Bis(tripyrazol-1-ylmethane)nickel(II) tetra­cyanidonickelate(II) dihydrate

Lyubartseva, G.; Parkin, S.

doi:10.1107/S1600536809046108

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1530

doi:10.1107/S1600536809046108

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Bis(tripyrazol-1-ylmethane)nickel(II) tetracyanidonickelate(II) dihydrate

Ganna Lyubartseva ^a ^* and Sean Parkin ^b

^aDepartment of Biology and Chemistry, College of Science and Technology, Southern Arkansas University, Magnolia AR 71753, USA, and ^bDepartment of Chemistry, University of Kentucky, Lexington KY 40506, USA
^*Correspondence e-mail: GannaLyubartseva@saumag.edu

(Received 21 October 2009; accepted 2 November 2009; online 7 November 2009)

The title complex, [Ni(C₁₀H₁₀N₆)₂][Ni(CN)₄]·2H₂O, contains an octahedral nickel(II) cation and a square-planar nickel(II) anion. Both the cation and the anion reside on a crystallographic center of inversion. The Ni^II center in the cation is coordinated by six pyrazol-1-yl rings of two chelating tripyrazol-1-ylmethane [HC(pz)₃] ligands, with Ni—N distances that range between 2.0647 (19) and 2.0828 (19) Å. The Ni^II center in the anion is coordinated by four cyanide ligands, with Ni—C distances in the range 1.869 (2)–1.869 (3) Å. The [Ni(CN)₄]²⁻ anions are linked by inversion-related water molecules into extended chains that run parallel to the a axis.

Related literature

For the ligand synthesis, see: Reger et al. (2000 ). For allowed and forbidden d–d transitions in poly(3,5-dimethylpyrazolyl)methane complexes of nickel(II), see: Nolet et al. (2006 ). For coupled electron-transfer and spin-exchange reactions of metal-bis[tris(pyrazolyl)methane] complexes, see: Sheets & Schultz (2004 ). For structural, spectroscopic and angular-overlap studies of tris(pyrazol-1-yl)methane complexes, see: Astley et al. (1993 ). For nickel(II) complexes of some poly(1-pyrazolyl)alkane ligands, see: Mesubi & Ekemenzie (1984 ). For the coordination chemistry of geminal poly(1-pyrazolyl)alkanes, see: Trofimenko et al. (1970 ).

Experimental

Crystal data

[Ni(C₁₀H₁₀N₆)₂][Ni(CN)₄]·2H₂O
M_r = 686.01
Triclinic, $[P \overline 1]$
a = 8.4840 (2) Å
b = 8.7355 (2) Å
c = 10.7522 (3) Å
α = 75.5129 (11)°
β = 75.2713 (12)°
γ = 89.2534 (12)°
V = 745.09 (3) Å³
Z = 1
Mo Kα radiation
μ = 1.32 mm⁻¹
T = 90 K
0.24 × 0.21 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.743, T_max = 0.779
13964 measured reflections
3404 independent reflections
2664 reflections with I > 2σ(I)
R_int = 0.063

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.108
S = 1.08
3404 reflections
209 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.80 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯N8	0.83 (2)	1.97 (2)	2.798 (3)	176 (3)
O1W—H2W⋯N7ⁱ	0.83 (2)	1.99 (2)	2.815 (3)	174 (3)
Symmetry code: (i) x-1, y, z.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); 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: SHELXL97 and local procedures.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809046108/om2294sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809046108/om2294Isup2.hkl

checkCIF report

Comment top

Tris(pyrazolyl)methane ligands, which are isoelectronic to the poly(pyrazolyl)borate ligand, are well known for their modulating ability towards magnetic, spectroscopic and catalytic properties of transition metal compounds (Nolet et al. (2006), Sheets et al. (2004), Astley et al. (1993), by Mesubi et al. (1984), Trofimenko et al. (1970)). They are also relatively easy to synthesize. During our search for a better catalyst for a large range of chemical reactions, we found tris(polypyrazolyl)methane ligand very promising. Here we report a new nickel (II) complex with this ligand as the tetracyanonickelate salt.

The title complex, [Ni(HC(pz)~3~)~2~][Ni(CN)~4~].2H~2Õ, where HC(pz)~3~ is tris(1-pyrazolyl)methane, contains an octahedral nickel(II) cation and a square planar nickel(II) anion (Fig. 1). Both the cation and the anion reside on a crystallographic center of inversion.The nickel atom in the cation is coordinated by six pyrazolyl rings of two chelating HC(pz)~3~ ligands, with Ni—N distances that range between 2.0647 (19) Å and 2.0828 (19) Å. The nickel atom in the anion part is coordinated by four cyanide ligands, with Ni—C distances in the range 1.869 (2) Å to 1.869 (3) Å. The Ni(CN)₄^2- anions are linked by inversion-related water molecules into extended chains that run parallel to the a axis.

Related literature top

For the ligand synthesis, see: Reger et al. (2000). For allowed and forbidden d–d transitions in poly(3,5-dimethylpyrazolyl)methane complexes of nickel(II), see: Nolet et al. (2006). For coupled electron-transfer and spin-exchange reactions of metal-bis[tris(pyrazolyl)methane] complexes, see: Sheets et al. (2004). For structural, spectroscopic and angular-overlap studies of tris(pyrazol-1-yl)methane complexes, see: Astley et al. (1993). For nickel(II) complexes of some poly(1-pyrazolyl)alkane ligands, see: Mesubi et al. (1984). For the coordination chemistry of geminal poly(1-pyrazolyl)alkanes, see: Trofimenko et al. (1970).

Experimental top

Tris(pyrazolyl)methane ligand was synthesized according to the previously published procedure by Reger et al. (2000). Tetraethyl ammonium cyanide was purchased from Aldrich and used as received. NiCl~2~.6H~2~0(475 mg, 2 mmol) was dissolved in 5 ml methanol. Tris(pyrazolyl)methane (428 mg, 2 mmol) was dissolved in 5 ml methanol. The ligand solution was added dropwise to metal solution and with moderate stirring. Once the addition was complete, solid tetraethylammonium cyanide (938 mg, 6 mmol) was added. The clear solution was filtered and methanol was evaporated slowly. Pink crystals were obtained after 3 days (463 mg, 67% yield). Elemental analysis, calculated for Ni~2~C~24~H~24Ñ~16Õ~2~: C 42.02, H 3.53, N 32.67; found C 41.95, H 3.30, N 32.45. IR (cm^-1^): 3330, 3279, 3145, 3110, 2986, 2132, 1687, 1516, 1450,1441, 1402, 1285, 1252, 1219, 1088, 1057, 987, 859, 791, 770, 658, 607, 414.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); 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: SHELXL97 (Sheldrick, 2008) and local procedures.

Figures top

Fig. 1. View of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Bis(tripyrazol-1-ylmethane)nickel(II) tetracyanidonickelate(II) dihydrate top

Crystal data top

[Ni(C₁₀H₁₀N₆)₂][Ni(CN)₄]·2H₂O	Z = 1
M_r = 686.01	F(000) = 352
Triclinic, P1	D_x = 1.529 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4840 (2) Å	Cell parameters from 3304 reflections
b = 8.7355 (2) Å	θ = 1.0–27.5°
c = 10.7522 (3) Å	µ = 1.32 mm⁻¹
α = 75.5129 (11)°	T = 90 K
β = 75.2713 (12)°	Block, pink
γ = 89.2534 (12)°	0.24 × 0.21 × 0.20 mm
V = 745.09 (3) Å³

Data collection top

Nonius KappaCCD diffractometer	3404 independent reflections
Radiation source: fine-focus sealed tube	2664 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
Detector resolution: 9.1 pixels mm^-1	θ_max = 27.5°, θ_min = 2.0°
ω scans at fixed χ = 55°	h = −10→11
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −11→11
T_min = 0.743, T_max = 0.779	l = −13→13
13964 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0568P)² + 0.2597P] where P = (F_o² + 2F_c²)/3
3404 reflections	(Δ/σ)_max < 0.001
209 parameters	Δρ_max = 0.70 e Å⁻³
3 restraints	Δρ_min = −0.80 e Å⁻³

Crystal data top

[Ni(C₁₀H₁₀N₆)₂][Ni(CN)₄]·2H₂O	γ = 89.2534 (12)°
M_r = 686.01	V = 745.09 (3) Å³
Triclinic, P1	Z = 1
a = 8.4840 (2) Å	Mo Kα radiation
b = 8.7355 (2) Å	µ = 1.32 mm⁻¹
c = 10.7522 (3) Å	T = 90 K
α = 75.5129 (11)°	0.24 × 0.21 × 0.20 mm
β = 75.2713 (12)°

Data collection top

Nonius KappaCCD diffractometer	3404 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	2664 reflections with I > 2σ(I)
T_min = 0.743, T_max = 0.779	R_int = 0.063
13964 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	3 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.70 e Å⁻³
3404 reflections	Δρ_min = −0.80 e Å⁻³
209 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 > 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.

Three restraints (DFIX in SHELXL97) were used to ensure the geometry of the water molecule remained chemically reasonable.

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

	x	y	z	U_iso*/U_eq
Ni1	0.5000	0.5000	1.0000	0.01475 (13)
N1	0.7163 (2)	0.4988 (2)	0.85558 (19)	0.0177 (4)
C1	0.8185 (3)	0.3933 (3)	0.8155 (2)	0.0218 (5)
H1	0.8023	0.2821	0.8520	0.026*
N2	0.7864 (2)	0.6416 (2)	0.77724 (18)	0.0165 (4)
C2	0.9533 (3)	0.4679 (3)	0.7125 (2)	0.0236 (5)
H2	1.0423	0.4185	0.6673	0.028*
N3	0.6175 (2)	0.6834 (2)	1.03923 (19)	0.0191 (4)
C3	0.9294 (3)	0.6262 (3)	0.6912 (2)	0.0204 (5)
H3	0.9996	0.7095	0.6281	0.024*
N4	0.7081 (2)	0.7950 (2)	0.93389 (19)	0.0179 (4)
C4	0.6513 (3)	0.7139 (3)	1.1448 (2)	0.0231 (5)
H4	0.6050	0.6554	1.2339	0.028*
N5	0.5640 (2)	0.3277 (2)	1.14631 (19)	0.0193 (4)
C5	0.7636 (3)	0.8429 (3)	1.1081 (3)	0.0272 (6)
H5	0.8065	0.8873	1.1655	0.033*
N6	0.4508 (2)	0.2078 (2)	1.21934 (19)	0.0184 (4)
C6	0.7992 (3)	0.8923 (3)	0.9720 (3)	0.0237 (5)
H6	0.8726	0.9775	0.9159	0.028*
C7	0.5121 (3)	0.0982 (3)	1.3053 (2)	0.0214 (5)
H7	0.4560	0.0050	1.3661	0.026*
C8	0.6700 (3)	0.1472 (3)	1.2881 (2)	0.0233 (5)
H8	0.7458	0.0954	1.3339	0.028*
C9	0.6972 (3)	0.2894 (3)	1.1892 (2)	0.0214 (5)
H9	0.7975	0.3510	1.1567	0.026*
C10	0.7123 (3)	0.7855 (3)	0.7998 (2)	0.0177 (5)
H10	0.7806	0.8779	0.7348	0.021*
Ni2	0.5000	0.5000	0.5000	0.01604 (13)
N7	0.7352 (2)	0.7733 (3)	0.4652 (2)	0.0219 (5)
N8	0.2614 (3)	0.7476 (3)	0.4345 (2)	0.0258 (5)
C11	0.6471 (3)	0.6668 (3)	0.4813 (2)	0.0193 (5)
C12	0.3489 (3)	0.6500 (3)	0.4610 (2)	0.0190 (5)
O1W	0.0369 (2)	0.9370 (2)	0.32515 (19)	0.0279 (4)
H1W	0.101 (3)	0.877 (3)	0.358 (3)	0.042*
H2W	−0.053 (3)	0.894 (3)	0.369 (3)	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0122 (2)	0.0154 (2)	0.0150 (2)	−0.00204 (16)	−0.00209 (16)	−0.00215 (16)
N1	0.0165 (10)	0.0172 (9)	0.0178 (10)	−0.0021 (8)	−0.0031 (8)	−0.0027 (8)
C1	0.0178 (12)	0.0212 (12)	0.0275 (13)	0.0020 (10)	−0.0064 (10)	−0.0076 (10)
N2	0.0144 (10)	0.0186 (10)	0.0156 (9)	−0.0024 (8)	−0.0028 (8)	−0.0037 (7)
C2	0.0162 (12)	0.0310 (14)	0.0243 (13)	0.0041 (10)	−0.0030 (10)	−0.0109 (11)
N3	0.0175 (10)	0.0191 (10)	0.0173 (10)	−0.0041 (8)	−0.0019 (8)	−0.0011 (8)
C3	0.0130 (12)	0.0304 (13)	0.0165 (11)	−0.0032 (10)	−0.0014 (9)	−0.0058 (10)
N4	0.0171 (10)	0.0172 (10)	0.0166 (10)	−0.0055 (8)	0.0003 (8)	−0.0040 (8)
C4	0.0246 (13)	0.0272 (13)	0.0172 (12)	−0.0033 (10)	−0.0030 (10)	−0.0075 (10)
N5	0.0145 (10)	0.0209 (10)	0.0193 (10)	−0.0014 (8)	−0.0023 (8)	−0.0017 (8)
C5	0.0284 (15)	0.0304 (14)	0.0254 (13)	−0.0048 (11)	−0.0066 (11)	−0.0120 (11)
N6	0.0187 (10)	0.0177 (10)	0.0167 (10)	−0.0013 (8)	−0.0029 (8)	−0.0022 (8)
C6	0.0232 (14)	0.0200 (12)	0.0270 (13)	−0.0057 (10)	−0.0039 (10)	−0.0065 (10)
C7	0.0282 (14)	0.0175 (11)	0.0170 (12)	0.0033 (10)	−0.0050 (10)	−0.0025 (9)
C8	0.0221 (13)	0.0233 (12)	0.0263 (13)	0.0059 (10)	−0.0089 (10)	−0.0070 (10)
C9	0.0167 (12)	0.0246 (12)	0.0245 (13)	0.0029 (10)	−0.0072 (10)	−0.0076 (10)
C10	0.0160 (12)	0.0187 (11)	0.0162 (11)	−0.0012 (9)	−0.0023 (9)	−0.0020 (9)
Ni2	0.0109 (2)	0.0195 (2)	0.0168 (2)	−0.00070 (16)	−0.00297 (16)	−0.00337 (16)
N7	0.0150 (10)	0.0243 (11)	0.0240 (11)	−0.0005 (9)	−0.0023 (8)	−0.0046 (9)
N8	0.0160 (11)	0.0288 (12)	0.0312 (12)	−0.0002 (9)	−0.0060 (9)	−0.0053 (9)
C11	0.0143 (12)	0.0240 (12)	0.0181 (12)	0.0038 (10)	−0.0053 (9)	−0.0019 (9)
C12	0.0137 (12)	0.0244 (12)	0.0180 (12)	−0.0038 (10)	−0.0026 (9)	−0.0051 (9)
O1W	0.0168 (9)	0.0253 (10)	0.0340 (11)	−0.0026 (8)	−0.0064 (8)	0.0060 (8)

Geometric parameters (Å, º) top

Ni1—N5	2.0647 (19)	N5—N6	1.367 (3)
Ni1—N5ⁱ	2.0647 (19)	C5—C6	1.372 (4)
Ni1—N3	2.081 (2)	C5—H5	0.9500
Ni1—N3ⁱ	2.081 (2)	N6—C7	1.353 (3)
Ni1—N1	2.0828 (19)	N6—C10ⁱ	1.448 (3)
Ni1—N1ⁱ	2.0828 (19)	C6—H6	0.9500
N1—C1	1.332 (3)	C7—C8	1.364 (4)
N1—N2	1.363 (3)	C7—H7	0.9500
C1—C2	1.405 (3)	C8—C9	1.396 (3)
C1—H1	0.9500	C8—H8	0.9500
N2—C3	1.354 (3)	C9—H9	0.9500
N2—C10	1.446 (3)	C10—N6ⁱ	1.448 (3)
C2—C3	1.365 (3)	C10—H10	1.0000
C2—H2	0.9500	Ni2—C12ⁱⁱ	1.869 (2)
N3—C4	1.326 (3)	Ni2—C12	1.869 (2)
N3—N4	1.360 (3)	Ni2—C11	1.869 (3)
C3—H3	0.9500	Ni2—C11ⁱⁱ	1.869 (3)
N4—C6	1.356 (3)	N7—C11	1.151 (3)
N4—C10	1.457 (3)	N8—C12	1.153 (3)
C4—C5	1.396 (4)	O1W—H1W	0.83 (2)
C4—H4	0.9500	O1W—H2W	0.83 (2)
N5—C9	1.334 (3)

N5—Ni1—N5ⁱ	180.00 (10)	C5—C4—H4	124.3
N5—Ni1—N3	93.82 (8)	C9—N5—N6	104.52 (18)
N5ⁱ—Ni1—N3	86.18 (8)	C9—N5—Ni1	137.45 (17)
N5—Ni1—N3ⁱ	86.18 (8)	N6—N5—Ni1	117.85 (14)
N5ⁱ—Ni1—N3ⁱ	93.82 (8)	C6—C5—C4	105.8 (2)
N3—Ni1—N3ⁱ	179.999 (1)	C6—C5—H5	127.1
N5—Ni1—N1	94.89 (8)	C4—C5—H5	127.1
N5ⁱ—Ni1—N1	85.12 (8)	C7—N6—N5	111.63 (19)
N3—Ni1—N1	85.04 (8)	C7—N6—C10ⁱ	129.2 (2)
N3ⁱ—Ni1—N1	94.96 (8)	N5—N6—C10ⁱ	119.13 (18)
N5—Ni1—N1ⁱ	85.11 (8)	N4—C6—C5	106.1 (2)
N5ⁱ—Ni1—N1ⁱ	94.88 (8)	N4—C6—H6	127.0
N3—Ni1—N1ⁱ	94.96 (8)	C5—C6—H6	127.0
N3ⁱ—Ni1—N1ⁱ	85.04 (8)	N6—C7—C8	106.9 (2)
N1—Ni1—N1ⁱ	180.00 (8)	N6—C7—H7	126.6
C1—N1—N2	104.50 (19)	C8—C7—H7	126.6
C1—N1—Ni1	138.05 (17)	C7—C8—C9	105.7 (2)
N2—N1—Ni1	117.40 (14)	C7—C8—H8	127.1
N1—C1—C2	111.3 (2)	C9—C8—H8	127.1
N1—C1—H1	124.4	N5—C9—C8	111.2 (2)
C2—C1—H1	124.4	N5—C9—H9	124.4
C3—N2—N1	112.04 (19)	C8—C9—H9	124.4
C3—N2—C10	128.24 (19)	N2—C10—N6ⁱ	111.23 (19)
N1—N2—C10	119.54 (18)	N2—C10—N4	109.41 (18)
C3—C2—C1	105.5 (2)	N6ⁱ—C10—N4	110.33 (18)
C3—C2—H2	127.3	N2—C10—H10	108.6
C1—C2—H2	127.3	N6ⁱ—C10—H10	108.6
C4—N3—N4	104.74 (19)	N4—C10—H10	108.6
C4—N3—Ni1	136.46 (17)	C12ⁱⁱ—Ni2—C12	179.999 (1)
N4—N3—Ni1	117.88 (15)	C12ⁱⁱ—Ni2—C11	91.72 (10)
N2—C3—C2	106.7 (2)	C12—Ni2—C11	88.28 (10)
N2—C3—H3	126.6	C12ⁱⁱ—Ni2—C11ⁱⁱ	88.28 (10)
C2—C3—H3	126.6	C12—Ni2—C11ⁱⁱ	91.72 (10)
C6—N4—N3	112.08 (19)	C11—Ni2—C11ⁱⁱ	179.999 (1)
C6—N4—C10	128.5 (2)	N7—C11—Ni2	177.0 (2)
N3—N4—C10	118.97 (19)	N8—C12—Ni2	176.9 (2)
N3—C4—C5	111.3 (2)	H1W—O1W—H2W	103 (2)
N3—C4—H4	124.3

N5—Ni1—N1—C1	39.3 (3)	Ni1—N3—C4—C5	167.67 (19)
N5ⁱ—Ni1—N1—C1	−140.7 (3)	N3—Ni1—N5—C9	−44.9 (3)
N3—Ni1—N1—C1	132.7 (3)	N3ⁱ—Ni1—N5—C9	135.1 (3)
N3ⁱ—Ni1—N1—C1	−47.3 (3)	N1—Ni1—N5—C9	40.5 (3)
N5—Ni1—N1—N2	−137.72 (16)	N1ⁱ—Ni1—N5—C9	−139.5 (3)
N5ⁱ—Ni1—N1—N2	42.28 (16)	N3—Ni1—N5—N6	140.99 (16)
N3—Ni1—N1—N2	−44.30 (16)	N3ⁱ—Ni1—N5—N6	−39.01 (16)
N3ⁱ—Ni1—N1—N2	135.70 (16)	N1—Ni1—N5—N6	−133.67 (16)
N2—N1—C1—C2	0.1 (3)	N1ⁱ—Ni1—N5—N6	46.33 (16)
Ni1—N1—C1—C2	−177.13 (18)	N3—C4—C5—C6	−0.1 (3)
C1—N1—N2—C3	−0.5 (3)	C9—N5—N6—C7	0.1 (3)
Ni1—N1—N2—C3	177.41 (15)	Ni1—N5—N6—C7	175.99 (15)
C1—N1—N2—C10	−176.0 (2)	C9—N5—N6—C10ⁱ	178.2 (2)
Ni1—N1—N2—C10	1.9 (3)	Ni1—N5—N6—C10ⁱ	−5.9 (3)
N1—C1—C2—C3	0.3 (3)	N3—N4—C6—C5	−1.0 (3)
N5—Ni1—N3—C4	−30.7 (3)	C10—N4—C6—C5	−173.0 (2)
N5ⁱ—Ni1—N3—C4	149.3 (3)	C4—C5—C6—N4	0.6 (3)
N1—Ni1—N3—C4	−125.3 (3)	N5—N6—C7—C8	−0.2 (3)
N1ⁱ—Ni1—N3—C4	54.7 (3)	C10ⁱ—N6—C7—C8	−178.1 (2)
N5—Ni1—N3—N4	136.29 (17)	N6—C7—C8—C9	0.2 (3)
N5ⁱ—Ni1—N3—N4	−43.71 (17)	N6—N5—C9—C8	0.0 (3)
N1—Ni1—N3—N4	41.71 (16)	Ni1—N5—C9—C8	−174.60 (18)
N1ⁱ—Ni1—N3—N4	−138.29 (16)	C7—C8—C9—N5	−0.1 (3)
N1—N2—C3—C2	0.7 (3)	C3—N2—C10—N6ⁱ	123.8 (2)
C10—N2—C3—C2	175.7 (2)	N1—N2—C10—N6ⁱ	−61.6 (3)
C1—C2—C3—N2	−0.6 (3)	C3—N2—C10—N4	−114.1 (2)
C4—N3—N4—C6	0.9 (3)	N1—N2—C10—N4	60.6 (3)
Ni1—N3—N4—C6	−169.89 (16)	C6—N4—C10—N2	107.9 (3)
C4—N3—N4—C10	173.8 (2)	N3—N4—C10—N2	−63.7 (3)
Ni1—N3—N4—C10	3.0 (3)	C6—N4—C10—N6ⁱ	−129.4 (2)
N4—N3—C4—C5	−0.5 (3)	N3—N4—C10—N6ⁱ	59.0 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···N8	0.83 (2)	1.97 (2)	2.798 (3)	176 (3)
O1W—H2W···N7ⁱⁱⁱ	0.83 (2)	1.99 (2)	2.815 (3)	174 (3)

Symmetry code: (iii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[Ni(C₁₀H₁₀N₆)₂][Ni(CN)₄]·2H₂O
M_r	686.01
Crystal system, space group	Triclinic, P1
Temperature (K)	90
a, b, c (Å)	8.4840 (2), 8.7355 (2), 10.7522 (3)
α, β, γ (°)	75.5129 (11), 75.2713 (12), 89.2534 (12)
V (Å³)	745.09 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.32
Crystal size (mm)	0.24 × 0.21 × 0.20

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.743, 0.779
No. of measured, independent and observed [I > 2σ(I)] reflections	13964, 3404, 2664
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.108, 1.08
No. of reflections	3404
No. of parameters	209
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.80

Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and local procedures.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···N8	0.83 (2)	1.97 (2)	2.798 (3)	176 (3)
O1W—H2W···N7ⁱ	0.83 (2)	1.99 (2)	2.815 (3)	174 (3)

Symmetry code: (i) x−1, y, z.

Acknowledgements

GL gratefully acknowledges the Department of Biology and Chemistry, Southern Arkansas University, for financial support.

References

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