Ethyl 2-(5-bromo-2-iodo­anilino)cyclo­pent-1-ene-1-carboxyl­ate

Barnes, P.; Storey, J.M.D.; Harrison, W.T.A.

doi:10.1107/S2414314615021781

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 1| January 2016| x152178

https://doi.org/10.1107/S2414314615021781

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Ethyl 2-(5-bromo-2-iodoanilino)cyclopent-1-ene-1-carboxylate

Paul Barnes,^a John M. D. Storey ^a and William T. A. Harrison ^a ^*

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, UK
^*Correspondence e-mail: w.harrison@abdn.ac.uk

Edited by M. Weil, Vienna University of Technology, Austria (Received 29 October 2015; accepted 16 November 2015; online 1 January 2016)

In the title compound, C₁₄H₁₅BrINO₂, the conformation of the C—O—CH₂—CH₃ grouping is anti [torsion angle = 173.8 (6)°] and the bond-angle sum at the N atom bridging the two rings is 360°. An unusual intramolecular bifurcated N—H⋯(O,I) hydrogen bond helps to establish the molecular conformation, in which the I atom and the C=O grouping are syn. In the crystal, inversion dimers created by pairs of short intermolecular C—I⋯O interactions [C—I = 2.080 (7) Å; I⋯O = 3.211 (5) Å; C—I⋯O = 152.4 (2)°] occur.

Keywords: Bifurcated hydogen bond; cyclopentene; C—I⋯O interaction; crystal structure.

CCDC reference: 1440896

Structure description

The essentally planar cyclopentene ring (r.m.s. deviation = 0.012 Å) subtends a dihedral angle of 4.9 (4)° with the benzene ring. The conformation of the C—O—CH₂—CH₃ grouping is anti [torsion angle = 173.8 (6)°] and the bond-angle sum at the N atom bridging the two rings is 360°. The N—C_p (p = cyclopentene) bond [1.368 (9) Å] is slightly shorter than the N—C_b (b = benzene) bond [1.381 (8) Å]. An unusual intramolecular bifurcated N—H⋯(O,I) hydrogen bond (Fig. 1, Table 1) helps to establish the molecular conformation, in which the I atom and the C=O grouping are syn. In the crystal, inversion dimers created by pairs of short intermolecular C—I⋯O interactions [C—I = 2.080 (7) Å; I⋯O = 3.211 (5) Å; C—I⋯O = 152.4 (2)°] occur (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.83 (8)	2.03 (8)	2.733 (7)	143 (7)
N1—H1⋯I1	0.83 (8)	2.77 (8)	3.257 (6)	120 (7)

Figure 1
The molecular structure of (I) showing displacement ellipsoids at the 50% probability level. The bifurcated N—H⋯(O,I) hydrogen bond is indicated by double-dashed lines.

Figure 2
The inversion dimer in (I) arising from a pair of C—I⋯O interactions (double-dashed lines). All H atoms except H1 omitted for clarity. Symmetry code: (i) −x, 2 − y, 1 − z.

Background to C—I⋯O interactions is discussed by Glidewell et al. (2005 ). van der Waals radius data (Bondi, 1964 ) indicate an expected O⋯I contact distance of about 3.50 Å. Another compound containing benzene and cyclopentene rings bridged by an NH group and a discussion of resonance contributers to the structure is given by Huang et al. (1997 ).

Synthesis and crystallization

For the synthesis, see Barnes & Storey (2015 ).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₅BrINO₂
M_r	436.08
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	120
a, b, c (Å)	7.3066 (4), 7.9672 (4), 12.8467 (7)
α, β, γ (°)	72.994 (3), 86.500 (3), 87.152 (3)
V (Å³)	713.42 (7)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	5.04
Crystal size (mm)	0.22 × 0.04 × 0.02

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003 )
T_min, T_max	0.403, 0.906
No. of measured, independent and observed [I > 2σ(I)] reflections	14788, 3285, 2527
R_int	0.143
(sin θ/λ)_max (Å⁻¹)	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.133, 1.03
No. of reflections	3285
No. of parameters	177
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.05, −1.71
Computer programs: COLLECT (Nonius, 1998 ), HKL DENZO and SCALEPACK (Otwinowski & Minor 1997 ) and SORTAV (Blessing 1995 ), SHELXS97 (Sheldrick, 2008 ), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012 ).

Structural data

CCDC reference: 1440896

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314615021781/wm4001sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314615021781/wm4001Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314615021781/wm4001Isup3.cml

checkCIF report

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997) and SORTAV (Blessing 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Ethyl 2-(5-bromo-2-iodoanilino)cyclopent-1-ene-1-carboxylate top

Crystal data top

C₁₄H₁₅BrINO₂	Z = 2
M_r = 436.08	F(000) = 420
Triclinic, P1	D_x = 2.030 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3066 (4) Å	Cell parameters from 14824 reflections
b = 7.9672 (4) Å	θ = 2.9–27.5°
c = 12.8467 (7) Å	µ = 5.04 mm⁻¹
α = 72.994 (3)°	T = 120 K
β = 86.500 (3)°	Needle, colourless
γ = 87.152 (3)°	0.22 × 0.04 × 0.02 mm
V = 713.42 (7) Å³

Data collection top

Nonius KappaCCD diffractometer	3285 independent reflections
Radiation source: fine-focus sealed tube	2527 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.143
ω scans	θ_max = 27.6°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −9→9
T_min = 0.403, T_max = 0.906	k = −10→10
14788 measured reflections	l = −16→16

Refinement top

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)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.133	w = 1/[σ²(F_o²) + (0.0553P)² + 2.3708P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3285 reflections	Δρ_max = 1.05 e Å⁻³
177 parameters	Δρ_min = −1.71 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0093 (13)

Special details top

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.

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

	x	y	z	U_iso*/U_eq
C1	0.6550 (9)	0.6004 (9)	0.8087 (5)	0.0201 (14)
C2	0.5142 (10)	0.6597 (10)	0.8689 (6)	0.0253 (15)
H2	0.5224	0.6454	0.9446	0.030*
C3	0.3633 (9)	0.7398 (10)	0.8136 (6)	0.0242 (15)
H3	0.2627	0.7768	0.8529	0.029*
C4	0.3530 (9)	0.7681 (9)	0.7028 (6)	0.0204 (14)
C5	0.4978 (8)	0.7090 (9)	0.6414 (5)	0.0172 (13)
C6	0.6508 (9)	0.6245 (10)	0.6984 (5)	0.0220 (15)
H6	0.7514	0.5840	0.6607	0.026*
C7	0.5955 (9)	0.7049 (9)	0.4509 (5)	0.0182 (13)
C8	0.7856 (8)	0.6187 (9)	0.4674 (5)	0.0190 (14)
H8A	0.7792	0.4971	0.5162	0.023*
H8B	0.8650	0.6861	0.4992	0.023*
C9	0.8591 (9)	0.6199 (9)	0.3527 (5)	0.0203 (14)
H9A	0.8836	0.4982	0.3495	0.024*
H9B	0.9752	0.6835	0.3342	0.024*
C10	0.7123 (9)	0.7127 (10)	0.2713 (5)	0.0212 (14)
H10A	0.7589	0.8219	0.2193	0.025*
H10B	0.6732	0.6345	0.2300	0.025*
C11	0.5574 (8)	0.7521 (9)	0.3443 (5)	0.0180 (14)
C12	0.3846 (8)	0.8408 (9)	0.3055 (5)	0.0181 (14)
C13	0.2133 (9)	0.9780 (10)	0.1495 (6)	0.0248 (16)
H13A	0.1904	1.0835	0.1748	0.030*
H13B	0.1063	0.9018	0.1726	0.030*
C14	0.2436 (10)	1.0299 (11)	0.0271 (6)	0.0275 (17)
H14A	0.1353	1.0960	−0.0068	0.041*
H14B	0.2641	0.9242	0.0032	0.041*
H14C	0.3511	1.1034	0.0055	0.041*
N1	0.4806 (8)	0.7386 (8)	0.5310 (5)	0.0197 (12)
H1	0.385 (11)	0.787 (11)	0.504 (7)	0.024*
O1	0.2578 (6)	0.8759 (7)	0.3612 (4)	0.0260 (11)
O2	0.3804 (6)	0.8831 (6)	0.1946 (4)	0.0205 (10)
Br1	0.86744 (10)	0.49046 (11)	0.88327 (6)	0.0289 (2)
I1	0.11622 (6)	0.89708 (6)	0.63303 (4)	0.02154 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.020 (3)	0.022 (3)	0.018 (3)	−0.001 (3)	−0.003 (3)	−0.004 (3)
C2	0.027 (4)	0.029 (4)	0.020 (3)	0.000 (3)	−0.003 (3)	−0.008 (3)
C3	0.022 (3)	0.037 (4)	0.021 (3)	0.003 (3)	0.003 (3)	−0.020 (3)
C4	0.018 (3)	0.021 (3)	0.025 (3)	0.001 (3)	0.001 (3)	−0.011 (3)
C5	0.012 (3)	0.025 (4)	0.016 (3)	0.001 (3)	−0.002 (2)	−0.009 (3)
C6	0.021 (3)	0.031 (4)	0.014 (3)	−0.001 (3)	0.000 (3)	−0.005 (3)
C7	0.017 (3)	0.022 (3)	0.018 (3)	−0.001 (3)	−0.002 (2)	−0.009 (3)
C8	0.015 (3)	0.027 (4)	0.013 (3)	0.001 (3)	0.001 (2)	−0.003 (3)
C9	0.018 (3)	0.023 (4)	0.022 (3)	0.007 (3)	−0.004 (3)	−0.009 (3)
C10	0.019 (3)	0.028 (4)	0.019 (3)	0.002 (3)	−0.005 (3)	−0.010 (3)
C11	0.013 (3)	0.024 (4)	0.017 (3)	0.004 (3)	0.001 (2)	−0.009 (3)
C12	0.015 (3)	0.025 (4)	0.014 (3)	0.002 (3)	0.001 (2)	−0.005 (3)
C13	0.017 (3)	0.026 (4)	0.028 (4)	0.006 (3)	−0.004 (3)	−0.002 (3)
C14	0.019 (3)	0.040 (5)	0.021 (3)	0.001 (3)	−0.004 (3)	−0.006 (3)
N1	0.015 (3)	0.022 (3)	0.020 (3)	0.004 (2)	−0.001 (2)	−0.004 (3)
O1	0.018 (2)	0.040 (3)	0.018 (2)	0.009 (2)	−0.0009 (19)	−0.007 (2)
O2	0.016 (2)	0.030 (3)	0.015 (2)	0.0049 (19)	−0.0036 (18)	−0.005 (2)
Br1	0.0242 (4)	0.0394 (5)	0.0209 (4)	0.0053 (3)	−0.0086 (3)	−0.0047 (3)
I1	0.0173 (2)	0.0250 (3)	0.0225 (3)	0.00316 (16)	−0.00201 (16)	−0.00777 (19)

Geometric parameters (Å, º) top

C1—C6	1.376 (9)	C9—C10	1.548 (9)
C1—C2	1.395 (10)	C9—H9A	0.9900
C1—Br1	1.910 (7)	C9—H9B	0.9900
C2—C3	1.374 (10)	C10—C11	1.506 (9)
C2—H2	0.9500	C10—H10A	0.9900
C3—C4	1.381 (10)	C10—H10B	0.9900
C3—H3	0.9500	C11—C12	1.458 (9)
C4—C5	1.424 (9)	C12—O1	1.208 (8)
C4—I1	2.080 (7)	C12—O2	1.366 (8)
C5—N1	1.381 (8)	C13—O2	1.462 (8)
C5—C6	1.406 (9)	C13—C14	1.509 (10)
C6—H6	0.9500	C13—H13A	0.9900
C7—C11	1.352 (9)	C13—H13B	0.9900
C7—N1	1.368 (9)	C14—H14A	0.9800
C7—C8	1.517 (9)	C14—H14B	0.9800
C8—C9	1.534 (9)	C14—H14C	0.9800
C8—H8A	0.9900	N1—H1	0.83 (8)
C8—H8B	0.9900

C6—C1—C2	123.1 (6)	C10—C9—H9B	110.1
C6—C1—Br1	119.0 (5)	H9A—C9—H9B	108.4
C2—C1—Br1	117.8 (5)	C11—C10—C9	103.0 (5)
C3—C2—C1	116.9 (6)	C11—C10—H10A	111.2
C3—C2—H2	121.6	C9—C10—H10A	111.2
C1—C2—H2	121.6	C11—C10—H10B	111.2
C2—C3—C4	122.2 (6)	C9—C10—H10B	111.2
C2—C3—H3	118.9	H10A—C10—H10B	109.1
C4—C3—H3	118.9	C7—C11—C12	122.0 (6)
C3—C4—C5	120.8 (6)	C7—C11—C10	113.8 (6)
C3—C4—I1	116.5 (5)	C12—C11—C10	124.2 (6)
C5—C4—I1	122.7 (5)	O1—C12—O2	122.2 (6)
N1—C5—C6	124.3 (6)	O1—C12—C11	126.2 (6)
N1—C5—C4	118.7 (6)	O2—C12—C11	111.6 (5)
C6—C5—C4	117.0 (6)	O2—C13—C14	106.6 (5)
C1—C6—C5	120.0 (6)	O2—C13—H13A	110.4
C1—C6—H6	120.0	C14—C13—H13A	110.4
C5—C6—H6	120.0	O2—C13—H13B	110.4
C11—C7—N1	124.1 (6)	C14—C13—H13B	110.4
C11—C7—C8	110.6 (6)	H13A—C13—H13B	108.6
N1—C7—C8	125.3 (6)	C13—C14—H14A	109.5
C7—C8—C9	104.6 (5)	C13—C14—H14B	109.5
C7—C8—H8A	110.8	H14A—C14—H14B	109.5
C9—C8—H8A	110.8	C13—C14—H14C	109.5
C7—C8—H8B	110.8	H14A—C14—H14C	109.5
C9—C8—H8B	110.8	H14B—C14—H14C	109.5
H8A—C8—H8B	108.9	C7—N1—C5	132.6 (6)
C8—C9—C10	108.0 (5)	C7—N1—H1	109 (6)
C8—C9—H9A	110.1	C5—N1—H1	118 (6)
C10—C9—H9A	110.1	C12—O2—C13	114.7 (5)
C8—C9—H9B	110.1

C6—C1—C2—C3	2.4 (11)	N1—C7—C11—C12	−1.7 (11)
Br1—C1—C2—C3	179.5 (5)	C8—C7—C11—C12	−178.8 (6)
C1—C2—C3—C4	−2.8 (12)	N1—C7—C11—C10	175.4 (6)
C2—C3—C4—C5	2.3 (12)	C8—C7—C11—C10	−1.7 (9)
C2—C3—C4—I1	−178.4 (6)	C9—C10—C11—C7	2.8 (8)
C3—C4—C5—N1	179.3 (7)	C9—C10—C11—C12	179.8 (6)
I1—C4—C5—N1	0.1 (9)	C7—C11—C12—O1	−2.7 (12)
C3—C4—C5—C6	−1.1 (11)	C10—C11—C12—O1	−179.4 (7)
I1—C4—C5—C6	179.6 (5)	C7—C11—C12—O2	177.0 (7)
C2—C1—C6—C5	−1.4 (12)	C10—C11—C12—O2	0.3 (10)
Br1—C1—C6—C5	−178.4 (5)	C11—C7—N1—C5	−176.6 (7)
N1—C5—C6—C1	−179.7 (7)	C8—C7—N1—C5	0.1 (12)
C4—C5—C6—C1	0.7 (11)	C6—C5—N1—C7	−2.4 (12)
C11—C7—C8—C9	−0.2 (8)	C4—C5—N1—C7	177.1 (7)
N1—C7—C8—C9	−177.2 (7)	O1—C12—O2—C13	1.7 (10)
C7—C8—C9—C10	1.9 (7)	C11—C12—O2—C13	−178.0 (6)
C8—C9—C10—C11	−2.7 (8)	C14—C13—O2—C12	173.8 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.83 (8)	2.03 (8)	2.733 (7)	143 (7)
N1—H1···I1	0.83 (8)	2.77 (8)	3.257 (6)	120 (7)

Acknowledgements

We thank the EPSRC National Crystallography Service (University of Southampton) for the data collection.

References

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