Bis(tripyrazol-1-ylmethane)nickel(II) tetra-cyanidonickelate(II) dihydrate.

The title complex, [Ni(C(10)H(10)N(6))(2)][Ni(CN)(4)]·2H(2)O, contains an octa-hedral 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 mol-ecules 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 = 686.01

Triclinic,

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[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.108

S = 1.08

3404 reflections

209 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.70 e Å−3

Δρmin = −0.80 e Å−3

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.

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ni(C10H10N6)2][Ni(CN)4]·2H2O	Z = 1
Mr = 686.01	F(000) = 352
Triclinic, P1	Dx = 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

Nonius KappaCCD diffractometer	3404 independent reflections
Radiation source: fine-focus sealed tube	2664 reflections with I > 2σ(I)
graphite	Rint = 0.063
Detector resolution: 9.1 pixels mm-1	θmax = 27.5°, θmin = 2.0°
ω scans at fixed χ = 55°	h = −10→11
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −11→11
Tmin = 0.743, Tmax = 0.779	l = −13→13
13964 measured reflections

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(Fo2) + (0.0568P)2 + 0.2597P] where P = (Fo2 + 2Fc2)/3
3404 reflections	(Δ/σ)max < 0.001
209 parameters	Δρmax = 0.70 e Å−3
3 restraints	Δρmin = −0.80 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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)

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) .