Bis[1-meth-oxy-2,2,2-tris-(pyrazol-1-yl-κN (2))ethane]-nickel(II) bis-(tri-fluoro-methane-sulfonate) methanol disolvate.

In the title salt, [Ni(C12H14N6O)2](CF3SO3)2·2CH3OH, the Ni(II) ion is coordinated by six N atoms from two tridentate 1-meth-oxy-2,2,2-tris-(pyrazol-1-yl)ethane ligands in a distorted octa-hedral geometry. The Ni(II) ion is situated on an inversion centre. The Ni-N distances range from 2.0589 (19) to 2.0757 (19) Å, intra-ligand N-Ni-N angles range from 84.50 (8) to 85.15 (8)°, and adjacent inter-ligand N-Ni-N angles range between 94.85 (8) and 95.50 (8)°. In the crystal, O-H⋯O hydrogen bonds between methanol solvent mol-ecules and tri-fluoro-methane-sulfonate anions are observed.

Related literature

Pyrazole-based tridentate ligands are drawing attention because of their topology and the nature of the donor atoms, see: Paulo et al. (2004 ▶); Bigmore et al. (2005 ▶). For the synthesis of the ligand, see: Maria et al. (2007 ▶). The compound reported here was prepared as part of our ongoing research effort to study nitro­gen donor tridentate scorpionate ligands coordinating to nickel, see: Lyubartseva et al. (2011 ▶, 2012 ▶); Lyubartseva & Parkin (2009 ▶).

Experimental

Crystal data

[Ni(C12H14N6O)2](CF3O3S)2·2CH4O

M = 937.52

Triclinic,

a = 9.0025 (2) Å

b = 9.5921 (2) Å

c = 11.9914 (2) Å

α = 105.2683 (8)°

β = 103.4796 (8)°

γ = 102.2596 (8)°

V = 929.15 (3) Å3

Z = 1

Mo Kα radiation

μ = 0.74 mm−1

T = 90 K

0.19 × 0.18 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ▶) T min = 0.753, T max = 0.898

22611 measured reflections

4271 independent reflections

3292 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.105

S = 1.10

4271 reflections

271 parameters

H-atom parameters constrained

Δρmax = 0.45 e Å−3

Δρmin = −0.48 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, 2008b ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008b ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008b ▶); software used to prepare material for publication: SHELXL2013.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813024653/lh5647sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813024653/lh5647Isup2.hkl

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

[Ni(C12H14N6O)2](CF3O3S)2·2CH4O	Z = 1
Mr = 937.52	F(000) = 482
Triclinic, P1	Dx = 1.675 Mg m−3
a = 9.0025 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.5921 (2) Å	Cell parameters from 4236 reflections
c = 11.9914 (2) Å	θ = 1.0–27.5°
α = 105.2683 (8)°	µ = 0.74 mm−1
β = 103.4796 (8)°	T = 90 K
γ = 102.2596 (8)°	Block, pink
V = 929.15 (3) Å3	0.19 × 0.18 × 0.15 mm

Nonius KappaCCD diffractometer	4271 independent reflections
Radiation source: fine-focus sealed-tube	3292 reflections with I > 2σ(I)
Detector resolution: 9.1 pixels mm-1	Rint = 0.040
φ and ω scans at fixed χ = 55°	θmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −11→11
Tmin = 0.753, Tmax = 0.898	k = −12→12
22611 measured reflections	l = −15→15

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.0411P)2 + 1.0985P] where P = (Fo2 + 2Fc2)/3
4271 reflections	(Δ/σ)max < 0.001
271 parameters	Δρmax = 0.45 e Å−3
0 restraints	Δρmin = −0.48 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.

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.5000	0.5000	0.01541 (12)
N1	0.5656 (2)	0.7100 (2)	0.63001 (18)	0.0170 (4)
N2	0.7195 (2)	0.7717 (2)	0.70477 (17)	0.0146 (4)
C1	0.4910 (3)	0.8115 (3)	0.6624 (2)	0.0183 (5)
H1	0.3814	0.7993	0.6255	0.022*
C2	0.5939 (3)	0.9387 (3)	0.7576 (2)	0.0215 (5)
H2	0.5688	1.0264	0.7968	0.026*
C3	0.7388 (3)	0.9105 (3)	0.7828 (2)	0.0188 (5)
H3	0.8347	0.9757	0.8433	0.023*
N3	0.6331 (2)	0.4422 (2)	0.63761 (18)	0.0166 (4)
N4	0.7765 (2)	0.5424 (2)	0.71273 (17)	0.0148 (4)
C4	0.6123 (3)	0.3275 (3)	0.6808 (2)	0.0199 (5)
H4	0.5224	0.2401	0.6468	0.024*
C5	0.7402 (3)	0.3530 (3)	0.7828 (2)	0.0211 (5)
H5	0.7536	0.2881	0.8296	0.025*
C6	0.8421 (3)	0.4903 (3)	0.8014 (2)	0.0187 (5)
H6	0.9405	0.5400	0.8646	0.022*
N5	0.7151 (2)	0.5746 (2)	0.47104 (17)	0.0162 (4)
N6	0.8478 (2)	0.6538 (2)	0.56911 (17)	0.0156 (4)
C7	0.7638 (3)	0.5711 (3)	0.3745 (2)	0.0195 (5)
H7	0.6968	0.5233	0.2929	0.023*
C8	0.9267 (3)	0.6469 (3)	0.4085 (2)	0.0210 (5)
H8	0.9895	0.6592	0.3563	0.025*
C9	0.9763 (3)	0.6993 (3)	0.5324 (2)	0.0185 (5)
H9	1.0812	0.7569	0.5835	0.022*
C10	0.8346 (3)	0.6854 (3)	0.6921 (2)	0.0150 (5)
C11	0.9962 (3)	0.7798 (3)	0.7859 (2)	0.0170 (5)
H11A	1.0337	0.8761	0.7712	0.020*
H11B	0.9858	0.8034	0.8688	0.020*
O1	1.10620 (19)	0.69583 (18)	0.77534 (15)	0.0191 (4)
C12	1.2450 (3)	0.7555 (3)	0.8798 (2)	0.0267 (6)
H12A	1.3066	0.8544	0.8824	0.040*
H12B	1.3111	0.6864	0.8752	0.040*
H12C	1.2124	0.7667	0.9534	0.040*
S1A	0.85393 (7)	0.75255 (7)	0.11470 (5)	0.02007 (15)
O1A	0.8467 (3)	0.6007 (2)	0.11115 (19)	0.0381 (5)
O2A	0.8839 (2)	0.8585 (2)	0.23378 (15)	0.0252 (4)
O3A	0.9434 (2)	0.8109 (3)	0.04420 (17)	0.0406 (6)
C1A	0.6486 (3)	0.7358 (3)	0.0358 (2)	0.0261 (6)
F1A	0.60356 (18)	0.64929 (18)	−0.08066 (13)	0.0306 (4)
F2A	0.6306 (3)	0.8709 (2)	0.03702 (18)	0.0555 (6)
F3A	0.5478 (2)	0.6780 (2)	0.08729 (17)	0.0503 (5)
O1S	0.7190 (2)	0.9839 (2)	0.38362 (17)	0.0275 (4)
H1S	0.7699	0.9374	0.3445	0.041*
C1S	0.7689 (3)	0.9892 (3)	0.5057 (3)	0.0286 (6)
H1S1	0.8850	1.0335	0.5393	0.043*
H1S2	0.7396	0.8866	0.5096	0.043*
H1S3	0.7167	1.0512	0.5529	0.043*

	U11	U22	U33	U12	U13	U23
Ni1	0.0140 (2)	0.0148 (2)	0.0151 (2)	0.00295 (17)	0.00210 (17)	0.00417 (17)
N1	0.0132 (10)	0.0165 (10)	0.0173 (10)	0.0023 (8)	0.0016 (8)	0.0039 (8)
N2	0.0119 (9)	0.0146 (9)	0.0155 (10)	0.0033 (8)	0.0024 (8)	0.0039 (8)
C1	0.0184 (12)	0.0176 (12)	0.0196 (12)	0.0078 (10)	0.0047 (10)	0.0064 (10)
C2	0.0225 (13)	0.0173 (12)	0.0246 (13)	0.0075 (10)	0.0075 (10)	0.0051 (10)
C3	0.0188 (12)	0.0154 (12)	0.0178 (12)	0.0023 (9)	0.0042 (10)	0.0020 (9)
N3	0.0129 (9)	0.0153 (10)	0.0167 (10)	0.0006 (8)	0.0009 (8)	0.0036 (8)
N4	0.0136 (9)	0.0137 (9)	0.0150 (10)	0.0030 (8)	0.0023 (8)	0.0039 (8)
C4	0.0207 (12)	0.0174 (12)	0.0212 (12)	0.0035 (10)	0.0058 (10)	0.0079 (10)
C5	0.0229 (13)	0.0207 (12)	0.0210 (13)	0.0056 (10)	0.0053 (10)	0.0109 (10)
C6	0.0185 (12)	0.0198 (12)	0.0181 (12)	0.0067 (10)	0.0039 (10)	0.0073 (10)
N5	0.0143 (10)	0.0168 (10)	0.0130 (10)	0.0014 (8)	0.0006 (8)	0.0031 (8)
N6	0.0144 (10)	0.0172 (10)	0.0127 (9)	0.0035 (8)	0.0026 (8)	0.0032 (8)
C7	0.0209 (12)	0.0199 (12)	0.0165 (12)	0.0047 (10)	0.0058 (10)	0.0050 (10)
C8	0.0234 (13)	0.0219 (13)	0.0222 (13)	0.0077 (10)	0.0122 (10)	0.0092 (10)
C9	0.0150 (11)	0.0188 (12)	0.0223 (13)	0.0046 (9)	0.0068 (10)	0.0072 (10)
C10	0.0144 (11)	0.0154 (11)	0.0147 (11)	0.0041 (9)	0.0028 (9)	0.0059 (9)
C11	0.0140 (11)	0.0160 (11)	0.0168 (12)	0.0028 (9)	0.0021 (9)	0.0024 (9)
O1	0.0132 (8)	0.0203 (9)	0.0198 (9)	0.0063 (7)	0.0003 (7)	0.0034 (7)
C12	0.0170 (13)	0.0287 (14)	0.0262 (14)	0.0077 (11)	−0.0035 (11)	0.0040 (11)
S1A	0.0172 (3)	0.0233 (3)	0.0172 (3)	0.0048 (2)	0.0039 (2)	0.0049 (2)
O1A	0.0420 (12)	0.0284 (11)	0.0354 (12)	0.0180 (9)	−0.0050 (9)	0.0053 (9)
O2A	0.0288 (10)	0.0268 (10)	0.0166 (9)	0.0059 (8)	0.0059 (8)	0.0043 (7)
O3A	0.0269 (11)	0.0574 (14)	0.0206 (10)	−0.0127 (10)	0.0082 (8)	0.0045 (10)
C1A	0.0256 (14)	0.0271 (14)	0.0246 (14)	0.0103 (11)	0.0070 (11)	0.0053 (11)
F1A	0.0256 (8)	0.0333 (9)	0.0226 (8)	0.0081 (7)	−0.0013 (6)	0.0008 (7)
F2A	0.0671 (14)	0.0359 (10)	0.0487 (12)	0.0332 (10)	−0.0113 (10)	0.0014 (9)
F3A	0.0248 (9)	0.0771 (14)	0.0403 (11)	0.0038 (9)	0.0153 (8)	0.0096 (10)
O1S	0.0268 (10)	0.0322 (11)	0.0262 (10)	0.0138 (8)	0.0083 (8)	0.0096 (8)
C1S	0.0317 (15)	0.0238 (14)	0.0305 (15)	0.0068 (12)	0.0099 (12)	0.0098 (12)

Ni1—N5i	2.0589 (19)	N6—C10	1.464 (3)
Ni1—N5	2.059 (2)	C7—C8	1.399 (3)
Ni1—N1i	2.0611 (19)	C7—H7	0.9500
Ni1—N1	2.0611 (19)	C8—C9	1.364 (3)
Ni1—N3i	2.0757 (19)	C8—H8	0.9500
Ni1—N3	2.0757 (19)	C9—H9	0.9500
N1—C1	1.323 (3)	C10—C11	1.531 (3)
N1—N2	1.366 (3)	C11—O1	1.410 (3)
N2—C3	1.359 (3)	C11—H11A	0.9900
N2—C10	1.468 (3)	C11—H11B	0.9900
C1—C2	1.394 (3)	O1—C12	1.431 (3)
C1—H1	0.9500	C12—H12A	0.9800
C2—C3	1.369 (3)	C12—H12B	0.9800
C2—H2	0.9500	C12—H12C	0.9800
C3—H3	0.9500	S1A—O3A	1.432 (2)
N3—C4	1.331 (3)	S1A—O1A	1.433 (2)
N3—N4	1.369 (3)	S1A—O2A	1.4437 (18)
N4—C6	1.357 (3)	S1A—C1A	1.821 (3)
N4—C10	1.466 (3)	C1A—F3A	1.318 (3)
C4—C5	1.396 (3)	C1A—F2A	1.336 (3)
C4—H4	0.9500	C1A—F1A	1.337 (3)
C5—C6	1.364 (4)	O1S—C1S	1.411 (3)
C5—H5	0.9500	O1S—H1S	0.8400
C6—H6	0.9500	C1S—H1S1	0.9800
N5—C7	1.324 (3)	C1S—H1S2	0.9800
N5—N6	1.370 (3)	C1S—H1S3	0.9800
N6—C9	1.359 (3)
N5i—Ni1—N5	180.0	C9—N6—C10	129.4 (2)
N5i—Ni1—N1i	85.15 (8)	N5—N6—C10	119.86 (18)
N5—Ni1—N1i	94.85 (8)	N5—C7—C8	111.1 (2)
N5i—Ni1—N1	94.85 (8)	N5—C7—H7	124.4
N5—Ni1—N1	85.15 (8)	C8—C7—H7	124.4
N1i—Ni1—N1	180.00 (11)	C9—C8—C7	105.6 (2)
N5i—Ni1—N3i	84.78 (8)	C9—C8—H8	127.2
N5—Ni1—N3i	95.22 (8)	C7—C8—H8	127.2
N1i—Ni1—N3i	84.50 (8)	N6—C9—C8	107.2 (2)
N1—Ni1—N3i	95.50 (8)	N6—C9—H9	126.4
N5i—Ni1—N3	95.22 (8)	C8—C9—H9	126.4
N5—Ni1—N3	84.78 (8)	N6—C10—N4	109.33 (18)
N1i—Ni1—N3	95.50 (8)	N6—C10—N2	109.35 (18)
N1—Ni1—N3	84.50 (8)	N4—C10—N2	108.62 (18)
N3i—Ni1—N3	180.00 (8)	N6—C10—C11	110.37 (19)
C1—N1—N2	105.50 (19)	N4—C10—C11	110.87 (18)
C1—N1—Ni1	134.77 (17)	N2—C10—C11	108.27 (18)
N2—N1—Ni1	119.73 (14)	O1—C11—C10	108.34 (18)
C3—N2—N1	110.70 (19)	O1—C11—H11A	110.0
C3—N2—C10	130.25 (19)	C10—C11—H11A	110.0
N1—N2—C10	119.05 (18)	O1—C11—H11B	110.0
N1—C1—C2	111.3 (2)	C10—C11—H11B	110.0
N1—C1—H1	124.4	H11A—C11—H11B	108.4
C2—C1—H1	124.4	C11—O1—C12	111.62 (18)
C3—C2—C1	105.5 (2)	O1—C12—H12A	109.5
C3—C2—H2	127.2	O1—C12—H12B	109.5
C1—C2—H2	127.2	H12A—C12—H12B	109.5
N2—C3—C2	107.0 (2)	O1—C12—H12C	109.5
N2—C3—H3	126.5	H12A—C12—H12C	109.5
C2—C3—H3	126.5	H12B—C12—H12C	109.5
C4—N3—N4	105.24 (19)	O3A—S1A—O1A	115.91 (14)
C4—N3—Ni1	135.74 (16)	O3A—S1A—O2A	113.55 (12)
N4—N3—Ni1	118.90 (14)	O1A—S1A—O2A	115.10 (12)
C6—N4—N3	110.88 (19)	O3A—S1A—C1A	103.65 (13)
C6—N4—C10	129.58 (19)	O1A—S1A—C1A	102.79 (12)
N3—N4—C10	119.51 (18)	O2A—S1A—C1A	103.55 (12)
N3—C4—C5	110.9 (2)	F3A—C1A—F2A	107.0 (2)
N3—C4—H4	124.6	F3A—C1A—F1A	108.1 (2)
C5—C4—H4	124.6	F2A—C1A—F1A	106.9 (2)
C6—C5—C4	105.9 (2)	F3A—C1A—S1A	111.68 (19)
C6—C5—H5	127.0	F2A—C1A—S1A	111.05 (19)
C4—C5—H5	127.0	F1A—C1A—S1A	111.86 (18)
N4—C6—C5	107.1 (2)	C1S—O1S—H1S	109.5
N4—C6—H6	126.5	O1S—C1S—H1S1	109.5
C5—C6—H6	126.5	O1S—C1S—H1S2	109.5
C7—N5—N6	105.39 (19)	H1S1—C1S—H1S2	109.5
C7—N5—Ni1	135.53 (16)	O1S—C1S—H1S3	109.5
N6—N5—Ni1	119.02 (14)	H1S1—C1S—H1S3	109.5
C9—N6—N5	110.65 (18)	H1S2—C1S—H1S3	109.5
C1—N1—N2—C3	0.1 (3)	N5—N6—C10—N4	59.9 (2)
Ni1—N1—N2—C3	179.31 (15)	C9—N6—C10—N2	117.0 (2)
C1—N1—N2—C10	179.7 (2)	N5—N6—C10—N2	−58.9 (3)
Ni1—N1—N2—C10	−1.1 (3)	C9—N6—C10—C11	−2.0 (3)
N2—N1—C1—C2	−0.2 (3)	N5—N6—C10—C11	−177.94 (18)
Ni1—N1—C1—C2	−179.22 (17)	C6—N4—C10—N6	124.2 (2)
N1—C1—C2—C3	0.2 (3)	N3—N4—C10—N6	−58.1 (3)
N1—N2—C3—C2	0.0 (3)	C6—N4—C10—N2	−116.5 (2)
C10—N2—C3—C2	−179.5 (2)	N3—N4—C10—N2	61.2 (3)
C1—C2—C3—N2	−0.1 (3)	C6—N4—C10—C11	2.3 (3)
C4—N3—N4—C6	−0.4 (3)	N3—N4—C10—C11	−179.97 (19)
Ni1—N3—N4—C6	176.26 (15)	C3—N2—C10—N6	−120.8 (2)
C4—N3—N4—C10	−178.5 (2)	N1—N2—C10—N6	59.7 (3)
Ni1—N3—N4—C10	−1.8 (3)	C3—N2—C10—N4	120.0 (2)
N4—N3—C4—C5	0.1 (3)	N1—N2—C10—N4	−59.5 (2)
Ni1—N3—C4—C5	−175.75 (18)	C3—N2—C10—C11	−0.5 (3)
N3—C4—C5—C6	0.2 (3)	N1—N2—C10—C11	−179.99 (19)
N3—N4—C6—C5	0.6 (3)	N6—C10—C11—O1	−61.4 (2)
C10—N4—C6—C5	178.4 (2)	N4—C10—C11—O1	59.9 (2)
C4—C5—C6—N4	−0.5 (3)	N2—C10—C11—O1	178.97 (18)
C7—N5—N6—C9	0.5 (3)	C10—C11—O1—C12	−163.6 (2)
Ni1—N5—N6—C9	−177.23 (15)	O3A—S1A—C1A—F3A	177.87 (19)
C7—N5—N6—C10	177.1 (2)	O1A—S1A—C1A—F3A	56.8 (2)
Ni1—N5—N6—C10	−0.6 (3)	O2A—S1A—C1A—F3A	−63.4 (2)
N6—N5—C7—C8	0.1 (3)	O3A—S1A—C1A—F2A	−62.8 (2)
Ni1—N5—C7—C8	177.22 (17)	O1A—S1A—C1A—F2A	176.2 (2)
N5—C7—C8—C9	−0.6 (3)	O2A—S1A—C1A—F2A	56.0 (2)
N5—N6—C9—C8	−0.9 (3)	O3A—S1A—C1A—F1A	56.6 (2)
C10—N6—C9—C8	−177.1 (2)	O1A—S1A—C1A—F1A	−64.5 (2)
C7—C8—C9—N6	0.9 (3)	O2A—S1A—C1A—F1A	175.33 (18)
C9—N6—C10—N4	−124.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1S—H1S···O2A	0.84	1.96	2.782 (3)	168

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1S—H1S⋯O2A	0.84	1.96	2.782 (3)	168