trans,trans,trans-Diacetonitriledibromo­bis(4-fluoro­aniline)nickel(II)

Fawcett, J.; Sicilia, F.; Solan, G.A.

doi:10.1107/S1600536805016995

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 61| Part 7| July 2005| Pages m1256-m1257

https://doi.org/10.1107/S1600536805016995

trans,trans,trans-Diacetonitriledibromobis(4-fluoroaniline)nickel(II)

John Fawcett,^a Fabrizio Sicilia ^a and Gregory A Solan ^a ^*

^aDepartment of Chemistry, University of Leicester, Leicester LE1 7RH, England
^*Correspondence e-mail: jxf@leicester.ac.uk

(Received 19 May 2005; accepted 27 May 2005; online 10 June 2005)

The structure of the centrosymmetric title compound, [(4-F-C₆H₄NH₂)₂(MeCN)₂NiBr₂] or [NiBr₂(C₆H₆FN)₂(C₂H₃N)₂], reveals each of the pairs of bromide, acetonitrile and 4-fluoroaniline ligands arranged trans to each other with a near octahedral geometry at the Ni atom.

Comment

While fluorinated anilines, C₆F_xH_yNH₂ (x = 1 and y = 4; x = 2 and y = 3; x = 5 and y = 0), have been extensively used as precursors to Schiff base ligands, crystallographically characterized examples of transition metal complexes containing the bound aniline itself are rare (Padmanabhan et al., 1985 ; Visalakshi & Patel, 1994 ).

We report here the synthesis and crystal structure of trans,trans,trans-[(4-F-C₆H₄NH₂)₂(MeCN)₂NiBr₂], (I). The Ni atom is located on a centre of symmetry. The geometry at the Ni atom is approximately octahedral, the largest deviation from the ideal bond angles being observed for N1—Ni1—N2 [83.79 (8)°]. The bond distances at nickel are: Ni1—Br1 = 2.5634 (3) Å, Ni1—N1 = 2.0915 (18) Å and Ni1—N2 = 2.0629 (19) Å. Each Br atom is surrounded by H atoms with three intra- and four intermolecular H⋯Br distances in the range 2.58–3.25 Å. The structure of (I) resembles the trans disposition of ligand pairs found in trans,trans,trans-[(H₂O)₂(MeCN)₂NiCl₂] (Piggot et al., 2004 ).

Figure 1
The molecular structure of (I)

, showing the atom numbering scheme and 50% displacement ellipsoids. The molecule is located on a centre of symmetry [primed atoms are generated by (−x, 1 − y, 1 − z)].

Experimental

Under a nitrogen atmosphere, 4-fluoroaniline (0.02 g, 0.18 mmol) was added to a solution of (DME)NiBr₂ (DME = 1,2-dimethoxyethane) (0.05 g, 0.16 mmol) in dichloromethane (20 ml) and the reaction mixture stirred for 12 h at room temperature. The volatiles were removed under reduced pressure and the residue dried overnight. Extraction of the residue into hot acetonitrile and prolonged standing of the solution at room temperature gave pale-green crystals of the title compound suitable for single-crystal X-ray diffraction analysis (0.02 g, 23% yield).

Crystal data

[NiBr₂(C₆H₆FN)₂(C₂H₃N)₂]
M_r = 522.87
Monoclinic, P 2₁ /c
a = 11.4533 (14) Å
b = 12.9875 (15) Å
c = 6.2590 (7) Å
β = 99.191 (2)°
V = 919.07 (19) Å³
Z = 2
D_x = 1.889 Mg m⁻³
Mo Kα radiation
Cell parameters from 4651 reflections
θ = 2.4–28.8°
μ = 5.43 mm⁻¹
T = 150 (2) K
Plate, pale green
0.32 × 0.19 × 0.09 mm

Data collection

Bruker APEX CCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 1996 )T_min = 0.315, T_max = 0.613
7593 measured reflections
1995 independent reflections
1823 reflections with I > 2σ(I)
R_int = 0.052
θ_max = 27.0°
h = −14 → 14
k = −16 → 16
l = −7 → 7

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.069
S = 1.02
1995 reflections
116 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0421P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br1ⁱ	0.92	2.71	3.5498 (19)	152
N1—H1B⋯Br1ⁱⁱ	0.92	2.58	3.4789 (19)	167
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z.

All H atoms were included in calculated positions and treated as riding, with C—H = 0.95–0.98 and N—H = 0.92 Å. For methyl H atoms, U_iso(H) values were set at 1.5U_eq of the C atom and at 1.2U_eq for all other H atoms.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805016995/rz6087sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805016995/rz6087Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

trans-trans-trans-Dibromobis(4-fluoroaniline)bis(acetonitrile)nickel(II) top

Crystal data top

[NiBr₂(C₆H₆FN)₂(C₂H₃N)₂]	F(000) = 516
M_r = 522.87	D_x = 1.889 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4651 reflections
a = 11.4533 (14) Å	θ = 2.4–28.8°
b = 12.9875 (15) Å	µ = 5.43 mm⁻¹
c = 6.2590 (7) Å	T = 150 K
β = 99.191 (2)°	Plate, pale green
V = 919.07 (19) Å³	0.32 × 0.19 × 0.09 mm
Z = 2

Data collection top

Bruker APEX CCD area-detector diffractometer	1995 independent reflections
Radiation source: fine-focus sealed tube	1823 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
φ and ω scans	θ_max = 27.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.315, T_max = 0.613	k = −16→16
7593 measured reflections	l = −7→7

Refinement top

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.069	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0421P)²] where P = (F_o² + 2F_c²)/3
1995 reflections	(Δ/σ)_max < 0.001
116 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Special details top

Experimental. absorption correction based on 5283 reflections (SADABS); R_int 0.126 before correction and 0.031 after correction.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.02345 (2)	0.632904 (16)	0.20705 (3)	0.02041 (10)
Ni1	0.0000	0.5000	0.5000	0.01528 (12)
N2	−0.15001 (18)	0.44011 (14)	0.3156 (3)	0.0198 (4)
C1	0.2126 (2)	0.38636 (17)	0.3677 (4)	0.0196 (5)
C7	−0.2080 (2)	0.38921 (18)	0.1966 (4)	0.0207 (5)
F1	0.57305 (15)	0.37955 (12)	0.4412 (3)	0.0459 (5)
N1	0.08695 (17)	0.38864 (14)	0.3421 (3)	0.0184 (4)
H1A	0.0627	0.3253	0.3842	0.022*
H1B	0.0593	0.3947	0.1964	0.022*
C2	0.2695 (2)	0.42016 (18)	0.2041 (4)	0.0246 (5)
H2	0.2246	0.4446	0.0730	0.030*
C6	0.2778 (2)	0.35105 (18)	0.5588 (4)	0.0258 (6)
H6	0.2387	0.3283	0.6732	0.031*
C8	−0.2798 (2)	0.3224 (2)	0.0440 (4)	0.0267 (5)
H8A	−0.2854	0.3512	−0.1020	0.040*
H8B	−0.3592	0.3169	0.0827	0.040*
H8C	−0.2435	0.2540	0.0479	0.040*
C3	0.3910 (2)	0.4190 (2)	0.2280 (4)	0.0309 (6)
H3	0.4307	0.4428	0.1153	0.037*
C4	0.4534 (2)	0.38288 (19)	0.4180 (5)	0.0313 (6)
C5	0.3993 (3)	0.34882 (19)	0.5833 (4)	0.0312 (6)
H5	0.4447	0.3239	0.7134	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02936 (17)	0.01745 (14)	0.01536 (14)	−0.00154 (8)	0.00643 (10)	0.00117 (8)
Ni1	0.0186 (2)	0.0147 (2)	0.0128 (2)	−0.00185 (15)	0.00356 (15)	−0.00117 (14)
N2	0.0219 (10)	0.0195 (10)	0.0184 (9)	−0.0021 (8)	0.0045 (8)	−0.0004 (8)
C1	0.0247 (13)	0.0146 (10)	0.0204 (11)	0.0007 (9)	0.0061 (9)	−0.0030 (9)
C7	0.0218 (12)	0.0229 (11)	0.0183 (11)	0.0014 (10)	0.0061 (10)	0.0039 (10)
F1	0.0261 (9)	0.0440 (10)	0.0688 (13)	0.0103 (7)	0.0109 (9)	−0.0030 (8)
N1	0.0226 (10)	0.0172 (9)	0.0160 (9)	−0.0012 (8)	0.0051 (8)	−0.0006 (7)
C2	0.0313 (14)	0.0200 (12)	0.0239 (12)	0.0035 (10)	0.0088 (10)	0.0028 (10)
C6	0.0340 (15)	0.0209 (12)	0.0230 (12)	0.0019 (10)	0.0057 (11)	0.0018 (10)
C8	0.0269 (14)	0.0285 (13)	0.0241 (12)	−0.0079 (11)	0.0022 (10)	−0.0053 (11)
C3	0.0332 (15)	0.0264 (13)	0.0374 (15)	0.0024 (11)	0.0184 (12)	0.0011 (11)
C4	0.0239 (14)	0.0234 (13)	0.0474 (17)	0.0040 (10)	0.0086 (12)	−0.0043 (11)
C5	0.0372 (16)	0.0240 (13)	0.0305 (14)	0.0102 (11)	−0.0005 (12)	0.0025 (10)

Geometric parameters (Å, º) top

Br1—Ni1	2.5634 (3)	N1—H1B	0.9200
Ni1—N2	2.0629 (19)	C2—C3	1.376 (4)
Ni1—N2ⁱ	2.063 (2)	C2—H2	0.9500
Ni1—N1ⁱ	2.0915 (18)	C6—C5	1.376 (4)
Ni1—N1	2.0915 (18)	C6—H6	0.9500
Ni1—Br1ⁱ	2.5634 (3)	C8—H8A	0.9800
N2—C7	1.129 (3)	C8—H8B	0.9800
C1—C2	1.371 (3)	C8—H8C	0.9800
C1—C6	1.383 (3)	C3—C4	1.369 (4)
C1—N1	1.422 (3)	C3—H3	0.9500
C7—C8	1.445 (3)	C4—C5	1.362 (4)
F1—C4	1.356 (3)	C5—H5	0.9500
N1—H1A	0.9200

N2—Ni1—N2ⁱ	180.00 (10)	Ni1—N1—H1B	107.1
N2—Ni1—N1ⁱ	96.21 (8)	H1A—N1—H1B	106.8
N2ⁱ—Ni1—N1ⁱ	83.79 (8)	C1—C2—C3	120.6 (2)
N2—Ni1—N1	83.79 (8)	C1—C2—H2	119.7
N2ⁱ—Ni1—N1	96.21 (8)	C3—C2—H2	119.7
N1ⁱ—Ni1—N1	180.00 (9)	C5—C6—C1	120.0 (3)
N2—Ni1—Br1ⁱ	88.46 (5)	C5—C6—H6	120.0
N2ⁱ—Ni1—Br1ⁱ	91.54 (5)	C1—C6—H6	120.0
N1ⁱ—Ni1—Br1ⁱ	90.88 (5)	C7—C8—H8A	109.5
N1—Ni1—Br1ⁱ	89.12 (5)	C7—C8—H8B	109.5
N2—Ni1—Br1	91.54 (5)	H8A—C8—H8B	109.5
N2ⁱ—Ni1—Br1	88.46 (5)	C7—C8—H8C	109.5
N1ⁱ—Ni1—Br1	89.12 (5)	H8A—C8—H8C	109.5
N1—Ni1—Br1	90.88 (5)	H8B—C8—H8C	109.5
Br1ⁱ—Ni1—Br1	180.0	C4—C3—C2	118.5 (2)
C7—N2—Ni1	160.0 (2)	C4—C3—H3	120.8
C2—C1—C6	119.8 (2)	C2—C3—H3	120.8
C2—C1—N1	120.1 (2)	F1—C4—C5	118.9 (3)
C6—C1—N1	120.1 (2)	F1—C4—C3	118.8 (3)
N2—C7—C8	178.6 (3)	C5—C4—C3	122.2 (3)
C1—N1—Ni1	120.71 (14)	C4—C5—C6	118.9 (2)
C1—N1—H1A	107.1	C4—C5—H5	120.6
Ni1—N1—H1A	107.1	C6—C5—H5	120.6
C1—N1—H1B	107.1

N1—Ni1—N2—C7	1.8 (5)	N1—C1—C2—C3	179.5 (2)
Br1ⁱ—Ni1—N2—C7	−87.5 (5)	C2—C1—C6—C5	−0.7 (4)
Br1—Ni1—N2—C7	92.5 (5)	N1—C1—C6—C5	180.0 (2)
C2—C1—N1—Ni1	−105.1 (2)	C1—C2—C3—C4	0.4 (4)
C6—C1—N1—Ni1	74.2 (2)	C2—C3—C4—F1	178.7 (2)
N2—Ni1—N1—C1	172.55 (17)	C2—C3—C4—C5	−0.4 (4)
N2ⁱ—Ni1—N1—C1	−7.45 (17)	F1—C4—C5—C6	−179.2 (2)
Br1ⁱ—Ni1—N1—C1	−98.90 (16)	C3—C4—C5—C6	−0.2 (4)
Br1—Ni1—N1—C1	81.10 (16)	C1—C6—C5—C4	0.7 (4)
C6—C1—C2—C3	0.2 (4)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1ⁱⁱ	0.92	2.71	3.5498 (19)	152
N1—H1B···Br1ⁱⁱⁱ	0.92	2.58	3.4789 (19)	167

Symmetry codes: (ii) −x, y−1/2, −z+1/2; (iii) −x, −y+1, −z.

Acknowledgements

The authors thank the University of Leicester for financial assistance.

References

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