Comparison of computationally cheap methods for providing insight into the crystal packing of highly bromo­methyl­ated azo­benzenes

For five bromo­methyl­ated azo­benzenes, namely (E)-[4-(bromo­meth­yl)phen­yl][4-(di­bromo­meth­yl)phen­yl]diazene, C₁₄H₁₁Br₃N₂, (E)-1,2-bis­[4-(di­bromo­meth­yl)phen­yl]diazene, C₁₄H₁₀Br₄N₂, (E)-[3-(bromo­meth­yl)phen­yl][3-(di­bromo­meth­yl)phen­yl]diazene, C₁₄H₁₁Br₃N₂, (E)-[3-(di­bromo­meth­yl)phen­yl][3-(tri­bromo­meth­yl)phen­yl]diazene, C₁₄H₁₀Br₄N₂, and (E)-1,2-bis­[3-(di­bromo­meth­yl)phen­yl]diazene, C₁₄H₉Br₅N₂, the computationally cheap CLP PIXEL approach and CrystalExplorer were used for calculating lattice energies and performing Hirshfeld surface analysis via the enrichment ratios of atomic contacts. The procedures and caveats are discussed in detail. The findings from these tools are contrasted with the results of geometric analysis of the structures. We conclude that an energy-based discussion of the crystal packing provides substanti­ally more insight than one based purely on geometry, as has so long been the custom in crystallography. In addition, we find a surprising shortage of halogen–halogen inter­actions in these highly bromo­methyl­ated compounds.

Computing details

For all structures, data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015) and shelXle(Hübschle et al., 2011); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015).

(E)-[4-(Bromomethyl)phenyl][4-(dibromomethyl)phenyl]diazene (5)

Crystal data

C14H11Br3N2	Dx = 2.036 Mg m^−3
Mr = 446.98	Melting point: 146–148 C K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.538 (1) Å	Cell parameters from 6003 reflections
b = 5.283 (1) Å	θ = 2.5–31.0°
c = 32.801 (4) Å	µ = 8.29 mm^−1
β = 99.692 (5)°	T = 100 K
V = 1458.4 (4) Å^3	Plate, orange
Z = 4	0.45 × 0.35 × 0.18 mm
F(000) = 856

Data collection

Bruker SMART 1000 diffractometer	4445 independent reflections
Radiation source: fine-focus sealed tube	3947 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
ω scans	θmax = 31.4°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −12→12
Tmin = 0.316, Tmax = 0.746	k = −7→7
13694 measured reflections	l = −47→46

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H-atom parameters constrained
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0221P)^2 + 4.4145P] where P = (Fo^2 + 2Fc^2)/3
4445 reflections	(Δ/σ)max = 0.003
172 parameters	Δρmax = 1.41 e Å^−3
0 restraints	Δρmin = −1.06 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Br1	0.61597 (4)	1.05498 (6)	0.95232 (2)	0.01420 (8)
Br2	0.92730 (4)	0.72243 (7)	0.95898 (2)	0.01715 (9)
Br3	0.67770 (4)	1.00291 (6)	0.54184 (2)	0.01277 (8)
N1	0.6931 (4)	0.7036 (6)	0.75752 (9)	0.0146 (5)
N2	0.8014 (4)	0.8208 (6)	0.74401 (8)	0.0142 (5)
C1	0.6963 (4)	0.7378 (6)	0.80072 (9)	0.0123 (6)
C2	0.7807 (4)	0.9300 (7)	0.82415 (10)	0.0137 (6)
H2	0.837587	1.052512	0.811275	0.016*
C3	0.7804 (4)	0.9398 (6)	0.86638 (10)	0.0115 (6)
H3	0.836770	1.070822	0.882433	0.014*
C4	0.6985 (4)	0.7599 (6)	0.88542 (9)	0.0106 (6)
C5	0.6105 (4)	0.5728 (6)	0.86189 (10)	0.0126 (6)
H5	0.552169	0.452275	0.874761	0.015*
C6	0.6084 (4)	0.5639 (7)	0.81934 (10)	0.0137 (6)
H6	0.547020	0.438890	0.803044	0.016*
C7	0.7088 (4)	0.7544 (6)	0.93152 (10)	0.0109 (6)
H7	0.648722	0.603256	0.938825	0.013*
C11	0.8005 (4)	0.7837 (6)	0.70107 (10)	0.0120 (6)
C12	0.7182 (4)	0.5901 (7)	0.67781 (10)	0.0139 (6)
H12	0.658565	0.471034	0.690584	0.017*
C13	0.7239 (4)	0.5723 (6)	0.63590 (10)	0.0129 (6)
H13	0.668797	0.439258	0.620078	0.015*
C14	0.8103 (4)	0.7486 (6)	0.61663 (10)	0.0120 (6)
C15	0.8945 (4)	0.9373 (7)	0.64037 (10)	0.0140 (6)
H15	0.955100	1.055490	0.627698	0.017*
C16	0.8909 (4)	0.9551 (7)	0.68238 (10)	0.0140 (6)
H16	0.949921	1.083574	0.698432	0.017*
C17	0.8106 (4)	0.7318 (6)	0.57118 (10)	0.0139 (6)
H17A	0.768991	0.564811	0.560795	0.017*
H17B	0.920742	0.747939	0.565756	0.017*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.01541 (16)	0.01421 (16)	0.01425 (15)	0.00470 (12)	0.00615 (11)	−0.00083 (11)
Br2	0.00833 (15)	0.0289 (2)	0.01414 (15)	0.00497 (13)	0.00154 (11)	0.00409 (12)
Br3	0.00854 (15)	0.01608 (16)	0.01370 (14)	−0.00059 (12)	0.00187 (11)	0.00244 (11)
N1	0.0130 (13)	0.0186 (14)	0.0126 (12)	−0.0007 (11)	0.0031 (10)	0.0008 (10)
N2	0.0145 (13)	0.0177 (14)	0.0111 (12)	−0.0002 (11)	0.0037 (10)	0.0001 (10)
C1	0.0090 (14)	0.0173 (16)	0.0108 (13)	0.0018 (12)	0.0022 (11)	0.0003 (11)
C2	0.0130 (15)	0.0151 (15)	0.0136 (14)	−0.0015 (12)	0.0045 (12)	0.0018 (11)
C3	0.0078 (14)	0.0121 (14)	0.0151 (14)	−0.0030 (11)	0.0037 (11)	−0.0005 (11)
C4	0.0076 (13)	0.0130 (14)	0.0119 (13)	0.0028 (11)	0.0039 (11)	0.0013 (11)
C5	0.0078 (14)	0.0143 (15)	0.0164 (14)	−0.0031 (12)	0.0038 (11)	0.0008 (11)
C6	0.0104 (15)	0.0167 (16)	0.0142 (14)	−0.0023 (12)	0.0026 (11)	−0.0008 (12)
C7	0.0075 (13)	0.0116 (14)	0.0147 (14)	0.0013 (11)	0.0047 (11)	−0.0010 (11)
C11	0.0083 (14)	0.0157 (15)	0.0121 (13)	0.0019 (12)	0.0015 (11)	0.0015 (11)
C12	0.0126 (15)	0.0154 (15)	0.0138 (14)	−0.0005 (12)	0.0027 (11)	0.0019 (11)
C13	0.0100 (14)	0.0141 (15)	0.0144 (14)	−0.0011 (12)	0.0019 (11)	−0.0006 (11)
C14	0.0104 (14)	0.0134 (15)	0.0126 (13)	0.0028 (12)	0.0031 (11)	−0.0003 (11)
C15	0.0104 (15)	0.0176 (16)	0.0148 (14)	−0.0024 (12)	0.0049 (11)	0.0005 (12)
C16	0.0100 (15)	0.0181 (16)	0.0139 (14)	−0.0021 (12)	0.0023 (11)	−0.0030 (12)
C17	0.0147 (15)	0.0141 (15)	0.0135 (14)	0.0023 (12)	0.0044 (12)	0.0003 (11)

Geometric parameters (Å, º)

Br1—C7	1.948 (3)	C6—H6	0.9500
Br2—C7	1.938 (3)	C7—H7	1.0000
Br3—C17	1.974 (3)	C11—C12	1.393 (5)
N1—N2	1.254 (4)	C11—C16	1.397 (5)
N1—C1	1.424 (4)	C12—C13	1.387 (4)
N2—C11	1.421 (4)	C12—H12	0.9500
C1—C6	1.391 (5)	C13—C14	1.403 (5)
C1—C2	1.398 (5)	C13—H13	0.9500
C2—C3	1.386 (4)	C14—C15	1.389 (5)
C2—H2	0.9500	C14—C17	1.494 (4)
C3—C4	1.389 (4)	C15—C16	1.387 (4)
C3—H3	0.9500	C15—H15	0.9500
C4—C5	1.394 (5)	C16—H16	0.9500
C4—C7	1.500 (4)	C17—H17A	0.9900
C5—C6	1.394 (4)	C17—H17B	0.9900
C5—H5	0.9500
N2—N1—C1	113.4 (3)	Br1—C7—H7	108.2
N1—N2—C11	113.6 (3)	C12—C11—C16	120.0 (3)
C6—C1—C2	120.3 (3)	C12—C11—N2	124.2 (3)
C6—C1—N1	115.6 (3)	C16—C11—N2	115.7 (3)
C2—C1—N1	124.1 (3)	C13—C12—C11	119.6 (3)
C3—C2—C1	119.3 (3)	C13—C12—H12	120.2
C3—C2—H2	120.4	C11—C12—H12	120.2
C1—C2—H2	120.4	C12—C13—C14	120.7 (3)
C2—C3—C4	120.6 (3)	C12—C13—H13	119.7
C2—C3—H3	119.7	C14—C13—H13	119.7
C4—C3—H3	119.7	C15—C14—C13	119.1 (3)
C3—C4—C5	120.1 (3)	C15—C14—C17	120.9 (3)
C3—C4—C7	121.2 (3)	C13—C14—C17	120.0 (3)
C5—C4—C7	118.6 (3)	C16—C15—C14	120.6 (3)
C6—C5—C4	119.6 (3)	C16—C15—H15	119.7
C6—C5—H5	120.2	C14—C15—H15	119.7
C4—C5—H5	120.2	C15—C16—C11	119.9 (3)
C1—C6—C5	120.0 (3)	C15—C16—H16	120.0
C1—C6—H6	120.0	C11—C16—H16	120.0
C5—C6—H6	120.0	C14—C17—Br3	110.3 (2)
C4—C7—Br2	111.0 (2)	C14—C17—H17A	109.6
C4—C7—Br1	112.3 (2)	Br3—C17—H17A	109.6
Br2—C7—Br1	108.96 (15)	C14—C17—H17B	109.6
C4—C7—H7	108.2	Br3—C17—H17B	109.6
Br2—C7—H7	108.2	H17A—C17—H17B	108.1
C1—N1—N2—C11	178.9 (3)	C5—C4—C7—Br1	−117.6 (3)
N2—N1—C1—C6	−163.6 (3)	N1—N2—C11—C12	−16.0 (5)
N2—N1—C1—C2	16.2 (5)	N1—N2—C11—C16	164.7 (3)
C6—C1—C2—C3	2.3 (5)	C16—C11—C12—C13	−1.4 (5)
N1—C1—C2—C3	−177.5 (3)	N2—C11—C12—C13	179.4 (3)
C1—C2—C3—C4	0.6 (5)	C11—C12—C13—C14	−0.7 (5)
C2—C3—C4—C5	−2.5 (5)	C12—C13—C14—C15	2.0 (5)
C2—C3—C4—C7	174.6 (3)	C12—C13—C14—C17	−177.9 (3)
C3—C4—C5—C6	1.6 (5)	C13—C14—C15—C16	−1.3 (5)
C7—C4—C5—C6	−175.5 (3)	C17—C14—C15—C16	178.6 (3)
C2—C1—C6—C5	−3.2 (5)	C14—C15—C16—C11	−0.8 (5)
N1—C1—C6—C5	176.7 (3)	C12—C11—C16—C15	2.1 (5)
C4—C5—C6—C1	1.2 (5)	N2—C11—C16—C15	−178.6 (3)
C3—C4—C7—Br2	−57.0 (4)	C15—C14—C17—Br3	−73.7 (4)
C5—C4—C7—Br2	120.1 (3)	C13—C14—C17—Br3	106.1 (3)
C3—C4—C7—Br1	65.3 (4)

(E)-1,2-Bis[4-(dibromomethyl)phenyl]diazene (6)

Crystal data

C14H10Br4N2	Dx = 2.220 Mg m^−3
Mr = 525.88	Melting point: 151-153 C K
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.379 (3) Å	Cell parameters from 2626 reflections
b = 8.6401 (10) Å	θ = 2.4–30.9°
c = 9.8451 (10) Å	µ = 10.22 mm^−1
β = 114.797 (2)°	T = 100 K
V = 1573.7 (3) Å^3	Block, red
Z = 4	0.51 × 0.48 × 0.38 mm
F(000) = 992

Data collection

Bruker SMART 1000 diffractometer	2322 independent reflections
Radiation source: fine-focus sealed tube	2049 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω scans	θmax = 31.2°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −24→29
Tmin = 0.406, Tmax = 0.746	k = −12→12
5663 measured reflections	l = −14→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.024	H-atom parameters constrained
wR(F^2) = 0.056	w = 1/[σ^2(Fo^2) + (0.0249P)^2 + 1.3279P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.002
2322 reflections	Δρmax = 0.82 e Å^−3
92 parameters	Δρmin = −0.60 e Å^−3
0 restraints	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00183 (16)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Br1	0.23156 (2)	0.44833 (3)	0.27413 (3)	0.01427 (7)
Br2	0.36677 (2)	0.26407 (2)	0.50812 (3)	0.01505 (8)
N1	0.48068 (10)	0.9973 (2)	0.5356 (2)	0.0120 (4)
C1	0.44107 (11)	0.8564 (2)	0.5167 (2)	0.0096 (4)
C2	0.44206 (13)	0.7356 (2)	0.4222 (3)	0.0124 (4)
H2	0.470686	0.743489	0.367280	0.015*
C3	0.40098 (13)	0.6056 (2)	0.4103 (3)	0.0124 (4)
H3	0.401720	0.522915	0.347309	0.015*
C4	0.35791 (12)	0.5935 (2)	0.4902 (2)	0.0102 (4)
C5	0.35691 (12)	0.7138 (2)	0.5828 (3)	0.0116 (4)
H5	0.327697	0.706657	0.636582	0.014*
C6	0.39902 (12)	0.8452 (2)	0.5966 (3)	0.0119 (4)
H6	0.398937	0.927179	0.660821	0.014*
C7	0.31141 (13)	0.4548 (2)	0.4738 (3)	0.0118 (4)
H7	0.290721	0.461829	0.549495	0.014*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.00683 (12)	0.01807 (11)	0.01567 (13)	−0.00205 (7)	0.00252 (9)	−0.00163 (8)
Br2	0.01663 (14)	0.00894 (10)	0.01627 (13)	−0.00040 (7)	0.00363 (10)	0.00142 (7)
N1	0.0100 (10)	0.0096 (7)	0.0146 (10)	−0.0021 (6)	0.0032 (8)	0.0006 (6)
C1	0.0058 (10)	0.0094 (8)	0.0104 (10)	−0.0015 (7)	0.0004 (8)	0.0003 (7)
C2	0.0119 (11)	0.0125 (9)	0.0136 (11)	−0.0025 (8)	0.0060 (9)	−0.0026 (8)
C3	0.0133 (11)	0.0110 (9)	0.0138 (11)	−0.0019 (7)	0.0065 (9)	−0.0031 (7)
C4	0.0079 (10)	0.0092 (8)	0.0113 (10)	−0.0019 (7)	0.0017 (8)	0.0006 (7)
C5	0.0103 (11)	0.0122 (9)	0.0129 (11)	−0.0010 (7)	0.0055 (9)	0.0007 (7)
C6	0.0115 (11)	0.0103 (8)	0.0133 (11)	−0.0006 (7)	0.0046 (9)	−0.0009 (7)
C7	0.0111 (11)	0.0104 (9)	0.0144 (11)	−0.0023 (7)	0.0057 (9)	−0.0021 (7)

Geometric parameters (Å, º)

Br1—C7	1.958 (2)	C3—C4	1.407 (3)
Br2—C7	1.945 (2)	C3—H3	0.9500
N1—N1^i	1.255 (4)	C4—C5	1.388 (3)
N1—C1	1.429 (3)	C4—C7	1.494 (3)
C1—C6	1.389 (3)	C5—C6	1.395 (3)
C1—C2	1.404 (3)	C5—H5	0.9500
C2—C3	1.376 (3)	C6—H6	0.9500
C2—H2	0.9500	C7—H7	1.0000
N1^i—N1—C1	114.3 (2)	C4—C5—C6	119.7 (2)
C6—C1—C2	120.49 (19)	C4—C5—H5	120.2
C6—C1—N1	115.77 (18)	C6—C5—H5	120.2
C2—C1—N1	123.7 (2)	C1—C6—C5	120.2 (2)
C3—C2—C1	119.1 (2)	C1—C6—H6	119.9
C3—C2—H2	120.5	C5—C6—H6	119.9
C1—C2—H2	120.5	C4—C7—Br2	111.44 (16)
C2—C3—C4	120.8 (2)	C4—C7—Br1	110.73 (15)
C2—C3—H3	119.6	Br2—C7—Br1	109.11 (10)
C4—C3—H3	119.6	C4—C7—H7	108.5
C5—C4—C3	119.76 (19)	Br2—C7—H7	108.5
C5—C4—C7	119.2 (2)	Br1—C7—H7	108.5
C3—C4—C7	120.99 (19)
N1^i—N1—C1—C6	178.6 (2)	C7—C4—C5—C6	−178.7 (2)
N1^i—N1—C1—C2	−2.6 (4)	C2—C1—C6—C5	−0.4 (3)
C6—C1—C2—C3	−0.2 (3)	N1—C1—C6—C5	178.4 (2)
N1—C1—C2—C3	−179.0 (2)	C4—C5—C6—C1	0.8 (3)
C1—C2—C3—C4	0.6 (3)	C5—C4—C7—Br2	−128.80 (19)
C2—C3—C4—C5	−0.3 (3)	C3—C4—C7—Br2	52.9 (3)
C2—C3—C4—C7	178.0 (2)	C5—C4—C7—Br1	109.6 (2)
C3—C4—C5—C6	−0.4 (3)	C3—C4—C7—Br1	−68.7 (2)

Symmetry code: (i) −x+1, −y+2, −z+1.

(E)-[3-(Bromomethyl)phenyl][3-(dibromomethyl)phenyl]diazene (7)

Crystal data

C14H11Br3N2	Dx = 2.006 Mg m^−3
Mr = 446.98	Melting point: 120-121 C K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.1219 (12) Å	Cell parameters from 3951 reflections
b = 16.904 (2) Å	θ = 2.4–30.6°
c = 10.3633 (14) Å	µ = 8.16 mm^−1
β = 112.122 (2)°	T = 100 K
V = 1480.4 (3) Å^3	Plate, orange
Z = 4	0.52 × 0.45 × 0.15 mm
F(000) = 856

Data collection

Bruker SMART 1000 diffractometer	4362 independent reflections
Radiation source: fine-focus sealed tube	3587 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ω scans	θmax = 31.2°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −12→9
Tmin = 0.349, Tmax = 0.746	k = −23→23
12573 measured reflections	l = −15→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.104	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0501P)^2 + 3.0958P] where P = (Fo^2 + 2Fc^2)/3
4362 reflections	(Δ/σ)max = 0.001
172 parameters	Δρmax = 2.24 e Å^−3
0 restraints	Δρmin = −1.56 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Br1	1.09235 (4)	0.54419 (2)	0.34234 (3)	0.01965 (10)
Br2	0.94505 (5)	0.41237 (2)	0.11026 (4)	0.02092 (10)
Br3	−0.00058 (5)	0.24139 (2)	0.40366 (4)	0.02690 (11)
N1	0.4960 (4)	0.43930 (17)	0.3487 (3)	0.0157 (6)
N2	0.5936 (3)	0.39273 (16)	0.4327 (3)	0.0136 (5)
C1	0.5604 (4)	0.48745 (18)	0.2701 (3)	0.0134 (6)
C2	0.7098 (4)	0.47785 (19)	0.2674 (3)	0.0139 (6)
H2	0.779123	0.438302	0.322746	0.017*
C3	0.7572 (4)	0.52686 (19)	0.1825 (3)	0.0138 (6)
C4	0.6551 (4)	0.58540 (19)	0.1023 (3)	0.0166 (6)
H4	0.688248	0.618877	0.044799	0.020*
C5	0.5056 (4)	0.5950 (2)	0.1060 (3)	0.0177 (7)
H5	0.437065	0.635233	0.052167	0.021*
C6	0.4570 (4)	0.54534 (19)	0.1888 (3)	0.0157 (6)
H6	0.353993	0.550622	0.190390	0.019*
C7	0.9147 (4)	0.51828 (19)	0.1700 (3)	0.0157 (6)
H7	0.917280	0.556187	0.096781	0.019*
C11	0.5242 (4)	0.34393 (18)	0.5071 (3)	0.0133 (6)
C12	0.3667 (4)	0.34994 (19)	0.4934 (3)	0.0144 (6)
H12	0.298856	0.387776	0.431683	0.017*
C13	0.3095 (4)	0.3004 (2)	0.5702 (3)	0.0153 (6)
C14	0.4110 (4)	0.2447 (2)	0.6609 (3)	0.0178 (7)
H14	0.371548	0.210409	0.712955	0.021*
C15	0.5673 (5)	0.2392 (2)	0.6753 (3)	0.0184 (7)
H15	0.635204	0.201636	0.737713	0.022*
C16	0.6254 (4)	0.2887 (2)	0.5980 (3)	0.0160 (6)
H16	0.732794	0.285066	0.607032	0.019*
C17	0.1423 (5)	0.3077 (2)	0.5578 (4)	0.0226 (7)
H17A	0.108921	0.363708	0.540690	0.027*
H17B	0.133999	0.291236	0.646449	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.00936 (17)	0.02557 (18)	0.02167 (16)	−0.00070 (13)	0.00316 (13)	−0.00445 (13)
Br2	0.0205 (2)	0.01986 (16)	0.02431 (17)	0.00050 (13)	0.01055 (14)	−0.00337 (12)
Br3	0.01277 (19)	0.0289 (2)	0.0310 (2)	−0.00430 (15)	−0.00094 (14)	0.00581 (15)
N1	0.0137 (15)	0.0168 (12)	0.0150 (12)	−0.0008 (11)	0.0036 (11)	0.0013 (10)
N2	0.0107 (14)	0.0148 (12)	0.0141 (11)	0.0004 (10)	0.0034 (10)	0.0010 (10)
C1	0.0125 (16)	0.0140 (13)	0.0115 (12)	−0.0020 (12)	0.0021 (11)	−0.0012 (11)
C2	0.0109 (16)	0.0150 (14)	0.0125 (13)	−0.0004 (12)	0.0006 (11)	0.0002 (11)
C3	0.0120 (16)	0.0137 (13)	0.0122 (12)	0.0000 (12)	0.0007 (11)	−0.0013 (11)
C4	0.0169 (18)	0.0144 (14)	0.0154 (14)	−0.0015 (13)	0.0025 (13)	0.0029 (11)
C5	0.0152 (17)	0.0167 (14)	0.0170 (14)	0.0010 (13)	0.0012 (12)	0.0032 (12)
C6	0.0105 (16)	0.0165 (14)	0.0172 (14)	−0.0001 (12)	0.0020 (12)	−0.0003 (12)
C7	0.0159 (17)	0.0161 (14)	0.0144 (13)	−0.0018 (13)	0.0048 (12)	−0.0012 (11)
C11	0.0131 (16)	0.0131 (13)	0.0122 (12)	−0.0024 (12)	0.0029 (11)	−0.0015 (11)
C12	0.0130 (16)	0.0151 (14)	0.0133 (13)	0.0012 (12)	0.0030 (12)	0.0000 (11)
C13	0.0128 (16)	0.0176 (14)	0.0148 (13)	−0.0018 (12)	0.0044 (12)	−0.0050 (11)
C14	0.0171 (18)	0.0198 (15)	0.0152 (14)	−0.0054 (14)	0.0045 (13)	0.0003 (12)
C15	0.0173 (18)	0.0161 (14)	0.0163 (14)	−0.0006 (13)	0.0001 (12)	0.0032 (12)
C16	0.0105 (16)	0.0174 (14)	0.0177 (14)	−0.0027 (13)	0.0024 (12)	−0.0007 (12)
C17	0.0166 (19)	0.0266 (18)	0.0269 (17)	−0.0027 (15)	0.0108 (15)	−0.0020 (14)

Geometric parameters (Å, º)

Br1—C7	1.957 (3)	C6—H6	0.9500
Br2—C7	1.948 (3)	C7—H7	1.0000
Br3—C17	1.985 (4)	C11—C12	1.393 (5)
N1—N2	1.260 (4)	C11—C16	1.398 (5)
N1—C1	1.425 (4)	C12—C13	1.385 (5)
N2—C11	1.430 (4)	C12—H12	0.9500
C1—C2	1.383 (5)	C13—C14	1.404 (5)
C1—C6	1.400 (5)	C13—C17	1.487 (5)
C2—C3	1.390 (4)	C14—C15	1.380 (6)
C2—H2	0.9500	C14—H14	0.9500
C3—C4	1.398 (4)	C15—C16	1.395 (5)
C3—C7	1.497 (5)	C15—H15	0.9500
C4—C5	1.388 (5)	C16—H16	0.9500
C4—H4	0.9500	C17—H17A	0.9900
C5—C6	1.387 (5)	C17—H17B	0.9900
C5—H5	0.9500
N2—N1—C1	114.6 (3)	Br1—C7—H7	107.5
N1—N2—C11	113.1 (3)	C12—C11—C16	120.8 (3)
C2—C1—C6	121.0 (3)	C12—C11—N2	123.5 (3)
C2—C1—N1	124.5 (3)	C16—C11—N2	115.7 (3)
C6—C1—N1	114.4 (3)	C13—C12—C11	119.6 (3)
C1—C2—C3	119.1 (3)	C13—C12—H12	120.2
C1—C2—H2	120.4	C11—C12—H12	120.2
C3—C2—H2	120.4	C12—C13—C14	119.6 (3)
C2—C3—C4	120.1 (3)	C12—C13—C17	119.7 (3)
C2—C3—C7	122.3 (3)	C14—C13—C17	120.6 (3)
C4—C3—C7	117.6 (3)	C15—C14—C13	120.8 (3)
C5—C4—C3	120.5 (3)	C15—C14—H14	119.6
C5—C4—H4	119.7	C13—C14—H14	119.6
C3—C4—H4	119.7	C14—C15—C16	119.9 (3)
C6—C5—C4	119.5 (3)	C14—C15—H15	120.1
C6—C5—H5	120.2	C16—C15—H15	120.1
C4—C5—H5	120.2	C15—C16—C11	119.4 (3)
C5—C6—C1	119.7 (3)	C15—C16—H16	120.3
C5—C6—H6	120.2	C11—C16—H16	120.3
C1—C6—H6	120.2	C13—C17—Br3	111.4 (2)
C3—C7—Br2	111.9 (2)	C13—C17—H17A	109.4
C3—C7—Br1	113.0 (2)	Br3—C17—H17A	109.4
Br2—C7—Br1	109.14 (17)	C13—C17—H17B	109.4
C3—C7—H7	107.5	Br3—C17—H17B	109.4
Br2—C7—H7	107.5	H17A—C17—H17B	108.0
C1—N1—N2—C11	−178.5 (3)	C4—C3—C7—Br1	114.7 (3)
N2—N1—C1—C2	9.4 (5)	N1—N2—C11—C12	−3.0 (4)
N2—N1—C1—C6	−173.0 (3)	N1—N2—C11—C16	177.5 (3)
C6—C1—C2—C3	0.2 (5)	C16—C11—C12—C13	−0.3 (5)
N1—C1—C2—C3	177.6 (3)	N2—C11—C12—C13	−179.7 (3)
C1—C2—C3—C4	0.6 (5)	C11—C12—C13—C14	−0.1 (5)
C1—C2—C3—C7	−177.8 (3)	C11—C12—C13—C17	178.8 (3)
C2—C3—C4—C5	−0.3 (5)	C12—C13—C14—C15	0.5 (5)
C7—C3—C4—C5	178.2 (3)	C17—C13—C14—C15	−178.3 (3)
C3—C4—C5—C6	−0.8 (5)	C13—C14—C15—C16	−0.7 (5)
C4—C5—C6—C1	1.5 (5)	C14—C15—C16—C11	0.3 (5)
C2—C1—C6—C5	−1.2 (5)	C12—C11—C16—C15	0.2 (5)
N1—C1—C6—C5	−178.9 (3)	N2—C11—C16—C15	179.6 (3)
C2—C3—C7—Br2	56.7 (4)	C12—C13—C17—Br3	88.1 (3)
C4—C3—C7—Br2	−121.7 (3)	C14—C13—C17—Br3	−93.0 (3)
C2—C3—C7—Br1	−66.9 (4)

(E)-1,2-Bis[3-(dibromomethyl)phenyl]diazene (8)

Crystal data

C14H10Br4N2	F(000) = 248
Mr = 525.88	Dx = 2.274 Mg m^−3
Triclinic, P1	Melting point: 130-132 C K
a = 4.899 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.294 (2) Å	Cell parameters from 2578 reflections
c = 9.942 (3) Å	θ = 2.5–31.2°
α = 98.103 (4)°	µ = 10.47 mm^−1
β = 103.640 (3)°	T = 100 K
γ = 96.650 (3)°	Block, red
V = 384.0 (2) Å^3	0.45 × 0.25 × 0.20 mm
Z = 1

Data collection

Bruker SMART 1000 diffractometer	2249 independent reflections
Radiation source: fine-focus sealed tube	1993 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω scans	θmax = 31.2°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −6→7
Tmin = 0.308, Tmax = 0.746	k = −11→11
5417 measured reflections	l = −14→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.085	w = 1/[σ^2(Fo^2) + (0.0356P)^2 + 0.5445P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
2249 reflections	Δρmax = 1.08 e Å^−3
92 parameters	Δρmin = −1.11 e Å^−3
0 restraints	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.022 (2)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Br1	0.70209 (6)	0.44619 (3)	0.34815 (3)	0.01868 (11)
Br2	0.20145 (6)	0.33924 (4)	0.06638 (3)	0.01621 (11)
N1	0.0313 (5)	−0.0658 (3)	0.4728 (3)	0.0132 (5)
C1	0.4352 (5)	0.1125 (3)	0.2374 (3)	0.0112 (5)
C2	0.5243 (6)	−0.0295 (4)	0.1812 (3)	0.0120 (5)
H2	0.638710	−0.023851	0.116479	0.014*
C3	0.4455 (6)	−0.1808 (4)	0.2198 (3)	0.0139 (5)
H3	0.505053	−0.277981	0.181129	0.017*
C4	0.2802 (6)	−0.1874 (3)	0.3148 (3)	0.0134 (5)
H4	0.225421	−0.289857	0.340843	0.016*
C5	0.1935 (5)	−0.0453 (3)	0.3726 (3)	0.0112 (5)
C6	0.2684 (6)	0.1049 (3)	0.3332 (3)	0.0121 (5)
H6	0.206496	0.201498	0.371228	0.015*
C7	0.5238 (6)	0.2695 (4)	0.1914 (3)	0.0128 (5)
H7	0.667019	0.248602	0.136699	0.015*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.02306 (17)	0.00910 (16)	0.01960 (17)	−0.00228 (11)	0.00056 (11)	0.00057 (11)
Br2	0.01474 (16)	0.01765 (18)	0.01783 (17)	0.00473 (11)	0.00286 (10)	0.00875 (11)
N1	0.0128 (10)	0.0114 (11)	0.0144 (11)	0.0008 (9)	0.0016 (8)	0.0026 (9)
C1	0.0096 (11)	0.0097 (12)	0.0123 (12)	0.0010 (9)	−0.0007 (8)	0.0021 (9)
C2	0.0128 (11)	0.0116 (13)	0.0098 (11)	0.0021 (10)	0.0000 (9)	0.0009 (10)
C3	0.0187 (13)	0.0075 (12)	0.0140 (12)	0.0035 (10)	0.0019 (10)	−0.0004 (10)
C4	0.0165 (12)	0.0070 (12)	0.0146 (12)	0.0006 (10)	0.0010 (9)	0.0011 (10)
C5	0.0099 (11)	0.0106 (13)	0.0117 (11)	0.0002 (9)	0.0005 (8)	0.0024 (9)
C6	0.0126 (11)	0.0093 (12)	0.0136 (12)	0.0019 (9)	0.0016 (9)	0.0024 (10)
C7	0.0114 (11)	0.0102 (12)	0.0150 (12)	0.0005 (9)	0.0007 (9)	0.0018 (10)

Geometric parameters (Å, º)

Br1—C7	1.938 (3)	C2—H2	0.9500
Br2—C7	1.965 (3)	C3—C4	1.384 (4)
N1—N1^i	1.253 (5)	C3—H3	0.9500
N1—C5	1.429 (4)	C4—C5	1.393 (4)
C1—C2	1.393 (4)	C4—H4	0.9500
C1—C6	1.397 (4)	C5—C6	1.393 (4)
C1—C7	1.491 (4)	C6—H6	0.9500
C2—C3	1.402 (4)	C7—H7	1.0000
N1^i—N1—C5	113.9 (3)	C4—C5—C6	120.1 (3)
C2—C1—C6	120.1 (3)	C4—C5—N1	115.8 (2)
C2—C1—C7	117.7 (2)	C6—C5—N1	124.1 (3)
C6—C1—C7	122.2 (2)	C5—C6—C1	119.6 (3)
C1—C2—C3	120.1 (3)	C5—C6—H6	120.2
C1—C2—H2	119.9	C1—C6—H6	120.2
C3—C2—H2	119.9	C1—C7—Br1	112.63 (19)
C4—C3—C2	119.4 (3)	C1—C7—Br2	111.38 (18)
C4—C3—H3	120.3	Br1—C7—Br2	109.85 (14)
C2—C3—H3	120.3	C1—C7—H7	107.6
C3—C4—C5	120.6 (3)	Br1—C7—H7	107.6
C3—C4—H4	119.7	Br2—C7—H7	107.6
C5—C4—H4	119.7
C6—C1—C2—C3	0.4 (4)	C4—C5—C6—C1	−1.2 (4)
C7—C1—C2—C3	−179.5 (2)	N1—C5—C6—C1	178.0 (2)
C1—C2—C3—C4	−0.4 (4)	C2—C1—C6—C5	0.4 (4)
C2—C3—C4—C5	−0.4 (4)	C7—C1—C6—C5	−179.7 (2)
C3—C4—C5—C6	1.2 (4)	C2—C1—C7—Br1	−128.1 (2)
C3—C4—C5—N1	−178.1 (3)	C6—C1—C7—Br1	52.1 (3)
N1^i—N1—C5—C4	176.8 (3)	C2—C1—C7—Br2	108.0 (2)
N1^i—N1—C5—C6	−2.4 (4)	C6—C1—C7—Br2	−71.9 (3)

Symmetry code: (i) −x, −y, −z+1.

(E)-[3-(Dibromomethyl)phenyl][3-(tribromomethyl)phenyl]diazene (9)

Crystal data

C14H9Br5N2	F(000) = 564
Mr = 604.78	Dx = 2.375 Mg m^−3
Triclinic, P1	Melting point: 142-143 C K
a = 7.0161 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.5634 (13) Å	Cell parameters from 1139 reflections
c = 14.897 (2) Å	θ = 2.5–31.1°
α = 103.257 (2)°	µ = 11.87 mm^−1
β = 102.974 (2)°	T = 100 K
γ = 91.703 (2)°	Block, orange
V = 845.8 (2) Å^3	0.45 × 0.43 × 0.21 mm
Z = 2

Data collection

Bruker SMART 1000 diffractometer	6827 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.066
ω scans	θmax = 31.3°, θmin = 1.5°
Absorption correction: multi-scan (TWINABS; Sheldrick, 2012)	h = −10→9
Tmin = 0.014, Tmax = 0.052	k = −12→12
15148 measured reflections	l = 0→21
8987 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.137	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0797P)^2] where P = (Fo^2 + 2Fc^2)/3
8987 reflections	(Δ/σ)max = 0.001
213 parameters	Δρmax = 1.81 e Å^−3
58 restraints	Δρmin = −1.56 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refined as a 2-component twin. The structure was solved using direct methods with only the non-overlapping reflections of component 1. The structure was refined using the hklf 5 routine with all reflections of both components (including the overlapping ones), resulting in a BASF value of 0.481 (1).

Minor but clearly resolved disorder was observed for the dibromomethyl group. The major and minor moieties were restrained to have similar geometries (SAME restraint of SHELXL, e.s.d. 0.02 Angstrom). The carbon atom C10 was included in the disorder modeling and 1,2 and 1,3 C—C distances involving the major and minor components of C10 were restrained to be similar (SADI restraint of SHELXL, e.s.d. 0.02 Angstrom). U^ij components of ADPs for disordered atoms closer to each other than 2.0 Angstrom were restrained to be similar. Subject to these conditions the occupancy ratio refined to 0.9601 (19) to 0.0399 (19).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	0.90836 (8)	1.08792 (7)	0.36771 (5)	0.02429 (15)
Br2	0.46223 (8)	1.07967 (7)	0.37101 (5)	0.02458 (15)
N1	0.7664 (6)	0.6292 (6)	0.5351 (3)	0.0191 (9)
N2	0.7756 (6)	0.4901 (6)	0.5496 (3)	0.0206 (9)
C1	0.7187 (7)	0.6301 (7)	0.4368 (4)	0.0181 (10)
C3	0.6536 (7)	0.9644 (6)	0.3090 (4)	0.0177 (10)
C4	0.6279 (8)	0.6584 (7)	0.2506 (4)	0.0203 (10)
H4	0.595699	0.667201	0.186613	0.024*
C5	0.7064 (7)	0.7811 (7)	0.4171 (4)	0.0179 (10)
H5	0.729007	0.874865	0.467909	0.021*
C6	0.6409 (8)	0.5070 (7)	0.2697 (4)	0.0238 (11)
H6	0.619070	0.413565	0.218693	0.029*
C7	0.8868 (8)	0.3130 (8)	0.7556 (4)	0.0258 (12)
H7	0.901178	0.208546	0.766690	0.031*
C8	0.9118 (8)	0.4452 (7)	0.8309 (4)	0.0251 (12)
H8	0.944967	0.431907	0.893937	0.030*
C9	0.6853 (8)	0.4911 (7)	0.3621 (4)	0.0212 (10)
H9	0.693124	0.387486	0.374978	0.025*
C11	0.8212 (7)	0.4838 (7)	0.6464 (4)	0.0191 (10)
C12	0.8889 (8)	0.5986 (7)	0.8152 (4)	0.0228 (11)
C14	0.8450 (7)	0.6200 (7)	0.7228 (4)	0.0205 (10)
H14	0.831452	0.724552	0.711806	0.025*
C15	0.8403 (8)	0.3321 (7)	0.6629 (4)	0.0217 (11)
H15	0.821753	0.240510	0.610947	0.026*
C16	0.6612 (7)	0.7963 (7)	0.3236 (4)	0.0186 (10)
Br3	0.58568 (11)	0.97768 (9)	0.17782 (4)	0.03647 (18)
C10	0.9060 (9)	0.7456 (8)	0.8944 (4)	0.0281 (13)	0.9601 (19)
H10	0.878219	0.840293	0.866313	0.034*	0.9601 (19)
Br4	0.71615 (10)	0.72607 (10)	0.97006 (5)	0.0349 (2)	0.9601 (19)
Br5	1.16852 (11)	0.78735 (12)	0.98005 (6)	0.0371 (2)	0.9601 (19)
C10B	0.942 (6)	0.735 (2)	0.9006 (16)	0.034 (7)	0.0399 (19)
H10B	0.851659	0.724703	0.942383	0.041*	0.0399 (19)
Br4B	0.910 (3)	0.930 (2)	0.8670 (14)	0.049 (5)	0.0399 (19)
Br5B	1.209 (3)	0.711 (3)	0.9683 (15)	0.0371 (2)	0.0399 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0214 (3)	0.0195 (3)	0.0315 (3)	0.00001 (18)	0.0047 (2)	0.0070 (2)
Br2	0.0248 (3)	0.0212 (3)	0.0314 (3)	0.0066 (2)	0.0109 (2)	0.0091 (2)
N1	0.020 (2)	0.020 (2)	0.017 (2)	0.0008 (16)	0.0021 (16)	0.0049 (18)
N2	0.024 (2)	0.020 (2)	0.019 (2)	0.0013 (17)	0.0053 (17)	0.0067 (19)
C1	0.018 (2)	0.017 (3)	0.018 (2)	−0.0003 (17)	0.0016 (18)	0.004 (2)
C3	0.025 (2)	0.017 (3)	0.009 (2)	0.0005 (18)	0.0024 (18)	−0.0006 (19)
C4	0.024 (2)	0.021 (3)	0.014 (2)	0.0005 (19)	0.0027 (19)	0.000 (2)
C5	0.023 (2)	0.016 (3)	0.012 (2)	0.0020 (18)	0.0036 (18)	−0.0009 (19)
C6	0.025 (3)	0.021 (3)	0.021 (3)	0.000 (2)	0.002 (2)	−0.001 (2)
C7	0.028 (3)	0.024 (3)	0.031 (3)	0.005 (2)	0.009 (2)	0.015 (2)
C8	0.027 (3)	0.025 (3)	0.026 (3)	0.004 (2)	0.005 (2)	0.012 (2)
C9	0.024 (2)	0.014 (3)	0.023 (3)	−0.0007 (19)	0.004 (2)	0.003 (2)
C11	0.019 (2)	0.021 (3)	0.018 (3)	0.0020 (18)	0.0026 (19)	0.007 (2)
C12	0.023 (3)	0.025 (3)	0.021 (3)	0.001 (2)	0.005 (2)	0.007 (2)
C14	0.022 (2)	0.018 (3)	0.023 (3)	0.0022 (19)	0.005 (2)	0.008 (2)
C15	0.025 (2)	0.017 (3)	0.025 (3)	0.0035 (19)	0.006 (2)	0.006 (2)
C16	0.019 (2)	0.021 (3)	0.017 (3)	0.0016 (18)	0.0063 (19)	0.006 (2)
Br3	0.0642 (4)	0.0289 (4)	0.0136 (3)	0.0024 (3)	0.0029 (3)	0.0060 (2)
C10	0.035 (3)	0.030 (3)	0.017 (3)	0.001 (2)	0.000 (2)	0.007 (3)
Br4	0.0415 (4)	0.0424 (4)	0.0201 (3)	0.0067 (3)	0.0107 (3)	0.0022 (3)
Br5	0.0384 (4)	0.0395 (5)	0.0274 (4)	−0.0099 (3)	−0.0045 (3)	0.0095 (3)
C10B	0.040 (11)	0.035 (11)	0.022 (10)	−0.002 (10)	−0.001 (10)	0.007 (10)
Br4B	0.063 (10)	0.045 (10)	0.027 (9)	0.009 (8)	−0.004 (7)	0.000 (8)
Br5B	0.0384 (4)	0.0395 (5)	0.0274 (4)	−0.0099 (3)	−0.0045 (3)	0.0095 (3)

Geometric parameters (Å, º)

Br1—C3	1.960 (5)	C7—H7	0.9500
Br2—C3	1.962 (5)	C8—C12	1.394 (8)
N1—N2	1.259 (7)	C8—H8	0.9500
N1—C1	1.428 (7)	C9—H9	0.9500
N2—C11	1.420 (7)	C11—C15	1.381 (8)
C1—C5	1.391 (8)	C11—C14	1.407 (8)
C1—C9	1.403 (8)	C12—C14	1.398 (8)
C3—C16	1.505 (8)	C12—C10B	1.484 (19)
C3—Br3	1.935 (5)	C12—C10	1.495 (9)
C4—C16	1.383 (7)	C14—H14	0.9500
C4—C6	1.392 (8)	C15—H15	0.9500
C4—H4	0.9500	C10—Br4	1.954 (7)
C5—C16	1.394 (7)	C10—Br5	1.960 (6)
C5—H5	0.9500	C10—H10	1.0000
C6—C9	1.381 (8)	C10B—Br4B	1.86 (2)
C6—H6	0.9500	C10B—Br5B	1.95 (3)
C7—C8	1.374 (9)	C10B—H10B	1.0000
C7—C15	1.394 (8)
N2—N1—C1	113.7 (5)	C15—C11—C14	120.3 (5)
N1—N2—C11	115.5 (5)	C15—C11—N2	115.8 (5)
C5—C1—C9	119.9 (5)	C14—C11—N2	123.9 (5)
C5—C1—N1	115.8 (5)	C8—C12—C14	120.3 (6)
C9—C1—N1	124.2 (5)	C8—C12—C10B	116.3 (10)
C16—C3—Br3	115.2 (4)	C14—C12—C10B	122.8 (11)
C16—C3—Br1	110.3 (3)	C8—C12—C10	122.6 (6)
Br3—C3—Br1	106.9 (3)	C14—C12—C10	117.1 (6)
C16—C3—Br2	110.6 (3)	C12—C14—C11	118.7 (5)
Br3—C3—Br2	107.0 (2)	C12—C14—H14	120.7
Br1—C3—Br2	106.4 (2)	C11—C14—H14	120.7
C16—C4—C6	120.8 (5)	C11—C15—C7	120.3 (6)
C16—C4—H4	119.6	C11—C15—H15	119.9
C6—C4—H4	119.6	C7—C15—H15	119.9
C1—C5—C16	120.7 (5)	C4—C16—C5	118.8 (5)
C1—C5—H5	119.6	C4—C16—C3	124.0 (5)
C16—C5—H5	119.6	C5—C16—C3	117.1 (5)
C9—C6—C4	120.7 (5)	C12—C10—Br4	111.1 (4)
C9—C6—H6	119.7	C12—C10—Br5	112.4 (4)
C4—C6—H6	119.7	Br4—C10—Br5	107.9 (3)
C8—C7—C15	119.9 (6)	C12—C10—H10	108.4
C8—C7—H7	120.0	Br4—C10—H10	108.4
C15—C7—H7	120.0	Br5—C10—H10	108.4
C7—C8—C12	120.4 (6)	C12—C10B—Br4B	110.8 (14)
C7—C8—H8	119.8	C12—C10B—Br5B	107.0 (18)
C12—C8—H8	119.8	Br4B—C10B—Br5B	115 (2)
C6—C9—C1	119.1 (5)	C12—C10B—H10B	108.1
C6—C9—H9	120.5	Br4B—C10B—H10B	108.1
C1—C9—H9	120.5	Br5B—C10B—H10B	108.1
C1—N1—N2—C11	−179.5 (4)	N2—C11—C15—C7	179.4 (5)
N2—N1—C1—C5	179.9 (4)	C8—C7—C15—C11	0.6 (8)
N2—N1—C1—C9	−0.3 (7)	C6—C4—C16—C5	−0.6 (8)
C9—C1—C5—C16	0.0 (8)	C6—C4—C16—C3	178.8 (5)
N1—C1—C5—C16	179.8 (4)	C1—C5—C16—C4	0.3 (8)
C16—C4—C6—C9	0.7 (8)	C1—C5—C16—C3	−179.2 (4)
C15—C7—C8—C12	0.7 (8)	Br3—C3—C16—C4	1.6 (7)
C4—C6—C9—C1	−0.5 (8)	Br1—C3—C16—C4	−119.5 (5)
C5—C1—C9—C6	0.1 (8)	Br2—C3—C16—C4	123.0 (5)
N1—C1—C9—C6	−179.7 (5)	Br3—C3—C16—C5	−179.0 (4)
N1—N2—C11—C15	−177.1 (5)	Br1—C3—C16—C5	59.9 (5)
N1—N2—C11—C14	3.4 (7)	Br2—C3—C16—C5	−57.5 (5)
C7—C8—C12—C14	−1.6 (8)	C8—C12—C10—Br4	−58.4 (7)
C7—C8—C12—C10B	−173 (2)	C14—C12—C10—Br4	120.5 (5)
C7—C8—C12—C10	177.3 (5)	C8—C12—C10—Br5	62.7 (7)
C8—C12—C14—C11	1.1 (8)	C14—C12—C10—Br5	−118.4 (5)
C10B—C12—C14—C11	172 (2)	C8—C12—C10B—Br4B	178.3 (15)
C10—C12—C14—C11	−177.9 (5)	C14—C12—C10B—Br4B	7 (3)
C15—C11—C14—C12	0.3 (8)	C8—C12—C10B—Br5B	53 (3)
N2—C11—C14—C12	179.7 (5)	C14—C12—C10B—Br5B	−118.3 (12)
C14—C11—C15—C7	−1.1 (8)