(E)-2-[2-(4-Bromo­benzoyl­methylene)­imidazolidin-1-yl]ethyl 4-bromo­benzoate

Yu, C.-Y.; Yuan, X.-N.; Wang, L.-B.; Huang, Z.-T.

doi:10.1107/S1600536807025974

(E)-2-[2-(4-Bromobenzoylmethylene)imidazolidin-1-yl]ethyl 4-bromobenzoate

C.-Y. Yu, X.-N. Yuan, L.-B. Wang and Z.-T. Huang

The title compound, C₂₀H₁₈Br₂N₂O₃, exhibits intermolecular N—H

O hydrogen bonds which form pseudo-dimers across inversion centres. Intramolecular N—H

O hydrogen bonds and weak intramolecular C—H

π hydrogen-bonding interactions are also present within the molecule.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025974/dn2178sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025974/dn2178Isup2.hkl Contains datablock I

CCDC reference: 654847

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.008 Å
R factor = 0.050
wR factor = 0.137
Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.73
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.74 Ratio
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       2.55 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C18
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.03
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          8

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.729
            Tmax scaled      0.241 Tmin scaled      0.213

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Heterocyclic ketene aminals (HKAs) are bis-nucleophiles which are valuable synthons for heterocyclic synthesis (Huang & Wang, 2002). The title compound, (I), (Fig. 1) is an N-alkylation product of a HKA. The crystal structure of (I) was determined in order to provide information regarding its electronic conjugation properties and to examine a possible intramolecular hydrogen bond (Wang et al.,1987).

In the title compound, the two substituted phenyl rings make dihedral angle of 84.0 (2)°, such conformation results from the occurrence of C—H···π interaction between the C15—C20 and C6—C11 rings (Fig.1, Table 1). The H atom attached to N1 is engaged in intramolecular and intermolecular hydrogen bonds. The intermolecular hydrogen bond results in the formation of pseudo dimers which are further interconnected through C—H···O weak hydrogen bonds to form a three dimensionnal network (Fig. 2, Table 1). The bond distances and bond angles are within the expected range observed for related compounds.

Related literature top

For related literature, see: Huang & Wang (2002); Wang & Huang (1996); Wang et al. (1987).

Experimental top

Compound (I) was prepared according to the procedure of Wang et al. (1996) and purified by recrystallization from acetone in 19% yield (m.p. 449–450 K). Anal. Calcd for C₂₀H₁₈Br₂N₂O₃: C 48.61, H 3.67, N 5.67, Br 32.34%; found: C 48.64, H 3.64, N 5.38, Br 32.47%.

Structure description top

For related literature, see: Huang & Wang (2002); Wang & Huang (1996); Wang et al. (1987).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. The C—H···π and N—H···O intramolecular interactions are shown as dashed lines (CT1 is the centroid of the C6–C11 phenyl ring).
	Fig. 2. Partial packing view showing the N—H···O and C—H···O hydrogen bonds network. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) 2 - x, 1 - y, 1 - z; (ii) 1 - x, -y, -z; (iii) x - 1, y, z].

(E)-2-[2-(4-Bromobenzoylmethylene)imidazolidin-1-yl]ethyl 4-bromobenzoate top

Crystal data top

C₂₀H₁₈Br₂N₂O₃	Z = 2
M_r = 494.18	F(000) = 492
Triclinic, P1	D_x = 1.687 Mg m⁻³
Hall symbol: -P 1	Melting point: 449 K
a = 7.3733 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.117 (2) Å	Cell parameters from 1807 reflections
c = 12.954 (2) Å	θ = 2.9–25.4°
α = 104.635 (10)°	µ = 4.19 mm⁻¹
β = 105.108 (11)°	T = 294 K
γ = 96.700 (9)°	Prism, colourless
V = 972.7 (3) Å³	0.39 × 0.37 × 0.34 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3389 independent reflections
Radiation source: fine-focus sealed tube	2404 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
φ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −4→8
T_min = 0.292, T_max = 0.330	k = −13→11
4924 measured reflections	l = −15→15

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0744P)² + 0.4017P] where P = (F_o² + 2F_c²)/3
3389 reflections	(Δ/σ)_max < 0.001
247 parameters	Δρ_max = 0.88 e Å⁻³
0 restraints	Δρ_min = −0.78 e Å⁻³

Crystal data top

C₂₀H₁₈Br₂N₂O₃	γ = 96.700 (9)°
M_r = 494.18	V = 972.7 (3) Å³
Triclinic, P1	Z = 2
a = 7.3733 (15) Å	Mo Kα radiation
b = 11.117 (2) Å	µ = 4.19 mm⁻¹
c = 12.954 (2) Å	T = 294 K
α = 104.635 (10)°	0.39 × 0.37 × 0.34 mm
β = 105.108 (11)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3389 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	2404 reflections with I > 2σ(I)
T_min = 0.292, T_max = 0.330	R_int = 0.024
4924 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.88 e Å⁻³
3389 reflections	Δρ_min = −0.78 e Å⁻³
247 parameters

Special details top

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	0.11210 (7)	0.92243 (5)	0.38589 (6)	0.0615 (2)
Br2	0.22475 (12)	0.75878 (7)	−0.04472 (7)	0.0909 (3)
N1	0.8470 (6)	0.3228 (4)	0.3643 (4)	0.0445 (11)
H1	0.904 (8)	0.388 (5)	0.405 (5)	0.053*
N2	0.5887 (5)	0.1767 (4)	0.2816 (4)	0.0459 (10)
O1	0.8064 (4)	0.5665 (3)	0.4319 (3)	0.0473 (9)
O2	0.2955 (6)	0.2177 (3)	0.0964 (3)	0.0669 (12)
O3	0.2102 (9)	0.1289 (4)	−0.0866 (4)	0.121 (2)
C1	0.6565 (6)	0.3019 (4)	0.3296 (4)	0.0346 (10)
C2	0.9211 (7)	0.2063 (5)	0.3468 (5)	0.0569 (14)
H2A	0.9879	0.1942	0.4175	0.068*
H2B	1.0075	0.2062	0.3017	0.068*
C3	0.7435 (8)	0.1057 (5)	0.2862 (5)	0.0583 (15)
H3A	0.7447	0.0616	0.2116	0.070*
H3B	0.7313	0.0445	0.3269	0.070*
C4	0.5481 (6)	0.3957 (4)	0.3401 (4)	0.0343 (10)
H4	0.4154	0.3720	0.3129	0.041*
C5	0.6293 (6)	0.5236 (4)	0.3895 (4)	0.0312 (10)
C6	0.4998 (6)	0.6184 (4)	0.3882 (3)	0.0289 (9)
C7	0.3073 (6)	0.5882 (4)	0.3806 (3)	0.0318 (10)
H7	0.2549	0.5059	0.3755	0.038*
C8	0.1921 (6)	0.6777 (4)	0.3803 (4)	0.0355 (11)
H8	0.0641	0.6568	0.3764	0.043*
C9	0.2711 (6)	0.7988 (4)	0.3861 (4)	0.0361 (11)
C10	0.4601 (6)	0.8321 (4)	0.3943 (4)	0.0405 (12)
H10	0.5111	0.9142	0.3980	0.049*
C11	0.5735 (6)	0.7422 (4)	0.3969 (4)	0.0388 (11)
H11	0.7028	0.7652	0.4046	0.047*
C12	0.3886 (8)	0.1157 (5)	0.2361 (5)	0.0628 (16)
H12A	0.3151	0.1671	0.2748	0.075*
H12B	0.3738	0.0342	0.2505	0.075*
C13	0.3079 (9)	0.0958 (5)	0.1128 (6)	0.079 (2)
H13A	0.3906	0.0557	0.0735	0.095*
H13B	0.1820	0.0415	0.0843	0.095*
C14	0.2466 (9)	0.2216 (6)	−0.0085 (6)	0.0720 (19)
C15	0.2433 (7)	0.3529 (5)	−0.0155 (4)	0.0515 (14)
C16	0.2172 (8)	0.3767 (6)	−0.1179 (5)	0.0683 (17)
H16	0.2028	0.3100	−0.1814	0.082*
C17	0.2120 (9)	0.4968 (6)	−0.1280 (5)	0.0667 (16)
H17	0.1944	0.5119	−0.1971	0.080*
C18	0.2339 (7)	0.5940 (5)	−0.0324 (5)	0.0540 (14)
C19	0.2565 (8)	0.5734 (5)	0.0685 (5)	0.0549 (14)
H19	0.2674	0.6401	0.1313	0.066*
C20	0.2631 (8)	0.4530 (5)	0.0773 (4)	0.0559 (14)
H20	0.2812	0.4391	0.1468	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0415 (3)	0.0467 (3)	0.0999 (5)	0.0273 (2)	0.0168 (3)	0.0240 (3)
Br2	0.1142 (6)	0.0704 (5)	0.0953 (6)	0.0032 (4)	0.0313 (5)	0.0441 (4)
N1	0.032 (2)	0.049 (3)	0.056 (3)	0.0215 (19)	0.011 (2)	0.017 (2)
N2	0.036 (2)	0.037 (2)	0.064 (3)	0.0206 (18)	0.005 (2)	0.017 (2)
O1	0.0207 (17)	0.0457 (19)	0.073 (2)	0.0117 (14)	0.0064 (16)	0.0178 (17)
O2	0.069 (3)	0.035 (2)	0.067 (3)	0.0199 (17)	−0.021 (2)	0.0036 (18)
O3	0.173 (6)	0.066 (3)	0.070 (3)	0.057 (3)	−0.024 (3)	−0.023 (3)
C1	0.030 (2)	0.043 (3)	0.040 (3)	0.017 (2)	0.011 (2)	0.022 (2)
C2	0.044 (3)	0.061 (3)	0.069 (4)	0.036 (3)	0.012 (3)	0.019 (3)
C3	0.054 (3)	0.056 (3)	0.084 (4)	0.042 (3)	0.027 (3)	0.034 (3)
C4	0.024 (2)	0.044 (3)	0.039 (3)	0.0146 (19)	0.0058 (19)	0.021 (2)
C5	0.024 (2)	0.042 (3)	0.031 (2)	0.0128 (19)	0.0062 (19)	0.017 (2)
C6	0.023 (2)	0.036 (2)	0.029 (2)	0.0089 (18)	0.0058 (18)	0.0131 (19)
C7	0.024 (2)	0.037 (2)	0.035 (3)	0.0072 (18)	0.0079 (19)	0.013 (2)
C8	0.022 (2)	0.041 (3)	0.043 (3)	0.0079 (19)	0.008 (2)	0.012 (2)
C9	0.030 (2)	0.037 (2)	0.043 (3)	0.0172 (19)	0.007 (2)	0.013 (2)
C10	0.026 (2)	0.033 (2)	0.064 (3)	0.0073 (19)	0.012 (2)	0.019 (2)
C11	0.024 (2)	0.041 (3)	0.054 (3)	0.0082 (19)	0.012 (2)	0.017 (2)
C12	0.050 (3)	0.037 (3)	0.104 (5)	0.012 (2)	0.015 (3)	0.032 (3)
C13	0.060 (4)	0.032 (3)	0.110 (6)	0.008 (3)	−0.022 (4)	0.009 (3)
C14	0.063 (4)	0.056 (4)	0.063 (4)	0.028 (3)	−0.021 (3)	−0.009 (3)
C15	0.038 (3)	0.054 (3)	0.043 (3)	0.020 (2)	−0.008 (2)	−0.002 (3)
C16	0.065 (4)	0.072 (4)	0.051 (4)	0.020 (3)	0.012 (3)	−0.008 (3)
C17	0.067 (4)	0.084 (5)	0.050 (4)	0.012 (3)	0.020 (3)	0.021 (3)
C18	0.043 (3)	0.061 (3)	0.060 (4)	0.005 (3)	0.014 (3)	0.024 (3)
C19	0.062 (4)	0.050 (3)	0.044 (3)	0.015 (3)	0.007 (3)	0.007 (3)
C20	0.068 (4)	0.051 (3)	0.039 (3)	0.019 (3)	0.000 (3)	0.010 (3)

Geometric parameters (Å, º) top

Br1—C9	1.908 (4)	C7—H7	0.9300
Br2—C18	1.886 (6)	C8—C9	1.378 (6)
N1—C1	1.331 (6)	C8—H8	0.9300
N1—C2	1.452 (6)	C9—C10	1.368 (6)
N1—H1	0.78 (5)	C10—C11	1.377 (6)
N2—C1	1.346 (6)	C10—H10	0.9300
N2—C12	1.447 (6)	C11—H11	0.9300
N2—C3	1.459 (6)	C12—C13	1.499 (9)
O1—C5	1.258 (5)	C12—H12A	0.9700
O2—C14	1.324 (8)	C12—H12B	0.9700
O2—C13	1.434 (6)	C13—H13A	0.9700
O3—C14	1.194 (7)	C13—H13B	0.9700
C1—C4	1.387 (6)	C14—C15	1.488 (8)
C2—C3	1.503 (8)	C15—C20	1.379 (7)
C2—H2A	0.9700	C15—C16	1.387 (8)
C2—H2B	0.9700	C16—C17	1.378 (9)
C3—H3A	0.9700	C16—H16	0.9300
C3—H3B	0.9700	C17—C18	1.381 (8)
C4—C5	1.390 (6)	C17—H17	0.9300
C4—H4	0.9300	C18—C19	1.355 (8)
C5—C6	1.503 (6)	C19—C20	1.377 (7)
C6—C11	1.385 (6)	C19—H19	0.9300
C6—C7	1.391 (5)	C20—H20	0.9300
C7—C8	1.382 (6)

C1—N1—C2	112.6 (4)	C9—C10—C11	119.0 (4)
C1—N1—H1	119 (4)	C9—C10—H10	120.5
C2—N1—H1	125 (4)	C11—C10—H10	120.5
C1—N2—C12	125.8 (4)	C10—C11—C6	121.6 (4)
C1—N2—C3	111.5 (4)	C10—C11—H11	119.2
C12—N2—C3	122.6 (4)	C6—C11—H11	119.2
C14—O2—C13	116.7 (5)	N2—C12—C13	113.7 (5)
N1—C1—N2	109.0 (4)	N2—C12—H12A	108.8
N1—C1—C4	124.7 (4)	C13—C12—H12A	108.8
N2—C1—C4	126.3 (4)	N2—C12—H12B	108.8
N1—C2—C3	103.2 (4)	C13—C12—H12B	108.8
N1—C2—H2A	111.1	H12A—C12—H12B	107.7
C3—C2—H2A	111.1	O2—C13—C12	107.6 (4)
N1—C2—H2B	111.1	O2—C13—H13A	110.2
C3—C2—H2B	111.1	C12—C13—H13A	110.2
H2A—C2—H2B	109.1	O2—C13—H13B	110.2
N2—C3—C2	103.6 (4)	C12—C13—H13B	110.2
N2—C3—H3A	111.0	H13A—C13—H13B	108.5
C2—C3—H3A	111.0	O3—C14—O2	122.6 (6)
N2—C3—H3B	111.0	O3—C14—C15	125.3 (6)
C2—C3—H3B	111.0	O2—C14—C15	112.1 (5)
H3A—C3—H3B	109.0	C20—C15—C16	118.2 (5)
C1—C4—C5	122.9 (4)	C20—C15—C14	121.9 (5)
C1—C4—H4	118.6	C16—C15—C14	119.9 (5)
C5—C4—H4	118.6	C17—C16—C15	121.6 (5)
O1—C5—C4	124.2 (4)	C17—C16—H16	119.2
O1—C5—C6	117.2 (4)	C15—C16—H16	119.2
C4—C5—C6	118.6 (4)	C16—C17—C18	117.9 (6)
C11—C6—C7	117.7 (4)	C16—C17—H17	121.1
C11—C6—C5	119.4 (4)	C18—C17—H17	121.1
C7—C6—C5	122.9 (4)	C19—C18—C17	121.9 (5)
C8—C7—C6	121.5 (4)	C19—C18—Br2	119.6 (4)
C8—C7—H7	119.2	C17—C18—Br2	118.5 (4)
C6—C7—H7	119.2	C18—C19—C20	119.5 (5)
C9—C8—C7	118.5 (4)	C18—C19—H19	120.3
C9—C8—H8	120.7	C20—C19—H19	120.3
C7—C8—H8	120.7	C19—C20—C15	120.9 (5)
C10—C9—C8	121.6 (4)	C19—C20—H20	119.6
C10—C9—Br1	119.9 (3)	C15—C20—H20	119.6
C8—C9—Br1	118.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.78 (5)	2.16 (5)	2.706 (5)	128 (5)
N1—H1···O1ⁱ	0.78 (5)	2.48 (6)	3.020 (5)	128 (5)
C3—H3A···O3ⁱⁱ	0.97	2.43	3.296 (7)	148
C8—H8···O1ⁱⁱⁱ	0.93	2.40	3.264 (5)	154
C19—H19···Cg1	0.93	3.07	3.841 (6)	141

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

Experimental details

Crystal data
Chemical formula	C₂₀H₁₈Br₂N₂O₃
M_r	494.18
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	7.3733 (15), 11.117 (2), 12.954 (2)
α, β, γ (°)	104.635 (10), 105.108 (11), 96.700 (9)
V (Å³)	972.7 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.19
Crystal size (mm)	0.39 × 0.37 × 0.34

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.292, 0.330
No. of measured, independent and observed [I > 2σ(I)] reflections	4924, 3389, 2404
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.137, 1.04
No. of reflections	3389
No. of parameters	247
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.88, −0.78

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), SHELXL97.