The crystal structures of two bromo–hydroxy–benzoic acid derivatives, namely, methyl 4-bromo-2-(methoxymethoxy)benzoate, (I), and 4-bromo-3-(methoxymethoxy)benzoic acid, (II), are compared. Compound (II) crystallizes with two independent molecules in the asymmetric unit. In the crystal structures of both compounds, two-dimensional architectures are formed principally by C—H⋯O hydrogen bonds, and by Br⋯O interactions in (I) and by π–π interactions in (II).
Keywords: crystal structure, bromo hydroxy benzoic acids, C—H⋯πaryl interactions, π–π interactions, hydrogen bonding
Abstract
The title compounds, C10H11BrO4, (I), and C9H9BrO4, (II), are derivatives of bromo–hydroxy–benzoic acids. Compound (II) crystallizes with two independent molecules (A and B) in the asymmetric unit. In both (I) and (II), the O—CH2—O—CH3 side chain is not in its fully extended conformation; the O—C—O—C torsion angle is 67.3 (3) ° in (I), and −65.8 (3) and −74.1 (3)° in molecules A and B, respectively, in compound (II). In the crystal of (I), molecules are linked by C—H⋯O hydrogen bonds, forming C(5) chains along [010]. The chains are linked by short Br⋯O contacts [3.047 (2) Å], forming sheets parallel to the bc plane. The sheets are linked via C—H⋯π interactions, forming a three-dimensional architecture. In the crystal of (II), molecules A and B are linked to form R 2 2(8) dimers via two strong O—H⋯O hydrogen bonds. These dimers are linked into ⋯A–B⋯A–B⋯A–B⋯ [C 2 2(15)] chains along [011] by C—H⋯O hydrogen bonds. The chains are linked by slipped parallel π–π interactions [inter-centroid distances = 3.6787 (18) and 3.8431 (17) Å], leading to the formation of slabs parallel to the bc plane.
Chemical context
Ester derivatives of many compounds exhibit a variety of pharmacological properties, such as anticancer, antitumor and antimicrobial activities (Anadu et al., 2006 ▸; Bartzatt et al., 2004 ▸; Bi et al., 2012 ▸). Salicylic acid and derivatives of salicylic acid are of great biological importance. For example, they are known for their analgesic and anti-inflammatory activities in the treatment of rheumatoid arthritis (Anderson et al., 2014 ▸; Hardie, 2013 ▸). They are also known for their use as antibacterial and antimycobacterial agents (Silva et al., 2008 ▸). In view of the above, compounds (I) and (II) were synthesized and we report herein on their crystal structures.
Structural commentary
The molecular structure of compound (I), is illustrated in Fig. 1 ▸. The –O–CH2–O-CH3 side chain is not in its fully extended conformation, with torsion angle O3—C9—O4—C10 being 67.3 (3)°. The dihedral angle between the benzene ring and the ester segment (O1/C7/O2/C8) is 14.5 (2)°, while the plane through atoms C10/O4/C9 of the methoxymethoxy side chain is inclined to the benzene ring by 82.5 (3)°.
Figure 1.
A view of the molecular structure of compound (I), showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
The molecular structure of compound (II), is illustrated in Fig. 2 ▸. It crystallizes with two independent molecules (A and B) in the asymmetric unit. The conformations of the two molecules differ in the torsion angles of the –O–CH2–O–CH3 side chains and the orientation of the –COO– group with respect to the benzene ring, as shown in the AutoMolFit diagram (Fig. 3 ▸; Spek, 2009 ▸). The –O–CH2–O–CH3 side chains in molecules A and B are not in their fully extended conformation; torsion angle O3A—C8A—O4A—C9A in molecule A is −65.8 (3)°, and torsion angle O3B—C8B—O4B–-C9B in molecule B is −74.1 (3)°. The dihedral angle between the benzene ring and the plane through atoms C8A/O4A/C9A of the methoxymethoxy side chain in molecule A is 79.2 (3)°, while the corresponding dihedral angle in molecule B, between the benzene ring and plane C9B/O4B/O8B is 67.1 (3)°. This is less than in compound (I) and further, the dihedral angle between the benzene ring and the –COO– group is 6.6 (4)° in A and 9.1 (4)° in B; also less than observed in compound (I), viz. 14.5 (2)°.
Figure 2.
A view of the molecular structure of compound (II), showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. O—H⋯O hydrogen bonds are shown as dashed lines (see Table 2 ▸).
Figure 3.
A view of the molecular fit of molecules A (black) and B (red) of compound (II).
Supramolecular features
In the crystal of (I), molecules are linked by structure-directing C8—H8A⋯O1 hydrogen bonds (Table 1 ▸ and Fig. 4 ▸), forming C(5) chains along the b axis. Adjacent chains are linked by short Br1⋯O4i contacts [d Br⋯O = 3.047 (2) Å; symmetry code (i): −x, −y, −z + 1] leading to the formation of sheets parallel to plane (100). The sheets are linked by C5—H5⋯π interactions (centroid of the benzene ring C1–C6) along the a-axis direction, forming a three-dimensional structure (Table 1 ▸ and Fig. 5 ▸).
Table 1. Hydrogen-bond geometry (Å, °) for (I) .
Cg1 is the centroid of the C1–C6 benzene ring.
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C8—H8A⋯O1i | 0.98 | 2.58 | 3.439 (5) | 147 |
| C5—H5⋯Cg1ii | 0.95 | 2.95 | 3.765 (4) | 129 |
Symmetry codes: (i) 
; (ii) 
.
Figure 4.
A view along the a axis of the crystal packing of compound (I). C—H⋯O and Br⋯O interactions are shown as dashed lines (see Table 1 ▸). H atoms not involved in these interactions have been omitted for clarity.
Figure 5.
A view along the b axis of the crystal packing of compound (I). C—H⋯O and Br⋯O interactions are shown as dashed lines (see Table 1 ▸). H atoms not involved in these interactions have been omitted for clarity.
In the crystal of (II), molecules A and B are linked via two strong O—H⋯O hydrogen bonds, namely, O2A–-H2A⋯O1B and O2B–-H2B⋯O1A, forming dimers with an 
(8) ring motif (Table 2 ▸ and Fig. 6 ▸). Adjacent dimers are linked by C8B—H8B2⋯·O3A hydrogen bonds (Table 2 ▸), forming chains along [011]. The chains are linked via slipped parallel π–π interactions between B molecules [Cg2⋯Cg2ii distance = 3.6792 (18) Å; Cg2 is the centroid of ring C1B–C6B; inter-planar distance = 3.3691 (12) Å; slippage = 1.477 Å; symmetry code (ii): −x, −y + 2, −z + 1], and between A and B molecules [Cg1⋯Cg2iii = 3.8431 (17) Å; Cg1 is the centroid of the ring C1A–C6A; inter-planar distance = 3.5538 (12) Å; slippage 1.98 Å; symmetry code (iii): −x + 1, −y + 1, −z + 1], thus forming slabs lying parallel to the bc plane (Fig. 7 ▸).
Table 2. Hydrogen-bond geometry (Å, °) for (II) .
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O2A—H2A⋯O1B | 0.84 (5) | 1.80 (5) | 2.635 (4) | 178 (5) |
| O2B—H2B⋯O1A | 0.82 (5) | 1.81 (5) | 2.621 (4) | 167 (5) |
| C8B—H8B2⋯O3A i | 0.99 | 2.52 | 3.420 (4) | 150 |
Symmetry code: (i) 
.
Figure 6.
A partial view along the a axis of the crystal packing of compound (II). O—H⋯O and C—-H⋯O hydrogen bonds are shown as dashed lines (see Table 2 ▸). H atoms not involved in these interactions have been omitted for clarity.
Figure 7.
A view of the π–π stacking observed in the crystal of (II); molecule A green, molecule B blue.
Synthesis and crystallization
Synthesis of methyl 4-bromo-2-(methoxymethoxy) benzoate (I)
To a stirred solution of methyl 4-bromo-2-hydroxy-benzoate (1.0 g, 4.32 mmol) in dichloromethane (15 ml) (DCM) was added N,N-diisopropylethylamine (1.5 ml, 8.65 mmol) (DIPEA), followed by chloromethyl methyl ether (0.49 ml, 6.49 mmol) (MOM-Cl), at 273 K and the reaction mixture was stirred at room temperature overnight. The reaction mixture was then diluted with water (50 ml) and the organic layer was extracted with ethyl acetate (2 × 50 ml). The combined organic layers were washed successively with water, brine, dried over anhydrous magnesium sulfate (MgSO4), filtered and the filtrate was concentrated under reduced pressure. The crude product was purified by column chromatography using ethyl acetate:hexane (1:9) as eluent to afford (I) as an off-white coloured solid (yield: 0.851g, 71.4%; m.p.: 353 K). 1H NMR (DMSO-d 6, 400 MHz, p.p.m.): δ = 3.39 (3H, s), 3.79 (3H, s), 5.29 (2H, s) 7.29 (1H, dd, J = 1.20 Hz, 1.20 Hz), 7.44 (1H, s), 7.60 (1H, d, J = 8.00 Hz).
Synthesis of 4-bromo-3-(methoxymethoxy)benzoic acid (II)
A mixture of methyl 4-bromo-3-(methoxymethoxy) benzoate (1 g, 3.63 mmol), 10% aqueous potassium hydroxide (0.61 g, 3.0 mmol), tetrahydrofuran (5 ml) and methanol (20 ml) was stirred at room temperature for 2 h. The mixture was then concentrated to remove organic solvents and the aqueous layer was acidified with 6 N hydrochloric acid. The precipitated solid was filtered, dried under vacuum to afford (II) as a white solid (yield: 0.86g, 91%; m.p.: 433 K). 1H NMR (DMSO-d 6, 400 MHz, p.p.m.): δ = 3.39 (3H, s), 5.28 (2H, s), 7.26 (1H, dd, J = 1.20 Hz, 1.20 Hz), 7.40 (1H, s), 7.59 (1H, d, J = 8.00 Hz), 12.90 (1H, s).
Single crystals of compounds (I) and (II), suitable for X-ray diffraction studies, were obtained by solvent evaporation using methanol:chloroform (2:1) as the solvent mixture.
Refinement details
Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. The H atoms of the OH groups in (II) were located in a difference Fourier map and refined with a distance restraint: O—H = 0.84 (5) Å. The C-bound H atoms in (I) and (II) were positioned with idealized geometry and refined using a riding model: C—H = 0.95–0.99 Å, with U iso(H) = 1.5U eq(C-methyl) and 1.2U eq(C) for other H atoms. In the final cycles of refinement reflection (0 0 2) in (I) and reflections (4 1 0), (6 − 4 6), (5 − 5 7), (4 2 0) and (0 − 1 6) in (II) were omitted due to large differences in F 2 obs and F 2 calc, considerably improving the values of R1, wR2, and GOF.
Table 3. Experimental details.
| (I) | (II) | |
|---|---|---|
| Crystal data | ||
| Chemical formula | C10H11BrO4 | C9H9BrO4 |
| M r | 275.10 | 261.07 |
| Crystal system, space group | Orthorhombic, P b c a | Triclinic, P
|
| Temperature (K) | 173 | 173 |
| a, b, c (Å) | 8.8487 (13), 8.1514 (11), 29.284 (4) | 7.7211 (3), 9.6881 (4), 14.2627 (6) |
| α, β, γ (°) | 90, 90, 90 | 73.635 (1), 77.664 (1), 69.577 (1) |
| V (Å3) | 2112.2 (5) | 951.40 (7) |
| Z | 8 | 4 |
| Radiation type | Cu Kα | Cu Kα |
| μ (mm−1) | 5.27 | 5.82 |
| Crystal size (mm) | 0.29 × 0.22 × 0.19 | 0.28 × 0.25 × 0.22 |
| Data collection | ||
| Diffractometer | Bruker APEXII | Bruker APEXII |
| Absorption correction | Multi-scan (SADABS; Bruker, 2009 ▸) | Multi-scan (SADABS; Bruker, 2009 ▸) |
| T min, T max | 0.286, 0.367 | 0.245, 0.278 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 8999, 1751, 1720 | 11112, 3031, 2930 |
| R int | 0.052 | 0.040 |
| (sin θ/λ)max (Å−1) | 0.590 | 0.585 |
| Refinement | ||
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.052, 0.139, 1.14 | 0.039, 0.120, 1.09 |
| No. of reflections | 1751 | 3031 |
| No. of parameters | 138 | 261 |
| No. of restraints | 0 | 2 |
| H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 1.87, −0.97 | 0.67, −1.08 |
Supplementary Material
Crystal structure: contains datablock(s) I, II, Global. DOI: 10.1107/S2056989016003777/su5284sup1.cif
Supporting information file. DOI: 10.1107/S2056989016003777/su5284Isup2.cml
Supporting information file. DOI: 10.1107/S2056989016003777/su5284IIsup3.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors are grateful to the Institution of Excellence, Vijnana Bhavana, University of Mysore, Mysore, for providing the single-crystal X-ray diffraction data.
supplementary crystallographic information
Crystal data
| C9H9BrO4 | Z = 4 |
| Mr = 261.07 | F(000) = 520 |
| Triclinic, P1 | Dx = 1.823 Mg m−3 |
| Hall symbol: -P 1 | Melting point: 433 K |
| a = 7.7211 (3) Å | Cu Kα radiation, λ = 1.54178 Å |
| b = 9.6881 (4) Å | Cell parameters from 123 reflections |
| c = 14.2627 (6) Å | θ = 3.3–64.4° |
| α = 73.635 (1)° | µ = 5.82 mm−1 |
| β = 77.664 (1)° | T = 173 K |
| γ = 69.577 (1)° | Prism, colourless |
| V = 951.40 (7) Å3 | 0.28 × 0.25 × 0.22 mm |
Data collection
| Bruker APEXII diffractometer | 3031 independent reflections |
| Radiation source: fine-focus sealed tube | 2930 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.040 |
| phi and φ scans | θmax = 64.4°, θmin = 3.3° |
| Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −8→8 |
| Tmin = 0.245, Tmax = 0.278 | k = −11→11 |
| 11112 measured reflections | l = −15→16 |
Refinement
| 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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.09 | w = 1/[σ2(Fo2) + (0.0844P)2 + 0.9411P] where P = (Fo2 + 2Fc2)/3 |
| 3031 reflections | (Δ/σ)max = 0.001 |
| 261 parameters | Δρmax = 0.67 e Å−3 |
| 2 restraints | Δρmin = −1.08 e Å−3 |
Special details
| Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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)
| x | y | z | Uiso*/Ueq | ||
| Br1B | −0.40349 (5) | 1.06722 (4) | 0.30367 (2) | 0.01682 (17) | |
| Br1A | 1.35506 (5) | 0.17904 (4) | 0.90000 (2) | 0.01972 (17) | |
| O3B | −0.0105 (3) | 1.0670 (3) | 0.23290 (16) | 0.0159 (5) | |
| O3A | 0.9612 (3) | 0.1908 (2) | 0.96819 (15) | 0.0164 (5) | |
| O4B | 0.2558 (3) | 1.1441 (2) | 0.20751 (16) | 0.0204 (5) | |
| O4A | 0.6543 (3) | 0.3227 (3) | 1.02268 (16) | 0.0223 (5) | |
| O1A | 0.5360 (3) | 0.4837 (3) | 0.70491 (16) | 0.0210 (5) | |
| O2A | 0.7281 (3) | 0.5390 (3) | 0.56876 (16) | 0.0184 (5) | |
| O1B | 0.4376 (3) | 0.7142 (3) | 0.47778 (18) | 0.0219 (5) | |
| O2B | 0.2466 (4) | 0.6594 (3) | 0.61509 (17) | 0.0220 (5) | |
| C4A | 0.8598 (4) | 0.3942 (3) | 0.7147 (2) | 0.0113 (6) | |
| C7B | 0.2753 (5) | 0.7246 (3) | 0.5251 (2) | 0.0141 (6) | |
| C4B | 0.1108 (5) | 0.8140 (3) | 0.4734 (2) | 0.0138 (7) | |
| C2A | 0.9761 (5) | 0.2599 (3) | 0.8698 (2) | 0.0135 (6) | |
| C7A | 0.6971 (5) | 0.4759 (3) | 0.6597 (2) | 0.0125 (6) | |
| C5A | 1.0392 (5) | 0.3920 (3) | 0.6689 (2) | 0.0150 (7) | |
| H5A | 1.0601 | 0.4358 | 0.6006 | 0.018* | |
| C3A | 0.8282 (5) | 0.3270 (3) | 0.8147 (2) | 0.0134 (6) | |
| H3A | 0.7058 | 0.3274 | 0.8447 | 0.016* | |
| C3B | 0.1349 (5) | 0.9014 (3) | 0.3777 (2) | 0.0127 (6) | |
| H3B | 0.2555 | 0.9065 | 0.3476 | 0.015* | |
| C2B | −0.0179 (5) | 0.9803 (3) | 0.3272 (2) | 0.0133 (7) | |
| C5B | −0.0660 (5) | 0.8083 (3) | 0.5191 (2) | 0.0153 (7) | |
| H5B | −0.0822 | 0.7511 | 0.5846 | 0.018* | |
| C6B | −0.2167 (5) | 0.8863 (3) | 0.4684 (2) | 0.0153 (7) | |
| H6B | −0.3375 | 0.8823 | 0.4987 | 0.018* | |
| C1B | −0.1937 (5) | 0.9706 (3) | 0.3735 (2) | 0.0148 (7) | |
| C6A | 1.1867 (5) | 0.3251 (3) | 0.7243 (2) | 0.0155 (7) | |
| H6A | 1.3099 | 0.3221 | 0.6942 | 0.019* | |
| C9A | 0.7006 (6) | 0.3967 (4) | 1.0828 (3) | 0.0285 (8) | |
| H9A1 | 0.7188 | 0.3296 | 1.1481 | 0.043* | |
| H9A2 | 0.5993 | 0.4899 | 1.0894 | 0.043* | |
| H9A3 | 0.8157 | 0.4213 | 1.0522 | 0.043* | |
| C8A | 0.7818 (5) | 0.1825 (4) | 1.0171 (2) | 0.0174 (7) | |
| H8A1 | 0.7332 | 0.1324 | 0.9816 | 0.021* | |
| H8A2 | 0.7952 | 0.1192 | 1.0847 | 0.021* | |
| C8B | 0.1691 (5) | 1.0616 (4) | 0.1787 (2) | 0.0154 (7) | |
| H8B1 | 0.2491 | 0.9549 | 0.1876 | 0.018* | |
| H8B2 | 0.1561 | 1.1016 | 0.1077 | 0.018* | |
| C1A | 1.1533 (5) | 0.2628 (3) | 0.8237 (2) | 0.0155 (7) | |
| C9B | 0.1791 (6) | 1.3037 (4) | 0.1746 (3) | 0.0292 (8) | |
| H9B1 | 0.1718 | 1.3290 | 0.1037 | 0.044* | |
| H9B2 | 0.2588 | 1.3541 | 0.1875 | 0.044* | |
| H9B3 | 0.0539 | 1.3378 | 0.2100 | 0.044* | |
| H2A | 0.634 (6) | 0.593 (5) | 0.541 (3) | 0.035* | |
| H2B | 0.330 (6) | 0.612 (5) | 0.650 (3) | 0.035* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1B | 0.0115 (3) | 0.0212 (2) | 0.0153 (2) | −0.00265 (17) | −0.00350 (16) | −0.00218 (16) |
| Br1A | 0.0121 (3) | 0.0260 (2) | 0.0181 (2) | −0.00483 (17) | −0.00408 (16) | −0.00011 (16) |
| O3B | 0.0121 (12) | 0.0222 (11) | 0.0109 (11) | −0.0052 (10) | −0.0023 (9) | 0.0005 (9) |
| O3A | 0.0138 (12) | 0.0219 (12) | 0.0085 (10) | −0.0029 (10) | −0.0007 (9) | 0.0005 (9) |
| O4B | 0.0222 (13) | 0.0189 (11) | 0.0203 (12) | −0.0083 (10) | −0.0063 (9) | 0.0003 (9) |
| O4A | 0.0164 (13) | 0.0267 (12) | 0.0164 (11) | 0.0021 (10) | −0.0016 (9) | −0.0052 (9) |
| O1A | 0.0144 (14) | 0.0289 (12) | 0.0159 (11) | −0.0062 (11) | −0.0022 (9) | 0.0004 (9) |
| O2A | 0.0200 (13) | 0.0212 (11) | 0.0105 (11) | −0.0058 (10) | −0.0034 (9) | 0.0023 (9) |
| O1B | 0.0158 (13) | 0.0243 (12) | 0.0233 (12) | −0.0044 (10) | −0.0052 (10) | −0.0018 (10) |
| O2B | 0.0237 (14) | 0.0244 (12) | 0.0149 (12) | −0.0091 (11) | −0.0088 (10) | 0.0067 (9) |
| C4A | 0.0135 (17) | 0.0104 (13) | 0.0110 (14) | −0.0045 (12) | −0.0002 (12) | −0.0042 (11) |
| C7B | 0.0193 (18) | 0.0122 (14) | 0.0120 (15) | −0.0055 (13) | −0.0022 (12) | −0.0036 (11) |
| C4B | 0.0182 (18) | 0.0120 (14) | 0.0125 (15) | −0.0053 (13) | −0.0016 (12) | −0.0042 (11) |
| C2A | 0.0177 (18) | 0.0124 (14) | 0.0092 (15) | −0.0037 (13) | −0.0008 (12) | −0.0022 (12) |
| C7A | 0.0156 (17) | 0.0110 (14) | 0.0125 (15) | −0.0046 (12) | −0.0007 (12) | −0.0053 (11) |
| C5A | 0.0194 (18) | 0.0115 (14) | 0.0113 (14) | −0.0028 (13) | 0.0009 (12) | −0.0027 (11) |
| C3A | 0.0137 (17) | 0.0145 (14) | 0.0130 (15) | −0.0063 (13) | −0.0002 (12) | −0.0032 (12) |
| C3B | 0.0108 (16) | 0.0137 (14) | 0.0137 (15) | −0.0039 (12) | −0.0006 (12) | −0.0038 (12) |
| C2B | 0.0173 (18) | 0.0143 (14) | 0.0096 (15) | −0.0066 (13) | −0.0016 (12) | −0.0025 (11) |
| C5B | 0.0214 (18) | 0.0152 (14) | 0.0102 (14) | −0.0073 (13) | −0.0012 (12) | −0.0025 (11) |
| C6B | 0.0153 (18) | 0.0180 (15) | 0.0151 (15) | −0.0067 (13) | 0.0005 (12) | −0.0073 (12) |
| C1B | 0.0169 (18) | 0.0116 (14) | 0.0166 (16) | −0.0022 (13) | −0.0034 (13) | −0.0061 (12) |
| C6A | 0.0147 (18) | 0.0166 (15) | 0.0161 (15) | −0.0076 (13) | 0.0015 (13) | −0.0044 (12) |
| C9A | 0.033 (2) | 0.0260 (18) | 0.0227 (18) | −0.0002 (16) | −0.0086 (15) | −0.0083 (14) |
| C8A | 0.0133 (18) | 0.0233 (16) | 0.0134 (15) | −0.0059 (14) | −0.0005 (12) | −0.0013 (12) |
| C8B | 0.0127 (17) | 0.0217 (16) | 0.0125 (15) | −0.0066 (13) | −0.0011 (12) | −0.0038 (12) |
| C1A | 0.0160 (18) | 0.0133 (14) | 0.0158 (16) | −0.0020 (13) | −0.0020 (13) | −0.0041 (12) |
| C9B | 0.037 (2) | 0.0185 (16) | 0.033 (2) | −0.0084 (16) | −0.0077 (16) | −0.0052 (14) |
Geometric parameters (Å, º)
| Br1B—C1B | 1.897 (3) | C2A—C1A | 1.391 (5) |
| Br1A—C1A | 1.901 (3) | C5A—C6A | 1.387 (5) |
| O3B—C2B | 1.371 (4) | C5A—H5A | 0.9500 |
| O3B—C8B | 1.428 (4) | C3A—H3A | 0.9500 |
| O3A—C2A | 1.374 (4) | C3B—C2B | 1.385 (5) |
| O3A—C8A | 1.430 (4) | C3B—H3B | 0.9500 |
| O4B—C8B | 1.390 (4) | C2B—C1B | 1.400 (5) |
| O4B—C9B | 1.426 (4) | C5B—C6B | 1.373 (5) |
| O4A—C8A | 1.383 (4) | C5B—H5B | 0.9500 |
| O4A—C9A | 1.426 (4) | C6B—C1B | 1.380 (5) |
| O1A—C7A | 1.260 (4) | C6B—H6B | 0.9500 |
| O2A—C7A | 1.279 (4) | C6A—C1A | 1.383 (5) |
| O2A—H2A | 0.83 (3) | C6A—H6A | 0.9500 |
| O1B—C7B | 1.275 (4) | C9A—H9A1 | 0.9800 |
| O2B—C7B | 1.271 (4) | C9A—H9A2 | 0.9800 |
| O2B—H2B | 0.82 (3) | C9A—H9A3 | 0.9800 |
| C4A—C5A | 1.395 (5) | C8A—H8A1 | 0.9900 |
| C4A—C3A | 1.398 (4) | C8A—H8A2 | 0.9900 |
| C4A—C7A | 1.482 (5) | C8B—H8B1 | 0.9900 |
| C7B—C4B | 1.476 (5) | C8B—H8B2 | 0.9900 |
| C4B—C5B | 1.394 (5) | C9B—H9B1 | 0.9800 |
| C4B—C3B | 1.402 (4) | C9B—H9B2 | 0.9800 |
| C2A—C3A | 1.386 (5) | C9B—H9B3 | 0.9800 |
| C2B—O3B—C8B | 117.7 (2) | C5B—C6B—C1B | 120.4 (3) |
| C2A—O3A—C8A | 118.1 (2) | C5B—C6B—H6B | 119.8 |
| C8B—O4B—C9B | 113.7 (3) | C1B—C6B—H6B | 119.8 |
| C8A—O4A—C9A | 113.3 (3) | C6B—C1B—C2B | 121.2 (3) |
| C7A—O2A—H2A | 116 (3) | C6B—C1B—Br1B | 118.9 (3) |
| C7B—O2B—H2B | 124 (4) | C2B—C1B—Br1B | 119.9 (2) |
| C5A—C4A—C3A | 120.9 (3) | C1A—C6A—C5A | 119.5 (3) |
| C5A—C4A—C7A | 120.5 (3) | C1A—C6A—H6A | 120.2 |
| C3A—C4A—C7A | 118.5 (3) | C5A—C6A—H6A | 120.2 |
| O2B—C7B—O1B | 123.3 (3) | O4A—C9A—H9A1 | 109.5 |
| O2B—C7B—C4B | 117.5 (3) | O4A—C9A—H9A2 | 109.5 |
| O1B—C7B—C4B | 119.1 (3) | H9A1—C9A—H9A2 | 109.5 |
| C5B—C4B—C3B | 120.6 (3) | O4A—C9A—H9A3 | 109.5 |
| C5B—C4B—C7B | 119.9 (3) | H9A1—C9A—H9A3 | 109.5 |
| C3B—C4B—C7B | 119.4 (3) | H9A2—C9A—H9A3 | 109.5 |
| O3A—C2A—C3A | 124.7 (3) | O4A—C8A—O3A | 113.1 (3) |
| O3A—C2A—C1A | 116.6 (3) | O4A—C8A—H8A1 | 109.0 |
| C3A—C2A—C1A | 118.6 (3) | O3A—C8A—H8A1 | 109.0 |
| O1A—C7A—O2A | 123.3 (3) | O4A—C8A—H8A2 | 109.0 |
| O1A—C7A—C4A | 118.9 (3) | O3A—C8A—H8A2 | 109.0 |
| O2A—C7A—C4A | 117.8 (3) | H8A1—C8A—H8A2 | 107.8 |
| C6A—C5A—C4A | 119.2 (3) | O4B—C8B—O3B | 113.0 (3) |
| C6A—C5A—H5A | 120.4 | O4B—C8B—H8B1 | 109.0 |
| C4A—C5A—H5A | 120.4 | O3B—C8B—H8B1 | 109.0 |
| C2A—C3A—C4A | 119.8 (3) | O4B—C8B—H8B2 | 109.0 |
| C2A—C3A—H3A | 120.1 | O3B—C8B—H8B2 | 109.0 |
| C4A—C3A—H3A | 120.1 | H8B1—C8B—H8B2 | 107.8 |
| C2B—C3B—C4B | 119.7 (3) | C6A—C1A—C2A | 122.0 (3) |
| C2B—C3B—H3B | 120.1 | C6A—C1A—Br1A | 119.1 (3) |
| C4B—C3B—H3B | 120.1 | C2A—C1A—Br1A | 119.0 (2) |
| O3B—C2B—C3B | 124.8 (3) | O4B—C9B—H9B1 | 109.5 |
| O3B—C2B—C1B | 116.4 (3) | O4B—C9B—H9B2 | 109.5 |
| C3B—C2B—C1B | 118.8 (3) | H9B1—C9B—H9B2 | 109.5 |
| C6B—C5B—C4B | 119.3 (3) | O4B—C9B—H9B3 | 109.5 |
| C6B—C5B—H5B | 120.4 | H9B1—C9B—H9B3 | 109.5 |
| C4B—C5B—H5B | 120.4 | H9B2—C9B—H9B3 | 109.5 |
| O2B—C7B—C4B—C5B | −8.5 (4) | C4B—C3B—C2B—C1B | 0.0 (4) |
| O1B—C7B—C4B—C5B | 170.4 (3) | C3B—C4B—C5B—C6B | 1.7 (4) |
| O2B—C7B—C4B—C3B | 172.9 (3) | C7B—C4B—C5B—C6B | −176.9 (3) |
| O1B—C7B—C4B—C3B | −8.3 (4) | C4B—C5B—C6B—C1B | −0.6 (4) |
| C8A—O3A—C2A—C3A | 2.2 (4) | C5B—C6B—C1B—C2B | −0.8 (4) |
| C8A—O3A—C2A—C1A | −178.5 (3) | C5B—C6B—C1B—Br1B | 176.5 (2) |
| C5A—C4A—C7A—O1A | −175.6 (3) | O3B—C2B—C1B—C6B | 180.0 (3) |
| C3A—C4A—C7A—O1A | 0.8 (4) | C3B—C2B—C1B—C6B | 1.1 (4) |
| C5A—C4A—C7A—O2A | 2.4 (4) | O3B—C2B—C1B—Br1B | 2.7 (4) |
| C3A—C4A—C7A—O2A | 178.9 (3) | C3B—C2B—C1B—Br1B | −176.2 (2) |
| C3A—C4A—C5A—C6A | −1.5 (4) | C4A—C5A—C6A—C1A | −0.4 (4) |
| C7A—C4A—C5A—C6A | 174.8 (3) | C9A—O4A—C8A—O3A | −65.8 (3) |
| O3A—C2A—C3A—C4A | −180.0 (3) | C2A—O3A—C8A—O4A | −65.6 (3) |
| C1A—C2A—C3A—C4A | 0.7 (4) | C9B—O4B—C8B—O3B | −74.1 (3) |
| C5A—C4A—C3A—C2A | 1.3 (4) | C2B—O3B—C8B—O4B | −76.2 (3) |
| C7A—C4A—C3A—C2A | −175.1 (3) | C5A—C6A—C1A—C2A | 2.5 (4) |
| C5B—C4B—C3B—C2B | −1.4 (4) | C5A—C6A—C1A—Br1A | −177.4 (2) |
| C7B—C4B—C3B—C2B | 177.2 (3) | O3A—C2A—C1A—C6A | 178.0 (3) |
| C8B—O3B—C2B—C3B | 7.7 (4) | C3A—C2A—C1A—C6A | −2.6 (4) |
| C8B—O3B—C2B—C1B | −171.1 (3) | O3A—C2A—C1A—Br1A | −2.2 (4) |
| C4B—C3B—C2B—O3B | −178.8 (3) | C3A—C2A—C1A—Br1A | 177.2 (2) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2A—H2A···O1B | 0.84 (5) | 1.80 (5) | 2.635 (4) | 178 (5) |
| O2B—H2B···O1A | 0.82 (5) | 1.81 (5) | 2.621 (4) | 167 (5) |
| C8B—H8B2···O3Ai | 0.99 | 2.52 | 3.420 (4) | 150 |
Symmetry code: (i) x−1, y+1, z−1.
References
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I, II, Global. DOI: 10.1107/S2056989016003777/su5284sup1.cif
Supporting information file. DOI: 10.1107/S2056989016003777/su5284Isup2.cml
Supporting information file. DOI: 10.1107/S2056989016003777/su5284IIsup3.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report