[4-Bromo-N-(pyridin-2-yl-methyl-idene)aniline-κN,N']bis-(1,1,1,5,5,5-hexa-fluoro-pentane-2,4-dionato-κO,O')nickel(II).

The title compound, [Ni(C(5)HF(6)O(2))(2)(C(12)H(9)BrN(2))], the Ni(II) atom exhibits a pseudo-octa-hedral coordination geometry. The structure packs through C-H⋯Br inter-actions, forming a hydrogen-bonded ladder. There are also strong hydrogen-bonding inter-actions between two of the O atoms of the β-diketonate ligands and two H atoms on the pyridine ring of the Schiff base ligand.

Related literature

For related structures, see: Harding, Harding, Sophonrat & Adams (2010 ▶); Harding, Harding, Tinpun et al. (2010 ▶); Aakeröy et al. (2004 ▶, 2005 ▶, 2007 ▶). For an introduction to crystal engineering, see: Braga et al. (2002 ▶). For details concerning the coordination of additional ligands to β-diketon­ate complexes, see: Chassot & Emmenegger (1996 ▶); Emmenegger et al. (2001 ▶). For a description of the Cambridge Structural database, see: Allen et al. (2002 ▶).

Experimental

Crystal data

[Ni(C5HF6O2)2(C12H9BrN2)]

M = 733.95

Monoclinic,

a = 31.251 (8) Å

b = 10.006 (3) Å

c = 17.653 (5) Å

β = 103.952 (5)°

V = 5358 (2) Å3

Z = 8

Mo Kα radiation

μ = 2.33 mm−1

T = 150 K

0.22 × 0.12 × 0.11 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T min = 0.628, T max = 0.784

27645 measured reflections

5988 independent reflections

3422 reflections with I > 2σ(I)

R int = 0.145

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.132

S = 0.91

5988 reflections

379 parameters

H-atom parameters constrained

Δρmax = 1.24 e Å−3

Δρmin = −1.12 e Å−3

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 and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005599/zb2010sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005599/zb2010Isup2.hkl

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

[Ni(C5HF6O2)2(C12H9BrN2)]	F(000) = 2880
Mr = 733.95	Dx = 1.820 Mg m−3
Monoclinic, C2/c	Melting point: 429 K
Hall symbol: -C2yc	Mo Kα radiation, λ = 0.71073 Å
a = 31.251 (8) Å	Cell parameters from 3767 reflections
b = 10.006 (3) Å	θ = 2.4–24.9°
c = 17.653 (5) Å	µ = 2.33 mm−1
β = 103.952 (5)°	T = 150 K
V = 5358 (2) Å3	Block, brown
Z = 8	0.22 × 0.12 × 0.11 mm

Bruker SMART CCD area-detector diffractometer	5988 independent reflections
Radiation source: fine-focus sealed tube	3422 reflections with I > 2σ(I)
graphite	Rint = 0.145
Detector resolution: 100 pixels mm-1	θmax = 27.5°, θmin = 1.3°
φ and ω scans	h = −39→40
Absorption correction: multi-scan (SADABS; Bruker, 1997)	k = −12→12
Tmin = 0.628, Tmax = 0.784	l = −22→22
27645 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132	H-atom parameters constrained
S = 0.91	w = 1/[σ2(Fo2) + (0.0546P)2] where P = (Fo2 + 2Fc2)/3
5988 reflections	(Δ/σ)max < 0.001
379 parameters	Δρmax = 1.24 e Å−3
0 restraints	Δρmin = −1.12 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 > 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
Ni1	0.089498 (18)	0.60018 (5)	0.17271 (3)	0.01947 (16)
Br1	0.279804 (16)	0.50379 (5)	−0.01356 (3)	0.03493 (16)
N1	0.10544 (11)	0.4874 (3)	0.0821 (2)	0.0180 (8)
N2	0.03045 (12)	0.5037 (3)	0.1283 (2)	0.0193 (8)
O1	0.06741 (10)	0.7013 (3)	0.25796 (16)	0.0227 (7)
O2	0.07571 (10)	0.7678 (3)	0.10485 (16)	0.0206 (7)
O3	0.14882 (9)	0.6873 (3)	0.21444 (17)	0.0253 (7)
O4	0.10989 (9)	0.4413 (3)	0.24516 (16)	0.0215 (7)
C1	0.22491 (15)	0.4979 (4)	0.0144 (3)	0.0268 (11)
C2	0.20348 (15)	0.3757 (5)	0.0139 (3)	0.0318 (12)
H2	0.2157	0.2965	−0.0018	0.038*
C3	0.16424 (15)	0.3716 (4)	0.0365 (3)	0.0269 (11)
H3	0.1497	0.2885	0.0375	0.032*
C4	0.14579 (14)	0.4876 (4)	0.0578 (3)	0.0197 (10)
C5	0.16748 (15)	0.6093 (4)	0.0566 (3)	0.0257 (11)
H5	0.1549	0.6892	0.0707	0.031*
C6	0.20726 (14)	0.6144 (4)	0.0351 (3)	0.0236 (10)
H6	0.2221	0.6971	0.0347	0.028*
C7	0.07464 (14)	0.4036 (4)	0.0519 (3)	0.0222 (10)
H7	0.0788	0.3410	0.0139	0.027*
C8	0.03340 (13)	0.4058 (4)	0.0765 (2)	0.0168 (9)
C9	−0.00087 (15)	0.3178 (4)	0.0481 (3)	0.0255 (11)
H9	0.0019	0.2505	0.0116	0.031*
C10	−0.03943 (15)	0.3295 (4)	0.0736 (3)	0.0261 (11)
H10	−0.0632	0.2691	0.0560	0.031*
C11	−0.04250 (15)	0.4301 (5)	0.1249 (3)	0.0265 (11)
H11	−0.0687	0.4407	0.1426	0.032*
C12	−0.00710 (14)	0.5167 (4)	0.1508 (3)	0.0223 (10)
H12	−0.0098	0.5870	0.1855	0.027*
C13	0.07108 (15)	0.8261 (4)	0.2653 (2)	0.0236 (10)
C14	0.06750 (18)	0.8781 (5)	0.3451 (3)	0.0326 (12)
C15	0.07746 (15)	0.9195 (4)	0.2105 (3)	0.0249 (11)
H15	0.0810	1.0110	0.2250	0.030*
C16	0.07882 (15)	0.8822 (4)	0.1348 (3)	0.0241 (11)
C17	0.08415 (17)	0.9929 (4)	0.0773 (3)	0.0278 (11)
C18	0.18236 (15)	0.6331 (4)	0.2566 (3)	0.0227 (10)
C19	0.22211 (17)	0.7250 (6)	0.2750 (3)	0.0410 (14)
C20	0.18587 (15)	0.5046 (4)	0.2881 (3)	0.0281 (11)
H20	0.2140	0.4740	0.3162	0.034*
C21	0.14966 (15)	0.4192 (4)	0.2797 (3)	0.0232 (10)
C22	0.15671 (15)	0.2806 (5)	0.3172 (3)	0.0286 (11)
F1	0.11909 (12)	0.9686 (3)	0.0484 (2)	0.0590 (10)
F2	0.04965 (11)	0.9967 (3)	0.01655 (16)	0.0474 (9)
F3	0.08890 (12)	1.1150 (3)	0.10758 (16)	0.0516 (9)
F4	0.03084 (12)	0.8339 (3)	0.3627 (2)	0.0651 (10)
F5	0.06729 (15)	1.0080 (3)	0.35147 (18)	0.0703 (12)
F6	0.09967 (13)	0.8311 (4)	0.40128 (18)	0.0775 (13)
F7	0.22453 (10)	0.8019 (3)	0.2159 (2)	0.0584 (10)
F8	0.21997 (13)	0.8058 (4)	0.3339 (2)	0.0789 (13)
F9	0.26008 (10)	0.6604 (4)	0.2971 (3)	0.0827 (14)
F10	0.13059 (10)	0.2608 (3)	0.3655 (2)	0.0540 (9)
F11	0.19792 (9)	0.2582 (3)	0.35786 (17)	0.0395 (8)
F12	0.14753 (11)	0.1857 (3)	0.26264 (18)	0.0522 (9)

	U11	U22	U33	U12	U13	U23
Ni1	0.0209 (3)	0.0193 (3)	0.0168 (3)	−0.0020 (2)	0.0019 (2)	−0.0002 (2)
Br1	0.0284 (3)	0.0261 (3)	0.0550 (4)	−0.0007 (2)	0.0192 (3)	−0.0007 (2)
N1	0.0176 (19)	0.0186 (19)	0.020 (2)	0.0011 (15)	0.0087 (16)	0.0019 (15)
N2	0.019 (2)	0.0198 (18)	0.0171 (19)	0.0022 (15)	0.0002 (16)	0.0014 (15)
O1	0.0265 (17)	0.0234 (17)	0.0181 (16)	−0.0041 (13)	0.0051 (14)	−0.0022 (13)
O2	0.0269 (17)	0.0229 (16)	0.0123 (15)	−0.0012 (13)	0.0052 (14)	0.0002 (12)
O3	0.0202 (17)	0.0289 (17)	0.0248 (17)	−0.0049 (14)	0.0014 (15)	−0.0015 (14)
O4	0.0239 (17)	0.0250 (16)	0.0134 (15)	−0.0003 (13)	0.0001 (14)	0.0030 (13)
C1	0.023 (3)	0.026 (2)	0.028 (3)	0.003 (2)	0.000 (2)	0.001 (2)
C2	0.021 (3)	0.025 (3)	0.055 (4)	0.002 (2)	0.019 (2)	0.000 (2)
C3	0.024 (3)	0.018 (2)	0.041 (3)	−0.0019 (18)	0.013 (2)	0.000 (2)
C4	0.020 (2)	0.020 (2)	0.019 (2)	−0.0013 (18)	0.005 (2)	0.0001 (18)
C5	0.031 (3)	0.023 (2)	0.024 (2)	0.000 (2)	0.008 (2)	−0.002 (2)
C6	0.019 (2)	0.025 (2)	0.032 (3)	−0.0018 (19)	0.016 (2)	0.002 (2)
C7	0.028 (3)	0.016 (2)	0.019 (2)	0.0015 (19)	0.000 (2)	0.0013 (18)
C8	0.016 (2)	0.021 (2)	0.014 (2)	0.0027 (18)	0.0062 (18)	0.0056 (18)
C9	0.030 (3)	0.019 (2)	0.023 (2)	−0.0042 (19)	−0.001 (2)	−0.0012 (19)
C10	0.020 (3)	0.035 (3)	0.023 (3)	−0.008 (2)	0.005 (2)	−0.001 (2)
C11	0.023 (3)	0.038 (3)	0.020 (2)	−0.001 (2)	0.007 (2)	0.002 (2)
C12	0.022 (3)	0.027 (2)	0.017 (2)	0.0056 (19)	0.003 (2)	0.0011 (18)
C13	0.029 (3)	0.024 (2)	0.017 (2)	−0.005 (2)	0.003 (2)	−0.0033 (19)
C14	0.049 (3)	0.027 (3)	0.024 (3)	−0.012 (2)	0.012 (3)	−0.005 (2)
C15	0.031 (3)	0.020 (2)	0.025 (3)	−0.0018 (19)	0.009 (2)	−0.0032 (19)
C16	0.025 (3)	0.019 (2)	0.023 (2)	−0.0035 (18)	−0.003 (2)	0.0025 (19)
C17	0.034 (3)	0.024 (2)	0.026 (3)	−0.001 (2)	0.009 (2)	0.001 (2)
C18	0.025 (3)	0.029 (3)	0.015 (2)	−0.005 (2)	0.007 (2)	−0.0012 (19)
C19	0.030 (3)	0.044 (3)	0.046 (4)	−0.011 (3)	0.003 (3)	0.005 (3)
C20	0.020 (2)	0.034 (3)	0.027 (3)	0.001 (2)	0.000 (2)	0.002 (2)
C21	0.026 (3)	0.026 (2)	0.016 (2)	0.002 (2)	0.002 (2)	−0.0045 (19)
C22	0.023 (3)	0.033 (3)	0.030 (3)	0.001 (2)	0.008 (2)	0.003 (2)
F1	0.064 (2)	0.051 (2)	0.075 (3)	0.0070 (17)	0.042 (2)	0.0280 (18)
F2	0.059 (2)	0.0475 (19)	0.0271 (16)	−0.0053 (15)	−0.0060 (16)	0.0152 (14)
F3	0.100 (3)	0.0219 (15)	0.0304 (17)	−0.0123 (16)	0.0116 (18)	0.0018 (13)
F4	0.077 (3)	0.076 (2)	0.058 (2)	−0.030 (2)	0.045 (2)	−0.0352 (19)
F5	0.158 (4)	0.0290 (18)	0.0383 (19)	−0.0167 (19)	0.052 (2)	−0.0129 (14)
F6	0.086 (3)	0.113 (3)	0.0216 (17)	0.031 (2)	−0.0094 (19)	−0.0215 (19)
F7	0.050 (2)	0.066 (2)	0.056 (2)	−0.0321 (17)	0.0068 (18)	0.0199 (18)
F8	0.081 (3)	0.090 (3)	0.069 (3)	−0.051 (2)	0.022 (2)	−0.045 (2)
F9	0.0247 (18)	0.076 (3)	0.136 (4)	−0.0113 (18)	−0.004 (2)	0.041 (3)
F10	0.046 (2)	0.054 (2)	0.072 (2)	0.0198 (15)	0.0331 (19)	0.0345 (17)
F11	0.0330 (16)	0.0378 (16)	0.0419 (18)	0.0070 (13)	−0.0021 (15)	0.0108 (13)
F12	0.068 (2)	0.0274 (16)	0.050 (2)	0.0015 (15)	−0.0074 (18)	−0.0033 (15)

Ni1—O3	2.020 (3)	C9—H9	0.9500
Ni1—O4	2.044 (3)	C10—C11	1.372 (6)
Ni1—O2	2.045 (3)	C10—H10	0.9500
Ni1—N2	2.063 (3)	C11—C12	1.393 (6)
Ni1—O1	2.066 (3)	C11—H11	0.9500
Ni1—N1	2.113 (4)	C12—H12	0.9500
Br1—C1	1.897 (5)	C13—C15	1.394 (6)
N1—C7	1.291 (5)	C13—C14	1.531 (7)
N1—C4	1.426 (6)	C14—F5	1.304 (5)
N2—C12	1.332 (6)	C14—F6	1.317 (6)
N2—C8	1.358 (5)	C14—F4	1.332 (6)
O1—C13	1.258 (5)	C15—C16	1.399 (6)
O2—C16	1.255 (5)	C15—H15	0.9500
O3—C18	1.253 (5)	C16—C17	1.538 (6)
O4—C21	1.265 (5)	C17—F2	1.326 (5)
C1—C6	1.376 (6)	C17—F3	1.327 (5)
C1—C2	1.393 (6)	C17—F1	1.334 (6)
C2—C3	1.379 (6)	C18—C20	1.394 (6)
C2—H2	0.9500	C18—C19	1.517 (7)
C3—C4	1.388 (6)	C19—F7	1.313 (6)
C3—H3	0.9500	C19—F9	1.325 (6)
C4—C5	1.396 (6)	C19—F8	1.331 (7)
C5—C6	1.386 (6)	C20—C21	1.397 (6)
C5—H5	0.9500	C20—H20	0.9500
C6—H6	0.9500	C21—C22	1.529 (6)
C7—C8	1.456 (6)	C22—F10	1.330 (6)
C7—H7	0.9500	C22—F12	1.333 (5)
C8—C9	1.384 (6)	C22—F11	1.333 (5)
C9—C10	1.390 (7)
O3—Ni1—O4	89.27 (12)	C11—C10—C9	118.7 (4)
O3—Ni1—O2	84.55 (12)	C11—C10—H10	120.7
O4—Ni1—O2	173.82 (12)	C9—C10—H10	120.7
O3—Ni1—N2	177.27 (13)	C10—C11—C12	119.8 (5)
O4—Ni1—N2	89.36 (12)	C10—C11—H11	120.1
O2—Ni1—N2	96.80 (12)	C12—C11—H11	120.1
O3—Ni1—O1	87.79 (12)	N2—C12—C11	121.9 (4)
O4—Ni1—O1	91.93 (12)	N2—C12—H12	119.1
O2—Ni1—O1	87.99 (12)	C11—C12—H12	119.1
N2—Ni1—O1	94.62 (13)	O1—C13—C15	128.3 (4)
O3—Ni1—N1	98.24 (13)	O1—C13—C14	114.1 (4)
O4—Ni1—N1	87.91 (12)	C15—C13—C14	117.7 (4)
O2—Ni1—N1	92.82 (12)	F5—C14—F6	108.1 (4)
N2—Ni1—N1	79.35 (14)	F5—C14—F4	106.8 (5)
O1—Ni1—N1	173.97 (13)	F6—C14—F4	104.4 (4)
C7—N1—C4	120.1 (4)	F5—C14—C13	114.9 (4)
C7—N1—Ni1	111.8 (3)	F6—C14—C13	111.0 (4)
C4—N1—Ni1	127.9 (3)	F4—C14—C13	111.0 (4)
C12—N2—C8	118.6 (4)	C13—C15—C16	121.8 (4)
C12—N2—Ni1	127.8 (3)	C13—C15—H15	119.1
C8—N2—Ni1	113.2 (3)	C16—C15—H15	119.1
C13—O1—Ni1	121.6 (3)	O2—C16—C15	129.0 (4)
C16—O2—Ni1	121.2 (3)	O2—C16—C17	112.9 (4)
C18—O3—Ni1	126.3 (3)	C15—C16—C17	118.1 (4)
C21—O4—Ni1	124.0 (3)	F2—C17—F3	106.8 (4)
C6—C1—C2	121.5 (5)	F2—C17—F1	106.0 (4)
C6—C1—Br1	119.2 (3)	F3—C17—F1	107.4 (4)
C2—C1—Br1	119.2 (3)	F2—C17—C16	111.0 (4)
C3—C2—C1	118.9 (4)	F3—C17—C16	114.7 (4)
C3—C2—H2	120.5	F1—C17—C16	110.5 (4)
C1—C2—H2	120.5	O3—C18—C20	127.6 (4)
C2—C3—C4	120.7 (4)	O3—C18—C19	112.9 (4)
C2—C3—H3	119.7	C20—C18—C19	119.5 (4)
C4—C3—H3	119.7	F7—C19—F9	107.5 (5)
C3—C4—C5	119.4 (4)	F7—C19—F8	106.8 (5)
C3—C4—N1	122.4 (4)	F9—C19—F8	106.1 (5)
C5—C4—N1	118.2 (4)	F7—C19—C18	112.7 (4)
C6—C5—C4	120.5 (4)	F9—C19—C18	113.3 (4)
C6—C5—H5	119.8	F8—C19—C18	110.0 (5)
C4—C5—H5	119.8	C18—C20—C21	122.6 (4)
C1—C6—C5	119.0 (4)	C18—C20—H20	118.7
C1—C6—H6	120.5	C21—C20—H20	118.7
C5—C6—H6	120.5	O4—C21—C20	128.4 (4)
N1—C7—C8	119.5 (4)	O4—C21—C22	112.9 (4)
N1—C7—H7	120.3	C20—C21—C22	118.7 (4)
C8—C7—H7	120.3	F10—C22—F12	107.4 (4)
N2—C8—C9	122.1 (4)	F10—C22—F11	107.0 (4)
N2—C8—C7	114.9 (4)	F12—C22—F11	106.3 (4)
C9—C8—C7	123.0 (4)	F10—C22—C21	111.5 (4)
C8—C9—C10	119.0 (4)	F12—C22—C21	110.5 (4)
C8—C9—H9	120.5	F11—C22—C21	113.9 (4)
C10—C9—H9	120.5

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Br1i	0.95	3.02	3.870 (3)	151
C2—H2···Br1ii	0.95	3.02	3.833 (3)	145
C12—H12···O1iii	0.95	2.53	3.320 (4)	140
C11—H11···O4iii	0.95	2.61	3.470 (3)	151

Table 1

Selected bond lengths (Å)

Ni1—O3	2.020 (3)
Ni1—O4	2.044 (3)
Ni1—O2	2.045 (3)
Ni1—N2	2.063 (3)
Ni1—O1	2.066 (3)
Ni1—N1	2.113 (4)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯Br1i	0.95	3.02	3.870 (3)	151
C2—H2⋯Br1ii	0.95	3.02	3.833 (3)	145
C12—H12⋯O1iii	0.95	2.53	3.320 (4)	140
C11—H11⋯O4iii	0.95	2.61	3.470 (3)	151

Symmetry codes: (i) ; (ii) ; (iii) .