Hydrogen and halogen bonding in the haloetherification products in chalcone

Cooperative action of hydrogen and halogen bonding in the reaction of 3-(3,5-di-tert-butyl-4-hy­droxy­phen­yl)-1-phenyl­prop-2-en-1-one with HCl or HBr in alcohol medium under microwave irradiation (20 W, 80 °C, 10 min) allows the isolation of the haloetherification products (2S,3S)-3-(3-tert-butyl-5-chloro-4-hy­droxy­phen­yl)-2-chloro-3-eth­oxy-1-phenyl­propan-1-one, C₂₁H₂₄Cl₂O₃, (2S,3S)-2-bromo-3-(3-tert-butyl-5-bromo-4-hy­droxy­phen­yl)-3-meth­oxy-1-phenyl­propan-1-one, C₂₀H₂₂Br₂O₃, and (2S,3S)-2-bromo-3-(3-tert-butyl-5-bromo-4-hy­droxy­phen­yl)-3-eth­oxy-1-phenyl­propan-1-one, C₂₁H₂₄Br₂O₃, in good yields. Both types of noncovalent interactions, e.g. hydrogen and halogen bonds, are formed to stabilize the obtained products in the solid state.

Computing details

For all structures, data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

3-(3-tert-Butyl-5-chloro-4-hydroxyphenyl)-2-chloro-3-ethoxy-1-phenylpropan-1-one (2)

Crystal data

C21H24Cl2O3	F(000) = 832
Mr = 395.30	Dx = 1.271 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.4460 (13) Å	Cell parameters from 4304 reflections
b = 19.783 (3) Å	θ = 2.4–25.9°
c = 11.0766 (15) Å	µ = 0.33 mm^−1
β = 93.821 (3)°	T = 296 K
V = 2065.2 (5) Å^3	Prism, colorless
Z = 4	0.22 × 0.18 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer	2932 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.025
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 26.0°, θmin = 2.1°
Tmin = 0.926, Tmax = 0.940	h = −9→11
15808 measured reflections	k = −24→24
4061 independent reflections	l = −13→13

Refinement

Refinement on F^2	87 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.159	w = 1/[σ^2(Fo^2) + (0.0767P)^2 + 0.9719P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
4061 reflections	Δρmax = 0.59 e Å^−3
257 parameters	Δρmin = −0.52 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. The C16 and C17 atoms of the ethyl fragment are disordered over two position. The disorder was modeled and refined including alternative positions with relative occupancies of 0.53 (4):0.47 (4).

Moreover, in compound 2, the RIGU routine (Sheldrick, 2015) in SHELXTL-97 program (Sheldrick, 2015) was applied to remove diffuse electron density caused by badly disordered tetrasbusbtituted phenyl ring.

The X-ray diffraction patterns of 2–4 were collected using a Bruker SMART APEXII CCD area detector equipped with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at room temperature. Absorption correction was applied by SADABS (Bruker, 2016). The structure was solved by direct methods and refined on F² by full-matrix least-squares using Bruker SHELXTL97 (Sheldrick, 2015), operating within the OLEX2 program (Dolomanov et al., 2009). All non-H atoms were refined anisotropically. The details of the crystallographic data are summarized in Table 1. Crystallographic data for the structural analysis have been deposited to the Cambridge Crystallographic Data Center (CCDC 1523181–1523183 for 2–4). Copy of this information can be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: [phone]; E-mail: [e-mail] or www.ccdc.cam.ac.uk/data_request/cif). ORTEP views were drawn using OLEX2 software (Dolomanov et al., 2009).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.24488 (10)	0.87305 (6)	0.63611 (8)	0.0963 (4)
Cl2	0.38524 (8)	0.66698 (3)	0.25768 (7)	0.0682 (3)
O1	0.5186 (3)	0.96553 (11)	0.71645 (19)	0.0900 (8)
O2	0.19073 (19)	0.75530 (9)	0.11081 (16)	0.0606 (5)
H2	0.208465	0.713680	0.100376	0.091*
O3	0.6277 (2)	0.87499 (9)	0.51819 (15)	0.0588 (5)
C1	0.5284 (3)	0.87510 (14)	0.8534 (2)	0.0535 (6)
C2	0.5174 (3)	0.80689 (17)	0.8749 (3)	0.0697 (8)
H2A	0.487106	0.777887	0.812350	0.084*
C3	0.5513 (4)	0.7813 (2)	0.9896 (3)	0.0897 (11)
H3	0.545243	0.735103	1.003683	0.108*
C4	0.5934 (4)	0.8237 (3)	1.0813 (3)	0.0956 (13)
H4	0.615053	0.806347	1.158340	0.115*
C5	0.6043 (4)	0.8911 (3)	1.0621 (3)	0.0896 (11)
H5	0.632819	0.919698	1.125738	0.107*
C6	0.5730 (3)	0.91718 (18)	0.9483 (2)	0.0703 (8)
H6	0.581957	0.963357	0.934989	0.084*
C7	0.4973 (3)	0.90655 (14)	0.7334 (2)	0.0582 (7)
C8	0.4311 (3)	0.86385 (14)	0.6290 (2)	0.0562 (7)
H8	0.457265	0.816331	0.641878	0.067*
C9	0.4790 (3)	0.88716 (13)	0.5073 (2)	0.0522 (6)
H9	0.462327	0.935881	0.498950	0.063*
C10	0.4049 (3)	0.85116 (12)	0.4009 (2)	0.0493 (5)
C11	0.3101 (3)	0.88559 (13)	0.3229 (2)	0.0497 (5)
H11	0.295200	0.931307	0.336924	0.060*
C12	0.2362 (3)	0.85555 (13)	0.2249 (2)	0.0521 (4)
C13	0.2610 (3)	0.78690 (12)	0.2057 (2)	0.0466 (5)
C14	0.3566 (3)	0.75237 (13)	0.2839 (2)	0.0482 (5)
C15	0.4285 (3)	0.78350 (12)	0.3806 (2)	0.0499 (5)
H15	0.492111	0.759246	0.431507	0.060*
C16	0.7039 (14)	0.9057 (9)	0.4296 (9)	0.079 (5)	0.53 (4)
H16A	0.650841	0.944408	0.397525	0.095*	0.53 (4)
H16B	0.712965	0.873976	0.363758	0.095*	0.53 (4)
C17	0.8426 (17)	0.9275 (10)	0.4734 (14)	0.109 (5)	0.53 (4)
H17A	0.889649	0.948113	0.408543	0.164*	0.53 (4)
H17B	0.834522	0.959732	0.537319	0.164*	0.53 (4)
H17C	0.896680	0.889261	0.503533	0.164*	0.53 (4)
C17'	0.848 (3)	0.908 (2)	0.449 (3)	0.205 (14)	0.47 (4)
H17D	0.895678	0.936845	0.395758	0.308*	0.47 (4)
H17E	0.882200	0.916356	0.531228	0.308*	0.47 (4)
H17F	0.866444	0.861366	0.429311	0.308*	0.47 (4)
C16'	0.707 (2)	0.9194 (12)	0.437 (2)	0.120 (9)	0.47 (4)
H16C	0.672903	0.911328	0.353322	0.144*	0.47 (4)
H16D	0.688673	0.966371	0.455337	0.144*	0.47 (4)
C18	0.1320 (3)	0.89641 (14)	0.1377 (2)	0.0580 (4)
C19	0.1224 (3)	0.96988 (14)	0.1807 (3)	0.0657 (5)
H19A	0.091715	0.970664	0.261619	0.099*
H19B	0.055502	0.994094	0.127917	0.099*
H19C	0.213944	0.990844	0.179599	0.099*
C20	−0.0161 (3)	0.86616 (16)	0.1369 (3)	0.0688 (6)
H20A	−0.080473	0.892837	0.085884	0.103*
H20B	−0.046896	0.865820	0.217740	0.103*
H20C	−0.014373	0.820736	0.106533	0.103*
C21	0.1862 (3)	0.89659 (17)	0.0118 (2)	0.0689 (6)
H21A	0.119196	0.919435	−0.042989	0.103*
H21B	0.197870	0.850881	−0.014878	0.103*
H21C	0.275806	0.919583	0.013585	0.103*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0675 (6)	0.1426 (9)	0.0784 (6)	−0.0109 (5)	0.0009 (4)	−0.0293 (5)
Cl2	0.0785 (5)	0.0533 (4)	0.0699 (5)	0.0106 (3)	−0.0165 (4)	−0.0122 (3)
O1	0.146 (2)	0.0521 (12)	0.0667 (13)	−0.0168 (13)	−0.0297 (13)	−0.0032 (10)
O2	0.0624 (10)	0.0635 (8)	0.0530 (7)	0.0020 (7)	−0.0180 (7)	−0.0097 (6)
O3	0.0582 (12)	0.0671 (12)	0.0487 (10)	−0.0090 (9)	−0.0143 (8)	0.0087 (8)
C1	0.0511 (16)	0.0656 (16)	0.0435 (13)	0.0005 (12)	0.0007 (11)	−0.0051 (11)
C2	0.081 (2)	0.0748 (19)	0.0529 (16)	0.0000 (16)	0.0037 (15)	0.0039 (14)
C3	0.092 (3)	0.102 (3)	0.075 (2)	0.000 (2)	0.0016 (19)	0.029 (2)
C4	0.073 (2)	0.163 (4)	0.0503 (18)	−0.009 (2)	−0.0038 (16)	0.026 (2)
C5	0.077 (2)	0.144 (4)	0.0457 (17)	−0.019 (2)	−0.0058 (15)	−0.006 (2)
C6	0.0668 (19)	0.093 (2)	0.0507 (15)	−0.0081 (16)	−0.0017 (13)	−0.0107 (15)
C7	0.0689 (18)	0.0551 (16)	0.0492 (14)	−0.0027 (13)	−0.0069 (13)	−0.0063 (12)
C8	0.0653 (18)	0.0543 (15)	0.0473 (13)	−0.0050 (13)	−0.0093 (12)	−0.0048 (11)
C9	0.0620 (17)	0.0464 (13)	0.0461 (13)	−0.0012 (12)	−0.0137 (11)	0.0010 (10)
C10	0.0516 (10)	0.0514 (7)	0.0435 (8)	0.0012 (6)	−0.0071 (7)	−0.0007 (5)
C11	0.0523 (10)	0.0506 (7)	0.0449 (7)	0.0011 (6)	−0.0078 (7)	−0.0006 (5)
C12	0.0521 (8)	0.0564 (6)	0.0461 (6)	0.0021 (5)	−0.0090 (6)	−0.0028 (4)
C13	0.0427 (9)	0.0557 (6)	0.0404 (7)	−0.0020 (5)	−0.0038 (6)	−0.0026 (4)
C14	0.0461 (9)	0.0551 (7)	0.0424 (7)	0.0006 (5)	−0.0047 (7)	−0.0033 (5)
C15	0.0525 (10)	0.0516 (7)	0.0438 (7)	0.0019 (6)	−0.0098 (7)	−0.0012 (6)
C16	0.067 (9)	0.131 (11)	0.038 (4)	−0.040 (8)	−0.009 (4)	0.022 (4)
C17	0.079 (9)	0.169 (10)	0.081 (6)	−0.074 (9)	0.018 (5)	0.009 (6)
C17'	0.15 (2)	0.35 (3)	0.124 (15)	0.09 (2)	0.033 (12)	0.113 (19)
C16'	0.112 (18)	0.096 (9)	0.154 (17)	0.022 (10)	0.019 (11)	0.046 (9)
C18	0.0552 (7)	0.0648 (7)	0.0519 (7)	0.0045 (6)	−0.0121 (6)	0.0021 (6)
C19	0.0654 (13)	0.0648 (7)	0.0639 (11)	0.0100 (7)	−0.0176 (11)	0.0013 (7)
C20	0.0541 (8)	0.0718 (11)	0.0780 (15)	0.0043 (8)	−0.0131 (7)	0.0066 (10)
C21	0.0698 (13)	0.0815 (13)	0.0541 (7)	0.0187 (11)	−0.0064 (8)	0.0098 (8)

Geometric parameters (Å, º)

Cl1—C8	1.776 (3)	C12—C13	1.397 (4)
Cl2—C14	1.738 (3)	C12—C18	1.559 (3)
O1—C7	1.201 (3)	C13—C14	1.388 (3)
O2—H2	0.8497	C14—C15	1.375 (3)
O2—C13	1.358 (3)	C15—H15	0.9300
O3—C9	1.422 (3)	C16—H16A	0.9700
O3—C16	1.394 (13)	C16—H16B	0.9700
O3—C16'	1.50 (2)	C16—C17	1.434 (19)
C1—C2	1.375 (4)	C17—H17A	0.9600
C1—C6	1.384 (4)	C17—H17B	0.9600
C1—C7	1.479 (4)	C17—H17C	0.9600
C2—H2A	0.9300	C17'—H17D	0.9600
C2—C3	1.385 (4)	C17'—H17E	0.9600
C3—H3	0.9300	C17'—H17F	0.9600
C3—C4	1.357 (6)	C17'—C16'	1.35 (3)
C4—H4	0.9300	C16'—H16C	0.9700
C4—C5	1.354 (6)	C16'—H16D	0.9700
C5—H5	0.9300	C18—C19	1.534 (4)
C5—C6	1.376 (5)	C18—C20	1.521 (4)
C6—H6	0.9300	C18—C21	1.517 (4)
C7—C8	1.532 (3)	C19—H19A	0.9600
C8—H8	0.9800	C19—H19B	0.9600
C8—C9	1.521 (4)	C19—H19C	0.9600
C9—H9	0.9800	C20—H20A	0.9600
C9—C10	1.509 (3)	C20—H20B	0.9600
C10—C11	1.381 (3)	C20—H20C	0.9600
C10—C15	1.378 (3)	C21—H21A	0.9600
C11—H11	0.9300	C21—H21B	0.9600
C11—C12	1.385 (3)	C21—H21C	0.9600
C13—O2—H2	117.4	C10—C15—H15	120.5
C9—O3—C16'	112.4 (8)	C14—C15—C10	119.1 (2)
C16—O3—C9	114.8 (6)	C14—C15—H15	120.5
C2—C1—C6	118.7 (3)	O3—C16—H16A	108.9
C2—C1—C7	123.8 (2)	O3—C16—H16B	108.9
C6—C1—C7	117.5 (3)	O3—C16—C17	113.4 (9)
C1—C2—H2A	119.9	H16A—C16—H16B	107.7
C1—C2—C3	120.1 (3)	C17—C16—H16A	108.9
C3—C2—H2A	119.9	C17—C16—H16B	108.9
C2—C3—H3	120.0	C16—C17—H17A	109.5
C4—C3—C2	120.0 (4)	C16—C17—H17B	109.5
C4—C3—H3	120.0	C16—C17—H17C	109.5
C3—C4—H4	119.6	H17A—C17—H17B	109.5
C5—C4—C3	120.8 (3)	H17A—C17—H17C	109.5
C5—C4—H4	119.6	H17B—C17—H17C	109.5
C4—C5—H5	120.0	H17D—C17'—H17E	109.5
C4—C5—C6	120.0 (3)	H17D—C17'—H17F	109.5
C6—C5—H5	120.0	H17E—C17'—H17F	109.5
C1—C6—H6	119.8	C16'—C17'—H17D	109.5
C5—C6—C1	120.4 (3)	C16'—C17'—H17E	109.5
C5—C6—H6	119.8	C16'—C17'—H17F	109.5
O1—C7—C1	121.6 (2)	O3—C16'—H16C	109.3
O1—C7—C8	118.8 (2)	O3—C16'—H16D	109.3
C1—C7—C8	119.5 (2)	C17'—C16'—O3	111.5 (18)
Cl1—C8—H8	109.4	C17'—C16'—H16C	109.3
C7—C8—Cl1	105.42 (19)	C17'—C16'—H16D	109.3
C7—C8—H8	109.4	H16C—C16'—H16D	108.0
C9—C8—Cl1	111.25 (19)	C19—C18—C12	110.3 (2)
C9—C8—C7	111.8 (2)	C20—C18—C12	110.0 (2)
C9—C8—H8	109.4	C20—C18—C19	107.5 (2)
O3—C9—C8	102.96 (19)	C21—C18—C12	109.5 (2)
O3—C9—H9	109.1	C21—C18—C19	108.3 (2)
O3—C9—C10	113.0 (2)	C21—C18—C20	111.2 (2)
C8—C9—H9	109.1	C18—C19—H19A	109.5
C10—C9—C8	113.5 (2)	C18—C19—H19B	109.5
C10—C9—H9	109.1	C18—C19—H19C	109.5
C11—C10—C9	120.2 (2)	H19A—C19—H19B	109.5
C15—C10—C9	121.0 (2)	H19A—C19—H19C	109.5
C15—C10—C11	118.8 (2)	H19B—C19—H19C	109.5
C10—C11—H11	118.3	C18—C20—H20A	109.5
C10—C11—C12	123.4 (2)	C18—C20—H20B	109.5
C12—C11—H11	118.3	C18—C20—H20C	109.5
C11—C12—C13	117.1 (2)	H20A—C20—H20B	109.5
C11—C12—C18	121.9 (2)	H20A—C20—H20C	109.5
C13—C12—C18	121.0 (2)	H20B—C20—H20C	109.5
O2—C13—C12	119.1 (2)	C18—C21—H21A	109.5
O2—C13—C14	121.4 (2)	C18—C21—H21B	109.5
C14—C13—C12	119.5 (2)	C18—C21—H21C	109.5
C13—C14—Cl2	118.43 (18)	H21A—C21—H21B	109.5
C15—C14—Cl2	119.42 (19)	H21A—C21—H21C	109.5
C15—C14—C13	122.1 (2)	H21B—C21—H21C	109.5
Cl1—C8—C9—O3	−179.02 (16)	C8—C9—C10—C15	−68.1 (3)
Cl1—C8—C9—C10	−56.5 (3)	C9—O3—C16—C17	145.5 (14)
Cl2—C14—C15—C10	−179.8 (2)	C9—O3—C16'—C17'	179 (3)
O1—C7—C8—Cl1	−87.0 (3)	C9—C10—C11—C12	−178.7 (3)
O1—C7—C8—C9	34.0 (4)	C9—C10—C15—C14	178.8 (2)
O2—C13—C14—Cl2	0.1 (3)	C10—C11—C12—C13	−0.2 (4)
O2—C13—C14—C15	−179.8 (2)	C10—C11—C12—C18	−179.0 (3)
O3—C9—C10—C11	−132.2 (2)	C11—C10—C15—C14	−0.3 (4)
O3—C9—C10—C15	48.7 (3)	C11—C12—C13—O2	179.9 (2)
C1—C2—C3—C4	1.0 (5)	C11—C12—C13—C14	0.0 (4)
C1—C7—C8—Cl1	90.7 (3)	C11—C12—C18—C19	−2.3 (4)
C1—C7—C8—C9	−148.3 (3)	C11—C12—C18—C20	−120.8 (3)
C2—C1—C6—C5	−0.7 (5)	C11—C12—C18—C21	116.7 (3)
C2—C1—C7—O1	−174.2 (3)	C12—C13—C14—Cl2	180.0 (2)
C2—C1—C7—C8	8.1 (4)	C12—C13—C14—C15	0.1 (4)
C2—C3—C4—C5	−0.7 (6)	C13—C12—C18—C19	179.0 (3)
C3—C4—C5—C6	−0.3 (6)	C13—C12—C18—C20	60.5 (3)
C4—C5—C6—C1	1.0 (5)	C13—C12—C18—C21	−62.0 (3)
C6—C1—C2—C3	−0.3 (5)	C13—C14—C15—C10	0.1 (4)
C6—C1—C7—O1	4.8 (4)	C15—C10—C11—C12	0.4 (4)
C6—C1—C7—C8	−172.8 (3)	C16—O3—C9—C8	−166.3 (8)
C7—C1—C2—C3	178.7 (3)	C16—O3—C9—C10	70.9 (8)
C7—C1—C6—C5	−179.7 (3)	C16'—O3—C9—C8	−155.2 (11)
C7—C8—C9—O3	63.4 (3)	C16'—O3—C9—C10	82.0 (11)
C7—C8—C9—C10	−174.1 (2)	C18—C12—C13—O2	−1.3 (4)
C8—C9—C10—C11	111.0 (3)	C18—C12—C13—C14	178.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···Cl2	0.85	2.51	2.9456 (19)	113
O2—H2···O3^i	0.85	2.10	2.823 (3)	143

Symmetry code: (i) x−1/2, −y+3/2, z−1/2.

2-Bromo-3-(3-tert-butyl-5-bromo-4-hydroxyphenyl)-3-methoxy-1-phenylpropan-1-one (3)

Crystal data

C20H22Br2O3	F(000) = 944
Mr = 470.19	Dx = 1.509 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.6343 (5) Å	Cell parameters from 2692 reflections
b = 19.5472 (10) Å	θ = 2.4–25.6°
c = 10.9965 (6) Å	µ = 3.93 mm^−1
β = 91.584 (2)°	T = 296 K
V = 2070.11 (19) Å^3	Prism, colorless
Z = 4	0.25 × 0.22 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer	3201 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.024
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 28.4°, θmin = 2.1°
Tmin = 0.387, Tmax = 0.420	h = −6→12
9119 measured reflections	k = −25→26
5067 independent reflections	l = −14→11

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.117	w = 1/[σ^2(Fo^2) + (0.0591P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
5067 reflections	Δρmax = 0.80 e Å^−3
230 parameters	Δρmin = −0.69 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. In the case of compound 3, the completeness was 0.979. The data for this compound,were collected properly. However, we have some problems with data processing, due to the crystal quality is not properly than the other samples.

In fact, this sample have decomposed during the measurement. We have made several attemps with this sample obtaining the same results.

The X-ray diffraction patterns of 2–4 were collected using a Bruker SMART APEXII CCD area detector equipped with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at room temperature. Absorption correction was applied by SADABS (Bruker, 2016). The structure was solved by direct methods and refined on F² by full-matrix least-squares using Bruker SHELXTL97 (Sheldrick, 2015), operating within the OLEX2 program (Dolomanov et al., 2009). All non-H atoms were refined anisotropically. The details of the crystallographic data are summarized in Table 1. Crystallographic data for the structural analysis have been deposited to the Cambridge Crystallographic Data Center (CCDC 1523181–1523183 for 2–4). Copy of this information can be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: [phone]; E-mail: [e-mail] or www.ccdc.cam.ac.uk/data_request/cif). ORTEP views were drawn using OLEX2 software (Dolomanov et al., 2009).

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

	x	y	z	Uiso*/Ueq
Br1	0.72394 (4)	0.37888 (3)	0.14883 (4)	0.0998 (2)
Br2	0.86866 (3)	0.15806 (2)	−0.24734 (3)	0.05642 (13)
O1	1.0189 (3)	0.46627 (12)	0.2145 (2)	0.0828 (8)
O2	0.6728 (2)	0.25862 (10)	−0.38036 (19)	0.0534 (5)
H2	0.694738	0.216686	−0.386848	0.080*
O3	1.1145 (2)	0.36877 (11)	0.0156 (2)	0.0541 (5)
C1	1.0156 (3)	0.37549 (17)	0.3543 (3)	0.0504 (7)
C2	0.9967 (4)	0.3075 (2)	0.3778 (3)	0.0689 (9)
H2A	0.961789	0.278725	0.316987	0.083*
C3	1.0298 (5)	0.2812 (2)	0.4933 (4)	0.0886 (13)
H3	1.017205	0.234832	0.508775	0.106*
C4	1.0796 (4)	0.3225 (3)	0.5821 (4)	0.0969 (15)
H4	1.102955	0.304465	0.658277	0.116*
C5	1.0962 (4)	0.3914 (3)	0.5604 (4)	0.0894 (14)
H5	1.127120	0.420149	0.622858	0.107*
C6	1.0674 (4)	0.4174 (2)	0.4479 (3)	0.0698 (10)
H6	1.082423	0.463589	0.433009	0.084*
C7	0.9895 (3)	0.40743 (17)	0.2342 (3)	0.0550 (8)
C8	0.9214 (3)	0.36509 (16)	0.1318 (3)	0.0517 (8)
H8	0.943152	0.316650	0.145178	0.062*
C9	0.9706 (3)	0.38605 (14)	0.0075 (3)	0.0470 (7)
H9	0.961066	0.435715	−0.001670	0.056*
C10	0.8949 (3)	0.35106 (13)	−0.0970 (3)	0.0429 (7)
C11	0.8015 (3)	0.38703 (14)	−0.1692 (3)	0.0466 (7)
H11	0.789487	0.433336	−0.153101	0.056*
C12	0.7237 (3)	0.35821 (13)	−0.2648 (3)	0.0412 (7)
C13	0.7453 (3)	0.28845 (14)	−0.2869 (3)	0.0416 (6)
C14	0.8396 (3)	0.25255 (13)	−0.2145 (3)	0.0405 (6)
C15	0.9147 (3)	0.28183 (14)	−0.1195 (3)	0.0448 (7)
H15	0.976668	0.256087	−0.072058	0.054*
C16	1.1976 (4)	0.4048 (3)	−0.0655 (4)	0.0906 (13)
H16A	1.292577	0.390812	−0.054205	0.136*
H16B	1.190015	0.452983	−0.050178	0.136*
H16C	1.166939	0.395223	−0.147553	0.136*
C17	0.6211 (3)	0.40095 (15)	−0.3431 (3)	0.0537 (8)
C18	0.6134 (4)	0.47467 (17)	−0.2953 (4)	0.0825 (13)
H18A	0.546656	0.500040	−0.343503	0.124*
H18B	0.702899	0.495889	−0.300410	0.124*
H18C	0.585815	0.474136	−0.212066	0.124*
C19	0.6699 (4)	0.40251 (19)	−0.4744 (3)	0.0742 (11)
H19A	0.670284	0.356851	−0.506556	0.111*
H19B	0.761967	0.421180	−0.476041	0.111*
H19C	0.607980	0.430470	−0.522940	0.111*
C20	0.4752 (3)	0.3707 (2)	−0.3379 (4)	0.0757 (11)
H20A	0.475207	0.325307	−0.371187	0.114*
H20B	0.411528	0.398823	−0.384388	0.114*
H20C	0.447026	0.368998	−0.254896	0.114*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0553 (2)	0.1649 (5)	0.0793 (3)	−0.0111 (3)	0.0019 (2)	−0.0321 (3)
Br2	0.0547 (2)	0.04056 (17)	0.0733 (3)	0.00571 (13)	−0.00985 (16)	−0.00330 (15)
O1	0.126 (2)	0.0566 (14)	0.0644 (16)	−0.0193 (15)	−0.0299 (16)	−0.0011 (13)
O2	0.0561 (12)	0.0463 (10)	0.0564 (13)	0.0008 (9)	−0.0213 (11)	−0.0054 (10)
O3	0.0475 (12)	0.0580 (12)	0.0559 (14)	−0.0007 (10)	−0.0149 (11)	0.0089 (11)
C1	0.0438 (16)	0.065 (2)	0.0421 (18)	−0.0001 (14)	−0.0010 (14)	−0.0022 (15)
C2	0.072 (2)	0.081 (2)	0.054 (2)	−0.002 (2)	0.0041 (18)	0.003 (2)
C3	0.106 (3)	0.100 (3)	0.060 (3)	−0.001 (3)	0.006 (2)	0.021 (2)
C4	0.068 (3)	0.171 (5)	0.051 (3)	0.004 (3)	−0.002 (2)	0.024 (3)
C5	0.069 (3)	0.145 (4)	0.054 (3)	−0.013 (3)	−0.007 (2)	−0.010 (3)
C6	0.064 (2)	0.093 (3)	0.052 (2)	−0.0047 (19)	−0.0052 (18)	−0.012 (2)
C7	0.0581 (19)	0.0570 (18)	0.0495 (19)	−0.0020 (15)	−0.0081 (16)	−0.0061 (15)
C8	0.0506 (18)	0.0547 (16)	0.0493 (19)	−0.0068 (14)	−0.0085 (15)	−0.0039 (15)
C9	0.0463 (16)	0.0461 (15)	0.0478 (18)	−0.0011 (12)	−0.0126 (14)	−0.0009 (13)
C10	0.0431 (15)	0.0445 (15)	0.0404 (16)	−0.0010 (12)	−0.0093 (13)	0.0028 (12)
C11	0.0477 (17)	0.0387 (13)	0.0528 (18)	0.0015 (12)	−0.0080 (14)	−0.0011 (13)
C12	0.0391 (14)	0.0414 (13)	0.0424 (17)	0.0023 (11)	−0.0095 (13)	0.0047 (12)
C13	0.0382 (14)	0.0457 (14)	0.0407 (16)	−0.0028 (12)	−0.0050 (13)	−0.0024 (13)
C14	0.0410 (14)	0.0343 (12)	0.0460 (16)	0.0009 (11)	−0.0027 (13)	0.0009 (12)
C15	0.0438 (15)	0.0436 (15)	0.0465 (17)	0.0027 (12)	−0.0101 (14)	0.0079 (13)
C16	0.065 (2)	0.121 (3)	0.086 (3)	−0.005 (2)	0.010 (2)	0.037 (3)
C17	0.0491 (17)	0.0458 (15)	0.065 (2)	0.0064 (13)	−0.0213 (16)	0.0026 (15)
C18	0.087 (3)	0.0505 (18)	0.107 (3)	0.0199 (18)	−0.046 (2)	−0.001 (2)
C19	0.082 (3)	0.076 (2)	0.063 (2)	0.007 (2)	−0.022 (2)	0.022 (2)
C20	0.0476 (19)	0.078 (2)	0.100 (3)	0.0113 (17)	−0.018 (2)	−0.001 (2)

Geometric parameters (Å, º)

Br1—C8	1.936 (3)	C10—C11	1.377 (4)
Br2—C14	1.904 (3)	C10—C15	1.390 (4)
O1—C7	1.206 (4)	C11—H11	0.9300
O2—H2	0.8499	C11—C12	1.393 (4)
O2—C13	1.358 (3)	C12—C13	1.402 (4)
O3—C9	1.427 (3)	C12—C17	1.540 (4)
O3—C16	1.404 (4)	C13—C14	1.382 (4)
C1—C2	1.367 (5)	C14—C15	1.378 (4)
C1—C6	1.396 (5)	C15—H15	0.9300
C1—C7	1.476 (4)	C16—H16A	0.9600
C2—H2A	0.9300	C16—H16B	0.9600
C2—C3	1.399 (5)	C16—H16C	0.9600
C3—H3	0.9300	C17—C18	1.536 (4)
C3—C4	1.346 (6)	C17—C19	1.531 (5)
C4—H4	0.9300	C17—C20	1.528 (5)
C4—C5	1.378 (7)	C18—H18A	0.9600
C5—H5	0.9300	C18—H18B	0.9600
C5—C6	1.359 (6)	C18—H18C	0.9600
C6—H6	0.9300	C19—H19A	0.9600
C7—C8	1.531 (4)	C19—H19B	0.9600
C8—H8	0.9800	C19—H19C	0.9600
C8—C9	1.516 (5)	C20—H20A	0.9600
C9—H9	0.9800	C20—H20B	0.9600
C9—C10	1.508 (4)	C20—H20C	0.9600
C13—O2—H2	110.7	C11—C12—C17	121.8 (2)
C16—O3—C9	114.3 (3)	C13—C12—C17	121.8 (2)
C2—C1—C6	118.5 (3)	O2—C13—C12	118.2 (2)
C2—C1—C7	124.1 (3)	O2—C13—C14	122.3 (2)
C6—C1—C7	117.4 (3)	C14—C13—C12	119.5 (2)
C1—C2—H2A	120.0	C13—C14—Br2	118.7 (2)
C1—C2—C3	120.1 (4)	C15—C14—Br2	118.01 (19)
C3—C2—H2A	120.0	C15—C14—C13	123.3 (2)
C2—C3—H3	119.8	C10—C15—H15	121.1
C4—C3—C2	120.4 (4)	C14—C15—C10	117.9 (2)
C4—C3—H3	119.8	C14—C15—H15	121.1
C3—C4—H4	120.0	O3—C16—H16A	109.5
C3—C4—C5	120.1 (4)	O3—C16—H16B	109.5
C5—C4—H4	120.0	O3—C16—H16C	109.5
C4—C5—H5	120.0	H16A—C16—H16B	109.5
C6—C5—C4	120.1 (4)	H16A—C16—H16C	109.5
C6—C5—H5	120.0	H16B—C16—H16C	109.5
C1—C6—H6	119.6	C18—C17—C12	110.7 (2)
C5—C6—C1	120.8 (4)	C19—C17—C12	109.2 (3)
C5—C6—H6	119.6	C19—C17—C18	108.8 (3)
O1—C7—C1	121.9 (3)	C20—C17—C12	110.3 (3)
O1—C7—C8	118.8 (3)	C20—C17—C18	107.3 (3)
C1—C7—C8	119.3 (3)	C20—C17—C19	110.5 (3)
Br1—C8—H8	109.0	C17—C18—H18A	109.5
C7—C8—Br1	104.8 (2)	C17—C18—H18B	109.5
C7—C8—H8	109.0	C17—C18—H18C	109.5
C9—C8—Br1	112.5 (2)	H18A—C18—H18B	109.5
C9—C8—C7	112.3 (3)	H18A—C18—H18C	109.5
C9—C8—H8	109.0	H18B—C18—H18C	109.5
O3—C9—C8	101.9 (2)	C17—C19—H19A	109.5
O3—C9—H9	109.2	C17—C19—H19B	109.5
O3—C9—C10	112.9 (2)	C17—C19—H19C	109.5
C8—C9—H9	109.2	H19A—C19—H19B	109.5
C10—C9—C8	114.1 (2)	H19A—C19—H19C	109.5
C10—C9—H9	109.2	H19B—C19—H19C	109.5
C11—C10—C9	120.2 (2)	C17—C20—H20A	109.5
C11—C10—C15	119.0 (2)	C17—C20—H20B	109.5
C15—C10—C9	120.8 (2)	C17—C20—H20C	109.5
C10—C11—H11	118.0	H20A—C20—H20B	109.5
C10—C11—C12	123.9 (3)	H20A—C20—H20C	109.5
C12—C11—H11	118.0	H20B—C20—H20C	109.5
C11—C12—C13	116.4 (2)
Br1—C8—C9—O3	−177.73 (17)	C7—C8—C9—C10	−173.7 (2)
Br1—C8—C9—C10	−55.7 (3)	C8—C9—C10—C11	107.5 (3)
Br2—C14—C15—C10	179.0 (2)	C8—C9—C10—C15	−70.4 (4)
O1—C7—C8—Br1	−89.9 (3)	C9—C10—C11—C12	−177.8 (3)
O1—C7—C8—C9	32.5 (4)	C9—C10—C15—C14	178.3 (3)
O2—C13—C14—Br2	0.1 (4)	C10—C11—C12—C13	−0.5 (5)
O2—C13—C14—C15	179.7 (3)	C10—C11—C12—C17	−179.7 (3)
O3—C9—C10—C11	−136.8 (3)	C11—C10—C15—C14	0.4 (5)
O3—C9—C10—C15	45.3 (4)	C11—C12—C13—O2	−179.2 (3)
C1—C2—C3—C4	0.4 (6)	C11—C12—C13—C14	0.2 (4)
C1—C7—C8—Br1	89.4 (3)	C11—C12—C17—C18	−3.3 (5)
C1—C7—C8—C9	−148.2 (3)	C11—C12—C17—C19	116.5 (3)
C2—C1—C6—C5	−1.1 (5)	C11—C12—C17—C20	−121.9 (3)
C2—C1—C7—O1	−173.4 (4)	C12—C13—C14—Br2	−179.3 (2)
C2—C1—C7—C8	7.4 (5)	C12—C13—C14—C15	0.3 (5)
C2—C3—C4—C5	1.1 (7)	C13—C12—C17—C18	177.5 (3)
C3—C4—C5—C6	−2.6 (7)	C13—C12—C17—C19	−62.7 (4)
C4—C5—C6—C1	2.6 (6)	C13—C12—C17—C20	58.9 (4)
C6—C1—C2—C3	−0.4 (5)	C13—C14—C15—C10	−0.6 (5)
C6—C1—C7—O1	4.3 (5)	C15—C10—C11—C12	0.1 (5)
C6—C1—C7—C8	−174.9 (3)	C16—O3—C9—C8	−157.1 (3)
C7—C1—C2—C3	177.3 (4)	C16—O3—C9—C10	80.1 (4)
C7—C1—C6—C5	−178.9 (4)	C17—C12—C13—O2	0.1 (4)
C7—C8—C9—O3	64.3 (3)	C17—C12—C13—C14	179.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···Br2	0.85	2.52	3.0676 (19)	123
O2—H2···O3^i	0.85	2.12	2.791 (3)	136

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.

2-Bromo-3-(3-tert-butyl-5-bromo-4-hydroxyphenyl)-3-ethoxy-1-phenylpropan-1-one (4)

Crystal data

C21H24Br2O3	F(000) = 976
Mr = 484.22	Dx = 1.515 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.6342 (4) Å	Cell parameters from 8670 reflections
b = 19.8082 (8) Å	θ = 2.4–27.2°
c = 11.1545 (5) Å	µ = 3.83 mm^−1
β = 94.076 (1)°	T = 296 K
V = 2123.30 (16) Å^3	Plate, colorless
Z = 4	0.17 × 0.14 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer	4192 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.028
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 28.3°, θmin = 2.1°
Tmin = 0.534, Tmax = 0.587	h = −12→12
24293 measured reflections	k = −26→26
5285 independent reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: difference Fourier map
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: mixed
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0421P)^2 + 1.0628P] where P = (Fo^2 + 2Fc^2)/3
5285 reflections	(Δ/σ)max = 0.001
239 parameters	Δρmax = 0.62 e Å^−3
2 restraints	Δρmin = −0.42 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. The C16 and C17 atoms of the ethyl fragment are disordered over two position. The disorder was modeled and refined including alternative positions with relative occupancies of 0.671 (12):0.329 (12).

The X-ray diffraction patterns of 2–4 were collected using a Bruker SMART APEXII CCD area detector equipped with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at room temperature. Absorption correction was applied by SADABS (Bruker, 2016). The structure was solved by direct methods and refined on F² by full-matrix least-squares using Bruker SHELXTL97 (Sheldrick, 2015), operating within the OLEX2 program (Dolomanov et al., 2009). All non-H atoms were refined anisotropically. The details of the crystallographic data are summarized in Table 1. Crystallographic data for the structural analysis have been deposited to the Cambridge Crystallographic Data Center (CCDC 1523181–1523183 for 2–4). Copy of this information can be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: [phone]; E-mail: [e-mail] or www.ccdc.cam.ac.uk/data_request/cif). ORTEP views were drawn using OLEX2 software (Dolomanov et al., 2009).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	0.73651 (3)	0.37129 (2)	1.14539 (3)	0.08009 (13)
Br2	0.88337 (3)	0.15837 (2)	0.76290 (2)	0.05127 (9)
O1	1.0271 (3)	0.46527 (9)	1.21533 (17)	0.0682 (6)
O2	0.68872 (17)	0.25493 (8)	0.61647 (14)	0.0468 (4)
H2O	0.7108	0.2150	0.6155	0.070*
O3	1.12383 (17)	0.37515 (9)	1.01606 (14)	0.0468 (4)
C1	1.0272 (2)	0.37619 (13)	1.3550 (2)	0.0419 (5)
C2	1.0118 (3)	0.30851 (15)	1.3783 (2)	0.0574 (7)
H2A	0.9810	0.2793	1.3167	0.069*
C3	1.0422 (4)	0.28382 (19)	1.4938 (3)	0.0759 (9)
H3A	1.0324	0.2380	1.5091	0.091*
C4	1.0862 (4)	0.3263 (2)	1.5845 (3)	0.0796 (10)
H4A	1.1055	0.3094	1.6618	0.096*
C5	1.1021 (3)	0.3934 (2)	1.5625 (3)	0.0749 (10)
H5A	1.1324	0.4222	1.6249	0.090*
C6	1.0736 (3)	0.41907 (16)	1.4483 (2)	0.0552 (6)
H6A	1.0853	0.4649	1.4338	0.066*
C7	1.0006 (3)	0.40688 (12)	1.2337 (2)	0.0440 (5)
C8	0.9362 (2)	0.36353 (12)	1.1309 (2)	0.0425 (5)
H8A	0.9648	0.3164	1.1434	0.051*
C9	0.9777 (2)	0.38723 (12)	1.0088 (2)	0.0412 (5)
H9A	0.9605	0.4358	1.0010	0.049*
C10	0.9023 (2)	0.35086 (11)	0.90430 (19)	0.0382 (5)
C11	0.8087 (2)	0.38528 (11)	0.82635 (19)	0.0391 (5)
H11A	0.7949	0.4311	0.8397	0.047*
C12	0.7345 (2)	0.35504 (11)	0.72937 (19)	0.0352 (4)
C13	0.7588 (2)	0.28615 (11)	0.71097 (18)	0.0348 (4)
C14	0.8531 (2)	0.25180 (11)	0.78932 (19)	0.0355 (4)
C15	0.9255 (2)	0.28292 (11)	0.88480 (19)	0.0389 (5)
H15A	0.9887	0.2588	0.9351	0.047*
C16	1.1948 (7)	0.4069 (6)	0.9213 (10)	0.0798 (16)	0.671 (12)
H16A	1.1402	0.4450	0.8903	0.096*	0.671 (12)
H16B	1.2020	0.3749	0.8562	0.096*	0.671 (12)
C17	1.3361 (6)	0.4306 (5)	0.9629 (6)	0.0798 (16)	0.671 (12)
H17A	1.3791	0.4512	0.8971	0.120*	0.671 (12)
H17B	1.3294	0.4629	1.0262	0.120*	0.671 (12)
H17C	1.3912	0.3929	0.9922	0.120*	0.671 (12)
C16'	1.1907 (14)	0.4227 (11)	0.940 (2)	0.0798 (16)	0.329 (12)
H16C	1.1915	0.4678	0.9740	0.096*	0.329 (12)
H16D	1.1441	0.4240	0.8599	0.096*	0.329 (12)
C17'	1.3360 (11)	0.3953 (9)	0.9370 (14)	0.0798 (16)	0.329 (12)
H17D	1.3890	0.4239	0.8879	0.120*	0.329 (12)
H17E	1.3793	0.3940	1.0172	0.120*	0.329 (12)
H17F	1.3323	0.3505	0.9040	0.120*	0.329 (12)
C18	0.6336 (2)	0.39565 (12)	0.6438 (2)	0.0427 (5)
C19	0.6227 (3)	0.46929 (13)	0.6853 (3)	0.0599 (7)
H19A	0.5885	0.4704	0.7641	0.090*
H19B	0.5600	0.4935	0.6301	0.090*
H19C	0.7130	0.4900	0.6878	0.090*
C20	0.4870 (3)	0.36535 (15)	0.6401 (3)	0.0594 (7)
H20A	0.4560	0.3640	0.7200	0.089*
H20B	0.4887	0.3204	0.6081	0.089*
H20C	0.4245	0.3927	0.5899	0.089*
C21	0.6866 (3)	0.39604 (16)	0.5171 (2)	0.0587 (7)
H21A	0.6228	0.4208	0.4637	0.088*
H21B	0.6936	0.3505	0.4888	0.088*
H21C	0.7765	0.4171	0.5196	0.088*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.04824 (17)	0.1229 (3)	0.0683 (2)	−0.00845 (17)	−0.00130 (14)	−0.02581 (19)
Br2	0.05516 (16)	0.03929 (13)	0.05715 (16)	0.00762 (10)	−0.01154 (11)	−0.00774 (10)
O1	0.1073 (17)	0.0435 (10)	0.0498 (11)	−0.0143 (10)	−0.0212 (10)	−0.0021 (8)
O2	0.0496 (9)	0.0446 (9)	0.0432 (9)	0.0005 (7)	−0.0179 (7)	−0.0097 (7)
O3	0.0460 (9)	0.0544 (10)	0.0381 (8)	−0.0084 (7)	−0.0105 (7)	0.0081 (7)
C1	0.0359 (11)	0.0553 (14)	0.0340 (11)	−0.0007 (10)	−0.0010 (9)	−0.0030 (10)
C2	0.0690 (18)	0.0609 (17)	0.0417 (14)	0.0002 (13)	0.0002 (12)	0.0036 (12)
C3	0.086 (2)	0.081 (2)	0.0601 (19)	−0.0001 (18)	0.0022 (16)	0.0247 (16)
C4	0.067 (2)	0.131 (3)	0.0400 (16)	−0.004 (2)	−0.0047 (13)	0.0195 (18)
C5	0.0642 (19)	0.123 (3)	0.0367 (14)	−0.0144 (19)	−0.0029 (13)	−0.0090 (17)
C6	0.0514 (15)	0.0742 (18)	0.0394 (13)	−0.0061 (13)	−0.0019 (11)	−0.0083 (12)
C7	0.0488 (13)	0.0441 (13)	0.0376 (12)	−0.0006 (10)	−0.0082 (10)	−0.0061 (9)
C8	0.0451 (13)	0.0434 (12)	0.0374 (12)	−0.0041 (10)	−0.0071 (9)	−0.0050 (9)
C9	0.0454 (12)	0.0386 (11)	0.0372 (11)	−0.0022 (9)	−0.0141 (9)	0.0001 (9)
C10	0.0414 (12)	0.0409 (12)	0.0306 (10)	−0.0037 (9)	−0.0090 (8)	−0.0008 (8)
C11	0.0438 (12)	0.0352 (11)	0.0369 (11)	−0.0008 (9)	−0.0068 (9)	−0.0001 (8)
C12	0.0325 (10)	0.0394 (11)	0.0329 (10)	0.0002 (8)	−0.0048 (8)	0.0014 (8)
C13	0.0329 (10)	0.0415 (11)	0.0291 (10)	−0.0041 (8)	−0.0034 (8)	−0.0024 (8)
C14	0.0377 (11)	0.0341 (10)	0.0342 (11)	0.0003 (8)	−0.0014 (8)	−0.0013 (8)
C15	0.0419 (12)	0.0391 (11)	0.0341 (11)	0.0020 (9)	−0.0084 (9)	0.0038 (9)
C16	0.0758 (17)	0.098 (5)	0.066 (3)	−0.022 (2)	0.0065 (15)	0.017 (3)
C17	0.0758 (17)	0.098 (5)	0.066 (3)	−0.022 (2)	0.0065 (15)	0.017 (3)
C16'	0.0758 (17)	0.098 (5)	0.066 (3)	−0.022 (2)	0.0065 (15)	0.017 (3)
C17'	0.0758 (17)	0.098 (5)	0.066 (3)	−0.022 (2)	0.0065 (15)	0.017 (3)
C18	0.0392 (12)	0.0459 (12)	0.0408 (12)	0.0057 (9)	−0.0125 (9)	0.0017 (10)
C19	0.0612 (17)	0.0476 (14)	0.0670 (17)	0.0113 (12)	−0.0221 (13)	0.0022 (13)
C20	0.0384 (13)	0.0682 (17)	0.0697 (18)	0.0038 (12)	−0.0095 (12)	−0.0061 (14)
C21	0.0605 (16)	0.0700 (18)	0.0432 (14)	0.0061 (13)	−0.0125 (12)	0.0117 (12)

Geometric parameters (Å, º)

Br1—C8	1.948 (2)	C12—C13	1.402 (3)
Br2—C14	1.900 (2)	C12—C18	1.541 (3)
O1—C7	1.205 (3)	C13—C14	1.393 (3)
O2—H2O	0.8199	C14—C15	1.377 (3)
O2—C13	1.360 (2)	C15—H15A	0.9300
O3—C9	1.425 (3)	C16—H16A	0.9700
O3—C16	1.443 (11)	C16—H16B	0.9700
O3—C16'	1.45 (3)	C16—C17	1.482 (8)
C1—C2	1.375 (4)	C17—H17A	0.9600
C1—C6	1.392 (3)	C17—H17B	0.9600
C1—C7	1.489 (3)	C17—H17C	0.9600
C2—H2A	0.9300	C16'—H16C	0.9700
C2—C3	1.390 (4)	C16'—H16D	0.9700
C3—H3A	0.9300	C16'—C17'	1.504 (10)
C3—C4	1.360 (5)	C17'—H17D	0.9600
C4—H4A	0.9300	C17'—H17E	0.9600
C4—C5	1.363 (5)	C17'—H17F	0.9600
C5—H5A	0.9300	C18—C19	1.536 (4)
C5—C6	1.381 (4)	C18—C20	1.532 (4)
C6—H6A	0.9300	C18—C21	1.536 (4)
C7—C8	1.529 (3)	C19—H19A	0.9600
C8—H8A	0.9800	C19—H19B	0.9600
C8—C9	1.520 (3)	C19—H19C	0.9600
C9—H9A	0.9800	C20—H20A	0.9600
C9—C10	1.512 (3)	C20—H20B	0.9600
C10—C11	1.386 (3)	C20—H20C	0.9600
C10—C15	1.384 (3)	C21—H21A	0.9600
C11—H11A	0.9300	C21—H21B	0.9600
C11—C12	1.389 (3)	C21—H21C	0.9600
C13—O2—H2O	109.5	C10—C15—H15A	120.7
C9—O3—C16	113.8 (4)	C14—C15—C10	118.58 (19)
C9—O3—C16'	109.6 (6)	C14—C15—H15A	120.7
C2—C1—C6	119.1 (2)	O3—C16—H16A	109.1
C2—C1—C7	123.7 (2)	O3—C16—H16B	109.1
C6—C1—C7	117.1 (2)	O3—C16—C17	112.4 (8)
C1—C2—H2A	120.0	H16A—C16—H16B	107.9
C1—C2—C3	120.0 (3)	C17—C16—H16A	109.1
C3—C2—H2A	120.0	C17—C16—H16B	109.1
C2—C3—H3A	119.8	C16—C17—H17A	109.5
C4—C3—C2	120.4 (3)	C16—C17—H17B	109.5
C4—C3—H3A	119.8	C16—C17—H17C	109.5
C3—C4—H4A	119.9	H17A—C17—H17B	109.5
C3—C4—C5	120.1 (3)	H17A—C17—H17C	109.5
C5—C4—H4A	119.9	H17B—C17—H17C	109.5
C4—C5—H5A	119.7	O3—C16'—H16C	111.1
C4—C5—C6	120.5 (3)	O3—C16'—H16D	111.1
C6—C5—H5A	119.7	O3—C16'—C17'	103.3 (16)
C1—C6—H6A	120.1	H16C—C16'—H16D	109.1
C5—C6—C1	119.8 (3)	C17'—C16'—H16C	111.1
C5—C6—H6A	120.1	C17'—C16'—H16D	111.1
O1—C7—C1	121.5 (2)	C16'—C17'—H17D	109.5
O1—C7—C8	119.4 (2)	C16'—C17'—H17E	109.5
C1—C7—C8	119.1 (2)	C16'—C17'—H17F	109.5
Br1—C8—H8A	109.4	H17D—C17'—H17E	109.5
C7—C8—Br1	104.12 (16)	H17D—C17'—H17F	109.5
C7—C8—H8A	109.4	H17E—C17'—H17F	109.5
C9—C8—Br1	111.95 (15)	C19—C18—C12	111.22 (18)
C9—C8—C7	112.3 (2)	C20—C18—C12	110.6 (2)
C9—C8—H8A	109.4	C20—C18—C19	107.3 (2)
O3—C9—C8	102.64 (17)	C20—C18—C21	110.1 (2)
O3—C9—H9A	109.3	C21—C18—C12	109.6 (2)
O3—C9—C10	112.46 (19)	C21—C18—C19	107.9 (2)
C8—C9—H9A	109.3	C18—C19—H19A	109.5
C10—C9—C8	113.66 (19)	C18—C19—H19B	109.5
C10—C9—H9A	109.3	C18—C19—H19C	109.5
C11—C10—C9	120.3 (2)	H19A—C19—H19B	109.5
C15—C10—C9	120.69 (19)	H19A—C19—H19C	109.5
C15—C10—C11	119.01 (19)	H19B—C19—H19C	109.5
C10—C11—H11A	118.3	C18—C20—H20A	109.5
C10—C11—C12	123.5 (2)	C18—C20—H20B	109.5
C12—C11—H11A	118.3	C18—C20—H20C	109.5
C11—C12—C13	116.85 (19)	H20A—C20—H20B	109.5
C11—C12—C18	121.7 (2)	H20A—C20—H20C	109.5
C13—C12—C18	121.47 (18)	H20B—C20—H20C	109.5
O2—C13—C12	118.52 (18)	C18—C21—H21A	109.5
O2—C13—C14	122.02 (19)	C18—C21—H21B	109.5
C14—C13—C12	119.47 (18)	C18—C21—H21C	109.5
C13—C14—Br2	118.62 (15)	H21A—C21—H21B	109.5
C15—C14—Br2	118.78 (16)	H21A—C21—H21C	109.5
C15—C14—C13	122.59 (19)	H21B—C21—H21C	109.5
Br1—C8—C9—O3	−178.02 (14)	C8—C9—C10—C15	−66.9 (3)
Br1—C8—C9—C10	−56.3 (2)	C9—O3—C16—C17	144.9 (9)
Br2—C14—C15—C10	−179.46 (17)	C9—O3—C16'—C17'	−168.9 (12)
O1—C7—C8—Br1	−92.8 (3)	C9—C10—C11—C12	−179.2 (2)
O1—C7—C8—C9	28.6 (3)	C9—C10—C15—C14	179.2 (2)
O2—C13—C14—Br2	−0.3 (3)	C10—C11—C12—C13	−0.7 (3)
O2—C13—C14—C15	179.5 (2)	C10—C11—C12—C18	−178.9 (2)
O3—C9—C10—C11	−130.8 (2)	C11—C10—C15—C14	−0.9 (3)
O3—C9—C10—C15	49.2 (3)	C11—C12—C13—O2	−179.6 (2)
C1—C2—C3—C4	0.5 (5)	C11—C12—C13—C14	0.5 (3)
C1—C7—C8—Br1	86.3 (2)	C11—C12—C18—C19	−3.2 (3)
C1—C7—C8—C9	−152.4 (2)	C11—C12—C18—C20	−122.4 (2)
C2—C1—C6—C5	−0.6 (4)	C11—C12—C18—C21	116.0 (3)
C2—C1—C7—O1	−173.4 (3)	C12—C13—C14—Br2	179.65 (16)
C2—C1—C7—C8	7.6 (4)	C12—C13—C14—C15	−0.6 (3)
C2—C3—C4—C5	−0.6 (5)	C13—C12—C18—C19	178.6 (2)
C3—C4—C5—C6	0.1 (5)	C13—C12—C18—C20	59.4 (3)
C4—C5—C6—C1	0.5 (5)	C13—C12—C18—C21	−62.2 (3)
C6—C1—C2—C3	0.1 (4)	C13—C14—C15—C10	0.7 (4)
C6—C1—C7—O1	4.9 (4)	C15—C10—C11—C12	0.9 (4)
C6—C1—C7—C8	−174.1 (2)	C16—O3—C9—C8	−167.1 (5)
C7—C1—C2—C3	178.4 (3)	C16—O3—C9—C10	70.3 (5)
C7—C1—C6—C5	−179.0 (3)	C16'—O3—C9—C8	−151.5 (9)
C7—C8—C9—O3	65.2 (2)	C16'—O3—C9—C10	85.9 (9)
C7—C8—C9—C10	−173.05 (19)	C18—C12—C13—O2	−1.4 (3)
C8—C9—C10—C11	113.1 (2)	C18—C12—C13—C14	178.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···Br2	0.82	2.52	3.0671 (16)	126
O2—H2O···O3^i	0.82	2.23	2.861 (2)	134

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.