Structures of 1-hydro­phenanthro­imidazoles: building blocks in the synthesis of expanded-ring bis­(imidazoles)

The structures of 1H-phenanthro[9,10-d]imidazole, C₁₅H₁₀N₂, (I), and 3,6-dibromo-1H-phenanthro[9,10-d]imidazole hemihydrate, C₁₅H₈Br₂N₂·0.5H₂O, (II), contain hydrogen-bonded polymeric chains linked by columns of π–π stacked essentially planar phenanthroimidazole monomers. In the structure of (I), the asymmetric unit consists of two independent mol­ecules, denoted (Ia) and (Ib), of 1H-phenanthro[9,10-d]imid­azole. Alternating mol­ecules of (Ia) and (Ib), canted by 79.07 (3)°, form hydrogen-bonded zigzag polymer chains along the a-cell direction. The chains are linked by π–π stacking of mol­ecules of (Ia) and (Ib) along the b-cell direction. In the structure of (II), the asymmetric unit consists of two independent mol­ecules of 3,6-dibromo-1H-phenanthro[9,10-d]imidazole, denoted (IIa) and (IIb), along with a mol­ecule of water. Alternating mol­ecules of (IIa), (IIb) and water form hydrogen-bonded polymer chains along the [110] direction. The donor–acceptor distances in these N(imine)...H—O(water)...H—N(amine) hydrogen bonds are the shortest thus far reported for imidazole amine and imine hydrogen-bond inter­actions with water. Centrosymmetrically related mol­ecules of (IIa) and (IIb) alternate in columns along the a-cell direction and are canted by 48.27 (3)°. The present study provides the first examples of structurally characterized 1H-phenanthroimidazoles.

S1. Comment

Bis(imidazoles) and bis(benzimidazoles) are versatile species with numerous applications. Structurally, they have been used as geometrically constraining ligands (Stibrany et al., 2004) and in the formation of metal–organic copolymers (Stibrany & Potenza, 2008). Functionally, they have been shown to act as proton sponges (Stibrany et al., 2002), and when complexed to copper, as polymerization catalysts (Stibrany et al., 2003; Stibrany & Kacker, 2002). Analytically, they have been used as agents in the study of electron transfer (Knapp et al., 1990), and fluorinated versions have been used as ¹⁹F NMR probes to study the active sites of copper polymerization catalysts (Stibrany, 2003). In the present study, we have investigated the structures of 1-H-phenanthroimidazoles, expanded-ring imidazoles, as potential building blocks for bis(phenanthroimidazoles). We have previously shown that 1-methylbenzimidazole can be used in the synthesis of bis(benzimidazole)ketones, which were found to be useful ligands for the chelation of metals (Gorun et al., 1996).

Crystals of 1-H-phenanthro[9,10-d]imidazole, (I), contain two independent molecules, (Ia) and (Ib), in the asymmetric unit, linked by N(amine)—H···N(imine) hydrogen bonds (Fig. 1, Table 1). Analysis of the structure reveals a two-site H-atom disorder, corresponding to overlapping N(imine)···H—N(amine) and N(amine)—H···N(imine) bonds and their associated molecules. Occupancy factors for the two H atoms, which were refined and constrained to add to 1, were 0.60 (3) and 0.40 (3). These data and the structure described below are consistent with racemic twinning in which the twins are related by rotation of 180° about the a unit-cell axis. We describe the structure below using the major component (60% occupancy) twin.

In the structure of (I), alternating molecules of (Ia) and I(b) are essentially planar, canted by 79.07 (3)°, and linked by the hydrogen bonds mentioned above to create zigzag polymeric chains which extend along the a cell direction (Fig. 2). In these chains, molecules of (Ia) and (Ib) stack along the b cell direction to yield columns in which the phenanthroimidazole planes are separated by interplanar distances consistent with π–π interactions, which have been taken as inter-ring contacts less than 3.8 Å (Janiak, 2000). The inter-ring contacts are listed in Table 3 and the several rings are enumerated in the second scheme. In each column, the planes of the rings are canted with respect to the ac plane such that, when viewed down the a axis along the polymer chains, the phenanthroimidazole columns appear as a criss-cross array of molecules of (Ia) and (Ib) in profile.

Crystals of 3,6-dibromo-1-H-phenanthro[9,10-d]imidazole hemihydrate, (II), contain a water molecule and two independent phenanthroimidazole molecules, (IIa) and (IIb), in the asymmetric unit (Fig. 3). The water molecule acts as both a donor (O—H) and an acceptor (O) to form two hydrogen bonds (Table 2), one to the N(amine) H atom of molecule (IIb) and the other to the N(imine) atom of molecule (IIa). In (II), the N···O distances (Table 2) in the N(imine)···H—O(H₂O)···H—N(amine) fragments are shorter than the corresponding N(imine)···O(H₂O) and N(amine)···O(H₂O) distances in similar hydrogen-bond networks, in which they range from 2.770–2.914 and 2.802–2.946 Å, respectively, for the imine and amine linkages [Cambridge Structural database (CSD), Version 5.30; Allen, 2002] (Botana et al., 2007; Freire et al., 2003; Fridman et al., 2006; Meng et al., 2006; Molina et al., 1998; Zhang et al., 2005). In (II), the hydrogen bonds lead to polymer chains consisting sequentially of molecules of (IIa), (IIb) and water. These hydrogen-bond chains extend along the [110] direction (Fig. 4), while centrosymmetrically related molecules of (IIa) and (IIb) stack in columns along the a-axis direction. The planes of (IIa) and (IIb) are canted by 48.27 (3)°. In the structure of (II), there are four π–π interactions and two short atom-to-ring interactions (Table 3; see also second scheme).

Compounds (I) and (II) are technically defined as extended-ring imidazole systems. The title compounds, which are 1,2-dihydro-substituted, are the first such to be structurally characterized. A total of 22 crystal structures containing phenanthroimidazoles reported in the CSD contain aromatic substitution at the 2-position. Synthetically, aromatic aldehydes facilitate the formation of phenanthroimidazole ring systems.

S2. Experimental

1-H-Phenanthro[9,10-d]imidazole, (I), was prepared according to the procedure of Steck & Day (1943). Into a 250 ml round-bottomed flask, phenanthroquinone (2.08 g, 9.99 mmol), hexamethylenetetramine (2.80 g, 20.0 mmol) and ammonium acetate (15.5 g) were placed. The solids were suspended in glacial acetic acid and refluxed for 1 h. The mixture was cooled and neutralized with concentrated ammonium hydroxide, followed by the addition of water to precipitate the product fully. The product was collected by filtration, washed with water and dried to constant weight in a vacuum oven to give the product as an off-white solid (yield 2.01 g, 92.2%; m.p. 564 K). Analysis: C₁₅H₁₀N₂, M_r = 218.25; ¹H NMR (400 MHz, CD₃SOCD₃, 298 K, δ, p.p.m.): 8.86 (br m, 2H), 8.51 (br m, 2H), 8.37 (s, 1H), 7.72 (br m, 2H), 7.64 (br m, 2H); ¹³C NMR (CD₃SOCD₃, δ, p.p.m.): 139.6, 136.2, 127.9, 127.8, 127.4, 125.4, 124.3, 122.0; R_f = 0.38 (ethyl acetate/silica). Single crystals of (I) were obtained by slow evaporation of a dimethylsulfoxide (DMSO) solution of the compound (m.p. 581 K).

Crystals of 3,6-dibromo-1-H-phenanthro[9,10-d]imidazole hemihydrate, (II), were prepared by following a procedure similar to that for (I). Into a 250 ml round-bottomed flask, 3,6-dibromophenanthro-9,10-quinone (2.08 g, 5.68 mmol) (Schmidt & Eitel, 1932; Bhatt, 1964), hexamethylenetetramine (1.59 g, 11.34 mmol) and ammonium acetate (14.0 g) were placed. The solids were suspended in glacial acetic acid and refluxed for 1 h. The mixture was cooled and neutralized with concentrated ammonium hydroxide, followed by the addition of water to precipitate the product fully. The product was collected by filtration, washed with water and dried to constant weight in a vacuum oven to give anhydrous (II) as a pale-gray solid (yield 2.02 g, 94.4%; m.p. 546 K). Analysis: C₁₅H₈Br₂N₂, M_r = 376.91; ¹H NMR (400 MHz, 323 K, CD₃SOCD₃, δ, p.p.m.): 8.85 (s, 2H), 8.19 (d, J = 6.4 Hz, 2H), 8.04 (s, 1H), 7.78 (dd, J = 1.8 and 8.6 Hz, 2H); ¹³C NMR (CD₃SOCD₃, 323 K, δ, p.p.m.): 139.7, 139.5, 130.6, 128.6, 126.7, 124.3, 119.1. R_f = 0.37 (ethyl acetate/silica). Single crystals of (II) were obtained by slow evaporation of a DMSO solution of of the compound [m.p. 453 K (opaque), 572 K (soften), 583 K (melt)]. The hemihydrate formed owing to the adventitious presence of water in the DMSO solvent.

S3. Refinement

C-bound H atoms were positioned geometrically using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The H atoms of the water molecule in (II) were located in a difference Fourier map and were allowed to refine with O—H distance restraints.

Friedel pairs in structure (I) were merged. Disordered atoms H11 and H43 (Fig. 1), which participate in the N—H···N hydrogen bonds, were located in a difference Fourier map. Their occupancy factors were constrained to add to unity and refined to 0.60 (3) and 0.40 (3). Refinement of the two-site model reduced the weighted R factor, wRF²(all), from 0.116 for the one-site model to 0.112. In several other structures containing benzimidazole units incapable of forming hydrogen bonds, residuals (Q-peaks) were located 0.44 to 0.88 Å from the N(imine) atoms and in the planes of the imidazole rings, and were refined for comparison with the present structure. Refinement as H atoms decreased the R factors in some instances and increased them in others. In imidazole-containing structures, approximate differences between the C2—N(amine) and C2—N(imine) bond lengths are 0.04 Å for systems with no amine–imine hydrogen bonding, while for dialkyl-substituted imidazolium ions, there is essentially no difference within experimental error. In the present structure, the difference is 0.020 Å, which is not inconsistent with the two-site disordered model described above. Taken together, these data provide moderate support for the disordered/twinned model.

Computing details

For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-32 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A view of the asymmetric unit of (I), showing the atom-numbering scheme for the repeat unit of (Ia) and (Ib). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines represent the superimposed N11—H11···H43 and N43—H43···N11 hydrogen bonds.
	Fig. 2. A view of the packing of (I), down the b axis, showing the hydrogen-bonded polymer chains (dashed lines). See Table 1 for symmetry code.
	Fig. 3. A view of the asymmetric unit of (II), showing the atom-numbering scheme for the repeat unit of (IIa), (IIb) and water. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
	Fig. 4. A view of the packing of (II), showing the hydrogen-bonded polymer chains (dashed lines). See Table 1 for symmetry code.

(I) 1-H-phenanthro[9,10-d]imidazole

Crystal data

C15H10N2	Dx = 1.426 Mg m^−3
Mr = 218.25	Melting point: 581 K
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 966 reflections
a = 19.559 (3) Å	θ = 2.9–25.0°
b = 5.2321 (8) Å	µ = 0.09 mm^−1
c = 19.871 (3) Å	T = 298 K
V = 2033.5 (5) Å^3	Plate, pale-brown
Z = 8	0.47 × 0.37 × 0.10 mm
F(000) = 912

Data collection

Bruker SMART CCD area-detector diffractometer	2095 independent reflections
Radiation source: sealed tube	1803 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ϕ and ω scans	θmax = 26.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Blessing, 1995)	h = −23→24
Tmin = 0.856, Tmax = 1.000	k = −6→6
18138 measured reflections	l = −24→24

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.112	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.076P)^2 + 0.260P] where P = (Fo^2 + 2Fc^2)/3
2095 reflections	(Δ/σ)max < 0.001
308 parameters	Δρmax = 0.22 e Å^−3
1 restraint	Δρmin = −0.12 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.

Friedel pairs in structure (I) were merged. Disordered atoms H11 and H43 (Fig. 1), which participate in the N—H···N hydrogen bonds, were located in a difference Fourier map. Their occupancy factors were constrained to add to unity and refined to 0.60 (3) and 0.40 (3). Refinement of the two-site model reduced the weighted R factor, wRF²(all), from 0.116 for the one-site model to 0.112. In several other structures containing benzimidazole units incapable of forming hydrogen bonds, residuals (Q-peaks) were located 0.44 to 0.88 Å from the N(imine) atoms and in the planes of the imidazole rings, and were refined for comparison with the present structure. Refinement as H atoms decreased the R factors in some instances and increased them in others. In imidazole-containing structures, approximate differences between the C2—N(amine) and C2—N(imine) bond lengths are 0.04 Å for systems with no amine–imine hydrogen bonding, while for dialkyl-substituted imidazolium ions, there is essentially no difference within experimental error. In the present structure, the difference is 0.020 Å, which is not inconsistent with the two-site disordered model described above. Taken together, these data provide moderate support for the disordered/twinned model.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N11	0.14125 (13)	0.4788 (5)	0.17659 (14)	0.0430 (6)
H11	0.1836	0.4700	0.1878	0.052*	0.60 (3)
N13	0.02974 (13)	0.3877 (5)	0.17243 (14)	0.0444 (6)
H13	−0.0089	0.3148	0.1801	0.053*	0.40 (3)
C11	0.11102 (13)	0.6514 (6)	0.13345 (15)	0.0370 (6)
C12	0.08998 (15)	0.3276 (6)	0.19714 (17)	0.0461 (7)
H12	0.0965	0.1913	0.2265	0.055*
C13	0.04282 (15)	0.5965 (6)	0.13091 (16)	0.0385 (7)
C14	−0.00325 (16)	0.7413 (6)	0.08938 (15)	0.0402 (7)
C15	0.02497 (16)	0.9427 (6)	0.05082 (17)	0.0418 (7)
C16	0.09839 (16)	0.9970 (6)	0.05263 (16)	0.0409 (7)
C17	0.14227 (15)	0.8501 (6)	0.09424 (16)	0.0376 (7)
C21	−0.01985 (17)	1.0895 (6)	0.01158 (18)	0.0483 (8)
H21	−0.0026	1.2243	−0.0137	0.058*
C22	−0.08843 (18)	1.0389 (7)	0.0097 (2)	0.0555 (9)
H22	−0.1170	1.1391	−0.0169	0.067*
C23	−0.11560 (17)	0.8415 (7)	0.0467 (2)	0.0555 (9)
H23	−0.1623	0.8079	0.0449	0.067*
C24	−0.07379 (16)	0.6944 (7)	0.08605 (17)	0.0479 (8)
H24	−0.0924	0.5613	0.1110	0.057*
C31	0.12841 (18)	1.1899 (6)	0.01361 (18)	0.0480 (8)
H31	0.1009	1.2888	−0.0143	0.058*
C32	0.19750 (18)	1.2364 (7)	0.01560 (18)	0.0518 (8)
H32	0.2160	1.3649	−0.0111	0.062*
C33	0.23962 (17)	1.0944 (7)	0.05677 (19)	0.0521 (9)
H33	0.2862	1.1288	0.0581	0.062*
C34	0.21293 (15)	0.9026 (7)	0.09573 (17)	0.0469 (8)
H34	0.2416	0.8068	0.1233	0.056*
N41	0.40116 (12)	0.4153 (4)	0.22151 (14)	0.0409 (6)
H41	0.4398	0.3433	0.2131	0.049*	0.60 (3)
N43	0.28930 (12)	0.4958 (5)	0.21919 (13)	0.0417 (6)
H43	0.2466	0.4844	0.2094	0.050*	0.40 (3)
C41	0.38937 (14)	0.6213 (5)	0.26271 (15)	0.0366 (6)
C42	0.33959 (15)	0.3502 (6)	0.19720 (17)	0.0453 (7)
H42	0.3330	0.2149	0.1676	0.054*
C43	0.32034 (14)	0.6706 (5)	0.26146 (15)	0.0378 (6)
C44	0.28936 (14)	0.8671 (6)	0.30040 (15)	0.0380 (7)
C45	0.33355 (15)	1.0193 (6)	0.34101 (16)	0.0379 (6)
C46	0.40754 (14)	0.9693 (5)	0.34161 (15)	0.0375 (6)
C47	0.43603 (15)	0.7688 (6)	0.30290 (15)	0.0364 (7)
C51	0.45302 (16)	1.1174 (6)	0.38034 (18)	0.0458 (8)
H51	0.4358	1.2523	0.4056	0.055*
C52	0.52135 (16)	1.0693 (6)	0.38192 (19)	0.0498 (8)
H52	0.5500	1.1700	0.4083	0.060*
C53	0.54821 (16)	0.8708 (7)	0.3443 (2)	0.0504 (8)
H53	0.5949	0.8382	0.3454	0.060*
C54	0.50629 (16)	0.7226 (6)	0.30570 (17)	0.0453 (7)
H54	0.5248	0.5888	0.2809	0.054*
C61	0.30349 (16)	1.2136 (6)	0.38032 (17)	0.0455 (7)
H61	0.3313	1.3174	0.4067	0.055*
C62	0.23426 (17)	1.2528 (7)	0.38043 (18)	0.0517 (8)
H62	0.2155	1.3812	0.4070	0.062*
C63	0.19211 (17)	1.1015 (7)	0.3411 (2)	0.0521 (8)
H63	0.1451	1.1281	0.3416	0.063*
C64	0.21929 (14)	0.9128 (7)	0.30129 (17)	0.0462 (8)
H64	0.1905	0.8142	0.2746	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0403 (14)	0.0430 (14)	0.0459 (15)	0.0000 (11)	−0.0001 (12)	0.0044 (12)
N13	0.0416 (14)	0.0466 (15)	0.0451 (15)	−0.0023 (11)	0.0009 (11)	−0.0014 (12)
C11	0.0338 (14)	0.0385 (14)	0.0388 (16)	0.0020 (12)	0.0003 (13)	−0.0004 (13)
C12	0.0493 (19)	0.0446 (16)	0.0446 (18)	0.0004 (14)	0.0015 (14)	0.0044 (14)
C13	0.0370 (14)	0.0405 (15)	0.0382 (16)	−0.0010 (12)	0.0030 (13)	−0.0042 (14)
C14	0.0374 (16)	0.0423 (16)	0.0407 (16)	0.0009 (12)	0.0022 (13)	−0.0068 (14)
C15	0.0407 (16)	0.0435 (16)	0.0410 (17)	0.0044 (13)	−0.0033 (14)	−0.0089 (15)
C16	0.0435 (16)	0.0402 (15)	0.0389 (16)	0.0005 (13)	−0.0008 (14)	−0.0034 (13)
C17	0.0383 (16)	0.0371 (15)	0.0376 (16)	−0.0007 (12)	−0.0024 (13)	−0.0055 (13)
C21	0.0485 (18)	0.0458 (16)	0.0507 (19)	0.0037 (14)	−0.0056 (15)	0.0026 (15)
C22	0.049 (2)	0.059 (2)	0.058 (2)	0.0119 (16)	−0.0134 (17)	−0.0048 (18)
C23	0.0354 (17)	0.066 (2)	0.065 (2)	0.0020 (15)	−0.0019 (16)	−0.0080 (19)
C24	0.0411 (17)	0.0527 (18)	0.0497 (19)	−0.0048 (14)	0.0011 (15)	−0.0009 (16)
C31	0.053 (2)	0.0431 (16)	0.048 (2)	−0.0005 (14)	−0.0038 (17)	0.0061 (15)
C32	0.055 (2)	0.0472 (18)	0.054 (2)	−0.0101 (16)	0.0039 (16)	0.0090 (17)
C33	0.0368 (17)	0.0548 (19)	0.065 (2)	−0.0083 (14)	−0.0005 (16)	0.0019 (18)
C34	0.0401 (18)	0.0491 (18)	0.0514 (19)	−0.0020 (13)	−0.0006 (15)	0.0049 (16)
N41	0.0403 (13)	0.0412 (13)	0.0410 (14)	0.0030 (11)	0.0016 (12)	0.0021 (12)
N43	0.0347 (13)	0.0452 (13)	0.0451 (15)	0.0010 (10)	−0.0045 (12)	0.0020 (12)
C41	0.0379 (15)	0.0353 (14)	0.0365 (15)	0.0012 (11)	0.0026 (12)	0.0064 (13)
C42	0.0491 (19)	0.0463 (17)	0.0405 (17)	−0.0014 (14)	−0.0021 (14)	−0.0037 (14)
C43	0.0354 (14)	0.0366 (14)	0.0413 (16)	−0.0018 (12)	0.0009 (13)	0.0069 (13)
C44	0.0355 (15)	0.0361 (15)	0.0425 (16)	0.0001 (12)	0.0039 (13)	0.0056 (13)
C45	0.0414 (15)	0.0354 (14)	0.0369 (15)	0.0014 (12)	0.0035 (14)	0.0085 (13)
C46	0.0382 (16)	0.0367 (14)	0.0376 (15)	−0.0025 (11)	0.0012 (13)	0.0060 (13)
C47	0.0327 (15)	0.0371 (15)	0.0394 (17)	−0.0018 (12)	0.0010 (13)	0.0082 (13)
C51	0.0481 (18)	0.0407 (16)	0.0487 (19)	−0.0023 (13)	−0.0012 (15)	0.0014 (15)
C52	0.0424 (18)	0.0523 (19)	0.055 (2)	−0.0122 (14)	−0.0033 (16)	0.0025 (17)
C53	0.0324 (15)	0.062 (2)	0.056 (2)	−0.0027 (14)	−0.0029 (16)	0.0069 (19)
C54	0.0376 (16)	0.0452 (17)	0.0531 (18)	0.0021 (13)	0.0038 (14)	0.0025 (16)
C61	0.0489 (18)	0.0416 (16)	0.0461 (18)	0.0030 (13)	0.0015 (15)	−0.0004 (15)
C62	0.0535 (19)	0.0487 (18)	0.0529 (19)	0.0135 (16)	0.0088 (17)	−0.0020 (17)
C63	0.0371 (16)	0.058 (2)	0.061 (2)	0.0116 (14)	0.0067 (16)	0.0024 (18)
C64	0.0314 (16)	0.0520 (19)	0.055 (2)	0.0019 (12)	0.0006 (15)	−0.0011 (17)

Geometric parameters (Å, º)

N11—C12	1.341 (4)	N41—C42	1.341 (4)
N11—C11	1.379 (4)	N41—C41	1.373 (4)
N11—H11	0.8600	N41—H41	0.8600
N13—C12	1.315 (4)	N43—C42	1.318 (4)
N13—C13	1.393 (4)	N43—C43	1.382 (4)
N13—H13	0.8600	N43—H43	0.8600
C11—C13	1.365 (4)	C41—C43	1.375 (4)
C11—C17	1.436 (4)	C41—C47	1.437 (4)
C12—H12	0.9300	C42—H42	0.9300
C13—C14	1.438 (4)	C43—C44	1.422 (4)
C14—C24	1.403 (5)	C44—C64	1.391 (4)
C14—C15	1.415 (4)	C44—C45	1.426 (4)
C15—C21	1.402 (4)	C45—C61	1.411 (4)
C15—C16	1.464 (4)	C45—C46	1.471 (4)
C16—C31	1.402 (5)	C46—C51	1.409 (4)
C16—C17	1.418 (4)	C46—C47	1.415 (4)
C17—C34	1.409 (4)	C47—C54	1.396 (4)
C21—C22	1.368 (5)	C51—C52	1.360 (5)
C21—H21	0.9300	C51—H51	0.9300
C22—C23	1.374 (5)	C52—C53	1.383 (5)
C22—H22	0.9300	C52—H52	0.9300
C23—C24	1.369 (5)	C53—C54	1.365 (5)
C23—H23	0.9300	C53—H53	0.9300
C24—H24	0.9300	C54—H54	0.9300
C31—C32	1.374 (5)	C61—C62	1.369 (4)
C31—H31	0.9300	C61—H61	0.9300
C32—C33	1.378 (5)	C62—C63	1.385 (5)
C32—H32	0.9300	C62—H62	0.9300
C33—C34	1.371 (5)	C63—C64	1.372 (5)
C33—H33	0.9300	C63—H63	0.9300
C34—H34	0.9300	C64—H64	0.9300
C12—N11—C11	104.8 (2)	C42—N41—C41	105.3 (2)
C12—N11—H11	127.6	C42—N41—H41	127.4
C11—N11—H11	127.6	C41—N41—H41	127.4
C12—N13—C13	104.1 (3)	C42—N43—C43	104.8 (2)
C12—N13—H13	127.9	C42—N43—H43	127.6
C13—N13—H13	127.9	C43—N43—H43	127.6
C13—C11—N11	107.7 (3)	N41—C41—C43	107.5 (3)
C13—C11—C17	123.2 (3)	N41—C41—C47	130.3 (3)
N11—C11—C17	129.0 (3)	C43—C41—C47	122.2 (3)
N13—C12—N11	114.6 (3)	N43—C42—N41	113.8 (3)
N13—C12—H12	122.7	N43—C42—H42	123.1
N11—C12—H12	122.7	N41—C42—H42	123.1
C11—C13—N13	108.8 (3)	C41—C43—N43	108.5 (3)
C11—C13—C14	121.5 (3)	C41—C43—C44	123.0 (3)
N13—C13—C14	129.7 (3)	N43—C43—C44	128.5 (2)
C24—C14—C15	119.2 (3)	C64—C44—C43	123.4 (3)
C24—C14—C13	123.5 (3)	C64—C44—C45	119.6 (3)
C15—C14—C13	117.3 (3)	C43—C44—C45	117.0 (2)
C21—C15—C14	117.7 (3)	C61—C45—C44	117.6 (3)
C21—C15—C16	121.4 (3)	C61—C45—C46	122.3 (3)
C14—C15—C16	120.9 (3)	C44—C45—C46	120.1 (3)
C31—C16—C17	117.3 (3)	C51—C46—C47	117.1 (3)
C31—C16—C15	122.5 (3)	C51—C46—C45	121.9 (3)
C17—C16—C15	120.2 (3)	C47—C46—C45	121.0 (3)
C34—C17—C16	120.0 (3)	C54—C47—C46	119.6 (3)
C34—C17—C11	123.2 (3)	C54—C47—C41	123.6 (3)
C16—C17—C11	116.8 (3)	C46—C47—C41	116.7 (3)
C22—C21—C15	121.5 (3)	C52—C51—C46	122.1 (3)
C22—C21—H21	119.3	C52—C51—H51	118.9
C15—C21—H21	119.3	C46—C51—H51	118.9
C21—C22—C23	120.7 (3)	C51—C52—C53	120.0 (3)
C21—C22—H22	119.7	C51—C52—H52	120.0
C23—C22—H22	119.7	C53—C52—H52	120.0
C24—C23—C22	119.8 (3)	C54—C53—C52	120.1 (3)
C24—C23—H23	120.1	C54—C53—H53	119.9
C22—C23—H23	120.1	C52—C53—H53	119.9
C23—C24—C14	121.1 (3)	C53—C54—C47	121.0 (3)
C23—C24—H24	119.5	C53—C54—H54	119.5
C14—C24—H24	119.5	C47—C54—H54	119.5
C32—C31—C16	121.6 (3)	C62—C61—C45	121.4 (3)
C32—C31—H31	119.2	C62—C61—H61	119.3
C16—C31—H31	119.2	C45—C61—H61	119.3
C31—C32—C33	120.6 (3)	C61—C62—C63	120.2 (3)
C31—C32—H32	119.7	C61—C62—H62	119.9
C33—C32—H32	119.7	C63—C62—H62	119.9
C34—C33—C32	120.2 (3)	C64—C63—C62	120.4 (3)
C34—C33—H33	119.9	C64—C63—H63	119.8
C32—C33—H33	119.9	C62—C63—H63	119.8
C33—C34—C17	120.3 (3)	C63—C64—C44	120.8 (3)
C33—C34—H34	119.9	C63—C64—H64	119.6
C17—C34—H34	119.9	C44—C64—H64	119.6
C12—N11—C11—C13	0.7 (3)	C42—N41—C41—C43	0.2 (3)
C12—N11—C11—C17	−176.7 (3)	C42—N41—C41—C47	179.1 (3)
C13—N13—C12—N11	0.8 (4)	C43—N43—C42—N41	−0.1 (4)
C11—N11—C12—N13	−1.0 (4)	C41—N41—C42—N43	−0.1 (4)
N11—C11—C13—N13	−0.2 (3)	N41—C41—C43—N43	−0.3 (3)
C17—C11—C13—N13	177.4 (3)	C47—C41—C43—N43	−179.2 (3)
N11—C11—C13—C14	−179.3 (3)	N41—C41—C43—C44	177.8 (3)
C17—C11—C13—C14	−1.7 (4)	C47—C41—C43—C44	−1.1 (4)
C12—N13—C13—C11	−0.4 (3)	C42—N43—C43—C41	0.2 (3)
C12—N13—C13—C14	178.6 (3)	C42—N43—C43—C44	−177.8 (3)
C11—C13—C14—C24	−178.9 (3)	C41—C43—C44—C64	−177.7 (3)
N13—C13—C14—C24	2.2 (5)	N43—C43—C44—C64	0.0 (5)
C11—C13—C14—C15	0.3 (4)	C41—C43—C44—C45	1.2 (4)
N13—C13—C14—C15	−178.5 (3)	N43—C43—C44—C45	178.9 (3)
C24—C14—C15—C21	1.0 (4)	C64—C44—C45—C61	−0.6 (4)
C13—C14—C15—C21	−178.3 (3)	C43—C44—C45—C61	−179.5 (3)
C24—C14—C15—C16	−179.7 (3)	C64—C44—C45—C46	178.7 (3)
C13—C14—C15—C16	1.0 (4)	C43—C44—C45—C46	−0.3 (4)
C21—C15—C16—C31	−2.6 (5)	C61—C45—C46—C51	−1.6 (4)
C14—C15—C16—C31	178.1 (3)	C44—C45—C46—C51	179.1 (3)
C21—C15—C16—C17	178.2 (3)	C61—C45—C46—C47	178.4 (3)
C14—C15—C16—C17	−1.1 (4)	C44—C45—C46—C47	−0.8 (4)
C31—C16—C17—C34	0.7 (5)	C51—C46—C47—C54	1.4 (4)
C15—C16—C17—C34	179.9 (3)	C45—C46—C47—C54	−178.6 (3)
C31—C16—C17—C11	−179.4 (3)	C51—C46—C47—C41	−179.0 (3)
C15—C16—C17—C11	−0.2 (4)	C45—C46—C47—C41	0.9 (4)
C13—C11—C17—C34	−178.5 (3)	N41—C41—C47—C54	0.8 (5)
N11—C11—C17—C34	−1.5 (5)	C43—C41—C47—C54	179.5 (3)
C13—C11—C17—C16	1.6 (4)	N41—C41—C47—C46	−178.7 (3)
N11—C11—C17—C16	178.6 (3)	C43—C41—C47—C46	0.0 (4)
C14—C15—C21—C22	−0.8 (5)	C47—C46—C51—C52	−1.1 (5)
C16—C15—C21—C22	179.9 (3)	C45—C46—C51—C52	178.9 (3)
C15—C21—C22—C23	0.2 (5)	C46—C51—C52—C53	0.4 (5)
C21—C22—C23—C24	0.3 (6)	C51—C52—C53—C54	−0.1 (5)
C22—C23—C24—C14	−0.1 (5)	C52—C53—C54—C47	0.4 (5)
C15—C14—C24—C23	−0.6 (5)	C46—C47—C54—C53	−1.1 (5)
C13—C14—C24—C23	178.7 (3)	C41—C47—C54—C53	179.4 (3)
C17—C16—C31—C32	−0.3 (5)	C44—C45—C61—C62	1.0 (5)
C15—C16—C31—C32	−179.4 (3)	C46—C45—C61—C62	−178.2 (3)
C16—C31—C32—C33	−0.5 (6)	C45—C61—C62—C63	−0.5 (5)
C31—C32—C33—C34	0.7 (5)	C61—C62—C63—C64	−0.5 (6)
C32—C33—C34—C17	−0.3 (5)	C62—C63—C64—C44	0.9 (5)
C16—C17—C34—C33	−0.4 (5)	C43—C44—C64—C63	178.5 (3)
C11—C17—C34—C33	179.7 (3)	C45—C44—C64—C63	−0.4 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···N43	0.86	2.16	3.018 (3)	173
N41—H41···N13^i	0.86	2.28	3.129 (3)	168
N13—H13···N41^ii	0.86	2.28	3.129 (3)	167
N43—H43···N11	0.86	2.16	3.018 (3)	175

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

(II) 3,6-dibromo-1-H-phenanthro[9,10-d]imidazole hemihydrate

Crystal data

C15H8Br2N2·0.5H2O	Z = 4
Mr = 385.04	F(000) = 748
Triclinic, P1	Dx = 1.898 Mg m^−3
Hall symbol: -P 1	Melting point: 583 K
a = 8.415 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.139 (2) Å	Cell parameters from 824 reflections
c = 17.227 (4) Å	θ = 2.2–23.9°
α = 101.683 (4)°	µ = 6.00 mm^−1
β = 101.398 (5)°	T = 298 K
γ = 104.109 (5)°	Plate, pale-yellow
V = 1347.9 (5) Å^3	0.40 × 0.37 × 0.19 mm

Data collection

Bruker SMART CCD area-detector diffractometer	5330 independent reflections
Radiation source: sealed tube	3658 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
ϕ and ω scans	θmax = 26.1°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Blessing, 1995)	h = −10→10
Tmin = 0.359, Tmax = 1.000	k = −12→12
12857 measured reflections	l = −21→21

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0728P)^2] where P = (Fo^2 + 2Fc^2)/3
5330 reflections	(Δ/σ)max < 0.001
360 parameters	Δρmax = 1.29 e Å^−3
2 restraints	Δρmin = −0.77 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
O1	1.1756 (6)	0.6635 (7)	0.2421 (4)	0.1129 (19)
H1O	1.112 (11)	0.724 (9)	0.244 (7)	0.18 (5)*
H2O	1.201 (13)	0.718 (10)	0.208 (5)	0.20 (5)*
Br53	0.43103 (6)	0.24240 (6)	0.61777 (3)	0.06234 (18)
Br63	1.04163 (10)	0.97232 (6)	0.67120 (4)	0.0945 (3)
N41	0.9268 (4)	0.5002 (4)	0.2891 (2)	0.0479 (9)
H41	1.0010	0.5656	0.2795	0.057*
N43	0.7364 (5)	0.2939 (4)	0.2688 (2)	0.0508 (9)
C41	0.8716 (5)	0.5075 (4)	0.3588 (3)	0.0427 (10)
C42	0.8439 (5)	0.3722 (5)	0.2384 (3)	0.0521 (11)
H42	0.8607	0.3417	0.1869	0.063*
C43	0.7523 (5)	0.3785 (4)	0.3461 (3)	0.0438 (10)
C44	0.6710 (5)	0.3458 (4)	0.4076 (3)	0.0417 (10)
C45	0.7172 (5)	0.4499 (4)	0.4833 (2)	0.0376 (9)
C46	0.8385 (5)	0.5888 (4)	0.4952 (3)	0.0409 (10)
C47	0.9164 (5)	0.6165 (4)	0.4320 (3)	0.0413 (10)
C51	0.5564 (6)	0.2153 (5)	0.3976 (3)	0.0526 (12)
H51	0.5274	0.1475	0.3478	0.063*
C52	0.4848 (6)	0.1836 (5)	0.4588 (3)	0.0535 (12)
H52	0.4068	0.0963	0.4510	0.064*
C53	0.5320 (5)	0.2856 (5)	0.5329 (3)	0.0473 (11)
C54	0.6426 (5)	0.4157 (4)	0.5453 (3)	0.0435 (10)
H54	0.6687	0.4823	0.5953	0.052*
C61	1.0320 (6)	0.7490 (5)	0.4423 (3)	0.0497 (11)
H61	1.0837	0.7659	0.4009	0.060*
C62	1.0686 (6)	0.8534 (5)	0.5135 (3)	0.0570 (12)
H62	1.1447	0.9413	0.5208	0.068*
C63	0.9901 (6)	0.8255 (5)	0.5743 (3)	0.0530 (12)
C64	0.8789 (6)	0.6966 (4)	0.5671 (3)	0.0494 (11)
H64	0.8309	0.6814	0.6100	0.059*
Br23	−0.32947 (6)	−0.35521 (6)	−0.23022 (3)	0.06483 (18)
Br33	0.33555 (9)	0.34459 (6)	−0.16606 (4)	0.0839 (2)
N11	0.4763 (5)	0.0408 (4)	0.1674 (2)	0.0502 (9)
H11	0.5635	0.1130	0.1911	0.060*
N13	0.2838 (5)	−0.1650 (4)	0.1477 (2)	0.0537 (10)
C11	0.3671 (5)	0.0154 (4)	0.0922 (2)	0.0413 (9)
C12	0.4198 (7)	−0.0696 (5)	0.1969 (3)	0.0591 (13)
H12	0.4728	−0.0776	0.2477	0.071*
C13	0.2492 (5)	−0.1118 (4)	0.0804 (3)	0.0434 (10)
C14	0.1146 (5)	−0.1736 (4)	0.0077 (3)	0.0420 (10)
C15	0.1036 (5)	−0.0967 (4)	−0.0522 (3)	0.0412 (9)
C16	0.2310 (5)	0.0396 (4)	−0.0397 (3)	0.0419 (10)
C17	0.3651 (5)	0.0964 (4)	0.0336 (3)	0.0412 (9)
C21	−0.0044 (6)	−0.3057 (4)	−0.0068 (3)	0.0491 (11)
H21	0.0052	−0.3570	0.0320	0.059*
C22	−0.1333 (6)	−0.3602 (5)	−0.0765 (3)	0.0542 (12)
H22	−0.2115	−0.4479	−0.0856	0.065*
C23	−0.1457 (5)	−0.2820 (4)	−0.1340 (3)	0.0461 (10)
C24	−0.0316 (5)	−0.1545 (4)	−0.1234 (3)	0.0479 (11)
H24	−0.0431	−0.1056	−0.1634	0.057*
C31	0.4856 (6)	0.2249 (4)	0.0442 (3)	0.0476 (11)
H31	0.5726	0.2617	0.0924	0.057*
C32	0.4793 (6)	0.2983 (5)	−0.0141 (3)	0.0534 (12)
H32	0.5611	0.3835	−0.0064	0.064*
C33	0.3486 (6)	0.2427 (5)	−0.0847 (3)	0.0515 (11)
C34	0.2254 (6)	0.1181 (4)	−0.0980 (3)	0.0505 (11)
H34	0.1377	0.0853	−0.1459	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.078 (3)	0.144 (5)	0.131 (5)	0.005 (3)	0.031 (3)	0.098 (4)
Br53	0.0566 (3)	0.0768 (4)	0.0568 (3)	0.0101 (2)	0.0176 (2)	0.0336 (3)
Br63	0.1571 (7)	0.0495 (3)	0.0525 (4)	0.0014 (3)	0.0144 (4)	0.0078 (3)
N41	0.045 (2)	0.049 (2)	0.053 (2)	0.0097 (16)	0.0176 (17)	0.0227 (18)
N43	0.049 (2)	0.054 (2)	0.046 (2)	0.0104 (17)	0.0133 (17)	0.0111 (18)
C41	0.034 (2)	0.046 (2)	0.052 (3)	0.0137 (18)	0.0075 (19)	0.021 (2)
C42	0.047 (3)	0.062 (3)	0.048 (3)	0.015 (2)	0.018 (2)	0.014 (2)
C43	0.039 (2)	0.048 (3)	0.042 (3)	0.0104 (19)	0.0065 (19)	0.013 (2)
C44	0.034 (2)	0.046 (2)	0.043 (2)	0.0109 (18)	0.0053 (18)	0.0149 (19)
C45	0.031 (2)	0.043 (2)	0.041 (2)	0.0126 (17)	0.0049 (17)	0.0182 (18)
C46	0.040 (2)	0.039 (2)	0.044 (2)	0.0150 (18)	0.0012 (18)	0.0155 (19)
C47	0.037 (2)	0.042 (2)	0.046 (2)	0.0132 (18)	0.0036 (18)	0.0185 (19)
C51	0.050 (3)	0.054 (3)	0.044 (3)	0.002 (2)	0.011 (2)	0.007 (2)
C52	0.046 (3)	0.053 (3)	0.052 (3)	−0.001 (2)	0.009 (2)	0.016 (2)
C53	0.042 (2)	0.063 (3)	0.046 (3)	0.015 (2)	0.0166 (19)	0.028 (2)
C54	0.042 (2)	0.049 (2)	0.040 (2)	0.0146 (19)	0.0077 (18)	0.0153 (19)
C61	0.050 (3)	0.046 (2)	0.056 (3)	0.014 (2)	0.012 (2)	0.022 (2)
C62	0.066 (3)	0.042 (3)	0.057 (3)	0.010 (2)	0.004 (2)	0.019 (2)
C63	0.067 (3)	0.041 (2)	0.041 (3)	0.012 (2)	−0.002 (2)	0.011 (2)
C64	0.058 (3)	0.046 (2)	0.042 (3)	0.013 (2)	0.003 (2)	0.018 (2)
Br23	0.0575 (3)	0.0680 (3)	0.0549 (3)	0.0085 (2)	0.0037 (2)	0.0080 (2)
Br33	0.1271 (5)	0.0599 (3)	0.0626 (4)	0.0119 (3)	0.0183 (3)	0.0372 (3)
N11	0.058 (2)	0.043 (2)	0.041 (2)	0.0030 (17)	0.0073 (17)	0.0143 (17)
N13	0.064 (2)	0.051 (2)	0.045 (2)	0.0088 (19)	0.0119 (19)	0.0224 (18)
C11	0.047 (2)	0.042 (2)	0.039 (2)	0.0146 (18)	0.0145 (19)	0.0152 (18)
C12	0.074 (3)	0.057 (3)	0.046 (3)	0.013 (3)	0.013 (2)	0.024 (2)
C13	0.057 (3)	0.038 (2)	0.042 (2)	0.0156 (19)	0.021 (2)	0.0170 (19)
C14	0.048 (2)	0.035 (2)	0.044 (2)	0.0115 (18)	0.0160 (19)	0.0123 (18)
C15	0.048 (2)	0.039 (2)	0.040 (2)	0.0149 (18)	0.0150 (19)	0.0104 (18)
C16	0.050 (2)	0.041 (2)	0.041 (2)	0.0162 (19)	0.0190 (19)	0.0137 (19)
C17	0.047 (2)	0.039 (2)	0.040 (2)	0.0146 (18)	0.0152 (19)	0.0098 (18)
C21	0.059 (3)	0.044 (2)	0.049 (3)	0.014 (2)	0.018 (2)	0.019 (2)
C22	0.056 (3)	0.044 (3)	0.060 (3)	0.006 (2)	0.018 (2)	0.014 (2)
C23	0.043 (2)	0.047 (2)	0.043 (3)	0.0118 (19)	0.0102 (19)	0.0045 (19)
C24	0.055 (3)	0.047 (3)	0.044 (3)	0.017 (2)	0.014 (2)	0.012 (2)
C31	0.054 (3)	0.043 (2)	0.043 (3)	0.007 (2)	0.013 (2)	0.0134 (19)
C32	0.065 (3)	0.038 (2)	0.061 (3)	0.010 (2)	0.023 (2)	0.019 (2)
C33	0.074 (3)	0.045 (3)	0.043 (3)	0.015 (2)	0.024 (2)	0.022 (2)
C34	0.068 (3)	0.046 (2)	0.037 (2)	0.015 (2)	0.013 (2)	0.015 (2)

Geometric parameters (Å, º)

O1—H1O	0.91 (10)	C64—H64	0.9300
O1—H2O	0.91 (10)	Br23—C23	1.903 (4)
Br53—C53	1.902 (4)	Br33—C33	1.904 (4)
Br63—C63	1.894 (5)	N11—C12	1.343 (6)
N41—C42	1.339 (6)	N11—C11	1.367 (5)
N41—C41	1.366 (5)	N11—H11	0.8600
N41—H41	0.8600	N13—C12	1.307 (6)
N43—C42	1.314 (6)	N13—C13	1.384 (5)
N43—C43	1.392 (5)	C11—C13	1.371 (5)
C41—C43	1.387 (6)	C11—C17	1.425 (6)
C41—C47	1.413 (6)	C12—H12	0.9300
C42—H42	0.9300	C13—C14	1.422 (6)
C43—C44	1.421 (6)	C14—C21	1.403 (5)
C44—C51	1.389 (6)	C14—C15	1.415 (6)
C44—C45	1.418 (6)	C15—C24	1.405 (6)
C45—C54	1.400 (6)	C15—C16	1.473 (5)
C45—C46	1.472 (5)	C16—C34	1.403 (6)
C46—C64	1.396 (6)	C16—C17	1.423 (6)
C46—C47	1.419 (6)	C17—C31	1.394 (6)
C47—C61	1.407 (6)	C21—C22	1.360 (6)
C51—C52	1.369 (6)	C21—H21	0.9300
C51—H51	0.9300	C22—C23	1.391 (6)
C52—C53	1.386 (6)	C22—H22	0.9300
C52—H52	0.9300	C23—C24	1.363 (6)
C53—C54	1.364 (6)	C24—H24	0.9300
C54—H54	0.9300	C31—C32	1.367 (6)
C61—C62	1.373 (7)	C31—H31	0.9300
C61—H61	0.9300	C32—C33	1.377 (6)
C62—C63	1.383 (7)	C32—H32	0.9300
C62—H62	0.9300	C33—C34	1.369 (6)
C63—C64	1.375 (6)	C34—H34	0.9300
H1O—O1—H2O	72 (8)	C12—N11—C11	106.1 (4)
C42—N41—C41	107.2 (4)	C12—N11—H11	126.9
C42—N41—H41	126.4	C11—N11—H11	126.9
C41—N41—H41	126.4	C12—N13—C13	103.8 (4)
C42—N43—C43	104.5 (4)	N11—C11—C13	106.0 (3)
N41—C41—C43	105.8 (4)	N11—C11—C17	130.7 (4)
N41—C41—C47	131.4 (4)	C13—C11—C17	123.3 (4)
C43—C41—C47	122.8 (4)	N13—C12—N11	114.0 (4)
N43—C42—N41	113.4 (4)	N13—C12—H12	123.0
N43—C42—H42	123.3	N11—C12—H12	123.0
N41—C42—H42	123.3	C11—C13—N13	110.1 (4)
C41—C43—N43	109.2 (4)	C11—C13—C14	122.1 (4)
C41—C43—C44	121.7 (4)	N13—C13—C14	127.8 (4)
N43—C43—C44	129.1 (4)	C21—C14—C15	119.6 (4)
C51—C44—C45	119.6 (4)	C21—C14—C13	123.1 (4)
C51—C44—C43	122.8 (4)	C15—C14—C13	117.3 (4)
C45—C44—C43	117.5 (4)	C24—C15—C14	118.0 (4)
C54—C45—C44	117.6 (4)	C24—C15—C16	121.4 (4)
C54—C45—C46	121.9 (4)	C14—C15—C16	120.6 (4)
C44—C45—C46	120.5 (4)	C34—C16—C17	117.6 (4)
C64—C46—C47	118.1 (4)	C34—C16—C15	122.2 (4)
C64—C46—C45	122.1 (4)	C17—C16—C15	120.2 (4)
C47—C46—C45	119.8 (4)	C31—C17—C16	119.5 (4)
C61—C47—C41	121.9 (4)	C31—C17—C11	123.9 (4)
C61—C47—C46	120.5 (4)	C16—C17—C11	116.6 (4)
C41—C47—C46	117.6 (4)	C22—C21—C14	121.4 (4)
C52—C51—C44	122.0 (4)	C22—C21—H21	119.3
C52—C51—H51	119.0	C14—C21—H21	119.3
C44—C51—H51	119.0	C21—C22—C23	118.5 (4)
C51—C52—C53	117.9 (4)	C21—C22—H22	120.7
C51—C52—H52	121.0	C23—C22—H22	120.7
C53—C52—H52	121.0	C24—C23—C22	122.3 (4)
C54—C53—C52	122.2 (4)	C24—C23—Br23	118.9 (3)
C54—C53—Br53	119.8 (3)	C22—C23—Br23	118.8 (3)
C52—C53—Br53	118.0 (3)	C23—C24—C15	120.1 (4)
C53—C54—C45	120.6 (4)	C23—C24—H24	119.9
C53—C54—H54	119.7	C15—C24—H24	119.9
C45—C54—H54	119.7	C32—C31—C17	121.8 (4)
C62—C61—C47	120.1 (4)	C32—C31—H31	119.1
C62—C61—H61	119.9	C17—C31—H31	119.1
C47—C61—H61	119.9	C31—C32—C33	118.2 (4)
C61—C62—C63	118.8 (4)	C31—C32—H32	120.9
C61—C62—H62	120.6	C33—C32—H32	120.9
C63—C62—H62	120.6	C34—C33—C32	122.6 (4)
C64—C63—C62	122.8 (4)	C34—C33—Br33	118.5 (3)
C64—C63—Br63	119.5 (4)	C32—C33—Br33	118.9 (3)
C62—C63—Br63	117.7 (3)	C33—C34—C16	120.2 (4)
C63—C64—C46	119.7 (4)	C33—C34—H34	119.9
C63—C64—H64	120.2	C16—C34—H34	119.9
C46—C64—H64	120.2
C42—N41—C41—C43	−0.4 (5)	C12—N11—C11—C13	−0.2 (5)
C42—N41—C41—C47	179.6 (4)	C12—N11—C11—C17	−179.9 (5)
C43—N43—C42—N41	−0.5 (5)	C13—N13—C12—N11	0.0 (6)
C41—N41—C42—N43	0.6 (5)	C11—N11—C12—N13	0.1 (6)
N41—C41—C43—N43	0.1 (5)	N11—C11—C13—N13	0.2 (5)
C47—C41—C43—N43	−179.9 (4)	C17—C11—C13—N13	180.0 (4)
N41—C41—C43—C44	177.8 (4)	N11—C11—C13—C14	−179.5 (4)
C47—C41—C43—C44	−2.2 (6)	C17—C11—C13—C14	0.3 (7)
C42—N43—C43—C41	0.2 (5)	C12—N13—C13—C11	−0.2 (5)
C42—N43—C43—C44	−177.3 (4)	C12—N13—C13—C14	179.6 (5)
C41—C43—C44—C51	−177.3 (4)	C11—C13—C14—C21	177.9 (4)
N43—C43—C44—C51	−0.1 (7)	N13—C13—C14—C21	−1.8 (7)
C41—C43—C44—C45	−0.5 (6)	C11—C13—C14—C15	−1.6 (6)
N43—C43—C44—C45	176.7 (4)	N13—C13—C14—C15	178.7 (4)
C51—C44—C45—C54	−0.4 (6)	C21—C14—C15—C24	2.3 (6)
C43—C44—C45—C54	−177.3 (4)	C13—C14—C15—C24	−178.2 (4)
C51—C44—C45—C46	180.0 (4)	C21—C14—C15—C16	−177.6 (4)
C43—C44—C45—C46	3.1 (6)	C13—C14—C15—C16	1.9 (6)
C54—C45—C46—C64	−3.5 (6)	C24—C15—C16—C34	−0.5 (6)
C44—C45—C46—C64	176.0 (4)	C14—C15—C16—C34	179.3 (4)
C54—C45—C46—C47	177.2 (4)	C24—C15—C16—C17	179.1 (4)
C44—C45—C46—C47	−3.2 (6)	C14—C15—C16—C17	−1.0 (6)
N41—C41—C47—C61	3.0 (7)	C34—C16—C17—C31	−0.8 (6)
C43—C41—C47—C61	−177.0 (4)	C15—C16—C17—C31	179.5 (4)
N41—C41—C47—C46	−177.9 (4)	C34—C16—C17—C11	179.4 (4)
C43—C41—C47—C46	2.1 (6)	C15—C16—C17—C11	−0.3 (6)
C64—C46—C47—C61	0.4 (6)	N11—C11—C17—C31	0.7 (7)
C45—C46—C47—C61	179.7 (4)	C13—C11—C17—C31	−179.1 (4)
C64—C46—C47—C41	−178.7 (4)	N11—C11—C17—C16	−179.6 (4)
C45—C46—C47—C41	0.6 (6)	C13—C11—C17—C16	0.7 (6)
C45—C44—C51—C52	0.4 (7)	C15—C14—C21—C22	−1.8 (7)
C43—C44—C51—C52	177.1 (4)	C13—C14—C21—C22	178.8 (4)
C44—C51—C52—C53	−1.0 (7)	C14—C21—C22—C23	0.0 (7)
C51—C52—C53—C54	1.8 (7)	C21—C22—C23—C24	1.3 (7)
C51—C52—C53—Br53	179.4 (4)	C21—C22—C23—Br23	−178.3 (3)
C52—C53—C54—C45	−1.9 (7)	C22—C23—C24—C15	−0.8 (7)
Br53—C53—C54—C45	−179.5 (3)	Br23—C23—C24—C15	178.8 (3)
C44—C45—C54—C53	1.1 (6)	C14—C15—C24—C23	−1.1 (6)
C46—C45—C54—C53	−179.3 (4)	C16—C15—C24—C23	178.8 (4)
C41—C47—C61—C62	178.2 (4)	C16—C17—C31—C32	−0.3 (7)
C46—C47—C61—C62	−0.8 (6)	C11—C17—C31—C32	179.4 (4)
C47—C61—C62—C63	0.0 (7)	C17—C31—C32—C33	0.6 (7)
C61—C62—C63—C64	1.2 (7)	C31—C32—C33—C34	0.4 (7)
C61—C62—C63—Br63	−179.4 (3)	C31—C32—C33—Br33	179.1 (4)
C62—C63—C64—C46	−1.6 (7)	C32—C33—C34—C16	−1.6 (7)
Br63—C63—C64—C46	179.0 (3)	Br33—C33—C34—C16	179.7 (3)
C47—C46—C64—C63	0.7 (6)	C17—C16—C34—C33	1.8 (6)
C45—C46—C64—C63	−178.5 (4)	C15—C16—C34—C33	−178.5 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···N43	0.86	2.05	2.892 (5)	165
N41—H41···O1	0.86	1.87	2.702 (5)	164
O1—H2O···N13^i	0.91 (10)	1.83 (10)	2.731 (8)	172 (13)

Symmetry code: (i) x+1, y+1, z.