2-Bromo-3,4,5-trimethoxy­benzyl 4-bromo-7-meth­oxy-1,3-benzodioxole-5-carboxyl­ate

The title compound, C₁₉H₁₈Br₂O₈, was synthesized in an anhydrous medium at 293 K. The five-membered ring adopts an envelope conformation. The dihedral angle between the two benzene rings is 2.6 (1)°.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.032
• wR factor = 0.078
• Data-to-parameter ratio = 17.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br2    ..  O4      ..       3.07 Ang.

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

   0 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
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 1999); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: CrystalStructure.

2-Bromo-3,4,5-trimethoxybenzyl 4-bromo-7-methoxy-1,3-benzodioxole-5-carboxylate

Crystal data

C19H18Br2O8	Z = 2
Mr = 534.15	F(000) = 532
Triclinic, P1	Dx = 1.758 Mg m^−3
Hall symbol: -P 1	Melting point: 394 K
a = 7.9131 (13) Å	Mo Kα radiation, λ = 0.71070 Å
b = 9.5314 (15) Å	Cell parameters from 2511 reflections
c = 13.949 (3) Å	θ = 3.3–27.5°
α = 77.692 (12)°	µ = 4.06 mm^−1
β = 79.132 (17)°	T = 294 K
γ = 88.946 (18)°	Block, colourless
V = 1009.2 (3) Å^3	0.12 × 0.10 × 0.08 mm

Data collection

Rigaku Saturn diffractometer	4595 independent reflections
Radiation source: rotating anode	3140 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.035
Detector resolution: 7.31 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ω scans	h = −10→10
Absorption correction: multi-scan (Jacobson, 1998)	k = −12→12
Tmin = 0.642, Tmax = 0.737	l = −18→18
10738 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.078	w = 1/[σ^2(Fo^2) + (0.0412P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.93	(Δ/σ)max = 0.001
4595 reflections	Δρmax = 0.62 e Å^−3
264 parameters	Δρmin = −0.54 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0077 (10)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.89428 (4)	0.44660 (3)	0.20999 (2)	0.05114 (11)
Br2	0.35230 (4)	−0.05540 (3)	0.68355 (2)	0.05472 (12)
O1	0.9501 (3)	0.8354 (2)	0.49618 (15)	0.0658 (6)
O2	1.1042 (2)	0.89345 (19)	0.29177 (14)	0.0553 (5)
O3	1.0836 (2)	0.74419 (19)	0.18312 (13)	0.0500 (5)
O4	0.6252 (3)	0.3351 (2)	0.39280 (14)	0.0808 (8)
O5	0.6642 (2)	0.35493 (18)	0.54297 (12)	0.0447 (4)
O6	0.2268 (2)	−0.03688 (18)	0.90085 (13)	0.0485 (5)
O7	0.2976 (2)	0.1708 (2)	0.99717 (13)	0.0527 (5)
O8	0.4809 (2)	0.40863 (19)	0.89615 (13)	0.0515 (5)
C1	0.9234 (3)	0.7422 (3)	0.4391 (2)	0.0428 (6)
C2	1.0005 (3)	0.7758 (3)	0.3398 (2)	0.0418 (6)
C3	0.9867 (3)	0.6871 (3)	0.27606 (18)	0.0390 (6)
C4	0.8933 (3)	0.5604 (3)	0.30511 (18)	0.0369 (5)
C5	0.8083 (3)	0.5250 (2)	0.40572 (18)	0.0360 (5)
C6	0.8260 (3)	0.6148 (3)	0.47018 (18)	0.0411 (6)
H6	0.7706	0.5887	0.5366	0.049*
C7	1.1325 (4)	0.8852 (3)	0.1885 (2)	0.0543 (7)
H7A	1.0643	0.9559	0.1526	0.065*
H7B	1.2529	0.9044	0.1584	0.065*
C8	0.8576 (4)	0.8134 (3)	0.5951 (2)	0.0689 (9)
H8A	0.8889	0.8873	0.6262	0.083*
H8B	0.8844	0.7213	0.6319	0.083*
H8C	0.7364	0.8168	0.5947	0.083*
C9	0.6932 (3)	0.3955 (3)	0.44311 (19)	0.0428 (6)
C10	0.5669 (3)	0.2221 (3)	0.58386 (18)	0.0422 (6)
H10A	0.6409	0.1414	0.5764	0.051*
H10B	0.4740	0.2178	0.5480	0.051*
C11	0.4940 (3)	0.2137 (3)	0.69313 (18)	0.0366 (5)
C12	0.3956 (3)	0.0936 (3)	0.74681 (19)	0.0392 (6)
C13	0.3287 (3)	0.0805 (3)	0.84821 (19)	0.0394 (6)
C14	0.3575 (3)	0.1877 (3)	0.89558 (18)	0.0402 (6)
C15	0.4564 (3)	0.3100 (3)	0.84238 (19)	0.0399 (6)
C16	0.5232 (3)	0.3215 (3)	0.74140 (18)	0.0385 (6)
H16	0.5882	0.4026	0.7057	0.046*
C17	0.3212 (4)	−0.1572 (3)	0.9403 (2)	0.0635 (8)
H17A	0.2428	−0.2349	0.9755	0.076*
H17B	0.3868	−0.1309	0.9853	0.076*
H17C	0.3978	−0.1869	0.8865	0.076*
C18	0.1467 (4)	0.2458 (3)	1.0231 (2)	0.0612 (8)
H18A	0.1133	0.2281	1.0945	0.073*
H18B	0.0560	0.2136	0.9954	0.073*
H18C	0.1678	0.3469	0.9970	0.073*
C19	0.5800 (4)	0.5345 (3)	0.8454 (2)	0.0607 (8)
H19A	0.5874	0.5948	0.8916	0.073*
H19B	0.5259	0.5856	0.7926	0.073*
H19C	0.6935	0.5082	0.8178	0.073*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0617 (2)	0.05447 (19)	0.04128 (16)	−0.00370 (13)	−0.00652 (13)	−0.02142 (13)
Br2	0.0674 (2)	0.04424 (18)	0.05471 (19)	−0.01557 (13)	−0.00981 (15)	−0.01545 (14)
O1	0.0845 (15)	0.0579 (12)	0.0595 (13)	−0.0271 (11)	−0.0013 (11)	−0.0307 (10)
O2	0.0591 (12)	0.0459 (11)	0.0570 (12)	−0.0182 (9)	−0.0013 (10)	−0.0093 (9)
O3	0.0539 (11)	0.0496 (11)	0.0415 (10)	−0.0122 (9)	0.0002 (9)	−0.0059 (9)
O4	0.1217 (19)	0.0771 (16)	0.0437 (12)	−0.0573 (14)	−0.0069 (12)	−0.0156 (11)
O5	0.0546 (11)	0.0445 (10)	0.0345 (9)	−0.0157 (8)	−0.0066 (8)	−0.0072 (8)
O6	0.0379 (10)	0.0434 (10)	0.0561 (11)	−0.0062 (8)	−0.0030 (9)	0.0024 (9)
O7	0.0507 (11)	0.0668 (13)	0.0363 (10)	0.0064 (9)	−0.0026 (9)	−0.0071 (9)
O8	0.0585 (12)	0.0548 (12)	0.0456 (11)	−0.0079 (9)	−0.0066 (9)	−0.0225 (9)
C1	0.0475 (15)	0.0405 (15)	0.0447 (15)	−0.0052 (12)	−0.0093 (12)	−0.0175 (12)
C2	0.0383 (14)	0.0368 (14)	0.0495 (16)	−0.0059 (11)	−0.0078 (12)	−0.0073 (12)
C3	0.0367 (14)	0.0421 (14)	0.0380 (13)	0.0017 (11)	−0.0077 (11)	−0.0077 (11)
C4	0.0394 (14)	0.0377 (14)	0.0364 (13)	0.0009 (11)	−0.0097 (11)	−0.0121 (11)
C5	0.0400 (14)	0.0338 (13)	0.0360 (13)	−0.0021 (10)	−0.0086 (11)	−0.0101 (11)
C6	0.0485 (15)	0.0434 (15)	0.0326 (13)	−0.0036 (12)	−0.0072 (12)	−0.0110 (11)
C7	0.0538 (17)	0.0506 (17)	0.0524 (17)	−0.0082 (13)	−0.0051 (14)	−0.0011 (14)
C8	0.095 (3)	0.067 (2)	0.0527 (18)	−0.0074 (18)	−0.0121 (17)	−0.0320 (16)
C9	0.0540 (16)	0.0412 (14)	0.0340 (13)	−0.0073 (12)	−0.0057 (12)	−0.0117 (12)
C10	0.0490 (15)	0.0393 (14)	0.0394 (14)	−0.0097 (11)	−0.0074 (12)	−0.0110 (11)
C11	0.0359 (13)	0.0372 (13)	0.0374 (13)	0.0005 (10)	−0.0085 (11)	−0.0079 (11)
C12	0.0371 (13)	0.0395 (14)	0.0425 (14)	−0.0028 (11)	−0.0086 (11)	−0.0109 (12)
C13	0.0328 (13)	0.0381 (14)	0.0443 (14)	0.0004 (11)	−0.0074 (12)	−0.0022 (12)
C14	0.0364 (13)	0.0489 (16)	0.0334 (13)	0.0033 (11)	−0.0047 (11)	−0.0068 (12)
C15	0.0386 (14)	0.0422 (14)	0.0420 (14)	0.0025 (11)	−0.0107 (12)	−0.0132 (12)
C16	0.0409 (14)	0.0337 (13)	0.0402 (14)	−0.0046 (11)	−0.0062 (12)	−0.0072 (11)
C17	0.0605 (19)	0.0549 (19)	0.0636 (19)	0.0029 (15)	−0.0084 (16)	0.0099 (16)
C18	0.0533 (18)	0.078 (2)	0.0471 (17)	0.0030 (15)	0.0055 (14)	−0.0146 (16)
C19	0.0629 (19)	0.0566 (19)	0.070 (2)	−0.0080 (15)	−0.0122 (16)	−0.0289 (16)

Geometric parameters (Å, º)

Br1—C4	1.883 (2)	C7—H7A	0.97
Br2—C12	1.892 (2)	C7—H7B	0.97
O1—C1	1.356 (3)	C8—H8A	0.96
O1—C8	1.409 (3)	C8—H8B	0.96
O2—C2	1.373 (3)	C8—H8C	0.96
O2—C7	1.435 (3)	C10—C11	1.510 (3)
O3—C3	1.380 (3)	C10—H10A	0.97
O3—C7	1.426 (3)	C10—H10B	0.97
O4—C9	1.200 (3)	C11—C12	1.388 (3)
O5—C9	1.340 (3)	C11—C16	1.388 (3)
O5—C10	1.443 (3)	C12—C13	1.393 (3)
O6—C13	1.379 (3)	C13—C14	1.373 (3)
O6—C17	1.425 (3)	C14—C15	1.403 (3)
O7—C14	1.382 (3)	C15—C16	1.389 (3)
O7—C18	1.408 (3)	C16—H16	0.93
O8—C15	1.359 (3)	C17—H17A	0.96
O8—C19	1.420 (3)	C17—H17B	0.96
C1—C2	1.376 (4)	C17—H17C	0.96
C1—C6	1.393 (3)	C18—H18A	0.96
C2—C3	1.370 (3)	C18—H18B	0.96
C3—C4	1.371 (3)	C18—H18C	0.96
C4—C5	1.409 (3)	C19—H19A	0.96
C5—C6	1.393 (3)	C19—H19B	0.96
C5—C9	1.488 (3)	C19—H19C	0.96
C6—H6	0.93
C1—O1—C8	118.6 (2)	O5—C10—H10A	109.8
C2—O2—C7	104.1 (2)	C11—C10—H10A	109.8
C3—O3—C7	104.94 (19)	O5—C10—H10B	109.8
C9—O5—C10	115.14 (19)	C11—C10—H10B	109.8
C13—O6—C17	113.85 (19)	H10A—C10—H10B	108.2
C14—O7—C18	114.7 (2)	C12—C11—C16	119.2 (2)
C15—O8—C19	117.9 (2)	C12—C11—C10	118.7 (2)
O1—C1—C2	117.1 (2)	C16—C11—C10	122.1 (2)
O1—C1—C6	127.0 (2)	C11—C12—C13	120.4 (2)
C2—C1—C6	116.0 (2)	C11—C12—Br2	120.42 (18)
C3—C2—O2	111.0 (2)	C13—C12—Br2	119.13 (18)
C3—C2—C1	122.0 (2)	C14—C13—O6	119.3 (2)
O2—C2—C1	127.0 (2)	C14—C13—C12	120.2 (2)
C2—C3—C4	123.2 (2)	O6—C13—C12	120.4 (2)
C2—C3—O3	109.3 (2)	C13—C14—O7	119.8 (2)
C4—C3—O3	127.5 (2)	C13—C14—C15	120.1 (2)
C3—C4—C5	116.3 (2)	O7—C14—C15	120.0 (2)
C3—C4—Br1	118.07 (18)	O8—C15—C16	125.0 (2)
C5—C4—Br1	125.64 (18)	O8—C15—C14	115.8 (2)
C6—C5—C4	120.0 (2)	C16—C15—C14	119.2 (2)
C6—C5—C9	119.3 (2)	C11—C16—C15	120.9 (2)
C4—C5—C9	120.6 (2)	C11—C16—H16	119.5
C1—C6—C5	122.6 (2)	C15—C16—H16	119.5
C1—C6—H6	118.7	O6—C17—H17A	109.5
C5—C6—H6	118.7	O6—C17—H17B	109.5
O3—C7—O2	108.1 (2)	H17A—C17—H17B	109.5
O3—C7—H7A	110.1	O6—C17—H17C	109.5
O2—C7—H7A	110.1	H17A—C17—H17C	109.5
O3—C7—H7B	110.1	H17B—C17—H17C	109.5
O2—C7—H7B	110.1	O7—C18—H18A	109.5
H7A—C7—H7B	108.4	O7—C18—H18B	109.5
O1—C8—H8A	109.5	H18A—C18—H18B	109.5
O1—C8—H8B	109.5	O7—C18—H18C	109.5
H8A—C8—H8B	109.5	H18A—C18—H18C	109.5
O1—C8—H8C	109.5	H18B—C18—H18C	109.5
H8A—C8—H8C	109.5	O8—C19—H19A	109.5
H8B—C8—H8C	109.5	O8—C19—H19B	109.5
O4—C9—O5	121.9 (2)	H19A—C19—H19B	109.5
O4—C9—C5	125.8 (2)	O8—C19—H19C	109.5
O5—C9—C5	112.2 (2)	H19A—C19—H19C	109.5
O5—C10—C11	109.44 (19)	H19B—C19—H19C	109.5
C8—O1—C1—C2	172.8 (3)	C6—C5—C9—O5	−20.9 (3)
C8—O1—C1—C6	−7.4 (4)	C4—C5—C9—O5	161.8 (2)
C7—O2—C2—C3	9.2 (3)	C9—O5—C10—C11	−161.5 (2)
C7—O2—C2—C1	−173.4 (3)	O5—C10—C11—C12	180.0 (2)
O1—C1—C2—C3	177.9 (2)	O5—C10—C11—C16	−0.3 (3)
C6—C1—C2—C3	−1.9 (4)	C16—C11—C12—C13	−0.9 (4)
O1—C1—C2—O2	0.8 (4)	C10—C11—C12—C13	178.8 (2)
C6—C1—C2—O2	−179.0 (2)	C16—C11—C12—Br2	179.78 (18)
O2—C2—C3—C4	178.8 (2)	C10—C11—C12—Br2	−0.5 (3)
C1—C2—C3—C4	1.3 (4)	C17—O6—C13—C14	−96.1 (3)
O2—C2—C3—O3	0.6 (3)	C17—O6—C13—C12	86.8 (3)
C1—C2—C3—O3	−176.9 (2)	C11—C12—C13—C14	1.1 (4)
C7—O3—C3—C2	−10.2 (3)	Br2—C12—C13—C14	−179.58 (18)
C7—O3—C3—C4	171.7 (3)	C11—C12—C13—O6	178.1 (2)
C2—C3—C4—C5	0.7 (4)	Br2—C12—C13—O6	−2.5 (3)
O3—C3—C4—C5	178.5 (2)	O6—C13—C14—O7	5.9 (3)
C2—C3—C4—Br1	−177.49 (19)	C12—C13—C14—O7	−177.0 (2)
O3—C3—C4—Br1	0.4 (3)	O6—C13—C14—C15	−178.0 (2)
C3—C4—C5—C6	−1.8 (3)	C12—C13—C14—C15	−0.9 (4)
Br1—C4—C5—C6	176.20 (18)	C18—O7—C14—C13	−102.2 (3)
C3—C4—C5—C9	175.5 (2)	C18—O7—C14—C15	81.7 (3)
Br1—C4—C5—C9	−6.5 (3)	C19—O8—C15—C16	1.1 (4)
O1—C1—C6—C5	−179.1 (2)	C19—O8—C15—C14	−179.8 (2)
C2—C1—C6—C5	0.7 (4)	C13—C14—C15—O8	−178.6 (2)
C4—C5—C6—C1	1.1 (4)	O7—C14—C15—O8	−2.5 (3)
C9—C5—C6—C1	−176.2 (2)	C13—C14—C15—C16	0.6 (4)
C3—O3—C7—O2	15.9 (3)	O7—C14—C15—C16	176.6 (2)
C2—O2—C7—O3	−15.4 (3)	C12—C11—C16—C15	0.5 (4)
C10—O5—C9—O4	8.8 (4)	C10—C11—C16—C15	−179.1 (2)
C10—O5—C9—C5	−174.4 (2)	O8—C15—C16—C11	178.7 (2)
C6—C5—C9—O4	155.8 (3)	C14—C15—C16—C11	−0.4 (4)
C4—C5—C9—O4	−21.5 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O5	0.93	2.37	2.713 (3)	101
C8—H8A···O2^i	0.96	2.59	3.533 (3)	166
C16—H16···O5	0.93	2.37	2.735 (3)	103
C17—H17B···O7^ii	0.96	2.57	3.287 (3)	132
C17—H17C···Br2	0.96	2.93	3.468 (3)	117

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