2,4-Di­aryl­pyrroles: synthesis, characterization and crystallographic insights

Three 2,4-di­aryl­pyrroles were synthesized starting from 4-nitro­butano­nes and the crystal structures of two derivatives were analysed. These are 4-(4-meth­oxy­phen­yl)-2-(thio­phen-2-yl)-1H-pyrrole, C₁₅H₁₃NOS, and 3-(4-bromo­phen­yl)-2-nitroso-5-phenyl-1H-pyrrole, C₁₆H₁₁BrN₂O. Although pyrroles without sub­stituents at the α-position with respect to the N atom are very air sensitive and tend to polymerize, we succeeded in growing an adequate crystal for X-ray diffraction analysis. Further derivatization using sodium nitrite afforded a nitrosyl pyrrole derivative, which crystallized in the triclinic space group P with Z = 6. Thus, herein we report the first crystal structure of a nitrosyl pyrrole. Inter­estingly, the co-operative hydrogen bonds in this NO-substituted pyrrole lead to a trimeric structure with bifurcated halogen bonds at the ends, forming a two-dimensional (2D) layer with inter­stitial voids having a radius of 5 Å, similar to some reported macrocyclic porphyrins.

Computing details

4-(4-Methoxyphenyl)-2-(thiophen-2-yl)-1H-pyrrole (3a)

Crystal data

C15H13NOS	F(000) = 536
Mr = 255.32	Dx = 1.366 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9266 reflections
a = 7.4695 (11) Å	θ = 2.7–24.9°
b = 5.7626 (7) Å	µ = 0.25 mm^−1
c = 28.907 (4) Å	T = 296 K
β = 93.662 (5)°	Plate, yellow
V = 1241.7 (3) Å^3	0.29 × 0.15 × 0.06 mm
Z = 4

Data collection

Bruker APEXII diffractometer	2985 independent reflections
Radiation source: sealed x-ray tube	1981 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.075
φ or ω oscillation scans	θmax = 29.4°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −9→9
Tmin = 0.702, Tmax = 0.746	k = −7→7
52264 measured reflections	l = −39→37

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.071	w = 1/[σ^2(Fo^2) + (0.1237P)^2 + 0.3542P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.208	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.57 e Å^−3
2985 reflections	Δρmin = −0.59 e Å^−3
195 parameters	Extinction correction: SHELXL2019 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
177 restraints	Extinction coefficient: 0.113 (13)
0 constraints

Special details

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O2	0.8488 (3)	0.4150 (3)	0.44624 (6)	0.0627 (5)
C1	0.7263 (3)	0.2441 (4)	0.17693 (9)	0.0462 (6)
C2	0.6970 (3)	0.3508 (4)	0.21820 (8)	0.0470 (6)
H2	0.643701	0.495168	0.221474	0.056*
C3	0.7615 (3)	0.2045 (4)	0.25504 (8)	0.0437 (5)
C4	0.8265 (4)	0.0098 (4)	0.23438 (9)	0.0562 (7)
H4	0.876483	−0.118433	0.249863	0.067*
C5	0.7738 (3)	0.2574 (4)	0.30487 (8)	0.0438 (6)
C6	0.6995 (3)	0.4580 (4)	0.32227 (9)	0.0497 (6)
H6	0.63354	0.555533	0.302013	0.06*
C7	0.7205 (3)	0.5179 (4)	0.36887 (9)	0.0520 (6)
H7	0.668373	0.652678	0.379539	0.062*
C8	0.8194 (3)	0.3754 (4)	0.39915 (8)	0.0478 (6)
C9	0.8950 (3)	0.1751 (4)	0.38279 (9)	0.0532 (6)
H9	0.961225	0.078386	0.403156	0.064*
C10	0.8730 (3)	0.1179 (4)	0.33661 (9)	0.0502 (6)
H10	0.925533	−0.017198	0.326245	0.06*
C11	0.7810 (5)	0.6229 (5)	0.46406 (11)	0.0725 (8)
H11A	0.829792	0.752819	0.448315	0.109*
H11B	0.814548	0.633209	0.496613	0.109*
H11C	0.652637	0.624096	0.459379	0.109*
N1	0.8057 (3)	0.0353 (4)	0.18772 (8)	0.0575 (6)
H1	0.821 (5)	−0.058 (6)	0.1711 (13)	0.086*
C12	0.699 (4)	0.341 (4)	0.1314 (4)	0.041 (3)	0.5
C13	0.766 (3)	0.207 (3)	0.0898 (5)	0.0593 (15)	0.5
H13	0.828894	0.068114	0.090437	0.071*	0.5
C14	0.7077 (18)	0.3477 (18)	0.0486 (5)	0.0593 (15)	0.5
H14	0.730966	0.305849	0.018525	0.071*	0.5
C15	0.618 (2)	0.541 (2)	0.0589 (3)	0.063 (2)	0.5
H15	0.576746	0.650797	0.037139	0.075*	0.5
S1	0.5896 (8)	0.5614 (8)	0.11682 (18)	0.0691 (7)	0.5
C12A	0.694 (5)	0.306 (4)	0.1276 (4)	0.048 (4)	0.5
C13A	0.611 (3)	0.543 (3)	0.1195 (6)	0.0593 (15)	0.5
H13A	0.574746	0.647517	0.141495	0.071*	0.5
C14A	0.602 (2)	0.569 (3)	0.0685 (4)	0.0593 (15)	0.5
H14A	0.54185	0.691536	0.053536	0.071*	0.5
C15A	0.6868 (17)	0.4046 (15)	0.0452 (4)	0.0575 (18)	0.5
H15A	0.698297	0.404653	0.013303	0.069*	0.5
S1A	0.7714 (6)	0.1927 (7)	0.08301 (10)	0.0504 (5)	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2	0.0738 (13)	0.0640 (11)	0.0503 (10)	0.0101 (10)	0.0038 (9)	0.0027 (8)
C1	0.0381 (11)	0.0441 (12)	0.0566 (14)	−0.0047 (9)	0.0043 (10)	−0.0024 (10)
C2	0.0434 (12)	0.0429 (11)	0.0547 (14)	0.0011 (9)	0.0035 (10)	−0.0010 (10)
C3	0.0364 (11)	0.0412 (11)	0.0537 (13)	−0.0017 (9)	0.0047 (9)	0.0011 (9)
C4	0.0593 (15)	0.0466 (13)	0.0625 (16)	0.0107 (11)	0.0029 (12)	−0.0004 (11)
C5	0.0360 (11)	0.0397 (11)	0.0564 (14)	−0.0008 (9)	0.0074 (9)	0.0063 (10)
C6	0.0485 (13)	0.0474 (13)	0.0533 (14)	0.0122 (10)	0.0036 (10)	0.0054 (10)
C7	0.0515 (14)	0.0462 (12)	0.0586 (15)	0.0095 (10)	0.0070 (11)	0.0032 (10)
C8	0.0442 (12)	0.0492 (12)	0.0504 (13)	0.0007 (10)	0.0069 (10)	0.0053 (10)
C9	0.0514 (14)	0.0476 (13)	0.0606 (15)	0.0091 (10)	0.0026 (11)	0.0126 (11)
C10	0.0508 (13)	0.0411 (11)	0.0591 (15)	0.0092 (10)	0.0075 (11)	0.0037 (10)
C11	0.087 (2)	0.0721 (18)	0.0593 (17)	0.0114 (16)	0.0148 (15)	−0.0067 (14)
N1	0.0662 (14)	0.0498 (12)	0.0567 (14)	0.0092 (10)	0.0053 (11)	−0.0085 (9)
C12	0.037 (5)	0.036 (5)	0.049 (4)	−0.008 (5)	0.001 (3)	−0.015 (3)
C13	0.063 (3)	0.060 (3)	0.055 (3)	−0.004 (2)	0.000 (2)	−0.010 (2)
C14	0.063 (3)	0.060 (3)	0.055 (3)	−0.004 (2)	0.000 (2)	−0.010 (2)
C15	0.075 (5)	0.065 (5)	0.047 (4)	−0.004 (4)	−0.009 (4)	0.011 (4)
S1	0.0677 (17)	0.0677 (13)	0.0712 (13)	0.0068 (9)	−0.0013 (11)	0.0083 (10)
C12A	0.046 (5)	0.048 (8)	0.051 (4)	−0.018 (5)	0.005 (5)	−0.007 (5)
C13A	0.063 (3)	0.060 (3)	0.055 (3)	−0.004 (2)	0.000 (2)	−0.010 (2)
C14A	0.063 (3)	0.060 (3)	0.055 (3)	−0.004 (2)	0.000 (2)	−0.010 (2)
C15A	0.069 (4)	0.049 (5)	0.054 (3)	0.005 (4)	−0.003 (3)	0.001 (3)
S1A	0.0583 (9)	0.0494 (9)	0.0439 (11)	0.0004 (7)	0.0058 (8)	−0.0096 (8)

Geometric parameters (Å, º)

O2—C8	1.384 (3)	C10—H10	0.93
O2—C11	1.411 (3)	C11—H11A	0.96
C1—N1	1.368 (3)	C11—H11B	0.96
C1—C2	1.372 (3)	C11—H11C	0.96
C1—C12	1.433 (8)	N1—H1	0.73 (4)
C1—C12A	1.474 (9)	C12—C13	1.54 (2)
C2—C3	1.418 (3)	C12—S1	1.554 (18)
C2—H2	0.93	C13—C14	1.482 (17)
C3—C4	1.374 (3)	C13—H13	0.93
C3—C5	1.469 (3)	C14—C15	1.344 (8)
C4—N1	1.356 (4)	C14—H14	0.93
C4—H4	0.93	C15—S1	1.705 (8)
C5—C6	1.390 (3)	C15—H15	0.93
C5—C10	1.396 (3)	C12A—C13A	1.51 (2)
C6—C7	1.390 (4)	C12A—S1A	1.59 (2)
C6—H6	0.93	C13A—C14A	1.481 (16)
C7—C8	1.380 (3)	C13A—H13A	0.93
C7—H7	0.93	C14A—C15A	1.344 (8)
C8—C9	1.381 (3)	C14A—H14A	0.93
C9—C10	1.375 (4)	C15A—S1A	1.732 (7)
C9—H9	0.93	C15A—H15A	0.93
C8—O2—C11	117.5 (2)	O2—C11—H11B	109.5
N1—C1—C2	106.7 (2)	H11A—C11—H11B	109.5
N1—C1—C12	125.9 (9)	O2—C11—H11C	109.5
C2—C1—C12	127.1 (9)	H11A—C11—H11C	109.5
N1—C1—C12A	118.4 (10)	H11B—C11—H11C	109.5
C2—C1—C12A	134.9 (10)	C4—N1—C1	110.0 (2)
C1—C2—C3	108.7 (2)	C4—N1—H1	124 (3)
C1—C2—H2	125.6	C1—N1—H1	125 (3)
C3—C2—H2	125.6	C1—C12—C13	119.3 (15)
C4—C3—C2	105.7 (2)	C1—C12—S1	127.5 (15)
C4—C3—C5	126.4 (2)	C13—C12—S1	112.9 (7)
C2—C3—C5	127.6 (2)	C14—C13—C12	105.2 (14)
N1—C4—C3	108.8 (2)	C14—C13—H13	127.4
N1—C4—H4	125.6	C12—C13—H13	127.4
C3—C4—H4	125.6	C15—C14—C13	113.5 (15)
C6—C5—C10	116.6 (2)	C15—C14—H14	123.2
C6—C5—C3	121.7 (2)	C13—C14—H14	123.2
C10—C5—C3	121.5 (2)	C14—C15—S1	111.6 (12)
C7—C6—C5	122.3 (2)	C14—C15—H15	124.2
C7—C6—H6	118.8	S1—C15—H15	124.2
C5—C6—H6	118.8	C12—S1—C15	96.5 (8)
C8—C7—C6	119.3 (2)	C1—C12A—C13A	114.2 (16)
C8—C7—H7	120.4	C1—C12A—S1A	129.7 (17)
C6—C7—H7	120.4	C13A—C12A—S1A	114.4 (7)
C7—C8—C9	119.6 (2)	C14A—C13A—C12A	103.9 (14)
C7—C8—O2	124.8 (2)	C14A—C13A—H13A	128.1
C9—C8—O2	115.6 (2)	C12A—C13A—H13A	128.1
C10—C9—C8	120.5 (2)	C15A—C14A—C13A	115.8 (15)
C10—C9—H9	119.8	C15A—C14A—H14A	122.1
C8—C9—H9	119.8	C13A—C14A—H14A	122.1
C9—C10—C5	121.7 (2)	C14A—C15A—S1A	110.1 (13)
C9—C10—H10	119.1	C14A—C15A—H15A	124.9
C5—C10—H10	119.1	S1A—C15A—H15A	124.9
O2—C11—H11A	109.5	C12A—S1A—C15A	94.9 (7)
N1—C1—C2—C3	0.5 (3)	C12—C1—N1—C4	173.4 (18)
C12—C1—C2—C3	−172.9 (18)	C12A—C1—N1—C4	179.3 (17)
C12A—C1—C2—C3	−179 (2)	N1—C1—C12—C13	−1 (3)
C1—C2—C3—C4	−0.8 (3)	C2—C1—C12—C13	171.1 (16)
C1—C2—C3—C5	173.6 (2)	N1—C1—C12—S1	171.8 (17)
C2—C3—C4—N1	0.8 (3)	C2—C1—C12—S1	−16 (4)
C5—C3—C4—N1	−173.7 (2)	C1—C12—C13—C14	177 (2)
C4—C3—C5—C6	−178.5 (2)	S1—C12—C13—C14	3 (3)
C2—C3—C5—C6	8.2 (4)	C12—C13—C14—C15	0 (2)
C4—C3—C5—C10	6.7 (4)	C13—C14—C15—S1	−2.6 (16)
C2—C3—C5—C10	−166.6 (2)	C1—C12—S1—C15	−177 (3)
C10—C5—C6—C7	−0.6 (4)	C13—C12—S1—C15	−4 (2)
C3—C5—C6—C7	−175.6 (2)	C14—C15—S1—C12	4.0 (18)
C5—C6—C7—C8	0.5 (4)	N1—C1—C12A—C13A	−178.1 (18)
C6—C7—C8—C9	−0.4 (4)	C2—C1—C12A—C13A	1 (4)
C6—C7—C8—O2	−179.5 (2)	N1—C1—C12A—S1A	−14 (4)
C11—O2—C8—C7	−3.7 (4)	C2—C1—C12A—S1A	165.0 (15)
C11—O2—C8—C9	177.2 (2)	C1—C12A—C13A—C14A	177 (2)
C7—C8—C9—C10	0.3 (4)	S1A—C12A—C13A—C14A	10 (3)
O2—C8—C9—C10	179.5 (2)	C12A—C13A—C14A—C15A	−9 (3)
C8—C9—C10—C5	−0.4 (4)	C13A—C14A—C15A—S1A	4.2 (18)
C6—C5—C10—C9	0.5 (4)	C1—C12A—S1A—C15A	−171 (3)
C3—C5—C10—C9	175.5 (2)	C13A—C12A—S1A—C15A	−8 (3)
C3—C4—N1—C1	−0.5 (3)	C14A—C15A—S1A—C12A	2.1 (17)
C2—C1—N1—C4	0.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···S1Ab^i	0.93	3	3.821 (5)	148
C14a—H14a···O2^ii	0.93	2.64	3.544 (14)	163

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

3-(4-Bromophenyl)-2-nitroso-5-phenyl-1H-pyrrole (4)

Crystal data

C16H11BrN2O^+[solvent]	Z = 6
Mr = 327.18	F(000) = 984
Triclinic, P1	Dx = 1.348 Mg m^−3
a = 10.2533 (19) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.689 (3) Å	Cell parameters from 9924 reflections
c = 17.003 (3) Å	θ = 2.2–25.0°
α = 104.713 (6)°	µ = 2.55 mm^−1
β = 91.812 (6)°	T = 297 K
γ = 101.544 (6)°	Prism, green
V = 2417.5 (8) Å^3	0.23 × 0.19 × 0.14 mm

Data collection

Bruker APEXII diffractometer	6774 reflections with I > 2σ(I)
Radiation source: sealed x-ray tube	Rint = 0.082
φ or ω oscillation scans	θmax = 27.9°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −13→13
Tmin = 0.666, Tmax = 0.746	k = −19→19
134671 measured reflections	l = −22→22
11584 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.175	w = 1/[σ^2(Fo^2) + (0.083P)^2 + 2.0664P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
11584 reflections	Δρmax = 0.59 e Å^−3
547 parameters	Δρmin = −0.69 e Å^−3

Special details

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

Refinement. X-ray crystallographic data was obtained using a Bruker APEXII diffractometer with a CCD area detector (Mo Kα = 0.71073 Å, monochromator: graphite). Indexing, data integration and reduction were carried out using APEX5. All reflection data set were corrected for polarization effects. The structures were solved in the WinGX (Farrugia, 2012) suite of programs by intrinsic phasing using SHELXT (Sheldrick, 2015b) and refined using full-matrix least-squares/difference Fourier techniques on F² using SHELXL (Sheldrick, 2015b). All non-H atoms were refined using anisotropic displacement parameters. H atoms were set geometrically and constrained to ride on their associated atoms. Mercury (Macrae et al., 2020) and ORTEP-3 (Farrugia, 2012) programs were used to prepare artwork representations. For the nitrosylpyrrole 4, crystal structure data was analysed with PLATON (Spek, 2020) and treated using the SQUEEZE routine (Spek, 2015). Table 1 summarizes crystallographic data and structure refinement details. The crystal structures have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under numbers 2361143 (3a) and 2361144 (4). Copies can be obtained on request, free of charge via www.ccdc.cam.ac.uk/data_request/cif or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK (fax: [phone] or email: [email protected]).

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

	x	y	z	Uiso*/Ueq
Br2	−0.08774 (5)	0.83243 (4)	0.07627 (3)	0.07290 (17)
O1	0.5893 (3)	0.5229 (3)	0.3902 (2)	0.0746 (9)
N1	0.7207 (3)	0.3801 (2)	0.3834 (2)	0.0524 (8)
H1	0.675942	0.370253	0.337264	0.070 (14)*
O2	0.4417 (3)	0.5365 (2)	0.23024 (19)	0.0694 (8)
N2	0.6565 (4)	0.5269 (3)	0.4560 (2)	0.0599 (9)
O3	0.5655 (4)	0.3533 (3)	0.22658 (19)	0.0781 (10)
N3	0.4408 (3)	0.6705 (2)	0.3723 (2)	0.0535 (8)
H3A	0.491460	0.632948	0.380118	0.055 (12)*
N4	0.3655 (4)	0.5943 (3)	0.2278 (2)	0.0586 (9)
C4	0.8035 (4)	0.3256 (3)	0.3998 (2)	0.0509 (9)
N5	0.4513 (3)	0.3696 (3)	0.0866 (2)	0.0551 (8)
H5	0.436773	0.414550	0.126733	0.050 (12)*
C5	0.8339 (4)	0.2431 (3)	0.3414 (2)	0.0517 (10)
N6	0.5761 (4)	0.2899 (3)	0.1613 (2)	0.0615 (9)
C6	0.7506 (5)	0.1935 (3)	0.2713 (3)	0.0657 (12)
H6	0.672650	0.213203	0.260610	0.093 (18)*
C7	0.7825 (6)	0.1156 (4)	0.2174 (3)	0.0752 (14)
H7	0.726092	0.082734	0.170558	0.090*
C8	0.8970 (6)	0.0867 (4)	0.2326 (3)	0.0835 (16)
H8	0.916699	0.032853	0.196704	0.100*
C10	0.9503 (5)	0.2133 (4)	0.3546 (3)	0.0790 (15)
H10	1.008040	0.245748	0.400944	0.095*
C9	0.9815 (6)	0.1348 (4)	0.2987 (4)	0.0933 (19)
H9	1.060823	0.115707	0.307250	0.112*
C2	0.8050 (4)	0.4434 (3)	0.5154 (2)	0.0503 (9)
C3	0.8561 (4)	0.3645 (3)	0.4816 (2)	0.0537 (10)
H3	0.916215	0.340440	0.508433	0.064*
Br3	0.78367 (6)	−0.10641 (4)	−0.10174 (3)	0.07482 (18)
Br1	0.93593 (6)	0.68790 (4)	0.87090 (3)	0.07679 (18)
C1	0.7187 (4)	0.4539 (3)	0.4515 (2)	0.0514 (9)
C15	0.7772 (4)	0.6114 (3)	0.7204 (3)	0.0594 (11)
H15	0.717292	0.646307	0.746492	0.071*
C11	0.8340 (4)	0.5039 (3)	0.5999 (2)	0.0488 (9)
C12	0.9543 (4)	0.5076 (3)	0.6431 (3)	0.0570 (10)
H12	1.014629	0.472724	0.617435	0.068*
C13	0.9854 (4)	0.5626 (3)	0.7240 (3)	0.0607 (11)
H13	1.065614	0.564701	0.752222	0.073*
C14	0.8958 (4)	0.6132 (3)	0.7608 (2)	0.0549 (10)
C19	0.3331 (4)	0.7910 (3)	0.3921 (3)	0.0597 (11)
H19	0.304133	0.846355	0.417710	0.072*
C20	0.4206 (4)	0.7480 (3)	0.4276 (2)	0.0533 (10)
C21	0.4867 (4)	0.7827 (3)	0.5110 (3)	0.0559 (10)
C22	0.4693 (6)	0.8697 (4)	0.5629 (3)	0.0826 (16)
H22	0.412080	0.903277	0.544723	0.099*
C23	0.5339 (6)	0.9066 (4)	0.6393 (4)	0.0945 (19)
H23	0.522190	0.965085	0.671926	0.113*
C24	0.6159 (6)	0.8569 (5)	0.6675 (3)	0.0867 (17)
H24	0.658950	0.881183	0.719796	0.104*
C25	0.6346 (6)	0.7728 (4)	0.6197 (3)	0.0921 (18)
H25	0.691335	0.739823	0.639148	0.111*
C26	0.5697 (5)	0.7348 (4)	0.5414 (3)	0.0771 (15)
H26	0.582746	0.676319	0.509423	0.15 (3)*
C27	0.2070 (4)	0.7571 (3)	0.2526 (3)	0.0541 (10)
C28	0.2025 (5)	0.8520 (3)	0.2565 (3)	0.0725 (14)
H28	0.259026	0.901227	0.295722	0.087*
C29	0.1170 (5)	0.8762 (4)	0.2042 (3)	0.0729 (14)
H29	0.116050	0.940214	0.207445	0.087*
C30	0.0336 (4)	0.8020 (3)	0.1474 (3)	0.0576 (11)
C31	0.0339 (5)	0.7077 (3)	0.1418 (3)	0.0670 (12)
H31	−0.024196	0.658826	0.103272	0.080*
C32	0.1211 (5)	0.6856 (3)	0.1940 (3)	0.0658 (12)
H32	0.122096	0.621354	0.189660	0.079*
C33	0.5197 (4)	0.2997 (3)	0.0929 (3)	0.0528 (10)
C34	0.5222 (4)	0.2399 (3)	0.0133 (3)	0.0522 (10)
C35	0.4521 (4)	0.2754 (3)	−0.0387 (3)	0.0554 (10)
H35	0.435154	0.249895	−0.094879	0.067*
C36	0.4108 (4)	0.3565 (3)	0.0079 (2)	0.0522 (10)
C37	0.3393 (4)	0.4196 (3)	−0.0220 (3)	0.0552 (10)
C38	0.2857 (5)	0.4895 (4)	0.0295 (3)	0.0737 (14)
H38	0.293182	0.497464	0.085569	0.077 (15)*
C39	0.2206 (6)	0.5477 (4)	−0.0036 (3)	0.0815 (15)
H39	0.186430	0.595278	0.031320	0.098*
C40	0.2056 (5)	0.5370 (4)	−0.0848 (3)	0.0744 (14)
H40	0.157868	0.574628	−0.105366	0.089*
C41	0.2612 (5)	0.4703 (4)	−0.1367 (3)	0.0763 (14)
H41	0.254315	0.464447	−0.192492	0.092*
C42	0.3272 (5)	0.4121 (3)	−0.1060 (3)	0.0664 (12)
H42	0.364422	0.366969	−0.141686	0.080*
C43	0.5850 (4)	0.1570 (3)	−0.0115 (3)	0.0534 (10)
C44	0.7070 (4)	0.1543 (3)	0.0248 (3)	0.0586 (11)
H44	0.749689	0.205816	0.067868	0.070*
C45	0.7657 (4)	0.0771 (3)	−0.0016 (3)	0.0623 (11)
H45	0.847393	0.076283	0.023337	0.075*
C46	0.7029 (4)	0.0009 (3)	−0.0651 (3)	0.0547 (10)
C47	0.5820 (5)	0.0005 (3)	−0.1032 (3)	0.0633 (12)
H47	0.540250	−0.051404	−0.146205	0.076*
C48	0.5247 (4)	0.0782 (3)	−0.0763 (3)	0.0593 (11)
H48	0.443354	0.078566	−0.101862	0.071*
C16	0.7475 (4)	0.5568 (3)	0.6398 (3)	0.0573 (11)
H16	0.667349	0.555923	0.612201	0.069*
C17	0.3660 (4)	0.6610 (3)	0.3003 (2)	0.0519 (10)
C18	0.2973 (4)	0.7374 (3)	0.3129 (3)	0.0553 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br2	0.0766 (3)	0.0829 (3)	0.0596 (3)	0.0334 (3)	−0.0150 (2)	0.0098 (2)
O1	0.082 (2)	0.082 (2)	0.0625 (19)	0.0403 (18)	−0.0196 (17)	0.0095 (17)
N1	0.0536 (19)	0.055 (2)	0.0489 (19)	0.0203 (16)	−0.0061 (15)	0.0083 (15)
O2	0.083 (2)	0.071 (2)	0.0567 (18)	0.0339 (18)	0.0022 (16)	0.0082 (15)
N2	0.064 (2)	0.064 (2)	0.053 (2)	0.0251 (18)	−0.0076 (17)	0.0105 (17)
O3	0.104 (3)	0.085 (2)	0.0485 (18)	0.047 (2)	−0.0134 (17)	0.0066 (17)
N3	0.060 (2)	0.053 (2)	0.0471 (19)	0.0200 (17)	−0.0017 (16)	0.0078 (16)
N4	0.067 (2)	0.058 (2)	0.051 (2)	0.0208 (18)	0.0032 (17)	0.0089 (17)
C4	0.049 (2)	0.054 (2)	0.049 (2)	0.0153 (18)	−0.0041 (18)	0.0110 (18)
N5	0.062 (2)	0.055 (2)	0.0487 (19)	0.0197 (17)	−0.0069 (16)	0.0090 (16)
C5	0.060 (2)	0.049 (2)	0.047 (2)	0.0187 (19)	−0.0019 (18)	0.0111 (18)
N6	0.075 (2)	0.061 (2)	0.050 (2)	0.0248 (19)	−0.0061 (18)	0.0112 (18)
C6	0.083 (3)	0.061 (3)	0.054 (3)	0.028 (2)	−0.012 (2)	0.008 (2)
C7	0.097 (4)	0.062 (3)	0.060 (3)	0.025 (3)	−0.014 (3)	0.001 (2)
C8	0.096 (4)	0.069 (3)	0.079 (4)	0.035 (3)	0.003 (3)	−0.004 (3)
C10	0.072 (3)	0.080 (3)	0.077 (3)	0.034 (3)	−0.015 (3)	−0.005 (3)
C9	0.086 (4)	0.091 (4)	0.091 (4)	0.051 (3)	−0.018 (3)	−0.018 (3)
C2	0.052 (2)	0.053 (2)	0.045 (2)	0.0133 (18)	−0.0031 (17)	0.0102 (18)
C3	0.055 (2)	0.062 (3)	0.047 (2)	0.021 (2)	−0.0056 (18)	0.0142 (19)
Br3	0.0921 (4)	0.0769 (3)	0.0643 (3)	0.0490 (3)	0.0009 (2)	0.0114 (2)
Br1	0.0966 (4)	0.0837 (4)	0.0482 (3)	0.0407 (3)	−0.0121 (2)	0.0000 (2)
C1	0.051 (2)	0.054 (2)	0.050 (2)	0.0181 (19)	−0.0022 (18)	0.0112 (18)
C15	0.062 (3)	0.066 (3)	0.055 (2)	0.028 (2)	0.004 (2)	0.013 (2)
C11	0.053 (2)	0.049 (2)	0.046 (2)	0.0148 (18)	0.0004 (17)	0.0118 (17)
C12	0.056 (2)	0.066 (3)	0.050 (2)	0.026 (2)	−0.0034 (19)	0.008 (2)
C13	0.057 (2)	0.074 (3)	0.052 (2)	0.025 (2)	−0.008 (2)	0.012 (2)
C14	0.068 (3)	0.055 (2)	0.043 (2)	0.019 (2)	−0.0020 (19)	0.0115 (18)
C19	0.065 (3)	0.053 (2)	0.060 (3)	0.025 (2)	−0.002 (2)	0.006 (2)
C20	0.056 (2)	0.060 (3)	0.043 (2)	0.013 (2)	−0.0026 (18)	0.0126 (19)
C21	0.064 (3)	0.057 (2)	0.047 (2)	0.020 (2)	0.0004 (19)	0.0097 (19)
C22	0.090 (4)	0.090 (4)	0.062 (3)	0.046 (3)	−0.017 (3)	−0.008 (3)
C23	0.100 (4)	0.092 (4)	0.076 (4)	0.049 (3)	−0.016 (3)	−0.024 (3)
C24	0.097 (4)	0.110 (4)	0.047 (3)	0.033 (3)	−0.019 (3)	0.005 (3)
C25	0.119 (5)	0.089 (4)	0.070 (3)	0.042 (4)	−0.032 (3)	0.014 (3)
C26	0.100 (4)	0.073 (3)	0.058 (3)	0.036 (3)	−0.017 (3)	0.007 (2)
C27	0.056 (2)	0.056 (2)	0.051 (2)	0.018 (2)	−0.0032 (19)	0.0110 (19)
C28	0.080 (3)	0.058 (3)	0.070 (3)	0.013 (2)	−0.028 (2)	0.006 (2)
C29	0.086 (3)	0.058 (3)	0.073 (3)	0.022 (2)	−0.021 (3)	0.013 (2)
C30	0.058 (2)	0.070 (3)	0.046 (2)	0.022 (2)	0.0002 (19)	0.012 (2)
C31	0.066 (3)	0.061 (3)	0.065 (3)	0.017 (2)	−0.013 (2)	0.001 (2)
C32	0.074 (3)	0.052 (2)	0.067 (3)	0.020 (2)	−0.013 (2)	0.003 (2)
C33	0.057 (2)	0.052 (2)	0.051 (2)	0.0180 (19)	−0.0050 (19)	0.0132 (18)
C34	0.052 (2)	0.049 (2)	0.050 (2)	0.0103 (18)	−0.0075 (18)	0.0061 (18)
C35	0.062 (3)	0.052 (2)	0.051 (2)	0.019 (2)	−0.0100 (19)	0.0072 (19)
C36	0.056 (2)	0.049 (2)	0.050 (2)	0.0113 (18)	−0.0101 (18)	0.0116 (18)
C37	0.056 (2)	0.050 (2)	0.057 (2)	0.0151 (19)	−0.0117 (19)	0.0085 (19)
C38	0.089 (3)	0.074 (3)	0.058 (3)	0.037 (3)	−0.014 (2)	0.004 (2)
C39	0.104 (4)	0.077 (3)	0.071 (3)	0.052 (3)	−0.006 (3)	0.010 (3)
C40	0.080 (3)	0.071 (3)	0.077 (3)	0.029 (3)	−0.019 (3)	0.021 (3)
C41	0.092 (4)	0.080 (3)	0.064 (3)	0.030 (3)	−0.012 (3)	0.025 (3)
C42	0.079 (3)	0.066 (3)	0.058 (3)	0.030 (2)	−0.002 (2)	0.012 (2)
C43	0.056 (2)	0.050 (2)	0.055 (2)	0.0176 (19)	−0.0022 (19)	0.0109 (19)
C44	0.056 (2)	0.052 (2)	0.062 (3)	0.0136 (19)	−0.009 (2)	0.005 (2)
C45	0.053 (2)	0.077 (3)	0.061 (3)	0.027 (2)	−0.005 (2)	0.015 (2)
C46	0.064 (3)	0.055 (2)	0.050 (2)	0.027 (2)	0.0024 (19)	0.0118 (19)
C47	0.077 (3)	0.058 (3)	0.051 (2)	0.027 (2)	−0.010 (2)	0.001 (2)
C48	0.064 (3)	0.060 (3)	0.051 (2)	0.023 (2)	−0.016 (2)	0.005 (2)
C16	0.055 (2)	0.064 (3)	0.052 (2)	0.020 (2)	−0.0079 (19)	0.010 (2)
C17	0.055 (2)	0.056 (2)	0.044 (2)	0.0142 (19)	−0.0029 (18)	0.0118 (18)
C18	0.060 (2)	0.051 (2)	0.053 (2)	0.0153 (19)	−0.0015 (19)	0.0089 (19)

Geometric parameters (Å, º)

Br2—C30	1.901 (4)	C19—C20	1.397 (6)
O1—N2	1.277 (4)	C20—C21	1.471 (6)
N1—C4	1.346 (5)	C21—C26	1.372 (6)
N1—C1	1.374 (5)	C21—C22	1.404 (6)
O2—N4	1.270 (5)	C22—C23	1.365 (7)
N2—C1	1.341 (5)	C23—C24	1.366 (8)
O3—N6	1.279 (5)	C24—C25	1.348 (8)
N3—C20	1.337 (5)	C25—C26	1.395 (7)
N3—C17	1.385 (5)	C27—C32	1.384 (6)
N4—C17	1.365 (5)	C27—C28	1.389 (6)
C4—C3	1.405 (5)	C27—C18	1.480 (6)
C4—C5	1.453 (6)	C28—C29	1.386 (6)
N5—C36	1.342 (5)	C29—C30	1.376 (6)
N5—C33	1.378 (5)	C30—C31	1.365 (6)
C5—C10	1.381 (6)	C31—C32	1.380 (6)
C5—C6	1.388 (6)	C33—C34	1.417 (6)
N6—C33	1.335 (5)	C34—C35	1.383 (6)
C6—C7	1.376 (7)	C34—C43	1.465 (6)
C7—C8	1.365 (7)	C35—C36	1.403 (6)
C8—C9	1.343 (7)	C36—C37	1.464 (6)
C10—C9	1.396 (7)	C37—C38	1.386 (6)
C2—C3	1.368 (6)	C37—C42	1.404 (6)
C2—C1	1.437 (5)	C38—C39	1.393 (7)
C2—C11	1.470 (5)	C39—C40	1.349 (7)
Br3—C46	1.901 (4)	C40—C41	1.370 (7)
Br1—C14	1.898 (4)	C41—C42	1.377 (6)
C15—C14	1.371 (6)	C43—C44	1.391 (6)
C15—C16	1.389 (6)	C43—C48	1.399 (6)
C11—C16	1.378 (6)	C44—C45	1.372 (6)
C11—C12	1.400 (6)	C45—C46	1.373 (6)
C12—C13	1.398 (6)	C46—C47	1.379 (6)
C13—C14	1.365 (6)	C47—C48	1.370 (6)
C19—C18	1.372 (6)	C17—C18	1.415 (6)
C4—N1—C1	109.6 (3)	C32—C27—C28	117.3 (4)
O1—N2—C1	114.7 (4)	C32—C27—C18	123.6 (4)
C20—N3—C17	108.3 (3)	C28—C27—C18	119.0 (4)
O2—N4—C17	114.0 (3)	C29—C28—C27	122.5 (4)
N1—C4—C3	107.8 (4)	C30—C29—C28	117.5 (4)
N1—C4—C5	125.0 (4)	C31—C30—C29	122.0 (4)
C3—C4—C5	127.2 (4)	C31—C30—Br2	119.3 (3)
C36—N5—C33	109.1 (4)	C29—C30—Br2	118.7 (3)
C10—C5—C6	118.3 (4)	C30—C31—C32	119.3 (4)
C10—C5—C4	119.5 (4)	C31—C32—C27	121.3 (4)
C6—C5—C4	122.1 (4)	N6—C33—N5	126.6 (4)
O3—N6—C33	115.4 (4)	N6—C33—C34	125.4 (4)
C7—C6—C5	120.5 (4)	N5—C33—C34	108.0 (3)
C8—C7—C6	120.0 (5)	C35—C34—C33	106.1 (4)
C9—C8—C7	120.9 (5)	C35—C34—C43	125.5 (4)
C5—C10—C9	120.2 (5)	C33—C34—C43	128.4 (4)
C8—C9—C10	120.0 (5)	C34—C35—C36	108.3 (4)
C3—C2—C1	105.8 (3)	N5—C36—C35	108.4 (4)
C3—C2—C11	126.3 (4)	N5—C36—C37	124.3 (4)
C1—C2—C11	128.0 (4)	C35—C36—C37	127.3 (4)
C2—C3—C4	109.3 (3)	C38—C37—C42	117.7 (4)
N2—C1—N1	126.4 (4)	C38—C37—C36	122.8 (4)
N2—C1—C2	125.8 (4)	C42—C37—C36	119.4 (4)
N1—C1—C2	107.5 (3)	C37—C38—C39	119.4 (5)
C14—C15—C16	119.2 (4)	C40—C39—C38	122.0 (5)
C16—C11—C12	117.6 (4)	C39—C40—C41	119.7 (5)
C16—C11—C2	123.3 (4)	C40—C41—C42	119.9 (5)
C12—C11—C2	119.1 (4)	C41—C42—C37	121.3 (5)
C13—C12—C11	121.2 (4)	C44—C43—C48	117.5 (4)
C14—C13—C12	118.7 (4)	C44—C43—C34	122.5 (4)
C13—C14—C15	121.6 (4)	C48—C43—C34	120.0 (4)
C13—C14—Br1	119.3 (3)	C45—C44—C43	121.2 (4)
C15—C14—Br1	119.0 (3)	C44—C45—C46	119.5 (4)
C18—C19—C20	108.3 (4)	C45—C46—C47	121.4 (4)
N3—C20—C19	109.2 (4)	C45—C46—Br3	119.7 (3)
N3—C20—C21	123.9 (4)	C47—C46—Br3	119.0 (3)
C19—C20—C21	126.9 (4)	C48—C47—C46	118.5 (4)
C26—C21—C22	116.8 (4)	C47—C48—C43	122.0 (4)
C26—C21—C20	122.9 (4)	C11—C16—C15	121.6 (4)
C22—C21—C20	120.3 (4)	N4—C17—N3	126.3 (4)
C23—C22—C21	122.0 (5)	N4—C17—C18	125.4 (4)
C22—C23—C24	119.6 (5)	N3—C17—C18	108.1 (3)
C25—C24—C23	120.2 (5)	C19—C18—C17	106.2 (4)
C24—C25—C26	120.7 (5)	C19—C18—C27	126.6 (4)
C21—C26—C25	120.7 (5)	C17—C18—C27	127.2 (4)
C1—N1—C4—C3	0.6 (5)	C30—C31—C32—C27	0.9 (8)
C1—N1—C4—C5	−177.8 (4)	C28—C27—C32—C31	−0.4 (7)
N1—C4—C5—C10	157.7 (5)	C18—C27—C32—C31	176.6 (4)
C3—C4—C5—C10	−20.4 (7)	O3—N6—C33—N5	−0.9 (7)
N1—C4—C5—C6	−21.0 (7)	O3—N6—C33—C34	178.1 (4)
C3—C4—C5—C6	160.8 (5)	C36—N5—C33—N6	179.3 (4)
C10—C5—C6—C7	1.3 (7)	C36—N5—C33—C34	0.2 (5)
C4—C5—C6—C7	−179.9 (5)	N6—C33—C34—C35	179.9 (4)
C5—C6—C7—C8	−0.2 (8)	N5—C33—C34—C35	−1.1 (5)
C6—C7—C8—C9	−1.8 (9)	N6—C33—C34—C43	−0.2 (7)
C6—C5—C10—C9	−0.6 (8)	N5—C33—C34—C43	178.9 (4)
C4—C5—C10—C9	−179.4 (5)	C33—C34—C35—C36	1.5 (5)
C7—C8—C9—C10	2.5 (10)	C43—C34—C35—C36	−178.4 (4)
C5—C10—C9—C8	−1.3 (10)	C33—N5—C36—C35	0.7 (5)
C1—C2—C3—C4	−0.7 (5)	C33—N5—C36—C37	−177.6 (4)
C11—C2—C3—C4	179.4 (4)	C34—C35—C36—N5	−1.4 (5)
N1—C4—C3—C2	0.1 (5)	C34—C35—C36—C37	176.9 (4)
C5—C4—C3—C2	178.5 (4)	N5—C36—C37—C38	−11.7 (7)
O1—N2—C1—N1	3.0 (6)	C35—C36—C37—C38	170.3 (5)
O1—N2—C1—C2	177.2 (4)	N5—C36—C37—C42	166.3 (4)
C4—N1—C1—N2	174.1 (4)	C35—C36—C37—C42	−11.8 (7)
C4—N1—C1—C2	−1.0 (5)	C42—C37—C38—C39	1.2 (7)
C3—C2—C1—N2	−174.1 (4)	C36—C37—C38—C39	179.1 (5)
C11—C2—C1—N2	5.9 (7)	C37—C38—C39—C40	1.3 (9)
C3—C2—C1—N1	1.0 (5)	C38—C39—C40—C41	−3.2 (9)
C11—C2—C1—N1	−179.0 (4)	C39—C40—C41—C42	2.6 (9)
C3—C2—C11—C16	−154.4 (4)	C40—C41—C42—C37	−0.2 (8)
C1—C2—C11—C16	25.7 (7)	C38—C37—C42—C41	−1.7 (7)
C3—C2—C11—C12	24.7 (7)	C36—C37—C42—C41	−179.8 (5)
C1—C2—C11—C12	−155.3 (4)	C35—C34—C43—C44	142.3 (5)
C16—C11—C12—C13	0.3 (7)	C33—C34—C43—C44	−37.6 (7)
C2—C11—C12—C13	−178.8 (4)	C35—C34—C43—C48	−35.1 (7)
C11—C12—C13—C14	0.1 (7)	C33—C34—C43—C48	145.0 (5)
C12—C13—C14—C15	−0.2 (7)	C48—C43—C44—C45	−0.3 (7)
C12—C13—C14—Br1	179.7 (3)	C34—C43—C44—C45	−177.7 (4)
C16—C15—C14—C13	−0.1 (7)	C43—C44—C45—C46	0.0 (7)
C16—C15—C14—Br1	180.0 (3)	C44—C45—C46—C47	0.2 (7)
C17—N3—C20—C19	−0.6 (5)	C44—C45—C46—Br3	−179.9 (4)
C17—N3—C20—C21	−178.1 (4)	C45—C46—C47—C48	−0.1 (7)
C18—C19—C20—N3	0.8 (5)	Br3—C46—C47—C48	−180.0 (4)
C18—C19—C20—C21	178.2 (4)	C46—C47—C48—C43	−0.3 (7)
N3—C20—C21—C26	−4.1 (7)	C44—C43—C48—C47	0.5 (7)
C19—C20—C21—C26	178.8 (5)	C34—C43—C48—C47	177.9 (4)
N3—C20—C21—C22	174.2 (5)	C12—C11—C16—C15	−0.6 (7)
C19—C20—C21—C22	−2.9 (7)	C2—C11—C16—C15	178.5 (4)
C26—C21—C22—C23	1.5 (9)	C14—C15—C16—C11	0.5 (7)
C20—C21—C22—C23	−176.9 (6)	O2—N4—C17—N3	0.7 (6)
C21—C22—C23—C24	−1.5 (10)	O2—N4—C17—C18	175.6 (4)
C22—C23—C24—C25	1.1 (11)	C20—N3—C17—N4	175.8 (4)
C23—C24—C25—C26	−0.7 (10)	C20—N3—C17—C18	0.2 (5)
C22—C21—C26—C25	−1.1 (8)	C20—C19—C18—C17	−0.6 (5)
C20—C21—C26—C25	177.2 (5)	C20—C19—C18—C27	−179.5 (4)
C24—C25—C26—C21	0.8 (10)	N4—C17—C18—C19	−175.4 (4)
C32—C27—C28—C29	−0.4 (8)	N3—C17—C18—C19	0.3 (5)
C18—C27—C28—C29	−177.6 (5)	N4—C17—C18—C27	3.5 (7)
C27—C28—C29—C30	0.6 (8)	N3—C17—C18—C27	179.2 (4)
C28—C29—C30—C31	−0.1 (8)	C32—C27—C18—C19	−145.2 (5)
C28—C29—C30—Br2	178.6 (4)	C28—C27—C18—C19	31.8 (7)
C29—C30—C31—C32	−0.7 (8)	C32—C27—C18—C17	36.1 (7)
Br2—C30—C31—C32	−179.4 (4)	C28—C27—C18—C17	−146.9 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3	0.86	2.10	2.957 (5)	177
N3—H3A···O1	0.86	2.10	2.956 (5)	171
N5—H5···O2	0.86	2.16	3.009 (5)	169
C6—H6···N6	0.93	2.53	3.294 (6)	139
C26—H26···N2	0.93	2.43	3.338 (7)	165
C38—H38···N4	0.93	2.48	3.331 (6)	153
C6—H6···O3	0.93	2.69	3.505 (6)	146
C26—H26···O1	0.93	2.43	3.543 (6)	165
C38—H38···O2	0.93	2.72	3.564 (6)	151