Crystal structures of three N-(3-acetyl-phen-yl)quinoline-2-carboxamides.

In the title compounds, N-(5-acetyl-2-methyl-phen-yl)quinoline-2-carboxamide [C19H16N2O2, (I)], N-(5-acetyl-2-bromo-phen-yl)quinoline-2-carboxamide [C18H13BrN2O2, (II)] and N-(5-acetyl-2-ethynylphen-yl)quinoline-2-carboxamide [C20H14N2O2, (III)], the quinoline ring system is essentially planar and forms a dihedral angles of 3.68 (5) (I), 5.59 (7) (II) and 1.87 (6)° (III) with the acetyl-substituted ring. The mol-ecular structures of (I) and (III) each feature an intra-molecular N-H⋯N hydrogen bond, forming an S(5) ring, while in (II) an intra-molecular bifurcated N-H⋯(N,Br) hydrogen bond forms two S(5) rings. In the crystals, weak C-H⋯O hydrogen bonds link mol-ecules of (I) into C(7) chains long [010], mol-ecules of (II) into chains of R22(8) rings along [110] and mol-ecules of (III) into C(8) chains along [010]. In (I), there are no significant π-π stacking inter-actions under 4 Å, but in both (II) and (III), π-π inter-actions link the weak hydrogen-bonded chains into layers parallel to (001) [centroid-centroid disttances of 3.748 (1) Å in (II) and 3.577 (1), 3.784 (1) and 3.780 (1) Å in (III)].

Chemical context

Amino­aceto­phenones, quinolines and carboxamides have been reported to possess many inter­esting pharmacological activities and they are characteristic components of a large number of biologically active compounds. The wide spectrum of biological effects of these kind of compounds includes anti­microbial (Nawar & Hosny, 2000 ▸), anti­convulsant (Pandeya et al., 1998 ▸), cytotoxic (Zhao et al., 2005 ▸), anti-malarial (Egan et al., 1994 ▸), anti­proliferative (Chen et al., 2006 ▸), anti­tuberculosis/anti­mycobacterial (Gonec et al., 2012 ▸) activities, radioligands (Matarrese et al., 2001 ▸, Belloli et al., 2004 ▸), calpain inhibitors (Nam et al., 2008 ▸), TPSO ligand (Blair et al., 2013 ▸) and pharmaceutical medicaments (Weidmann et al., 2008 ▸), among others.

Structural commentary

The mol­ecular structure of title compounds (I), (II) and (III) are shown in Figs. 1 ▸, 2 ▸ and 3 ▸, respectively. The quinoline ring system [C1–C9/N1 in (I), C2–C10/N1 in (II) and C12–C20/N2 in (III)] in each compound is essentially planar with maximum deviations of 0.015 (1) Å for C3 in (I), 0.017 (2) Å for C3 in (II) and 0.013 (2) Å for C17 in (III). The quinoline ring system forms dihedral angles of 3.68 (5)° (I), 5.59 (7)° (II) and 1.87 (6)° (III) with the acetyl-substituted ring [C11–C16 in (I) and (II), C3–C8 in (III)]. In the mol­ecular structures of (I) and (III), an intra­molecular N—H⋯N hydrogen bond forms an S(5) ring while in (II) an intra­molecular bifurcated N—H⋯(N,Br) hydrogen bond forms two S(5) rings (Tables 1 ▸–3 ▸ ▸).

Figure 1

The mol­ecular structure of (I), with the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level.

Figure 2

The mol­ecular structure of (II), with the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level.

Figure 3

The mol­ecular structure of (III), with the-atom numbering scheme and displacement ellipsoids drawn at the 50% probability level.

Table 1

Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1	0.86	2.15	2.619 (2)	114
C17—H17⋯O1i	0.96	2.49	3.424 (2)	164

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1	0.86	2.19	2.629 (2)	112
C3—H3⋯O1i	0.93	2.55	3.410 (2)	154
C18—H18⋯O2ii	0.96	2.49	3.444 (2)	171
N2—H2⋯Br1	0.86	2.58	3.081 (1)	118

Symmetry codes: (i) ; (ii) .

Table 3

Hydrogen-bond geometry (Å, °) for (III)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2	0.86	2.23	2.666 (2)	111
C10—H10⋯O2i	0.93	2.36	3.103 (2)	136

Symmetry code: (i) .

Supra­molecular features

In the crystals, weak C—H⋯O hydrogen bonds link mol­ecules of (I) into C(7) chains along [010] (Fig. 4 ▸), mol­ecules of (II) into chains of (8) rings along [110] (Fig. 5 ▸) and mol­ecules of (III) into C(8) chains along [010] (Fig. 6 ▸). In (I), there are no significant π–π stacking inter­actions under 4 Å but in (II) π–π inter­actions link the weak hydrogen-bonded chains into layers parallel to (001) [centroid–centroid distance Cg1⋯Cg2(1 + x, y, z) = 3.748 (1) Å; Cg1 and Cg2 are the centroids of the C5–C10 and N1/C2–C6 rings, respectively]. In (III), π–π inter­actions link the weak hydrogen-bonded chains into layers parallel to (001) with centroid–centroid distances Cg3⋯Cg4(−1 + x, −1 + y, −1 + z) = 3.577 (1), Cg4⋯Cg5(−x + 1, −y + 1, −z + 1) 3.784 (1) and Cg4⋯Cg5(−x + 2, −y + 1, −z + 1) = 3.780 (1) Å; Cg3, Cg4, and Cg5 are the centroids of the N2/C12–C16, C3–C8 and C15–C20 rings, respectively].

Figure 4

Part of the crystal structure of (I), with inter­molecular and intra­molecular hydrogen bonds shown as black dotted lines. Only H atoms involved in hydrogen bonds are shown.

Figure 5

Part of the crystal structure of (II), with inter­molecular and intra­molecular hydrogen bonds shown as black dotted lines. Only H atoms involved in hydrogen bonds are shown.

Figure 6

Part of the crystal structure of (III), with inter­molecular and intra­molecular hydrogen bonds shown as black dotted lines. Only H atoms involved in hydrogen bonds are shown.

Database survey

A search of the Cambridge Structural Database (Groom et al. 2016 ▸; Version 1.18, April 2016) for similar compounds with an N-phenyl­quinoline-2-carboxamide skeleton resulted in twelve hits. One entry for the compound without substituents is reported (Jing & Qin, 2007 ▸). Eight are structures substituted in the 4-position of the phenyl group: one meth­oxy group (Qi et al., 2003 ▸) and another a nitro group (Jing & Qin, 2008 ▸); one chlorine and one fluorine (Khavasi et al., 2014 ▸), and two reports each for bromine (Bobal et al., 2012 ▸; Khavasi et al., 2014 ▸) and iodine (Qi et al., 2003 ▸; Khavasi et al., 2014 ▸). The rest have large organic substituents.

Synthesis and crystallization

Compounds (I)–(III) were prepared by refluxing a mixture of quinaldic acid, tri­ethyl­amine, p-toluene­sulfonyl chloride and the corresponding substituted amino­aceto­phenones (1a–c) for 24 h in DCM (Fig. 7 ▸). Acetic acid 5% was added to quench the reaction, and the organic phase was washed three times with water. After evaporation of DCM, the compounds were purified by silica column chromatography (penta­ne:ethyl acetate 2:1). Single crystals were obtained by slow evaporation of the respective solutions of the compounds in di­chloro­methane into a closed flask with petroleum ether.

Figure 7

The reaction scheme for the synthesis of the title compounds

-(5-acetyl-2-methyl­phen­yl)quinoline-2-carboxamide (I) Light-yellow solid (0.700 g, yield quant, R f PE/EA 2:1 0.52). 8.95 (d, = 7.7 Hz, 1H, quinol), 8.40 (s, 2H, ArH quinol), 8.17 (d, = 8.5 Hz, 1H, ArH), 7.93 (d, = 9.0 Hz, 1H, quinol), 7.82 (ddd, = 8.4, = 6.9 Hz, 1H, quinol), 7.73 (dd, = 7.9, 1H, ArH), 7.67 (ddd, = 8.1, = 6.9 Hz, 1H, quinol), 7.35 (d, = 7.9 Hz, 1H, quinol), 2.65 (s, 3H, CH3), 2.55 (s, 3H, COCH3). 197.8 (Cquat), 162.2 (Cquat), 149.5 (Cquat), 146.2 (Cquat), 138.0 (Cquat), 136.2 (Cquat), 133.5 (Cquat), 130.7 (Cquat), 130.4 (+), 129.8 (+), 129.5 (+), 128.3 (+), 127.8 (+), 124.1 (+), 121.5 (+), 118.6 (+), 26.7 (+), 18.0 (+).

-(5-acetyl-2-bromo­phen­yl)quinoline-2-carboxamide (II) Yellow solid (0.700 g, yield quant, R f PE/EA 2:1 0.60). 9.32 (s, 1H), 8.40 (d, = 3.0 Hz, 2H), 8.23 (d, = 8.5 Hz, 1H), 7.94 (d, = 8.8 Hz, 1H), 7.83 (t, = 7.0 Hz, 1H), 7.69 (m, 3H), 2.68 (s, 3H, COCH3). 197.3 (Cquat), 162.6 (Cquat), 149.1 (Cquat), 146.3 (Cquat), 138.2 (Cquat), 137.2 (Cquat), 136.3 (Cquat), 132.8 (+), 130.6 (+), 130.5 (+), 130.6 (+), 128.5 (+), 127.8 (+), 124.1 (+), 121.1 (+), 118.9 (+), 118.5 (+), 26.7 (+).

-(5-acetyl-2-ethynylphen­yl)quinoline-2-carboxamide (III) Light-brown solid (0.700 g, yield quant, R f PE/EA 2:1 0.20). 9.36 (d, = 1.6 Hz, 1H), 8.40 (s, 2H), 8.15 (d, = 8.5 Hz, 1H), 7.94 (d, = 8.2 Hz, 1H), 7.82 (dd, = 11.2, 4.2 Hz, 1H), 7.73 (dd, = 8.1, = 1.7 Hz, 1H), 7.71 (m, 1H), 7.63 (d, J = 8.1 Hz, 1H), 3.87 (s, 1H, CCH), 2.70 (s, 3H, CH3). = 197.6 (Cquat), 162.8 (Cquat), 149.2 (Cquat), 146.3 (Cquat), 140.1 (Cquat), 138.0 (Cquat), 132.5 (+), 130.4 (+), 129.9 (+), 129.5 (+), 128.4 (+), 127.8 (+), 122.6 (+), 119.1 (+), 118.6 (+), 115.7 (+), 87.1 (Cquat), 79.0 (+), 26.8 (+).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4 ▸. All non-hydrogen atoms were refined anisotropically. Hydrogen-atom positions were calculated geometrically and refined using the riding model. N–H = 0.86 Å, C—H = 0.96 Å for methyl H atoms and 0.93 Å for all other; U iso(H) = 1.2U eq(C,N) or 1.5U eq(Cmeth­yl).

Table 4

Experimental details

	(I)	(II)	(III)
Crystal data
Chemical formula	C19H16N2O2	C18H13BrN2O2	C20H14N2O2
M r	304.34	369.21	314.33
Crystal system, space group	Monoclinic, P21/c	Triclinic, P	Triclinic, P
Temperature (K)	123	123	123
a, b, c (Å)	4.5787 (2), 14.7986 (7), 22.3732 (12)	4.29848 (12), 11.6353 (3), 15.5888 (4)	7.3075 (6), 8.2605 (4), 13.8196 (9)
α, β, γ (°)	90, 92.130 (5), 90	103.788 (2), 95.515 (2), 96.195 (2)	92.734 (5), 100.608 (6), 108.989 (6)
V (Å3)	1514.93 (12)	746.76 (3)	770.11 (10)
Z	4	2	2
Radiation type	Cu Kα	Cu Kα	Mo Kα
μ (mm−1)	0.71	3.85	0.09
Crystal size (mm)	0.33 × 0.12 × 0.07	0.65 × 0.10 × 0.06	0.19 × 0.08 × 0.05
Data collection
Diffractometer	Agilent TitanS2 GV1000	Agilent TitanS2 GV1000	Agilent SuperNova Single source at offset, Eos
Absorption correction	Analytical [CrysAlis PRO (Rigaku OD, 2015 ▸), based on expressions derived by Clark & Reid (1995 ▸)]	Gaussian [CrysAlis PRO (Rigaku OD, 2015 ▸), based on expressions derived by Clark & Reid (1995 ▸)]	Analytical [CrysAlis PRO (Rigaku OD, 2015 ▸), based on expressions derived by Clark & Reid (1995 ▸)]
T min, T max	0.869, 0.958	0.540, 0.900	0.987, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	6056, 2935, 2562	12899, 2966, 2870	20693, 5173, 3687
R int	0.020	0.033	0.060
(sin θ/λ)max (Å−1)	0.625	0.622	0.753
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.038, 0.106, 1.04	0.024, 0.065, 1.05	0.056, 0.151, 1.04
No. of reflections	2935	2966	5173
No. of parameters	210	210	218
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.20, −0.21	0.48, −0.65	0.42, −0.26

Computer programs: CrysAlis PRO (Rigaku OD, 2015 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2014 (Sheldrick, 2015b ▸) and OLEX2 (Dolomanov et al., 2009 ▸).

Crystal structure: contains datablock(s) I, II, III. DOI: 10.1107/S2056989017006272/lh5839sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017006272/lh5839Isup2.hkl

Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989017006272/lh5839IIsup3.hkl

Structure factors: contains datablock(s) III. DOI: 10.1107/S2056989017006272/lh5839IIIsup4.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989017006272/lh5839Isup5.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989017006272/lh5839IIsup6.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989017006272/lh5839IIIsup7.cml

CCDC references: 1546038, 1546037, 1546036

Additional supporting information: crystallographic information; 3D view; checkCIF report

C19H16N2O2	F(000) = 640
Mr = 304.34	Dx = 1.334 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 4.5787 (2) Å	Cell parameters from 3477 reflections
b = 14.7986 (7) Å	θ = 6.0–74.2°
c = 22.3732 (12) Å	µ = 0.71 mm−1
β = 92.130 (5)°	T = 123 K
V = 1514.93 (12) Å3	Block, dark gray
Z = 4	0.33 × 0.12 × 0.07 mm

Agilent TitanS2 GV1000 diffractometer	2935 independent reflections
Radiation source: gradient vaccum rotating-anode X-ray tube, GV1000 (Cu) X-ray Source	2562 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.020
Detector resolution: 4.1818 pixels mm-1	θmax = 74.4°, θmin = 3.6°
ω scans	h = −5→5
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	k = −18→17
Tmin = 0.869, Tmax = 0.958	l = −27→21
6056 measured reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038	H-atom parameters constrained
wR(F2) = 0.106	w = 1/[σ2(Fo2) + (0.0608P)2 + 0.2546P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
2935 reflections	Δρmax = 0.20 e Å−3
210 parameters	Δρmin = −0.21 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.59998 (18)	0.50983 (6)	0.24602 (4)	0.0250 (2)
O2	1.4993 (2)	0.62002 (8)	0.05885 (5)	0.0410 (3)
N2	0.7067 (2)	0.65842 (7)	0.26763 (5)	0.0217 (2)
H2	0.6628	0.7001	0.2925	0.026*
N1	0.3450 (2)	0.65936 (7)	0.35561 (5)	0.0223 (2)
C10	0.5705 (2)	0.57873 (8)	0.27553 (5)	0.0197 (2)
C9	0.3690 (2)	0.58150 (8)	0.32767 (5)	0.0200 (2)
C16	1.0023 (2)	0.62534 (8)	0.18077 (5)	0.0225 (3)
H16	0.9290	0.5668	0.1784	0.027*
C11	0.9095 (2)	0.68391 (8)	0.22502 (5)	0.0205 (3)
C12	1.0191 (2)	0.77271 (8)	0.22953 (6)	0.0223 (3)
C8	0.2199 (2)	0.50181 (8)	0.34310 (6)	0.0229 (3)
H8	0.2444	0.4485	0.3219	0.028*
C15	1.2058 (2)	0.65473 (8)	0.13999 (6)	0.0239 (3)
C6	0.1639 (2)	0.66364 (9)	0.40278 (5)	0.0242 (3)
C17	0.9276 (3)	0.83545 (8)	0.27837 (6)	0.0257 (3)
H17A	0.7217	0.8470	0.2739	0.039*
H17B	1.0329	0.8913	0.2758	0.039*
H17C	0.9700	0.8080	0.3166	0.039*
C13	1.2190 (3)	0.80052 (8)	0.18796 (6)	0.0252 (3)
H13	1.2917	0.8592	0.1899	0.030*
C14	1.3123 (3)	0.74284 (9)	0.14374 (6)	0.0268 (3)
H14	1.4464	0.7630	0.1165	0.032*
C7	0.0383 (3)	0.50538 (9)	0.39030 (6)	0.0260 (3)
H7	−0.0619	0.4539	0.4018	0.031*
C5	0.0036 (2)	0.58715 (9)	0.42139 (6)	0.0256 (3)
C18	1.3186 (3)	0.59328 (9)	0.09298 (6)	0.0284 (3)
C1	0.1359 (3)	0.74684 (10)	0.43341 (6)	0.0309 (3)
H1	0.2429	0.7969	0.4218	0.037*
C4	−0.1839 (3)	0.59647 (11)	0.47008 (6)	0.0337 (3)
H4	−0.2897	0.5469	0.4830	0.040*
C3	−0.2098 (3)	0.67783 (12)	0.49810 (6)	0.0395 (4)
H3	−0.3356	0.6835	0.5296	0.047*
C2	−0.0478 (3)	0.75369 (11)	0.47989 (7)	0.0371 (3)
H2A	−0.0665	0.8085	0.4997	0.045*
C19	1.2077 (4)	0.49817 (10)	0.08911 (8)	0.0446 (4)
H19A	1.2992	0.4673	0.0570	0.067*
H19B	0.9998	0.4988	0.0818	0.067*
H19C	1.2530	0.4674	0.1261	0.067*

	U11	U22	U33	U12	U13	U23
O1	0.0249 (4)	0.0214 (4)	0.0291 (5)	0.0003 (3)	0.0072 (3)	−0.0016 (3)
O2	0.0414 (5)	0.0441 (6)	0.0388 (6)	−0.0028 (4)	0.0208 (4)	0.0001 (5)
N2	0.0217 (5)	0.0199 (5)	0.0239 (5)	0.0002 (4)	0.0055 (4)	−0.0005 (4)
N1	0.0195 (5)	0.0248 (5)	0.0226 (5)	0.0028 (4)	0.0008 (4)	0.0000 (4)
C10	0.0152 (5)	0.0210 (5)	0.0228 (6)	0.0018 (4)	0.0002 (4)	0.0018 (4)
C9	0.0163 (5)	0.0233 (5)	0.0202 (6)	0.0018 (4)	−0.0006 (4)	0.0015 (4)
C16	0.0197 (5)	0.0229 (5)	0.0250 (6)	0.0013 (4)	0.0017 (4)	0.0028 (5)
C11	0.0159 (5)	0.0229 (5)	0.0226 (6)	0.0009 (4)	0.0008 (4)	0.0050 (4)
C12	0.0188 (5)	0.0222 (6)	0.0258 (6)	0.0021 (4)	−0.0014 (4)	0.0035 (5)
C8	0.0201 (5)	0.0246 (6)	0.0240 (6)	−0.0003 (4)	0.0007 (4)	0.0011 (5)
C15	0.0200 (5)	0.0277 (6)	0.0242 (6)	0.0030 (4)	0.0028 (4)	0.0047 (5)
C6	0.0197 (5)	0.0316 (6)	0.0210 (6)	0.0051 (5)	−0.0010 (4)	0.0006 (5)
C17	0.0275 (6)	0.0211 (5)	0.0286 (6)	−0.0011 (5)	0.0017 (5)	0.0013 (5)
C13	0.0217 (5)	0.0228 (5)	0.0312 (7)	−0.0023 (4)	0.0002 (5)	0.0072 (5)
C14	0.0216 (6)	0.0308 (6)	0.0283 (7)	0.0000 (5)	0.0050 (5)	0.0081 (5)
C7	0.0201 (5)	0.0322 (6)	0.0256 (6)	−0.0028 (5)	0.0008 (5)	0.0050 (5)
C5	0.0185 (5)	0.0377 (7)	0.0205 (6)	0.0034 (5)	−0.0002 (4)	0.0038 (5)
C18	0.0246 (6)	0.0340 (7)	0.0268 (6)	0.0034 (5)	0.0057 (5)	0.0039 (5)
C1	0.0310 (6)	0.0346 (7)	0.0270 (7)	0.0079 (5)	−0.0014 (5)	−0.0046 (5)
C4	0.0243 (6)	0.0522 (8)	0.0249 (7)	0.0045 (6)	0.0047 (5)	0.0061 (6)
C3	0.0304 (7)	0.0648 (10)	0.0236 (7)	0.0138 (7)	0.0054 (5)	−0.0011 (7)
C2	0.0360 (7)	0.0479 (8)	0.0273 (7)	0.0147 (6)	−0.0015 (5)	−0.0097 (6)
C19	0.0536 (9)	0.0348 (8)	0.0472 (9)	−0.0030 (6)	0.0261 (7)	−0.0092 (7)

O1—C10	1.2249 (15)	C17—H17A	0.9600
O2—C18	1.2129 (17)	C17—H17B	0.9600
N2—H2	0.8600	C17—H17C	0.9600
N2—C10	1.3490 (15)	C13—H13	0.9300
N2—C11	1.4068 (15)	C13—C14	1.3861 (19)
N1—C9	1.3175 (15)	C14—H14	0.9300
N1—C6	1.3674 (16)	C7—H7	0.9300
C10—C9	1.5142 (16)	C7—C5	1.4075 (19)
C9—C8	1.4120 (16)	C5—C4	1.4188 (18)
C16—H16	0.9300	C18—C19	1.498 (2)
C16—C11	1.3940 (17)	C1—H1	0.9300
C16—C15	1.3973 (17)	C1—C2	1.365 (2)
C11—C12	1.4090 (16)	C4—H4	0.9300
C12—C17	1.5051 (17)	C4—C3	1.365 (2)
C12—C13	1.3912 (17)	C3—H3	0.9300
C8—H8	0.9300	C3—C2	1.414 (2)
C8—C7	1.3694 (17)	C2—H2A	0.9300
C15—C14	1.3937 (18)	C19—H19A	0.9600
C15—C18	1.4970 (18)	C19—H19B	0.9600
C6—C5	1.4200 (18)	C19—H19C	0.9600
C6—C1	1.4172 (18)
C10—N2—H2	115.0	C12—C13—H13	119.2
C10—N2—C11	130.05 (10)	C14—C13—C12	121.53 (11)
C11—N2—H2	115.0	C14—C13—H13	119.2
C9—N1—C6	118.07 (10)	C15—C14—H14	119.9
O1—C10—N2	126.59 (11)	C13—C14—C15	120.17 (11)
O1—C10—C9	121.36 (10)	C13—C14—H14	119.9
N2—C10—C9	112.04 (10)	C8—C7—H7	120.1
N1—C9—C10	116.96 (10)	C8—C7—C5	119.81 (11)
N1—C9—C8	124.38 (11)	C5—C7—H7	120.1
C8—C9—C10	118.66 (10)	C7—C5—C6	118.13 (11)
C11—C16—H16	120.1	C7—C5—C4	123.06 (12)
C11—C16—C15	119.89 (11)	C4—C5—C6	118.81 (12)
C15—C16—H16	120.1	O2—C18—C15	120.37 (13)
N2—C11—C12	116.35 (10)	O2—C18—C19	120.53 (13)
C16—C11—N2	122.74 (11)	C15—C18—C19	119.10 (11)
C16—C11—C12	120.91 (11)	C6—C1—H1	119.9
C11—C12—C17	121.28 (11)	C2—C1—C6	120.15 (14)
C13—C12—C11	118.00 (11)	C2—C1—H1	119.9
C13—C12—C17	120.71 (11)	C5—C4—H4	119.9
C9—C8—H8	121.0	C3—C4—C5	120.25 (14)
C7—C8—C9	118.00 (11)	C3—C4—H4	119.9
C7—C8—H8	121.0	C4—C3—H3	119.6
C16—C15—C18	121.71 (11)	C4—C3—C2	120.85 (13)
C14—C15—C16	119.50 (12)	C2—C3—H3	119.6
C14—C15—C18	118.77 (11)	C1—C2—C3	120.34 (14)
N1—C6—C5	121.61 (11)	C1—C2—H2A	119.8
N1—C6—C1	118.80 (12)	C3—C2—H2A	119.8
C1—C6—C5	119.59 (12)	C18—C19—H19A	109.5
C12—C17—H17A	109.5	C18—C19—H19B	109.5
C12—C17—H17B	109.5	C18—C19—H19C	109.5
C12—C17—H17C	109.5	H19A—C19—H19B	109.5
H17A—C17—H17B	109.5	H19A—C19—H19C	109.5
H17A—C17—H17C	109.5	H19B—C19—H19C	109.5
H17B—C17—H17C	109.5
O1—C10—C9—N1	−178.04 (10)	C11—C16—C15—C14	−0.49 (18)
O1—C10—C9—C8	1.81 (16)	C11—C16—C15—C18	178.04 (11)
N2—C10—C9—N1	2.76 (14)	C11—C12—C13—C14	−0.89 (17)
N2—C10—C9—C8	−177.40 (10)	C12—C13—C14—C15	0.12 (19)
N2—C11—C12—C17	1.36 (16)	C8—C7—C5—C6	−0.83 (17)
N2—C11—C12—C13	−179.66 (10)	C8—C7—C5—C4	178.99 (11)
N1—C9—C8—C7	−0.09 (18)	C15—C16—C11—N2	−179.62 (10)
N1—C6—C5—C7	0.80 (17)	C15—C16—C11—C12	−0.31 (17)
N1—C6—C5—C4	−179.03 (11)	C6—N1—C9—C10	179.88 (9)
N1—C6—C1—C2	178.65 (12)	C6—N1—C9—C8	0.04 (17)
C10—N2—C11—C16	0.95 (19)	C6—C5—C4—C3	0.34 (18)
C10—N2—C11—C12	−178.39 (11)	C6—C1—C2—C3	0.4 (2)
C10—C9—C8—C7	−179.93 (10)	C17—C12—C13—C14	178.09 (11)
C9—N1—C6—C5	−0.41 (16)	C14—C15—C18—O2	−0.05 (19)
C9—N1—C6—C1	179.89 (11)	C14—C15—C18—C19	179.31 (13)
C9—C8—C7—C5	0.49 (17)	C7—C5—C4—C3	−179.48 (12)
C16—C11—C12—C17	−177.99 (11)	C5—C6—C1—C2	−1.07 (19)
C16—C11—C12—C13	0.99 (17)	C5—C4—C3—C2	−1.0 (2)
C16—C15—C14—C13	0.59 (18)	C18—C15—C14—C13	−177.99 (11)
C16—C15—C18—O2	−178.60 (12)	C1—C6—C5—C7	−179.50 (11)
C16—C15—C18—C19	0.76 (19)	C1—C6—C5—C4	0.67 (17)
C11—N2—C10—O1	0.6 (2)	C4—C3—C2—C1	0.6 (2)
C11—N2—C10—C9	179.74 (10)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1	0.86	2.15	2.619 (2)	114
C17—H17···O1i	0.96	2.49	3.424 (2)	164

C18H13BrN2O2	Z = 2
Mr = 369.21	F(000) = 372
Triclinic, P1	Dx = 1.642 Mg m−3
a = 4.29848 (12) Å	Cu Kα radiation, λ = 1.54184 Å
b = 11.6353 (3) Å	Cell parameters from 10806 reflections
c = 15.5888 (4) Å	θ = 3.9–73.8°
α = 103.788 (2)°	µ = 3.85 mm−1
β = 95.515 (2)°	T = 123 K
γ = 96.195 (2)°	Plank, clear colourless
V = 746.76 (3) Å3	0.65 × 0.10 × 0.06 mm

Agilent TitanS2 GV1000 diffractometer	2966 independent reflections
Radiation source: gradient vaccum rotating-anode X-ray tube, GV1000 (Cu) X-ray Source	2870 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.033
Detector resolution: 4.1818 pixels mm-1	θmax = 73.7°, θmin = 2.9°
ω scans	h = −5→5
Absorption correction: gaussian [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	k = −13→14
Tmin = 0.540, Tmax = 0.900	l = −19→19
12899 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.024	w = 1/[σ2(Fo2) + (0.039P)2 + 0.3702P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.065	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.48 e Å−3
2966 reflections	Δρmin = −0.65 e Å−3
210 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0018 (3)

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.

	x	y	z	Uiso*/Ueq
Br1	0.61589 (4)	0.18439 (2)	0.04683 (2)	0.02135 (9)
O1	0.5793 (3)	0.36128 (11)	0.39598 (8)	0.0221 (3)
O2	1.3517 (3)	−0.04850 (12)	0.36241 (9)	0.0289 (3)
N2	0.5689 (3)	0.29917 (12)	0.24400 (9)	0.0152 (3)
H2	0.4949	0.3149	0.1955	0.018*
N1	0.2021 (3)	0.45877 (12)	0.22055 (9)	0.0155 (3)
C11	0.7457 (4)	0.20417 (15)	0.23433 (11)	0.0144 (3)
C1	0.4988 (4)	0.37012 (15)	0.32082 (11)	0.0161 (3)
C6	0.0260 (4)	0.54368 (15)	0.20390 (11)	0.0159 (3)
C15	1.0588 (4)	0.07376 (15)	0.29489 (11)	0.0161 (3)
C12	0.7872 (4)	0.13977 (15)	0.14896 (11)	0.0161 (3)
C2	0.3045 (4)	0.46475 (15)	0.30427 (11)	0.0156 (3)
C16	0.8882 (4)	0.16983 (15)	0.30694 (11)	0.0158 (3)
H16	0.8683	0.2121	0.3644	0.019*
C13	0.9537 (4)	0.04208 (16)	0.13641 (11)	0.0185 (3)
H13	0.9742	−0.0006	0.0791	0.022*
C3	0.2451 (4)	0.55339 (16)	0.37799 (11)	0.0202 (4)
H3	0.3202	0.5528	0.4358	0.024*
C14	1.0880 (4)	0.00874 (16)	0.20912 (11)	0.0183 (3)
H14	1.1978	−0.0569	0.2010	0.022*
C18	1.2121 (4)	0.11879 (17)	0.46469 (11)	0.0219 (4)
H18A	0.9983	0.1174	0.4778	0.033*
H18B	1.2985	0.1991	0.4666	0.033*
H18C	1.3353	0.0903	0.5080	0.033*
C17	1.2189 (4)	0.03975 (16)	0.37334 (11)	0.0187 (3)
C7	−0.0919 (4)	0.53725 (16)	0.11481 (11)	0.0190 (3)
H7	−0.0509	0.4752	0.0692	0.023*
C8	−0.2654 (4)	0.62145 (17)	0.09514 (12)	0.0231 (4)
H8	−0.3398	0.6169	0.0362	0.028*
C9	−0.3322 (4)	0.71549 (17)	0.16407 (13)	0.0241 (4)
H9	−0.4509	0.7723	0.1501	0.029*
C4	0.0744 (4)	0.63973 (16)	0.36164 (12)	0.0221 (4)
H4	0.0344	0.7000	0.4087	0.026*
C10	−0.2242 (4)	0.72361 (16)	0.25081 (13)	0.0220 (4)
H10	−0.2703	0.7858	0.2955	0.026*
C5	−0.0422 (4)	0.63791 (15)	0.27334 (12)	0.0179 (3)

	U11	U22	U33	U12	U13	U23
Br1	0.03126 (13)	0.02289 (13)	0.01153 (11)	0.00980 (8)	0.00226 (7)	0.00496 (8)
O1	0.0320 (7)	0.0228 (7)	0.0123 (6)	0.0102 (5)	0.0028 (5)	0.0033 (5)
O2	0.0414 (8)	0.0268 (7)	0.0214 (6)	0.0190 (6)	0.0013 (6)	0.0062 (5)
N2	0.0197 (7)	0.0159 (7)	0.0116 (6)	0.0069 (5)	0.0031 (5)	0.0042 (5)
N1	0.0181 (6)	0.0141 (7)	0.0149 (6)	0.0026 (5)	0.0049 (5)	0.0034 (5)
C11	0.0159 (7)	0.0133 (8)	0.0145 (7)	0.0019 (6)	0.0036 (6)	0.0039 (6)
C1	0.0172 (7)	0.0155 (8)	0.0155 (8)	0.0016 (6)	0.0039 (6)	0.0032 (6)
C6	0.0162 (7)	0.0138 (8)	0.0189 (8)	0.0031 (6)	0.0063 (6)	0.0046 (6)
C15	0.0171 (7)	0.0164 (8)	0.0155 (8)	0.0019 (6)	0.0027 (6)	0.0053 (6)
C12	0.0194 (8)	0.0181 (8)	0.0113 (7)	0.0022 (6)	0.0018 (6)	0.0049 (6)
C2	0.0179 (7)	0.0138 (8)	0.0156 (8)	0.0026 (6)	0.0056 (6)	0.0029 (6)
C16	0.0185 (7)	0.0166 (8)	0.0126 (7)	0.0028 (6)	0.0038 (6)	0.0036 (6)
C13	0.0238 (8)	0.0173 (9)	0.0138 (8)	0.0047 (7)	0.0050 (6)	0.0007 (6)
C3	0.0250 (8)	0.0211 (9)	0.0138 (8)	0.0044 (7)	0.0041 (6)	0.0017 (7)
C14	0.0212 (8)	0.0148 (8)	0.0196 (8)	0.0054 (6)	0.0044 (7)	0.0033 (7)
C18	0.0300 (9)	0.0223 (9)	0.0156 (8)	0.0090 (7)	0.0026 (7)	0.0070 (7)
C17	0.0211 (8)	0.0196 (9)	0.0177 (8)	0.0052 (7)	0.0040 (6)	0.0074 (7)
C7	0.0234 (8)	0.0170 (9)	0.0176 (8)	0.0059 (7)	0.0055 (7)	0.0038 (7)
C8	0.0261 (9)	0.0232 (10)	0.0229 (9)	0.0069 (7)	0.0028 (7)	0.0098 (7)
C9	0.0238 (9)	0.0181 (9)	0.0336 (10)	0.0086 (7)	0.0051 (7)	0.0096 (8)
C4	0.0270 (9)	0.0180 (9)	0.0191 (8)	0.0062 (7)	0.0068 (7)	−0.0023 (7)
C10	0.0235 (8)	0.0135 (8)	0.0291 (9)	0.0060 (7)	0.0085 (7)	0.0015 (7)
C5	0.0183 (8)	0.0139 (8)	0.0215 (8)	0.0027 (6)	0.0071 (6)	0.0026 (7)

Br1—C12	1.8968 (16)	C13—H13	0.9300
O1—C1	1.221 (2)	C13—C14	1.379 (2)
O2—C17	1.213 (2)	C3—H3	0.9300
N2—H2	0.8600	C3—C4	1.363 (3)
N2—C11	1.395 (2)	C14—H14	0.9300
N2—C1	1.363 (2)	C18—H18A	0.9600
N1—C6	1.365 (2)	C18—H18B	0.9600
N1—C2	1.320 (2)	C18—H18C	0.9600
C11—C12	1.401 (2)	C18—C17	1.505 (2)
C11—C16	1.397 (2)	C7—H7	0.9300
C1—C2	1.506 (2)	C7—C8	1.366 (3)
C6—C7	1.413 (2)	C8—H8	0.9300
C6—C5	1.423 (2)	C8—C9	1.415 (3)
C15—C16	1.388 (2)	C9—H9	0.9300
C15—C14	1.395 (2)	C9—C10	1.365 (3)
C15—C17	1.501 (2)	C4—H4	0.9300
C12—C13	1.392 (2)	C4—C5	1.413 (3)
C2—C3	1.414 (2)	C10—H10	0.9300
C16—H16	0.9300	C10—C5	1.419 (3)
C11—N2—H2	116.0	C15—C14—H14	120.1
C1—N2—H2	116.0	C13—C14—C15	119.79 (16)
C1—N2—C11	128.05 (14)	C13—C14—H14	120.1
C2—N1—C6	117.86 (14)	H18A—C18—H18B	109.5
N2—C11—C12	119.73 (14)	H18A—C18—H18C	109.5
N2—C11—C16	122.69 (14)	H18B—C18—H18C	109.5
C16—C11—C12	117.58 (15)	C17—C18—H18A	109.5
O1—C1—N2	125.78 (16)	C17—C18—H18B	109.5
O1—C1—C2	121.70 (15)	C17—C18—H18C	109.5
N2—C1—C2	112.53 (14)	O2—C17—C15	120.30 (16)
N1—C6—C7	118.71 (15)	O2—C17—C18	121.59 (16)
N1—C6—C5	122.01 (15)	C15—C17—C18	118.10 (15)
C7—C6—C5	119.28 (16)	C6—C7—H7	119.7
C16—C15—C14	120.08 (15)	C8—C7—C6	120.57 (16)
C16—C15—C17	120.76 (15)	C8—C7—H7	119.7
C14—C15—C17	119.14 (15)	C7—C8—H8	119.9
C11—C12—Br1	120.33 (13)	C7—C8—C9	120.21 (17)
C13—C12—Br1	118.19 (12)	C9—C8—H8	119.9
C13—C12—C11	121.48 (15)	C8—C9—H9	119.7
N1—C2—C1	116.81 (14)	C10—C9—C8	120.64 (17)
N1—C2—C3	124.47 (16)	C10—C9—H9	119.7
C3—C2—C1	118.73 (15)	C3—C4—H4	119.9
C11—C16—H16	119.4	C3—C4—C5	120.19 (16)
C15—C16—C11	121.17 (15)	C5—C4—H4	119.9
C15—C16—H16	119.4	C9—C10—H10	119.8
C12—C13—H13	120.1	C9—C10—C5	120.48 (16)
C14—C13—C12	119.84 (15)	C5—C10—H10	119.8
C14—C13—H13	120.1	C4—C5—C6	117.53 (16)
C2—C3—H3	121.0	C4—C5—C10	123.66 (16)
C4—C3—C2	117.93 (16)	C10—C5—C6	118.80 (16)
C4—C3—H3	121.0
Br1—C12—C13—C14	178.46 (13)	C2—N1—C6—C7	−178.60 (15)
O1—C1—C2—N1	−173.05 (15)	C2—N1—C6—C5	1.4 (2)
O1—C1—C2—C3	7.2 (2)	C2—C3—C4—C5	1.1 (3)
N2—C11—C12—Br1	2.1 (2)	C16—C11—C12—Br1	−177.52 (12)
N2—C11—C12—C13	−177.97 (15)	C16—C11—C12—C13	2.5 (2)
N2—C11—C16—C15	179.08 (15)	C16—C15—C14—C13	1.7 (2)
N2—C1—C2—N1	7.0 (2)	C16—C15—C17—O2	175.63 (17)
N2—C1—C2—C3	−172.76 (15)	C16—C15—C17—C18	−5.1 (2)
N1—C6—C7—C8	−179.06 (16)	C3—C4—C5—C6	0.0 (3)
N1—C6—C5—C4	−1.3 (2)	C3—C4—C5—C10	179.32 (17)
N1—C6—C5—C10	179.38 (15)	C14—C15—C16—C11	−0.7 (2)
N1—C2—C3—C4	−1.0 (3)	C14—C15—C17—O2	−5.5 (2)
C11—N2—C1—O1	−0.7 (3)	C14—C15—C17—C18	173.78 (16)
C11—N2—C1—C2	179.29 (14)	C17—C15—C16—C11	178.22 (14)
C11—C12—C13—C14	−1.5 (3)	C17—C15—C14—C13	−177.24 (15)
C1—N2—C11—C12	178.73 (15)	C7—C6—C5—C4	178.70 (15)
C1—N2—C11—C16	−1.7 (3)	C7—C6—C5—C10	−0.7 (2)
C1—C2—C3—C4	178.68 (15)	C7—C8—C9—C10	0.1 (3)
C6—N1—C2—C1	−179.91 (14)	C8—C9—C10—C5	0.2 (3)
C6—N1—C2—C3	−0.2 (2)	C9—C10—C5—C6	0.1 (3)
C6—C7—C8—C9	−0.7 (3)	C9—C10—C5—C4	−179.22 (17)
C12—C11—C16—C15	−1.4 (2)	C5—C6—C7—C8	1.0 (3)
C12—C13—C14—C15	−0.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1	0.86	2.19	2.629 (2)	112
C3—H3···O1i	0.93	2.55	3.410 (2)	154
C18—H18···O2ii	0.96	2.49	3.444 (2)	171
N2—H2···Br1	0.86	2.58	3.081 (1)	118

C20H14N2O2	Z = 2
Mr = 314.33	F(000) = 328
Triclinic, P1	Dx = 1.356 Mg m−3
a = 7.3075 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.2605 (4) Å	Cell parameters from 5519 reflections
c = 13.8196 (9) Å	θ = 3.1–32.0°
α = 92.734 (5)°	µ = 0.09 mm−1
β = 100.608 (6)°	T = 123 K
γ = 108.989 (6)°	Block, colourless
V = 770.11 (10) Å3	0.19 × 0.08 × 0.05 mm

Agilent SuperNova Single source at offset, Eos diffractometer	5173 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	3687 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.060
Detector resolution: 7.9851 pixels mm-1	θmax = 32.3°, θmin = 3.0°
ω scans	h = −10→10
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	k = −12→12
Tmin = 0.987, Tmax = 0.996	l = −20→20
20693 measured reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.056	H-atom parameters constrained
wR(F2) = 0.151	w = 1/[σ2(Fo2) + (0.0577P)2 + 0.282P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
5173 reflections	Δρmax = 0.42 e Å−3
218 parameters	Δρmin = −0.26 e Å−3

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.

	x	y	z	Uiso*/Ueq
O2	0.81853 (17)	0.81639 (13)	0.58241 (8)	0.0298 (3)
O1	0.69300 (18)	0.80001 (15)	1.00770 (8)	0.0344 (3)
N1	0.73126 (17)	0.52751 (15)	0.59954 (8)	0.0204 (2)
H1	0.7132	0.4296	0.5678	0.025*
N2	0.76917 (16)	0.45956 (15)	0.41516 (8)	0.0204 (2)
C11	0.7866 (2)	0.66691 (18)	0.54929 (10)	0.0211 (3)
C16	0.78375 (19)	0.41914 (18)	0.32020 (10)	0.0205 (3)
C8	0.6340 (2)	0.49494 (18)	0.88964 (10)	0.0225 (3)
H8	0.6117	0.4859	0.9536	0.027*
C3	0.69438 (19)	0.65661 (18)	0.85563 (9)	0.0199 (3)
C9	0.6242 (2)	0.20816 (18)	0.66981 (10)	0.0235 (3)
C4	0.72565 (19)	0.67055 (17)	0.75912 (9)	0.0201 (3)
H4	0.7637	0.7782	0.7364	0.024*
C6	0.64210 (19)	0.36039 (17)	0.73190 (9)	0.0200 (3)
C5	0.69995 (19)	0.52316 (17)	0.69665 (9)	0.0190 (3)
C15	0.8349 (2)	0.54711 (19)	0.25516 (10)	0.0226 (3)
C12	0.80629 (19)	0.62324 (17)	0.44536 (9)	0.0198 (3)
C2	0.7259 (2)	0.81339 (19)	0.92427 (10)	0.0238 (3)
C13	0.8613 (2)	0.75994 (18)	0.38704 (10)	0.0235 (3)
H13	0.8881	0.8734	0.4126	0.028*
C7	0.6074 (2)	0.34872 (18)	0.82831 (10)	0.0227 (3)
H7	0.5661	0.2413	0.8511	0.027*
C17	0.7457 (2)	0.24391 (19)	0.28605 (11)	0.0264 (3)
H17	0.7138	0.1593	0.3282	0.032*
C10	0.6224 (2)	0.0885 (2)	0.61968 (12)	0.0305 (3)
H10	0.6210	−0.0063	0.5800	0.037*
C14	0.8738 (2)	0.72010 (19)	0.29172 (10)	0.0249 (3)
H14	0.9079	0.8069	0.2511	0.030*
C20	0.8445 (2)	0.4964 (2)	0.15714 (10)	0.0283 (3)
H20	0.8776	0.5790	0.1140	0.034*
C18	0.7560 (2)	0.2000 (2)	0.19069 (12)	0.0309 (3)
H18	0.7302	0.0851	0.1685	0.037*
C19	0.8051 (2)	0.3267 (2)	0.12586 (11)	0.0315 (3)
H19	0.8108	0.2945	0.0614	0.038*
C1	0.8052 (3)	0.9875 (2)	0.89000 (11)	0.0326 (4)
H1A	0.8080	1.0748	0.9392	0.049*
H1B	0.7214	0.9926	0.8288	0.049*
H1C	0.9369	1.0066	0.8801	0.049*

	U11	U22	U33	U12	U13	U23
O2	0.0459 (7)	0.0218 (5)	0.0232 (5)	0.0113 (5)	0.0114 (5)	0.0015 (4)
O1	0.0440 (7)	0.0339 (6)	0.0211 (5)	0.0056 (5)	0.0126 (5)	−0.0035 (4)
N1	0.0256 (6)	0.0189 (5)	0.0162 (5)	0.0063 (4)	0.0057 (4)	0.0002 (4)
N2	0.0197 (5)	0.0215 (5)	0.0187 (5)	0.0054 (4)	0.0043 (4)	0.0001 (4)
C11	0.0238 (6)	0.0227 (6)	0.0167 (6)	0.0079 (5)	0.0042 (5)	0.0012 (5)
C16	0.0180 (6)	0.0240 (7)	0.0180 (6)	0.0060 (5)	0.0034 (5)	−0.0014 (5)
C8	0.0225 (6)	0.0279 (7)	0.0173 (6)	0.0077 (5)	0.0062 (5)	0.0034 (5)
C3	0.0189 (6)	0.0236 (6)	0.0161 (5)	0.0064 (5)	0.0032 (5)	−0.0011 (5)
C9	0.0234 (7)	0.0252 (7)	0.0224 (6)	0.0072 (5)	0.0071 (5)	0.0070 (5)
C4	0.0207 (6)	0.0211 (6)	0.0173 (6)	0.0055 (5)	0.0039 (5)	0.0012 (5)
C6	0.0195 (6)	0.0214 (6)	0.0186 (6)	0.0061 (5)	0.0041 (5)	0.0015 (5)
C5	0.0182 (6)	0.0231 (6)	0.0158 (5)	0.0067 (5)	0.0047 (4)	0.0026 (5)
C15	0.0192 (6)	0.0308 (7)	0.0164 (6)	0.0072 (5)	0.0031 (5)	0.0014 (5)
C12	0.0201 (6)	0.0217 (6)	0.0165 (5)	0.0058 (5)	0.0036 (5)	0.0006 (5)
C2	0.0241 (7)	0.0273 (7)	0.0184 (6)	0.0083 (6)	0.0027 (5)	−0.0022 (5)
C13	0.0280 (7)	0.0209 (6)	0.0196 (6)	0.0057 (5)	0.0045 (5)	0.0016 (5)
C7	0.0238 (7)	0.0225 (6)	0.0219 (6)	0.0066 (5)	0.0071 (5)	0.0044 (5)
C17	0.0250 (7)	0.0247 (7)	0.0278 (7)	0.0068 (6)	0.0061 (6)	−0.0023 (5)
C10	0.0358 (8)	0.0276 (7)	0.0272 (7)	0.0098 (6)	0.0065 (6)	0.0020 (6)
C14	0.0266 (7)	0.0266 (7)	0.0202 (6)	0.0059 (6)	0.0066 (5)	0.0063 (5)
C20	0.0256 (7)	0.0418 (9)	0.0177 (6)	0.0119 (6)	0.0048 (5)	0.0020 (6)
C18	0.0285 (8)	0.0317 (8)	0.0302 (8)	0.0103 (6)	0.0038 (6)	−0.0090 (6)
C19	0.0295 (8)	0.0453 (9)	0.0197 (6)	0.0152 (7)	0.0037 (6)	−0.0059 (6)
C1	0.0483 (10)	0.0241 (7)	0.0223 (7)	0.0107 (7)	0.0044 (6)	−0.0023 (6)

O2—C11	1.2279 (17)	C6—C7	1.4033 (18)
O1—C2	1.2231 (17)	C15—C14	1.411 (2)
N1—H1	0.8600	C15—C20	1.4195 (19)
N1—C11	1.3595 (18)	C12—C13	1.4130 (19)
N1—C5	1.4025 (16)	C2—C1	1.501 (2)
N2—C16	1.3704 (17)	C13—H13	0.9300
N2—C12	1.3197 (17)	C13—C14	1.3692 (19)
C11—C12	1.5082 (18)	C7—H7	0.9300
C16—C15	1.422 (2)	C17—H17	0.9300
C16—C17	1.421 (2)	C17—C18	1.372 (2)
C8—H8	0.9300	C10—H10	0.9300
C8—C3	1.397 (2)	C14—H14	0.9300
C8—C7	1.3799 (19)	C20—H20	0.9300
C3—C4	1.3979 (18)	C20—C19	1.367 (2)
C3—C2	1.4962 (19)	C18—H18	0.9300
C9—C6	1.4435 (19)	C18—C19	1.411 (2)
C9—C10	1.175 (2)	C19—H19	0.9300
C4—H4	0.9300	C1—H1A	0.9600
C4—C5	1.3979 (18)	C1—H1B	0.9600
C6—C5	1.4115 (18)	C1—H1C	0.9600
C11—N1—H1	115.9	O1—C2—C3	120.60 (13)
C11—N1—C5	128.21 (12)	O1—C2—C1	120.68 (13)
C5—N1—H1	115.9	C3—C2—C1	118.69 (12)
C12—N2—C16	117.64 (12)	C12—C13—H13	121.0
O2—C11—N1	125.11 (12)	C14—C13—C12	117.90 (13)
O2—C11—C12	121.14 (12)	C14—C13—H13	121.0
N1—C11—C12	113.75 (11)	C8—C7—C6	120.69 (13)
N2—C16—C15	121.91 (12)	C8—C7—H7	119.7
N2—C16—C17	118.75 (13)	C6—C7—H7	119.7
C17—C16—C15	119.33 (12)	C16—C17—H17	120.1
C3—C8—H8	120.0	C18—C17—C16	119.78 (14)
C7—C8—H8	120.0	C18—C17—H17	120.1
C7—C8—C3	119.98 (12)	C9—C10—H10	180.0
C8—C3—C4	120.17 (12)	C15—C14—H14	120.0
C8—C3—C2	118.92 (12)	C13—C14—C15	119.92 (13)
C4—C3—C2	120.92 (12)	C13—C14—H14	120.0
C10—C9—C6	175.76 (16)	C15—C20—H20	119.8
C3—C4—H4	119.9	C19—C20—C15	120.33 (15)
C3—C4—C5	120.21 (12)	C19—C20—H20	119.8
C5—C4—H4	119.9	C17—C18—H18	119.5
C5—C6—C9	119.94 (12)	C17—C18—C19	120.92 (14)
C7—C6—C9	120.52 (12)	C19—C18—H18	119.5
C7—C6—C5	119.51 (12)	C20—C19—C18	120.49 (14)
N1—C5—C6	117.23 (12)	C20—C19—H19	119.8
C4—C5—N1	123.36 (12)	C18—C19—H19	119.8
C4—C5—C6	119.41 (12)	C2—C1—H1A	109.5
C14—C15—C16	117.90 (12)	C2—C1—H1B	109.5
C14—C15—C20	122.96 (14)	C2—C1—H1C	109.5
C20—C15—C16	119.14 (13)	H1A—C1—H1B	109.5
N2—C12—C11	117.50 (12)	H1A—C1—H1C	109.5
N2—C12—C13	124.71 (12)	H1B—C1—H1C	109.5
C13—C12—C11	117.78 (12)
O2—C11—C12—N2	−179.91 (13)	C9—C6—C5—C4	−177.04 (12)
O2—C11—C12—C13	−0.5 (2)	C9—C6—C7—C8	176.73 (13)
N1—C11—C12—N2	−0.07 (18)	C4—C3—C2—O1	177.96 (13)
N1—C11—C12—C13	179.34 (12)	C4—C3—C2—C1	−4.1 (2)
N2—C16—C15—C14	0.9 (2)	C5—N1—C11—O2	−0.2 (2)
N2—C16—C15—C20	−179.00 (12)	C5—N1—C11—C12	180.00 (12)
N2—C16—C17—C18	178.87 (13)	C5—C6—C7—C8	−1.6 (2)
N2—C12—C13—C14	1.2 (2)	C15—C16—C17—C18	−0.9 (2)
C11—N1—C5—C4	−1.0 (2)	C15—C20—C19—C18	−0.5 (2)
C11—N1—C5—C6	179.84 (13)	C12—N2—C16—C15	−0.63 (19)
C11—C12—C13—C14	−178.19 (12)	C12—N2—C16—C17	179.63 (12)
C16—N2—C12—C11	178.94 (11)	C12—C13—C14—C15	−0.8 (2)
C16—N2—C12—C13	−0.4 (2)	C2—C3—C4—C5	178.53 (12)
C16—C15—C14—C13	−0.1 (2)	C7—C8—C3—C4	0.8 (2)
C16—C15—C20—C19	−0.1 (2)	C7—C8—C3—C2	−178.82 (13)
C16—C17—C18—C19	0.4 (2)	C7—C6—C5—N1	−179.53 (12)
C8—C3—C4—C5	−1.1 (2)	C7—C6—C5—C4	1.28 (19)
C8—C3—C2—O1	−2.4 (2)	C17—C16—C15—C14	−179.36 (13)
C8—C3—C2—C1	175.51 (13)	C17—C16—C15—C20	0.7 (2)
C3—C8—C7—C6	0.5 (2)	C17—C18—C19—C20	0.3 (2)
C3—C4—C5—N1	−179.10 (12)	C14—C15—C20—C19	−179.97 (14)
C3—C4—C5—C6	0.04 (19)	C20—C15—C14—C13	179.78 (13)
C9—C6—C5—N1	2.14 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2	0.86	2.23	2.666 (2)	111
C10—H10···O2i	0.93	2.36	3.103 (2)	136