Bromidotricarbon­yl[4-iodo-N-(pyridin-2-yl­methyl­idene)aniline-κ2N,N′]rhenium(I)

Dehghanpour, S.; Mahmoudi, A.

doi:10.1107/S1600536810037104

metal-organic compounds

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Volume 66| Part 10| October 2010| Page m1335

doi:10.1107/S1600536810037104

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Bromidotricarbonyl[4-iodo-N-(pyridin-2-ylmethylidene)aniline-κ²N,N′]rhenium(I)

Saeed Dehghanpour ^a ^* and Ali Mahmoudi ^a

^aDepartment of Chemistry, Islamic Azad University, Karaj Branch, Karaj, Iran
^*Correspondence e-mail: dehganpour_farasha@yahoo.com

(Received 24 August 2010; accepted 16 September 2010; online 30 September 2010)

In the title compound, [ReBr(C₁₂H₉IN₂)(CO)₃], the coordination geometry of the Re^I ion is a distorted fac-ReC₃BrN₂ octahedron, arising from the N,N′-bidentate ligand, a bromide ion and a facial arrangement of three carbonyl ligands. The dihedral angle between the aromatic rings in the 4-iodo-N-(pyridin-2-ylmethylidene)aniline ligand is 46.2 (3)°. The bromide ion and its corresponding trans CO molecule are disordered over two sets of sites in a 0.966 (3):0.034 (3) ratio.

Related literature

For the synthesis of the ligand, see: Dehghanpour et al. (2009a ). For background to diimine complexes and related structures see: Dehghanpour et al. (2009b , 2010 ).

Experimental

Crystal data

[ReBr(C₁₂H₉IN₂)(CO)₃]
M_r = 658.25
Triclinic, $[P \overline 1]$
a = 8.8850 (4) Å
b = 9.0239 (4) Å
c = 10.9736 (4) Å
α = 75.202 (2)°
β = 80.885 (3)°
γ = 84.668 (3)°
V = 838.64 (6) Å³
Z = 2
Mo Kα radiation
μ = 11.48 mm⁻¹
T = 150 K
0.08 × 0.07 × 0.03 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.463, T_max = 0.707
9719 measured reflections
3796 independent reflections
3256 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.108
S = 1.04
3796 reflections
212 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 2.74 e Å⁻³
Δρ_min = −2.80 e Å⁻³

Table 1
Selected bond lengths (Å)

Re1—C2	1.919 (7)
Re1—C3	1.924 (8)
Re1—C1	1.928 (11)
Re1—N1	2.179 (6)
Re1—N2	2.188 (5)
Re1—Br1	2.6139 (8)

Data collection: COLLECT (Nonius, 2002 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037104/hb5621sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810037104/hb5621Isup2.hkl

checkCIF report

Comment top

In our ongoing studies on the synthesis, structural and spectroscopic characterization of transition metal complexes with diimine ligands (Dehghanpour et al., 2009a; Dehghanpour et al., 2010), here we report crystal structure of the title complex. The title complex, (I), Fig. 1, was prepared by the reaction of Re(CO)₅Br with the bidentate ligand (4-iodophenyl)pyridin-2-ylmethyleneamine (Dehghanpour et al., 2009b);(Scheme I).

The rhenium atom is coordinated by the N1 pyridine and N2 imine atoms, affording a five-membered chelate ring, as well as three carbonyl carbon atoms and a bromide atom. The resulting coordination geometry can be described as distorted octahedral [the main distortion being the N1–Re1–N2 and C3–Re1–N2 angles]. The rhenium–carbonyl bond lengths do not show any significant differences and The Re–N bond lengths are similar and within the range expected for such complexes.

Related literature top

For the synthesis of the ligand, see: Dehghanpour et al. (2009a). For background to diimine complexes and related structures see: Dehghanpour et al. (2009b, 2010).

Experimental top

A mixture of [Re(CO)₅Br] (406 mg, 1 mmol) and ligand (308 mg, 1 mmol) in dry, degassed toluene (30 cm3) was heated to reflux for 4 h under N₂ to give a bright red solution. The solvent was removed under vacuum and the crude material recrystallized from CH₂Cl₂/hexane to give red blocks of (I). Yield: 89%. Calc. for C₁₅H₉BrIN₂O₃Re: C 27.37, H 1.37, N 4.26%; found: C 27.30, H 1.42, N 4.20%.

Computing details top

Data collection: COLLECT (Nonius, 2002); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the structure of the title complex, with displacement ellipsoids drawn at the 50% probability level [H atoms are represented as spheres of arbitrary radius].

Bromidotricarbonyl[4-iodo-N-(pyridin-2-ylmethylidene)aniline- κ²N,N']rhenium(I) top

Crystal data top

[ReBr(C₁₂H₉IN₂)(CO)₃]	Z = 2
M_r = 658.25	F(000) = 600
Triclinic, P1	D_x = 2.607 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8850 (4) Å	Cell parameters from 9719 reflections
b = 9.0239 (4) Å	θ = 2.7–27.5°
c = 10.9736 (4) Å	µ = 11.48 mm⁻¹
α = 75.202 (2)°	T = 150 K
β = 80.885 (3)°	Block, red
γ = 84.668 (3)°	0.08 × 0.07 × 0.03 mm
V = 838.64 (6) Å³

Data collection top

Nonius KappaCCD diffractometer	3796 independent reflections
Radiation source: fine-focus sealed tube	3256 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 2.7°
ϕ scans and ω scans with κ offsets	h = −10→11
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −11→11
T_min = 0.463, T_max = 0.707	l = −12→14
9719 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0591P)² + 1.7708P] where P = (F_o² + 2F_c²)/3
3796 reflections	(Δ/σ)_max = 0.001
212 parameters	Δρ_max = 2.74 e Å⁻³
1 restraint	Δρ_min = −2.80 e Å⁻³

Crystal data top

[ReBr(C₁₂H₉IN₂)(CO)₃]	γ = 84.668 (3)°
M_r = 658.25	V = 838.64 (6) Å³
Triclinic, P1	Z = 2
a = 8.8850 (4) Å	Mo Kα radiation
b = 9.0239 (4) Å	µ = 11.48 mm⁻¹
c = 10.9736 (4) Å	T = 150 K
α = 75.202 (2)°	0.08 × 0.07 × 0.03 mm
β = 80.885 (3)°

Data collection top

Nonius KappaCCD diffractometer	3796 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	3256 reflections with I > 2σ(I)
T_min = 0.463, T_max = 0.707	R_int = 0.059
9719 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	1 restraint
wR(F²) = 0.108	H-atom parameters constrained
S = 1.04	Δρ_max = 2.74 e Å⁻³
3796 reflections	Δρ_min = −2.80 e Å⁻³
212 parameters

Special details top

Experimental. multi-scan from symmetry-related measurements SORTAV (Blessing 1995)

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	Occ. (<1)
Re1	0.71427 (3)	0.42431 (3)	0.25069 (2)	0.02270 (11)
I1	1.35429 (6)	−0.18136 (6)	0.09158 (5)	0.03272 (15)
Br1	0.77459 (9)	0.28546 (8)	0.47903 (6)	0.0279 (2)	0.966 (3)
O1	0.6470 (7)	0.5896 (8)	−0.0170 (7)	0.0374 (14)
O2	0.6352 (7)	0.7283 (6)	0.3297 (6)	0.0395 (13)
O3	1.0434 (6)	0.5242 (6)	0.1639 (5)	0.0387 (13)
N1	0.4879 (7)	0.3344 (6)	0.3111 (5)	0.0222 (12)
N2	0.7420 (7)	0.1892 (6)	0.2274 (5)	0.0224 (12)
C1	0.6686 (12)	0.5243 (11)	0.0821 (10)	0.028 (2)
C2	0.6644 (8)	0.6156 (8)	0.2979 (7)	0.0293 (16)
C3	0.9211 (9)	0.4851 (8)	0.1974 (7)	0.0270 (15)
C4	0.3602 (9)	0.4075 (8)	0.3539 (7)	0.0293 (16)
H4A	0.3651	0.5104	0.3590	0.035*
C5	0.2205 (7)	0.3394 (7)	0.3913 (6)	0.0191 (13)
H5A	0.1333	0.3936	0.4244	0.023*
C6	0.2107 (9)	0.1929 (9)	0.3795 (7)	0.0318 (17)
H6A	0.1153	0.1463	0.4006	0.038*
C7	0.3416 (9)	0.1134 (9)	0.3365 (7)	0.0323 (17)
H7A	0.3381	0.0109	0.3299	0.039*
C8	0.4770 (9)	0.1874 (8)	0.3036 (6)	0.0279 (15)
C9	0.6197 (8)	0.1133 (8)	0.2602 (6)	0.0258 (15)
H9A	0.6234	0.0092	0.2559	0.031*
C10	0.8834 (8)	0.1079 (7)	0.1978 (6)	0.0217 (14)
C11	0.9899 (8)	0.1744 (8)	0.0970 (6)	0.0257 (15)
H11A	0.9705	0.2764	0.0495	0.031*
C12	1.1240 (9)	0.0943 (9)	0.0646 (7)	0.0310 (16)
H12A	1.1953	0.1396	−0.0062	0.037*
C13	1.1535 (8)	−0.0534 (8)	0.1370 (7)	0.0261 (15)
C14	1.0489 (9)	−0.1201 (8)	0.2407 (6)	0.0274 (15)
H14A	1.0700	−0.2207	0.2901	0.033*
C15	0.9143 (9)	−0.0397 (8)	0.2718 (6)	0.0269 (15)
H15A	0.8431	−0.0844	0.3429	0.032*
Br1A	0.652 (6)	0.551 (5)	0.040 (3)	0.030*	0.034 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Re1	0.02352 (18)	0.01442 (16)	0.02889 (18)	−0.00057 (11)	−0.00101 (12)	−0.00477 (11)
I1	0.0290 (3)	0.0314 (3)	0.0382 (3)	0.0068 (2)	−0.0042 (2)	−0.0126 (2)
Br1	0.0331 (4)	0.0230 (4)	0.0266 (4)	0.0010 (3)	−0.0037 (3)	−0.0056 (3)
O1	0.038 (3)	0.034 (4)	0.038 (4)	−0.002 (3)	−0.002 (3)	−0.007 (3)
O2	0.046 (3)	0.021 (3)	0.055 (3)	0.001 (2)	−0.008 (3)	−0.015 (2)
O3	0.027 (3)	0.035 (3)	0.051 (3)	−0.011 (2)	−0.001 (3)	−0.004 (3)
N1	0.024 (3)	0.019 (3)	0.022 (3)	0.001 (2)	−0.002 (2)	−0.003 (2)
N2	0.031 (3)	0.015 (3)	0.020 (3)	0.004 (2)	−0.003 (2)	−0.006 (2)
C1	0.023 (4)	0.016 (5)	0.047 (6)	−0.002 (3)	0.000 (5)	−0.016 (4)
C2	0.024 (4)	0.026 (4)	0.035 (4)	0.002 (3)	−0.001 (3)	−0.004 (3)
C3	0.028 (4)	0.021 (3)	0.030 (4)	0.002 (3)	−0.009 (3)	−0.002 (3)
C4	0.031 (4)	0.022 (4)	0.034 (4)	0.003 (3)	−0.005 (3)	−0.006 (3)
C5	0.015 (3)	0.022 (3)	0.019 (3)	0.001 (3)	−0.005 (2)	−0.003 (2)
C6	0.031 (4)	0.030 (4)	0.033 (4)	−0.011 (3)	−0.004 (3)	−0.002 (3)
C7	0.040 (4)	0.024 (4)	0.034 (4)	−0.005 (3)	−0.007 (3)	−0.006 (3)
C8	0.031 (4)	0.028 (4)	0.026 (3)	0.001 (3)	−0.004 (3)	−0.009 (3)
C9	0.033 (4)	0.017 (3)	0.027 (3)	−0.006 (3)	−0.002 (3)	−0.004 (3)
C10	0.026 (3)	0.015 (3)	0.024 (3)	0.000 (3)	−0.002 (3)	−0.007 (3)
C11	0.029 (4)	0.018 (3)	0.029 (3)	0.003 (3)	−0.003 (3)	−0.005 (3)
C12	0.032 (4)	0.032 (4)	0.028 (4)	−0.007 (3)	0.007 (3)	−0.008 (3)
C13	0.025 (4)	0.025 (4)	0.031 (4)	0.004 (3)	0.000 (3)	−0.016 (3)
C14	0.035 (4)	0.022 (3)	0.025 (3)	0.003 (3)	−0.008 (3)	−0.006 (3)
C15	0.035 (4)	0.023 (3)	0.022 (3)	−0.005 (3)	−0.004 (3)	−0.003 (3)

Geometric parameters (Å, º) top

Re1—C2	1.919 (7)	C5—C6	1.373 (10)
Re1—C3	1.924 (8)	C5—H5A	0.9500
Re1—C1	1.928 (11)	C6—C7	1.391 (11)
Re1—N1	2.179 (6)	C6—H6A	0.9500
Re1—N2	2.188 (5)	C7—C8	1.383 (11)
Re1—Br1A	2.43 (3)	C7—H7A	0.9500
Re1—Br1	2.6139 (8)	C8—C9	1.447 (10)
I1—C13	2.096 (7)	C9—H9A	0.9500
O1—Br1A	0.64 (3)	C10—C11	1.383 (9)
O1—C1	1.133 (13)	C10—C15	1.400 (9)
O2—C2	1.153 (9)	C11—C12	1.380 (10)
O3—C3	1.148 (9)	C11—H11A	0.9500
N1—C4	1.339 (9)	C12—C13	1.392 (10)
N1—C8	1.364 (9)	C12—H12A	0.9500
N2—C9	1.291 (9)	C13—C14	1.394 (10)
N2—C10	1.430 (9)	C14—C15	1.381 (10)
C1—Br1A	0.50 (3)	C14—H14A	0.9500
C4—C5	1.391 (10)	C15—H15A	0.9500
C4—H4A	0.9500

C2—Re1—C3	88.3 (3)	C6—C5—C4	119.0 (6)
C2—Re1—C1	88.8 (4)	C6—C5—H5A	120.5
C3—Re1—C1	88.9 (4)	C4—C5—H5A	120.5
C2—Re1—N1	96.6 (3)	C5—C6—C7	119.3 (7)
C3—Re1—N1	174.8 (3)	C5—C6—H6A	120.3
C1—Re1—N1	92.7 (3)	C7—C6—H6A	120.3
C2—Re1—N2	169.6 (3)	C8—C7—C6	118.3 (7)
C3—Re1—N2	99.9 (3)	C8—C7—H7A	120.8
C1—Re1—N2	97.5 (3)	C6—C7—H7A	120.8
N1—Re1—N2	75.0 (2)	N1—C8—C7	123.0 (7)
C2—Re1—Br1A	88.4 (12)	N1—C8—C9	114.5 (6)
C3—Re1—Br1A	89.8 (12)	C7—C8—C9	122.4 (7)
C1—Re1—Br1A	1.0 (14)	N2—C9—C8	119.8 (6)
N1—Re1—Br1A	91.9 (12)	N2—C9—H9A	120.1
N2—Re1—Br1A	97.8 (12)	C8—C9—H9A	120.1
C2—Re1—Br1	91.8 (2)	C11—C10—C15	119.9 (6)
C3—Re1—Br1	91.6 (2)	C11—C10—N2	120.4 (6)
C1—Re1—Br1	179.2 (3)	C15—C10—N2	119.7 (6)
N1—Re1—Br1	86.79 (14)	C12—C11—C10	120.8 (6)
N2—Re1—Br1	81.81 (14)	C12—C11—H11A	119.6
Br1A—Re1—Br1	178.6 (12)	C10—C11—H11A	119.6
Br1A—O1—C1	6 (5)	C11—C12—C13	119.2 (6)
C4—N1—C8	117.2 (6)	C11—C12—H12A	120.4
C4—N1—Re1	127.3 (5)	C13—C12—H12A	120.4
C8—N1—Re1	115.5 (5)	C12—C13—C14	120.5 (6)
C9—N2—C10	118.1 (6)	C12—C13—I1	121.0 (5)
C9—N2—Re1	115.1 (5)	C14—C13—I1	118.5 (5)
C10—N2—Re1	126.1 (4)	C15—C14—C13	119.9 (7)
Br1A—C1—O1	7 (7)	C15—C14—H14A	120.0
Br1A—C1—Re1	175 (7)	C13—C14—H14A	120.0
O1—C1—Re1	176.0 (8)	C14—C15—C10	119.6 (6)
O2—C2—Re1	178.0 (7)	C14—C15—H15A	120.2
O3—C3—Re1	178.5 (7)	C10—C15—H15A	120.2
N1—C4—C5	123.0 (7)	C1—Br1A—O1	167 (10)
N1—C4—H4A	118.5	C1—Br1A—Re1	4 (6)
C5—C4—H4A	118.5	O1—Br1A—Re1	170 (6)

Experimental details

Crystal data
Chemical formula	[ReBr(C₁₂H₉IN₂)(CO)₃]
M_r	658.25
Crystal system, space group	Triclinic, P1
Temperature (K)	150
a, b, c (Å)	8.8850 (4), 9.0239 (4), 10.9736 (4)
α, β, γ (°)	75.202 (2), 80.885 (3), 84.668 (3)
V (Å³)	838.64 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	11.48
Crystal size (mm)	0.08 × 0.07 × 0.03

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995)
T_min, T_max	0.463, 0.707
No. of measured, independent and observed [I > 2σ(I)] reflections	9719, 3796, 3256
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.108, 1.04
No. of reflections	3796
No. of parameters	212
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.74, −2.80

Computer programs: COLLECT (Nonius, 2002), DENZO-SMN (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Selected bond lengths (Å) top

Re1—C2	1.919 (7)	Re1—N1	2.179 (6)
Re1—C3	1.924 (8)	Re1—N2	2.188 (5)
Re1—C1	1.928 (11)	Re1—Br1	2.6139 (8)

Acknowledgements

SD would like to acknowledge the Islamic Azad University Research Council for partial support of this work.

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Dehghanpour, S., Khalaj, M. & Mahmoudi, A. (2009a). Polyhedron, 28, 1205–1210. Web of Science CSD CrossRef CAS Google Scholar
Dehghanpour, S., Khalaj, M. & Mahmoudi, A. (2009b). Inorg. Chem. Commun. 12, 231–233. Web of Science CSD CrossRef CAS Google Scholar
Dehghanpour, S., Lipkowski, J., Mahmoudi, A. & Khalaj, M. (2010). J. Coord. Chem. 63, 1473–1479. Web of Science CSD CrossRef CAS Google Scholar
Nonius (2002). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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