{2,6-Bis[(2,6-diisopropyl-phosphan-yl)-oxy]-4-fluoro-phenyl-κ(3)P,C(1),P'}(1H-pyrazole-κN(2))nickel(II) hexa-fluoro-phosphate.

The title compound, [Ni(C(18)H(30)FO(2)P(2))(C(3)H(4)N(2))]PF(6), was prepared by halide abstraction with TlPF(6) in the presence of CH(3)CN in CDCl(3) from the respective neutral pincer chlorido analogue followed by addition of pyrazole. The PO-C-OP pincer ligand acts in typical trans-P(2) tridentate fashion to generate a distorted square-planar nickel structure. The Ni-N(pyrazole) distance is 1.925 (2) Å and the plane of the pyrazole ligand is rotated 56.2 (1)° relative to the approximate square plane surrounding the Ni(II) center in which the pyrazole is bound to the Ni(II) atom through its sp(2)-hybridized N atom. This Ni-N distance is similar to bond lengths in the other reported Ni(II) pincer-ligand square-planar pyrazole complex structures; however, its dihedral angle is significantly larger than any of those for the latter set of pyrazole complexes.

Related literature

For recent studies on the chemistry of d-block PO—C—OP pincer complexes, see Chen et al. (2012 ▶); Zhang et al. (2012 ▶); Salah & Zargarian (2011 ▶); Hoffman et al. (2009 ▶); Wicker et al. (2011 ▶). For structures of other NiII pincer-ligand square-planar pyrazole complexes, see Salem et al. (2007 ▶, 2008 ▶); Peng et al. (2010 ▶). For information regarding the 19F NMR reference, see: Ji et al. (2005 ▶).

Experimental

Crystal data

[Ni(C18H30FO2P2)(C3H4N2)]PF6

M = 631.12

Monoclinic,

a = 9.0380 (9) Å

b = 20.1878 (16) Å

c = 16.1480 (16) Å

β = 98.659 (8)°

V = 2912.7 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.90 mm−1

T = 290 K

0.58 × 0.52 × 0.34 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.265, T max = 0.315

5464 measured reflections

5122 independent reflections

3432 reflections with I > 2σ(I)

R int = 0.024

3 standard reflections every 120 min intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.100

S = 1.00

5122 reflections

325 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.29 e Å−3

Data collection: CAD-4-PC (Enraf–Nonius, 1993 ▶); cell refinement: CAD-4-PC; data reduction: XCAD4-PC (Harms & Wocadlo, 1995) ▶; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812039207/hg5249sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812039207/hg5249Isup2.hkl

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

[Ni(C18H30FO2P2)(C3H4N2)]PF6	F(000) = 1304
Mr = 631.12	Dx = 1.439 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 9.0380 (9) Å	θ = 9.5–13.0°
b = 20.1878 (16) Å	µ = 0.90 mm−1
c = 16.1480 (16) Å	T = 290 K
β = 98.659 (8)°	Prism, yellow
V = 2912.7 (5) Å3	0.58 × 0.52 × 0.34 mm
Z = 4

Enraf–Nonius CAD-4 diffractometer	3432 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
Graphite monochromator	θmax = 25.0°, θmin = 2.0°
θ/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = 0→23
Tmin = 0.265, Tmax = 0.315	l = −19→18
5464 measured reflections	3 standard reflections every 120 min
5122 independent reflections	intensity decay: none

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0436P)2 + 0.9656P] where P = (Fo2 + 2Fc2)/3
5122 reflections	(Δ/σ)max < 0.001
325 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.29 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.

	x	y	z	Uiso*/Ueq
Ni1	0.32898 (5)	0.127947 (18)	0.28825 (2)	0.04161 (12)
P1	0.23694 (10)	0.18930 (4)	0.37905 (6)	0.0479 (2)
P2	0.39378 (11)	0.04384 (4)	0.21782 (5)	0.0479 (2)
P3	0.20240 (11)	0.13469 (5)	0.89133 (6)	0.0559 (2)
O1	0.1773 (3)	0.13751 (11)	0.44521 (15)	0.0617 (7)
O2	0.3652 (3)	−0.02228 (10)	0.27213 (14)	0.0609 (7)
N1	0.3831 (3)	0.19614 (12)	0.21502 (16)	0.0446 (6)
N2	0.4812 (3)	0.24504 (14)	0.23638 (18)	0.0568 (7)
H2A	0.5305	0.2502	0.2858	0.068*
F1	0.1762 (3)	−0.08905 (11)	0.51487 (15)	0.0953 (8)
F2	0.1974 (3)	0.21394 (10)	0.87960 (15)	0.0789 (7)
F3	0.1327 (3)	0.14307 (11)	0.97561 (13)	0.0792 (7)
F4	0.0382 (2)	0.13121 (10)	0.84026 (14)	0.0761 (6)
F5	0.2707 (3)	0.12876 (13)	0.80763 (16)	0.0966 (8)
F6	0.2071 (3)	0.05746 (10)	0.90361 (15)	0.0837 (7)
F7	0.3643 (3)	0.14096 (13)	0.94371 (17)	0.0969 (8)
C1	0.2761 (4)	0.05995 (15)	0.3580 (2)	0.0487 (8)
C2	0.2103 (4)	0.07201 (16)	0.4286 (2)	0.0519 (8)
C3	0.1765 (4)	0.02385 (18)	0.4828 (2)	0.0658 (10)
H3A	0.1341	0.0340	0.5303	0.079*
C4	0.2087 (5)	−0.04016 (19)	0.4630 (2)	0.0680 (11)
C5	0.2699 (5)	−0.05769 (17)	0.3935 (2)	0.0650 (10)
H5A	0.2883	−0.1017	0.3813	0.078*
C6	0.3028 (4)	−0.00660 (16)	0.3426 (2)	0.0527 (8)
C7	0.3621 (4)	0.24172 (17)	0.4498 (2)	0.0573 (9)
H7A	0.4045	0.2751	0.4161	0.069*
C8	0.4897 (5)	0.1988 (2)	0.4920 (3)	0.0838 (13)
H8A	0.5581	0.2255	0.5291	0.126*
H8B	0.5413	0.1794	0.4501	0.126*
H8C	0.4503	0.1643	0.5233	0.126*
C9	0.2836 (5)	0.2780 (2)	0.5141 (3)	0.0912 (15)
H9A	0.3545	0.3054	0.5487	0.137*
H9B	0.2422	0.2463	0.5485	0.137*
H9C	0.2047	0.3051	0.4855	0.137*
C10	0.0709 (4)	0.23715 (19)	0.3406 (3)	0.0684 (10)
H10A	0.0314	0.2559	0.3888	0.082*
C11	0.1109 (5)	0.2940 (2)	0.2859 (3)	0.0895 (14)
H11A	0.0225	0.3190	0.2659	0.134*
H11B	0.1525	0.2765	0.2392	0.134*
H11C	0.1831	0.3223	0.3183	0.134*
C12	−0.0481 (5)	0.1917 (2)	0.2934 (3)	0.1067 (18)
H12A	−0.1359	0.2171	0.2730	0.160*
H12B	−0.0734	0.1577	0.3304	0.160*
H12C	−0.0099	0.1717	0.2470	0.160*
C13	0.2776 (4)	0.02806 (16)	0.1181 (2)	0.0573 (9)
H13A	0.3016	0.0619	0.0786	0.069*
C14	0.1133 (5)	0.0365 (2)	0.1272 (3)	0.0880 (14)
H14A	0.0522	0.0287	0.0742	0.132*
H14B	0.0968	0.0808	0.1456	0.132*
H14C	0.0875	0.0054	0.1677	0.132*
C15	0.3067 (7)	−0.0397 (2)	0.0809 (3)	0.1052 (18)
H15A	0.2431	−0.0450	0.0281	0.158*
H15B	0.2856	−0.0740	0.1187	0.158*
H15C	0.4095	−0.0425	0.0727	0.158*
C16	0.5878 (4)	0.03345 (18)	0.2048 (2)	0.0621 (10)
H16A	0.5979	−0.0099	0.1789	0.074*
C17	0.6377 (5)	0.0857 (2)	0.1476 (3)	0.0824 (13)
H17A	0.7405	0.0783	0.1417	0.124*
H17B	0.6274	0.1288	0.1713	0.124*
H17C	0.5767	0.0832	0.0936	0.124*
C18	0.6859 (5)	0.0334 (3)	0.2900 (3)	0.1030 (16)
H18A	0.7886	0.0275	0.2828	0.155*
H18B	0.6562	−0.0023	0.3233	0.155*
H18C	0.6748	0.0747	0.3177	0.155*
C19	0.4934 (5)	0.28489 (18)	0.1717 (2)	0.0706 (11)
H19A	0.5543	0.3221	0.1725	0.085*
C20	0.4012 (5)	0.26112 (18)	0.1053 (2)	0.0665 (10)
H20A	0.3859	0.2782	0.0512	0.080*
C21	0.3346 (4)	0.20647 (16)	0.1337 (2)	0.0535 (9)
H21A	0.2648	0.1800	0.1008	0.064*

	U11	U22	U33	U12	U13	U23
Ni1	0.0490 (2)	0.0336 (2)	0.0428 (2)	−0.00062 (18)	0.00846 (17)	−0.00333 (17)
P1	0.0493 (5)	0.0408 (4)	0.0564 (5)	−0.0048 (4)	0.0168 (4)	−0.0095 (4)
P2	0.0663 (6)	0.0357 (4)	0.0420 (5)	0.0042 (4)	0.0095 (4)	−0.0027 (3)
P3	0.0559 (6)	0.0504 (5)	0.0615 (6)	0.0087 (4)	0.0092 (4)	0.0069 (4)
O1	0.0703 (16)	0.0510 (14)	0.0714 (16)	−0.0127 (12)	0.0351 (13)	−0.0105 (12)
O2	0.0977 (19)	0.0355 (12)	0.0512 (14)	0.0088 (12)	0.0169 (13)	0.0017 (10)
N1	0.0494 (16)	0.0355 (14)	0.0489 (16)	−0.0027 (12)	0.0070 (13)	−0.0046 (11)
N2	0.0654 (19)	0.0532 (16)	0.0511 (17)	−0.0163 (15)	0.0069 (14)	−0.0071 (14)
F1	0.145 (2)	0.0653 (15)	0.0830 (16)	−0.0156 (15)	0.0418 (16)	0.0215 (13)
F2	0.0833 (16)	0.0520 (12)	0.0982 (17)	0.0014 (11)	0.0041 (13)	0.0099 (12)
F3	0.0881 (16)	0.0868 (16)	0.0655 (14)	0.0200 (13)	0.0205 (12)	0.0081 (12)
F4	0.0689 (14)	0.0729 (14)	0.0799 (15)	−0.0058 (11)	−0.0105 (11)	0.0113 (12)
F5	0.119 (2)	0.0951 (18)	0.0864 (17)	0.0124 (15)	0.0492 (15)	0.0068 (14)
F6	0.1030 (19)	0.0539 (13)	0.0971 (18)	0.0157 (12)	0.0244 (14)	0.0103 (12)
F7	0.0593 (14)	0.109 (2)	0.116 (2)	0.0090 (14)	−0.0080 (13)	0.0128 (16)
C1	0.055 (2)	0.0428 (17)	0.0487 (19)	−0.0047 (15)	0.0081 (16)	−0.0002 (14)
C2	0.056 (2)	0.0430 (18)	0.058 (2)	−0.0083 (16)	0.0145 (17)	−0.0068 (16)
C3	0.081 (3)	0.063 (2)	0.057 (2)	−0.016 (2)	0.024 (2)	0.0002 (19)
C4	0.086 (3)	0.057 (2)	0.062 (2)	−0.016 (2)	0.014 (2)	0.0118 (19)
C5	0.092 (3)	0.0413 (19)	0.063 (2)	−0.0023 (18)	0.014 (2)	0.0042 (17)
C6	0.070 (2)	0.0414 (17)	0.0461 (19)	−0.0010 (16)	0.0062 (17)	0.0003 (15)
C7	0.064 (2)	0.053 (2)	0.057 (2)	−0.0149 (17)	0.0145 (17)	−0.0149 (17)
C8	0.075 (3)	0.086 (3)	0.085 (3)	−0.015 (2)	−0.006 (2)	−0.004 (2)
C9	0.117 (4)	0.084 (3)	0.079 (3)	−0.018 (3)	0.034 (3)	−0.037 (3)
C10	0.056 (2)	0.067 (2)	0.085 (3)	0.0098 (19)	0.019 (2)	−0.015 (2)
C11	0.092 (3)	0.072 (3)	0.104 (4)	0.032 (3)	0.014 (3)	0.007 (3)
C12	0.058 (3)	0.104 (4)	0.149 (5)	0.007 (3)	−0.013 (3)	−0.032 (3)
C13	0.085 (3)	0.0400 (18)	0.0441 (19)	−0.0001 (18)	0.0004 (18)	−0.0052 (15)
C14	0.082 (3)	0.093 (3)	0.083 (3)	−0.020 (3)	−0.008 (2)	−0.007 (3)
C15	0.187 (5)	0.054 (2)	0.064 (3)	0.021 (3)	−0.013 (3)	−0.025 (2)
C16	0.067 (2)	0.056 (2)	0.064 (2)	0.0121 (19)	0.0124 (19)	−0.0068 (18)
C17	0.073 (3)	0.083 (3)	0.098 (3)	0.009 (2)	0.035 (2)	0.004 (3)
C18	0.080 (3)	0.130 (4)	0.094 (4)	0.011 (3)	−0.003 (3)	0.013 (3)
C19	0.087 (3)	0.056 (2)	0.072 (3)	−0.022 (2)	0.023 (2)	0.004 (2)
C20	0.093 (3)	0.055 (2)	0.051 (2)	0.004 (2)	0.012 (2)	0.0097 (18)
C21	0.066 (2)	0.0458 (19)	0.046 (2)	0.0012 (17)	−0.0004 (17)	−0.0013 (15)

Ni1—C1	1.883 (3)	C8—H8C	0.9600
Ni1—N1	1.925 (2)	C9—H9A	0.9600
Ni1—P2	2.1727 (9)	C9—H9B	0.9600
Ni1—P1	2.1779 (9)	C9—H9C	0.9600
P1—O1	1.643 (2)	C10—C11	1.525 (5)
P1—C10	1.814 (4)	C10—C12	1.528 (5)
P1—C7	1.821 (3)	C10—H10A	0.9800
P2—O2	1.639 (2)	C11—H11A	0.9600
P2—C16	1.810 (4)	C11—H11B	0.9600
P2—C13	1.814 (3)	C11—H11C	0.9600
P3—F6	1.571 (2)	C12—H12A	0.9600
P3—F5	1.573 (2)	C12—H12B	0.9600
P3—F7	1.581 (2)	C12—H12C	0.9600
P3—F4	1.587 (2)	C13—C14	1.523 (5)
P3—F3	1.592 (2)	C13—C15	1.532 (5)
P3—F2	1.611 (2)	C13—H13A	0.9800
O1—C2	1.391 (4)	C14—H14A	0.9600
O2—C6	1.380 (4)	C14—H14B	0.9600
N1—C21	1.337 (4)	C14—H14C	0.9600
N1—N2	1.337 (3)	C15—H15A	0.9600
N2—C19	1.336 (4)	C15—H15B	0.9600
N2—H2A	0.8600	C15—H15C	0.9600
F1—C4	1.355 (4)	C16—C17	1.515 (5)
C1—C2	1.384 (4)	C16—C18	1.521 (5)
C1—C6	1.394 (4)	C16—H16A	0.9800
C2—C3	1.373 (5)	C17—H17A	0.9600
C3—C4	1.373 (5)	C17—H17B	0.9600
C3—H3A	0.9300	C17—H17C	0.9600
C4—C5	1.370 (5)	C18—H18A	0.9600
C5—C6	1.379 (5)	C18—H18B	0.9600
C5—H5A	0.9300	C18—H18C	0.9600
C7—C8	1.519 (5)	C19—C20	1.344 (5)
C7—C9	1.530 (5)	C19—H19A	0.9300
C7—H7A	0.9800	C20—C21	1.369 (5)
C8—H8A	0.9600	C20—H20A	0.9300
C8—H8B	0.9600	C21—H21A	0.9300
C1—Ni1—N1	178.79 (12)	H8B—C8—H8C	109.5
C1—Ni1—P2	81.73 (10)	C7—C9—H9A	109.5
N1—Ni1—P2	97.11 (8)	C7—C9—H9B	109.5
C1—Ni1—P1	81.64 (10)	H9A—C9—H9B	109.5
N1—Ni1—P1	99.49 (8)	C7—C9—H9C	109.5
P2—Ni1—P1	163.19 (4)	H9A—C9—H9C	109.5
O1—P1—C10	103.04 (16)	H9B—C9—H9C	109.5
O1—P1—C7	101.28 (15)	C11—C10—C12	111.9 (4)
C10—P1—C7	108.00 (18)	C11—C10—P1	110.0 (3)
O1—P1—Ni1	105.77 (9)	C12—C10—P1	109.6 (3)
C10—P1—Ni1	116.93 (14)	C11—C10—H10A	108.4
C7—P1—Ni1	119.25 (12)	C12—C10—H10A	108.4
O2—P2—C16	101.63 (16)	P1—C10—H10A	108.4
O2—P2—C13	102.43 (15)	C10—C11—H11A	109.5
C16—P2—C13	108.56 (18)	C10—C11—H11B	109.5
O2—P2—Ni1	106.24 (9)	H11A—C11—H11B	109.5
C16—P2—Ni1	119.58 (13)	C10—C11—H11C	109.5
C13—P2—Ni1	115.87 (12)	H11A—C11—H11C	109.5
F6—P3—F5	91.51 (14)	H11B—C11—H11C	109.5
F6—P3—F7	90.39 (14)	C10—C12—H12A	109.5
F5—P3—F7	90.82 (16)	C10—C12—H12B	109.5
F6—P3—F4	91.55 (13)	H12A—C12—H12B	109.5
F5—P3—F4	90.44 (14)	C10—C12—H12C	109.5
F7—P3—F4	177.66 (15)	H12A—C12—H12C	109.5
F6—P3—F3	90.24 (13)	H12B—C12—H12C	109.5
F5—P3—F3	178.25 (14)	C14—C13—C15	111.4 (4)
F7—P3—F3	89.28 (14)	C14—C13—P2	109.7 (3)
F4—P3—F3	89.40 (13)	C15—C13—P2	113.2 (3)
F6—P3—F2	179.49 (15)	C14—C13—H13A	107.4
F5—P3—F2	88.98 (14)	C15—C13—H13A	107.4
F7—P3—F2	89.46 (13)	P2—C13—H13A	107.4
F4—P3—F2	88.59 (12)	C13—C14—H14A	109.5
F3—P3—F2	89.27 (13)	C13—C14—H14B	109.5
C2—O1—P1	112.2 (2)	H14A—C14—H14B	109.5
C6—O2—P2	111.79 (19)	C13—C14—H14C	109.5
C21—N1—N2	104.2 (3)	H14A—C14—H14C	109.5
C21—N1—Ni1	129.7 (2)	H14B—C14—H14C	109.5
N2—N1—Ni1	126.1 (2)	C13—C15—H15A	109.5
C19—N2—N1	111.9 (3)	C13—C15—H15B	109.5
C19—N2—H2A	124.1	H15A—C15—H15B	109.5
N1—N2—H2A	124.1	C13—C15—H15C	109.5
C2—C1—C6	115.1 (3)	H15A—C15—H15C	109.5
C2—C1—Ni1	122.9 (2)	H15B—C15—H15C	109.5
C6—C1—Ni1	121.9 (3)	C17—C16—C18	111.5 (4)
C3—C2—C1	124.4 (3)	C17—C16—P2	111.9 (3)
C3—C2—O1	118.4 (3)	C18—C16—P2	109.8 (3)
C1—C2—O1	117.2 (3)	C17—C16—H16A	107.9
C4—C3—C2	116.3 (3)	C18—C16—H16A	107.9
C4—C3—H3A	121.9	P2—C16—H16A	107.9
C2—C3—H3A	121.9	C16—C17—H17A	109.5
F1—C4—C5	118.0 (3)	C16—C17—H17B	109.5
F1—C4—C3	117.9 (4)	H17A—C17—H17B	109.5
C5—C4—C3	124.0 (3)	C16—C17—H17C	109.5
C4—C5—C6	116.4 (3)	H17A—C17—H17C	109.5
C4—C5—H5A	121.8	H17B—C17—H17C	109.5
C6—C5—H5A	121.8	C16—C18—H18A	109.5
C5—C6—O2	118.1 (3)	C16—C18—H18B	109.5
C5—C6—C1	123.7 (3)	H18A—C18—H18B	109.5
O2—C6—C1	118.1 (3)	C16—C18—H18C	109.5
C8—C7—C9	111.6 (3)	H18A—C18—H18C	109.5
C8—C7—P1	107.9 (2)	H18B—C18—H18C	109.5
C9—C7—P1	113.3 (3)	N2—C19—C20	107.1 (3)
C8—C7—H7A	107.9	N2—C19—H19A	126.4
C9—C7—H7A	107.9	C20—C19—H19A	126.4
P1—C7—H7A	107.9	C19—C20—C21	105.7 (3)
C7—C8—H8A	109.5	C19—C20—H20A	127.1
C7—C8—H8B	109.5	C21—C20—H20A	127.1
H8A—C8—H8B	109.5	N1—C21—C20	111.1 (3)
C7—C8—H8C	109.5	N1—C21—H21A	124.5
H8A—C8—H8C	109.5	C20—C21—H21A	124.5