Structural phase transitions, and Br...N and Br...Br interactions in 1-phenyl-2-methyl-4-nitro-5-bromoimidazole

Crystals of C₁₀H₈N₃O₂Br undergo two reversible phase transitions between 295 and 100 K. The first, of an order–disorder nature, is a second-order transition and takes place continuously over a wide temperature range. This transition is connected with the doubling of the length of the c axis of the unit cell and with the change of the space group from P2₁/m with Z′ = 1/2 (room-temperature α-phase) to P2₁/c, Z′ = 1 (β-phase, 200–120 K). During this transition the molecule loses the C_s symmetry of the α-phase. The second transition takes place between 118 and 115 K, and is accompanied by a change of the crystal symmetry to the triclinic space group P (low-temperature γ-phase). This second phase transition is accompanied by the twinning of the crystal. Neither the molecular geometry nor the crystal packing shows any dramatic changes during these phase transitions. Halogen bonds C—Br...N and dihalogen interactions Br...Br play a crucial role in determining the crystal packing and compete successfully with other kinds of weak intermolecular interactions.

Computing details

For all compounds, data collection: CrysAlis CCD v.169 (Oxford Diffraction, 2003a); cell refinement: CrysAlis CCD v.169 (Oxford Diffraction, 2003a); data reduction: CrysAlis RED v.169 (Oxford Diffraction, 2003b). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for 295K, 250K, 200K, 170K, 150K, 120K; SIR2002 (Burla et al., 2003) for 100K. For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

Figures

(295K) 1-phenyl-4-nitro-5-bromo-imidazole

Crystal data

C10H8BrN3O2	F(000) = 280
Mr = 282.10	Dx = 1.735 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybm	Cell parameters from 4253 reflections
a = 7.0281 (10) Å	θ = 3–20°
b = 6.9388 (9) Å	µ = 3.80 mm^−1
c = 11.5612 (15) Å	T = 295 K
β = 106.735 (12)°	Prism, colourless
V = 539.92 (13) Å^3	0.3 × 0.25 × 0.1 mm
Z = 2

Data collection

KUMA KM4CCD four-circle diffractometer	1521 independent reflections
Radiation source: fine-focus sealed tube	1342 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω–scan	θmax = 29.7°, θmin = 3.0°
Absorption correction: multi-scan SORTAV (Blessing, 1989)	h = −9→9
Tmin = 0.382, Tmax = 0.696	k = −9→9
5105 measured reflections	l = −6→15

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0509P)^2] where P = (Fo^2 + 2Fc^2)/3
1521 reflections	(Δ/σ)max = 0.001
93 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −1.18 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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
N1	0.8140 (3)	0.2500	0.6559 (2)	0.0348 (5)
C11	0.9755 (4)	0.2500	0.7656 (3)	0.0404 (6)
C12	1.0488 (4)	0.4233 (5)	0.8165 (3)	0.0633 (7)
H12	0.9998	0.5391	0.7792	0.101 (9)*
C13	1.1989 (5)	0.4205 (7)	0.9258 (3)	0.0859 (11)
H13	1.2510	0.5361	0.9622	0.101 (9)*
C14	1.2701 (6)	0.2500	0.9801 (4)	0.0897 (19)
H14	1.3674	0.2500	1.0543	0.101 (9)*
C2	0.6149 (4)	0.2500	0.6500 (3)	0.0388 (6)
C21	0.5452 (5)	0.2500	0.7604 (3)	0.0580 (10)
H21B	0.4027	0.2500	0.7370	0.096 (10)*
H21A	0.5940	0.3629	0.8075	0.096 (10)*
N3	0.5025 (3)	0.2500	0.5386 (2)	0.0384 (5)
C4	0.6319 (4)	0.2500	0.4693 (3)	0.0346 (5)
N4	0.5583 (4)	0.2500	0.3412 (2)	0.0477 (6)
O41	0.3787 (4)	0.2500	0.2954 (2)	0.0762 (9)
O42	0.6777 (4)	0.2500	0.2822 (2)	0.0709 (9)
C5	0.8257 (4)	0.2500	0.5388 (3)	0.0317 (5)
Br5	1.07071 (3)	0.2500	0.50807 (2)	0.03540 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0254 (9)	0.0524 (13)	0.0271 (11)	0.000	0.0086 (8)	0.000
C11	0.0265 (11)	0.0667 (18)	0.0283 (14)	0.000	0.0082 (10)	0.000
C12	0.0515 (13)	0.0791 (19)	0.0522 (14)	−0.0040 (12)	0.0038 (11)	−0.0177 (14)
C13	0.0587 (15)	0.133 (3)	0.0548 (18)	−0.0138 (18)	−0.0012 (13)	−0.041 (2)
C14	0.047 (2)	0.190 (6)	0.0266 (18)	0.000	0.0010 (15)	0.000
C2	0.0265 (11)	0.0560 (17)	0.0349 (15)	0.000	0.0104 (10)	0.000
C21	0.0391 (15)	0.102 (3)	0.0369 (17)	0.000	0.0181 (13)	0.000
N3	0.0255 (10)	0.0557 (14)	0.0352 (13)	0.000	0.0104 (9)	0.000
C4	0.0271 (12)	0.0456 (14)	0.0310 (14)	0.000	0.0081 (10)	0.000
N4	0.0378 (12)	0.0725 (18)	0.0299 (13)	0.000	0.0054 (10)	0.000
O41	0.0365 (12)	0.143 (3)	0.0404 (14)	0.000	−0.0030 (10)	0.000
O42	0.0525 (14)	0.130 (3)	0.0337 (13)	0.000	0.0177 (11)	0.000
C5	0.0254 (10)	0.0367 (13)	0.0339 (14)	0.000	0.0096 (10)	0.000
Br5	0.02744 (15)	0.04150 (17)	0.04068 (19)	0.000	0.01527 (11)	0.000

Geometric parameters (Å, º)

N1—C5	1.380 (3)	C2—N3	1.303 (4)
N1—C2	1.381 (3)	C2—C21	1.493 (4)
N1—C11	1.438 (4)	C21—H21B	0.9598
C11—C12	1.372 (3)	C21—H21A	0.9595
C11—C12^i	1.372 (3)	N3—C4	1.374 (4)
C12—C13	1.394 (4)	C4—C5	1.367 (4)
C12—H12	0.9300	C4—N4	1.421 (4)
C13—C14	1.365 (5)	N4—O41	1.220 (4)
C13—H13	0.9300	N4—O42	1.225 (4)
C14—C13^i	1.365 (5)	C5—Br5	1.855 (2)
C14—H14	0.9300
C5—N1—C2	107.3 (2)	N3—C2—C21	126.2 (3)
C5—N1—C11	127.6 (2)	N1—C2—C21	122.3 (3)
C2—N1—C11	125.1 (2)	C2—C21—H21B	109.4
C12—C11—C12^i	122.4 (3)	C2—C21—H21A	109.5
C12—C11—N1	118.79 (16)	H21B—C21—H21A	109.5
C12^i—C11—N1	118.79 (16)	C2—N3—C4	105.1 (2)
C11—C12—C13	118.0 (3)	C5—C4—N3	111.9 (3)
C11—C12—H12	121.0	C5—C4—N4	127.9 (2)
C13—C12—H12	121.0	N3—C4—N4	120.2 (2)
C14—C13—C12	120.7 (4)	O41—N4—O42	123.1 (3)
C14—C13—H13	119.7	O41—N4—C4	118.3 (3)
C12—C13—H13	119.7	O42—N4—C4	118.6 (2)
C13^i—C14—C13	120.2 (4)	C4—C5—N1	104.2 (2)
C13^i—C14—H14	119.9	C4—C5—Br5	135.2 (2)
C13—C14—H14	119.9	N1—C5—Br5	120.56 (19)
N3—C2—N1	111.5 (2)
C5—N1—C11—C12	90.5 (2)	C2—N3—C4—C5	0.000 (1)
C2—N1—C11—C12	−89.5 (2)	C2—N3—C4—N4	180.0
C5—N1—C11—C12^i	−90.5 (2)	C5—C4—N4—O41	180.0
C2—N1—C11—C12^i	89.5 (2)	N3—C4—N4—O41	0.0
C12^i—C11—C12—C13	−2.0 (5)	C5—C4—N4—O42	0.0
N1—C11—C12—C13	177.0 (3)	N3—C4—N4—O42	180.0
C11—C12—C13—C14	0.0 (5)	N3—C4—C5—N1	0.0
C12—C13—C14—C13^i	2.0 (7)	N4—C4—C5—N1	180.0
C5—N1—C2—N3	0.0	N3—C4—C5—Br5	180.0
C11—N1—C2—N3	180.000 (1)	N4—C4—C5—Br5	0.000 (1)
C5—N1—C2—C21	180.000 (1)	C2—N1—C5—C4	0.0
C11—N1—C2—C21	0.000 (1)	C11—N1—C5—C4	180.000 (1)
N1—C2—N3—C4	0.0	C2—N1—C5—Br5	180.0
C21—C2—N3—C4	180.000 (1)	C11—N1—C5—Br5	0.000 (1)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O41^ii	0.93	2.77	3.502 (5)	137
C21—H21B···Br5^iii	0.96	2.98	3.746 (4)	137

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

(250K) 1-phenyl-4-nitro-5-bromo-imidazole

Crystal data

C10H8BrN3O2	F(000) = 280
Mr = 282.10	Dx = 1.743 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybm	Cell parameters from 668 reflections
a = 7.0180 (14) Å	θ = 3–20°
b = 6.9160 (12) Å	µ = 3.81 mm^−1
c = 11.546 (2) Å	T = 250 K
β = 106.410 (15)°	Prism, colourless
V = 537.57 (17) Å^3	0.5 × 0.3 × 0.1 mm
Z = 2

Data collection

KUMA KM4CCD four-circle diffractometer	1473 independent reflections
Radiation source: fine-focus sealed tube	1097 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
ω–scan	θmax = 29.6°, θmin = 3.0°
Absorption correction: multi-scan SORTAV (Blessing, 1989)	h = −6→9
Tmin = 0.326, Tmax = 0.673	k = −9→9
3360 measured reflections	l = −15→15

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.047P)^2] where P = (Fo^2 + 2Fc^2)/3
1473 reflections	(Δ/σ)max < 0.001
91 parameters	Δρmax = 0.74 e Å^−3
0 restraints	Δρmin = −0.96 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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
N1	0.8125 (5)	0.2500	0.6549 (4)	0.0314 (9)
C11	0.9758 (7)	0.2500	0.7651 (5)	0.0375 (12)
C12	1.0493 (6)	0.4233 (7)	0.8177 (4)	0.0562 (11)
H12	0.9870	0.5380	0.7743	0.077*
C13	1.1975 (6)	0.4206 (10)	0.9259 (4)	0.0760 (16)
H13	1.2508	0.5418	0.9592	0.074*
C14	1.2719 (10)	0.2500	0.9819 (6)	0.077 (2)
H14	1.3699	0.2500	1.0549	0.090*
C2	0.6162 (6)	0.2500	0.6506 (4)	0.0330 (11)
C21	0.5449 (8)	0.2500	0.7609 (5)	0.0512 (15)
H21A	0.4002	0.2500	0.7365	0.115*
H21B	0.5936	0.3651	0.8090	0.109*
N3	0.5020 (6)	0.2500	0.5381 (4)	0.0327 (9)
C4	0.6321 (6)	0.2500	0.4698 (4)	0.0294 (10)
N4	0.5584 (6)	0.2500	0.3410 (4)	0.0422 (11)
O41	0.6790 (6)	0.2500	0.2821 (4)	0.0647 (13)
O42	0.3789 (6)	0.2500	0.2951 (4)	0.0669 (13)
C5	0.8259 (6)	0.2500	0.5377 (5)	0.0291 (10)
Br5	1.07177 (6)	0.2500	0.50783 (5)	0.03340 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0212 (18)	0.042 (2)	0.032 (2)	0.000	0.0098 (16)	0.000
C11	0.024 (2)	0.057 (3)	0.033 (3)	0.000	0.010 (2)	0.000
C12	0.042 (2)	0.067 (3)	0.055 (3)	−0.003 (2)	0.0063 (19)	−0.015 (2)
C13	0.050 (3)	0.112 (4)	0.059 (3)	−0.009 (3)	0.002 (2)	−0.034 (3)
C14	0.038 (3)	0.156 (8)	0.034 (3)	0.000	0.004 (3)	0.000
C2	0.017 (2)	0.050 (3)	0.032 (3)	0.000	0.0062 (18)	0.000
C21	0.034 (3)	0.087 (4)	0.039 (3)	0.000	0.020 (2)	0.000
N3	0.0216 (17)	0.042 (2)	0.036 (2)	0.000	0.0114 (17)	0.000
C4	0.020 (2)	0.039 (3)	0.031 (2)	0.000	0.0093 (18)	0.000
N4	0.027 (2)	0.060 (3)	0.040 (3)	0.000	0.0109 (19)	0.000
O41	0.046 (2)	0.115 (4)	0.040 (2)	0.000	0.0229 (19)	0.000
O42	0.030 (2)	0.119 (4)	0.047 (3)	0.000	0.0034 (18)	0.000
C5	0.023 (2)	0.023 (2)	0.045 (3)	0.000	0.017 (2)	0.000
Br5	0.0239 (2)	0.0355 (3)	0.0453 (3)	0.000	0.0170 (2)	0.000

Geometric parameters (Å, º)

N1—C2	1.365 (6)	C2—N3	1.320 (6)
N1—C5	1.382 (6)	C2—C21	1.494 (7)
N1—C11	1.452 (6)	C21—H21A	0.9745
C11—C12	1.376 (5)	C21—H21B	0.9750
C11—C12^i	1.376 (5)	N3—C4	1.364 (6)
C12—C13	1.382 (6)	C4—C5	1.364 (6)
C12—H12	0.9735	C4—N4	1.430 (6)
C13—C14	1.376 (7)	N4—O42	1.221 (5)
C13—H13	0.9528	N4—O41	1.226 (5)
C14—C13^i	1.376 (7)	C5—Br5	1.853 (4)
C14—H14	0.9251
C2—N1—C5	108.1 (4)	N3—C2—C21	125.7 (4)
C2—N1—C11	124.8 (4)	N1—C2—C21	123.1 (4)
C5—N1—C11	127.1 (4)	C2—C21—H21A	109.0
C12—C11—C12^i	121.1 (5)	C2—C21—H21B	109.7
C12—C11—N1	119.4 (3)	H21A—C21—H21B	109.5
C12^i—C11—N1	119.4 (3)	C2—N3—C4	104.4 (4)
C11—C12—C13	118.7 (5)	C5—C4—N3	112.9 (4)
C11—C12—H12	115.1	C5—C4—N4	127.3 (4)
C13—C12—H12	126.2	N3—C4—N4	119.7 (4)
C14—C13—C12	121.7 (6)	O42—N4—O41	123.3 (5)
C14—C13—H13	120.7	O42—N4—C4	118.5 (4)
C12—C13—H13	117.5	O41—N4—C4	118.2 (4)
C13^i—C14—C13	118.2 (6)	C4—C5—N1	103.3 (4)
C13^i—C14—H14	120.9	C4—C5—Br5	136.3 (4)
C13—C14—H14	120.9	N1—C5—Br5	120.4 (3)
N3—C2—N1	111.2 (4)
C2—N1—C11—C12	−88.7 (4)	C2—N3—C4—C5	0.000 (2)
C5—N1—C11—C12	91.3 (4)	C2—N3—C4—N4	180.000 (1)
C2—N1—C11—C12^i	88.7 (4)	C5—C4—N4—O42	180.000 (1)
C5—N1—C11—C12^i	−91.3 (4)	N3—C4—N4—O42	0.000 (1)
C12^i—C11—C12—C13	−0.9 (8)	C5—C4—N4—O41	0.000 (1)
N1—C11—C12—C13	176.6 (4)	N3—C4—N4—O41	180.000 (1)
C11—C12—C13—C14	−0.2 (8)	N3—C4—C5—N1	0.000 (1)
C12—C13—C14—C13^i	1.3 (10)	N4—C4—C5—N1	180.000 (1)
C5—N1—C2—N3	0.000 (1)	N3—C4—C5—Br5	180.000 (1)
C11—N1—C2—N3	180.000 (2)	N4—C4—C5—Br5	0.000 (2)
C5—N1—C2—C21	180.000 (2)	C2—N1—C5—C4	0.000 (2)
C11—N1—C2—C21	0.000 (2)	C11—N1—C5—C4	180.000 (2)
N1—C2—N3—C4	0.000 (1)	C2—N1—C5—Br5	180.000 (1)
C21—C2—N3—C4	180.000 (2)	C11—N1—C5—Br5	0.000 (2)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O41^ii	0.93	2.89	3.819 (8)	180
C21—H21A···Br5^iii	0.97	2.97	3.753 (6)	138

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

(200K) 1-phenyl-4-nitro-5-bromo-imidazole

Crystal data

C10H8BrN3O2	F(000) = 560
Mr = 282.10	Dx = 1.769 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2101 reflections
a = 6.9955 (9) Å	θ = 3–22°
b = 6.8657 (8) Å	µ = 3.87 mm^−1
c = 22.990 (2) Å	T = 200 K
β = 106.356 (10)°	Prism, colourless
V = 1059.5 (2) Å^3	0.5 × 0.3 × 0.1 mm
Z = 4

Data collection

KUMA KM4CCD four-circle diffractometer	2719 independent reflections
Radiation source: fine-focus sealed tube	1610 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
ω–scan	θmax = 29.4°, θmin = 3.0°
Absorption correction: multi-scan SORTAV (Blessing, 1989)	h = −9→9
Tmin = 0.355, Tmax = 0.725	k = 0→9
13871 measured reflections	l = 0→30

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0626P)^2] where P = (Fo^2 + 2Fc^2)/3
2719 reflections	(Δ/σ)max = 0.001
148 parameters	Δρmax = 1.14 e Å^−3
0 restraints	Δρmin = −1.08 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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
N1	0.6874 (5)	0.2365 (5)	0.42266 (16)	0.0270 (8)
C11	0.5246 (6)	0.2265 (6)	0.36738 (19)	0.0267 (9)
C12	0.4554 (7)	0.0490 (8)	0.3435 (2)	0.0438 (14)
H12	0.5092	−0.0684	0.3634	0.084 (10)*
C13	0.3039 (8)	0.0456 (10)	0.2894 (3)	0.0588 (18)
H13	0.2517	−0.0764	0.2728	0.084 (10)*
C14	0.2277 (8)	0.2124 (10)	0.2593 (2)	0.0567 (19)
H14	0.1277	0.2058	0.2215	0.084 (10)*
C15	0.2973 (9)	0.3899 (10)	0.2842 (3)	0.0618 (19)
H15	0.2431	0.5066	0.2640	0.084 (10)*
C16	0.4474 (8)	0.3992 (8)	0.3391 (3)	0.0482 (15)
H16	0.4955	0.5213	0.3566	0.084 (10)*
C2	0.8855 (6)	0.2356 (6)	0.4247 (2)	0.0276 (9)
C21	0.9561 (7)	0.2258 (7)	0.3698 (2)	0.0400 (13)
H21A	0.9114	0.3420	0.3449	0.062 (11)*
H21B	0.9016	0.1092	0.3464	0.062 (11)*
H21C	1.1020	0.2199	0.3817	0.062 (11)*
N3	0.9993 (5)	0.2477 (5)	0.48111 (16)	0.0270 (7)
C4	0.8681 (6)	0.2571 (6)	0.51534 (19)	0.0250 (8)
N4	0.9422 (5)	0.2716 (6)	0.57967 (18)	0.0330 (9)
O41	1.1223 (5)	0.2786 (5)	0.60241 (16)	0.0506 (10)
O42	0.8201 (5)	0.2801 (5)	0.60897 (16)	0.0475 (10)
C5	0.6737 (5)	0.2473 (6)	0.48091 (19)	0.0237 (8)
Br5	0.42742 (5)	0.25117 (6)	0.496046 (18)	0.02643 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0172 (15)	0.036 (2)	0.0296 (18)	−0.0028 (17)	0.0103 (13)	0.0021 (17)
C11	0.0172 (17)	0.038 (3)	0.027 (2)	−0.0019 (19)	0.0091 (15)	0.001 (2)
C12	0.033 (3)	0.053 (3)	0.042 (3)	−0.005 (2)	0.004 (2)	−0.013 (3)
C13	0.043 (4)	0.085 (5)	0.043 (4)	−0.005 (3)	0.005 (3)	−0.024 (3)
C14	0.030 (3)	0.112 (6)	0.027 (2)	−0.001 (3)	0.006 (2)	0.000 (3)
C15	0.039 (4)	0.089 (5)	0.050 (4)	0.008 (3)	0.001 (3)	0.025 (4)
C16	0.037 (3)	0.052 (3)	0.053 (4)	−0.006 (3)	0.007 (3)	0.011 (3)
C2	0.0178 (17)	0.037 (2)	0.028 (2)	−0.003 (2)	0.0058 (15)	0.003 (2)
C21	0.028 (2)	0.064 (4)	0.032 (2)	−0.006 (2)	0.0152 (19)	−0.009 (3)
N3	0.0182 (14)	0.0350 (18)	0.0302 (18)	−0.0025 (18)	0.0105 (14)	−0.0024 (18)
C4	0.0174 (17)	0.0294 (19)	0.030 (2)	−0.001 (2)	0.0099 (15)	−0.001 (2)
N4	0.0262 (18)	0.042 (2)	0.033 (2)	0.0006 (18)	0.0113 (15)	−0.0009 (18)
O41	0.0229 (16)	0.090 (3)	0.0369 (19)	0.0004 (19)	0.0052 (14)	−0.002 (2)
O42	0.0365 (18)	0.078 (3)	0.0338 (18)	−0.0026 (19)	0.0198 (15)	−0.0088 (18)
C5	0.0178 (16)	0.0215 (17)	0.035 (2)	−0.0057 (19)	0.0132 (15)	−0.001 (2)
Br5	0.0186 (2)	0.0283 (2)	0.0360 (3)	−0.0004 (2)	0.01365 (16)	0.0003 (2)

Geometric parameters (Å, º)

N1—C5	1.371 (5)	C16—H16	0.9500
N1—C2	1.373 (5)	C2—N3	1.319 (5)
N1—C11	1.450 (5)	C2—C21	1.482 (6)
C11—C12	1.368 (6)	C21—H21A	0.9800
C11—C16	1.387 (6)	C21—H21B	0.9800
C12—C13	1.389 (7)	C21—H21C	0.9800
C12—H12	0.9500	N3—C4	1.369 (6)
C13—C14	1.367 (8)	C4—C5	1.369 (5)
C13—H13	0.9500	C4—N4	1.426 (6)
C14—C15	1.376 (9)	N4—O41	1.221 (5)
C14—H14	0.9500	N4—O42	1.229 (5)
C15—C16	1.397 (8)	C5—Br5	1.851 (4)
C15—H15	0.9500
C5—N1—C2	108.3 (3)	C15—C16—H16	120.7
C5—N1—C11	127.2 (3)	N3—C2—N1	111.0 (4)
C2—N1—C11	124.5 (4)	N3—C2—C21	125.9 (4)
C12—C11—C16	121.8 (5)	N1—C2—C21	123.1 (4)
C12—C11—N1	119.7 (4)	C2—C21—H21A	109.5
C16—C11—N1	118.5 (4)	C2—C21—H21B	109.5
C11—C12—C13	117.9 (5)	H21A—C21—H21B	109.5
C11—C12—H12	121.0	C2—C21—H21C	109.5
C13—C12—H12	121.0	H21A—C21—H21C	109.5
C14—C13—C12	122.1 (6)	H21B—C21—H21C	109.5
C14—C13—H13	119.0	C2—N3—C4	104.5 (3)
C12—C13—H13	119.0	N3—C4—C5	112.5 (4)
C13—C14—C15	119.3 (5)	N3—C4—N4	119.5 (4)
C13—C14—H14	120.4	C5—C4—N4	127.9 (4)
C15—C14—H14	120.4	O41—N4—O42	123.8 (4)
C14—C15—C16	120.3 (6)	O41—N4—C4	118.4 (4)
C14—C15—H15	119.8	O42—N4—C4	117.8 (4)
C16—C15—H15	119.8	C4—C5—N1	103.6 (3)
C11—C16—C15	118.6 (5)	C4—C5—Br5	135.7 (3)
C11—C16—H16	120.7	N1—C5—Br5	120.6 (3)
C5—N1—C11—C12	−92.2 (6)	N1—C2—N3—C4	−0.2 (5)
C2—N1—C11—C12	87.6 (6)	C21—C2—N3—C4	178.7 (5)
C5—N1—C11—C16	89.8 (6)	C2—N3—C4—C5	1.1 (5)
C2—N1—C11—C16	−90.4 (6)	C2—N3—C4—N4	−180.0 (4)
C16—C11—C12—C13	0.2 (8)	N3—C4—N4—O41	1.2 (7)
N1—C11—C12—C13	−177.8 (5)	C5—C4—N4—O41	180.0 (5)
C11—C12—C13—C14	1.7 (9)	N3—C4—N4—O42	179.9 (4)
C12—C13—C14—C15	−2.5 (9)	C5—C4—N4—O42	−1.4 (8)
C13—C14—C15—C16	1.4 (9)	N3—C4—C5—N1	−1.6 (6)
C12—C11—C16—C15	−1.2 (8)	N4—C4—C5—N1	179.6 (4)
N1—C11—C16—C15	176.8 (5)	N3—C4—C5—Br5	180.0 (3)
C14—C15—C16—C11	0.4 (9)	N4—C4—C5—Br5	1.2 (9)
C5—N1—C2—N3	−0.8 (5)	C2—N1—C5—C4	1.4 (5)
C11—N1—C2—N3	179.5 (4)	C11—N1—C5—C4	−178.9 (4)
C5—N1—C2—C21	−179.7 (4)	C2—N1—C5—Br5	−179.9 (3)
C11—N1—C2—C21	0.5 (7)	C11—N1—C5—Br5	−0.1 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O41^i	0.95	2.73	3.472 (6)	136
C21—H21C···Br5^ii	0.98	2.96	3.733 (5)	137

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

(170K) 1-phenyl-4-nitro-5-bromo-imidazole

Crystal data

C10H8BrN3O2	F(000) = 560
Mr = 282.10	Dx = 1.776 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1833 reflections
a = 6.9923 (12) Å	θ = 3–20°
b = 6.8497 (10) Å	µ = 3.88 mm^−1
c = 22.9702 (16) Å	T = 170 K
β = 106.419 (14)°	Prism, colourless
V = 1055.3 (2) Å^3	0.5 × 0.3 × 0.1 mm
Z = 4

Data collection

KUMA KM4CCD four-circle diffractometer	2673 independent reflections
Radiation source: fine-focus sealed tube	1387 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
ω–scan	θmax = 29.5°, θmin = 3.0°
Absorption correction: multi-scan SORTAV (Blessing, 1989)	h = −6→9
Tmin = 0.348, Tmax = 0.659	k = −9→9
6354 measured reflections	l = −30→30

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.032P)^2] where P = (Fo^2 + 2Fc^2)/3
2673 reflections	(Δ/σ)max < 0.001
148 parameters	Δρmax = 0.82 e Å^−3
0 restraints	Δρmin = −0.99 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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
N1	0.6880 (4)	0.2287 (6)	0.42271 (15)	0.0230 (8)
C11	0.5251 (6)	0.2174 (6)	0.36776 (19)	0.0257 (11)
C12	0.4562 (7)	0.0384 (8)	0.3440 (2)	0.0385 (14)
H12	0.5121	−0.0779	0.3643	0.054 (8)*
C13	0.3053 (8)	0.0289 (9)	0.2903 (3)	0.0517 (17)
H13	0.2546	−0.0949	0.2745	0.054 (8)*
C14	0.2267 (8)	0.1959 (9)	0.2593 (2)	0.0507 (18)
H14	0.1258	0.1881	0.2217	0.054 (8)*
C15	0.2973 (8)	0.3743 (9)	0.2837 (3)	0.0529 (17)
H15	0.2426	0.4906	0.2631	0.054 (8)*
C16	0.4469 (8)	0.3867 (8)	0.3381 (3)	0.0408 (15)
H16	0.4949	0.5103	0.3546	0.054 (8)*
C2	0.8860 (5)	0.2287 (7)	0.42496 (19)	0.0233 (9)
C21	0.9558 (6)	0.2127 (7)	0.3697 (2)	0.0343 (13)
H21A	0.9054	0.3237	0.3429	0.057 (9)*
H21B	0.9063	0.0908	0.3485	0.057 (9)*
H21C	1.1019	0.2130	0.3815	0.057 (9)*
N3	0.9992 (5)	0.2474 (6)	0.48141 (14)	0.0229 (7)
C4	0.8686 (5)	0.2584 (7)	0.51525 (17)	0.0204 (8)
N4	0.9422 (5)	0.2829 (5)	0.57967 (16)	0.0275 (9)
O41	1.1226 (4)	0.2910 (5)	0.60235 (15)	0.0422 (10)
O42	0.8193 (5)	0.2936 (5)	0.60888 (15)	0.0415 (9)
C5	0.6742 (5)	0.2484 (7)	0.48074 (18)	0.0214 (8)
Br5	0.42698 (5)	0.25148 (7)	0.495917 (18)	0.02324 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0159 (14)	0.029 (2)	0.0264 (18)	−0.0010 (17)	0.0106 (13)	−0.0012 (18)
C11	0.0154 (18)	0.041 (3)	0.022 (2)	−0.001 (2)	0.0071 (16)	−0.005 (2)
C12	0.032 (3)	0.039 (3)	0.042 (4)	−0.003 (2)	0.007 (3)	−0.009 (3)
C13	0.039 (3)	0.070 (4)	0.042 (4)	−0.009 (3)	0.005 (3)	−0.024 (3)
C14	0.026 (3)	0.101 (6)	0.023 (3)	−0.002 (3)	0.004 (2)	−0.001 (3)
C15	0.036 (4)	0.071 (5)	0.046 (4)	0.008 (3)	0.002 (3)	0.022 (3)
C16	0.032 (3)	0.040 (3)	0.048 (4)	−0.005 (2)	0.009 (3)	0.011 (3)
C2	0.0145 (17)	0.032 (3)	0.024 (2)	−0.001 (2)	0.0063 (15)	0.001 (2)
C21	0.023 (2)	0.052 (4)	0.033 (3)	−0.001 (2)	0.0149 (19)	−0.002 (2)
N3	0.0179 (14)	0.0276 (16)	0.0253 (18)	0.000 (2)	0.0091 (13)	−0.002 (2)
C4	0.0159 (17)	0.026 (2)	0.0209 (19)	−0.003 (2)	0.0077 (14)	−0.004 (2)
N4	0.0216 (17)	0.036 (3)	0.027 (2)	−0.0027 (17)	0.0101 (15)	−0.0013 (17)
O41	0.0203 (15)	0.072 (3)	0.0339 (19)	−0.0033 (17)	0.0062 (14)	−0.0023 (18)
O42	0.0339 (17)	0.065 (3)	0.0319 (19)	−0.0047 (17)	0.0191 (15)	−0.0065 (17)
C5	0.0182 (16)	0.0181 (17)	0.033 (2)	−0.001 (2)	0.0155 (16)	0.001 (3)
Br5	0.01722 (18)	0.0237 (2)	0.0323 (2)	0.0002 (2)	0.01257 (15)	−0.0001 (3)

Geometric parameters (Å, º)

N1—C5	1.370 (5)	C16—H16	0.9500
N1—C2	1.371 (5)	C2—N3	1.321 (5)
N1—C11	1.443 (5)	C2—C21	1.486 (6)
C11—C12	1.373 (6)	C21—H21A	0.9800
C11—C16	1.378 (6)	C21—H21B	0.9800
C12—C13	1.379 (7)	C21—H21C	0.9800
C12—H12	0.9500	N3—C4	1.359 (5)
C13—C14	1.378 (7)	C4—C5	1.368 (5)
C13—H13	0.9500	C4—N4	1.432 (5)
C14—C15	1.377 (8)	N4—O41	1.223 (4)
C14—H14	0.9500	N4—O42	1.233 (4)
C15—C16	1.386 (7)	C5—Br5	1.857 (3)
C15—H15	0.9500
C5—N1—C2	108.2 (3)	C15—C16—H16	120.4
C5—N1—C11	126.9 (3)	N3—C2—N1	110.8 (3)
C2—N1—C11	124.9 (3)	N3—C2—C21	126.5 (3)
C12—C11—C16	120.6 (5)	N1—C2—C21	122.7 (4)
C12—C11—N1	119.8 (4)	C2—C21—H21A	109.5
C16—C11—N1	119.5 (4)	C2—C21—H21B	109.5
C11—C12—C13	119.5 (5)	H21A—C21—H21B	109.5
C11—C12—H12	120.3	C2—C21—H21C	109.5
C13—C12—H12	120.3	H21A—C21—H21C	109.5
C14—C13—C12	121.0 (6)	H21B—C21—H21C	109.5
C14—C13—H13	119.5	C2—N3—C4	104.7 (3)
C12—C13—H13	119.5	N3—C4—C5	112.6 (4)
C15—C14—C13	118.8 (5)	N3—C4—N4	119.6 (3)
C15—C14—H14	120.6	C5—C4—N4	127.8 (4)
C13—C14—H14	120.6	O41—N4—O42	124.0 (4)
C14—C15—C16	120.9 (5)	O41—N4—C4	118.1 (3)
C14—C15—H15	119.5	O42—N4—C4	117.8 (3)
C16—C15—H15	119.5	C4—C5—N1	103.7 (3)
C11—C16—C15	119.2 (5)	C4—C5—Br5	135.7 (3)
C11—C16—H16	120.4	N1—C5—Br5	120.6 (3)
C5—N1—C11—C12	−95.2 (6)	N1—C2—N3—C4	0.3 (6)
C2—N1—C11—C12	87.4 (6)	C21—C2—N3—C4	179.3 (5)
C5—N1—C11—C16	88.0 (6)	C2—N3—C4—C5	−0.5 (6)
C2—N1—C11—C16	−89.4 (6)	C2—N3—C4—N4	−179.0 (4)
C16—C11—C12—C13	−1.0 (7)	N3—C4—N4—O41	−0.8 (7)
N1—C11—C12—C13	−177.8 (5)	C5—C4—N4—O41	−179.1 (5)
C11—C12—C13—C14	2.0 (9)	N3—C4—N4—O42	179.6 (4)
C12—C13—C14—C15	−2.1 (9)	C5—C4—N4—O42	1.2 (8)
C13—C14—C15—C16	1.1 (9)	N3—C4—C5—N1	0.5 (6)
C12—C11—C16—C15	0.0 (7)	N4—C4—C5—N1	178.9 (5)
N1—C11—C16—C15	176.8 (5)	N3—C4—C5—Br5	179.2 (4)
C14—C15—C16—C11	−0.1 (9)	N4—C4—C5—Br5	−2.4 (10)
C5—N1—C2—N3	0.0 (6)	C2—N1—C5—C4	−0.3 (6)
C11—N1—C2—N3	177.8 (4)	C11—N1—C5—C4	−178.0 (4)
C5—N1—C2—C21	−179.1 (4)	C2—N1—C5—Br5	−179.3 (3)
C11—N1—C2—C21	−1.3 (7)	C11—N1—C5—Br5	3.0 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O41^i	0.95	2.74	3.471 (6)	135
C21—H21C···Br5^ii	0.98	2.96	3.732 (5)	136

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

(150K) 1-phenyl-4-nitro-5-bromo-imidazole

Crystal data

C10H8BrN3O2	F(000) = 560
Mr = 282.10	Dx = 1.783 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2489 reflections
a = 6.9854 (12) Å	θ = 3–20°
b = 6.8362 (9) Å	µ = 3.90 mm^−1
c = 22.945 (2) Å	T = 150 K
β = 106.466 (13)°	Prism, colourless
V = 1050.8 (2) Å^3	0.5 × 0.3 × 0.1 mm
Z = 4

Data collection

KUMA KM4CCD four-circle diffractometer	2676 independent reflections
Radiation source: fine-focus sealed tube	1445 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.069
ω–scan	θmax = 29.5°, θmin = 3.1°
Absorption correction: multi-scan SORTAV (Blessing, 1989)	h = −9→6
Tmin = 0.321, Tmax = 0.717	k = −9→9
6609 measured reflections	l = −30→30

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0305P)^2] where P = (Fo^2 + 2Fc^2)/3
2676 reflections	(Δ/σ)max = 0.001
148 parameters	Δρmax = 0.85 e Å^−3
0 restraints	Δρmin = −1.00 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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
N1	0.6877 (4)	0.2255 (5)	0.42295 (15)	0.0199 (7)
C11	0.5249 (5)	0.2125 (6)	0.36758 (18)	0.0213 (10)
C12	0.4569 (7)	0.0327 (7)	0.3447 (2)	0.0345 (12)
H12	0.5128	−0.0829	0.3657	0.050 (7)*
C13	0.3065 (7)	0.0207 (8)	0.2908 (2)	0.0466 (15)
H13	0.2570	−0.1037	0.2752	0.050 (7)*
C14	0.2270 (7)	0.1887 (8)	0.2594 (2)	0.0451 (15)
H14	0.1260	0.1800	0.2217	0.050 (7)*
C15	0.2965 (8)	0.3688 (9)	0.2835 (3)	0.0482 (15)
H15	0.2408	0.4849	0.2628	0.050 (7)*
C16	0.4463 (7)	0.3813 (7)	0.3375 (2)	0.0375 (13)
H16	0.4948	0.5054	0.3538	0.050 (7)*
C2	0.8870 (5)	0.2261 (6)	0.42508 (18)	0.0215 (9)
C21	0.9567 (6)	0.2079 (6)	0.3698 (2)	0.0307 (12)
H21A	0.9042	0.3170	0.3422	0.051 (9)*
H21B	0.9090	0.0840	0.3493	0.051 (9)*
H21C	1.1030	0.2104	0.3815	0.051 (9)*
N3	1.0000 (4)	0.2476 (5)	0.48130 (14)	0.0211 (6)
C4	0.8686 (5)	0.2594 (7)	0.51525 (16)	0.0182 (7)
N4	0.9424 (5)	0.2860 (5)	0.57954 (16)	0.0261 (9)
O41	1.1228 (4)	0.2965 (5)	0.60233 (14)	0.0391 (9)
O42	0.8202 (4)	0.2996 (5)	0.60881 (15)	0.0380 (9)
C5	0.6743 (5)	0.2476 (7)	0.48080 (17)	0.0199 (7)
Br5	0.42680 (5)	0.25172 (7)	0.495877 (17)	0.02096 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0153 (14)	0.023 (2)	0.0235 (17)	−0.0014 (15)	0.0085 (12)	−0.0024 (16)
C11	0.0139 (17)	0.032 (3)	0.019 (2)	−0.0037 (17)	0.0058 (15)	−0.0037 (18)
C12	0.030 (3)	0.035 (3)	0.037 (3)	−0.001 (2)	0.008 (2)	−0.008 (2)
C13	0.040 (3)	0.062 (4)	0.032 (3)	−0.006 (3)	0.002 (2)	−0.020 (3)
C14	0.023 (2)	0.087 (5)	0.025 (3)	−0.001 (3)	0.006 (2)	−0.003 (3)
C15	0.035 (3)	0.060 (4)	0.044 (4)	0.002 (3)	0.003 (3)	0.023 (3)
C16	0.031 (3)	0.038 (3)	0.042 (3)	−0.001 (2)	0.006 (2)	0.009 (2)
C2	0.0138 (16)	0.028 (3)	0.022 (2)	−0.0014 (19)	0.0037 (14)	0.001 (2)
C21	0.023 (2)	0.049 (4)	0.024 (2)	−0.003 (2)	0.0137 (18)	−0.005 (2)
N3	0.0159 (13)	0.0260 (16)	0.0241 (17)	0.002 (2)	0.0099 (12)	−0.0015 (19)
C4	0.0158 (16)	0.0214 (18)	0.0193 (18)	−0.004 (2)	0.0080 (13)	−0.001 (2)
N4	0.0205 (17)	0.032 (3)	0.026 (2)	0.0000 (16)	0.0086 (14)	−0.0016 (16)
O41	0.0176 (14)	0.066 (3)	0.0324 (19)	−0.0008 (15)	0.0046 (13)	−0.0040 (16)
O42	0.0303 (16)	0.057 (2)	0.0315 (19)	−0.0012 (15)	0.0169 (14)	−0.0082 (15)
C5	0.0157 (15)	0.0153 (16)	0.032 (2)	0.000 (2)	0.0125 (15)	0.001 (2)
Br5	0.01606 (17)	0.02094 (18)	0.0288 (2)	−0.0002 (2)	0.01110 (13)	−0.0004 (2)

Geometric parameters (Å, º)

N1—C5	1.365 (5)	C16—H16	0.9500
N1—C2	1.379 (5)	C2—N3	1.316 (5)
N1—C11	1.448 (5)	C2—C21	1.487 (5)
C11—C12	1.368 (5)	C21—H21A	0.9800
C11—C16	1.377 (6)	C21—H21B	0.9800
C12—C13	1.379 (6)	C21—H21C	0.9800
C12—H12	0.9500	N3—C4	1.364 (4)
C13—C14	1.386 (7)	C4—C5	1.366 (5)
C13—H13	0.9500	C4—N4	1.430 (5)
C14—C15	1.381 (8)	N4—O41	1.222 (4)
C14—H14	0.9500	N4—O42	1.230 (4)
C15—C16	1.379 (7)	C5—Br5	1.857 (3)
C15—H15	0.9500
C5—N1—C2	108.2 (3)	C15—C16—H16	120.3
C5—N1—C11	127.3 (3)	N3—C2—N1	110.7 (3)
C2—N1—C11	124.4 (3)	N3—C2—C21	126.5 (3)
C12—C11—C16	121.0 (4)	N1—C2—C21	122.8 (3)
C12—C11—N1	119.5 (4)	C2—C21—H21A	109.5
C16—C11—N1	119.4 (4)	C2—C21—H21B	109.5
C11—C12—C13	119.4 (5)	H21A—C21—H21B	109.5
C11—C12—H12	120.3	C2—C21—H21C	109.5
C13—C12—H12	120.3	H21A—C21—H21C	109.5
C12—C13—C14	120.6 (5)	H21B—C21—H21C	109.5
C12—C13—H13	119.7	C2—N3—C4	104.6 (3)
C14—C13—H13	119.7	N3—C4—C5	112.7 (3)
C15—C14—C13	119.1 (5)	N3—C4—N4	119.5 (3)
C15—C14—H14	120.4	C5—C4—N4	127.8 (3)
C13—C14—H14	120.4	O41—N4—O42	123.6 (4)
C16—C15—C14	120.4 (5)	O41—N4—C4	118.4 (3)
C16—C15—H15	119.8	O42—N4—C4	118.0 (3)
C14—C15—H15	119.8	N1—C5—C4	103.8 (3)
C11—C16—C15	119.5 (5)	N1—C5—Br5	120.5 (3)
C11—C16—H16	120.3	C4—C5—Br5	135.7 (3)
C5—N1—C11—C12	−95.1 (5)	N1—C2—N3—C4	0.4 (5)
C2—N1—C11—C12	88.0 (5)	C21—C2—N3—C4	179.4 (5)
C5—N1—C11—C16	87.5 (6)	C2—N3—C4—C5	−0.7 (6)
C2—N1—C11—C16	−89.4 (5)	C2—N3—C4—N4	−179.2 (4)
C16—C11—C12—C13	−0.4 (7)	N3—C4—N4—O41	−0.4 (7)
N1—C11—C12—C13	−177.8 (4)	C5—C4—N4—O41	−178.7 (5)
C11—C12—C13—C14	1.2 (8)	N3—C4—N4—O42	178.7 (4)
C12—C13—C14—C15	−1.8 (8)	C5—C4—N4—O42	0.4 (8)
C13—C14—C15—C16	1.5 (8)	C2—N1—C5—C4	−0.4 (5)
C12—C11—C16—C15	0.1 (7)	C11—N1—C5—C4	−177.7 (4)
N1—C11—C16—C15	177.5 (4)	C2—N1—C5—Br5	−179.6 (3)
C14—C15—C16—C11	−0.7 (8)	C11—N1—C5—Br5	3.1 (6)
C5—N1—C2—N3	0.0 (5)	N3—C4—C5—N1	0.6 (6)
C11—N1—C2—N3	177.4 (4)	N4—C4—C5—N1	179.1 (4)
C5—N1—C2—C21	−179.1 (4)	N3—C4—C5—Br5	179.7 (4)
C11—N1—C2—C21	−1.7 (7)	N4—C4—C5—Br5	−1.9 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O41^i	0.95	2.74	3.469 (6)	134
C21—H21C···Br5^ii	0.98	2.95	3.722 (4)	136

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

(120K) 1-phenyl-4-nitro-5-bromo-imidazole

Crystal data

C10H8BrN3O2	F(000) = 560
Mr = 282.10	Dx = 1.795 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3121 reflections
a = 6.9723 (5) Å	θ = 3–20°
b = 6.8169 (4) Å	µ = 3.93 mm^−1
c = 22.9000 (12) Å	T = 120 K
β = 106.478 (6)°	Prism, colourless
V = 1043.72 (11) Å^3	0.3 × 0.25 × 0.1 mm
Z = 4

Data collection

KUMA KM4CCD four-circle diffractometer	2788 independent reflections
Radiation source: fine-focus sealed tube	2349 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ω–scan	θmax = 29.8°, θmin = 3.1°
Absorption correction: multi-scan SORTAV (Blessing, 1989)	h = −7→9
Tmin = 0.378, Tmax = 0.573	k = −7→9
13861 measured reflections	l = −31→30

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	All H-atom parameters refined
wR(F^2) = 0.068	w = 1/[σ^2(Fo^2) + (0.P)^2 + 2.850P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
2788 reflections	Δρmax = 0.71 e Å^−3
178 parameters	Δρmin = −0.52 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0095 (9)

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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
N1	0.6875 (3)	0.2210 (3)	0.42263 (9)	0.0140 (4)
C11	0.5253 (3)	0.2058 (4)	0.36720 (11)	0.0151 (5)
C12	0.4574 (4)	0.0223 (5)	0.34512 (14)	0.0256 (6)
H12	0.518 (5)	−0.087 (5)	0.3681 (16)	0.030 (9)*
C13	0.3061 (5)	0.0104 (6)	0.29057 (15)	0.0338 (7)
H13	0.259 (7)	−0.107 (8)	0.275 (2)	0.069 (15)*
C14	0.2258 (4)	0.1786 (6)	0.25930 (14)	0.0326 (7)
H14	0.128 (6)	0.169 (6)	0.2209 (19)	0.044 (11)*
C15	0.2940 (5)	0.3607 (6)	0.28268 (15)	0.0356 (8)
H15	0.235 (6)	0.472 (6)	0.264 (2)	0.052 (12)*
C16	0.4448 (4)	0.3763 (5)	0.33738 (14)	0.0273 (6)
H16	0.497 (6)	0.497 (6)	0.3532 (18)	0.040 (11)*
C2	0.8879 (3)	0.2209 (4)	0.42527 (11)	0.0149 (5)
C21	0.9579 (4)	0.1999 (5)	0.37037 (13)	0.0220 (6)
H21A	0.905 (6)	0.302 (6)	0.3432 (18)	0.043 (11)*
H21B	0.908 (6)	0.077 (6)	0.3511 (17)	0.040 (10)*
H21C	1.088 (6)	0.197 (5)	0.3815 (16)	0.033 (10)*
N3	1.0005 (3)	0.2457 (4)	0.48137 (9)	0.0153 (4)
C4	0.8695 (3)	0.2636 (4)	0.51549 (10)	0.0132 (4)
N4	0.9426 (3)	0.2931 (3)	0.57956 (10)	0.0175 (4)
O41	1.1249 (3)	0.3044 (3)	0.60261 (9)	0.0275 (5)
O42	0.8205 (3)	0.3077 (3)	0.60895 (9)	0.0268 (5)
C5	0.6734 (3)	0.2467 (4)	0.48058 (10)	0.0138 (4)
Br5	0.42674 (3)	0.25220 (4)	0.495852 (10)	0.01471 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0112 (8)	0.0174 (11)	0.0127 (9)	−0.0010 (8)	0.0025 (7)	−0.0015 (7)
C11	0.0107 (10)	0.0218 (13)	0.0125 (11)	−0.0011 (9)	0.0026 (8)	−0.0004 (9)
C12	0.0252 (14)	0.0258 (15)	0.0217 (14)	−0.0008 (12)	−0.0001 (11)	−0.0041 (11)
C13	0.0278 (15)	0.0435 (19)	0.0258 (16)	−0.0046 (14)	0.0005 (12)	−0.0141 (14)
C14	0.0197 (13)	0.062 (2)	0.0136 (13)	−0.0005 (14)	0.0009 (10)	−0.0004 (13)
C15	0.0272 (16)	0.047 (2)	0.0271 (17)	0.0027 (14)	−0.0020 (13)	0.0157 (14)
C16	0.0240 (14)	0.0271 (15)	0.0271 (15)	−0.0010 (12)	0.0013 (11)	0.0081 (12)
C2	0.0116 (10)	0.0155 (12)	0.0176 (11)	−0.0011 (9)	0.0040 (8)	0.0001 (9)
C21	0.0165 (12)	0.0340 (16)	0.0176 (13)	−0.0016 (11)	0.0083 (10)	−0.0033 (11)
N3	0.0127 (8)	0.0198 (10)	0.0138 (9)	0.0009 (9)	0.0045 (7)	−0.0011 (9)
C4	0.0118 (9)	0.0143 (10)	0.0134 (10)	0.0009 (9)	0.0033 (8)	−0.0017 (9)
N4	0.0170 (9)	0.0181 (11)	0.0163 (10)	−0.0005 (8)	0.0030 (8)	−0.0010 (8)
O41	0.0152 (9)	0.0457 (13)	0.0184 (9)	−0.0016 (8)	−0.0006 (7)	−0.0027 (8)
O42	0.0235 (9)	0.0434 (13)	0.0158 (9)	−0.0015 (9)	0.0092 (7)	−0.0053 (8)
C5	0.0124 (9)	0.0128 (10)	0.0169 (11)	−0.0013 (9)	0.0052 (8)	−0.0023 (10)
Br5	0.01168 (12)	0.01573 (13)	0.01764 (13)	0.00000 (10)	0.00566 (8)	−0.00018 (10)

Geometric parameters (Å, º)

N1—C5	1.369 (3)	C16—H16	0.93 (4)
N1—C2	1.382 (3)	C2—N3	1.313 (3)
N1—C11	1.444 (3)	C2—C21	1.479 (3)
C11—C12	1.382 (4)	C21—H21A	0.93 (4)
C11—C16	1.384 (4)	C21—H21B	0.97 (4)
C12—C13	1.390 (4)	C21—H21C	0.87 (4)
C12—H12	0.94 (4)	N3—C4	1.366 (3)
C13—C14	1.383 (5)	C4—C5	1.379 (3)
C13—H13	0.90 (5)	C4—N4	1.424 (3)
C14—C15	1.382 (5)	N4—O42	1.230 (3)
C14—H14	0.95 (4)	N4—O41	1.233 (3)
C15—C16	1.392 (4)	C5—Br5	1.850 (2)
C15—H15	0.91 (4)
C5—N1—C2	107.88 (19)	C15—C16—H16	122 (2)
C5—N1—C11	127.41 (19)	N3—C2—N1	111.1 (2)
C2—N1—C11	124.6 (2)	N3—C2—C21	126.5 (2)
C12—C11—C16	122.1 (3)	N1—C2—C21	122.4 (2)
C12—C11—N1	119.2 (2)	C2—C21—H21A	109 (2)
C16—C11—N1	118.7 (2)	C2—C21—H21B	108 (2)
C11—C12—C13	118.4 (3)	H21A—C21—H21B	109 (3)
C11—C12—H12	117 (2)	C2—C21—H21C	109 (2)
C13—C12—H12	124 (2)	H21A—C21—H21C	113 (3)
C14—C13—C12	120.6 (3)	H21B—C21—H21C	109 (3)
C14—C13—H13	119 (3)	C2—N3—C4	105.07 (19)
C12—C13—H13	120 (3)	N3—C4—C5	112.0 (2)
C15—C14—C13	120.0 (3)	N3—C4—N4	120.03 (19)
C15—C14—H14	120 (2)	C5—C4—N4	127.9 (2)
C13—C14—H14	120 (3)	O42—N4—O41	123.4 (2)
C14—C15—C16	120.4 (3)	O42—N4—C4	118.3 (2)
C14—C15—H15	120 (3)	O41—N4—C4	118.3 (2)
C16—C15—H15	119 (3)	N1—C5—C4	103.94 (19)
C11—C16—C15	118.5 (3)	N1—C5—Br5	120.76 (16)
C11—C16—H16	120 (2)	C4—C5—Br5	135.30 (18)
C5—N1—C11—C12	−95.2 (3)	N1—C2—N3—C4	−0.5 (3)
C2—N1—C11—C12	88.1 (3)	C21—C2—N3—C4	178.1 (3)
C5—N1—C11—C16	85.8 (3)	C2—N3—C4—C5	1.0 (3)
C2—N1—C11—C16	−91.0 (3)	C2—N3—C4—N4	−179.8 (2)
C16—C11—C12—C13	1.3 (4)	N3—C4—N4—O42	−179.7 (2)
N1—C11—C12—C13	−177.7 (3)	C5—C4—N4—O42	−0.6 (4)
C11—C12—C13—C14	−0.1 (5)	N3—C4—N4—O41	0.9 (4)
C12—C13—C14—C15	−0.9 (5)	C5—C4—N4—O41	179.9 (3)
C13—C14—C15—C16	0.6 (5)	C2—N1—C5—C4	0.8 (3)
C12—C11—C16—C15	−1.6 (4)	C11—N1—C5—C4	−176.4 (2)
N1—C11—C16—C15	177.4 (3)	C2—N1—C5—Br5	−179.33 (18)
C14—C15—C16—C11	0.6 (5)	C11—N1—C5—Br5	3.5 (4)
C5—N1—C2—N3	−0.2 (3)	N3—C4—C5—N1	−1.1 (3)
C11—N1—C2—N3	177.1 (2)	N4—C4—C5—N1	179.8 (2)
C5—N1—C2—C21	−178.9 (2)	N3—C4—C5—Br5	179.0 (2)
C11—N1—C2—C21	−1.6 (4)	N4—C4—C5—Br5	−0.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O41^i	0.95 (4)	2.71 (4)	3.457 (4)	136 (3)
C21—H21C···Br5^ii	0.87 (4)	3.01 (4)	3.707 (3)	138 (3)

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

(100K) 1-phenyl-4-nitro-5-bromo-imidazole

Crystal data

C10H8BrN3O2	Z = 2
Mr = 282.10	F(000) = 280
Triclinic, P1	Dx = 1.806 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9654 (10) Å	Cell parameters from 1221 reflections
b = 6.8215 (10) Å	θ = 4–22°
c = 11.3983 (17) Å	µ = 3.95 mm^−1
α = 92.683 (13)°	T = 100 K
β = 106.506 (12)°	Prism, colourless
γ = 90.277 (12)°	0.5 × 0.3 × 0.1 mm
V = 518.60 (14) Å^3

Data collection

KUMA KM4CCD four-circle diffractometer	1720 independent reflections
Radiation source: fine-focus sealed tube	1586 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.072
ω–scan	θmax = 29.9°, θmin = 3.7°
Absorption correction: multi-scan SORTAV (Blessing, 1989)	h = −9→9
Tmin = 0.305, Tmax = 0.594	k = −9→9
6344 measured reflections	l = −15→15

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.161	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0209P)^2 + 5.8358P] where P = (Fo^2 + 2Fc^2)/3
1720 reflections	(Δ/σ)max = 0.027
146 parameters	Δρmax = 1.82 e Å^−3
0 restraints	Δρmin = −1.85 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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
N1	0.8092 (9)	0.7313 (11)	0.1534 (6)	0.0217 (14)
C11	0.9712 (10)	0.7195 (14)	0.2643 (6)	0.0228 (17)
C12	1.0368 (12)	0.5357 (14)	0.3087 (8)	0.0232 (16)
H12	0.9795	0.4172	0.2655	0.028*
C13	1.1894 (13)	0.5338 (14)	0.4187 (8)	0.0251 (17)
H13	1.2374	0.4118	0.4512	0.030*
C14	1.2728 (12)	0.7090 (15)	0.4819 (7)	0.0278 (18)
H14	1.3757	0.7057	0.5572	0.033*
C15	1.2063 (14)	0.8830 (17)	0.4354 (9)	0.035 (2)
H15	1.2647	1.0015	0.4781	0.042*
C16	1.0547 (14)	0.8918 (17)	0.3266 (9)	0.034 (2)
H16	1.0088	1.0151	0.2953	0.041*
C2	0.6094 (11)	0.7311 (14)	0.1477 (7)	0.0232 (17)
C21	0.5387 (11)	0.7104 (15)	0.2581 (7)	0.0256 (18)
H21A	0.6152	0.6084	0.3081	0.033*
H21B	0.3962	0.6735	0.2327	0.033*
H21C	0.5582	0.8355	0.3062	0.033*
N3	0.4962 (9)	0.7493 (9)	0.0351 (5)	0.0127 (11)
C4	0.6271 (10)	0.7560 (11)	−0.0337 (6)	0.0161 (14)
N4	0.5557 (10)	0.7883 (12)	−0.1618 (6)	0.0253 (15)
O41	0.6784 (8)	0.7969 (10)	−0.2206 (5)	0.0271 (13)
O42	0.3742 (8)	0.8015 (10)	−0.2077 (5)	0.0267 (13)
C5	0.8233 (10)	0.7505 (10)	0.0378 (6)	0.0147 (13)
Br5	1.07127 (10)	0.75271 (10)	0.00703 (6)	0.0131 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.007 (3)	0.049 (4)	0.009 (3)	−0.004 (3)	0.004 (2)	0.002 (3)
C11	0.006 (3)	0.056 (5)	0.005 (3)	−0.003 (3)	0.001 (2)	−0.003 (3)
C12	0.015 (4)	0.038 (5)	0.014 (4)	0.004 (3)	0.001 (3)	0.007 (3)
C13	0.022 (4)	0.035 (5)	0.017 (4)	0.002 (3)	0.001 (3)	0.005 (3)
C14	0.016 (4)	0.057 (6)	0.008 (3)	0.002 (4)	0.000 (3)	0.005 (3)
C15	0.019 (4)	0.053 (6)	0.026 (5)	−0.003 (4)	−0.002 (3)	−0.014 (4)
C16	0.018 (4)	0.060 (7)	0.020 (4)	0.005 (4)	−0.002 (3)	−0.002 (4)
C2	0.007 (3)	0.052 (5)	0.012 (4)	−0.001 (3)	0.005 (3)	0.001 (3)
C21	0.010 (3)	0.056 (6)	0.012 (3)	0.000 (3)	0.004 (3)	0.003 (3)
N3	0.010 (3)	0.020 (3)	0.010 (3)	−0.002 (2)	0.004 (2)	−0.001 (2)
C4	0.006 (3)	0.030 (4)	0.012 (3)	−0.005 (3)	0.003 (2)	0.000 (3)
N4	0.009 (3)	0.056 (5)	0.011 (3)	−0.003 (3)	0.004 (2)	0.001 (3)
O41	0.016 (3)	0.054 (4)	0.014 (3)	0.000 (3)	0.009 (2)	0.003 (2)
O42	0.011 (3)	0.054 (4)	0.013 (3)	0.002 (2)	0.000 (2)	0.002 (2)
C5	0.012 (3)	0.020 (3)	0.013 (3)	−0.005 (3)	0.006 (3)	−0.005 (2)
Br5	0.0081 (3)	0.0181 (4)	0.0141 (4)	−0.0012 (2)	0.0049 (2)	−0.0002 (2)

Geometric parameters (Å, º)

N1—C5	1.360 (9)	C2—N3	1.313 (10)
N1—C2	1.375 (9)	C2—C21	1.488 (10)
N1—C11	1.442 (9)	N3—C4	1.363 (8)
C11—C16	1.380 (14)	C4—C5	1.380 (9)
C11—C12	1.404 (13)	C4—N4	1.430 (10)
C12—C13	1.395 (11)	N4—O42	1.229 (8)
C13—C14	1.400 (13)	N4—O41	1.230 (8)
C14—C15	1.352 (15)	C5—Br5	1.858 (7)
C15—C16	1.386 (13)
C5—N1—C2	107.7 (6)	N3—C2—C21	126.3 (6)
C5—N1—C11	127.4 (6)	N1—C2—C21	122.2 (7)
C2—N1—C11	124.9 (6)	C2—N3—C4	104.8 (6)
C16—C11—C12	121.4 (8)	N3—C4—C5	111.7 (6)
C16—C11—N1	118.5 (8)	N3—C4—N4	120.1 (6)
C12—C11—N1	120.0 (8)	C5—C4—N4	127.8 (6)
C13—C12—C11	117.4 (8)	O42—N4—O41	123.5 (7)
C12—C13—C14	121.0 (8)	O42—N4—C4	118.1 (6)
C15—C14—C13	119.7 (8)	O41—N4—C4	118.4 (6)
C14—C15—C16	121.2 (10)	N1—C5—C4	104.3 (6)
C11—C16—C15	119.3 (10)	N1—C5—Br5	120.7 (5)
N3—C2—N1	111.5 (6)	C4—C5—Br5	134.9 (5)
C5—N1—C11—C16	86.3 (11)	N1—C2—N3—C4	1.7 (9)
C2—N1—C11—C16	−91.5 (11)	C21—C2—N3—C4	−177.8 (9)
C5—N1—C11—C12	−95.6 (10)	C2—N3—C4—C5	−2.7 (9)
C2—N1—C11—C12	86.6 (11)	C2—N3—C4—N4	−176.0 (8)
C16—C11—C12—C13	0.2 (11)	N3—C4—N4—O42	−2.9 (12)
N1—C11—C12—C13	−177.8 (7)	C5—C4—N4—O42	−175.1 (8)
C11—C12—C13—C14	0.1 (13)	N3—C4—N4—O41	178.8 (7)
C12—C13—C14—C15	−0.6 (12)	C5—C4—N4—O41	6.6 (13)
C13—C14—C15—C16	0.8 (14)	C2—N1—C5—C4	−1.5 (9)
C12—C11—C16—C15	−0.1 (13)	C11—N1—C5—C4	−179.6 (8)
N1—C11—C16—C15	178.0 (8)	C2—N1—C5—Br5	−179.0 (6)
C14—C15—C16—C11	−0.5 (15)	C11—N1—C5—Br5	2.9 (12)
C5—N1—C2—N3	−0.1 (10)	N3—C4—C5—N1	2.6 (9)
C11—N1—C2—N3	178.1 (8)	N4—C4—C5—N1	175.3 (8)
C5—N1—C2—C21	179.4 (8)	N3—C4—C5—Br5	179.5 (6)
C11—N1—C2—C21	−2.5 (14)	N4—C4—C5—Br5	−7.8 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O42^i	0.95	2.77	3.553 (11)	140
C21—H21B···Br5^ii	0.98	2.98	3.697 (8)	131

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