Methyl (Z)-2-(bromo­meth­yl)-3-(3,4-methyl­enedioxy­phen­yl)prop-2-enoate

The title compound, C₁₂H₁₁BrO₄, is an allylic bromide, which is an inter­esting precursor in organic synthesis. The skeleton of the mol­ecule is nearly planar, indicating delocalization. The crystal packing is governed by C—H...O hydrogen bonds, with the mol­ecules stacked along the [100] and [010] directions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.039
• wR factor = 0.111
• Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.32
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K

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

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

---

Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: SET4 in CAD-4 EXPRESS; data reduction: HELENA (Spek, 1996); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Methyl (Z)-2-(bromomethyl)-3-(3,4-methylenedioxyphenyl)prop-2-enoate

Crystal data

C12H11BrO4	Z = 2
Mr = 299.12	F(000) = 300
Triclinic, P1	Dx = 1.699 Mg m^−3
a = 6.725 (3) Å	Mo Kα radiation, λ = 0.71069 Å
b = 8.845 (2) Å	Cell parameters from 25 reflections
c = 9.941 (1) Å	θ = 4.1–13.4°
α = 91.41 (2)°	µ = 3.52 mm^−1
β = 90.98 (2)°	T = 293 K
γ = 98.490 (2)°	Irregular block, colorless
V = 584.5 (3) Å^3	0.50 × 0.47 × 0.43 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	1691 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.018
Graphite monochromator	θmax = 25.5°, θmin = 2.1°
ω–2θ scans	h = −8→8
Absorption correction: ψ scan (North et al., 1968)	k = −10→10
Tmin = 0.200, Tmax = 0.225	l = −12→1
2567 measured reflections	3 standard reflections every 200 reflections
2166 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0595P)^2 + 0.5446P] where P = (Fo^2 + 2Fc^2)/3
2166 reflections	(Δ/σ)max = 0.001
155 parameters	Δρmax = 0.99 e Å^−3
0 restraints	Δρmin = −0.43 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.9019 (5)	0.5965 (4)	0.7446 (3)	0.0384 (8)
C2	0.9570 (6)	0.4637 (4)	0.6828 (4)	0.0448 (8)
H2	0.8846	0.4159	0.6090	0.054*
C3	1.1194 (5)	0.4080 (4)	0.7346 (4)	0.0422 (8)
C4	1.2283 (5)	0.4754 (4)	0.8435 (4)	0.0404 (8)
C5	1.1813 (6)	0.6041 (4)	0.9062 (4)	0.0453 (9)
H5	1.2552	0.6490	0.9805	0.054*
C6	1.0179 (6)	0.6650 (4)	0.8540 (4)	0.0423 (8)
H6	0.9846	0.7543	0.8932	0.051*
C7	0.7290 (5)	0.6525 (4)	0.6832 (4)	0.0416 (8)
H7	0.6904	0.6061	0.6000	0.050*
C8	0.6144 (5)	0.7564 (4)	0.7214 (3)	0.0391 (8)
C9	0.4523 (5)	0.7800 (4)	0.6233 (4)	0.0410 (8)
C10	0.2000 (6)	0.9269 (5)	0.5684 (5)	0.0570 (10)
H10A	0.2548	0.9570	0.4829	0.086*
H10B	0.1348	1.0073	0.6059	0.086*
H10C	0.1041	0.8356	0.5564	0.086*
C11	1.3756 (7)	0.2801 (6)	0.7705 (5)	0.0645 (12)
H11A	1.4940	0.3014	0.7157	0.077*
H11B	1.3743	0.1803	0.8089	0.077*
C12	0.6267 (6)	0.8424 (4)	0.8525 (4)	0.0474 (9)
H12A	0.6781	0.7816	0.9213	0.057*
H12B	0.4928	0.8592	0.8777	0.057*
O1	1.1995 (5)	0.2815 (3)	0.6900 (3)	0.0654 (8)
O2	1.3809 (4)	0.3938 (3)	0.8750 (3)	0.0550 (7)
O3	0.3601 (4)	0.8981 (3)	0.6585 (3)	0.0507 (7)
O4	0.4062 (4)	0.7031 (4)	0.5248 (3)	0.0663 (9)
Br1	0.80250 (7)	1.04154 (5)	0.84506 (5)	0.0651 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0405 (19)	0.0337 (17)	0.0403 (19)	0.0041 (14)	−0.0058 (15)	0.0000 (14)
C2	0.045 (2)	0.0423 (19)	0.046 (2)	0.0071 (16)	−0.0101 (16)	−0.0077 (16)
C3	0.0416 (19)	0.0375 (18)	0.048 (2)	0.0101 (15)	−0.0039 (16)	−0.0039 (15)
C4	0.0376 (18)	0.0420 (18)	0.0419 (19)	0.0059 (15)	−0.0031 (15)	0.0080 (15)
C5	0.049 (2)	0.0441 (19)	0.042 (2)	0.0050 (16)	−0.0137 (17)	−0.0035 (16)
C6	0.047 (2)	0.0363 (18)	0.044 (2)	0.0088 (15)	−0.0088 (16)	−0.0049 (15)
C7	0.0419 (19)	0.0380 (18)	0.043 (2)	0.0034 (15)	−0.0088 (16)	−0.0058 (15)
C8	0.0410 (19)	0.0358 (17)	0.0400 (19)	0.0050 (14)	−0.0056 (15)	0.0005 (14)
C9	0.0380 (19)	0.0385 (18)	0.046 (2)	0.0052 (15)	−0.0049 (16)	−0.0026 (15)
C10	0.055 (2)	0.052 (2)	0.067 (3)	0.0204 (19)	−0.020 (2)	−0.002 (2)
C11	0.062 (3)	0.076 (3)	0.062 (3)	0.036 (2)	−0.011 (2)	−0.009 (2)
C12	0.054 (2)	0.050 (2)	0.040 (2)	0.0143 (17)	−0.0040 (17)	−0.0006 (16)
O1	0.0660 (19)	0.0571 (17)	0.077 (2)	0.0297 (14)	−0.0217 (16)	−0.0233 (15)
O2	0.0526 (15)	0.0570 (16)	0.0589 (17)	0.0220 (13)	−0.0156 (13)	−0.0009 (13)
O3	0.0543 (15)	0.0469 (14)	0.0537 (16)	0.0200 (12)	−0.0152 (12)	−0.0075 (12)
O4	0.0606 (18)	0.079 (2)	0.0638 (18)	0.0341 (15)	−0.0283 (15)	−0.0300 (16)
Br1	0.0721 (3)	0.0483 (3)	0.0737 (3)	0.0110 (2)	−0.0246 (2)	−0.0182 (2)

Geometric parameters (Å, º)

C1—C6	1.399 (5)	C8—C9	1.492 (5)
C1—C2	1.413 (5)	C9—O4	1.189 (4)
C1—C7	1.460 (5)	C9—O3	1.333 (4)
C2—C3	1.362 (5)	C10—O3	1.445 (4)
C2—H2	0.9300	C10—H10A	0.9600
C3—C4	1.370 (5)	C10—H10B	0.9600
C3—O1	1.378 (4)	C10—H10C	0.9600
C4—C5	1.365 (5)	C11—O1	1.419 (5)
C4—O2	1.375 (4)	C11—O2	1.424 (5)
C5—C6	1.392 (5)	C11—H11A	0.9700
C5—H5	0.9300	C11—H11B	0.9700
C6—H6	0.9300	C12—Br1	1.975 (4)
C7—C8	1.335 (5)	C12—H12A	0.9700
C7—H7	0.9300	C12—H12B	0.9700
C8—C12	1.488 (5)
C6—C1—C2	118.6 (3)	O4—C9—O3	122.6 (3)
C6—C1—C7	125.9 (3)	O4—C9—C8	125.0 (3)
C2—C1—C7	115.4 (3)	O3—C9—C8	112.5 (3)
C3—C2—C1	117.9 (3)	O3—C10—H10A	109.5
C3—C2—H2	121.1	O3—C10—H10B	109.5
C1—C2—H2	121.1	H10A—C10—H10B	109.5
C2—C3—C4	122.4 (3)	O3—C10—H10C	109.5
C2—C3—O1	127.6 (3)	H10A—C10—H10C	109.5
C4—C3—O1	110.0 (3)	H10B—C10—H10C	109.5
C5—C4—C3	121.9 (3)	O1—C11—O2	108.6 (3)
C5—C4—O2	128.3 (3)	O1—C11—H11A	110.0
C3—C4—O2	109.8 (3)	O2—C11—H11A	110.0
C4—C5—C6	117.0 (3)	O1—C11—H11B	110.0
C4—C5—H5	121.5	O2—C11—H11B	110.0
C6—C5—H5	121.5	H11A—C11—H11B	108.4
C5—C6—C1	122.2 (3)	C8—C12—Br1	112.1 (3)
C5—C6—H6	118.9	C8—C12—H12A	109.2
C1—C6—H6	118.9	Br1—C12—H12A	109.2
C8—C7—C1	133.5 (3)	C8—C12—H12B	109.2
C8—C7—H7	113.2	Br1—C12—H12B	109.2
C1—C7—H7	113.2	H12A—C12—H12B	107.9
C7—C8—C12	126.6 (3)	C3—O1—C11	105.3 (3)
C7—C8—C9	115.2 (3)	C4—O2—C11	105.4 (3)
C12—C8—C9	118.1 (3)	C9—O3—C10	115.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O4	0.93	2.33	2.756 (5)	108
C2—H2···O4^i	0.93	2.44	3.318 (5)	158
C11—H11A···O4^ii	0.97	2.50	3.300 (6)	140
C10—H10B···O1^iii	0.96	2.52	3.334 (5)	143
C12—H12A···O2^iv	0.97	2.58	3.458 (5)	150

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