Bis(2,3,5,6-tetra-2-pyridyl­pyrazine-κ3N2,N1,N6)nickel(II) dithio­cyanate dihydrate

De la Pinta, N.; Fidalgo, M.L.; Ezpeleta, J.M.; Cortés, R.; Madariaga, G.

doi:10.1107/S1600536810053419

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 1| January 2011| Pages m129-m130

https://doi.org/10.1107/S1600536810053419

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Bis(2,3,5,6-tetra-2-pyridylpyrazine-κ³N²,N¹,N⁶)nickel(II) dithiocyanate dihydrate

Noelia De la Pinta,^a M. Luz Fidalgo,^b José M. Ezpeleta,^c Roberto Cortés ^a and Gotzon Madariaga ^d ^*

^aDepartamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco, Apdo. 644, E-48080 Bilbao, Spain, ^bDepartamento de Química Inorgánica, Facultad de Farmacia, Universidad del País Vasco, Apdo. 450, E-01080 Vitoria, Spain, ^cDepartamento de Física Aplicada II, Facultad de Farmacia, Universidad del País Vasco, Apdo. 450, E-01080 Vitoria, Spain, and ^dDepartamento de Física de la Materia Condensada, Facultad de Ciencia y Tecnología, Universidad del País Vasco, Apdo. 644, E-48080 Bilbao, Spain
^*Correspondence e-mail: gotzon.madariaga@ehu.es

(Received 14 December 2010; accepted 20 December 2010; online 24 December 2010)

In the title compound, [Ni(C₂₄H₁₆N₆)₂](NCS)₂·2H₂O, the central Ni^II ion is octahedrally coordinated by six N atoms of two tridentate 2,3,5,6-tetra-2-pyridylpyrazine ligands (tppz). Two thiocyanate anions act as counter-ions and two water molecules act as solvation agents. O—H⋯N hydrogen bonds are observed in the crystral structure.

Related literature

For related structures including [M(II)(tppz)₂]²⁺ cations, see: Ruminski & Kiplinger (1990 ); Arana et al. (1992 ); Lainé et al. (1995 ); Allis et al. (2004 ); Burkholder & Zubieta (2004 ); Haines et al. (2000 ). For the aplication of a [Co(II)(tppz)₂]²⁺ complex as a homogeneous catalyst, see: Königstein & Bauer (1994 , 1997 ).

Experimental

Crystal data

[Ni(C₂₄H₁₆N₆)₂](NCS)₂·2H₂O
M_r = 987.76
Monoclinic, C 2/c
a = 17.9091 (4) Å
b = 13.6851 (2) Å
c = 19.4650 (4) Å
β = 106.161 (2)°
V = 4582.11 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 293 K
0.35 × 0.26 × 0.21 mm

Data collection

Oxford Diffraction Xcalibur Sapphire2 diffractometer
23806 measured reflections
7385 independent reflections
4946 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.123
S = 0.94
7385 reflections
320 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯N9ⁱ	0.85 (2)	2.28 (3)	3.116 (4)	166 (3)
O1W—H1W2⋯N1ⁱⁱ	0.85 (4)	2.20 (3)	3.044 (4)	173 (4)
Symmetry codes: (i) $[-x, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810053419/fj2379sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810053419/fj2379Isup2.hkl

checkCIF report

Comment top

The combination of divalent cations of the second half of the transition series with the ligand tppz, gives coordination cations of the type [M^II(tppz)₂]²⁺, where the terminal nitrogen atoms of one extreme of the tppz ligand are directed towards the metallic atoms and the corresponding N atoms of the other extreme remain uncoordinated (Lainé et al., 1995). These tppz cations are part of diferent coordination compounds (Allis et al., 2004, Burkholder & Zubieta, 2004, Ruminski et al., 1990, Haines et al., 2000, Arana et al., 1992, Köningstein et al., 1997,, 1994). We here report the crystal structure of a new compound, [Ni(C₂₄H₁₆N₆)₂](NCS)₂.2H₂O, which is made up of Ni^II cations coordinated to six nitrogen atoms of two tridentate tppz ligands. These monomeric entities reach the neutrality with two thiocianate anions and two molecules of water act as solvent agents. The nitrogen atoms of each tppz, coordinated to the cation, are in the same plane. The Ni^II cation has a distorted octahedral environment, in which the bonds to the two pyrazine nitrogen atoms (Ni1—N3 and Ni1—N7) are significantly shorter than the bonds to the pyridyl nitrogen atoms (Ni1—N2 and Ni1—N6). The N—Ni1—N angles involving the atoms of the equatorial plane with respect to the short axis differ remarkably from the ideal octahedral values, the Ni1 atom not deviating significantly [0.0006 (2) Å] from the average plane.

The individual pyridyl rings are planar (maximum average displacement with respect to the plane of the ring, 0.011 Å), while the two pyrazine rings are significantly puckered. Nitrogen atoms of the non-coordinated pyridyl rings of the two tppz ligands point to the ligand metalated side instead of the free nitrogen atom of the pyrazine ring. These structural features of the coordinated tppz ligand would account for its tendency to adopt bis-chelation in this type of complexes. Weak π-π interactions appear to occur due to overlap between the pyridyl rings labelled by N5 and N9ⁱⁱⁱ (iii= -x,-1 + y,1/2 - z) with a distance between the ring centroids of 3.7713 (12) Å.

The crystal packing of the bulky building block units leaves cavities of 116 Å³ where water molecules and NCS anions are located (Fig. 2). The low density of the material reflects this open structure. Most relevant H bonds are listed in Table 1.

Related literature top

For related structures including [M(II)(tppz)₂]²⁺ cations, see: Ruminski & Kiplinger (1990); Arana et al. (1992); Lainé et al. (1995); Allis et al. (2004); Burkholder & Zubieta (2004); Haines et al. (2000). For the aplication of a [Co(II)(tppz)₂]²⁺ complex as a homogeneous catalyst, see: Königstein & Bauer (1994, 1997).

Experimental top

Crystals of [Ni(C₂₄H₁₆N₆)₂](NCS)₂.2H₂O were prepared by mixing an acetonitrile solution (10 ml) of NiCl₂.6H₂O (112 mg, 0.50 mmol) and another acetonitrile solution (10 ml) of 2,3,5,6-tetra-2-pyridylpirazine (97.1 mg, 0.25 mmol). After a vigorous stirring of about 30 minutes at a temperature of 303 K, an aqua/acetonitrile (50%) solution (10 ml) of sodium thiocyanate (101.3 mg, 1.25 mmol) was added. The resultant solution was stirred at 313 K for 25 minutes and at room temperature for the following two days. Then the precipitate that did form was filtered off. Finally, the resulting solution was maintained at room temperature until prismatic green crystals were formed by slow evaporation. These crystals were found to be stable to X-ray exposure.

Structure description top

For related structures including [M(II)(tppz)₂]²⁺ cations, see: Ruminski & Kiplinger (1990); Arana et al. (1992); Lainé et al. (1995); Allis et al. (2004); Burkholder & Zubieta (2004); Haines et al. (2000). For the aplication of a [Co(II)(tppz)₂]²⁺ complex as a homogeneous catalyst, see: Königstein & Bauer (1994, 1997).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Asymmetric unit of [Ni(C₂₄H₁₆N₆)₂](NCS)₂.2H₂O showing the most relevant labels. H atoms excluded for clarity. Ellipsoids drawn at 50% probability level.
	Fig. 2. Projection of [Ni(C₂₄H₁₆N₆)₂](NCS)₂.2H₂O packing along the b axis showing the link between pyridyl and NCS groups through the N1—O1W—N9 H-bonds.

Bis(2,3,5,6-tetra-2-pyridylpyrazine- κ³N²,N¹,N⁶)nickel(II) dithiocyanate dihydrate top

Crystal data top

[Ni(C₂₄H₁₆N₆)₂](NCS)₂·2H₂O	F(000) = 2040
M_r = 987.76	D_x = 1.432 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9376 reflections
a = 17.9091 (4) Å	θ = 3.0–32.2°
b = 13.6851 (2) Å	µ = 0.57 mm⁻¹
c = 19.4650 (4) Å	T = 293 K
β = 106.161 (2)°	Prism, green
V = 4582.11 (15) Å³	0.35 × 0.26 × 0.21 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Sapphire2 window diffractometer	4946 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube	R_int = 0.031
Graphite monochromator	θ_max = 32.2°, θ_min = 3.0°
Detector resolution: 8.3504 pixels mm^-1	h = −25→21
ω scans	k = −18→20
23806 measured reflections	l = −28→29
7385 independent 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	w = 1/[σ²(F_o²) + (0.0771P)²] where P = (F_o² + 2F_c²)/3
7385 reflections	(Δ/σ)_max < 0.001
320 parameters	Δρ_max = 0.56 e Å⁻³
4 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

[Ni(C₂₄H₁₆N₆)₂](NCS)₂·2H₂O	V = 4582.11 (15) Å³
M_r = 987.76	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.9091 (4) Å	µ = 0.57 mm⁻¹
b = 13.6851 (2) Å	T = 293 K
c = 19.4650 (4) Å	0.35 × 0.26 × 0.21 mm
β = 106.161 (2)°

Data collection top

Oxford Diffraction Xcalibur Sapphire2 window diffractometer	4946 reflections with I > 2σ(I)
23806 measured reflections	R_int = 0.031
7385 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	4 restraints
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	Δρ_max = 0.56 e Å⁻³
7385 reflections	Δρ_min = −0.43 e Å⁻³
320 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.310758 (18)	0.25	0.03035 (9)
N1	0.30210 (13)	0.08495 (16)	0.16393 (13)	0.0748 (6)
C1	0.24787 (15)	0.05532 (16)	0.17858 (12)	0.0613 (6)
S1	0.17309 (4)	0.01597 (5)	0.20104 (4)	0.07129 (18)
N2	0.09989 (8)	0.27794 (9)	0.33345 (7)	0.0357 (3)
N3	0	0.16447 (12)	0.25	0.0275 (4)
N4	0	−0.03295 (12)	0.25	0.0297 (4)
N5	0.09070 (11)	−0.00169 (11)	0.43264 (8)	0.0519 (4)
N6	0.07402 (8)	0.34349 (10)	0.18698 (7)	0.0346 (3)
N7	0	0.45723 (12)	0.25	0.0282 (4)
N8	0	0.65503 (12)	0.25	0.0287 (4)
N9	0.01006 (10)	0.61824 (11)	0.07513 (8)	0.0450 (4)
C2	0.11628 (9)	0.18165 (10)	0.34250 (8)	0.0318 (3)
C3	0.18842 (10)	0.14902 (13)	0.38158 (11)	0.0451 (4)
H3	0.1988	0.0824	0.3867	0.068*
C4	0.24504 (12)	0.21619 (16)	0.41296 (13)	0.0603 (6)
H4	0.2941	0.1955	0.4393	0.09*
C5	0.22787 (13)	0.31443 (15)	0.40478 (13)	0.0631 (6)
H5	0.2649	0.3611	0.426	0.095*
C6	0.15514 (12)	0.34205 (14)	0.36470 (11)	0.0500 (5)
H6	0.1438	0.4084	0.359	0.075*
C7	0.05337 (9)	0.11697 (10)	0.30076 (8)	0.0279 (3)
C8	0.04567 (8)	0.01515 (10)	0.30544 (8)	0.0284 (3)
C9	0.08377 (9)	−0.04437 (11)	0.36910 (8)	0.0327 (3)
C10	0.10704 (10)	−0.13895 (12)	0.36186 (10)	0.0399 (4)
H10	0.0997	−0.1664	0.3168	0.06*
C11	0.14136 (11)	−0.19211 (14)	0.42277 (12)	0.0538 (5)
H11	0.1583	−0.2557	0.4197	0.081*
C12	0.14968 (14)	−0.14892 (19)	0.48751 (13)	0.0686 (7)
H12	0.1729	−0.1827	0.5295	0.103*
C13	0.12351 (16)	−0.05524 (19)	0.49030 (11)	0.0702 (7)
H13	0.129	−0.0275	0.535	0.105*
C14	0.08424 (9)	0.43995 (10)	0.17709 (8)	0.0299 (3)
C15	0.14292 (10)	0.47369 (12)	0.15021 (10)	0.0405 (4)
H15	0.1486	0.5402	0.1433	0.061*
C16	0.19345 (11)	0.40681 (14)	0.13364 (11)	0.0494 (5)
H16	0.2333	0.4279	0.1151	0.074*
C17	0.18406 (11)	0.30917 (13)	0.14488 (10)	0.0452 (4)
H17	0.2184	0.2634	0.1355	0.068*
C18	0.12336 (11)	0.28013 (12)	0.17007 (9)	0.0413 (4)
H18	0.116	0.2137	0.1757	0.062*
C19	0.03442 (9)	0.50448 (10)	0.20708 (8)	0.0282 (3)
C20	0.02362 (9)	0.60616 (10)	0.20014 (8)	0.0284 (3)
C21	0.03384 (9)	0.66321 (11)	0.13860 (8)	0.0314 (3)
C22	0.06215 (11)	0.75722 (12)	0.14626 (10)	0.0443 (4)
H22	0.078	0.7865	0.1911	0.066*
C23	0.06656 (12)	0.80718 (14)	0.08575 (12)	0.0551 (5)
H23	0.0854	0.8708	0.0894	0.083*
C24	0.04322 (13)	0.76275 (17)	0.02107 (13)	0.0601 (6)
H24	0.0457	0.7952	−0.0202	0.09*
C25	0.01589 (13)	0.66902 (18)	0.01790 (11)	0.0581 (5)
H25	0.0004	0.6387	−0.0266	0.087*
O1W	0.15572 (18)	0.5266 (3)	0.47152 (14)	0.1363 (10)
H1W1	0.1090 (10)	0.546 (3)	0.465 (2)	0.204*
H1W2	0.171 (2)	0.545 (4)	0.4359 (16)	0.204*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.04230 (17)	0.01832 (13)	0.03170 (15)	0	0.01241 (12)	0
N1	0.0666 (13)	0.0573 (12)	0.1034 (17)	0.0104 (10)	0.0287 (12)	0.0182 (11)
C1	0.0809 (16)	0.0431 (11)	0.0536 (12)	0.0199 (11)	0.0083 (11)	0.0009 (9)
S1	0.0804 (4)	0.0647 (4)	0.0714 (4)	0.0071 (3)	0.0255 (3)	0.0001 (3)
N2	0.0454 (8)	0.0242 (6)	0.0360 (7)	−0.0069 (5)	0.0086 (6)	−0.0026 (5)
N3	0.0302 (9)	0.0223 (8)	0.0298 (9)	0	0.0081 (7)	0
N4	0.0345 (9)	0.0217 (8)	0.0317 (9)	0	0.0073 (7)	0
N5	0.0743 (11)	0.0435 (9)	0.0326 (8)	−0.0023 (8)	0.0063 (8)	0.0012 (6)
N6	0.0471 (8)	0.0250 (6)	0.0346 (7)	0.0031 (5)	0.0160 (6)	−0.0022 (5)
N7	0.0346 (9)	0.0222 (8)	0.0300 (9)	0	0.0127 (7)	0
N8	0.0363 (9)	0.0219 (8)	0.0295 (9)	0	0.0117 (7)	0
N9	0.0563 (9)	0.0464 (9)	0.0335 (7)	−0.0011 (7)	0.0146 (7)	0.0023 (6)
C2	0.0375 (8)	0.0254 (7)	0.0310 (7)	−0.0036 (6)	0.0072 (6)	−0.0017 (6)
C3	0.0373 (9)	0.0359 (9)	0.0567 (11)	−0.0003 (7)	0.0039 (8)	−0.0016 (8)
C4	0.0395 (10)	0.0553 (12)	0.0736 (15)	−0.0079 (9)	−0.0048 (10)	−0.0044 (11)
C5	0.0536 (12)	0.0478 (12)	0.0753 (15)	−0.0209 (9)	−0.0029 (11)	−0.0068 (10)
C6	0.0578 (12)	0.0305 (8)	0.0548 (11)	−0.0128 (8)	0.0042 (9)	−0.0058 (8)
C7	0.0323 (7)	0.0235 (7)	0.0276 (7)	−0.0003 (5)	0.0078 (6)	−0.0007 (5)
C8	0.0315 (7)	0.0231 (7)	0.0296 (7)	0.0012 (5)	0.0070 (6)	0.0010 (5)
C9	0.0342 (8)	0.0276 (7)	0.0329 (8)	−0.0031 (6)	0.0038 (6)	0.0044 (6)
C10	0.0397 (9)	0.0313 (8)	0.0464 (10)	0.0011 (7)	0.0081 (7)	0.0075 (7)
C11	0.0410 (10)	0.0405 (10)	0.0753 (14)	0.0034 (8)	0.0087 (10)	0.0251 (10)
C12	0.0684 (14)	0.0713 (15)	0.0527 (13)	−0.0042 (12)	−0.0056 (11)	0.0324 (12)
C13	0.0956 (18)	0.0725 (16)	0.0327 (10)	−0.0073 (13)	0.0019 (11)	0.0079 (10)
C14	0.0380 (8)	0.0244 (7)	0.0287 (7)	0.0027 (6)	0.0117 (6)	−0.0017 (5)
C15	0.0464 (10)	0.0293 (8)	0.0521 (10)	−0.0007 (7)	0.0242 (8)	−0.0010 (7)
C16	0.0466 (10)	0.0456 (10)	0.0650 (12)	−0.0007 (8)	0.0306 (9)	−0.0082 (9)
C17	0.0485 (10)	0.0391 (9)	0.0523 (10)	0.0080 (7)	0.0208 (9)	−0.0096 (8)
C18	0.0550 (10)	0.0281 (8)	0.0444 (9)	0.0078 (7)	0.0197 (8)	−0.0051 (7)
C19	0.0347 (7)	0.0238 (7)	0.0281 (7)	0.0002 (5)	0.0121 (6)	0.0002 (5)
C20	0.0346 (7)	0.0222 (6)	0.0300 (7)	0.0002 (5)	0.0119 (6)	0.0021 (5)
C21	0.0361 (8)	0.0274 (7)	0.0344 (8)	0.0043 (6)	0.0158 (6)	0.0061 (6)
C22	0.0557 (11)	0.0321 (8)	0.0523 (11)	−0.0023 (7)	0.0267 (9)	0.0037 (7)
C23	0.0629 (13)	0.0405 (10)	0.0730 (14)	0.0026 (9)	0.0372 (11)	0.0207 (10)
C24	0.0595 (13)	0.0712 (14)	0.0579 (13)	0.0129 (10)	0.0300 (10)	0.0339 (11)
C25	0.0623 (13)	0.0775 (15)	0.0352 (10)	0.0049 (11)	0.0147 (9)	0.0107 (9)
O1W	0.144 (2)	0.167 (3)	0.108 (2)	0.035 (2)	0.0506 (18)	−0.0268 (18)

Geometric parameters (Å, º) top

Ni1—N3	2.0019 (17)	C6—H6	0.93
Ni1—N7	2.0045 (17)	C7—C8	1.4057 (19)
Ni1—N6ⁱ	2.0899 (14)	C8—C9	1.481 (2)
Ni1—N6	2.0899 (14)	C9—C10	1.379 (2)
Ni1—N2ⁱ	2.1030 (14)	C10—C11	1.381 (2)
Ni1—N2	2.1030 (14)	C10—H10	0.93
N1—C1	1.159 (3)	C11—C12	1.362 (3)
C1—S1	1.613 (3)	C11—H11	0.93
N2—C6	1.336 (2)	C12—C13	1.371 (4)
N2—C2	1.3509 (19)	C12—H12	0.93
N3—C7ⁱ	1.3366 (16)	C13—H13	0.93
N3—C7	1.3366 (16)	C14—C15	1.378 (2)
N4—C8	1.3325 (16)	C14—C19	1.485 (2)
N4—C8ⁱ	1.3325 (16)	C15—C16	1.387 (2)
N5—C13	1.332 (3)	C15—H15	0.93
N5—C9	1.342 (2)	C16—C17	1.372 (3)
N6—C18	1.343 (2)	C16—H16	0.93
N6—C14	1.3538 (19)	C17—C18	1.370 (3)
N7—C19	1.3353 (16)	C17—H17	0.93
N7—C19ⁱ	1.3353 (16)	C18—H18	0.93
N8—C20	1.3404 (17)	C19—C20	1.4062 (19)
N8—C20ⁱ	1.3404 (17)	C20—C21	1.483 (2)
N9—C21	1.339 (2)	C21—C22	1.376 (2)
N9—C25	1.342 (2)	C22—C23	1.383 (3)
C2—C3	1.378 (2)	C22—H22	0.93
C2—C7	1.484 (2)	C23—C24	1.355 (3)
C3—C4	1.379 (3)	C23—H23	0.93
C3—H3	0.93	C24—C25	1.368 (3)
C4—C5	1.378 (3)	C24—H24	0.93
C4—H4	0.93	C25—H25	0.93
C5—C6	1.372 (3)	O1W—H1W1	0.85 (2)
C5—H5	0.93	O1W—H1W2	0.85 (4)

N3—Ni1—N7	180	N5—C9—C10	123.34 (15)
N3—Ni1—N6ⁱ	102.38 (4)	N5—C9—C8	115.76 (14)
N7—Ni1—N6ⁱ	77.62 (4)	C10—C9—C8	120.84 (14)
N3—Ni1—N6	102.38 (4)	C9—C10—C11	118.80 (18)
N7—Ni1—N6	77.62 (4)	C9—C10—H10	120.6
N6ⁱ—Ni1—N6	155.25 (7)	C11—C10—H10	120.6
N3—Ni1—N2ⁱ	77.67 (4)	C12—C11—C10	118.28 (19)
N7—Ni1—N2ⁱ	102.33 (4)	C12—C11—H11	120.9
N6ⁱ—Ni1—N2ⁱ	87.53 (5)	C10—C11—H11	120.9
N6—Ni1—N2ⁱ	97.74 (5)	C11—C12—C13	119.46 (18)
N3—Ni1—N2	77.67 (4)	C11—C12—H12	120.3
N7—Ni1—N2	102.33 (4)	C13—C12—H12	120.3
N6ⁱ—Ni1—N2	97.74 (5)	N5—C13—C12	123.8 (2)
N6—Ni1—N2	87.53 (5)	N5—C13—H13	118.1
N2ⁱ—Ni1—N2	155.34 (7)	C12—C13—H13	118.1
N1—C1—S1	178.4 (2)	N6—C14—C15	121.91 (14)
C6—N2—C2	118.34 (15)	N6—C14—C19	113.83 (13)
C6—N2—Ni1	125.08 (12)	C15—C14—C19	123.72 (14)
C2—N2—Ni1	114.60 (10)	C14—C15—C16	118.90 (16)
C7ⁱ—N3—C7	121.80 (17)	C14—C15—H15	120.5
C7ⁱ—N3—Ni1	119.10 (9)	C16—C15—H15	120.5
C7—N3—Ni1	119.10 (9)	C17—C16—C15	119.27 (17)
C8—N4—C8ⁱ	120.79 (17)	C17—C16—H16	120.4
C13—N5—C9	116.30 (17)	C15—C16—H16	120.4
C18—N6—C14	118.07 (14)	C18—C17—C16	118.97 (16)
C18—N6—Ni1	125.01 (12)	C18—C17—H17	120.5
C14—N6—Ni1	115.18 (10)	C16—C17—H17	120.5
C19—N7—C19ⁱ	122.07 (18)	N6—C18—C17	122.84 (16)
C19—N7—Ni1	118.97 (9)	N6—C18—H18	118.6
C19ⁱ—N7—Ni1	118.97 (9)	C17—C18—H18	118.6
C20—N8—C20ⁱ	120.13 (17)	N7—C19—C20	117.66 (13)
C21—N9—C25	116.73 (17)	N7—C19—C14	112.97 (13)
N2—C2—C3	121.62 (14)	C20—C19—C14	129.22 (13)
N2—C2—C7	113.95 (13)	N8—C20—C19	119.14 (13)
C3—C2—C7	124.12 (14)	N8—C20—C21	117.19 (13)
C2—C3—C4	119.29 (17)	C19—C20—C21	123.62 (13)
C2—C3—H3	120.4	N9—C21—C22	122.87 (15)
C4—C3—H3	120.4	N9—C21—C20	115.10 (14)
C5—C4—C3	119.08 (19)	C22—C21—C20	121.96 (15)
C5—C4—H4	120.5	C21—C22—C23	118.46 (18)
C3—C4—H4	120.5	C21—C22—H22	120.8
C6—C5—C4	118.71 (17)	C23—C22—H22	120.8
C6—C5—H5	120.6	C24—C23—C22	119.57 (19)
C4—C5—H5	120.6	C24—C23—H23	120.2
N2—C6—C5	122.94 (18)	C22—C23—H23	120.2
N2—C6—H6	118.5	C23—C24—C25	118.46 (18)
C5—C6—H6	118.5	C23—C24—H24	120.8
N3—C7—C8	117.85 (13)	C25—C24—H24	120.8
N3—C7—C2	113.09 (13)	N9—C25—C24	123.9 (2)
C8—C7—C2	128.96 (13)	N9—C25—H25	118
N4—C8—C7	119.10 (13)	C24—C25—H25	118
N4—C8—C9	116.22 (13)	H1W1—O1W—H1W2	108 (4)
C7—C8—C9	124.66 (13)

N3—Ni1—N2—C6	167.18 (16)	C8ⁱ—N4—C8—C7	−8.67 (10)
N7—Ni1—N2—C6	−12.82 (16)	C8ⁱ—N4—C8—C9	170.04 (15)
N6ⁱ—Ni1—N2—C6	−91.77 (16)	N3—C7—C8—N4	17.43 (19)
N6—Ni1—N2—C6	63.94 (16)	C2—C7—C8—N4	−158.78 (13)
N2ⁱ—Ni1—N2—C6	167.18 (16)	N3—C7—C8—C9	−161.16 (13)
N3—Ni1—N2—C2	3.52 (10)	C2—C7—C8—C9	22.6 (2)
N7—Ni1—N2—C2	−176.48 (10)	C13—N5—C9—C10	1.5 (3)
N6ⁱ—Ni1—N2—C2	104.58 (11)	C13—N5—C9—C8	178.73 (18)
N6—Ni1—N2—C2	−99.71 (11)	N4—C8—C9—N5	−143.30 (14)
N2ⁱ—Ni1—N2—C2	3.52 (10)	C7—C8—C9—N5	35.3 (2)
N6ⁱ—Ni1—N3—C7ⁱ	89.60 (8)	N4—C8—C9—C10	34.0 (2)
N6—Ni1—N3—C7ⁱ	−90.40 (8)	C7—C8—C9—C10	−147.32 (16)
N2ⁱ—Ni1—N3—C7ⁱ	4.94 (8)	N5—C9—C10—C11	−2.0 (3)
N2—Ni1—N3—C7ⁱ	−175.06 (8)	C8—C9—C10—C11	−179.12 (16)
N6ⁱ—Ni1—N3—C7	−90.40 (8)	C9—C10—C11—C12	0.9 (3)
N6—Ni1—N3—C7	89.60 (8)	C10—C11—C12—C13	0.5 (3)
N2ⁱ—Ni1—N3—C7	−175.06 (8)	C9—N5—C13—C12	0.1 (4)
N2—Ni1—N3—C7	4.94 (8)	C11—C12—C13—N5	−1.0 (4)
N3—Ni1—N6—C18	−16.09 (14)	C18—N6—C14—C15	0.3 (2)
N7—Ni1—N6—C18	163.91 (14)	Ni1—N6—C14—C15	166.03 (13)
N6ⁱ—Ni1—N6—C18	163.91 (14)	C18—N6—C14—C19	−171.54 (14)
N2ⁱ—Ni1—N6—C18	−95.09 (14)	Ni1—N6—C14—C19	−5.83 (16)
N2—Ni1—N6—C18	60.72 (14)	N6—C14—C15—C16	−0.8 (3)
N3—Ni1—N6—C14	179.33 (10)	C19—C14—C15—C16	170.27 (16)
N7—Ni1—N6—C14	−0.67 (10)	C14—C15—C16—C17	−0.5 (3)
N6ⁱ—Ni1—N6—C14	−0.67 (10)	C15—C16—C17—C18	2.1 (3)
N2ⁱ—Ni1—N6—C14	100.33 (11)	C14—N6—C18—C17	1.4 (3)
N2—Ni1—N6—C14	−103.87 (11)	Ni1—N6—C18—C17	−162.77 (14)
N6ⁱ—Ni1—N7—C19	−171.86 (8)	C16—C17—C18—N6	−2.6 (3)
N6—Ni1—N7—C19	8.14 (8)	C19ⁱ—N7—C19—C20	−9.30 (10)
N2ⁱ—Ni1—N7—C19	−87.20 (8)	Ni1—N7—C19—C20	170.70 (10)
N2—Ni1—N7—C19	92.80 (8)	C19ⁱ—N7—C19—C14	166.59 (14)
N6ⁱ—Ni1—N7—C19ⁱ	8.14 (8)	Ni1—N7—C19—C14	−13.41 (14)
N6—Ni1—N7—C19ⁱ	−171.86 (8)	N6—C14—C19—N7	12.20 (18)
N2ⁱ—Ni1—N7—C19ⁱ	92.80 (8)	C15—C14—C19—N7	−159.49 (14)
N2—Ni1—N7—C19ⁱ	−87.20 (8)	N6—C14—C19—C20	−172.49 (15)
C6—N2—C2—C3	−1.4 (2)	C15—C14—C19—C20	15.8 (3)
Ni1—N2—C2—C3	163.47 (14)	C20ⁱ—N8—C20—C19	−9.49 (10)
C6—N2—C2—C7	−175.20 (15)	C20ⁱ—N8—C20—C21	168.10 (15)
Ni1—N2—C2—C7	−10.38 (17)	N7—C19—C20—N8	19.1 (2)
N2—C2—C3—C4	0.8 (3)	C14—C19—C20—N8	−156.03 (14)
C7—C2—C3—C4	174.00 (18)	N7—C19—C20—C21	−158.34 (13)
C2—C3—C4—C5	0.4 (3)	C14—C19—C20—C21	26.5 (2)
C3—C4—C5—C6	−0.9 (4)	C25—N9—C21—C22	0.8 (3)
C2—N2—C6—C5	0.8 (3)	C25—N9—C21—C20	177.73 (16)
Ni1—N2—C6—C5	−162.32 (18)	N8—C20—C21—N9	−140.33 (14)
C4—C5—C6—N2	0.4 (4)	C19—C20—C21—N9	37.1 (2)
C7ⁱ—N3—C7—C8	−8.50 (10)	N8—C20—C21—C22	36.6 (2)
Ni1—N3—C7—C8	171.50 (10)	C19—C20—C21—C22	−145.93 (17)
C7ⁱ—N3—C7—C2	168.30 (14)	N9—C21—C22—C23	−0.3 (3)
Ni1—N3—C7—C2	−11.70 (14)	C20—C21—C22—C23	−177.02 (16)
N2—C2—C7—N3	14.24 (18)	C21—C22—C23—C24	−0.1 (3)
C3—C2—C7—N3	−159.43 (15)	C22—C23—C24—C25	0.0 (3)
N2—C2—C7—C8	−169.40 (15)	C21—N9—C25—C24	−1.0 (3)
C3—C2—C7—C8	16.9 (3)	C23—C24—C25—N9	0.6 (3)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···N9ⁱ	0.85 (2)	2.28 (3)	3.116 (4)	166 (3)
O1W—H1W2···N1ⁱⁱ	0.85 (4)	2.20 (3)	3.044 (4)	173 (4)
C3—H3···N5	0.93	2.61	3.045 (3)	109

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

Experimental details

Crystal data
Chemical formula	[Ni(C₂₄H₁₆N₆)₂](NCS)₂·2H₂O
M_r	987.76
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	17.9091 (4), 13.6851 (2), 19.4650 (4)
β (°)	106.161 (2)
V (Å³)	4582.11 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.57
Crystal size (mm)	0.35 × 0.26 × 0.21

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire2 window
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	23806, 7385, 4946
R_int	0.031

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.123, 0.94
No. of reflections	7385
No. of parameters	320
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.43

Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···N9ⁱ	0.85 (2)	2.28 (3)	3.116 (4)	166 (3)
O1W—H1W2···N1ⁱⁱ	0.85 (4)	2.20 (3)	3.044 (4)	173 (4)
C3—H3···N5	0.93	2.61	3.045 (3)	109

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

Acknowledgements

This work was supported by the Universidad del País Vasco (UPV 00169.125–13956/2004), the Basque Government (IT-282–07), and the Ministerio de Ciencia y Tecnología (CTQ2005–05778-PPQ). NDelaP thanks the UPV/EHU for financial support under the "Convocatoria para la concesión de ayudas de especialización para investigadores doctores en la UPV/EHU (2008)"

References

Allis, D. G., Burkholder, E. & Zubieta, J. (2004). Polyhedron, 23, 1145–1152. Web of Science CSD CrossRef CAS Google Scholar
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Arana, C., Yan, S., Keshavarz, K. M., Potes, K. T. & Abruña, H. D. (1992). Inorg. Chem. 31, 3680–3682. CrossRef CAS Web of Science Google Scholar
Burkholder, E. & Zubieta, J. (2004). Inorg. Chim. Acta, 357, 1229–1235. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Haines, R. I., Hutchings, D. R. & Strickland, D. W. (2000). Inorganic Reaction Mechanisms (Amsterdam), 2, 223–233. CAS Google Scholar
Königstein, C. & Bauer, R. (1994). Hydrogen Energy Prog. X, Proc. World Hydrogen Energy Conf. 10th, 2, 717–725. Google Scholar
Königstein, C. & Bauer, R. (1997). Int. Journal Hydrogen Energy, 22, 471–474. Google Scholar
Lainé, P., Gourdon, A. & Launay, J. P. (1995). Inorg. Chem. 34, 5156–5165. Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Oxford Diffraction (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Ruminski, R. R. & Kiplinger, J. L. (1990). Inorg. Chem. 29, 4581–4584. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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