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

In the title salt, [Ni(C12H14N6O)2](CF3SO3)2·2H2O, the Ni(II) cation is located on an inversion centre and 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-N distances range from 2.0594 (12) to 2.0664 (12) Å, intra-ligand N-Ni-N angles range from 84.59 (5) to 86.06 (5)°, and adjacent inter-ligand N-Ni-N angles range between 93.94 (5) and 95.41 (5)°. In the crystal, inversion-related pyrazole rings are π-π stacked, with an inter-planar spacing of 3.4494 (18) Å, forming chains that propagate parallel to the a-axis direction. Inter-molecular O-H⋯O hydrogen bonds are present between water mol-ecules and tri-fluoro-methane-sulfonate anions.

Related literature

Pyrazole-based tridentate ligands are drawing more attention because of their topology and nature of donor atoms, see: Paulo et al. (2004 ▶); Bigmore et al. (2005 ▶). For the ligand synthesis, 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 coordinated to nickel, see: Lyubartseva et al. (2011 ▶, 2012 ▶); Lyubartseva & Parkin (2009 ▶).

Experimental

Crystal data

[Ni(C12H14N6O)2](CF3O3S)2·2H2O

M = 909.46

Triclinic,

a = 8.5582 (2) Å

b = 9.6515 (2) Å

c = 12.2347 (2) Å

α = 110.399 (1)°

β = 103.665 (1)°

γ = 97.317 (1)°

V = 895.66 (3) Å3

Z = 1

Mo Kα radiation

μ = 0.76 mm−1

T = 90 K

0.26 × 0.22 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ▶) T min = 0.760, T max = 0.862

25573 measured reflections

4095 independent reflections

3708 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.072

S = 1.07

4095 reflections

266 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.47 e Å−3

Δρmin = −0.49 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/S1600536813024252/tk5252sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813024252/tk5252Isup2.hkl

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

[Ni(C12H14N6O)2](CF3O3S)2·2H2O	Z = 1
Mr = 909.46	F(000) = 466
Triclinic, P1	Dx = 1.686 Mg m−3
a = 8.5582 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.6515 (2) Å	Cell parameters from 25674 reflections
c = 12.2347 (2) Å	θ = 1.0–27.5°
α = 110.399 (1)°	µ = 0.76 mm−1
β = 103.665 (1)°	T = 90 K
γ = 97.317 (1)°	Block, pink
V = 895.66 (3) Å3	0.26 × 0.22 × 0.15 mm

Nonius KappaCCD diffractometer	4095 independent reflections
Radiation source: fine-focus sealed-tube	3708 reflections with I > 2σ(I)
Detector resolution: 9.1 pixels mm-1	Rint = 0.023
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 = 0.760, Tmax = 0.862	k = −12→12
25573 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)] = 0.029	Hydrogen site location: difference Fourier map
wR(F2) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0311P)2 + 0.6676P] where P = (Fo2 + 2Fc2)/3
4095 reflections	(Δ/σ)max < 0.001
266 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.49 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	0.01222 (8)
N1	0.44622 (15)	0.29426 (14)	0.35443 (11)	0.0145 (3)
N2	0.30215 (15)	0.25366 (14)	0.26196 (11)	0.0130 (2)
C1	0.52676 (19)	0.18620 (17)	0.31824 (14)	0.0173 (3)
H1	0.6315	0.1839	0.3649	0.021*
C2	0.43694 (19)	0.07609 (18)	0.20223 (15)	0.0191 (3)
H2	0.4683	−0.0117	0.1563	0.023*
C3	0.29420 (19)	0.12165 (17)	0.16891 (14)	0.0167 (3)
H3	0.2062	0.0707	0.0948	0.020*
N3	0.39074 (15)	0.58147 (14)	0.37338 (11)	0.0149 (3)
N4	0.24408 (15)	0.49654 (14)	0.28723 (11)	0.0130 (2)
C4	0.4154 (2)	0.71338 (18)	0.36109 (14)	0.0173 (3)
H4	0.5085	0.7955	0.4093	0.021*
C5	0.2853 (2)	0.71481 (18)	0.26739 (15)	0.0192 (3)
H5	0.2738	0.7953	0.2407	0.023*
C6	0.17837 (19)	0.57573 (18)	0.22245 (14)	0.0169 (3)
H6	0.0772	0.5411	0.1581	0.020*
N5	0.26178 (15)	0.43228 (14)	0.50146 (11)	0.0139 (2)
N6	0.14141 (15)	0.35547 (14)	0.39195 (11)	0.0125 (2)
C7	0.19545 (19)	0.41516 (17)	0.58503 (14)	0.0160 (3)
H7	0.2508	0.4571	0.6704	0.019*
C8	0.03292 (19)	0.32692 (18)	0.53068 (14)	0.0170 (3)
H8	−0.0406	0.2992	0.5708	0.020*
C9	0.00275 (18)	0.28935 (17)	0.40787 (14)	0.0154 (3)
H9	−0.0963	0.2285	0.3453	0.018*
C10	0.17782 (18)	0.34450 (16)	0.27853 (13)	0.0127 (3)
C11	0.02317 (18)	0.26347 (17)	0.16833 (13)	0.0147 (3)
H11A	0.0485	0.2605	0.0928	0.018*
H11B	−0.0137	0.1577	0.1596	0.018*
O1	−0.10362 (13)	0.34191 (12)	0.18516 (10)	0.0167 (2)
C12	−0.25257 (19)	0.26218 (19)	0.08624 (15)	0.0204 (3)
H12A	−0.2344	0.2595	0.0095	0.031*
H12B	−0.3413	0.3143	0.1009	0.031*
H12C	−0.2839	0.1581	0.0807	0.031*
S1A	0.86275 (5)	0.86391 (4)	0.17962 (3)	0.01557 (9)
O1A	0.76221 (16)	0.97224 (14)	0.17899 (12)	0.0287 (3)
O2A	0.98159 (15)	0.86458 (15)	0.11398 (11)	0.0272 (3)
O3A	0.92445 (16)	0.85421 (15)	0.29641 (11)	0.0269 (3)
F1A	0.64625 (13)	0.67273 (12)	−0.02656 (9)	0.0292 (2)
F2A	0.79191 (16)	0.56755 (13)	0.07329 (13)	0.0497 (4)
F3A	0.59605 (16)	0.65956 (16)	0.13326 (12)	0.0500 (4)
C1A	0.7161 (2)	0.68201 (19)	0.08608 (16)	0.0220 (3)
O1W	0.76122 (18)	0.99331 (17)	0.48585 (14)	0.0368 (3)
H1W	0.848 (3)	1.032 (3)	0.563 (3)	0.055*
H2W	0.812 (3)	0.944 (3)	0.429 (3)	0.055*

	U11	U22	U33	U12	U13	U23
Ni1	0.01029 (13)	0.01323 (13)	0.01154 (13)	0.00243 (10)	0.00191 (10)	0.00400 (10)
N1	0.0101 (6)	0.0164 (6)	0.0136 (6)	0.0031 (5)	0.0010 (5)	0.0037 (5)
N2	0.0102 (6)	0.0146 (6)	0.0119 (6)	0.0027 (5)	0.0019 (5)	0.0037 (5)
C1	0.0134 (7)	0.0180 (7)	0.0198 (8)	0.0051 (6)	0.0045 (6)	0.0062 (6)
C2	0.0162 (8)	0.0165 (7)	0.0214 (8)	0.0050 (6)	0.0065 (6)	0.0029 (6)
C3	0.0150 (7)	0.0159 (7)	0.0152 (7)	0.0021 (6)	0.0040 (6)	0.0022 (6)
N3	0.0117 (6)	0.0157 (6)	0.0142 (6)	0.0005 (5)	0.0012 (5)	0.0050 (5)
N4	0.0105 (6)	0.0148 (6)	0.0117 (6)	0.0019 (5)	0.0011 (5)	0.0048 (5)
C4	0.0173 (7)	0.0164 (7)	0.0186 (7)	0.0025 (6)	0.0063 (6)	0.0070 (6)
C5	0.0202 (8)	0.0193 (7)	0.0218 (8)	0.0052 (6)	0.0068 (6)	0.0119 (6)
C6	0.0160 (7)	0.0210 (7)	0.0159 (7)	0.0065 (6)	0.0043 (6)	0.0095 (6)
N5	0.0119 (6)	0.0166 (6)	0.0105 (6)	0.0030 (5)	0.0014 (5)	0.0036 (5)
N6	0.0104 (6)	0.0146 (6)	0.0106 (6)	0.0017 (5)	0.0021 (5)	0.0038 (5)
C7	0.0177 (7)	0.0181 (7)	0.0132 (7)	0.0058 (6)	0.0054 (6)	0.0061 (6)
C8	0.0164 (7)	0.0191 (7)	0.0189 (8)	0.0047 (6)	0.0081 (6)	0.0093 (6)
C9	0.0120 (7)	0.0151 (7)	0.0189 (7)	0.0023 (5)	0.0049 (6)	0.0066 (6)
C10	0.0113 (7)	0.0141 (7)	0.0127 (7)	0.0036 (5)	0.0039 (5)	0.0047 (5)
C11	0.0113 (7)	0.0170 (7)	0.0124 (7)	0.0032 (6)	0.0013 (6)	0.0032 (6)
O1	0.0108 (5)	0.0193 (5)	0.0157 (5)	0.0048 (4)	0.0002 (4)	0.0039 (4)
C12	0.0122 (7)	0.0224 (8)	0.0213 (8)	0.0019 (6)	−0.0030 (6)	0.0082 (7)
S1A	0.01472 (18)	0.01723 (18)	0.01564 (18)	0.00405 (14)	0.00441 (14)	0.00749 (14)
O1A	0.0262 (7)	0.0202 (6)	0.0351 (7)	0.0104 (5)	0.0029 (5)	0.0081 (5)
O2A	0.0200 (6)	0.0363 (7)	0.0205 (6)	−0.0021 (5)	0.0088 (5)	0.0067 (5)
O3A	0.0297 (7)	0.0335 (7)	0.0178 (6)	0.0073 (5)	0.0035 (5)	0.0128 (5)
F1A	0.0236 (5)	0.0295 (5)	0.0251 (5)	−0.0015 (4)	−0.0035 (4)	0.0091 (4)
F2A	0.0461 (8)	0.0180 (5)	0.0645 (9)	0.0101 (5)	−0.0122 (6)	0.0102 (6)
F3A	0.0399 (7)	0.0563 (8)	0.0458 (7)	−0.0180 (6)	0.0195 (6)	0.0166 (6)
C1A	0.0208 (8)	0.0204 (8)	0.0266 (9)	0.0036 (6)	0.0052 (7)	0.0129 (7)
O1W	0.0266 (7)	0.0383 (8)	0.0339 (8)	0.0027 (6)	0.0103 (6)	0.0014 (6)

Ni1—N1	2.0594 (12)	N5—N6	1.3664 (17)
Ni1—N1i	2.0594 (12)	N6—C9	1.3625 (19)
Ni1—N3i	2.0602 (13)	N6—C10	1.4643 (18)
Ni1—N3	2.0602 (13)	C7—C8	1.403 (2)
Ni1—N5	2.0664 (12)	C7—H7	0.9500
Ni1—N5i	2.0664 (12)	C8—C9	1.367 (2)
N1—C1	1.3283 (19)	C8—H8	0.9500
N1—N2	1.3648 (17)	C9—H9	0.9500
N2—C3	1.3617 (19)	C10—C11	1.529 (2)
N2—C10	1.4689 (18)	C11—O1	1.4140 (18)
C1—C2	1.400 (2)	C11—H11A	0.9900
C1—H1	0.9500	C11—H11B	0.9900
C2—C3	1.370 (2)	O1—C12	1.4331 (18)
C2—H2	0.9500	C12—H12A	0.9800
C3—H3	0.9500	C12—H12B	0.9800
N3—C4	1.330 (2)	C12—H12C	0.9800
N3—N4	1.3671 (17)	S1A—O1A	1.4371 (12)
N4—C6	1.3600 (19)	S1A—O2A	1.4378 (12)
N4—C10	1.4618 (18)	S1A—O3A	1.4418 (12)
C4—C5	1.402 (2)	S1A—C1A	1.8237 (17)
C4—H4	0.9500	F1A—C1A	1.333 (2)
C5—C6	1.370 (2)	F2A—C1A	1.332 (2)
C5—H5	0.9500	F3A—C1A	1.322 (2)
C6—H6	0.9500	O1W—H1W	0.97 (3)
N5—C7	1.3278 (19)	O1W—H2W	0.94 (3)
N1—Ni1—N1i	180.0	C7—N5—Ni1	134.47 (10)
N1—Ni1—N3i	93.94 (5)	N6—N5—Ni1	118.35 (9)
N1i—Ni1—N3i	86.06 (5)	C9—N6—N5	110.86 (12)
N1—Ni1—N3	86.06 (5)	C9—N6—C10	129.46 (12)
N1i—Ni1—N3	93.94 (5)	N5—N6—C10	119.50 (12)
N3i—Ni1—N3	180.0	N5—C7—C8	111.13 (14)
N1—Ni1—N5	84.59 (5)	N5—C7—H7	124.4
N1i—Ni1—N5	95.41 (5)	C8—C7—H7	124.4
N3i—Ni1—N5	95.27 (5)	C9—C8—C7	105.44 (13)
N3—Ni1—N5	84.73 (5)	C9—C8—H8	127.3
N1—Ni1—N5i	95.41 (5)	C7—C8—H8	127.3
N1i—Ni1—N5i	84.59 (5)	N6—C9—C8	107.16 (13)
N3i—Ni1—N5i	84.73 (5)	N6—C9—H9	126.4
N3—Ni1—N5i	95.27 (5)	C8—C9—H9	126.4
N5—Ni1—N5i	180.00 (7)	N4—C10—N6	109.51 (11)
C1—N1—N2	105.55 (12)	N4—C10—N2	109.13 (11)
C1—N1—Ni1	135.27 (11)	N6—C10—N2	108.63 (11)
N2—N1—Ni1	118.89 (9)	N4—C10—C11	111.11 (12)
C3—N2—N1	110.80 (12)	N6—C10—C11	110.71 (12)
C3—N2—C10	129.99 (12)	N2—C10—C11	107.69 (11)
N1—N2—C10	118.99 (11)	O1—C11—C10	109.35 (12)
N1—C1—C2	111.08 (14)	O1—C11—H11A	109.8
N1—C1—H1	124.5	C10—C11—H11A	109.8
C2—C1—H1	124.5	O1—C11—H11B	109.8
C3—C2—C1	105.45 (14)	C10—C11—H11B	109.8
C3—C2—H2	127.3	H11A—C11—H11B	108.3
C1—C2—H2	127.3	C11—O1—C12	110.04 (11)
N2—C3—C2	107.11 (13)	O1—C12—H12A	109.5
N2—C3—H3	126.4	O1—C12—H12B	109.5
C2—C3—H3	126.4	H12A—C12—H12B	109.5
C4—N3—N4	105.69 (12)	O1—C12—H12C	109.5
C4—N3—Ni1	135.09 (11)	H12A—C12—H12C	109.5
N4—N3—Ni1	118.51 (9)	H12B—C12—H12C	109.5
C6—N4—N3	110.71 (12)	O1A—S1A—O2A	114.77 (8)
C6—N4—C10	129.53 (13)	O1A—S1A—O3A	114.93 (8)
N3—N4—C10	119.72 (12)	O2A—S1A—O3A	114.87 (8)
N3—C4—C5	110.81 (14)	O1A—S1A—C1A	103.12 (8)
N3—C4—H4	124.6	O2A—S1A—C1A	103.04 (8)
C5—C4—H4	124.6	O3A—S1A—C1A	103.80 (8)
C6—C5—C4	105.58 (14)	F3A—C1A—F2A	108.54 (15)
C6—C5—H5	127.2	F3A—C1A—F1A	107.47 (14)
C4—C5—H5	127.2	F2A—C1A—F1A	106.24 (14)
N4—C6—C5	107.21 (14)	F3A—C1A—S1A	112.04 (12)
N4—C6—H6	126.4	F2A—C1A—S1A	110.88 (12)
C5—C6—H6	126.4	F1A—C1A—S1A	111.42 (11)
C7—N5—N6	105.40 (12)	H1W—O1W—H2W	104 (2)
C1—N1—N2—C3	−0.31 (16)	N3—N4—C10—N6	63.30 (16)
Ni1—N1—N2—C3	174.45 (10)	C6—N4—C10—N2	126.87 (15)
C1—N1—N2—C10	174.92 (12)	N3—N4—C10—N2	−55.48 (16)
Ni1—N1—N2—C10	−10.32 (16)	C6—N4—C10—C11	8.3 (2)
N2—N1—C1—C2	0.58 (17)	N3—N4—C10—C11	−174.09 (12)
Ni1—N1—C1—C2	−172.90 (11)	C9—N6—C10—N4	132.03 (15)
N1—C1—C2—C3	−0.63 (19)	N5—N6—C10—N4	−53.32 (16)
N1—N2—C3—C2	−0.07 (17)	C9—N6—C10—N2	−108.88 (16)
C10—N2—C3—C2	−174.63 (14)	N5—N6—C10—N2	65.78 (16)
C1—C2—C3—N2	0.41 (18)	C9—N6—C10—C11	9.2 (2)
C4—N3—N4—C6	−0.20 (16)	N5—N6—C10—C11	−176.17 (12)
Ni1—N3—N4—C6	171.53 (10)	C3—N2—C10—N4	−120.06 (16)
C4—N3—N4—C10	−178.26 (12)	N1—N2—C10—N4	65.75 (16)
Ni1—N3—N4—C10	−6.53 (16)	C3—N2—C10—N6	120.60 (16)
N4—N3—C4—C5	0.07 (17)	N1—N2—C10—N6	−53.58 (16)
Ni1—N3—C4—C5	−169.62 (11)	C3—N2—C10—C11	0.7 (2)
N3—C4—C5—C6	0.09 (18)	N1—N2—C10—C11	−173.53 (12)
N3—N4—C6—C5	0.26 (17)	N4—C10—C11—O1	−64.66 (15)
C10—N4—C6—C5	178.07 (14)	N6—C10—C11—O1	57.25 (15)
C4—C5—C6—N4	−0.20 (17)	N2—C10—C11—O1	175.87 (11)
C7—N5—N6—C9	−1.01 (16)	C10—C11—O1—C12	−176.45 (12)
Ni1—N5—N6—C9	166.00 (10)	O1A—S1A—C1A—F3A	−60.94 (14)
C7—N5—N6—C10	−176.59 (12)	O2A—S1A—C1A—F3A	179.35 (13)
Ni1—N5—N6—C10	−9.58 (16)	O3A—S1A—C1A—F3A	59.25 (14)
N6—N5—C7—C8	0.35 (17)	O1A—S1A—C1A—F2A	177.62 (13)
Ni1—N5—C7—C8	−163.56 (11)	O2A—S1A—C1A—F2A	57.91 (14)
N5—C7—C8—C9	0.41 (18)	O3A—S1A—C1A—F2A	−62.19 (14)
N5—N6—C9—C8	1.28 (17)	O1A—S1A—C1A—F1A	59.51 (14)
C10—N6—C9—C8	176.30 (14)	O2A—S1A—C1A—F1A	−60.20 (13)
C7—C8—C9—N6	−1.00 (17)	O3A—S1A—C1A—F1A	179.70 (12)
C6—N4—C10—N6	−114.34 (16)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W···O3A	0.94 (3)	2.06 (3)	2.994 (2)	174 (2)
O1W—H1W···O3Aii	0.97 (3)	2.12 (3)	3.0613 (19)	163 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H2W⋯O3A	0.94 (3)	2.06 (3)	2.994 (2)	174 (2)
O1W—H1W⋯O3A i	0.97 (3)	2.12 (3)	3.0613 (19)	163 (2)

Symmetry code: (i) .