fac-[N,N'-Bis(3-chloro-2-fluoro-benzyl-idene)ethyl-enediamine]bromido-tri-carbonyl-rhenium(I).

In the title compound, [ReBr(C(16)H(12)Cl(2)F(2)N(2))(CO)(3)], the Re atom is in a slightly distorted octa-hedral coordination environment with the three carbonyl ligands having a fac configuration. The diimine ligand is equatorial and is bonded to the Re centre in an N,N'-bidentate chelating fashion, with a bite angle of 77.7 (2)°. The dihedral angle between the two benzene rings is 88.7 (6)°. In the crystal structure, there are F⋯O [2.856 (9) Å], Cl⋯C [3.150 (8) Å] and O⋯C [2.984 (10) Å] contacts which are shorter than the sum of the van der Waals radii for these atoms. In addition, symmetry-related mol-ecules are linked via inter-molecular C-H⋯O, C-H⋯Br and the F⋯O inter-actions into one-dimensional chains extending along the a axis. The crystal structure is further stabilized by inter-molecular π-π inter-actions [centroid-centroid distance = 3.571 (5) Å].

Related literature

For values of standard bond lengths, see Allen et al. (1987 ▶). For related structures, see, for example: Kia et al. (2007 ▶). For backgroud to the applications of rhenium tricarbonyl diimine complexes, see, for example: Lee (1987 ▶); Farrell & Vlcek (2000 ▶); Collin & Sauvage (1989 ▶); Balzani et al. (1996 ▶).

Experimental

Crystal data

[ReBr(C16H12Cl2F2N2)(CO)3]

M = 691.32

Triclinic,

a = 7.3238 (3) Å

b = 12.3077 (4) Å

c = 13.1984 (5) Å

α = 116.504 (2)°

β = 99.707 (2)°

γ = 90.404 (2)°

V = 1044.84 (7) Å3

Z = 2

Mo Kα radiation

μ = 8.03 mm−1

T = 100.0 (1) K

0.32 × 0.12 × 0.07 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.170, T max = 0.569

33300 measured reflections

9014 independent reflections

7668 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.154

S = 1.08

9014 reflections

265 parameters

H-atom parameters constrained

Δρmax = 4.36 e Å−3

Δρmin = −2.86 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809001044/lh2753sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809001044/lh2753Isup2.hkl

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

[ReBr(C16H12Cl2F2N2)(CO)3]	Z = 2
Mr = 691.32	F(000) = 652
Triclinic, P1	Dx = 2.197 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3238 (3) Å	Cell parameters from 9990 reflections
b = 12.3077 (4) Å	θ = 3.1–36.5°
c = 13.1984 (5) Å	µ = 8.03 mm−1
α = 116.504 (2)°	T = 100 K
β = 99.707 (2)°	Block, yellow
γ = 90.404 (2)°	0.32 × 0.12 × 0.07 mm
V = 1044.84 (7) Å3

Bruker SMART APEXII CCD area-detector diffractometer	9014 independent reflections
Radiation source: fine-focus sealed tube	7668 reflections with I > 2σ(I)
graphite	Rint = 0.030
φ and ω scans	θmax = 35.0°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→10
Tmin = 0.170, Tmax = 0.569	k = −19→19
33300 measured reflections	l = −21→21

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.043P)2 + 25.3509P] where P = (Fo2 + 2Fc2)/3
9014 reflections	(Δ/σ)max = 0.001
265 parameters	Δρmax = 4.36 e Å−3
0 restraints	Δρmin = −2.86 e Å−3

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Re1	0.41651 (4)	0.44687 (2)	0.17913 (2)	0.01814 (7)
Br1	0.59914 (10)	0.30823 (6)	0.26094 (6)	0.02132 (13)
Cl1	−0.2702 (4)	−0.0324 (3)	−0.2767 (2)	0.0453 (6)
Cl2	1.1905 (3)	0.8265 (2)	0.5091 (2)	0.0379 (5)
F1	−0.2477 (7)	0.1706 (5)	−0.0492 (5)	0.0332 (10)
F2	0.8904 (7)	0.6865 (5)	0.5305 (5)	0.0304 (10)
O1	0.1897 (9)	0.6185 (6)	0.1033 (7)	0.0365 (14)
O2	0.4182 (9)	0.2812 (6)	−0.0766 (5)	0.0291 (11)
O3	0.7869 (8)	0.5564 (6)	0.1675 (5)	0.0293 (11)
N1	0.1581 (9)	0.3695 (6)	0.1978 (5)	0.0216 (10)
N2	0.4113 (9)	0.5578 (6)	0.3623 (5)	0.0215 (10)
C1	0.2797 (10)	0.5521 (7)	0.1317 (6)	0.0236 (12)
C2	0.4139 (10)	0.3398 (7)	0.0196 (6)	0.0240 (12)
C3	0.6462 (10)	0.5171 (7)	0.1739 (6)	0.0231 (12)
C4	−0.0837 (11)	0.1231 (7)	−0.0633 (7)	0.0260 (13)
C5	−0.0743 (12)	0.0240 (7)	−0.1673 (7)	0.0275 (14)
C6	0.0927 (13)	−0.0300 (7)	−0.1816 (7)	0.0293 (15)
H6A	0.1011	−0.0974	−0.2506	0.035*
C7	0.2454 (12)	0.0175 (8)	−0.0925 (7)	0.0304 (15)
H7A	0.3565	−0.0185	−0.1019	0.036*
C8	0.2359 (10)	0.1165 (6)	0.0091 (6)	0.0209 (11)
H8A	0.3399	0.1465	0.0683	0.025*
C9	0.0687 (10)	0.1738 (7)	0.0249 (6)	0.0230 (12)
C10	0.0427 (10)	0.2764 (7)	0.1340 (6)	0.0237 (12)
H10A	−0.0681	0.2728	0.1584	0.028*
C11	0.1005 (10)	0.4586 (6)	0.3060 (6)	0.0219 (12)
H11A	0.0068	0.4196	0.3259	0.026*
H11B	0.0491	0.5263	0.2959	0.026*
C12	0.2731 (10)	0.5034 (7)	0.4001 (6)	0.0222 (12)
H12A	0.2437	0.5638	0.4720	0.027*
H12B	0.3218	0.4361	0.4121	0.027*
C13	0.5117 (10)	0.6545 (7)	0.4396 (6)	0.0231 (12)
H13A	0.5006	0.6803	0.5159	0.028*
C14	0.6436 (10)	0.7276 (6)	0.4158 (6)	0.0215 (11)
C15	0.8330 (10)	0.7421 (7)	0.4645 (6)	0.0237 (12)
C16	0.9615 (11)	0.8108 (7)	0.4457 (7)	0.0270 (14)
C17	0.8965 (15)	0.8671 (9)	0.3764 (7)	0.0369 (13)
H17A	0.9809	0.9116	0.3607	0.044*
C18	0.7106 (15)	0.8577 (8)	0.3315 (7)	0.0354 (19)
H18A	0.6697	0.9000	0.2898	0.042*
C19	0.5845 (16)	0.7865 (9)	0.3474 (7)	0.0369 (13)
H19A	0.4598	0.7770	0.3130	0.044*

	U11	U22	U33	U12	U13	U23
Re1	0.01889 (11)	0.01916 (11)	0.01800 (11)	0.00236 (8)	0.00407 (8)	0.00967 (8)
Br1	0.0215 (3)	0.0235 (3)	0.0214 (3)	0.0055 (2)	0.0059 (2)	0.0116 (2)
Cl1	0.0397 (12)	0.0435 (12)	0.0334 (10)	−0.0032 (9)	−0.0028 (9)	0.0041 (9)
Cl2	0.0277 (9)	0.0276 (9)	0.0590 (14)	0.0045 (7)	0.0142 (9)	0.0180 (9)
F1	0.025 (2)	0.032 (2)	0.039 (3)	0.0052 (19)	0.0086 (19)	0.012 (2)
F2	0.029 (2)	0.029 (2)	0.040 (3)	0.0031 (18)	0.0048 (19)	0.022 (2)
O1	0.033 (3)	0.040 (3)	0.053 (4)	0.015 (3)	0.012 (3)	0.035 (3)
O2	0.035 (3)	0.028 (3)	0.023 (2)	0.002 (2)	0.008 (2)	0.010 (2)
O3	0.027 (3)	0.035 (3)	0.031 (3)	0.001 (2)	0.006 (2)	0.019 (2)
N1	0.024 (3)	0.021 (2)	0.023 (3)	0.006 (2)	0.008 (2)	0.010 (2)
N2	0.022 (3)	0.022 (3)	0.023 (2)	0.005 (2)	0.007 (2)	0.011 (2)
C1	0.023 (3)	0.025 (3)	0.027 (3)	0.006 (2)	0.004 (2)	0.016 (3)
C2	0.023 (3)	0.026 (3)	0.024 (3)	0.002 (2)	0.006 (2)	0.012 (3)
C3	0.023 (3)	0.026 (3)	0.020 (3)	0.002 (2)	0.003 (2)	0.011 (2)
C4	0.027 (3)	0.025 (3)	0.028 (3)	0.000 (3)	0.009 (3)	0.013 (3)
C5	0.031 (4)	0.024 (3)	0.026 (3)	0.000 (3)	0.006 (3)	0.011 (3)
C6	0.040 (4)	0.021 (3)	0.028 (3)	0.002 (3)	0.011 (3)	0.010 (3)
C7	0.031 (4)	0.034 (4)	0.032 (4)	0.012 (3)	0.012 (3)	0.019 (3)
C8	0.020 (3)	0.017 (3)	0.026 (3)	0.001 (2)	0.003 (2)	0.011 (2)
C9	0.024 (3)	0.021 (3)	0.024 (3)	0.000 (2)	0.008 (2)	0.009 (2)
C10	0.021 (3)	0.024 (3)	0.027 (3)	0.004 (2)	0.008 (2)	0.011 (3)
C11	0.022 (3)	0.021 (3)	0.023 (3)	0.005 (2)	0.007 (2)	0.009 (2)
C12	0.023 (3)	0.024 (3)	0.024 (3)	0.004 (2)	0.009 (2)	0.013 (2)
C13	0.024 (3)	0.024 (3)	0.022 (3)	0.004 (2)	0.006 (2)	0.010 (2)
C14	0.026 (3)	0.018 (3)	0.020 (3)	0.000 (2)	0.005 (2)	0.008 (2)
C15	0.023 (3)	0.022 (3)	0.025 (3)	0.002 (2)	0.006 (2)	0.010 (2)
C16	0.027 (3)	0.019 (3)	0.030 (3)	0.000 (2)	0.009 (3)	0.005 (3)
C17	0.052 (4)	0.032 (3)	0.023 (2)	−0.001 (3)	0.010 (2)	0.009 (2)
C18	0.060 (6)	0.023 (3)	0.024 (3)	−0.003 (3)	0.004 (3)	0.012 (3)
C19	0.052 (4)	0.032 (3)	0.023 (2)	−0.001 (3)	0.010 (2)	0.009 (2)

Re1—C1	1.898 (7)	C7—C8	1.364 (11)
Re1—C3	1.911 (8)	C7—H7A	0.9300
Re1—C2	1.918 (7)	C8—C9	1.417 (10)
Re1—N2	2.190 (6)	C8—H8A	0.9300
Re1—N1	2.211 (6)	C9—C10	1.476 (10)
Re1—Br1	2.6564 (7)	C10—H10A	0.9300
Cl1—C5	1.737 (9)	C11—C12	1.514 (10)
Cl2—C16	1.711 (9)	C11—H11A	0.9700
F1—C4	1.344 (9)	C11—H11B	0.9700
F2—C15	1.347 (9)	C12—H12A	0.9700
O1—C1	1.201 (9)	C12—H12B	0.9700
O2—C2	1.153 (9)	C13—C14	1.478 (10)
O3—C3	1.167 (9)	C13—H13A	0.9300
N1—C10	1.273 (10)	C14—C15	1.401 (10)
N1—C11	1.494 (9)	C14—C19	1.408 (12)
N2—C13	1.284 (10)	C15—C16	1.385 (11)
N2—C12	1.476 (9)	C16—C17	1.402 (13)
C4—C9	1.376 (11)	C17—C18	1.372 (15)
C4—C5	1.384 (11)	C17—H17A	0.9300
C5—C6	1.397 (12)	C18—C19	1.373 (13)
C6—C7	1.382 (13)	C18—H18A	0.9300
C6—H6A	0.9300	C19—H19A	0.9300
C1—Re1—C3	91.3 (3)	C4—C9—C8	117.8 (7)
C1—Re1—C2	88.3 (3)	C4—C9—C10	117.9 (7)
C3—Re1—C2	84.4 (3)	C8—C9—C10	124.0 (7)
C1—Re1—N2	94.3 (3)	N1—C10—C9	126.0 (7)
C3—Re1—N2	98.8 (3)	N1—C10—H10A	117.0
C2—Re1—N2	175.8 (3)	C9—C10—H10A	117.0
C1—Re1—N1	90.7 (3)	N1—C11—C12	107.0 (6)
C3—Re1—N1	176.1 (3)	N1—C11—H11A	110.3
C2—Re1—N1	99.0 (3)	C12—C11—H11A	110.3
N2—Re1—N1	77.7 (2)	N1—C11—H11B	110.3
C1—Re1—Br1	175.6 (2)	C12—C11—H11B	110.3
C3—Re1—Br1	90.5 (2)	H11A—C11—H11B	108.6
C2—Re1—Br1	95.9 (2)	N2—C12—C11	107.3 (6)
N2—Re1—Br1	81.48 (16)	N2—C12—H12A	110.3
N1—Re1—Br1	87.24 (16)	C11—C12—H12A	110.3
C10—N1—C11	115.3 (6)	N2—C12—H12B	110.3
C10—N1—Re1	135.2 (5)	C11—C12—H12B	110.3
C11—N1—Re1	109.0 (4)	H12A—C12—H12B	108.5
C13—N2—C12	117.3 (6)	N2—C13—C14	124.7 (7)
C13—N2—Re1	131.3 (5)	N2—C13—H13A	117.7
C12—N2—Re1	111.3 (4)	C14—C13—H13A	117.7
O1—C1—Re1	178.3 (7)	C15—C14—C19	118.4 (7)
O2—C2—Re1	175.8 (7)	C15—C14—C13	119.6 (6)
O3—C3—Re1	177.7 (7)	C19—C14—C13	122.0 (7)
F1—C4—C9	119.6 (7)	F2—C15—C16	119.6 (7)
F1—C4—C5	118.3 (7)	F2—C15—C14	118.7 (6)
C9—C4—C5	122.1 (8)	C16—C15—C14	121.7 (7)
C4—C5—C6	119.1 (8)	C15—C16—C17	118.0 (8)
C4—C5—Cl1	119.7 (7)	C15—C16—Cl2	119.4 (7)
C6—C5—Cl1	121.2 (6)	C17—C16—Cl2	122.6 (7)
C7—C6—C5	119.4 (7)	C18—C17—C16	121.2 (9)
C7—C6—H6A	120.3	C18—C17—H17A	119.4
C5—C6—H6A	120.3	C16—C17—H17A	119.4
C8—C7—C6	121.2 (8)	C17—C18—C19	120.6 (9)
C8—C7—H7A	119.4	C17—C18—H18A	119.7
C6—C7—H7A	119.4	C19—C18—H18A	119.7
C7—C8—C9	120.4 (7)	C18—C19—C14	120.1 (10)
C7—C8—H8A	119.8	C18—C19—H19A	120.0
C9—C8—H8A	119.8	C14—C19—H19A	120.0
C1—Re1—N1—C10	95.2 (8)	C7—C8—C9—C10	176.2 (7)
C2—Re1—N1—C10	6.9 (8)	C11—N1—C10—C9	−178.1 (7)
N2—Re1—N1—C10	−170.6 (8)	Re1—N1—C10—C9	11.1 (12)
Br1—Re1—N1—C10	−88.7 (7)	C4—C9—C10—N1	−142.2 (8)
C1—Re1—N1—C11	−76.0 (5)	C8—C9—C10—N1	44.3 (12)
C2—Re1—N1—C11	−164.3 (5)	C10—N1—C11—C12	140.9 (7)
N2—Re1—N1—C11	18.2 (4)	Re1—N1—C11—C12	−46.0 (6)
Br1—Re1—N1—C11	100.1 (4)	C13—N2—C12—C11	141.5 (7)
C1—Re1—N2—C13	−81.1 (7)	Re1—N2—C12—C11	−41.9 (6)
C3—Re1—N2—C13	10.9 (7)	N1—C11—C12—N2	58.1 (7)
N1—Re1—N2—C13	−170.9 (7)	C12—N2—C13—C14	−173.8 (6)
Br1—Re1—N2—C13	100.1 (7)	Re1—N2—C13—C14	10.4 (11)
C1—Re1—N2—C12	102.9 (5)	N2—C13—C14—C15	−119.2 (8)
C3—Re1—N2—C12	−165.1 (5)	N2—C13—C14—C19	62.3 (11)
N1—Re1—N2—C12	13.2 (4)	C19—C14—C15—F2	179.7 (7)
Br1—Re1—N2—C12	−75.9 (4)	C13—C14—C15—F2	1.2 (10)
F1—C4—C5—C6	−177.1 (7)	C19—C14—C15—C16	−0.9 (11)
C9—C4—C5—C6	3.0 (12)	C13—C14—C15—C16	−179.4 (7)
F1—C4—C5—Cl1	2.0 (10)	F2—C15—C16—C17	179.9 (7)
C9—C4—C5—Cl1	−177.9 (6)	C14—C15—C16—C17	0.5 (11)
C4—C5—C6—C7	−0.9 (12)	F2—C15—C16—Cl2	−1.4 (10)
Cl1—C5—C6—C7	−180.0 (7)	C14—C15—C16—Cl2	179.2 (6)
C5—C6—C7—C8	−0.2 (13)	C15—C16—C17—C18	2.0 (12)
C6—C7—C8—C9	−0.8 (12)	Cl2—C16—C17—C18	−176.7 (7)
F1—C4—C9—C8	176.3 (7)	C16—C17—C18—C19	−4.0 (14)
C5—C4—C9—C8	−3.9 (11)	C17—C18—C19—C14	3.6 (13)
F1—C4—C9—C10	2.4 (11)	C15—C14—C19—C18	−1.2 (12)
C5—C4—C9—C10	−177.8 (7)	C13—C14—C19—C18	177.3 (8)
C7—C8—C9—C4	2.7 (11)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···Br1	0.93	2.80	3.691 (7)	161
C10—H10A···Br1i	0.93	2.93	3.845 (7)	170
C11—H11B···O3i	0.97	2.48	3.264 (10)	137

Re1—C1	1.898 (7)
Re1—C3	1.911 (8)
Re1—C2	1.918 (7)
Re1—N2	2.190 (6)
Re1—N1	2.211 (6)
Re1—Br1	2.6564 (7)

N2—Re1—N1

77.7 (2)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯Br1	0.93	2.80	3.691 (7)	161
C10—H10A⋯Br1i	0.93	2.93	3.845 (7)	170
C11—H11B⋯O3i	0.97	2.48	3.264 (10)	137

Symmetry code: (i) .