(II) sulfate hexahydrate (0.026 g, 0.1 mmol) was dissolved in methanol (5 ml) and mixed with a solution of 2,2'-bipyridine (0.312 g, 2 mmol) in methanol (5 ml), afterwards the resulting transparent blue solution was left to evaporate in the air at ambient temperature. During 12 h the blue polycrystalline product precipitated from the solution. It was filtered off, washed with diethyl ether and dried in the air. Yield: 85%. Elemental analysis calc. (%) for C₂₀H₂₂N₄NiO₇S: C 46.09; H 4.25; N 10.75; found: C 47.11; H 4.60; N 10.43.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound, with displacement ellipsoids shown at the 50% probability level. H atoms are drawn as spheres of arbitrary radii.
	Fig. 2. Crystal packing of the title compound. Hydrogen bonds are indicated by dashed lines. H atoms not involved in H-bonds are omitted for clarity.

Bis(2,2'-bipyridyl-κ²N,N')(sulfato-κ²O,O')nickel(II) 2.5-hydrate top

Crystal data top

[Ni(SO₄)(C₁₀H₈N₂)₂]·2.5H₂O	Z = 2
M_r = 512.18	F(000) = 530
Triclinic, P1	D_x = 1.559 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.045 (2) Å	Cell parameters from 1565 reflections
b = 10.393 (2) Å	θ = 3.0–25.5°
c = 11.028 (2) Å	µ = 1.03 mm⁻¹
α = 99.42 (3)°	T = 293 K
β = 101.97 (3)°	Block, blue
γ = 98.56 (3)°	0.32 × 0.22 × 0.11 mm
V = 1091.0 (4) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	3021 independent reflections
Radiation source: fine-focus sealed tube	2527 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	R_int = 0.030
Detector resolution: 9 pixels mm^-1	θ_max = 26.1°, θ_min = 1.9°
profile data from ω/2θ scans	h = 0→12
Absorption correction: ψ scan (North et al., 1968)	k = −12→12
T_min = 0.765, T_max = 0.897	l = −12→12
3228 measured reflections

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0784P)² + 0.7731P] where P = (F_o² + 2F_c²)/3
3021 reflections	(Δ/σ)_max < 0.001
301 parameters	Δρ_max = 0.76 e Å⁻³
12 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

[Ni(SO₄)(C₁₀H₈N₂)₂]·2.5H₂O	γ = 98.56 (3)°
M_r = 512.18	V = 1091.0 (4) Å³
Triclinic, P1	Z = 2
a = 10.045 (2) Å	Mo Kα radiation
b = 10.393 (2) Å	µ = 1.03 mm⁻¹
c = 11.028 (2) Å	T = 293 K
α = 99.42 (3)°	0.32 × 0.22 × 0.11 mm
β = 101.97 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	3021 independent reflections
Absorption correction: ψ scan (North et al., 1968)	2527 reflections with I > 2σ(I)
T_min = 0.765, T_max = 0.897	R_int = 0.030
3228 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	12 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 1.07	Δρ_max = 0.76 e Å⁻³
3021 reflections	Δρ_min = −0.44 e Å⁻³
301 parameters

Special details top

Experimental. The H₂O H atoms of the solvate water molecules were located from the difference Fourier map but constrained to ride on their parent atom, with U_iso = 1.5 U_eq(parent atom). One of the solvate water molecule was included into refinement with the occupancy factor of 0.5 (as an attempt to refine it with free variation of the occupancy factor resulted in its value of 1/2, and as O3W forms an H-bond with the tranlsational O3W water molecule through the hydrogen atom H1W3 which limits the occupancy of the latter by 1/2). The C—H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 and U_iso = 1.2U_eq(parent atom).

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)
S1	0.05920 (10)	0.23826 (10)	0.38907 (9)	0.0340 (3)
Ni1	0.23116 (5)	0.29554 (5)	0.24003 (4)	0.0288 (2)
O1	0.2111 (3)	0.2317 (3)	0.4097 (2)	0.0345 (6)
O2	0.0295 (3)	0.2855 (3)	0.2672 (2)	0.0342 (6)
O3	0.0352 (3)	0.3311 (3)	0.4914 (3)	0.0478 (8)
O4	−0.0214 (3)	0.1049 (3)	0.3732 (3)	0.0548 (9)
O1W	0.7471 (4)	−0.0268 (4)	0.4408 (4)	0.0751 (11)
H1W1	0.7839	−0.0894	0.4895	0.113*
H2W1	0.8304	0.0141	0.4490	0.113*
O2W	0.5607 (10)	−0.0896 (10)	0.2062 (10)	0.225 (4)
H1W2	0.5395	−0.1799	0.1620	0.337*
H2W2	0.6204	−0.0800	0.2757	0.337*
O3W	0.482 (2)	0.631 (2)	0.0491 (18)	0.237 (9)	0.50
H1W3	0.5088	0.5500	0.0081	0.356*	0.50
H2W3	0.4120	0.6030	0.0716	0.356*	0.50
N1	0.1856 (3)	0.3201 (3)	0.0539 (3)	0.0354 (8)
N2	0.2016 (3)	0.1024 (3)	0.1437 (3)	0.0324 (7)
N3	0.2837 (3)	0.4950 (3)	0.3228 (3)	0.0300 (7)
N4	0.4444 (3)	0.3267 (3)	0.2655 (3)	0.0312 (7)
C1	0.1708 (5)	0.4330 (4)	0.0137 (4)	0.0459 (11)
H1	0.1829	0.5105	0.0737	0.055*
C2	0.1387 (6)	0.4396 (5)	−0.1111 (4)	0.0542 (13)
H2	0.1279	0.5198	−0.1353	0.065*
C3	0.1227 (5)	0.3263 (5)	−0.2006 (4)	0.0475 (11)
H3	0.1034	0.3288	−0.2862	0.057*
C4	0.1356 (5)	0.2089 (4)	−0.1611 (4)	0.0410 (10)
H4	0.1237	0.1306	−0.2201	0.049*
C5	0.1663 (4)	0.2082 (4)	−0.0339 (4)	0.0324 (9)
C6	0.1766 (4)	0.0860 (4)	0.0172 (4)	0.0313 (9)
C7	0.1606 (5)	−0.0371 (4)	−0.0592 (4)	0.0418 (10)
H7	0.1424	−0.0468	−0.1467	0.050*
C8	0.1722 (5)	−0.1456 (4)	−0.0033 (4)	0.0495 (12)
H8	0.1614	−0.2296	−0.0530	0.059*
C9	0.1998 (5)	−0.1289 (4)	0.1260 (4)	0.0465 (11)
H9	0.2099	−0.2007	0.1653	0.056*
C10	0.2123 (5)	−0.0038 (4)	0.1963 (4)	0.0416 (10)
H10	0.2288	0.0074	0.2838	0.050*
C11	0.1965 (4)	0.5742 (4)	0.3500 (4)	0.0359 (9)
H11	0.1029	0.5374	0.3345	0.043*
C12	0.2385 (4)	0.7071 (4)	0.3996 (4)	0.0401 (10)
H12	0.1745	0.7595	0.4164	0.048*
C13	0.3771 (5)	0.7620 (4)	0.4242 (4)	0.0471 (11)
H13	0.4081	0.8525	0.4566	0.057*
C14	0.4694 (5)	0.6806 (4)	0.3999 (4)	0.0447 (11)
H14	0.5638	0.7152	0.4174	0.054*
C15	0.4197 (4)	0.5473 (4)	0.3494 (3)	0.0327 (9)
C16	0.5110 (4)	0.4517 (4)	0.3221 (3)	0.0327 (9)
C17	0.6536 (4)	0.4860 (4)	0.3560 (4)	0.0398 (10)
H17	0.6972	0.5725	0.3954	0.048*
C18	0.7305 (5)	0.3903 (5)	0.3306 (4)	0.0470 (11)
H18	0.8268	0.4114	0.3538	0.056*
C19	0.6657 (5)	0.2657 (5)	0.2719 (4)	0.0494 (12)
H19	0.7163	0.2004	0.2526	0.059*
C20	0.5228 (4)	0.2372 (4)	0.2410 (4)	0.0421 (10)
H20	0.4787	0.1510	0.2010	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0296 (6)	0.0366 (6)	0.0294 (5)	−0.0008 (4)	0.0026 (4)	0.0003 (4)
Ni1	0.0278 (3)	0.0261 (3)	0.0256 (3)	−0.0002 (2)	0.0010 (2)	−0.0033 (2)
O1	0.0318 (15)	0.0384 (15)	0.0293 (14)	0.0058 (12)	0.0018 (12)	0.0038 (12)
O2	0.0278 (14)	0.0357 (15)	0.0313 (15)	0.0009 (12)	−0.0034 (12)	0.0026 (12)
O3	0.0407 (17)	0.063 (2)	0.0349 (16)	0.0123 (15)	0.0082 (13)	−0.0041 (14)
O4	0.053 (2)	0.0452 (18)	0.056 (2)	−0.0144 (15)	0.0058 (16)	0.0120 (16)
O1W	0.065 (2)	0.064 (2)	0.103 (3)	0.0146 (19)	0.017 (2)	0.036 (2)
O2W	0.204 (7)	0.213 (7)	0.244 (8)	0.038 (6)	0.016 (6)	0.058 (6)
O3W	0.237 (12)	0.248 (12)	0.222 (12)	0.012 (9)	0.059 (9)	0.057 (9)
N1	0.0380 (19)	0.0312 (18)	0.0312 (18)	0.0005 (15)	0.0042 (15)	0.0007 (15)
N2	0.0331 (18)	0.0304 (17)	0.0281 (18)	0.0024 (14)	0.0015 (14)	0.0006 (14)
N3	0.0271 (18)	0.0314 (17)	0.0264 (17)	0.0023 (14)	0.0018 (14)	0.0000 (13)
N4	0.0309 (17)	0.0341 (18)	0.0252 (16)	0.0058 (15)	0.0036 (14)	0.0012 (14)
C1	0.061 (3)	0.036 (2)	0.037 (2)	0.006 (2)	0.005 (2)	0.0060 (19)
C2	0.078 (4)	0.039 (3)	0.045 (3)	0.011 (2)	0.011 (3)	0.012 (2)
C3	0.054 (3)	0.056 (3)	0.031 (2)	0.007 (2)	0.007 (2)	0.012 (2)
C4	0.047 (3)	0.040 (2)	0.029 (2)	0.004 (2)	0.0042 (19)	−0.0028 (18)
C5	0.030 (2)	0.033 (2)	0.029 (2)	0.0028 (17)	0.0041 (17)	−0.0027 (17)
C6	0.026 (2)	0.033 (2)	0.030 (2)	0.0015 (17)	0.0029 (16)	−0.0012 (17)
C7	0.047 (3)	0.039 (2)	0.031 (2)	0.006 (2)	0.0030 (19)	−0.0060 (18)
C8	0.060 (3)	0.029 (2)	0.049 (3)	0.002 (2)	0.005 (2)	−0.005 (2)
C9	0.057 (3)	0.031 (2)	0.047 (3)	0.005 (2)	0.006 (2)	0.003 (2)
C10	0.046 (3)	0.039 (2)	0.035 (2)	0.004 (2)	0.0043 (19)	0.0034 (19)
C11	0.031 (2)	0.036 (2)	0.037 (2)	0.0028 (18)	0.0057 (18)	0.0021 (18)
C12	0.045 (3)	0.032 (2)	0.041 (2)	0.012 (2)	0.009 (2)	0.0012 (18)
C13	0.054 (3)	0.031 (2)	0.046 (3)	0.000 (2)	0.003 (2)	−0.0045 (19)
C14	0.037 (2)	0.036 (2)	0.046 (3)	−0.009 (2)	−0.001 (2)	−0.004 (2)
C15	0.034 (2)	0.035 (2)	0.025 (2)	0.0027 (18)	0.0016 (17)	0.0051 (17)
C16	0.030 (2)	0.040 (2)	0.0235 (19)	−0.0003 (18)	0.0037 (16)	0.0041 (17)
C17	0.028 (2)	0.048 (3)	0.038 (2)	0.0006 (19)	0.0021 (18)	0.007 (2)
C18	0.029 (2)	0.065 (3)	0.047 (3)	0.009 (2)	0.007 (2)	0.015 (2)
C19	0.041 (3)	0.063 (3)	0.047 (3)	0.021 (2)	0.011 (2)	0.005 (2)
C20	0.038 (2)	0.038 (2)	0.046 (3)	0.008 (2)	0.008 (2)	−0.004 (2)

Geometric parameters (Å, º) top

S1—O3	1.445 (3)	C3—H3	0.9300
S1—O4	1.461 (3)	C4—C5	1.374 (6)
S1—O2	1.493 (3)	C4—H4	0.9300
S1—O1	1.509 (3)	C5—C6	1.480 (6)
S1—Ni1	2.6892 (13)	C6—C7	1.380 (6)
Ni1—N2	2.059 (3)	C7—C8	1.379 (6)
Ni1—N3	2.065 (3)	C7—H7	0.9300
Ni1—N4	2.070 (3)	C8—C9	1.372 (6)
Ni1—N1	2.075 (3)	C8—H8	0.9300
Ni1—O2	2.098 (3)	C9—C10	1.374 (6)
Ni1—O1	2.123 (3)	C9—H9	0.9300
O1W—H1W1	0.9753	C10—H10	0.9300
O1W—H2W1	0.8603	C11—C12	1.367 (6)
O2W—H1W2	0.9549	C11—H11	0.9300
O2W—H2W2	0.8500	C12—C13	1.376 (6)
O3W—H1W3	0.9888	C12—H12	0.9300
O3W—H2W3	0.8245	C13—C14	1.382 (6)
N1—C1	1.338 (5)	C13—H13	0.9300
N1—C5	1.347 (5)	C14—C15	1.380 (6)
N2—C10	1.335 (5)	C14—H14	0.9300
N2—C6	1.342 (5)	C15—C16	1.485 (6)
N3—C11	1.334 (5)	C16—C17	1.379 (6)
N3—C15	1.345 (5)	C17—C18	1.375 (6)
N4—C20	1.335 (5)	C17—H17	0.9300
N4—C16	1.352 (5)	C18—C19	1.349 (7)
C1—C2	1.362 (6)	C18—H18	0.9300
C1—H1	0.9300	C19—C20	1.379 (6)
C2—C3	1.372 (7)	C19—H19	0.9300
C2—H2	0.9300	C20—H20	0.9300
C3—C4	1.376 (6)

O3—S1—O4	112.5 (2)	C2—C3—C4	118.7 (4)
O3—S1—O2	111.38 (18)	C2—C3—H3	120.6
O4—S1—O2	109.64 (17)	C4—C3—H3	120.6
O3—S1—O1	110.62 (17)	C5—C4—C3	119.5 (4)
O4—S1—O1	109.38 (18)	C5—C4—H4	120.3
O2—S1—O1	102.89 (16)	C3—C4—H4	120.3
O3—S1—Ni1	125.58 (14)	N1—C5—C4	121.7 (4)
O4—S1—Ni1	121.92 (15)	N1—C5—C6	115.0 (3)
O2—S1—Ni1	50.95 (11)	C4—C5—C6	123.3 (4)
O1—S1—Ni1	51.94 (11)	N2—C6—C7	121.8 (4)
N2—Ni1—N3	171.54 (12)	N2—C6—C5	115.5 (3)
N2—Ni1—N4	93.94 (13)	C7—C6—C5	122.7 (4)
N3—Ni1—N4	79.32 (13)	C8—C7—C6	118.7 (4)
N2—Ni1—N1	78.92 (13)	C8—C7—H7	120.6
N3—Ni1—N1	96.65 (13)	C6—C7—H7	120.6
N4—Ni1—N1	96.66 (13)	C9—C8—C7	119.6 (4)
N2—Ni1—O2	96.16 (12)	C9—C8—H8	120.2
N3—Ni1—O2	91.51 (12)	C7—C8—H8	120.2
N4—Ni1—O2	164.38 (11)	C8—C9—C10	118.6 (4)
N1—Ni1—O2	96.95 (12)	C8—C9—H9	120.7
N2—Ni1—O1	91.50 (12)	C10—C9—H9	120.7
N3—Ni1—O1	94.73 (12)	N2—C10—C9	122.6 (4)
N4—Ni1—O1	100.34 (12)	N2—C10—H10	118.7
N1—Ni1—O1	161.03 (12)	C9—C10—H10	118.7
O2—Ni1—O1	67.57 (10)	N3—C11—C12	123.0 (4)
N2—Ni1—S1	94.37 (10)	N3—C11—H11	118.5
N3—Ni1—S1	93.99 (9)	C12—C11—H11	118.5
N4—Ni1—S1	133.72 (9)	C11—C12—C13	118.9 (4)
N1—Ni1—S1	129.62 (10)	C11—C12—H12	120.6
O2—Ni1—S1	33.54 (7)	C13—C12—H12	120.6
O1—Ni1—S1	34.03 (7)	C12—C13—C14	118.9 (4)
S1—O1—Ni1	94.03 (13)	C12—C13—H13	120.5
S1—O2—Ni1	95.51 (13)	C14—C13—H13	120.5
H1W1—O1W—H2W1	89.2	C15—C14—C13	119.1 (4)
H1W2—O2W—H2W2	110.8	C15—C14—H14	120.4
H1W3—O3W—H2W3	104.2	C13—C14—H14	120.4
C1—N1—C5	118.0 (4)	N3—C15—C14	121.6 (4)
C1—N1—Ni1	127.0 (3)	N3—C15—C16	115.4 (3)
C5—N1—Ni1	115.0 (3)	C14—C15—C16	123.0 (4)
C10—N2—C6	118.7 (3)	N4—C16—C17	122.0 (4)
C10—N2—Ni1	125.8 (3)	N4—C16—C15	115.2 (3)
C6—N2—Ni1	115.4 (3)	C17—C16—C15	122.7 (4)
C11—N3—C15	118.5 (3)	C18—C17—C16	119.0 (4)
C11—N3—Ni1	126.4 (3)	C18—C17—H17	120.5
C15—N3—Ni1	115.1 (3)	C16—C17—H17	120.5
C20—N4—C16	117.1 (3)	C19—C18—C17	119.7 (4)
C20—N4—Ni1	127.9 (3)	C19—C18—H18	120.1
C16—N4—Ni1	114.8 (3)	C17—C18—H18	120.1
N1—C1—C2	123.0 (4)	C18—C19—C20	118.6 (4)
N1—C1—H1	118.5	C18—C19—H19	120.7
C2—C1—H1	118.5	C20—C19—H19	120.7
C1—C2—C3	119.1 (4)	N4—C20—C19	123.5 (4)
C1—C2—H2	120.5	N4—C20—H20	118.2
C3—C2—H2	120.5	C19—C20—H20	118.2

O3—S1—Ni1—N2	175.62 (18)	N4—Ni1—N3—C15	1.3 (3)
O4—S1—Ni1—N2	−4.30 (19)	N1—Ni1—N3—C15	−94.2 (3)
O2—S1—Ni1—N2	−94.56 (16)	O2—Ni1—N3—C15	168.6 (3)
O1—S1—Ni1—N2	86.20 (16)	O1—Ni1—N3—C15	101.0 (3)
O3—S1—Ni1—N3	−3.11 (18)	S1—Ni1—N3—C15	135.1 (3)
O4—S1—Ni1—N3	176.96 (18)	N2—Ni1—N4—C20	−8.9 (4)
O2—S1—Ni1—N3	86.71 (16)	N3—Ni1—N4—C20	176.3 (4)
O1—S1—Ni1—N3	−92.54 (16)	N1—Ni1—N4—C20	−88.2 (3)
O3—S1—Ni1—N4	75.9 (2)	O2—Ni1—N4—C20	121.3 (5)
O4—S1—Ni1—N4	−104.0 (2)	O1—Ni1—N4—C20	83.3 (3)
O2—S1—Ni1—N4	165.74 (18)	S1—Ni1—N4—C20	91.0 (3)
O1—S1—Ni1—N4	−13.50 (18)	N2—Ni1—N4—C16	176.2 (3)
O3—S1—Ni1—N1	−105.1 (2)	N3—Ni1—N4—C16	1.3 (3)
O4—S1—Ni1—N1	74.9 (2)	N1—Ni1—N4—C16	96.9 (3)
O2—S1—Ni1—N1	−15.33 (18)	O2—Ni1—N4—C16	−53.6 (5)
O1—S1—Ni1—N1	165.43 (17)	O1—Ni1—N4—C16	−91.6 (3)
O3—S1—Ni1—O2	−89.8 (2)	S1—Ni1—N4—C16	−83.9 (3)
O4—S1—Ni1—O2	90.3 (2)	C5—N1—C1—C2	−0.7 (7)
O1—S1—Ni1—O2	−179.24 (19)	Ni1—N1—C1—C2	−179.1 (4)
O3—S1—Ni1—O1	89.4 (2)	N1—C1—C2—C3	−1.0 (8)
O4—S1—Ni1—O1	−90.5 (2)	C1—C2—C3—C4	1.8 (7)
O2—S1—Ni1—O1	179.24 (19)	C2—C3—C4—C5	−1.0 (7)
O3—S1—O1—Ni1	−119.66 (17)	C1—N1—C5—C4	1.6 (6)
O4—S1—O1—Ni1	115.88 (17)	Ni1—N1—C5—C4	−179.9 (3)
O2—S1—O1—Ni1	−0.60 (15)	C1—N1—C5—C6	−176.7 (4)
N2—Ni1—O1—S1	−95.60 (15)	Ni1—N1—C5—C6	1.8 (4)
N3—Ni1—O1—S1	90.14 (14)	C3—C4—C5—N1	−0.7 (6)
N4—Ni1—O1—S1	170.12 (13)	C3—C4—C5—C6	177.4 (4)
N1—Ni1—O1—S1	−36.6 (4)	C10—N2—C6—C7	0.6 (6)
O2—Ni1—O1—S1	0.45 (11)	Ni1—N2—C6—C7	177.2 (3)
O3—S1—O2—Ni1	119.14 (16)	C10—N2—C6—C5	−179.9 (3)
O4—S1—O2—Ni1	−115.69 (18)	Ni1—N2—C6—C5	−3.3 (4)
O1—S1—O2—Ni1	0.61 (15)	N1—C5—C6—N2	1.0 (5)
N2—Ni1—O2—S1	88.62 (15)	C4—C5—C6—N2	−177.3 (4)
N3—Ni1—O2—S1	−94.95 (14)	N1—C5—C6—C7	−179.5 (4)
N4—Ni1—O2—S1	−41.4 (5)	C4—C5—C6—C7	2.2 (6)
N1—Ni1—O2—S1	168.16 (14)	N2—C6—C7—C8	−0.7 (6)
O1—Ni1—O2—S1	−0.46 (11)	C5—C6—C7—C8	179.9 (4)
N2—Ni1—N1—C1	175.7 (4)	C6—C7—C8—C9	−0.3 (7)
N3—Ni1—N1—C1	−11.6 (4)	C7—C8—C9—C10	1.3 (7)
N4—Ni1—N1—C1	−91.6 (4)	C6—N2—C10—C9	0.5 (6)
O2—Ni1—N1—C1	80.7 (4)	Ni1—N2—C10—C9	−175.7 (3)
O1—Ni1—N1—C1	114.8 (4)	C8—C9—C10—N2	−1.5 (7)
S1—Ni1—N1—C1	89.2 (4)	C15—N3—C11—C12	2.3 (6)
N2—Ni1—N1—C5	−2.7 (3)	Ni1—N3—C11—C12	−176.9 (3)
N3—Ni1—N1—C5	170.0 (3)	N3—C11—C12—C13	−0.8 (6)
N4—Ni1—N1—C5	90.0 (3)	C11—C12—C13—C14	−1.1 (7)
O2—Ni1—N1—C5	−97.7 (3)	C12—C13—C14—C15	1.3 (7)
O1—Ni1—N1—C5	−63.5 (5)	C11—N3—C15—C14	−2.0 (6)
S1—Ni1—N1—C5	−89.2 (3)	Ni1—N3—C15—C14	177.2 (3)
N3—Ni1—N2—C10	120.5 (8)	C11—N3—C15—C16	177.2 (3)
N4—Ni1—N2—C10	83.6 (3)	Ni1—N3—C15—C16	−3.5 (4)
N1—Ni1—N2—C10	179.6 (4)	C13—C14—C15—N3	0.2 (6)
O2—Ni1—N2—C10	−84.5 (3)	C13—C14—C15—C16	−178.9 (4)
O1—Ni1—N2—C10	−16.9 (3)	C20—N4—C16—C17	−1.3 (6)
S1—Ni1—N2—C10	−50.8 (3)	Ni1—N4—C16—C17	174.2 (3)
N3—Ni1—N2—C6	−55.8 (9)	C20—N4—C16—C15	−179.0 (3)
N4—Ni1—N2—C6	−92.8 (3)	Ni1—N4—C16—C15	−3.5 (4)
N1—Ni1—N2—C6	3.3 (3)	N3—C15—C16—N4	4.7 (5)
O2—Ni1—N2—C6	99.2 (3)	C14—C15—C16—N4	−176.1 (4)
O1—Ni1—N2—C6	166.8 (3)	N3—C15—C16—C17	−173.0 (4)
S1—Ni1—N2—C6	132.8 (3)	C14—C15—C16—C17	6.2 (6)
N2—Ni1—N3—C11	142.9 (7)	N4—C16—C17—C18	0.5 (6)
N4—Ni1—N3—C11	−179.5 (3)	C15—C16—C17—C18	178.0 (4)
N1—Ni1—N3—C11	84.9 (3)	C16—C17—C18—C19	0.9 (7)
O2—Ni1—N3—C11	−12.2 (3)	C17—C18—C19—C20	−1.3 (7)
O1—Ni1—N3—C11	−79.8 (3)	C16—N4—C20—C19	0.9 (6)
S1—Ni1—N3—C11	−45.7 (3)	Ni1—N4—C20—C19	−173.9 (3)
N2—Ni1—N3—C15	−36.3 (9)	C18—C19—C20—N4	0.4 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O1ⁱ	0.98	1.99	2.925 (5)	160
O1W—H2W1···O4ⁱⁱ	0.86	2.04	2.819 (5)	150
O2W—H1W2···O3Wⁱⁱⁱ	0.95	2.08	3.03 (2)	174
O2W—H2W2···O1W	0.85	1.93	2.774 (11)	170
O3W—H1W3···O3W^iv	0.99	1.91	2.86 (4)	163

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

Experimental details

Crystal data
Chemical formula	[Ni(SO₄)(C₁₀H₈N₂)₂]·2.5H₂O
M_r	512.18
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	10.045 (2), 10.393 (2), 11.028 (2)
α, β, γ (°)	99.42 (3), 101.97 (3), 98.56 (3)
V (Å³)	1091.0 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.03
Crystal size (mm)	0.32 × 0.22 × 0.11

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.765, 0.897
No. of measured, independent and observed [I > 2σ(I)] reflections	3228, 3021, 2527
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.124, 1.07
No. of reflections	3021
No. of parameters	301
No. of restraints	12
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.76, −0.44

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O1ⁱ	0.98	1.99	2.925 (5)	159.7
O1W—H2W1···O4ⁱⁱ	0.86	2.04	2.819 (5)	150.1
O2W—H1W2···O3Wⁱⁱⁱ	0.95	2.08	3.03 (2)	173.8
O2W—H2W2···O1W	0.85	1.93	2.774 (11)	169.6
O3W—H1W3···O3W^iv	0.99	1.91	2.86 (4)	162.5

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

Acknowledgements

Financial support from the State Fund for Fundamental Researches of Ukraine (grant No. GP/F36/032) is gratefully acknowledged. I also thank Dr E. B. Rusanov, Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, for collecting the X-ray data.

References

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