Different supra­molecular inter­actions mediated by Br atoms in the crystal structures of three anisole derivatives

Three anisole building blocks featuring bis­(hy­droxy­meth­yl) or bis­(bromo­meth­yl) pendants have been analyzed with regard to their mol­ecular structures and packing behaviour. The compounds are ethyl 3,5-bis­(hy­droxy­meth­yl)-4-meth­oxy­benzoate, C₁₂H₁₆O₅, (I), [5-bromo-3-(hy­droxy­meth­yl)-2-meth­oxy­phen­yl]methanol [or 4-bromo-2,6-bis­(hy­droxy­meth­yl)anisole], C₉H₁₁BrO₃, (II), and 5-bromo-1,3-bis­(bromo­meth­yl)-2-meth­oxy­benzene [or 4-bromo-2,6-bis­(bromo­meth­yl)anisole], C₉H₉Br₃O, (III). A typical supra­molecular pattern involved C—H...π inter­actions generating mol­ecular stacks, while π–π inter­actions were only observed in the absence of bromine, indicating a striking influence on the distances between adjacent aromatic moieties. When comparing bis­(hy­droxy­meth­yl) compound (II) with bis­(bromo­meth­yl) compound (III), we found that the strong O—H...O hydrogen bonds in a zigzag arrangement in the first are replaced by C—H...Br inter­actions in the second without a change in the general packing.

Computing details

For all structures, data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 2012), publCIF (Westrip, 2010) and SHELXLE (Hübschle et al., 2011).

Ethyl 3,5-bis(hydroxymethyl)-4-methoxybenzoate (I)

Crystal data

C12H16O5	F(000) = 256
Mr = 240.25	Dx = 1.357 Mg m^−3
Triclinic, P1	Melting point: 340.15 K
a = 7.8601 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.2489 (11) Å	Cell parameters from 2183 reflections
c = 10.7883 (14) Å	θ = 2.0–27.4°
α = 81.538 (11)°	µ = 0.11 mm^−1
β = 72.352 (10)°	T = 203 K
γ = 61.930 (9)°	Piece, colorless
V = 588.15 (14) Å^3	0.35 × 0.32 × 0.28 mm
Z = 2

Data collection

Stoe IPDS 2 diffractometer	1705 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	Rint = 0.052
Plane graphite monochromator	θmax = 25.5°, θmin = 2.0°
Detector resolution: 6.67 pixels mm^-1	h = −9→9
rotation method scans	k = −9→9
4748 measured reflections	l = −13→13
2188 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.140	w = 1/[σ^2(Fo^2) + (0.0651P)^2 + 0.2206P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max < 0.001
2188 reflections	Δρmax = 0.23 e Å^−3
164 parameters	Δρmin = −0.26 e Å^−3

Special details

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. H atoms were positioned geometrically and allowed to ride on their parent atoms, C–H = 0.95-0.98 %A and Uiso(H) = 1.2-1.5 Ueq (parent atom). Hydrogen atoms bonded to O were located via electron density. Individual reflections were considered as outliers and therefore omitted.

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

	x	y	z	Uiso*/Ueq
O1	0.6177 (2)	0.0793 (2)	0.74711 (15)	0.0381 (4)
H1O	0.725 (5)	0.106 (4)	0.714 (3)	0.063 (9)*
O2	0.1535 (2)	0.6048 (2)	0.72607 (14)	0.0332 (4)
O3	0.0670 (2)	0.8314 (2)	0.36301 (15)	0.0375 (4)
H3O	−0.053 (5)	0.906 (4)	0.345 (3)	0.068 (9)*
O4	0.7377 (2)	0.0287 (2)	0.27189 (14)	0.0337 (4)
O5	0.5225 (2)	0.2543 (2)	0.17245 (13)	0.0333 (4)
C1	0.4636 (3)	0.2861 (3)	0.39511 (18)	0.0242 (4)
C2	0.5062 (3)	0.2150 (3)	0.51367 (19)	0.0257 (4)
H2	0.6094	0.0941	0.5179	0.031*
C3	0.3986 (3)	0.3202 (3)	0.62487 (19)	0.0263 (4)
C4	0.2463 (3)	0.4967 (3)	0.61648 (19)	0.0253 (4)
C5	0.1989 (3)	0.5687 (3)	0.49936 (19)	0.0255 (4)
C6	0.3094 (3)	0.4616 (3)	0.38892 (19)	0.0256 (4)
H6	0.2797	0.5082	0.3081	0.031*
C7	0.4465 (3)	0.2513 (3)	0.7539 (2)	0.0329 (5)
H7A	0.4672	0.3432	0.7887	0.040*
H7B	0.3298	0.2412	0.8159	0.040*
C8	−0.0362 (4)	0.6174 (4)	0.7980 (3)	0.0515 (7)
H8A	−0.0781	0.6774	0.8814	0.077*
H8B	−0.0270	0.4938	0.8139	0.077*
H8C	−0.1345	0.6897	0.7486	0.077*
C9	0.0352 (3)	0.7610 (3)	0.4921 (2)	0.0324 (5)
H9A	−0.0962	0.7595	0.5193	0.039*
H9B	0.0336	0.8418	0.5523	0.039*
C10	0.5892 (3)	0.1750 (3)	0.27619 (19)	0.0270 (4)
C11	0.6403 (4)	0.1645 (4)	0.0483 (2)	0.0429 (6)
H11A	0.5509	0.1828	−0.0057	0.051*
H11B	0.7165	0.0308	0.0621	0.051*
C12	0.7810 (5)	0.2422 (5)	−0.0196 (3)	0.0652 (8)
H12A	0.8573	0.1841	−0.1049	0.098*
H12B	0.8732	0.2188	0.0324	0.098*
H12C	0.7052	0.3749	−0.0312	0.098*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0355 (8)	0.0385 (9)	0.0355 (9)	−0.0116 (7)	−0.0154 (7)	0.0076 (7)
O2	0.0290 (7)	0.0382 (8)	0.0299 (8)	−0.0135 (6)	−0.0024 (6)	−0.0106 (6)
O3	0.0285 (8)	0.0354 (8)	0.0375 (9)	−0.0061 (6)	−0.0116 (6)	0.0070 (7)
O4	0.0285 (7)	0.0314 (8)	0.0322 (8)	−0.0042 (6)	−0.0094 (6)	−0.0047 (6)
O5	0.0330 (8)	0.0359 (8)	0.0234 (7)	−0.0083 (6)	−0.0095 (6)	−0.0007 (6)
C1	0.0228 (9)	0.0250 (10)	0.0248 (10)	−0.0111 (8)	−0.0062 (7)	0.0002 (8)
C2	0.0222 (9)	0.0250 (10)	0.0279 (10)	−0.0086 (8)	−0.0081 (8)	0.0011 (8)
C3	0.0260 (10)	0.0297 (10)	0.0263 (10)	−0.0146 (8)	−0.0089 (8)	0.0019 (8)
C4	0.0226 (9)	0.0289 (10)	0.0259 (10)	−0.0138 (8)	−0.0032 (7)	−0.0036 (8)
C5	0.0236 (9)	0.0237 (10)	0.0300 (10)	−0.0104 (8)	−0.0086 (8)	0.0001 (8)
C6	0.0261 (9)	0.0264 (10)	0.0262 (10)	−0.0123 (8)	−0.0103 (8)	0.0030 (8)
C7	0.0321 (11)	0.0362 (12)	0.0266 (11)	−0.0115 (9)	−0.0097 (8)	0.0014 (9)
C8	0.0346 (12)	0.0760 (19)	0.0401 (14)	−0.0267 (12)	0.0064 (10)	−0.0185 (13)
C9	0.0298 (10)	0.0266 (11)	0.0337 (11)	−0.0083 (8)	−0.0071 (8)	0.0013 (8)
C10	0.0244 (9)	0.0300 (11)	0.0264 (10)	−0.0121 (9)	−0.0069 (8)	0.0004 (8)
C11	0.0477 (13)	0.0480 (14)	0.0236 (11)	−0.0126 (11)	−0.0083 (9)	−0.0084 (10)
C12	0.0626 (18)	0.081 (2)	0.0404 (15)	−0.0330 (16)	0.0070 (13)	−0.0083 (14)

Geometric parameters (Å, º)

O1—C7	1.415 (3)	C5—C6	1.384 (3)
O1—H1O	0.92 (3)	C5—C9	1.511 (3)
O2—C4	1.379 (2)	C6—H6	0.9500
O2—C8	1.419 (3)	C7—H7A	0.9900
O3—C9	1.423 (3)	C7—H7B	0.9900
O3—H3O	0.91 (3)	C8—H8A	0.9800
O4—C10	1.216 (2)	C8—H8B	0.9800
O5—C10	1.332 (2)	C8—H8C	0.9800
O5—C11	1.447 (3)	C9—H9A	0.9900
C1—C6	1.393 (3)	C9—H9B	0.9900
C1—C2	1.395 (3)	C11—C12	1.486 (4)
C1—C10	1.479 (3)	C11—H11A	0.9900
C2—C3	1.381 (3)	C11—H11B	0.9900
C2—H2	0.9500	C12—H12A	0.9800
C3—C4	1.396 (3)	C12—H12B	0.9800
C3—C7	1.512 (3)	C12—H12C	0.9800
C4—C5	1.395 (3)
C7—O1—H1O	105 (2)	O2—C8—H8A	109.5
C4—O2—C8	115.78 (17)	O2—C8—H8B	109.5
C9—O3—H3O	110 (2)	H8A—C8—H8B	109.5
C10—O5—C11	117.40 (16)	O2—C8—H8C	109.5
C6—C1—C2	120.16 (17)	H8A—C8—H8C	109.5
C6—C1—C10	120.83 (17)	H8B—C8—H8C	109.5
C2—C1—C10	118.96 (17)	O3—C9—C5	110.39 (17)
C3—C2—C1	120.11 (17)	O3—C9—H9A	109.6
C3—C2—H2	119.9	C5—C9—H9A	109.6
C1—C2—H2	119.9	O3—C9—H9B	109.6
C2—C3—C4	118.91 (18)	C5—C9—H9B	109.6
C2—C3—C7	121.67 (18)	H9A—C9—H9B	108.1
C4—C3—C7	119.38 (17)	O4—C10—O5	123.23 (18)
O2—C4—C5	120.26 (17)	O4—C10—C1	124.56 (18)
O2—C4—C3	117.72 (18)	O5—C10—C1	112.21 (16)
C5—C4—C3	121.82 (17)	O5—C11—C12	109.7 (2)
C6—C5—C4	118.35 (17)	O5—C11—H11A	109.7
C6—C5—C9	120.67 (18)	C12—C11—H11A	109.7
C4—C5—C9	120.96 (18)	O5—C11—H11B	109.7
C5—C6—C1	120.63 (18)	C12—C11—H11B	109.7
C5—C6—H6	119.7	H11A—C11—H11B	108.2
C1—C6—H6	119.7	C11—C12—H12A	109.5
O1—C7—C3	114.12 (17)	C11—C12—H12B	109.5
O1—C7—H7A	108.7	H12A—C12—H12B	109.5
C3—C7—H7A	108.7	C11—C12—H12C	109.5
O1—C7—H7B	108.7	H12A—C12—H12C	109.5
C3—C7—H7B	108.7	H12B—C12—H12C	109.5
H7A—C7—H7B	107.6
C6—C1—C2—C3	−1.5 (3)	C9—C5—C6—C1	178.35 (18)
C10—C1—C2—C3	176.25 (17)	C2—C1—C6—C5	1.1 (3)
C1—C2—C3—C4	0.7 (3)	C10—C1—C6—C5	−176.65 (17)
C1—C2—C3—C7	−177.19 (18)	C2—C3—C7—O1	4.6 (3)
C8—O2—C4—C5	83.8 (2)	C4—C3—C7—O1	−173.27 (18)
C8—O2—C4—C3	−101.3 (2)	C6—C5—C9—O3	−22.3 (3)
C2—C3—C4—O2	−174.23 (16)	C4—C5—C9—O3	155.81 (18)
C7—C3—C4—O2	3.7 (3)	C11—O5—C10—O4	−3.3 (3)
C2—C3—C4—C5	0.6 (3)	C11—O5—C10—C1	176.13 (17)
C7—C3—C4—C5	178.51 (18)	C6—C1—C10—O4	172.68 (19)
O2—C4—C5—C6	173.67 (17)	C2—C1—C10—O4	−5.1 (3)
C3—C4—C5—C6	−1.0 (3)	C6—C1—C10—O5	−6.7 (3)
O2—C4—C5—C9	−4.5 (3)	C2—C1—C10—O5	175.55 (17)
C3—C4—C5—C9	−179.19 (18)	C10—O5—C11—C12	−93.5 (3)
C4—C5—C6—C1	0.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O3^i	0.92 (3)	1.87 (3)	2.788 (2)	176 (3)
O3—H3O···O4^ii	0.91 (3)	1.83 (3)	2.725 (2)	167 (3)
C9—H9B···O3^iii	0.99	2.65	3.555 (3)	153

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

[5-Bromo-3-(hydroxymethyl)-2-methoxyphenyl]methanol (II)

Crystal data

C9H11BrO3	Dx = 1.715 Mg m^−3
Mr = 247.09	Melting point: 400.15 K
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
a = 13.1596 (7) Å	Cell parameters from 5411 reflections
b = 16.2514 (9) Å	θ = 2.0–27.2°
c = 4.4735 (2) Å	µ = 4.27 mm^−1
V = 956.71 (9) Å^3	T = 173 K
Z = 4	Piece, colorless
F(000) = 496	0.45 × 0.27 × 0.15 mm

Data collection

Stoe IPDS 2 diffractometer	1904 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	1647 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.074
Detector resolution: 6.67 pixels mm^-1	θmax = 26.5°, θmin = 2.5°
rotation method scans	h = −13→16
Absorption correction: integration (X-AREA; Stoe & Cie, 2002)	k = −20→17
Tmin = 0.283, Tmax = 0.564	l = −5→5
4183 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.065	w = 1/[σ^2(Fo^2) + (0.123P)^2 + 3.1968P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.190	(Δ/σ)max < 0.001
S = 1.10	Δρmax = 0.82 e Å^−3
1904 reflections	Δρmin = −1.22 e Å^−3
127 parameters	Absolute structure: Classical Flack (1983) method preferred over Parsons because s.u. lower; ??? Friedel pairs
1 restraint	Absolute structure parameter: 0.01 (5)

Special details

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. H atoms were positioned geometrically and allowed to ride on their parent atoms, C–H = 0.95-0.98 %A and Uiso(H) = 1.2-1.5 Ueq (parent atom). Hydrogen atoms bonded to O were located via electron density. Individual reflections were considered as outliers and therefore omitted.

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

	x	y	z	Uiso*/Ueq
Br1	0.47945 (7)	0.58610 (5)	0.1742 (5)	0.0274 (4)
O1	0.1690 (7)	0.6471 (6)	0.924 (2)	0.0309 (18)
O2	0.2989 (7)	0.8804 (5)	0.7961 (19)	0.0284 (18)
O3	0.5787 (7)	0.9079 (5)	0.424 (2)	0.0248 (17)
C1	0.4222 (8)	0.6800 (6)	0.371 (2)	0.019 (2)
C2	0.3384 (9)	0.6688 (7)	0.554 (3)	0.023 (2)
H2	0.3111	0.6155	0.5870	0.028*
C3	0.2954 (7)	0.7370 (6)	0.689 (4)	0.0215 (19)
C4	0.3399 (8)	0.8139 (6)	0.640 (3)	0.019 (2)
C5	0.4253 (8)	0.8240 (6)	0.462 (2)	0.021 (2)
C6	0.4652 (8)	0.7551 (7)	0.321 (3)	0.023 (2)
H6	0.5220	0.7602	0.1915	0.027*
C7	0.2037 (9)	0.7300 (8)	0.889 (3)	0.027 (2)
H7A	0.2206	0.7529	1.0878	0.032*
H7B	0.1479	0.7636	0.8040	0.032*
C8	0.2333 (12)	0.9311 (9)	0.627 (5)	0.049 (5)
H8A	0.2158	0.9801	0.7438	0.073*
H8B	0.1713	0.9005	0.5787	0.073*
H8C	0.2674	0.9477	0.4420	0.073*
C9	0.4713 (10)	0.9082 (6)	0.411 (4)	0.029 (3)
H9A	0.4498	0.9286	0.2120	0.035*
H9B	0.4447	0.9467	0.5632	0.035*
H1	0.13 (2)	0.608 (14)	0.79 (5)	0.10 (9)*
H3	0.591 (14)	0.888 (10)	0.27 (4)	0.04 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0282 (6)	0.0184 (5)	0.0357 (6)	0.0039 (3)	0.0029 (8)	−0.0012 (7)
O1	0.029 (4)	0.040 (5)	0.024 (4)	−0.012 (4)	0.008 (3)	0.004 (4)
O2	0.030 (4)	0.025 (4)	0.030 (4)	0.004 (4)	0.002 (3)	−0.011 (3)
O3	0.021 (4)	0.022 (4)	0.031 (5)	−0.003 (3)	0.003 (3)	−0.004 (3)
C1	0.014 (5)	0.020 (5)	0.022 (5)	−0.005 (4)	0.000 (4)	0.000 (4)
C2	0.029 (6)	0.022 (5)	0.020 (4)	−0.007 (4)	−0.002 (4)	0.005 (4)
C3	0.021 (4)	0.022 (4)	0.021 (5)	0.001 (3)	−0.001 (7)	−0.001 (5)
C4	0.020 (4)	0.023 (4)	0.015 (5)	0.009 (4)	0.001 (4)	−0.005 (4)
C5	0.020 (5)	0.016 (5)	0.026 (5)	0.001 (4)	−0.002 (4)	0.001 (4)
C6	0.019 (5)	0.023 (5)	0.026 (6)	0.006 (4)	0.005 (4)	0.003 (5)
C7	0.021 (5)	0.037 (6)	0.023 (6)	−0.004 (5)	0.006 (4)	0.004 (4)
C8	0.035 (7)	0.038 (6)	0.074 (15)	0.017 (6)	0.002 (8)	−0.005 (8)
C9	0.032 (8)	0.010 (5)	0.046 (8)	−0.002 (4)	0.001 (5)	0.000 (4)

Geometric parameters (Å, º)

Br1—C1	1.916 (11)	C3—C7	1.506 (16)
O1—C7	1.431 (15)	C4—C5	1.387 (15)
O1—H1	1.0 (2)	C5—C6	1.388 (15)
O2—C4	1.396 (13)	C5—C9	1.513 (14)
O2—C8	1.411 (19)	C6—H6	0.9500
O3—C9	1.415 (17)	C7—H7A	0.9900
O3—H3	0.76 (16)	C7—H7B	0.9900
C1—C6	1.364 (15)	C8—H8A	0.9800
C1—C2	1.387 (15)	C8—H8B	0.9800
C2—C3	1.382 (17)	C8—H8C	0.9800
C2—H2	0.9500	C9—H9A	0.9900
C3—C4	1.397 (14)	C9—H9B	0.9900
C7—O1—H1	132 (10)	C5—C6—H6	120.3
C4—O2—C8	114.8 (11)	O1—C7—C3	113.1 (9)
C9—O3—H3	101 (10)	O1—C7—H7A	109.0
C6—C1—C2	123.0 (10)	C3—C7—H7A	109.0
C6—C1—Br1	118.3 (8)	O1—C7—H7B	109.0
C2—C1—Br1	118.7 (8)	C3—C7—H7B	109.0
C3—C2—C1	118.6 (10)	H7A—C7—H7B	107.8
C3—C2—H2	120.7	O2—C8—H8A	109.5
C1—C2—H2	120.7	O2—C8—H8B	109.5
C2—C3—C4	118.5 (11)	H8A—C8—H8B	109.5
C2—C3—C7	121.7 (9)	O2—C8—H8C	109.5
C4—C3—C7	119.8 (10)	H8A—C8—H8C	109.5
C5—C4—O2	120.6 (9)	H8B—C8—H8C	109.5
C5—C4—C3	122.4 (9)	O3—C9—C5	113.0 (9)
O2—C4—C3	116.9 (10)	O3—C9—H9A	109.0
C4—C5—C6	118.1 (10)	C5—C9—H9A	109.0
C4—C5—C9	121.2 (10)	O3—C9—H9B	109.0
C6—C5—C9	120.6 (11)	C5—C9—H9B	109.0
C1—C6—C5	119.4 (10)	H9A—C9—H9B	107.8
C1—C6—H6	120.3
C6—C1—C2—C3	1.2 (17)	C2—C1—C6—C5	0.9 (17)
Br1—C1—C2—C3	−178.1 (10)	Br1—C1—C6—C5	−179.8 (8)
C1—C2—C3—C4	−1.6 (18)	C4—C5—C6—C1	−2.5 (17)
C1—C2—C3—C7	179.4 (11)	C9—C5—C6—C1	−179.9 (11)
C8—O2—C4—C5	83.0 (14)	C2—C3—C7—O1	0.9 (17)
C8—O2—C4—C3	−101.3 (13)	C4—C3—C7—O1	−178.1 (12)
C2—C3—C4—C5	0.0 (19)	C4—C5—C9—O3	137.6 (12)
C7—C3—C4—C5	179.0 (11)	C6—C5—C9—O3	−45.0 (17)
C2—C3—C4—O2	−175.6 (11)	C2—C3—C7—O1	0.9 (17)
C7—C3—C4—O2	3.5 (17)	C4—C3—C7—O1	−178.1 (12)
O2—C4—C5—C6	177.5 (10)	C6—C5—C9—O3	−45.0 (17)
C3—C4—C5—C6	2.1 (18)	C4—C5—C9—O3	137.6 (12)
O2—C4—C5—C9	−5.1 (17)	C3—C4—O2—C8	−101.3 (13)
C3—C4—C5—C9	179.5 (12)	C5—C4—O2—C8	83.0 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···Br1^i	0.98	3.11	3.773 (13)	126
C8—H8B···Br1^ii	0.98	3.11	3.917 (19)	140
O1—H1···O3^ii	1.0 (2)	1.8 (2)	2.687 (13)	146 (20)
O3—H3···O1^iii	0.76 (16)	1.95 (17)	2.685 (13)	160 (18)

Symmetry codes: (i) −x+1/2, y+1/2, z+1/2; (ii) x−1/2, −y+3/2, z; (iii) x+1/2, −y+3/2, z−1.

5-Bromo-1,3-bis(bromomethyl)-2-methoxybenzene (III)

Crystal data

C9H9Br3O	Dx = 2.259 Mg m^−3
Mr = 372.89	Melting point: 358.15 K
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 33.315 (4) Å	Cell parameters from 6186 reflections
b = 4.3913 (3) Å	θ = 2.5–27.1°
c = 15.9655 (17) Å	µ = 11.00 mm^−1
β = 110.142 (8)°	T = 153 K
V = 2192.9 (4) Å^3	Piece, colorless
Z = 8	0.50 × 0.11 × 0.09 mm
F(000) = 1408

Data collection

Stoe IPDS 2T diffractometer	2197 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	1834 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.087
Detector resolution: 6.67 pixels mm^-1	θmax = 26.2°, θmin = 2.6°
rotation method scans	h = −33→40
Absorption correction: integration (X-AREA; Stoe & Cie, 2002)	k = −5→4
Tmin = 0.008, Tmax = 0.076	l = −19→19
5754 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.0412P)^2 + 2.9694P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.001
2197 reflections	Δρmax = 0.63 e Å^−3
119 parameters	Δρmin = −0.60 e Å^−3

Special details

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. H atoms were positioned geometrically and allowed to ride on their parent atoms, C–H = 0.95-0.98 %A and Uiso(H) = 1.2-1.5 Ueq (parent atom).

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

	x	y	z	Uiso*/Ueq
Br1	0.47987 (2)	0.49550 (12)	0.35631 (3)	0.03202 (15)
Br2	0.29357 (2)	0.25013 (12)	0.15688 (3)	0.03636 (16)
Br3	0.42282 (2)	0.06192 (11)	0.65117 (3)	0.03003 (14)
O1	0.32003 (9)	0.0508 (7)	0.4161 (2)	0.0277 (7)
C1	0.42990 (12)	0.3516 (10)	0.3754 (3)	0.0221 (8)
C2	0.39000 (13)	0.4533 (10)	0.3190 (3)	0.0244 (9)
H2	0.3880	0.5895	0.2715	0.029*
C3	0.35315 (12)	0.3527 (10)	0.3331 (3)	0.0205 (8)
C4	0.35679 (12)	0.1583 (9)	0.4038 (3)	0.0195 (8)
C5	0.39681 (13)	0.0557 (9)	0.4607 (3)	0.0208 (8)
C6	0.43327 (12)	0.1556 (10)	0.4443 (3)	0.0199 (8)
H6	0.4607	0.0868	0.4813	0.024*
C7	0.31004 (14)	0.4628 (11)	0.2722 (3)	0.0295 (10)
H7A	0.3112	0.6848	0.2625	0.035*
H7B	0.2883	0.4250	0.3004	0.035*
C8	0.30694 (14)	0.2317 (11)	0.4772 (3)	0.0296 (10)
H8A	0.2805	0.1481	0.4817	0.044*
H8B	0.3020	0.4419	0.4555	0.044*
H8C	0.3294	0.2284	0.5361	0.044*
C9	0.40141 (14)	−0.1557 (11)	0.5363 (3)	0.0273 (9)
H9A	0.4215	−0.3212	0.5359	0.033*
H9B	0.3733	−0.2488	0.5291	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0210 (2)	0.0455 (3)	0.0322 (3)	−0.00607 (19)	0.01262 (19)	−0.0037 (2)
Br2	0.0317 (2)	0.0407 (3)	0.0278 (3)	0.0014 (2)	−0.00112 (19)	−0.0017 (2)
Br3	0.0344 (2)	0.0322 (2)	0.0236 (3)	0.00105 (19)	0.01019 (19)	0.00098 (19)
O1	0.0219 (14)	0.0262 (15)	0.0382 (18)	−0.0063 (13)	0.0143 (14)	−0.0061 (15)
C1	0.0188 (18)	0.026 (2)	0.022 (2)	−0.0070 (17)	0.0084 (16)	−0.0090 (19)
C2	0.023 (2)	0.026 (2)	0.024 (2)	−0.0003 (17)	0.0084 (17)	−0.0005 (18)
C3	0.0182 (17)	0.0199 (19)	0.022 (2)	−0.0008 (17)	0.0051 (15)	−0.0056 (18)
C4	0.0204 (18)	0.0167 (17)	0.024 (2)	−0.0038 (16)	0.0106 (16)	−0.0088 (18)
C5	0.025 (2)	0.0151 (18)	0.024 (2)	−0.0018 (16)	0.0107 (17)	−0.0072 (17)
C6	0.0143 (16)	0.025 (2)	0.0174 (18)	0.0029 (17)	0.0021 (14)	−0.0061 (18)
C7	0.023 (2)	0.030 (2)	0.030 (2)	0.0078 (19)	0.0033 (19)	0.000 (2)
C8	0.023 (2)	0.035 (3)	0.035 (2)	0.0003 (19)	0.0148 (19)	0.000 (2)
C9	0.031 (2)	0.021 (2)	0.028 (2)	−0.0012 (19)	0.0081 (18)	−0.001 (2)

Geometric parameters (Å, º)

Br1—C1	1.901 (4)	C4—C5	1.404 (6)
Br2—C7	1.966 (5)	C5—C6	1.399 (6)
Br3—C9	1.971 (4)	C5—C9	1.488 (6)
O1—C4	1.387 (5)	C6—H6	0.9500
O1—C8	1.437 (5)	C7—H7A	0.9900
C1—C6	1.370 (6)	C7—H7B	0.9900
C1—C2	1.398 (6)	C8—H8A	0.9800
C2—C3	1.394 (6)	C8—H8B	0.9800
C2—H2	0.9500	C8—H8C	0.9800
C3—C4	1.387 (6)	C9—H9A	0.9900
C3—C7	1.510 (6)	C9—H9B	0.9900
C4—O1—C8	113.4 (3)	C3—C7—Br2	110.4 (3)
C6—C1—C2	121.0 (4)	C3—C7—H7A	109.6
C6—C1—Br1	120.2 (3)	Br2—C7—H7A	109.6
C2—C1—Br1	118.8 (3)	C3—C7—H7B	109.6
C3—C2—C1	119.3 (4)	Br2—C7—H7B	109.6
C3—C2—H2	120.3	H7A—C7—H7B	108.1
C1—C2—H2	120.3	O1—C8—H8A	109.5
C4—C3—C2	119.4 (4)	O1—C8—H8B	109.5
C4—C3—C7	121.2 (4)	H8A—C8—H8B	109.5
C2—C3—C7	119.3 (4)	O1—C8—H8C	109.5
C3—C4—O1	119.3 (3)	H8A—C8—H8C	109.5
C3—C4—C5	121.4 (4)	H8B—C8—H8C	109.5
O1—C4—C5	119.2 (4)	C5—C9—Br3	110.8 (3)
C6—C5—C4	118.1 (4)	C5—C9—H9A	109.5
C6—C5—C9	119.6 (4)	Br3—C9—H9A	109.5
C4—C5—C9	122.3 (4)	C5—C9—H9B	109.5
C1—C6—C5	120.7 (4)	Br3—C9—H9B	109.5
C1—C6—H6	119.6	H9A—C9—H9B	108.1
C5—C6—H6	119.6
C6—C1—C2—C3	−0.1 (7)	O1—C4—C5—C6	176.9 (3)
Br1—C1—C2—C3	−179.1 (3)	C3—C4—C5—C9	−179.3 (4)
C1—C2—C3—C4	1.2 (6)	O1—C4—C5—C9	−2.4 (6)
C1—C2—C3—C7	180.0 (4)	C2—C1—C6—C5	−1.0 (6)
C2—C3—C4—O1	−178.0 (4)	Br1—C1—C6—C5	178.0 (3)
C7—C3—C4—O1	3.3 (6)	C4—C5—C6—C1	1.0 (6)
C2—C3—C4—C5	−1.2 (6)	C9—C5—C6—C1	−179.6 (4)
C7—C3—C4—C5	−179.9 (4)	C4—C3—C7—Br2	−105.0 (4)
C8—O1—C4—C3	−94.0 (4)	C2—C3—C7—Br2	76.3 (5)
C8—O1—C4—C5	89.1 (4)	C6—C5—C9—Br3	74.9 (4)
C3—C4—C5—C6	0.1 (6)	C4—C5—C9—Br3	−105.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Br3^i	0.95	2.99	3.863 (5)	154
C7—H7A···Br2^ii	0.99	2.94	3.866 (5)	155

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