Anomalous halogen bonds in the crystal structures of 1,2,3-tri­bromo-5-nitro­benzene and 1,3-di­bromo-2-iodo-5-nitro­benzene

Two halogenated nitro­benzene derivatives have been characterized. The substitution of a Br substituent by an I atom modifies the network of halogen bonds, and gives rise to the formation of non-classical Br^δ+...I^δ- bonds.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.019 Å
• R factor = 0.066
• wR factor = 0.196
• Data-to-parameter ratio = 14.4

Structure: II

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.023 Å
• R factor = 0.061
• wR factor = 0.153
• Data-to-parameter ratio = 24.8

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level B
PLAT341_ALERT_3_B Low Bond Precision on  C-C Bonds ...............     0.0194 Ang.
PLAT431_ALERT_2_B Short Inter HL..A  Contact Br12   ..  O2      ..       3.01 Ang.

Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         48 %
PLAT334_ALERT_2_C Small Average Benzene  C-C Dist. C11    -C16           1.37 Ang.
PLAT431_ALERT_2_C Short Inter HL..A  Contact Br1    ..  O12     ..       3.23 Ang.
PLAT431_ALERT_2_C Short Inter HL..A  Contact Br3    ..  O11     ..       3.23 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......     15.447 Check
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.818 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.596         10 Report
PLAT975_ALERT_2_C Check Calcd Residual Density  1.08A From      O2       0.51 eA-3

Alert level G
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          1 Report
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......     Please Check

   0 ALERT level A = Most likely a serious problem - resolve or explain
   2 ALERT level B = A potentially serious problem, consider carefully
   8 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   2 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check




Datablock: II


Alert level B
PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low ....         36 %
PLAT342_ALERT_3_B Low Bond Precision on  C-C Bonds ...............     0.0227 Ang.

Alert level C
PLAT234_ALERT_4_C Large Hirshfeld Difference C4     --  C5      ..       0.16 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......     26.149 Check
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      3.177 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         48 Report

Alert level G
PLAT158_ALERT_4_G The Input Unitcell is NOT Standard/Reduced .....     Please Check
PLAT431_ALERT_2_G Short Inter HL..A  Contact I2     ..  O1      ..       3.22 Ang.
PLAT431_ALERT_2_G Short Inter HL..A  Contact I12    ..  O11     ..       3.25 Ang.
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          2 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         46 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   2 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

For both compounds, data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS (Bruker, 1997); data reduction: XSCANS (Bruker, 1997); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

(I) 1,2,3-Tribromo-5-nitrobenzene

Crystal data

C6H2Br3NO2	F(000) = 664
Mr = 359.82	Dx = 2.688 Mg m^−3
Triclinic, P1	Melting point: 380 K
a = 7.641 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.040 (5) Å	Cell parameters from 48 reflections
c = 14.917 (6) Å	θ = 4.8–12.4°
α = 83.91 (3)°	µ = 13.57 mm^−1
β = 79.86 (4)°	T = 298 K
γ = 81.49 (4)°	Irregular, colourless
V = 889.2 (8) Å^3	0.42 × 0.40 × 0.30 mm
Z = 4

Data collection

Bruker P4 diffractometer	1503 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.120
Graphite monochromator	θmax = 25.1°, θmin = 2.6°
ω scans	h = −8→9
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983)	k = −9→9
Tmin = 0.0002, Tmax = 0.001	l = 0→17
6070 measured reflections	3 standard reflections every 97 reflections
3141 independent reflections	intensity decay: 1%

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)] = 0.066	H-atom parameters constrained
wR(F^2) = 0.196	w = 1/[σ^2(Fo^2) + (0.050P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.47	(Δ/σ)max < 0.001
3141 reflections	Δρmax = 0.79 e Å^−3
218 parameters	Δρmin = −1.00 e Å^−3
0 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.0063 (12)
Primary atom site location: structure-invariant direct methods

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

	x	y	z	Uiso*/Ueq
Br1	0.1438 (2)	0.3194 (2)	0.05082 (13)	0.0863 (6)
Br2	0.2958 (2)	0.0254 (2)	0.20089 (11)	0.0855 (6)
Br3	0.4312 (2)	−0.3604 (2)	0.13778 (10)	0.0791 (5)
C1	0.2177 (18)	0.1018 (19)	0.0215 (9)	0.070 (4)
C2	0.2831 (17)	−0.0235 (17)	0.0860 (9)	0.063 (3)
C3	0.3360 (14)	−0.1910 (16)	0.0555 (8)	0.056 (3)
C4	0.3227 (18)	−0.2259 (19)	−0.0296 (9)	0.069 (4)
H4	0.3573	−0.3355	−0.0465	0.083*
C5	0.2615 (17)	−0.1072 (16)	−0.0895 (10)	0.064 (3)
C6	0.2067 (16)	0.0562 (16)	−0.0661 (9)	0.059 (3)
H6	0.1619	0.1373	−0.1085	0.071*
N1	0.2502 (16)	−0.1453 (18)	−0.1809 (8)	0.075 (3)
O1	0.2967 (16)	−0.2925 (16)	−0.2012 (7)	0.094 (3)
O2	0.1923 (18)	−0.0342 (15)	−0.2318 (8)	0.105 (4)
Br11	0.3943 (2)	0.2012 (2)	0.39885 (13)	0.0891 (6)
Br12	0.1013 (2)	0.1170 (2)	0.58586 (10)	0.0795 (6)
Br13	−0.3231 (2)	0.2845 (2)	0.59130 (11)	0.0865 (6)
C11	0.151 (2)	0.2912 (18)	0.4092 (12)	0.077 (4)
C12	0.0303 (18)	0.2505 (18)	0.4860 (10)	0.064 (3)
C13	−0.150 (2)	0.323 (2)	0.4913 (9)	0.073 (4)
C14	−0.2002 (19)	0.4188 (19)	0.4208 (9)	0.070 (4)
H14	−0.3207	0.4619	0.4232	0.084*
C15	−0.079 (2)	0.4583 (18)	0.3427 (8)	0.068 (4)
C16	0.0943 (19)	0.3923 (18)	0.3375 (9)	0.068 (4)
H16	0.1756	0.4155	0.2850	0.082*
N11	−0.1327 (18)	0.5801 (16)	0.2644 (10)	0.076 (3)
O11	−0.2882 (14)	0.6432 (13)	0.2757 (7)	0.083 (3)
O12	−0.0224 (17)	0.5952 (18)	0.1956 (8)	0.110 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0776 (11)	0.0671 (10)	0.1094 (12)	−0.0047 (8)	−0.0022 (9)	−0.0140 (8)
Br2	0.0876 (11)	0.0974 (13)	0.0716 (9)	−0.0124 (9)	−0.0075 (8)	−0.0164 (8)
Br3	0.0765 (10)	0.0789 (11)	0.0793 (10)	−0.0043 (8)	−0.0186 (8)	0.0070 (8)
C1	0.062 (8)	0.078 (10)	0.072 (9)	−0.013 (7)	−0.022 (7)	0.001 (7)
C2	0.058 (8)	0.068 (9)	0.062 (8)	−0.006 (7)	0.004 (6)	−0.026 (7)
C3	0.034 (6)	0.064 (8)	0.060 (7)	−0.001 (6)	0.001 (6)	0.012 (6)
C4	0.063 (8)	0.072 (9)	0.071 (9)	0.022 (7)	−0.018 (7)	−0.030 (7)
C5	0.056 (8)	0.051 (8)	0.087 (10)	−0.015 (6)	−0.021 (7)	0.009 (7)
C6	0.062 (8)	0.052 (8)	0.073 (8)	−0.019 (6)	−0.033 (7)	0.003 (6)
N1	0.079 (8)	0.081 (9)	0.080 (8)	−0.016 (7)	−0.036 (7)	−0.026 (7)
O1	0.119 (9)	0.095 (9)	0.071 (6)	−0.005 (7)	−0.017 (6)	−0.032 (6)
O2	0.151 (11)	0.087 (9)	0.089 (7)	−0.010 (8)	−0.061 (8)	0.004 (6)
Br11	0.0644 (10)	0.0993 (13)	0.1026 (12)	0.0018 (9)	−0.0185 (9)	−0.0137 (10)
Br12	0.0955 (12)	0.0701 (10)	0.0769 (9)	−0.0090 (8)	−0.0294 (9)	−0.0017 (7)
Br13	0.0785 (11)	0.0945 (13)	0.0808 (10)	−0.0202 (9)	0.0012 (8)	0.0067 (9)
C11	0.084 (10)	0.050 (8)	0.102 (11)	−0.013 (7)	−0.021 (9)	−0.015 (8)
C12	0.060 (8)	0.062 (8)	0.073 (9)	−0.018 (7)	−0.012 (8)	−0.008 (7)
C13	0.081 (10)	0.082 (10)	0.060 (8)	−0.020 (8)	−0.024 (7)	0.009 (7)
C14	0.056 (8)	0.080 (10)	0.065 (8)	−0.010 (7)	0.011 (7)	−0.007 (7)
C15	0.088 (10)	0.077 (10)	0.040 (6)	0.019 (8)	−0.034 (7)	−0.004 (6)
C16	0.070 (9)	0.072 (9)	0.062 (8)	−0.028 (8)	0.006 (7)	−0.003 (7)
N11	0.067 (8)	0.065 (8)	0.093 (10)	−0.005 (6)	−0.017 (7)	0.011 (7)
O11	0.074 (7)	0.079 (7)	0.099 (7)	0.003 (6)	−0.032 (6)	−0.014 (6)
O12	0.097 (8)	0.144 (12)	0.077 (7)	−0.012 (8)	−0.011 (7)	0.028 (7)

Geometric parameters (Å, º)

Br1—C1	1.831 (15)	Br11—C11	1.877 (15)
Br2—C2	1.821 (12)	Br12—C12	1.854 (14)
Br3—C3	1.886 (11)	Br13—C13	1.842 (15)
C1—C6	1.415 (18)	C11—C16	1.368 (19)
C1—C2	1.416 (18)	C11—C12	1.38 (2)
C2—C3	1.445 (18)	C12—C13	1.410 (19)
C3—C4	1.353 (17)	C13—C14	1.313 (18)
C4—C5	1.328 (17)	C14—C15	1.39 (2)
C4—H4	0.9300	C14—H14	0.9300
C5—C6	1.381 (19)	C15—C16	1.347 (19)
C5—N1	1.448 (18)	C15—N11	1.515 (16)
C6—H6	0.9300	C16—H16	0.9300
N1—O2	1.194 (15)	N11—O11	1.211 (15)
N1—O1	1.238 (16)	N11—O12	1.216 (16)
C6—C1—C2	119.0 (13)	C16—C11—C12	120.4 (14)
C6—C1—Br1	119.9 (9)	C16—C11—Br11	118.6 (13)
C2—C1—Br1	121.0 (10)	C12—C11—Br11	120.9 (11)
C1—C2—C3	116.2 (11)	C11—C12—C13	118.8 (13)
C1—C2—Br2	121.3 (10)	C11—C12—Br12	122.1 (10)
C3—C2—Br2	122.5 (9)	C13—C12—Br12	118.9 (10)
C4—C3—C2	121.8 (11)	C14—C13—C12	118.8 (14)
C4—C3—Br3	120.6 (10)	C14—C13—Br13	118.0 (11)
C2—C3—Br3	117.6 (9)	C12—C13—Br13	123.1 (10)
C5—C4—C3	121.5 (13)	C13—C14—C15	122.5 (13)
C5—C4—H4	119.3	C13—C14—H14	118.8
C3—C4—H4	119.3	C15—C14—H14	118.8
C4—C5—C6	120.7 (13)	C16—C15—C14	119.2 (11)
C4—C5—N1	121.1 (13)	C16—C15—N11	117.9 (13)
C6—C5—N1	118.2 (11)	C14—C15—N11	122.8 (12)
C5—C6—C1	120.8 (11)	C15—C16—C11	120.0 (14)
C5—C6—H6	119.6	C15—C16—H16	120.0
C1—C6—H6	119.6	C11—C16—H16	120.0
O2—N1—O1	123.6 (12)	O11—N11—O12	127.0 (13)
O2—N1—C5	118.3 (13)	O11—N11—C15	114.7 (13)
O1—N1—C5	118.1 (12)	O12—N11—C15	118.1 (12)
C6—C1—C2—C3	0.6 (19)	C16—C11—C12—C13	−4 (2)
Br1—C1—C2—C3	179.5 (9)	Br11—C11—C12—C13	179.1 (11)
C6—C1—C2—Br2	−178.5 (10)	C16—C11—C12—Br12	−178.9 (11)
Br1—C1—C2—Br2	0.3 (16)	Br11—C11—C12—Br12	4.0 (17)
C1—C2—C3—C4	−0.3 (19)	C11—C12—C13—C14	4 (2)
Br2—C2—C3—C4	178.8 (11)	Br12—C12—C13—C14	179.4 (12)
C1—C2—C3—Br3	178.0 (9)	C11—C12—C13—Br13	−178.0 (11)
Br2—C2—C3—Br3	−2.8 (14)	Br12—C12—C13—Br13	−2.7 (18)
C2—C3—C4—C5	1 (2)	C12—C13—C14—C15	−3 (2)
Br3—C3—C4—C5	−177.8 (11)	Br13—C13—C14—C15	178.7 (12)
C3—C4—C5—C6	−1 (2)	C13—C14—C15—C16	2 (2)
C3—C4—C5—N1	179.1 (13)	C13—C14—C15—N11	−174.8 (15)
C4—C5—C6—C1	1 (2)	C14—C15—C16—C11	−2 (2)
N1—C5—C6—C1	−178.8 (12)	N11—C15—C16—C11	175.4 (13)
C2—C1—C6—C5	−1 (2)	C12—C11—C16—C15	3 (2)
Br1—C1—C6—C5	−180.0 (10)	Br11—C11—C16—C15	179.8 (11)
C4—C5—N1—O2	179.2 (14)	C16—C15—N11—O11	−175.5 (13)
C6—C5—N1—O2	−1 (2)	C14—C15—N11—O11	1 (2)
C4—C5—N1—O1	1 (2)	C16—C15—N11—O12	10 (2)
C6—C5—N1—O1	−178.8 (13)	C14—C15—N11—O12	−173.5 (15)

(II) 1,3-Dibromo-2-iodo-5-nitrobenzene

Crystal data

C6H2Br2INO2	Dx = 2.864 Mg m^−3
Mr = 406.81	Melting point: 415 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.548 (3) Å	Cell parameters from 43 reflections
b = 20.037 (3) Å	θ = 5.7–12.5°
c = 9.123 (2) Å	µ = 11.82 mm^−1
β = 130.37 (2)°	T = 298 K
V = 1886.8 (8) Å^3	Prism, brown
Z = 8	0.50 × 0.22 × 0.12 mm
F(000) = 1472

Data collection

Bruker P4 diffractometer	1968 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.058
Graphite monochromator	θmax = 30.0°, θmin = 2.2°
2θ/ω scans	h = −14→19
Absorption correction: ψ scan (XSCANS; Bruker, 1997)	k = 0→28
Tmin = 0.429, Tmax = 0.988	l = −12→0
5716 measured reflections	3 standard reflections every 97 reflections
5407 independent reflections	intensity decay: 1%

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)] = 0.061	H-atom parameters constrained
wR(F^2) = 0.153	w = 1/[σ^2(Fo^2) + (0.053P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.95	(Δ/σ)max < 0.001
5407 reflections	Δρmax = 0.84 e Å^−3
218 parameters	Δρmin = −0.84 e Å^−3
0 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.00093 (11)
Primary atom site location: structure-invariant direct methods

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

	x	y	z	Uiso*/Ueq
Br1	0.30362 (13)	0.43988 (8)	0.2401 (2)	0.0615 (4)
I2	0.54556 (10)	0.36925 (4)	0.26460 (13)	0.0583 (3)
Br3	0.73278 (12)	0.49074 (7)	0.26614 (18)	0.0561 (4)
C1	0.4175 (11)	0.4967 (7)	0.2453 (16)	0.035 (3)
C2	0.5191 (11)	0.4723 (6)	0.2535 (13)	0.033 (3)
C3	0.5960 (11)	0.5182 (6)	0.2557 (17)	0.038 (3)
C4	0.5754 (12)	0.5862 (6)	0.2478 (17)	0.040 (3)
H4A	0.6264	0.6171	0.2474	0.048*
C5	0.4763 (13)	0.6050 (7)	0.2405 (15)	0.046 (4)
C6	0.3965 (12)	0.5642 (7)	0.2397 (18)	0.048 (4)
H6A	0.3307	0.5809	0.2355	0.057*
N1	0.4555 (13)	0.6807 (6)	0.2380 (17)	0.065 (3)
O1	0.5145 (11)	0.7161 (5)	0.2088 (17)	0.085 (4)
O2	0.3795 (15)	0.6989 (5)	0.2557 (18)	0.105 (4)
Br11	−0.18918 (13)	0.30721 (8)	0.2488 (2)	0.0620 (4)
I12	0.04866 (10)	0.37922 (4)	0.26639 (13)	0.0593 (3)
Br13	0.24427 (12)	0.25893 (8)	0.2825 (2)	0.0588 (4)
C11	−0.0736 (11)	0.2509 (7)	0.2562 (17)	0.039 (3)
C12	0.0237 (12)	0.2769 (7)	0.2619 (14)	0.035 (3)
C13	0.1046 (11)	0.2312 (6)	0.2672 (18)	0.039 (3)
C14	0.0869 (13)	0.1639 (6)	0.2665 (18)	0.045 (4)
H14A	0.1429	0.1344	0.2736	0.054*
C15	−0.0137 (13)	0.1391 (8)	0.2553 (16)	0.045 (4)
C16	−0.0922 (13)	0.1829 (6)	0.2507 (18)	0.043 (4)
H16A	−0.1596	0.1668	0.2437	0.052*
N11	−0.0302 (15)	0.0681 (6)	0.2483 (17)	0.066 (4)
O11	0.0350 (12)	0.0323 (6)	0.2418 (18)	0.099 (4)
O12	−0.1106 (14)	0.0493 (6)	0.2609 (17)	0.099 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0558 (8)	0.0680 (9)	0.0684 (9)	−0.0167 (7)	0.0437 (7)	−0.0035 (7)
I2	0.0737 (6)	0.0268 (4)	0.0723 (7)	0.0048 (5)	0.0464 (5)	0.0017 (4)
Br3	0.0484 (7)	0.0636 (9)	0.0654 (9)	0.0047 (7)	0.0409 (7)	0.0002 (7)
C1	0.041 (7)	0.035 (7)	0.033 (6)	−0.012 (6)	0.027 (5)	−0.007 (5)
C2	0.043 (7)	0.017 (6)	0.035 (8)	0.002 (5)	0.024 (6)	0.000 (4)
C3	0.042 (6)	0.033 (7)	0.041 (7)	0.003 (5)	0.028 (6)	−0.004 (5)
C4	0.037 (7)	0.036 (8)	0.048 (8)	−0.005 (6)	0.027 (6)	−0.003 (6)
C5	0.046 (7)	0.023 (7)	0.040 (8)	0.005 (6)	0.015 (6)	−0.002 (5)
C6	0.036 (7)	0.064 (10)	0.045 (8)	−0.003 (7)	0.027 (6)	−0.016 (7)
N1	0.066 (8)	0.031 (7)	0.075 (9)	0.010 (7)	0.036 (7)	−0.001 (6)
O1	0.091 (8)	0.030 (6)	0.108 (9)	−0.003 (6)	0.053 (7)	0.003 (6)
O2	0.163 (12)	0.050 (7)	0.137 (11)	0.050 (8)	0.112 (10)	0.016 (6)
Br11	0.0522 (8)	0.0681 (9)	0.0685 (9)	0.0108 (7)	0.0404 (7)	−0.0033 (7)
I12	0.0755 (6)	0.0283 (4)	0.0735 (7)	−0.0069 (5)	0.0479 (5)	−0.0038 (4)
Br13	0.0488 (7)	0.0631 (9)	0.0703 (9)	−0.0088 (7)	0.0412 (7)	−0.0014 (7)
C11	0.043 (7)	0.035 (7)	0.041 (7)	−0.002 (6)	0.028 (6)	0.002 (6)
C12	0.041 (7)	0.033 (8)	0.039 (8)	0.007 (6)	0.030 (6)	0.004 (4)
C13	0.033 (6)	0.037 (8)	0.042 (7)	−0.005 (5)	0.022 (6)	−0.005 (6)
C14	0.051 (8)	0.029 (7)	0.044 (8)	0.008 (6)	0.025 (6)	0.000 (6)
C15	0.063 (9)	0.028 (7)	0.056 (9)	−0.015 (6)	0.045 (8)	−0.006 (5)
C16	0.046 (7)	0.031 (7)	0.042 (7)	−0.021 (6)	0.024 (6)	−0.015 (5)
N11	0.096 (10)	0.034 (7)	0.073 (9)	−0.018 (7)	0.057 (8)	−0.006 (6)
O11	0.101 (9)	0.029 (6)	0.147 (11)	−0.010 (6)	0.072 (8)	−0.005 (7)
O12	0.144 (11)	0.061 (7)	0.130 (10)	−0.042 (8)	0.106 (9)	−0.012 (6)

Geometric parameters (Å, º)

Br1—C1	1.894 (12)	Br11—C11	1.895 (14)
I2—C2	2.088 (12)	I12—C12	2.074 (14)
Br3—C3	1.875 (13)	Br13—C13	1.888 (13)
C1—C6	1.375 (18)	C11—C12	1.387 (17)
C1—C2	1.416 (17)	C11—C16	1.381 (18)
C2—C3	1.380 (17)	C12—C13	1.405 (17)
C3—C4	1.384 (16)	C13—C14	1.370 (16)
C4—C5	1.353 (18)	C14—C15	1.390 (19)
C4—H4A	0.9300	C14—H14A	0.9300
C5—C6	1.35 (2)	C15—C16	1.359 (19)
C5—N1	1.539 (18)	C15—N11	1.435 (19)
C6—H6A	0.9300	C16—H16A	0.9300
N1—O2	1.199 (17)	N11—O11	1.168 (19)
N1—O1	1.221 (19)	N11—O12	1.226 (18)
C6—C1—C2	120.8 (13)	C12—C11—C16	121.2 (14)
C6—C1—Br1	116.4 (11)	C12—C11—Br11	121.4 (11)
C2—C1—Br1	122.8 (10)	C16—C11—Br11	117.3 (11)
C3—C2—C1	118.1 (12)	C11—C12—C13	117.3 (13)
C3—C2—I2	123.6 (10)	C11—C12—I12	120.7 (11)
C1—C2—I2	118.4 (10)	C13—C12—I12	122.0 (10)
C2—C3—C4	122.0 (13)	C14—C13—C12	120.8 (13)
C2—C3—Br3	121.2 (10)	C14—C13—Br13	117.0 (11)
C4—C3—Br3	116.8 (11)	C12—C13—Br13	122.2 (10)
C5—C4—C3	115.9 (13)	C13—C14—C15	120.8 (14)
C5—C4—H4A	122.0	C13—C14—H14A	119.6
C3—C4—H4A	122.0	C15—C14—H14A	119.6
C4—C5—C6	126.6 (14)	C16—C15—C14	118.8 (14)
C4—C5—N1	116.2 (15)	C16—C15—N11	122.8 (14)
C6—C5—N1	117.2 (15)	C14—C15—N11	118.3 (15)
C5—C6—C1	116.7 (13)	C15—C16—C11	121.0 (14)
C5—C6—H6A	121.7	C15—C16—H16A	119.5
C1—C6—H6A	121.7	C11—C16—H16A	119.5
O2—N1—O1	126.4 (14)	O11—N11—O12	124.2 (16)
O2—N1—C5	117.6 (14)	O11—N11—C15	120.6 (18)
O1—N1—C5	115.9 (17)	O12—N11—C15	115.0 (15)
C6—C1—C2—C3	0.0 (16)	C16—C11—C12—C13	−1.7 (16)
Br1—C1—C2—C3	179.7 (9)	Br11—C11—C12—C13	180.0 (9)
C6—C1—C2—I2	179.4 (9)	C16—C11—C12—I12	179.2 (9)
Br1—C1—C2—I2	−1.0 (12)	Br11—C11—C12—I12	0.8 (13)
C1—C2—C3—C4	−0.8 (17)	C11—C12—C13—C14	0.1 (17)
I2—C2—C3—C4	179.9 (9)	I12—C12—C13—C14	179.2 (9)
C1—C2—C3—Br3	−179.9 (9)	C11—C12—C13—Br13	−178.2 (9)
I2—C2—C3—Br3	0.7 (14)	I12—C12—C13—Br13	0.9 (14)
C2—C3—C4—C5	0.9 (18)	C12—C13—C14—C15	1.7 (19)
Br3—C3—C4—C5	−179.9 (9)	Br13—C13—C14—C15	−179.9 (10)
C3—C4—C5—C6	−0.2 (18)	C13—C14—C15—C16	−1.9 (18)
C3—C4—C5—N1	178.2 (11)	C13—C14—C15—N11	177.8 (12)
C4—C5—C6—C1	−0.5 (19)	C14—C15—C16—C11	0.3 (18)
N1—C5—C6—C1	−178.9 (10)	N11—C15—C16—C11	−179.5 (12)
C2—C1—C6—C5	0.6 (17)	C12—C11—C16—C15	1.6 (19)
Br1—C1—C6—C5	−179.1 (9)	Br11—C11—C16—C15	180.0 (10)
C4—C5—N1—O2	−171.0 (13)	C16—C15—N11—O11	175.7 (14)
C6—C5—N1—O2	7.6 (18)	C14—C15—N11—O11	−4 (2)
C4—C5—N1—O1	12.4 (17)	C16—C15—N11—O12	−8.3 (19)
C6—C5—N1—O1	−169.1 (12)	C14—C15—N11—O12	171.9 (13)