[Tris(3,5-diphenyl-pyrazol-yl)hydro-borato]nickel(II) bromide.

In the title tris-(pyrazol-yl)borate (Tp(Ph2)) complex, [NiBr(C(45)H(34)BN(6))], the Ni, Br and B atoms lie on a crystallographic threefold axis and a distorted NiN(3)Br tetra-hedral geometry arises for the metal ion. In the crystal, C-H⋯(C=C) and C-H⋯π inter-actions help to establish the polar crystal packing.

Related literature

For other TpNiX (X = Cl, Br) complexes, see: Desrochers et al. (2003 ▶, 2006 ▶); Kunrath et al. (2003 ▶); Uehara et al. (2002 ▶); Guo et al. (1998 ▶); Harding et al. (2007 ▶). For ionic radius data, see: Shannon (1976 ▶).

Experimental

Crystal data

[NiBr(C45H34BN6)]

M = 808.21

Trigonal,

a = 12.8227 (8) Å

c = 19.327 (3) Å

V = 2752.0 (5) Å3

Z = 3

Mo Kα radiation

μ = 1.66 mm−1

T = 150 K

0.24 × 0.24 × 0.21 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T min = 0.691, T max = 0.722

5609 measured reflections

2075 independent reflections

1943 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.063

S = 1.06

2075 reflections

163 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.29 e Å−3

Absolute structure: Flack (1983 ▶), 670 Friedel pairs

Flack parameter: 0.020 (8)

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809021606/hb2976sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021606/hb2976Isup2.hkl

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

[NiBr(C45H34BN6)]	Dx = 1.463 Mg m−3
Mr = 808.21	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 2851 reflections
Hall symbol: R 3	θ = 2.8–30.6°
a = 12.8227 (8) Å	µ = 1.66 mm−1
c = 19.327 (3) Å	T = 150 K
V = 2752.0 (5) Å3	Block, purple–pink
Z = 3	0.24 × 0.24 × 0.21 mm
F(000) = 1242

Bruker SMART CCD diffractometer	2075 independent reflections
Radiation source: fine-focus sealed tube	1943 reflections with I > 2σ(I)
graphite	Rint = 0.037
Detector resolution: 100 pixels mm-1	θmax = 27.5°, θmin = 2.1°
φ scans	h = −16→16
Absorption correction: multi-scan (SADABS; Bruker, 1997)	k = −11→16
Tmin = 0.691, Tmax = 0.722	l = −21→25
5609 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028	H-atom parameters constrained
wR(F2) = 0.063	w = 1/[σ2(Fo2) + (0.0169P)2] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
2075 reflections	Δρmax = 0.27 e Å−3
163 parameters	Δρmin = −0.29 e Å−3
1 restraint	Absolute structure: Flack (1983), 670 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.020 (8)

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 > σ(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
Br1	0.6667	0.3333	0.732391 (16)	0.02249 (14)
Ni1	0.6667	0.3333	0.61068 (2)	0.01335 (14)
N1	0.75319 (18)	0.26622 (19)	0.55312 (10)	0.0127 (4)
N2	0.75175 (19)	0.29001 (19)	0.48407 (10)	0.0128 (4)
B1	0.6667	0.3333	0.4567 (3)	0.0139 (10)
H1B	0.6667	0.3333	0.3983	0.017*
C1	0.8082 (2)	0.2003 (2)	0.55910 (12)	0.0146 (5)
C2	0.8419 (3)	0.1815 (3)	0.49355 (13)	0.0166 (6)
H2	0.8812	0.1373	0.4829	0.020*
C3	0.8064 (2)	0.2405 (2)	0.44716 (12)	0.0136 (5)
C4	0.8224 (3)	0.2532 (3)	0.37198 (14)	0.0135 (5)
C5	0.7922 (2)	0.1509 (2)	0.33065 (13)	0.0173 (6)
H5	0.7601	0.0738	0.3515	0.021*
C6	0.8094 (3)	0.1632 (3)	0.25990 (16)	0.0182 (7)
H6	0.7890	0.0942	0.2325	0.022*
C7	0.8557 (2)	0.2743 (3)	0.22844 (13)	0.0201 (6)
H7	0.8668	0.2814	0.1797	0.024*
C8	0.8860 (3)	0.3759 (3)	0.26839 (13)	0.0215 (6)
H8	0.9179	0.4525	0.2469	0.026*
C9	0.8698 (3)	0.3652 (3)	0.33951 (14)	0.0190 (6)
H9	0.8913	0.4350	0.3665	0.023*
C10	0.8239 (2)	0.1510 (3)	0.62468 (13)	0.0163 (6)
C11	0.8460 (2)	0.2131 (3)	0.68680 (14)	0.0185 (6)
H11	0.8564	0.2919	0.6872	0.022*
C12	0.8530 (3)	0.1605 (3)	0.74866 (17)	0.0230 (7)
H12	0.8650	0.2023	0.7912	0.028*
C13	0.8422 (3)	0.0472 (3)	0.74807 (16)	0.0269 (7)
H13	0.8468	0.0113	0.7901	0.032*
C14	0.8246 (3)	−0.0137 (3)	0.68574 (15)	0.0234 (7)
H14	0.8191	−0.0904	0.6849	0.028*
C15	0.8150 (3)	0.0381 (3)	0.62476 (16)	0.0209 (6)
H15	0.8022	−0.0041	0.5824	0.025*

	U11	U22	U33	U12	U13	U23
Br1	0.02665 (19)	0.02665 (19)	0.0142 (2)	0.01332 (9)	0.000	0.000
Ni1	0.0140 (2)	0.0140 (2)	0.0120 (3)	0.00702 (10)	0.000	0.000
N1	0.0107 (10)	0.0149 (11)	0.0121 (9)	0.0061 (9)	−0.0007 (8)	0.0007 (8)
N2	0.0137 (11)	0.0146 (11)	0.0096 (8)	0.0068 (9)	0.0007 (8)	0.0006 (8)
B1	0.0112 (15)	0.0112 (15)	0.019 (2)	0.0056 (8)	0.000	0.000
C1	0.0121 (13)	0.0105 (13)	0.0199 (12)	0.0047 (11)	−0.0016 (10)	0.0005 (10)
C2	0.0186 (14)	0.0165 (15)	0.0191 (16)	0.0122 (13)	−0.0028 (13)	0.0009 (12)
C3	0.0097 (13)	0.0094 (12)	0.0189 (12)	0.0026 (11)	−0.0001 (9)	0.0010 (9)
C4	0.0106 (13)	0.0148 (14)	0.0169 (12)	0.0077 (11)	0.0010 (10)	−0.0012 (11)
C5	0.0171 (15)	0.0124 (14)	0.0221 (13)	0.0071 (12)	0.0005 (11)	0.0031 (11)
C6	0.0191 (16)	0.0155 (15)	0.0234 (16)	0.0113 (13)	−0.0015 (13)	−0.0039 (13)
C7	0.0180 (15)	0.0237 (15)	0.0153 (12)	0.0080 (13)	0.0044 (11)	0.0003 (11)
C8	0.0210 (15)	0.0179 (15)	0.0210 (12)	0.0062 (12)	0.0060 (11)	0.0053 (11)
C9	0.0199 (16)	0.0172 (15)	0.0193 (13)	0.0087 (13)	0.0016 (11)	−0.0029 (11)
C10	0.0089 (13)	0.0166 (14)	0.0215 (13)	0.0049 (11)	0.0001 (10)	0.0043 (11)
C11	0.0136 (14)	0.0155 (14)	0.0233 (13)	0.0050 (12)	−0.0050 (11)	0.0012 (11)
C12	0.0204 (17)	0.0291 (19)	0.0180 (15)	0.0112 (15)	−0.0034 (13)	0.0002 (14)
C13	0.0206 (16)	0.0304 (17)	0.0268 (14)	0.0105 (14)	−0.0022 (13)	0.0126 (13)
C14	0.0206 (16)	0.0195 (16)	0.0333 (16)	0.0124 (13)	−0.0008 (12)	0.0075 (13)
C15	0.0185 (15)	0.0194 (16)	0.0257 (14)	0.0101 (14)	−0.0019 (12)	−0.0011 (12)

Ni1—Br1	2.3523 (6)	C5—H5	0.9500
Ni1—N1	2.041 (2)	C6—C7	1.380 (4)
Ni1—N1i	2.041 (2)	C6—H6	0.9500
Ni1—N1ii	2.041 (2)	C7—C8	1.392 (4)
N1—C1	1.350 (3)	C7—H7	0.9500
N1—N2	1.371 (3)	C8—C9	1.387 (4)
N2—C3	1.360 (3)	C8—H8	0.9500
N2—B1	1.544 (3)	C9—H9	0.9500
B1—N2i	1.544 (3)	C10—C11	1.389 (4)
B1—N2ii	1.544 (3)	C10—C15	1.394 (4)
B1—H1B	1.1278	C11—C12	1.397 (4)
C1—C2	1.398 (4)	C11—H11	0.9500
C1—C10	1.475 (3)	C12—C13	1.390 (5)
C2—C3	1.388 (3)	C12—H12	0.9500
C2—H2	0.9500	C13—C14	1.391 (5)
C3—C4	1.465 (4)	C13—H13	0.9500
C4—C9	1.397 (4)	C14—C15	1.388 (4)
C4—C5	1.415 (4)	C14—H14	0.9500
C5—C6	1.381 (4)	C15—H15	0.9500
N1—Ni1—N1i	93.11 (8)	C4—C5—H5	120.0
N1—Ni1—N1ii	93.11 (8)	C7—C6—C5	121.0 (3)
N1i—Ni1—N1ii	93.11 (8)	C7—C6—H6	119.5
N1—Ni1—Br1	123.04 (6)	C5—C6—H6	119.5
N1i—Ni1—Br1	123.04 (6)	C6—C7—C8	119.7 (2)
N1ii—Ni1—Br1	123.04 (6)	C6—C7—H7	120.1
C1—N1—N2	106.99 (19)	C8—C7—H7	120.1
C1—N1—Ni1	141.45 (17)	C9—C8—C7	119.9 (3)
N2—N1—Ni1	111.47 (15)	C9—C8—H8	120.0
C3—N2—N1	109.82 (19)	C7—C8—H8	120.0
C3—N2—B1	127.6 (2)	C8—C9—C4	120.9 (3)
N1—N2—B1	120.3 (2)	C8—C9—H9	119.5
N2—B1—N2i	108.89 (19)	C4—C9—H9	119.5
N2—B1—N2ii	108.89 (19)	C11—C10—C15	118.8 (3)
N2i—B1—N2ii	108.89 (19)	C11—C10—C1	121.9 (3)
N2—B1—H1B	110.0	C15—C10—C1	119.2 (2)
N2i—B1—H1B	110.0	C10—C11—C12	120.4 (3)
N2ii—B1—H1B	110.0	C10—C11—H11	119.8
N1—C1—C2	109.5 (2)	C12—C11—H11	119.8
N1—C1—C10	124.6 (2)	C13—C12—C11	120.1 (3)
C2—C1—C10	125.8 (2)	C13—C12—H12	120.0
C3—C2—C1	106.1 (2)	C11—C12—H12	120.0
C3—C2—H2	127.0	C14—C13—C12	119.8 (3)
C1—C2—H2	127.0	C14—C13—H13	120.1
N2—C3—C2	107.6 (2)	C12—C13—H13	120.1
N2—C3—C4	122.9 (2)	C15—C14—C13	119.7 (3)
C2—C3—C4	129.5 (2)	C15—C14—H14	120.2
C9—C4—C5	118.4 (2)	C13—C14—H14	120.2
C9—C4—C3	121.7 (3)	C14—C15—C10	121.1 (3)
C5—C4—C3	119.9 (2)	C14—C15—H15	119.4
C6—C5—C4	119.9 (3)	C10—C15—H15	119.4
C6—C5—H5	120.0

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···Cg1iii	0.95	2.73	3.589 (3)	151

Ni1—Br1	2.3523 (6)
Ni1—N1	2.041 (2)

N1—Ni1—N1i	93.11 (8)
N1—Ni1—Br1	123.04 (6)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯Cg1ii	0.95	2.73	3.589 (3)	151

Symmetry code: (ii) .