Crystal structures of methyl 3,5-di-bromo-4-cyano-benzoate and methyl 3,5-di-bromo-4-iso-cyano-benzoate.

The title crystals, C9H5Br2NO2, are the first reported 2,6-dihalophenyl cyanide-isocyanide pair that have neither three- nor two-dimensional isomorphism. Both crystals contain contacts between the carbonyl O atom and a Br atom. In the crystal of the cyanide, R22(10) inversion dimers form based on C≡N⋯Br contacts, a common packing feature in this series of crystals. In the isocyanide, the corresponding N≡C⋯Br contacts are not observed. Instead, the iso-cyano C atom forms contacts with the meth-oxy C atom. RNC was refined as a two-component pseudo-merohedral twin.

Chemical context & database survey

The crystal packing of 2,6-dihalophenyl cyanides and isocyanides is commonly influenced by C≡N⋯X or N≡C⋯X contacts, especially when X is Br or I (Desiraju & Harlow, 1989 ▸). The crystal structures of isomeric, non-ligand cyanides and isocyanides are usually very similar. There are six reported 2,6-dihalophenyl cyanide–isocyanide pairs (Fig. 1 ▸). Three are in the most recent update of the Cambridge Structural Database (CSD, Version 5.38, May 2017; Groom et al., 2016 ▸), and three were recently completed by our group. The penta­fluoro [(Ia); Bond et al., 2001 ▸) and (Ib); Lentz & Preugschat, 1993 ▸)], 2,6-di­bromo-4-methyl [(IIIa), (IIIb); Noland et al., 2017b ▸], 2,6-di­bromo-4-chloro [(IVa); Britton, 2005 ▸ and (IIVb); Noland & Tritch, 2018 ▸], and 2,4,6-tri­iodo [(VIa), (VIb); Noland et al. 2018 ▸] pairs are each isomorphous. The 2,4,6-tri­chloro [(IIa), (IIb); Pink et al., 2000 ▸] and 2,4,6-tri­bromo [(Va), (Vb); Britton et al., 2016 ▸] pairs each have two-dimensional isomorphism and are polytypic.

Figure 1

The six pairs of 2,6-dihalophenyl cyanides (_a) and isocyanides (_b) previously reported in the CSD. All corresponding crystal pairs are either isomorphous or polytypic.

Two simple 3,5-di­bromo­benzoate esters were found in the CSD (Fig. 2 ▸). Crystals of (VII) contain C(6) chains of C=O⋯Br contacts (Saeed et al., 2010 ▸), and crystals of (VIII) contain C(5) chains of Br⋯Br contacts (Reinhold & Rosati, 1994 ▸). A co-crystal of cyano acid (IXa) with anthracene was recently reported by our group (Noland et al. 2017a ▸). The corresponding iso­cyano acid (IXb) was not observed, probably because of the acid sensitivity of isocyanides (Ugi et al., 1965 ▸), preventing crystallographic comparison of (IXa) and (IXb). The title cyanide (RCN) and isocyanide (RNC) were synthetic inter­mediates to (IXa) and (IXb), and their crystals are presented instead.

Figure 2

3,5-Di­bromo­benzoates (VII) and (VIII) in the CSD. We recently reported (IXa); iso­cyano acid (IXb) was not observed.

Structural commentary

Mol­ecules of RCN and RNC (Fig. 3 ▸) occupy general positions and have similar, typical geometry. Both benzene rings are nearly planar, with mean atomic deviations of 0.005 (2) and 0.002 (3) Å for RCN and RNC, respectively. The most prominent difference between the mol­ecular conformations is the bond angles about the meth­oxy O atoms, which are 117.1 (2)° for C8—O2—C9, and 114.8 (3)° for C18—O12—C19. In RNC, the compression about O12 is probably caused by repulsion between methyl groups in adjacent mol­ecules, rather than the N11≡C17⋯C19 short contact (Table 1 ▸), because the C9—O2 and C19—O12 bond lengths are nearly identical.

Figure 3

The mol­ecular structures of (a) RCN and (b) RNC, with atom labeling and displacement ellipsoids at the 50% probability level.

Table 1

Contact geometry for RCN and RNC (Å, °)

A—B⋯C	A—B	B⋯C	A—B⋯C
C1≡N1⋯Br2i	1.138 (3)	3.041 (3)	128.6 (2)
C8=O1⋯Br6ii	1.201 (3)	3.025 (2)	143.7 (2)
N11≡C17⋯C19iii	1.162 (5)	3.240 (6)	112.9 (3)
C18=O11⋯Br16iv	1.207 (5)	3.133 (3)	146.6 (3)

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

Supra­molecular features

Mol­ecules of RCN form (10) inversion dimers based on C1≡N1⋯Br2 short contacts (Table 1 ▸), similar to the centric contacts found in crystals of (II) and (IV)–(VI). Adjacent dimers are connected along [201] by C8=O1⋯Br6 contacts similar to those found in (VII). Adjacent dimers are mutually inclined by 44.03 (7)°. The resulting sheet structure (Fig. 4 ▸) is staggered so that the methyl groups are spread apart to minimize steric congestion (Fig. 5 ▸). Crystals of RNC have a different packing motif, a slice of which is anti­parallel ribbons parallel to [001] (Fig. 6 ▸). Each mol­ecule of RNC participates in four short contacts between two pairs of mol­ecules that are related by the (x + 1, y, z) translation, forming a three-dimensional network. Contacted mol­ecules are mutually inclined by 42.0 (1)°. Half of the contacts are C18=O11⋯Br16 contacts, similar to those found in RCN and (VII). The other half are N11≡C17⋯C19 contacts, instead of the anti­cipated N11≡C17⋯Br12 contacts. It is inter­esting that the cyano group in RCN favors contacting a Br atom, but the iso­cyano group in RNC favors contacting the meth­oxy C atom.

Figure 4

The sheet structure in a crystal of RCN, viewed along [100]. Dashed magenta lines represent short contacts.

Figure 5

The sheet structure in a crystal of RCN, viewed along [503]. The same mol­ecules are shown as in Fig. 4 ▸.

Figure 6

A slice of a crystal of RNC parallel to (100), viewed nearly along [100].

Synthesis and crystallization

Methyl 4-amino-3,5-di­bromo­benzoate (RNH2) and methyl 3,5-di­bromo-4-cyano­benzoate (RCN) were taken from material prepared in our recent study (Noland et al. 2017a ▸; Fig. 7 ▸).

Figure 7

The synthesis of RCN and RNC.

Methyl 3,5-di­bromo-4-formamido­benzoate (RFA) was prepared from (RNH2, 1.24 g) by the formyl­ation procedure described by Britton et al. (2016 ▸), with 1,2-di­chloro­ethane in place of tetra­hydro­furan, giving white needles (1.31 g, 97%). M.p. 489–490 K; 1H NMR (300 MHz, (CD3)2CO) δ 9.203 (s, 1H), 8.441 (s, 1H), 8.226 (s, 2H), 3.928 (s, 3H); 13C NMR (126 MHz, (CD3)2SO) δ 163.5 (1C), 160.2 (1C), 139.5 (1C), 132.5 (2C), 130.7 (1C), 123.5 (2C), 52.9 (1C); IR (KBr, cm−1) 3153, 1727, 1664, 1524, 1282, 1154, 966, 765, 749; MS–ESI [M + Na]+ calculated for C9H7 79Br81BrNO3 359.8664, found 359.8662.

Methyl 3,5-di­bromo-4-iso­cyano­benzoate (RNC) was prepared from (RFA, 594 mg) by the dehydration procedure described by Britton et al. (2016 ▸), giving a brown powder (490 mg), which was crystallized as described below (453 mg, 84%). M.p. 391–392 K; 1H NMR (500 MHz, CD2Cl2) δ 8.278 (s, H13A, H15A), 3.930 (s, H19A, H19B, H19C); 13C NMR (126 MHz, (CD3)2SO) δ 174.1 (C17), 163.0 (C18), 132.5 (C13, C15), 132.3 (C14), 130.1 (C11), 121.0 (C12, C16), 53.2 (C19); IR (KBr, cm−1) 3073, 2961, 2853, 2122, 1722, 1426, 1275, 971, 764, 753; MS–EI [M]+ calculated for C9H5 79Br81BrNO2 316.8682, found 316.8699.

Crystallization: Crystals of RCN and RNC were grown by slow evaporation of solutions in di­chloro­methane–pentane, followed by deca­ntation, washing with pentane, and then drying at room temperature and reduced pressure (10 Pa, 4 h). RCN was obtained as colorless blocks, and RNC was obtained as colorless needles.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. A direct-methods solution was calculated, followed by full-matrix least squares/difference-Fourier cycles. All H atoms were placed in calculated positions and refined as riding atoms. For aryl H atoms, C—H = 0.95 Å and U iso(H) = 1.2U eq(C). For methyl H atoms, C—H = 0.98 Å and U iso(H) = 1.5U eq(C). RNC was refined as a two-component pseudo-merohedral twin in an 0.67:0.33 ratio, with a 180° rotation of [001] as the twinning symmetry element.

Table 2

Experimental details

	RCN	RNC
Crystal data
Chemical formula	C9H5Br2NO2	C9H5Br2NO2
M r	318.96	318.96
Crystal system, space group	Monoclinic, P21/c	Monoclinic, P21/n
Temperature (K)	173	173
a, b, c (Å)	3.9273 (18), 17.881 (8), 14.739 (7)	3.9233 (9), 13.554 (3), 18.672 (4)
β (°)	93.757 (7)	90.002 (3)
V (Å3)	1032.9 (8)	992.9 (4)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm−1)	7.82	8.13
Crystal size (mm)	0.32 × 0.27 × 0.25	0.50 × 0.12 × 0.03
Data collection
Diffractometer	Bruker APEXII CCD	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 ▸)	Multi-scan (SADABS; Sheldrick, 1996 ▸)
T min, T max	0.414, 0.746	0.418, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	11889, 2426, 2013	11400, 2277, 2132
R int	0.043	0.053
(sin θ/λ)max (Å−1)	0.657	0.650
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.026, 0.059, 1.07	0.029, 0.069, 1.02
No. of reflections	2426	2277
No. of parameters	128	129
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.37, −0.52	0.85, −0.65

Computer programs: APEX2 and SAINT (Bruker, 2012 ▸), SHELXT2014 (Sheldrick 2015a ▸), SHELXL2014 (Sheldrick, 2015b ▸), Mercury (Macrae et al., 2008 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) RCN, RNC. DOI: 10.1107/S2056989018002256/lh5870sup1.cif

Structure factors: contains datablock(s) RCN. DOI: 10.1107/S2056989018002256/lh5870RCNsup2.hkl

Structure factors: contains datablock(s) RNC. DOI: 10.1107/S2056989018002256/lh5870RNCsup3.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989018002256/lh5870RCNsup4.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989018002256/lh5870RNCsup5.cml

CCDC references: 1525814, 1525813

Additional supporting information: crystallographic information; 3D view; checkCIF report

C9H5Br2NO2	Dx = 2.051 Mg m−3
Mr = 318.96	Melting point: 410 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 3.9273 (18) Å	Cell parameters from 2977 reflections
b = 17.881 (8) Å	θ = 2.7–27.6°
c = 14.739 (7) Å	µ = 7.82 mm−1
β = 93.757 (7)°	T = 173 K
V = 1032.9 (8) Å3	Block, colourless
Z = 4	0.32 × 0.27 × 0.25 mm
F(000) = 608

Bruker APEXII CCD diffractometer	2013 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.043
φ and ω scans	θmax = 27.8°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→5
Tmin = 0.414, Tmax = 0.746	k = −23→23
11889 measured reflections	l = −19→19
2426 independent reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026	H-atom parameters constrained
wR(F2) = 0.059	w = 1/[σ2(Fo2) + (0.0274P)2 + 0.0295P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
2426 reflections	Δρmax = 0.37 e Å−3
128 parameters	Δρmin = −0.52 e Å−3

Experimental. Dr. K.J. Tritch / Prof. W.E. Noland

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.

	x	y	z	Uiso*/Ueq
C1	0.6370 (6)	0.65590 (14)	0.86321 (17)	0.0196 (5)
C2	0.7731 (6)	0.67398 (14)	0.95078 (16)	0.0199 (5)
Br2	0.74408 (8)	0.60384 (2)	1.04534 (2)	0.02954 (9)
C3	0.9245 (6)	0.74304 (14)	0.96807 (17)	0.0204 (5)
H3A	1.0169	0.7548	1.0275	0.024*
C4	0.9412 (6)	0.79516 (14)	0.89815 (17)	0.0197 (5)
C5	0.8100 (6)	0.77825 (14)	0.81049 (16)	0.0193 (5)
H5A	0.8216	0.8138	0.7629	0.023*
C6	0.6624 (6)	0.70889 (15)	0.79351 (16)	0.0193 (5)
Br6	0.49149 (7)	0.68383 (2)	0.67451 (2)	0.02395 (9)
C7	0.4695 (7)	0.58481 (16)	0.84529 (18)	0.0251 (6)
N1	0.3333 (6)	0.52966 (14)	0.82991 (16)	0.0359 (6)
C8	1.1066 (6)	0.86917 (14)	0.92064 (17)	0.0203 (5)
O1	1.2632 (5)	0.88220 (11)	0.99159 (14)	0.0357 (5)
O2	1.0590 (5)	0.91760 (10)	0.85308 (13)	0.0292 (5)
C9	1.2078 (8)	0.99150 (15)	0.8667 (2)	0.0326 (7)
H9A	1.1628	1.0215	0.8115	0.049*
H9B	1.4548	0.9868	0.8798	0.049*
H9C	1.1063	1.0161	0.9179	0.049*

	U11	U22	U33	U12	U13	U23
C1	0.0183 (13)	0.0179 (13)	0.0226 (13)	0.0008 (11)	0.0018 (10)	−0.0010 (11)
C2	0.0187 (13)	0.0237 (14)	0.0174 (12)	0.0018 (11)	0.0022 (10)	0.0039 (10)
Br2	0.03760 (18)	0.02881 (17)	0.02189 (15)	−0.00681 (12)	−0.00044 (12)	0.00724 (11)
C3	0.0225 (13)	0.0220 (14)	0.0164 (12)	0.0024 (11)	−0.0001 (10)	−0.0013 (10)
C4	0.0174 (13)	0.0198 (13)	0.0219 (13)	0.0036 (10)	0.0021 (10)	−0.0002 (10)
C5	0.0213 (14)	0.0189 (14)	0.0177 (13)	0.0009 (10)	0.0011 (10)	0.0011 (10)
C6	0.0164 (13)	0.0256 (14)	0.0158 (12)	0.0028 (10)	0.0002 (10)	−0.0029 (10)
Br6	0.02657 (15)	0.02717 (16)	0.01735 (14)	−0.00102 (11)	−0.00436 (10)	−0.00197 (10)
C7	0.0273 (15)	0.0289 (16)	0.0189 (13)	−0.0006 (12)	0.0009 (11)	0.0023 (11)
N1	0.0486 (17)	0.0303 (15)	0.0282 (13)	−0.0132 (12)	−0.0021 (11)	0.0024 (11)
C8	0.0214 (13)	0.0207 (14)	0.0187 (13)	0.0020 (11)	0.0014 (10)	0.0007 (10)
O1	0.0487 (13)	0.0283 (11)	0.0283 (11)	−0.0060 (10)	−0.0112 (10)	0.0008 (9)
O2	0.0403 (12)	0.0195 (10)	0.0270 (10)	−0.0074 (9)	−0.0036 (9)	0.0025 (8)
C9	0.0387 (17)	0.0196 (15)	0.0388 (17)	−0.0077 (12)	−0.0018 (13)	0.0053 (12)

C1—C2	1.402 (4)	C5—H5A	0.9500
C1—C6	1.406 (4)	C6—Br6	1.890 (2)
C1—C7	1.448 (4)	C7—N1	1.138 (3)
C2—C3	1.387 (3)	C8—O1	1.201 (3)
C2—Br2	1.884 (3)	C8—O2	1.324 (3)
C3—C4	1.394 (3)	O2—C9	1.454 (3)
C3—H3A	0.9500	C9—H9A	0.9800
C4—C5	1.393 (3)	C9—H9B	0.9800
C4—C8	1.502 (4)	C9—H9C	0.9800
C5—C6	1.385 (4)
C2—C1—C6	118.4 (2)	C5—C6—C1	121.4 (2)
C2—C1—C7	120.8 (2)	C5—C6—Br6	119.93 (19)
C6—C1—C7	120.8 (2)	C1—C6—Br6	118.71 (19)
C3—C2—C1	120.5 (2)	N1—C7—C1	178.6 (3)
C3—C2—Br2	120.19 (19)	O1—C8—O2	124.6 (2)
C1—C2—Br2	119.32 (19)	O1—C8—C4	123.6 (2)
C2—C3—C4	120.0 (2)	O2—C8—C4	111.9 (2)
C2—C3—H3A	120.0	C8—O2—C9	117.1 (2)
C4—C3—H3A	120.0	O2—C9—H9A	109.5
C5—C4—C3	120.5 (2)	O2—C9—H9B	109.5
C5—C4—C8	121.6 (2)	H9A—C9—H9B	109.5
C3—C4—C8	117.8 (2)	O2—C9—H9C	109.5
C6—C5—C4	119.2 (2)	H9A—C9—H9C	109.5
C6—C5—H5A	120.4	H9B—C9—H9C	109.5
C4—C5—H5A	120.4
C6—C1—C2—C3	0.9 (4)	C4—C5—C6—Br6	−178.62 (18)
C7—C1—C2—C3	−178.1 (2)	C2—C1—C6—C5	−1.6 (4)
C6—C1—C2—Br2	−179.76 (18)	C7—C1—C6—C5	177.4 (2)
C7—C1—C2—Br2	1.2 (3)	C2—C1—C6—Br6	178.18 (18)
C1—C2—C3—C4	0.2 (4)	C7—C1—C6—Br6	−2.8 (3)
Br2—C2—C3—C4	−179.11 (18)	C5—C4—C8—O1	−169.5 (3)
C2—C3—C4—C5	−0.7 (4)	C3—C4—C8—O1	10.1 (4)
C2—C3—C4—C8	179.8 (2)	C5—C4—C8—O2	10.4 (3)
C3—C4—C5—C6	0.0 (4)	C3—C4—C8—O2	−170.0 (2)
C8—C4—C5—C6	179.5 (2)	O1—C8—O2—C9	0.0 (4)
C4—C5—C6—C1	1.2 (4)	C4—C8—O2—C9	−179.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···Br6i	0.95	2.97	3.878 (3)	160

C9H5Br2NO2	Dx = 2.134 Mg m−3
Mr = 318.96	Melting point: 391 K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 3.9233 (9) Å	Cell parameters from 2953 reflections
b = 13.554 (3) Å	θ = 2.2–27.4°
c = 18.672 (4) Å	µ = 8.13 mm−1
β = 90.002 (3)°	T = 173 K
V = 992.9 (4) Å3	Needle, colourless
Z = 4	0.50 × 0.12 × 0.03 mm
F(000) = 608

Bruker APEXII CCD diffractometer	2132 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.053
φ and ω scans	θmax = 27.5°, θmin = 1.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→5
Tmin = 0.418, Tmax = 0.746	k = −17→17
11400 measured reflections	l = −24→24
2277 independent reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029	H-atom parameters constrained
wR(F2) = 0.069	w = 1/[σ2(Fo2) + (0.0385P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
2277 reflections	Δρmax = 0.85 e Å−3
129 parameters	Δρmin = −0.65 e Å−3

Experimental. Dr. K.J. Tritch / Prof. W.E. Noland

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. Refined as a 2-component pseudo-merohedral twin in an 0.67:0.33 ratio.

	x	y	z	Uiso*/Ueq
C11	0.5312 (10)	0.5930 (3)	0.6880 (2)	0.0187 (7)
C12	0.6653 (9)	0.5605 (2)	0.6228 (2)	0.0193 (7)
Br12	0.85319 (11)	0.43306 (2)	0.61597 (2)	0.02497 (11)
C13	0.6606 (10)	0.6211 (2)	0.5634 (2)	0.0216 (8)
H13A	0.7504	0.5983	0.5192	0.026*
C14	0.5246 (10)	0.7153 (2)	0.56835 (19)	0.0188 (8)
C15	0.3900 (9)	0.7501 (2)	0.63284 (19)	0.0185 (8)
H15A	0.2971	0.8147	0.6360	0.022*
C16	0.3944 (9)	0.6887 (3)	0.69219 (18)	0.0181 (7)
Br16	0.21859 (11)	0.73312 (2)	0.78028 (2)	0.02528 (11)
N11	0.5307 (9)	0.5321 (2)	0.74742 (17)	0.0240 (7)
C17	0.5282 (15)	0.4800 (3)	0.7968 (2)	0.0402 (11)
C18	0.5255 (11)	0.7760 (2)	0.5011 (2)	0.0210 (8)
O11	0.6712 (9)	0.75012 (19)	0.44732 (15)	0.0321 (7)
O12	0.3467 (8)	0.85902 (17)	0.50681 (14)	0.0270 (6)
C19	0.3135 (13)	0.9150 (3)	0.4408 (2)	0.0306 (9)
H19A	0.1794	0.9747	0.4498	0.046*
H19B	0.1984	0.8745	0.4046	0.046*
H19C	0.5404	0.9335	0.4234	0.046*

	U11	U22	U33	U12	U13	U23
C11	0.0214 (19)	0.0192 (16)	0.0153 (18)	−0.0050 (15)	−0.0002 (15)	−0.0001 (14)
C12	0.0169 (19)	0.0166 (15)	0.0246 (19)	−0.0021 (13)	−0.0002 (18)	−0.0022 (13)
Br12	0.0280 (2)	0.01584 (15)	0.0310 (2)	0.00238 (13)	0.0011 (2)	−0.00255 (14)
C13	0.021 (2)	0.0209 (16)	0.0231 (19)	−0.0018 (15)	0.0031 (16)	−0.0034 (14)
C14	0.023 (2)	0.0176 (16)	0.0160 (18)	−0.0025 (14)	0.0008 (15)	−0.0007 (14)
C15	0.020 (2)	0.0185 (15)	0.0175 (19)	−0.0019 (13)	−0.0019 (15)	−0.0022 (13)
C16	0.0196 (19)	0.0210 (16)	0.0138 (16)	−0.0049 (14)	0.0001 (14)	−0.0060 (13)
Br16	0.0296 (2)	0.02670 (18)	0.01950 (19)	−0.00182 (15)	0.00484 (19)	−0.00694 (13)
N11	0.0310 (19)	0.0198 (15)	0.0213 (17)	−0.0029 (13)	0.0011 (14)	−0.0014 (13)
C17	0.065 (3)	0.028 (2)	0.027 (2)	−0.008 (2)	−0.003 (2)	−0.0025 (19)
C18	0.027 (2)	0.0172 (17)	0.0187 (19)	−0.0031 (14)	−0.0015 (16)	−0.0021 (14)
O11	0.048 (2)	0.0235 (12)	0.0245 (15)	0.0022 (14)	0.0087 (16)	0.0019 (10)
O12	0.0391 (17)	0.0219 (12)	0.0201 (13)	0.0055 (12)	0.0001 (13)	0.0016 (10)
C19	0.039 (3)	0.0269 (18)	0.026 (2)	0.0042 (19)	−0.003 (2)	0.0071 (15)

C11—N11	1.383 (5)	C15—H15A	0.9500
C11—C12	1.396 (5)	C16—Br16	1.882 (3)
C11—C16	1.407 (5)	N11—C17	1.162 (5)
C12—C13	1.379 (5)	C18—O11	1.207 (5)
C12—Br12	1.883 (3)	C18—O12	1.331 (4)
C13—C14	1.387 (5)	O12—C19	1.454 (4)
C13—H13A	0.9500	C19—H19A	0.9800
C14—C15	1.397 (5)	C19—H19B	0.9800
C14—C18	1.501 (5)	C19—H19C	0.9800
C15—C16	1.386 (5)
N11—C11—C12	120.8 (3)	C15—C16—C11	120.9 (3)
N11—C11—C16	120.3 (3)	C15—C16—Br16	120.2 (3)
C12—C11—C16	118.9 (3)	C11—C16—Br16	118.9 (3)
C13—C12—C11	120.5 (3)	C17—N11—C11	179.1 (4)
C13—C12—Br12	119.8 (3)	O11—C18—O12	124.2 (4)
C11—C12—Br12	119.7 (3)	O11—C18—C14	122.6 (3)
C12—C13—C14	120.0 (3)	O12—C18—C14	113.2 (3)
C12—C13—H13A	120.0	C18—O12—C19	114.8 (3)
C14—C13—H13A	120.0	O12—C19—H19A	109.5
C13—C14—C15	120.9 (3)	O12—C19—H19B	109.5
C13—C14—C18	116.6 (3)	H19A—C19—H19B	109.5
C15—C14—C18	122.5 (3)	O12—C19—H19C	109.5
C16—C15—C14	118.8 (3)	H19A—C19—H19C	109.5
C16—C15—H15A	120.6	H19B—C19—H19C	109.5
C14—C15—H15A	120.6
N11—C11—C12—C13	179.1 (3)	C14—C15—C16—Br16	179.5 (3)
C16—C11—C12—C13	−0.6 (6)	N11—C11—C16—C15	−179.3 (4)
N11—C11—C12—Br12	−0.8 (5)	C12—C11—C16—C15	0.4 (5)
C16—C11—C12—Br12	179.5 (3)	N11—C11—C16—Br16	1.1 (5)
C11—C12—C13—C14	0.6 (6)	C12—C11—C16—Br16	−179.2 (3)
Br12—C12—C13—C14	−179.5 (3)	C13—C14—C18—O11	−8.6 (6)
C12—C13—C14—C15	−0.3 (6)	C15—C14—C18—O11	172.4 (4)
C12—C13—C14—C18	−179.3 (4)	C13—C14—C18—O12	170.5 (3)
C13—C14—C15—C16	0.0 (6)	C15—C14—C18—O12	−8.5 (6)
C18—C14—C15—C16	179.0 (3)	O11—C18—O12—C19	4.8 (6)
C14—C15—C16—C11	−0.1 (6)	C14—C18—O12—C19	−174.2 (4)