Crystal structure and Hirshfeld surface analysis of 5-amino-5'-bromo-2'-oxo-2,3-di-hydro-1H-spiro-[imidazo[1,2-a]pyridine-7,3'-indoline]-6,8-dicarbo-nitrile dimethyl sulfoxide disolvate.

In the title compound, C16H11BrN6O·2C2H6OS, the 1,2,3,7-tetra-hydro-imid-azo[1,2-a]pyridine ring system and the oxindole moiety are both nearly planar [maximum deviations = 0.042 (2) and 0.115 (2) Å, respectively] and their planes form a dihedral angle of 86.04 (5)° with each other. Inter-molecular N-H⋯O, C-H⋯O and C-H⋯N hydrogen bonds link mol-ecules in the crystal through the O atoms of the solvent mol-ecules, generating a three-dimensional network. A Hirshfeld surface analysis was performed to further analyse the inter-molecular inter-actions. © Naghiyev et al. 2022.

Chemical context

C—C and C—N bond-forming reactions represent a significant synthetic class because they play critical roles in various applications in different fields of chemistry (Yadigarov et al., 2009 ▸; Abdelhamid et al., 2011 ▸; Yin et al., 2020 ▸; Khalilov et al., 2021 ▸). Nitro­gen heterocycles, particularly those including the spiro­[imidazo[1,2-a]pyridine] moiety, play a key role in medi­cinal chemistry (Han et al., 2008 ▸; Mamedov et al., 2020 ▸; Samaneh et al., 2021 ▸). The conjugate addition to oxo­in­dol­inylidenemalono­nitriles has been well studied in simple two-component reactions with respect to producing spiro derivatives (Lu et al., 2012 ▸; Jun et al., 2019 ▸). We have previously reported the three-component reaction of 2-(2-oxoindolin-3-yl­idene)malono­nitrile with malono­nitrile and ethyl­enedi­amine which resulted in 5-amino-2′-oxo-2,3-di­hydro-1H-spiro­[imidazo[1,2-a]pyridine-7,3′-indoline]-6,8-dicarbo­nitrile (Magerramov et al., 2018 ▸). In the framework of our ongoing structural studies (Naghiyev et al., 2020 ▸, 2021a ▸,b ▸), herein the crystal structure and Hirshfeld surface analysis of 5-amino-5′-bromo-2′-oxo-2,3-di­hydro-1H-spiro­[imidazo[1,2-a]pyridine-7,3′-indoline]-6,8-dicarbo­nitrile, (1), is reported.

Structural commentary

In the title compound, (1) (see Scheme and Fig. 1 ▸), the 1,2,3,7-tetra­hydro­imidazo[1,2-a]pyridine ring system (N1/N4/C2/C3/C5–C8/C8A) and the oxindole moiety (O1/N2/C1/C7/C11–C16) are nearly planar, with maximum deviations of 0.042 (2) Å for C3 and 0.115 (2) Å for O1. These ring systems make a dihedral angle of 86.04 (5)° with each other. The cyano (–C≡N) and amine (NH2) groups form an inter­molecular hydrogen bond with one dimethyl sulfoxide (DMSO) group, giving an S(10) motif (Bernstein et al., 1995 ▸) (Table 1 ▸).

Figure 1

The title mol­ecule with the labelling scheme and displacement ellipsoids drawn at the 50% probability level. The minor components of the disorder are not shown.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2A i	0.90	1.98	2.855 (4)	165
N1—H1⋯O2B i	0.90	2.00	2.87 (4)	160
N2—H2⋯O2A ii	0.90	1.91	2.793 (5)	166
N2—H2⋯O2B ii	0.90	1.94	2.82 (5)	166
N5—H5A⋯O3A iii	0.90	2.20	3.034 (3)	155
N5—H5B⋯O3A	0.90	2.06	2.918 (3)	160
C2—H2B⋯N9iv	0.99	2.59	3.469 (4)	148
C19A—H19A⋯N9	0.98	2.41	3.114 (5)	128
C19A—H19C⋯O1v	0.98	2.52	3.392 (4)	148
C20A—H20B⋯O1v	0.98	2.46	3.359 (4)	152

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

Supra­molecular features and Hirshfeld surface analysis

In the crystal, mol­ecules are linked through the O atoms of the DMSO solvent mol­ecules by inter­molecular N—H⋯O and C—H⋯O hydrogen bonds which, together with C—H⋯N hydrogen bonds, form a three-dimensional (3D) network (Table 1 ▸ and Fig. 2 ▸). The π-cloud of the C8A—N1 bond (which has some multiple-bond character) acts as an electron donor to Br1 in a kind of ‘halogen bond’, with a Br1⋯C8A(−x + 1, −y + 1, −z) distance of 3.284 (2) Å.

Figure 2

A view of the mol­ecular packing of (1) along the a-axis direction.

The Hirshfeld surfaces were calculated and the two-dimensional (2D) fingerprint plots generated using CrystalExplorer (Version 17.5; Turner et al., 2017 ▸). Fig. 3 ▸ shows the 3D Hirshfeld surface of (1) with d norm (normalized contact distance) plotted over the range from −0.6206 to 1.3180 a.u. The inter­actions given in Table 1 ▸ play a key role in the mol­ecular packing of (1).

Figure 3

View of the 3D Hirshfeld surface of (1) plotted over d norm in the range from −0.6206 to 1.3180 a.u.

The overall 2D fingerprint plot for (1) is given in Fig. 4 ▸(a), and those delineated into H⋯H, N⋯H/H⋯N, O⋯H/H⋯O, C⋯H/H⋯C and Br⋯H/H⋯Br contacts are shown in Figs. 4 ▸(b)–(f). The percentage contributions to the Hirshfeld surfaces from the various inter­atomic contacts are as follows: H⋯H [Fig. 4 ▸(b); 27.1%], N⋯H/H⋯N [Fig. 4 ▸(c); 23.8%], O⋯H/H⋯O [Fig. 4 ▸(d); 15.7%], C⋯H/H⋯C [Fig. 4 ▸(e); 13.2%] and Br⋯H/H⋯Br [Fig. 4 ▸(f); 10.2%]. Other minor contributions to the Hirshfeld surface are from Br⋯C/C⋯Br (3.9%), Br⋯N/N⋯Br (2.0%), C⋯C (1.5%), S⋯C/C⋯S (0.8%), S⋯H/H⋯S (0.6%), S⋯N/N⋯S (0.4%), O⋯N/N⋯O (0.4%) and Br⋯O/O⋯Br (0.3%).

Figure 4

The full 2D fingerprint plots for (1), showing (a) all inter­actions, and delineated into (b) H⋯H, (c) N⋯H/H⋯N, (d) O⋯H/H⋯O, (e) C⋯H/H⋯C and (f) Br⋯H/H⋯Br inter­actions. The d i and d e values are the closest inter­nal and external distances (in Å) from given points on the Hirshfeld surface contacts.

Database survey

A search of the Cambridge Structural Database (CSD, Version 5.42, update of September 2021; Groom et al., 2016 ▸) for the 5-bromo-1,3-di­hydro-2H-indol-2-one unit of (1) gave 87 hits. The three compounds most resembling (1) are (I) (COGQAS; Nagalakshmi et al., 2014a ▸), (II) (WOPKAP; Nagalakshmi et al., 2014b ▸) and (III) (XODQOY; Nagalakshmi et al., 2014c ▸), showing very similar conformation of the mol­ecular core.

In the crystal of (I), N—H⋯O hydrogen bonds lead to the formation of chains along the c-axis direction. Within the chains there are further N—H⋯O and C—H⋯O hydrogen bonds enclosing (14) ring motifs. The chains are linked via N—H⋯O and C—H⋯O hydrogen bonds involving the dimethyl sulfoxide solvent mol­ecule which acts as both an acceptor and a donor.

In (II), the asymmetric unit contains two independent mol­ecules (A and B) having similar conformations. In the crystal, mol­ecules are linked by N—H⋯O hydrogen bonds, forming chains along the a axis which enclose (16) ring motifs. The rings are linked by weak N—H⋯O and C—H⋯O hydrogen bonds, and C—H⋯π inter­actions, forming sheets lying parallel to the (001) plane.

In (III), two intra­molecular N—H⋯O hydrogen bonds are formed, each closing an S(6) loop. In the crystal, strong N—H⋯O hydrogen bonds lead to the formation of zigzag chains along the c axis. These are consolidated in the 3D crystal packing by weak N—H⋯O hydrogen bonding, as well as by C—H⋯O, C—H⋯Br and C—H⋯π inter­actions.

Synthesis and crystallization

To a solution of 2-(5-bromo-2-oxoindolin-3-yl­idene)malono­nitrile (1.4 g, 5.1 mmol), which was previously prepared by a known procedure (Negar et al., 2012 ▸), and malono­nitrile (0.34 g, 5.2 mmol) in methanol (25 ml), ethyl­enedi­amine (0.31 g, 5.2 mmol) was added and the mixture was stirred at room temperature for 72 h (Fig. 5 ▸). Methanol (15 ml) was removed from the reaction mixture, which was left overnight. The precipitated crystals were separated by filtration and recrystallized from an ethanol–water (1:1 v/v) solution (yield 69%; m.p. 479–480 K). Single crystals of (1) were grown from DMSO solution.

Figure 5

The synthesis of 5-amino-5′-bromo-2′-oxo-2,3-di­hydro-1H-spiro­[imidazo[1,2-a]pyridine-7,3′-indoline]-6,8-dicarbo­nitrile by a reported procedure (Magerramov et al., 2018 ▸).

1H NMR (300 MHz, DMSO-d 6, ppm): δ 3.50 (t, 4H, 2CH2N), 6.61 (s, 2H, NH2), 6.78 (d, 1H, Ar-H, 3 J H-H = 7.8 Hz), 7.35 (s, 1H, Ar-H), 7.37 (d, 1H, Ar-H, 3 J H-H = 7.8 Hz), 7.73 (s, H, NH), 10.44 (s, H, NH). 13C NMR (75 MHz, DMSO-d 6, ppm): δ 42.46 (CH2N), 45.15 (CH2N), 51.24 (Cquat), 51.71 (=Cquat), 54.69 (=Cquat), 112.02 (CHarom), 114.43 (Br—Carom), 119.63 (CN), 120.15 (CN), 128.02 (CHarom), 131.90 (CHarom), 137.83 (Carom), 140.80 (Carom), 152.19 (=Cquat), 154.76 (=Cquat), 179.67 (O=C).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The H atoms were included in calculated positions and treated as riding atoms; N—H = 0.90 Å with U iso(H) = 1.2U eq(N), and C—H = 0.95–0.99 Å with U iso(H) = 1.2 or 1.5U eq(C). Both DMSO solvent mol­ecules are disordered over two positions, with final occupancies of 0.90:0.10 for the first and 0.95:0.05 for the second mol­ecule. In the first disordered DMSO molecule, the C17B and C18B atoms of the minor component were refined isotropically. The disordered atoms O2A/O2B, O3A/O3B, C19A/C19B and C20A/C20B were refined with anisotropic displacement parameters, constrained to be the same for both components. The S—C and S—O bond lengths in both disordered DMSO mol­ecules were restrained to similarity.

Table 2

Experimental details

Crystal data
Chemical formula	C16H11BrN6O·2C2H6OS
M r	539.47
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	100
a, b, c (Å)	10.3940 (1), 26.2421 (2), 8.9860 (1)
β (°)	108.056 (1)
V (Å3)	2330.32 (4)
Z	4
Radiation type	Cu Kα
μ (mm−1)	4.38
Crystal size (mm)	0.05 × 0.03 × 0.02
Data collection
Diffractometer	Rigaku XtaLAB Synergy Dualflex HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2021 ▸)
T min, T max	0.793, 0.899
No. of measured, independent and observed [I > 2σ(I)] reflections	31508, 5062, 5047
R int	0.029
(sin θ/λ)max (Å−1)	0.638
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.039, 0.094, 1.17
No. of reflections	5062
No. of parameters	331
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.63, −0.41

Computer programs: CrysAlis PRO (Rigaku OD, 2021 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL (Sheldrick, 2015b ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2020 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989022004741/zv2013sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989022004741/zv2013Isup2.hkl

CCDC reference: 2170241

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

C16H11BrN6O·2C2H6OS	F(000) = 1104
Mr = 539.47	Dx = 1.538 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 10.3940 (1) Å	Cell parameters from 27880 reflections
b = 26.2421 (2) Å	θ = 3.4–79.2°
c = 8.9860 (1) Å	µ = 4.38 mm−1
β = 108.056 (1)°	T = 100 K
V = 2330.32 (4) Å3	Prism, colourless
Z = 4	0.05 × 0.03 × 0.02 mm

Rigaku XtaLAB Synergy Dualflex HyPix diffractometer	5062 independent reflections
Radiation source: micro-focus sealed X-ray tube	5047 reflections with I > 2σ(I)
Detector resolution: 0 pixels mm-1	Rint = 0.029
φ and ω scans	θmax = 79.4°, θmin = 3.4°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2021)	h = −13→13
Tmin = 0.793, Tmax = 0.899	k = −31→33
31508 measured reflections	l = −11→11

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.039	w = 1/[σ2(Fo2) + (0.0287P)2 + 4.5523P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.094	(Δ/σ)max = 0.003
S = 1.17	Δρmax = 0.63 e Å−3
5062 reflections	Δρmin = −0.41 e Å−3
331 parameters	Extinction correction: SHELXL (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
6 restraints	Extinction coefficient: 0.00068 (7)

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	Occ. (<1)
Br1	0.43785 (3)	0.56355 (2)	0.19141 (3)	0.02651 (10)
O1	0.84018 (19)	0.31921 (7)	0.4894 (2)	0.0262 (4)
N1	0.7688 (2)	0.33596 (8)	−0.0737 (2)	0.0236 (4)
H1	0.846974	0.349380	−0.079035	0.028*
C1	0.7948 (2)	0.36248 (9)	0.4575 (3)	0.0195 (5)
N2	0.8234 (2)	0.40340 (8)	0.5544 (2)	0.0223 (4)
H2	0.883850	0.403189	0.650976	0.027*
C2	0.6818 (3)	0.30219 (12)	−0.1925 (3)	0.0311 (6)
H2A	0.730367	0.270499	−0.201996	0.037*
H2B	0.651308	0.319271	−0.295753	0.037*
C3	0.5622 (3)	0.29063 (10)	−0.1340 (3)	0.0269 (6)
H3A	0.476650	0.303812	−0.207158	0.032*
H3B	0.553120	0.253560	−0.119462	0.032*
N4	0.5981 (2)	0.31762 (8)	0.0156 (2)	0.0181 (4)
C5	0.5237 (2)	0.31827 (8)	0.1184 (3)	0.0162 (4)
N5	0.4101 (2)	0.28990 (8)	0.0779 (2)	0.0206 (4)
H5A	0.387282	0.271975	−0.011822	0.025*
H5B	0.357158	0.288865	0.140338	0.025*
C6	0.5691 (2)	0.34678 (9)	0.2534 (3)	0.0175 (4)
C7	0.6955 (2)	0.37927 (9)	0.2964 (3)	0.0164 (4)
C8	0.7672 (2)	0.37480 (9)	0.1734 (3)	0.0170 (4)
C8A	0.7175 (2)	0.34454 (9)	0.0441 (3)	0.0169 (4)
C9	0.4989 (3)	0.34610 (9)	0.3650 (3)	0.0227 (5)
N9	0.4511 (3)	0.34703 (10)	0.4650 (3)	0.0313 (5)
C10	0.8877 (3)	0.40296 (9)	0.1953 (3)	0.0219 (5)
N10	0.9860 (3)	0.42647 (10)	0.2186 (3)	0.0321 (5)
C11	0.7468 (2)	0.44627 (9)	0.4847 (3)	0.0198 (5)
C12	0.6681 (2)	0.43415 (9)	0.3327 (3)	0.0173 (4)
C13	0.5776 (2)	0.46901 (9)	0.2424 (3)	0.0187 (5)
H13	0.523468	0.461160	0.138649	0.022*
C14	0.5690 (2)	0.51605 (9)	0.3097 (3)	0.0208 (5)
C15	0.6498 (3)	0.52928 (10)	0.4587 (3)	0.0244 (5)
H15	0.642919	0.562266	0.499107	0.029*
C16	0.7414 (3)	0.49383 (10)	0.5490 (3)	0.0243 (5)
H16	0.798109	0.502105	0.651194	0.029*
S1A	0.13352 (7)	0.39460 (3)	0.95312 (8)	0.02416 (16)	0.9
O2A	−0.0128 (3)	0.38792 (11)	0.8623 (5)	0.0249 (7)	0.9
C17A	0.2226 (3)	0.38206 (13)	0.8160 (4)	0.0335 (7)	0.9
H17A	0.214127	0.345875	0.787662	0.050*	0.9
H17B	0.318415	0.390664	0.863195	0.050*	0.9
H17C	0.184208	0.402768	0.721890	0.050*	0.9
C18A	0.1618 (4)	0.46142 (14)	0.9724 (5)	0.0453 (9)	0.9
H18A	0.126943	0.477575	0.869331	0.068*	0.9
H18B	0.259115	0.468053	1.015790	0.068*	0.9
H18C	0.115059	0.475458	1.042574	0.068*	0.9
S1B	0.0823 (6)	0.4388 (2)	0.9322 (8)	0.0235 (12)	0.1
O2B	−0.024 (3)	0.3988 (13)	0.874 (6)	0.0249 (7)	0.1
C17B	0.224 (2)	0.4099 (11)	1.073 (3)	0.035 (6)*	0.1
H17D	0.252431	0.379726	1.026836	0.053*	0.1
H17E	0.198648	0.399764	1.165015	0.053*	0.1
H17F	0.299037	0.434301	1.104281	0.053*	0.1
C18B	0.150 (4)	0.4529 (15)	0.778 (3)	0.048 (8)*	0.1
H18D	0.168102	0.421089	0.730947	0.072*	0.1
H18E	0.234154	0.472179	0.819275	0.072*	0.1
H18F	0.084401	0.473284	0.697880	0.072*	0.1
S2A	0.11696 (8)	0.28805 (3)	0.26820 (8)	0.0263 (2)	0.948 (2)
O3A	0.24507 (19)	0.25919 (7)	0.2727 (2)	0.0245 (4)	0.95
C19A	0.1529 (3)	0.32357 (12)	0.4465 (4)	0.0286 (7)	0.95
H19A	0.214320	0.351728	0.444556	0.043*	0.95
H19B	0.195632	0.301184	0.535359	0.043*	0.95
H19C	0.068477	0.337256	0.457128	0.043*	0.95
C20A	0.0076 (3)	0.24245 (15)	0.3136 (6)	0.0422 (11)	0.95
H20A	−0.027573	0.219286	0.224693	0.063*	0.95
H20B	−0.067876	0.260108	0.334906	0.063*	0.95
H20C	0.058216	0.222893	0.406131	0.063*	0.95
S2B	0.0451 (16)	0.2982 (5)	0.2263 (16)	0.0263 (2)	0.052 (2)
O3B	0.165 (3)	0.2865 (13)	0.169 (4)	0.0245 (4)	0.05
C19B	0.149 (6)	0.306 (3)	0.425 (3)	0.0286 (7)	0.05
H19D	0.244796	0.302777	0.430774	0.043*	0.05
H19E	0.127063	0.279408	0.490034	0.043*	0.05
H19F	0.133444	0.339513	0.463042	0.043*	0.05
C20B	0.045 (10)	0.240 (2)	0.326 (11)	0.0422 (11)	0.05
H20D	−0.020108	0.241711	0.385397	0.063*	0.05
H20E	0.135442	0.233028	0.398604	0.063*	0.05
H20F	0.018655	0.211771	0.250113	0.063*	0.05

	U11	U22	U33	U12	U13	U23
Br1	0.02864 (16)	0.01708 (14)	0.03326 (17)	0.00539 (10)	0.00878 (11)	0.00476 (10)
O1	0.0292 (10)	0.0233 (9)	0.0252 (9)	0.0092 (7)	0.0069 (8)	0.0058 (7)
N1	0.0255 (11)	0.0263 (11)	0.0216 (10)	−0.0070 (9)	0.0111 (9)	−0.0061 (8)
C1	0.0192 (11)	0.0212 (11)	0.0186 (11)	0.0012 (9)	0.0067 (9)	0.0025 (9)
N2	0.0216 (10)	0.0247 (11)	0.0165 (9)	0.0033 (8)	−0.0002 (8)	0.0011 (8)
C2	0.0280 (14)	0.0391 (16)	0.0275 (13)	−0.0081 (12)	0.0106 (11)	−0.0137 (12)
C3	0.0325 (14)	0.0252 (13)	0.0228 (12)	−0.0088 (11)	0.0085 (11)	−0.0084 (10)
N4	0.0179 (9)	0.0202 (10)	0.0161 (9)	−0.0034 (8)	0.0054 (8)	−0.0035 (8)
C5	0.0178 (10)	0.0130 (10)	0.0179 (10)	0.0018 (8)	0.0056 (9)	0.0032 (8)
N5	0.0214 (10)	0.0218 (10)	0.0192 (10)	−0.0040 (8)	0.0074 (8)	−0.0034 (8)
C6	0.0196 (11)	0.0148 (10)	0.0188 (11)	−0.0009 (9)	0.0068 (9)	−0.0007 (8)
C7	0.0185 (11)	0.0136 (10)	0.0164 (10)	0.0000 (8)	0.0044 (9)	−0.0004 (8)
C8	0.0196 (11)	0.0144 (10)	0.0169 (11)	−0.0012 (8)	0.0054 (9)	0.0008 (8)
C8A	0.0176 (11)	0.0136 (10)	0.0192 (11)	0.0012 (8)	0.0052 (9)	0.0021 (8)
C9	0.0247 (12)	0.0192 (11)	0.0240 (12)	−0.0048 (9)	0.0073 (10)	−0.0059 (9)
N9	0.0330 (12)	0.0352 (13)	0.0300 (12)	−0.0105 (10)	0.0162 (10)	−0.0130 (10)
C10	0.0263 (13)	0.0197 (11)	0.0204 (11)	−0.0026 (10)	0.0084 (10)	−0.0031 (9)
N10	0.0312 (12)	0.0331 (13)	0.0339 (13)	−0.0126 (10)	0.0130 (10)	−0.0100 (10)
C11	0.0201 (11)	0.0202 (11)	0.0168 (11)	−0.0012 (9)	0.0025 (9)	0.0007 (9)
C12	0.0187 (11)	0.0159 (11)	0.0171 (11)	−0.0023 (8)	0.0052 (9)	−0.0025 (8)
C13	0.0205 (11)	0.0169 (11)	0.0170 (11)	−0.0019 (9)	0.0037 (9)	−0.0004 (9)
C14	0.0204 (11)	0.0170 (11)	0.0251 (12)	0.0004 (9)	0.0069 (10)	0.0029 (9)
C15	0.0307 (13)	0.0180 (11)	0.0258 (13)	−0.0031 (10)	0.0106 (11)	−0.0058 (10)
C16	0.0273 (13)	0.0243 (12)	0.0195 (11)	−0.0049 (10)	0.0046 (10)	−0.0065 (10)
S1A	0.0207 (3)	0.0278 (4)	0.0216 (3)	−0.0033 (3)	0.0030 (3)	0.0009 (3)
O2A	0.0197 (10)	0.0340 (18)	0.0191 (12)	−0.0052 (12)	0.0032 (8)	0.0003 (13)
C17A	0.0303 (16)	0.0348 (17)	0.0396 (18)	−0.0050 (13)	0.0172 (14)	0.0012 (14)
C18A	0.046 (2)	0.0296 (18)	0.064 (3)	−0.0077 (17)	0.0228 (19)	−0.0129 (17)
S1B	0.023 (3)	0.011 (3)	0.041 (3)	0.004 (2)	0.017 (3)	0.005 (2)
O2B	0.0197 (10)	0.0340 (18)	0.0191 (12)	−0.0052 (12)	0.0032 (8)	0.0003 (13)
S2A	0.0283 (4)	0.0275 (3)	0.0226 (3)	0.0065 (3)	0.0074 (3)	0.0015 (3)
O3A	0.0256 (10)	0.0235 (9)	0.0263 (10)	0.0008 (8)	0.0108 (8)	−0.0013 (7)
C19A	0.0278 (14)	0.0235 (15)	0.0378 (16)	−0.0057 (13)	0.0148 (12)	−0.0156 (12)
C20A	0.028 (2)	0.0434 (18)	0.062 (2)	−0.0157 (15)	0.023 (2)	−0.0283 (17)
S2B	0.0283 (4)	0.0275 (3)	0.0226 (3)	0.0065 (3)	0.0074 (3)	0.0015 (3)
O3B	0.0256 (10)	0.0235 (9)	0.0263 (10)	0.0008 (8)	0.0108 (8)	−0.0013 (7)
C19B	0.0278 (14)	0.0235 (15)	0.0378 (16)	−0.0057 (13)	0.0148 (12)	−0.0156 (12)
C20B	0.028 (2)	0.0434 (18)	0.062 (2)	−0.0157 (15)	0.023 (2)	−0.0283 (17)

Br1—C14	1.909 (2)	C16—H16	0.9500
O1—C1	1.229 (3)	S1A—O2A	1.497 (3)
N1—C8A	1.344 (3)	S1A—C18A	1.778 (4)
N1—C2	1.464 (3)	S1A—C17A	1.787 (3)
N1—H1	0.9000	C17A—H17A	0.9800
C1—N2	1.356 (3)	C17A—H17B	0.9800
C1—C7	1.559 (3)	C17A—H17C	0.9800
N2—C11	1.408 (3)	C18A—H18A	0.9800
N2—H2	0.8999	C18A—H18B	0.9800
C2—C3	1.523 (4)	C18A—H18C	0.9800
C2—H2A	0.9900	S1B—O2B	1.497 (4)
C2—H2B	0.9900	S1B—C18B	1.777 (5)
C3—N4	1.462 (3)	S1B—C17B	1.787 (5)
C3—H3A	0.9900	C17B—H17D	0.9800
C3—H3B	0.9900	C17B—H17E	0.9800
N4—C5	1.377 (3)	C17B—H17F	0.9800
N4—C8A	1.381 (3)	C18B—H18D	0.9800
C5—N5	1.347 (3)	C18B—H18E	0.9800
C5—C6	1.378 (3)	C18B—H18F	0.9800
N5—H5A	0.8996	S2A—O3A	1.521 (2)
N5—H5B	0.8999	S2A—C20A	1.782 (3)
C6—C9	1.412 (3)	S2A—C19A	1.790 (3)
C6—C7	1.513 (3)	C19A—H19A	0.9800
C7—C8	1.517 (3)	C19A—H19B	0.9800
C7—C12	1.523 (3)	C19A—H19C	0.9800
C8—C8A	1.369 (3)	C20A—H20A	0.9800
C8—C10	1.414 (3)	C20A—H20B	0.9800
C9—N9	1.154 (4)	C20A—H20C	0.9800
C10—N10	1.156 (4)	S2B—O3B	1.522 (4)
C11—C16	1.384 (4)	S2B—C20B	1.782 (5)
C11—C12	1.394 (3)	S2B—C19B	1.790 (4)
C12—C13	1.381 (3)	C19B—H19D	0.9800
C13—C14	1.390 (3)	C19B—H19E	0.9800
C13—H13	0.9500	C19B—H19F	0.9800
C14—C15	1.386 (4)	C20B—H20D	0.9800
C15—C16	1.397 (4)	C20B—H20E	0.9800
C15—H15	0.9500	C20B—H20F	0.9800
C8A—N1—C2	111.7 (2)	C11—C16—H16	121.1
C8A—N1—H1	124.1	C15—C16—H16	121.1
C2—N1—H1	124.2	O2A—S1A—C18A	106.15 (19)
O1—C1—N2	126.2 (2)	O2A—S1A—C17A	105.0 (2)
O1—C1—C7	125.0 (2)	C18A—S1A—C17A	98.23 (18)
N2—C1—C7	108.8 (2)	S1A—C17A—H17A	109.5
C1—N2—C11	111.5 (2)	S1A—C17A—H17B	109.5
C1—N2—H2	124.2	H17A—C17A—H17B	109.5
C11—N2—H2	124.3	S1A—C17A—H17C	109.5
N1—C2—C3	104.8 (2)	H17A—C17A—H17C	109.5
N1—C2—H2A	110.8	H17B—C17A—H17C	109.5
C3—C2—H2A	110.8	S1A—C18A—H18A	109.5
N1—C2—H2B	110.8	S1A—C18A—H18B	109.5
C3—C2—H2B	110.8	H18A—C18A—H18B	109.5
H2A—C2—H2B	108.9	S1A—C18A—H18C	109.5
N4—C3—C2	102.6 (2)	H18A—C18A—H18C	109.5
N4—C3—H3A	111.3	H18B—C18A—H18C	109.5
C2—C3—H3A	111.3	O2B—S1B—C18B	107 (2)
N4—C3—H3B	111.3	O2B—S1B—C17B	108 (2)
C2—C3—H3B	111.3	C18B—S1B—C17B	101.7 (16)
H3A—C3—H3B	109.2	S1B—C17B—H17D	109.5
C5—N4—C8A	121.9 (2)	S1B—C17B—H17E	109.5
C5—N4—C3	125.9 (2)	H17D—C17B—H17E	109.5
C8A—N4—C3	112.2 (2)	S1B—C17B—H17F	109.5
N5—C5—N4	116.1 (2)	H17D—C17B—H17F	109.5
N5—C5—C6	124.8 (2)	H17E—C17B—H17F	109.5
N4—C5—C6	119.1 (2)	S1B—C18B—H18D	109.5
C5—N5—H5A	119.8	S1B—C18B—H18E	109.5
C5—N5—H5B	120.2	H18D—C18B—H18E	109.5
H5A—N5—H5B	120.0	S1B—C18B—H18F	109.5
C5—C6—C9	120.5 (2)	H18D—C18B—H18F	109.5
C5—C6—C7	124.4 (2)	H18E—C18B—H18F	109.5
C9—C6—C7	115.1 (2)	O3A—S2A—C20A	105.94 (15)
C6—C7—C8	110.72 (19)	O3A—S2A—C19A	107.28 (13)
C6—C7—C12	112.51 (19)	C20A—S2A—C19A	96.65 (19)
C8—C7—C12	113.31 (19)	S2A—C19A—H19A	109.5
C6—C7—C1	110.56 (19)	S2A—C19A—H19B	109.5
C8—C7—C1	108.74 (19)	H19A—C19A—H19B	109.5
C12—C7—C1	100.51 (18)	S2A—C19A—H19C	109.5
C8A—C8—C10	120.4 (2)	H19A—C19A—H19C	109.5
C8A—C8—C7	121.5 (2)	H19B—C19A—H19C	109.5
C10—C8—C7	118.2 (2)	S2A—C20A—H20A	109.5
N1—C8A—C8	128.9 (2)	S2A—C20A—H20B	109.5
N1—C8A—N4	108.7 (2)	H20A—C20A—H20B	109.5
C8—C8A—N4	122.3 (2)	S2A—C20A—H20C	109.5
N9—C9—C6	174.4 (3)	H20A—C20A—H20C	109.5
N10—C10—C8	177.5 (3)	H20B—C20A—H20C	109.5
C16—C11—C12	121.8 (2)	O3B—S2B—C20B	97 (4)
C16—C11—N2	128.7 (2)	O3B—S2B—C19B	93 (3)
C12—C11—N2	109.4 (2)	C20B—S2B—C19B	72 (4)
C13—C12—C11	120.7 (2)	S2B—C19B—H19D	109.5
C13—C12—C7	129.7 (2)	S2B—C19B—H19E	109.5
C11—C12—C7	109.5 (2)	H19D—C19B—H19E	109.5
C12—C13—C14	117.1 (2)	S2B—C19B—H19F	109.5
C12—C13—H13	121.4	H19D—C19B—H19F	109.5
C14—C13—H13	121.4	H19E—C19B—H19F	109.5
C15—C14—C13	122.8 (2)	S2B—C20B—H20D	109.5
C15—C14—Br1	119.25 (19)	S2B—C20B—H20E	109.5
C13—C14—Br1	117.94 (18)	H20D—C20B—H20E	109.5
C14—C15—C16	119.6 (2)	S2B—C20B—H20F	109.5
C14—C15—H15	120.2	H20D—C20B—H20F	109.5
C16—C15—H15	120.2	H20E—C20B—H20F	109.5
C11—C16—C15	117.8 (2)
O1—C1—N2—C11	−175.7 (2)	C2—N1—C8A—C8	−178.1 (3)
C7—C1—N2—C11	5.0 (3)	C2—N1—C8A—N4	0.9 (3)
C8A—N1—C2—C3	1.0 (3)	C10—C8—C8A—N1	0.9 (4)
N1—C2—C3—N4	−2.3 (3)	C7—C8—C8A—N1	−179.2 (2)
C2—C3—N4—C5	−178.4 (2)	C10—C8—C8A—N4	−178.0 (2)
C2—C3—N4—C8A	3.0 (3)	C7—C8—C8A—N4	1.9 (3)
C8A—N4—C5—N5	−179.2 (2)	C5—N4—C8A—N1	178.8 (2)
C3—N4—C5—N5	2.4 (3)	C3—N4—C8A—N1	−2.6 (3)
C8A—N4—C5—C6	0.3 (3)	C5—N4—C8A—C8	−2.1 (3)
C3—N4—C5—C6	−178.2 (2)	C3—N4—C8A—C8	176.5 (2)
N5—C5—C6—C9	2.8 (4)	C1—N2—C11—C16	175.8 (3)
N4—C5—C6—C9	−176.6 (2)	C1—N2—C11—C12	−2.6 (3)
N5—C5—C6—C7	−178.9 (2)	C16—C11—C12—C13	−2.4 (4)
N4—C5—C6—C7	1.7 (3)	N2—C11—C12—C13	176.2 (2)
C5—C6—C7—C8	−1.8 (3)	C16—C11—C12—C7	−179.5 (2)
C9—C6—C7—C8	176.6 (2)	N2—C11—C12—C7	−1.0 (3)
C5—C6—C7—C12	126.2 (2)	C6—C7—C12—C13	−55.6 (3)
C9—C6—C7—C12	−55.4 (3)	C8—C7—C12—C13	70.9 (3)
C5—C6—C7—C1	−122.3 (2)	C1—C7—C12—C13	−173.2 (2)
C9—C6—C7—C1	56.1 (3)	C6—C7—C12—C11	121.2 (2)
O1—C1—C7—C6	56.6 (3)	C8—C7—C12—C11	−112.3 (2)
N2—C1—C7—C6	−124.1 (2)	C1—C7—C12—C11	3.6 (2)
O1—C1—C7—C8	−65.2 (3)	C11—C12—C13—C14	0.0 (4)
N2—C1—C7—C8	114.1 (2)	C7—C12—C13—C14	176.5 (2)
O1—C1—C7—C12	175.6 (2)	C12—C13—C14—C15	2.3 (4)
N2—C1—C7—C12	−5.1 (2)	C12—C13—C14—Br1	−176.74 (18)
C6—C7—C8—C8A	0.0 (3)	C13—C14—C15—C16	−2.1 (4)
C12—C7—C8—C8A	−127.5 (2)	Br1—C14—C15—C16	176.9 (2)
C1—C7—C8—C8A	121.6 (2)	C12—C11—C16—C15	2.5 (4)
C6—C7—C8—C10	179.8 (2)	N2—C11—C16—C15	−175.7 (2)
C12—C7—C8—C10	52.4 (3)	C14—C15—C16—C11	−0.3 (4)
C1—C7—C8—C10	−58.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2Ai	0.90	1.98	2.855 (4)	165
N1—H1···O2Bi	0.90	2.00	2.87 (4)	160
N2—H2···O2Aii	0.90	1.91	2.793 (5)	166
N2—H2···O2Bii	0.90	1.94	2.82 (5)	166
N5—H5A···O3Aiii	0.90	2.20	3.034 (3)	155
N5—H5B···O3A	0.90	2.06	2.918 (3)	160
C2—H2B···N9iv	0.99	2.59	3.469 (4)	148
C19A—H19A···N9	0.98	2.41	3.114 (5)	128
C19A—H19C···O1v	0.98	2.52	3.392 (4)	148
C20A—H20B···O1v	0.98	2.46	3.359 (4)	152