Crystal structure and Hirshfeld surface analysis of ethyl 2'-amino-5-bromo-3'-cyano-6'-methyl-2-oxo-spiro-[indoline-3,4'-pyran]-5'-carboxyl-ate.

The crystal used for structure determination contained, along with the title compound, C17H14BrN3O4, an admixture [0.0324 (11)] of its 7-bromo isomer. The 2,3-di-hydro-1H-indole ring system is nearly planar, while the conformation of the 4H-pyran ring is close to a flattened boat. The mean planes of these fragments form a dihedral angle of 86.67 (9)°. The carboxyl-ate group lies near the plane of 4H-pyran, its orientation is stabilized by an intra-molecular C-H⋯O contact. In the crystal, the mol-ecules are connected into layers by N-H⋯N and N-H⋯O hydrogen bonds. The most important contributions to the crystal packing are from H⋯H (33.1%), O⋯H/H⋯O (16.3%), N⋯H/H⋯N (12.1%), Br⋯H/H⋯Br (11.5%) and C⋯H/H⋯C (10.6%) inter-actions. © Naghiyev et al. 2022.

Chemical context

The reactions that form C—C, C—N and C—O bonds play critical roles in various applications and in different fields of chemistry (Aliyeva et al., 2011 ▸; Zubkov et al., 2018 ▸; Viswanathan et al., 2019 ▸; Duruskari et al., 2020 ▸). Nitro­gen heterocycles, especially those comprising indole fragments, are parts of various natural products and medicinal agents. This fragment constitutes the core of spiro-oxindole alkaloids, which exhibit a broad spectrum of biological activity (Edmondson et al., 1999 ▸; Ma & Hecht, 2004 ▸). The main synthetic pathway for the construction of spiro­[4H-pyran-oxindole] compounds is based on three-component reactions (Fig. 1 ▸) of two 1,3-dicarbonyl (or other active methyl­ene) compounds with isatin derivatives (Rad-Moghadam & Youseftabar-Miri, 2011 ▸).

Figure 1

The three-component synthesis of the title compound.

Thus, in the framework of our ongoing structural studies (Naghiyev, Akkurt et al., 2020 ▸; Naghiyev, Cisterna et al., 2020 ▸; Naghiyev, Tereshina et al., 2021 ▸; Naghiyev et al., 2022 ▸; Khalilov et al., 2022 ▸; Mamedov et al., 2022 ▸), we report the crystal structure and Hirshfeld surface analysis of the title compound.

Structural commentary

The crystal used for structure determination contained, along with the title compound, an admixture of its 7-bromo isomer. That is why the Br1 atom is distributed over two positions, at C5 and C7, in a 0.9676 (11):0.0324 (11) ratio, whereas the positions of other atoms of these isomers coincide with each other (Fig. 2 ▸). The 2,3-di­hydro-1H-indole ring system is nearly planar with the largest deviation from planarity being 0.048 (2) Å for C3A, while the conformation of the 4H-pyran ring is close to a flattened boat [puckering parameters (Cremer & Pople, 1975 ▸): Q T = 0.105 (2) Å, θ = 79.8 (11)° and φ = 196.9 (12)°], with the C8–C11 atoms forming the basal plane and O1 and C3 deviating from this plane by 0.063 (1) and 0.362 (2) Å, respectively. The mean planes of the 2,3-di­hydro-1H-indole system and the 4H-pyran ring are approximately perpendicular to each other, forming a dihedral angle of 86.67 (9)°. The carboxyl­ate group lies near the plane of 4H-pyran, with O3—C13—C10—C11 and O4—C13—C10—C3 torsion angles of −13.4 (3) and −8.8 (2)°, respectively. An intra­molecular C16—H16A⋯O3 contact stabilizes the conformation of the mol­ecule (Fig. 2 ▸, Table 1 ▸), generating an S(6) ring motif (Bernstein et al., 1995 ▸).

Figure 2

The mol­ecular structure of the title compound with the atom labelling and displacement ellipsoids drawn at the 50% probability level. Only the major position of Br1 [0.9676 (11)] is shown.

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 and Cg3 are the centroids of the 4H-pyran ring (O1/C3/C8-C11) and the benzene ring (C3A/C4–C7/C7A) of the 2,3-di­hydro-1H-indole ring system.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N12i	0.88 (3)	2.00 (3)	2.874 (3)	170 (2)
N8—H8A⋯O2ii	0.88 (3)	2.08 (3)	2.940 (2)	165 (3)
N8—H8B⋯O2iii	0.86 (3)	2.15 (3)	2.971 (2)	158 (2)
C16—H16A⋯O3	0.98	2.30	2.865 (3)	116
C14—H14A⋯Cg2iv	0.99	2.92	3.773 (3)	145
C15—H15B⋯Cg3	0.98	2.99	3.729 (3)	133

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

Supra­molecular features and Hirshfeld surface analysis

In the crystal, the mol­ecules are linked by N—H⋯N and N—H⋯O hydrogen bonds, forming double layers parallel to (001) (Table 1 ▸; Figs. 3 ▸–6 ▸ ▸ ▸). In addition, C—H⋯π inter­actions involving the centroids of the 4H-pyran and benzene rings link adjacent mol­ecules within these layers (Table 1 ▸; Fig. 7 ▸). The layers are joined by van der Waals inter­actions (Table 2 ▸).

Figure 3

A general view of the packing of the title compound with N—H⋯N and N—H⋯O hydrogen bonds. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity. Symmetry codes: (i) −x +  , y −  , z; (ii) −x + 1, y +  , −z +  ; (iii) −x +  , y +  , z; (iv) −x +  , y −  , z; (v) −x + 1, y −  , −z +  ; (vi) −x +  , y +  , z.

Figure 4

The packing of the title compound viewed along the a axis and showing the N—H⋯N and N—H⋯O hydrogen bonds. Only the hydrogen atoms involved in hydrogen bonding are shown.

Figure 5

The packing of the title compound viewed along the b axis and showing N—H⋯N and N—H⋯O hydrogen bonds.

Figure 6

The packing of the title compound viewed along the c axis and showing N—H⋯N and N—H⋯O hydrogen bonds.

Figure 7

A general view of the packing in the unit cell of the title compound with C—H⋯π inter­actions shown as dashed lines.

Table 2

Summary of short inter­atomic contacts (Å) in the title compound

Contact	Distance	Symmetry operation
H14B⋯Br1	3.07	−  + x,  − y, 1 − z
H6⋯Br1	3.07	+ x,  − y, 1 − z
H15A⋯Br1	2.99	1 − x, 1 − y, 1 − z
N12⋯H1	2.00	− x,  + y, z
Br1′⋯O3	2.775	1 + x, y, z
O2⋯H8A	2.08	1 − x, −  + y,  − z
N12⋯H8B	2.71	+ x, y,  − z
O2⋯H8B	2.15	− x, −  + y, z

A Hirshfeld surface analysis was performed to visualize the inter­molecular inter­actions, and the accompanying two-dimensional fingerprint plots were generated with CrystalExplorer17 (Turner et al., 2017 ▸). Fig. 8 ▸ depicts the Hirshfeld surface plotted over d norm in the range −0.5859 to 1.4054 a.u. N—H⋯N and N—H⋯O contacts appear as red spots on the Hirshfeld surface.

Figure 8

Front (a) and back (b) sides of the three-dimensional Hirshfeld surface of the title compound mapped over d norm, with a fixed colour scale of −0.5859 to 1.4054 a.u.

The full two-dimensional fingerprint plot and those delineated into the major contributions are shown in Fig. 9 ▸: the H⋯H inter­actions (33.1%) are the major factor in the crystal packing, with O⋯H/H⋯O (16.3%), N⋯H/H⋯N (12.1%), Br⋯H/H⋯Br (11.5%) and C⋯H/H⋯C (10.6%) inter­actions representing the next highest contributions. Other contributions listed in Table 3 ▸ are less than 4.0%.

Figure 9

The two-dimensional fingerprint plots of the title compound, showing (a) all inter­actions, and delineated into (b) H⋯H, (c) O⋯H/H⋯O, (d) N⋯H/H⋯N, (e) Br⋯H/H⋯Br and (f) C⋯H/H⋯C inter­actions. [d e and d i represent the distances from a point on the Hirshfeld surface to the nearest atoms outside (external) and inside (inter­nal) the surface, respectively].

Table 3

Percentage contributions of inter­atomic contacts to the Hirshfeld surface for the title compound

Contact	Percentage contribution
H⋯H	33.1
O⋯H/H⋯O	16.3
N⋯H/H⋯N	12.1
Br⋯H/H⋯Br	11.5
C⋯H/H⋯C	10.6
Br⋯O/O⋯Br	4.0
O⋯C/C⋯O	2.8
Br⋯Br	2.5
Br⋯C/C⋯Br	1.9
O⋯O	1.5
Br⋯N/N⋯Br	1.2
N⋯C/C⋯N	1.0
O⋯N/N⋯O	0.8
N⋯N	0.5
C⋯C	0.3

Database survey

A survey of the Cambridge Structural Database (CSD, Version 5.42, update of September 2021; Groom et al., 2016 ▸) using 2-amino-6-methyl-4H-pyran-3-carbo­nitrile as the main skeleton revealed the presence of three structures, CSD refcodes WIMBEC02 (I; Naghiyev, Grishina et al., 2021 ▸), HIRNUS (II; Athimoolam et al., 2007 ▸) and JEGWEX (III; Lokaj et al., 1990 ▸).

In the crystal of I, the mol­ecular conformation is maintained by an intra­molecular C—H⋯O inter­action, generating a S(6) ring motif. The mol­ecules are linked by pairs of N—H⋯O hydrogen bonds into ribbons extending along the b-axis direction and consisting of (8) and (14) rings. Between the ribbons, there are weak van der Waals contacts.

In the crystal of II, the six-membered pyran ring adopts a conformation close to a flattened boat, as in the title structure. The mol­ecules are joined by pairs of N—H⋯N hydrogen bonds into dimers, those are linked by N—H⋯O contacts to form ribbons along the a-axis direction.

In the crystal of III, the pyran ring is nearly planar. The mol­ecules are joined by pairs of N—H⋯N hydrogen bonds into centrosymmetric dimers, which are linked by N—H⋯O contacts into ribbons along the c-axis direction.

Synthesis and crystallization

The title compound was synthesized using the reported procedure (Rad-Moghadam & Youseftabar-Miri, 2011 ▸), and colourless crystals were obtained upon isothermal recrystallization from an ethanol/water (3:1) solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4 ▸. The Br1 and Br1′ atoms connected to the C5 and C7 atoms have occupancy ratios of 0.9676 (11):0.0324 (11). EXYZ and EADP instructions were used to refine the positional and displacement parameters of C5, C7 and their counterparts C5′, C7′. The H atoms of the NH and NH2 groups were located in a difference map, and their positional parameters were allowed to freely refine [N1—H1 = 0.88 (3), N8—H8A = 0.88 (3) and N8—H8B = 0.86 (3) Å], but their isotropic displacement parameters were constrained to take a value of 1.2U eq(N). All H atoms bound to C atoms were positioned geometrically and refined as riding with C—H = 0.95 (aromatic), 0.99 (methyl­ene) and 0.98 Å (meth­yl), withU iso(H) = 1.5U eq(C) for methyl H atoms and 1.2U eq(C) for all others.

Table 4

Experimental details

Crystal data
Chemical formula	C17H14BrN3O4
M r	404.22
Crystal system, space group	Orthorhombic, P b c a
Temperature (K)	100
a, b, c (Å)	9.3880 (9), 12.2260 (12), 28.693 (3)
V (Å3)	3293.3 (6)
Z	8
Radiation type	Synchrotron, λ = 0.74500 Å
μ (mm−1)	2.84
Crystal size (mm)	0.15 × 0.12 × 0.10
Data collection
Diffractometer	Rayonix SX-165 CCD
Absorption correction	Multi-scan (SCALA; Evans, 2006 ▸)
T min, T max	0.626, 0.716
No. of measured, independent and observed [I > 2σ(I)] reflections	29648, 4526, 4225
R int	0.058
(sin θ/λ)max (Å−1)	0.692
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.045, 0.091, 1.13
No. of reflections	4526
No. of parameters	248
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.79, −0.66

Computer programs: Marccd (Doyle, 2011 ▸), iMosflm (Battye et al., 2011 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL (Sheldrick, 2015b ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2020 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022008271/yk2174sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989022008271/yk2174Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989022008271/yk2174Isup3.cml

CCDC reference: 2202347

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

C17H14BrN3O4	Dx = 1.631 Mg m−3
Mr = 404.22	Synchrotron radiation, λ = 0.74500 Å
Orthorhombic, Pbca	Cell parameters from 1000 reflections
a = 9.3880 (9) Å	θ = 1.5–25.0°
b = 12.2260 (12) Å	µ = 2.84 mm−1
c = 28.693 (3) Å	T = 100 K
V = 3293.3 (6) Å3	Prism, colourless
Z = 8	0.15 × 0.12 × 0.10 mm
F(000) = 1632

Rayonix SX-165 CCD diffractometer	4225 reflections with I > 2σ(I)
/f scan	Rint = 0.058
Absorption correction: multi-scan (Scala; Evans, 2006)	θmax = 31.0°, θmin = 1.5°
Tmin = 0.626, Tmax = 0.716	h = −12→12
29648 measured reflections	k = −16→14
4526 independent reflections	l = −39→39

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.045	w = 1/[σ2(Fo2) + (0.017P)2 + 5.6891P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.091	(Δ/σ)max = 0.002
S = 1.13	Δρmax = 0.79 e Å−3
4526 reflections	Δρmin = −0.66 e Å−3
248 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0033 (5)

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	0.62887 (3)	0.85694 (2)	0.50801 (2)	0.02994 (10)	0.9676 (11)
Br1'	0.8404 (7)	0.5117 (6)	0.4176 (2)	0.025 (2)	0.0324 (11)
O1	0.18714 (16)	0.81785 (13)	0.30258 (5)	0.0224 (3)
O2	0.46032 (16)	0.57274 (12)	0.27537 (5)	0.0218 (3)
O3	0.12303 (17)	0.54444 (14)	0.39298 (6)	0.0273 (3)
O4	0.35898 (17)	0.51716 (13)	0.38771 (6)	0.0247 (3)
N1	0.62336 (19)	0.57936 (15)	0.33512 (6)	0.0221 (4)
H1	0.678 (3)	0.524 (2)	0.3268 (10)	0.026*
C2	0.5028 (2)	0.60843 (16)	0.31277 (7)	0.0187 (4)
C3	0.4272 (2)	0.69936 (16)	0.34194 (7)	0.0165 (3)
C3A	0.5230 (2)	0.70400 (16)	0.38470 (7)	0.0183 (4)
C4	0.5179 (2)	0.77196 (17)	0.42322 (7)	0.0212 (4)
H4	0.442127	0.822416	0.427551	0.025*
C5	0.6285 (2)	0.76336 (19)	0.45537 (7)	0.0248 (4)	0.9676 (11)
C5'	0.6285 (2)	0.76336 (19)	0.45537 (7)	0.0248 (4)	0.0324 (11)
H5'	0.627663	0.809277	0.482082	0.030*	0.0324 (11)
C6	0.7401 (2)	0.6898 (2)	0.44967 (8)	0.0266 (4)
H6	0.812267	0.684771	0.472782	0.032*
C7	0.7467 (2)	0.62349 (19)	0.41036 (8)	0.0254 (4)	0.9676 (11)
H7	0.822784	0.573406	0.405830	0.031*	0.9676 (11)
C7'	0.7467 (2)	0.62349 (19)	0.41036 (8)	0.0254 (4)	0.0324 (11)
C7A	0.6377 (2)	0.63345 (17)	0.37805 (7)	0.0210 (4)
C8	0.3205 (2)	0.86078 (17)	0.29895 (7)	0.0192 (4)
N8	0.3187 (2)	0.95830 (15)	0.27841 (7)	0.0223 (4)
H8A	0.396 (3)	0.987 (2)	0.2662 (10)	0.027*
H8B	0.240 (3)	0.988 (2)	0.2695 (9)	0.027*
C9	0.4361 (2)	0.80761 (16)	0.31652 (7)	0.0176 (4)
C10	0.2714 (2)	0.66972 (16)	0.34957 (7)	0.0185 (4)
C11	0.1654 (2)	0.72529 (17)	0.32916 (7)	0.0201 (4)
C12	0.5680 (2)	0.86311 (16)	0.31568 (7)	0.0206 (4)
N12	0.6748 (2)	0.90831 (17)	0.31616 (7)	0.0298 (4)
C13	0.2387 (2)	0.57211 (17)	0.37850 (7)	0.0206 (4)
C14	0.3525 (3)	0.42971 (18)	0.42180 (8)	0.0272 (5)
H14A	0.319199	0.361186	0.407002	0.033*
H14B	0.285916	0.449044	0.447248	0.033*
C15	0.5010 (3)	0.4153 (2)	0.44064 (11)	0.0428 (7)
H15A	0.501376	0.356587	0.463876	0.064*
H15B	0.532513	0.483667	0.455218	0.064*
H15C	0.565745	0.396395	0.415096	0.064*
C16	0.0088 (2)	0.7030 (2)	0.32966 (8)	0.0279 (5)
H16A	−0.007451	0.624599	0.334448	0.042*
H16B	−0.032855	0.725376	0.299839	0.042*
H16C	−0.035784	0.744306	0.355019	0.042*

	U11	U22	U33	U12	U13	U23
Br1	0.02753 (14)	0.03873 (16)	0.02357 (13)	−0.00819 (10)	−0.00248 (9)	−0.00799 (9)
Br1'	0.021 (3)	0.028 (4)	0.025 (3)	0.008 (3)	0.001 (2)	0.008 (2)
O1	0.0160 (7)	0.0240 (7)	0.0273 (7)	−0.0005 (6)	−0.0001 (6)	0.0033 (6)
O2	0.0213 (7)	0.0214 (7)	0.0228 (7)	−0.0018 (6)	0.0026 (5)	−0.0041 (5)
O3	0.0234 (8)	0.0299 (8)	0.0286 (8)	−0.0064 (6)	0.0053 (6)	0.0022 (6)
O4	0.0241 (8)	0.0206 (7)	0.0295 (8)	−0.0008 (6)	0.0050 (6)	0.0057 (6)
N1	0.0205 (8)	0.0208 (8)	0.0249 (8)	0.0054 (7)	0.0016 (7)	−0.0008 (7)
C2	0.0174 (9)	0.0164 (8)	0.0223 (9)	−0.0009 (7)	0.0039 (7)	0.0017 (7)
C3	0.0143 (8)	0.0153 (8)	0.0199 (8)	0.0001 (7)	0.0014 (7)	0.0004 (7)
C3A	0.0167 (8)	0.0178 (8)	0.0203 (9)	−0.0020 (7)	0.0005 (7)	0.0020 (7)
C4	0.0195 (9)	0.0222 (9)	0.0220 (9)	−0.0029 (8)	0.0010 (7)	−0.0007 (7)
C5	0.0231 (10)	0.0312 (11)	0.0200 (9)	−0.0065 (9)	−0.0006 (8)	−0.0013 (8)
C5'	0.0231 (10)	0.0312 (11)	0.0200 (9)	−0.0065 (9)	−0.0006 (8)	−0.0013 (8)
C6	0.0221 (10)	0.0331 (11)	0.0247 (10)	−0.0037 (9)	−0.0041 (8)	0.0053 (9)
C7	0.0190 (9)	0.0286 (10)	0.0287 (10)	0.0027 (8)	−0.0010 (8)	0.0054 (8)
C7'	0.0190 (9)	0.0286 (10)	0.0287 (10)	0.0027 (8)	−0.0010 (8)	0.0054 (8)
C7A	0.0196 (9)	0.0203 (9)	0.0232 (9)	−0.0005 (8)	0.0010 (7)	0.0028 (7)
C8	0.0182 (9)	0.0204 (9)	0.0189 (9)	−0.0007 (7)	0.0010 (7)	−0.0017 (7)
N8	0.0191 (8)	0.0221 (8)	0.0257 (9)	0.0020 (7)	−0.0005 (7)	0.0049 (7)
C9	0.0156 (8)	0.0164 (8)	0.0210 (9)	−0.0018 (7)	0.0003 (7)	−0.0006 (7)
C10	0.0174 (9)	0.0172 (8)	0.0208 (8)	−0.0027 (7)	0.0031 (7)	−0.0011 (7)
C11	0.0168 (9)	0.0217 (9)	0.0219 (9)	−0.0025 (7)	0.0024 (7)	−0.0026 (7)
C12	0.0233 (10)	0.0169 (8)	0.0216 (9)	−0.0007 (8)	−0.0019 (7)	0.0018 (7)
N12	0.0260 (10)	0.0294 (10)	0.0339 (10)	−0.0095 (8)	−0.0049 (8)	0.0070 (8)
C13	0.0225 (9)	0.0191 (9)	0.0200 (9)	−0.0032 (8)	0.0024 (7)	−0.0036 (7)
C14	0.0331 (12)	0.0201 (9)	0.0284 (10)	−0.0024 (9)	0.0039 (9)	0.0054 (8)
C15	0.0414 (15)	0.0389 (14)	0.0483 (16)	−0.0018 (12)	−0.0035 (12)	0.0206 (12)
C16	0.0160 (9)	0.0327 (11)	0.0350 (12)	−0.0029 (9)	0.0024 (8)	0.0039 (9)

Br1—C5	1.895 (2)	C6—C7	1.390 (3)
Br1'—C7'	1.639 (7)	C6—H6	0.9500
O1—C8	1.361 (2)	C7—C7A	1.386 (3)
O1—C11	1.380 (3)	C7—H7	0.9500
O2—C2	1.225 (3)	C7'—C7A	1.386 (3)
O3—C13	1.211 (3)	C8—N8	1.330 (3)
O4—C13	1.340 (3)	C8—C9	1.362 (3)
O4—C14	1.450 (3)	N8—H8A	0.88 (3)
N1—C2	1.349 (3)	N8—H8B	0.86 (3)
N1—C7A	1.404 (3)	C9—C12	1.412 (3)
N1—H1	0.88 (3)	C10—C11	1.340 (3)
C2—C3	1.562 (3)	C10—C13	1.486 (3)
C3—C9	1.513 (3)	C11—C16	1.494 (3)
C3—C3A	1.523 (3)	C12—N12	1.146 (3)
C3—C10	1.523 (3)	C14—C15	1.505 (4)
C3A—C4	1.383 (3)	C14—H14A	0.9900
C3A—C7A	1.393 (3)	C14—H14B	0.9900
C4—C5'	1.393 (3)	C15—H15A	0.9800
C4—C5	1.393 (3)	C15—H15B	0.9800
C4—H4	0.9500	C15—H15C	0.9800
C5—C6	1.390 (3)	C16—H16A	0.9800
C5'—C6	1.390 (3)	C16—H16B	0.9800
C5'—H5'	0.9500	C16—H16C	0.9800
C6—C7'	1.390 (3)
C8—O1—C11	119.65 (16)	C7—C7A—N1	128.0 (2)
C13—O4—C14	117.86 (17)	C3A—C7A—N1	109.74 (18)
C2—N1—C7A	111.92 (17)	N8—C8—O1	111.60 (18)
C2—N1—H1	124.4 (19)	N8—C8—C9	127.0 (2)
C7A—N1—H1	122.7 (18)	O1—C8—C9	121.37 (18)
O2—C2—N1	126.56 (19)	C8—N8—H8A	122.0 (19)
O2—C2—C3	125.12 (18)	C8—N8—H8B	121 (2)
N1—C2—C3	108.30 (17)	H8A—N8—H8B	115 (3)
C9—C3—C3A	108.85 (16)	C8—C9—C12	117.58 (18)
C9—C3—C10	109.30 (16)	C8—C9—C3	123.48 (18)
C3A—C3—C10	117.41 (16)	C12—C9—C3	118.49 (17)
C9—C3—C2	109.83 (15)	C11—C10—C13	119.88 (18)
C3A—C3—C2	100.96 (16)	C11—C10—C3	122.01 (18)
C10—C3—C2	110.12 (16)	C13—C10—C3	118.02 (17)
C4—C3A—C7A	120.55 (19)	C10—C11—O1	123.18 (18)
C4—C3A—C3	130.23 (19)	C10—C11—C16	129.3 (2)
C7A—C3A—C3	108.85 (17)	O1—C11—C16	107.50 (18)
C3A—C4—C5'	117.3 (2)	N12—C12—C9	178.3 (2)
C3A—C4—C5	117.3 (2)	O3—C13—O4	123.23 (19)
C3A—C4—H4	121.4	O3—C13—C10	126.9 (2)
C5—C4—H4	121.4	O4—C13—C10	109.82 (17)
C6—C5—C4	122.2 (2)	O4—C14—C15	106.84 (19)
C6—C5—Br1	118.89 (16)	O4—C14—H14A	110.4
C4—C5—Br1	118.93 (17)	C15—C14—H14A	110.4
C6—C5'—C4	122.2 (2)	O4—C14—H14B	110.4
C6—C5'—H5'	118.9	C15—C14—H14B	110.4
C4—C5'—H5'	118.9	H14A—C14—H14B	108.6
C7—C6—C5	120.4 (2)	C14—C15—H15A	109.5
C7'—C6—C5'	120.4 (2)	C14—C15—H15B	109.5
C7—C6—H6	119.8	H15A—C15—H15B	109.5
C5—C6—H6	119.8	C14—C15—H15C	109.5
C7A—C7—C6	117.3 (2)	H15A—C15—H15C	109.5
C7A—C7—H7	121.3	H15B—C15—H15C	109.5
C6—C7—H7	121.3	C11—C16—H16A	109.5
C7A—C7'—C6	117.3 (2)	C11—C16—H16B	109.5
C7A—C7'—Br1'	123.7 (3)	H16A—C16—H16B	109.5
C6—C7'—Br1'	114.0 (3)	C11—C16—H16C	109.5
C7'—C7A—C3A	122.2 (2)	H16A—C16—H16C	109.5
C7—C7A—C3A	122.2 (2)	H16B—C16—H16C	109.5
C7'—C7A—N1	128.0 (2)
C7A—N1—C2—O2	−178.0 (2)	C4—C3A—C7A—N1	−175.73 (18)
C7A—N1—C2—C3	3.9 (2)	C3—C3A—C7A—N1	−2.1 (2)
O2—C2—C3—C9	−68.0 (2)	C2—N1—C7A—C7'	179.5 (2)
N1—C2—C3—C9	110.08 (18)	C2—N1—C7A—C7	179.5 (2)
O2—C2—C3—C3A	177.15 (19)	C2—N1—C7A—C3A	−1.2 (2)
N1—C2—C3—C3A	−4.7 (2)	C11—O1—C8—N8	−170.14 (17)
O2—C2—C3—C10	52.4 (3)	C11—O1—C8—C9	7.7 (3)
N1—C2—C3—C10	−129.51 (18)	N8—C8—C9—C12	4.1 (3)
C9—C3—C3A—C4	61.3 (3)	O1—C8—C9—C12	−173.39 (18)
C10—C3—C3A—C4	−63.5 (3)	N8—C8—C9—C3	176.28 (19)
C2—C3—C3A—C4	176.8 (2)	O1—C8—C9—C3	−1.2 (3)
C9—C3—C3A—C7A	−111.51 (18)	C3A—C3—C9—C8	−136.6 (2)
C10—C3—C3A—C7A	123.70 (19)	C10—C3—C9—C8	−7.1 (3)
C2—C3—C3A—C7A	4.0 (2)	C2—C3—C9—C8	113.8 (2)
C7A—C3A—C4—C5'	−2.4 (3)	C3A—C3—C9—C12	35.6 (2)
C3—C3A—C4—C5'	−174.5 (2)	C10—C3—C9—C12	165.02 (18)
C7A—C3A—C4—C5	−2.4 (3)	C2—C3—C9—C12	−74.1 (2)
C3—C3A—C4—C5	−174.5 (2)	C9—C3—C10—C11	10.0 (3)
C3A—C4—C5—C6	−0.2 (3)	C3A—C3—C10—C11	134.6 (2)
C3A—C4—C5—Br1	178.57 (15)	C2—C3—C10—C11	−110.7 (2)
C3A—C4—C5'—C6	−0.2 (3)	C9—C3—C10—C13	−173.50 (16)
C4—C5—C6—C7	1.8 (3)	C3A—C3—C10—C13	−48.9 (2)
Br1—C5—C6—C7	−176.99 (17)	C2—C3—C10—C13	65.8 (2)
C4—C5'—C6—C7'	1.8 (3)	C13—C10—C11—O1	178.68 (18)
C5—C6—C7—C7A	−0.7 (3)	C3—C10—C11—O1	−4.9 (3)
C5'—C6—C7'—C7A	−0.7 (3)	C13—C10—C11—C16	−1.6 (3)
C5'—C6—C7'—Br1'	−156.6 (3)	C3—C10—C11—C16	174.8 (2)
C6—C7'—C7A—C3A	−2.0 (3)	C8—O1—C11—C10	−4.6 (3)
Br1'—C7'—C7A—C3A	151.5 (3)	C8—O1—C11—C16	175.58 (18)
C6—C7'—C7A—N1	177.2 (2)	C14—O4—C13—O3	−8.9 (3)
Br1'—C7'—C7A—N1	−29.3 (4)	C14—O4—C13—C10	170.02 (17)
C6—C7—C7A—C3A	−2.0 (3)	C11—C10—C13—O3	−13.4 (3)
C6—C7—C7A—N1	177.2 (2)	C3—C10—C13—O3	170.1 (2)
C4—C3A—C7A—C7'	3.6 (3)	C11—C10—C13—O4	167.81 (18)
C3—C3A—C7A—C7'	177.22 (19)	C3—C10—C13—O4	−8.8 (2)
C4—C3A—C7A—C7	3.6 (3)	C13—O4—C14—C15	−156.2 (2)
C3—C3A—C7A—C7	177.22 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N12i	0.88 (3)	2.00 (3)	2.874 (3)	170 (2)
N8—H8A···O2ii	0.88 (3)	2.08 (3)	2.940 (2)	165 (3)
N8—H8B···O2iii	0.86 (3)	2.15 (3)	2.971 (2)	158 (2)
C16—H16A···O3	0.98	2.30	2.865 (3)	116
C14—H14A···Cg2iv	0.99	2.92	3.773 (3)	145
C15—H15B···Cg3	0.98	2.99	3.729 (3)	133
C15—H15B···Cg4	0.98	2.99	3.729 (3)	133