Crystal structure of N-(2-amino-5-cyano-4-methyl­sulfanyl-6-oxo-1,6-dihydropyrimidin-1-yl)-4-bromo­benzene­sulfonamide di­methyl­formamide monosolvate

Elgemeie, G.H.; Mohamed, R.A.; Hussein, H.A.; Jones, P.G.

doi:10.1107/S2056989015018903

research communications

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ISSN: 2056-9890

Volume 71| Part 11| November 2015| Pages 1322-1324

https://doi.org/10.1107/S2056989015018903

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Crystal structure of N-(2-amino-5-cyano-4-methylsulfanyl-6-oxo-1,6-dihydropyrimidin-1-yl)-4-bromobenzenesulfonamide dimethylformamide monosolvate

Galal H. Elgemeie,^a Reham A. Mohamed,^a Hoda A. Hussein ^b and Peter G. Jones ^c ^*

^aChemistry Department, Faculty of Science, Helwan University, Cairo, Egypt, ^bPhotochemistry Department, National Research Center, Dokki, Cairo, Egypt, and ^cInstitut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Postfach 3329, D-38023 Braunschweig, Germany
^*Correspondence e-mail: p.jones@tu-bs.de

Edited by A. J. Lough, University of Toronto, Canada (Received 18 September 2015; accepted 7 October 2015; online 14 October 2015)

The title compound, C₁₂H₁₀BrN₅O₃S₂·C₃H₇NO, displays an almost planar amine group. The interplanar angle between the rings is 31.72 (6)°. The residues are associated into ribbons parallel to [110] by three classical hydrogen bonds; one from each amine H_amine to O_DMF and one from NH_amide to O_oxo. Adjacent ribbons are connected by translation parallel to the c axis by a `weak' hydrogen bond H_methyl⋯O_sulfonyl to form a layer structure parallel to (1-10), while a further contact H_bromophenyl⋯O_sulfonyl connects the residues in the third dimension.

Keywords: crystal structure; pyrimidine; bromobenzenesulfonamide; hydrogen bonding.

CCDC reference: 1430044

1. Chemical context

We are conducting studies directed towards exploring the synthetic potential of dimethyl N-cyanoimido-S,S-dimethyl-dithiocarbonate and other ketene dithioacetals for synthesizing new classes of antimetabolites (Elgemeie & Mohamed, 2014 ; Elgemeie et al., 2007 , 2009 ). We have recently reported various successful approaches to the synthesis of mercaptopyrimidines by the reaction of this compound with active methylene functions (Elgemeie & Sood, 2001 ; Elgemeie et al., 2003 ). In an extension of this work, we describe a one-pot synthesis of N-(2-amino-5-cyano-4-(methylthio)-6-oxopyrimidin-1(6H)-yl)-4-bromobenzenesulfonamide (I) by the reaction of dimethyl N-cyanodithioiminocarbonate with N′-(4-bromophenyl)sulfonyl-2-cyanoethanehydrazide. The chemical nature was proposed on the basis of elemental analysis and spectroscopic data and its X-ray structure determination was undertaken to confirm the nature of the product. We have recently presented the structure of a related pyrimidine (Elgemeie et al., 2015 ).

2. Structural commentary

The structure of the title compound, which proved to be the dimethylformamide solvate (I)·DMF, is shown in Fig. 1. The ring systems are as expected almost planar, with r.m.s. deviations of 0.002 Å for the phenyl and 0.04 Å for the pyrimidine ring. The substituent atoms N4 and S1 deviate significantly from the pyrimidine plane [by 0.199 (2) and 0.257 (2) Å respectively, to opposite sides of the plane]. The interplanar angle is 31.72 (6)°, and is also associated with the torsion angles C12—C11—S2—N2 88.10 (12), C11—S2—N2—N1 78.98 (11) and S2—N2—N1—C2 100.31 (12)°. The amino group at N4 is almost planar, with the nitrogen atom lying just 0.035 (11) Å out of the plane of its substituents.

Figure 1
The formula unit of compound (I)·DMF in the crystal. Displacement ellipsoids correspond to 50% probability levels. The hydrogen bond H03⋯O4 is drawn as a thin dashed line.

3. Supramolecular features

The components are associated into ribbons parallel to [110] (Fig. 2) by three classical hydrogen bonds (Table 1). Two of these, H02⋯O4(1 − x, −y, 1 − z) and H03⋯O4, involve the dimethylformamide oxygen atom and lead to the formation of inversion-symmetric rings of graph set R₄²(8). The third hydrogen bond, H01⋯O1(2 − x, 1 − y, 1 − z), also forms inversion-symmetric rings, but of graph set R₂²(10).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H01⋯O1ⁱ	0.80 (2)	2.00 (2)	2.7784 (15)	165.5 (19)
N4—H02⋯O4ⁱⁱ	0.86 (2)	1.98 (2)	2.8382 (16)	177.9 (19)
N4—H03⋯O4	0.85 (2)	2.07 (2)	2.8005 (16)	143.1 (18)
C12—H12⋯O2ⁱⁱⁱ	0.95	2.46	3.4096 (18)	173
C7—H7B⋯O3^iv	0.98	2.45	3.2848 (19)	143
C17—H17⋯Br1^v	0.95	3.05	3.6686 (15)	124
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+1, -y, -z+1; (iii) -x+1, -y+1, -z+1; (iv) x, y, z+1; (v) x, y-1, z.

Figure 2
Packing diagram of compound (I)· DMF viewed perpendicular to (1 $[\overline{1}]$ 0). For clarity, only the ipso carbons of the bromophenyl groups are shown. Classical hydrogen bonds are indicated by dashed lines.

There are two short and acceptably linear C—H⋯O contacts that may be assumed to represent `weak' hydrogen bonds; H7B⋯O3 connects neighbouring ribbons by translation parallel to the c axis, thus completing a layer structure parallel to (1 $[\overline{1}]$ 0), while H12⋯O2 connects the residues in the third dimension via the inversion operator (1 − x, 1 − y, 1 − z).

The bromine atom is involved in two secondary contacts: a halogen bond of 3.4582 (10) Å with O1(2 − x, 2 − y,1 − z) and a weak hydrogen bond of 3.05 Å from H17(x, 1 + y, z), with an angle of 124° at hydrogen. These interactions also connect the residues in the third dimension.

4. Synthesis and crystallization

Dimethyl N-cyanoimido-S,S-dimethyl-dithiocarbonate (0.01 mol) was added to a stirred solution of N′-(4-bromophenyl)sulfonyl-2-cyanoethanehydrazide (0.01 mol) in dry dioxane (50 mL) containing potassium hydroxide (0.01 mol) at room temperature. The reaction mixture was stirred for 30 min at room temperature; the precipitated solid was collected by filtration and crystallized from dimethyl formamide to give pale yellow crystals, m.p. 483–485 K, yield 85%.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The NH hydrogens were refined freely. The methyl groups were refined as idealized rigid groups allowed to rotate but not tip. Other H were included using a riding model starting from calculated positions [C—H = 0.95–0.98 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms].

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₁₀BrN₅O₃S₂·C₃H₇NO
M_r	489.38
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	9.1107 (4), 9.9911 (4), 11.6498 (6)
α, β, γ (°)	96.482 (4), 107.802 (4), 99.322 (4)
V (Å³)	981.33 (8)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	2.34
Crystal size (mm)	0.45 × 0.40 × 0.40

Data collection
Diffractometer	Oxford Diffraction Xcalibur, Eos
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013 )
T_min, T_max	0.824, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	52130, 5844, 5306
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.722

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.061, 1.06
No. of reflections	5844
No. of parameters	268
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.76, −0.39
Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS97, SHELXL97 and XP in SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 1430044

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989015018903/lh5790sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015018903/lh5790Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015018903/lh5790Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

N-(2-Amino-5-cyano-4-methylsulfanyl-6-oxo-1,6-dihydropyrimidin-1-yl)-4-bromobenzenesulfonamide dimethylformamide monosolvate top

Crystal data top

C₁₂H₁₀BrN₅O₃S₂·C₃H₇NO	Z = 2
M_r = 489.38	F(000) = 496
Triclinic, P1	D_x = 1.656 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1107 (4) Å	Cell parameters from 16424 reflections
b = 9.9911 (4) Å	θ = 2.6–30.4°
c = 11.6498 (6) Å	µ = 2.34 mm⁻¹
α = 96.482 (4)°	T = 100 K
β = 107.802 (4)°	Block, colourless
γ = 99.322 (4)°	0.45 × 0.40 × 0.40 mm
V = 981.33 (8) Å³

Data collection top

Oxford Diffraction Xcalibur, Eos diffractometer	5844 independent reflections
Radiation source: Enhance (Mo) X-ray Source	5306 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 16.1419 pixels mm^-1	θ_max = 30.9°, θ_min = 2.4°
ω–scan	h = −12→13
Absorption correction: multi-scan (CrysAlisPro; Agilent, 2013)	k = −14→14
T_min = 0.824, T_max = 1.000	l = −16→16
52130 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0248P)² + 0.6489P] where P = (F_o² + 2F_c²)/3
5844 reflections	(Δ/σ)_max = 0.001
268 parameters	Δρ_max = 0.76 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Special details top

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.

Non-bonded contact:

3.4582 (0.0010) Br1 - O1_$6

Operator for generating equivalent atoms: $6 - x + 2, -y + 2, -z + 1

============================================================================

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

8.0547 (0.0765) x - 4.9253 (0.0915) y + 0.8579 (0.2093) z = 4.7396 (0.0731)

* 0.0000 (0.0001) C2 * 0.0000 (0.0001) H02 * 0.0000 (0.0000) H03 0.0352 (0.0108) N4

Rms deviation of fitted atoms = 0.0000

7.4457 (0.0028) x - 5.9260 (0.0044) y + 1.6748 (0.0062) z = 4.4689 (0.0045)

Angle to previous plane (with approximate e.s.d.) = 7.74 (1.41)

* -0.0578 (0.0009) N1 * 0.0522 (0.0009) C2 * 0.0025 (0.0009) N3 * -0.0485 (0.0010) C4 * 0.0394 (0.0010) C5 * 0.0122 (0.0009) C6 0.1986 (0.0021) N4 - 0.2565 (0.0018) S1 - 0.3373 (0.0028) C7 0.1276 (0.0023) C8 0.2186 (0.0028) N5 0.0409 (0.0018) O1 - 0.0581 (0.0020) N2

Rms deviation of fitted atoms = 0.0411

6.0229 (0.0041) x - 2.3534 (0.0057) y + 5.9679 (0.0059) z = 4.9873 (0.0043)

Angle to previous plane (with approximate e.s.d.) = 31.72 (0.06)

* -0.0028 (0.0010) C11 * 0.0004 (0.0010) C12 * 0.0025 (0.0010) C13 * -0.0031 (0.0010) C14 * 0.0007 (0.0010) C15 * 0.0023 (0.0010) C16 - 0.0142 (0.0020) Br1 0.0055 (0.0019) S2

Rms deviation of fitted atoms = 0.0022

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 (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.74640 (5)	0.49517 (4)	0.94893 (3)	0.02271 (8)
S2	0.64492 (4)	0.41433 (3)	0.34915 (3)	0.01389 (7)
Br1	0.903097 (18)	1.043895 (15)	0.333551 (15)	0.02167 (5)
N1	0.78069 (13)	0.40042 (11)	0.57992 (10)	0.0118 (2)
C2	0.70629 (16)	0.30239 (14)	0.62952 (12)	0.0132 (2)
N2	0.77711 (15)	0.36204 (12)	0.45978 (10)	0.0130 (2)
H01	0.863 (2)	0.3749 (19)	0.4545 (17)	0.020 (5)*
N3	0.69682 (14)	0.33056 (12)	0.74159 (11)	0.0151 (2)
C4	0.77293 (17)	0.45373 (14)	0.80858 (12)	0.0147 (3)
C5	0.87008 (16)	0.55054 (14)	0.77173 (12)	0.0142 (2)
C6	0.87526 (15)	0.52734 (13)	0.65034 (12)	0.0122 (2)
C7	0.6131 (2)	0.34218 (18)	0.95215 (15)	0.0254 (3)
H7A	0.5211	0.3215	0.8774	0.038*
H7B	0.5787	0.3573	1.0236	0.038*
H7C	0.6669	0.2646	0.9572	0.038*
C8	0.96232 (18)	0.67418 (15)	0.85179 (13)	0.0186 (3)
N4	0.64153 (15)	0.17814 (13)	0.56513 (12)	0.0169 (2)
H02	0.597 (2)	0.119 (2)	0.5990 (18)	0.024 (5)*
H03	0.633 (2)	0.159 (2)	0.4900 (19)	0.025 (5)*
N5	1.03702 (19)	0.77174 (15)	0.91924 (14)	0.0298 (3)
O1	0.95091 (12)	0.60446 (10)	0.60406 (9)	0.01553 (19)
O2	0.50567 (12)	0.40373 (11)	0.38292 (10)	0.0196 (2)
O3	0.64611 (14)	0.33408 (11)	0.23994 (9)	0.0215 (2)
C11	0.71531 (16)	0.58768 (14)	0.34507 (12)	0.0140 (2)
C12	0.68353 (17)	0.69127 (15)	0.41854 (13)	0.0162 (3)
H12	0.6237	0.6690	0.4703	0.019*
C13	0.74062 (17)	0.82758 (15)	0.41502 (13)	0.0175 (3)
H13	0.7206	0.8999	0.4646	0.021*
C14	0.82751 (17)	0.85737 (15)	0.33814 (13)	0.0167 (3)
C15	0.86007 (17)	0.75425 (15)	0.26524 (13)	0.0179 (3)
H15	0.9202	0.7767	0.2137	0.021*
C16	0.80332 (17)	0.61764 (15)	0.26891 (13)	0.0162 (3)
H16	0.8244	0.5454	0.2199	0.019*
N6	0.33893 (15)	0.04126 (13)	0.14664 (11)	0.0182 (2)
O4	0.50814 (13)	0.02165 (11)	0.32929 (10)	0.0198 (2)
C17	0.48080 (18)	0.04576 (14)	0.22375 (13)	0.0174 (3)
H17	0.5681	0.0692	0.1963	0.021*
C18	0.2020 (2)	0.0087 (2)	0.18574 (17)	0.0322 (4)
H18A	0.1941	−0.0837	0.2071	0.048*
H18B	0.1066	0.0117	0.1191	0.048*
H18C	0.2132	0.0762	0.2574	0.048*
C19	0.3164 (2)	0.08261 (18)	0.02765 (15)	0.0274 (3)
H19A	0.4184	0.1036	0.0146	0.041*
H19B	0.2700	0.1646	0.0248	0.041*
H19C	0.2456	0.0075	−0.0366	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0325 (2)	0.02259 (18)	0.01318 (16)	0.00060 (15)	0.01114 (15)	0.00105 (13)
S2	0.01596 (16)	0.01541 (15)	0.01050 (14)	0.00078 (12)	0.00523 (12)	0.00418 (11)
Br1	0.02029 (8)	0.01729 (7)	0.02730 (9)	0.00028 (5)	0.00798 (6)	0.00829 (6)
N1	0.0146 (5)	0.0130 (5)	0.0090 (5)	0.0013 (4)	0.0062 (4)	0.0024 (4)
C2	0.0140 (6)	0.0143 (6)	0.0120 (6)	0.0018 (5)	0.0050 (5)	0.0048 (5)
N2	0.0151 (6)	0.0159 (5)	0.0107 (5)	0.0033 (4)	0.0077 (4)	0.0034 (4)
N3	0.0178 (6)	0.0167 (5)	0.0110 (5)	0.0015 (4)	0.0058 (4)	0.0033 (4)
C4	0.0160 (6)	0.0179 (6)	0.0106 (6)	0.0041 (5)	0.0046 (5)	0.0037 (5)
C5	0.0155 (6)	0.0141 (6)	0.0124 (6)	0.0023 (5)	0.0040 (5)	0.0018 (5)
C6	0.0105 (6)	0.0124 (6)	0.0141 (6)	0.0032 (5)	0.0038 (5)	0.0034 (5)
C7	0.0280 (8)	0.0315 (8)	0.0170 (7)	−0.0022 (6)	0.0117 (6)	0.0051 (6)
C8	0.0223 (7)	0.0173 (6)	0.0167 (7)	0.0042 (5)	0.0067 (6)	0.0044 (5)
N4	0.0226 (6)	0.0150 (5)	0.0125 (6)	−0.0014 (5)	0.0075 (5)	0.0026 (4)
N5	0.0357 (8)	0.0210 (7)	0.0259 (7)	0.0004 (6)	0.0043 (6)	0.0005 (5)
O1	0.0151 (5)	0.0149 (4)	0.0189 (5)	0.0013 (4)	0.0091 (4)	0.0051 (4)
O2	0.0147 (5)	0.0246 (5)	0.0205 (5)	0.0017 (4)	0.0069 (4)	0.0091 (4)
O3	0.0318 (6)	0.0194 (5)	0.0113 (5)	−0.0003 (4)	0.0077 (4)	0.0014 (4)
C11	0.0146 (6)	0.0153 (6)	0.0132 (6)	0.0028 (5)	0.0047 (5)	0.0062 (5)
C12	0.0161 (6)	0.0194 (6)	0.0163 (6)	0.0053 (5)	0.0076 (5)	0.0075 (5)
C13	0.0175 (7)	0.0187 (7)	0.0176 (7)	0.0058 (5)	0.0061 (5)	0.0045 (5)
C14	0.0140 (6)	0.0166 (6)	0.0182 (7)	0.0012 (5)	0.0032 (5)	0.0071 (5)
C15	0.0171 (7)	0.0212 (7)	0.0179 (7)	0.0027 (5)	0.0083 (5)	0.0084 (5)
C16	0.0173 (7)	0.0199 (7)	0.0129 (6)	0.0040 (5)	0.0063 (5)	0.0051 (5)
N6	0.0199 (6)	0.0184 (6)	0.0158 (6)	0.0022 (5)	0.0054 (5)	0.0049 (5)
O4	0.0222 (5)	0.0175 (5)	0.0161 (5)	−0.0018 (4)	0.0036 (4)	0.0044 (4)
C17	0.0203 (7)	0.0134 (6)	0.0174 (7)	−0.0009 (5)	0.0071 (5)	0.0016 (5)
C18	0.0204 (8)	0.0526 (11)	0.0288 (9)	0.0110 (8)	0.0106 (7)	0.0167 (8)
C19	0.0315 (9)	0.0315 (8)	0.0177 (7)	0.0026 (7)	0.0059 (6)	0.0101 (6)

Geometric parameters (Å, º) top

S1—C4	1.7392 (14)	C15—C16	1.389 (2)
S1—C7	1.8036 (16)	N6—C17	1.320 (2)
S2—O3	1.4292 (11)	N6—C19	1.4551 (19)
S2—O2	1.4305 (11)	N6—C18	1.455 (2)
S2—N2	1.6707 (13)	O4—C17	1.2373 (18)
S2—C11	1.7580 (14)	N2—H01	0.80 (2)
Br1—C14	1.8920 (14)	C7—H7A	0.9800
N1—C2	1.3801 (16)	C7—H7B	0.9800
N1—N2	1.3979 (15)	C7—H7C	0.9800
N1—C6	1.4150 (17)	N4—H02	0.86 (2)
C2—N4	1.3167 (18)	N4—H03	0.85 (2)
C2—N3	1.3361 (17)	C12—H12	0.9500
N3—C4	1.3342 (18)	C13—H13	0.9500
C4—C5	1.3971 (19)	C15—H15	0.9500
C5—C6	1.4235 (18)	C16—H16	0.9500
C5—C8	1.4235 (19)	C17—H17	0.9500
C6—O1	1.2281 (16)	C18—H18A	0.9800
C8—N5	1.147 (2)	C18—H18B	0.9800
C11—C12	1.392 (2)	C18—H18C	0.9800
C11—C16	1.3918 (19)	C19—H19A	0.9800
C12—C13	1.387 (2)	C19—H19B	0.9800
C13—C14	1.391 (2)	C19—H19C	0.9800
C14—C15	1.388 (2)

C4—S1—C7	101.66 (7)	C17—N6—C18	119.55 (13)
O3—S2—O2	121.50 (7)	C19—N6—C18	118.46 (13)
O3—S2—N2	103.18 (6)	O4—C17—N6	124.64 (14)
O2—S2—N2	106.00 (6)	N1—N2—H01	111.8 (14)
O3—S2—C11	107.29 (6)	S2—N2—H01	113.5 (14)
O2—S2—C11	109.08 (7)	S1—C7—H7A	109.5
N2—S2—C11	109.23 (6)	S1—C7—H7B	109.5
C2—N1—N2	116.88 (11)	H7A—C7—H7B	109.5
C2—N1—C6	122.54 (11)	S1—C7—H7C	109.5
N2—N1—C6	120.02 (11)	H7A—C7—H7C	109.5
N4—C2—N3	118.74 (12)	H7B—C7—H7C	109.5
N4—C2—N1	119.66 (12)	C2—N4—H02	117.5 (13)
N3—C2—N1	121.60 (12)	C2—N4—H03	121.9 (14)
N1—N2—S2	117.24 (9)	H02—N4—H03	120.2 (19)
C4—N3—C2	117.70 (12)	C13—C12—H12	120.5
N3—C4—C5	123.85 (13)	C11—C12—H12	120.5
N3—C4—S1	117.37 (10)	C12—C13—H13	120.3
C5—C4—S1	118.77 (11)	C14—C13—H13	120.3
C4—C5—C6	119.61 (12)	C14—C15—H15	120.6
C4—C5—C8	121.71 (13)	C16—C15—H15	120.6
C6—C5—C8	118.67 (12)	C15—C16—H16	120.3
O1—C6—N1	119.46 (12)	C11—C16—H16	120.3
O1—C6—C5	126.95 (13)	O4—C17—H17	117.7
N1—C6—C5	113.59 (11)	N6—C17—H17	117.7
N5—C8—C5	177.93 (16)	N6—C18—H18A	109.5
C12—C11—C16	121.64 (13)	N6—C18—H18B	109.5
C12—C11—S2	119.54 (10)	H18A—C18—H18B	109.5
C16—C11—S2	118.82 (11)	N6—C18—H18C	109.5
C13—C12—C11	118.95 (13)	H18A—C18—H18C	109.5
C12—C13—C14	119.35 (13)	H18B—C18—H18C	109.5
C15—C14—C13	121.82 (13)	N6—C19—H19A	109.5
C15—C14—Br1	119.39 (11)	N6—C19—H19B	109.5
C13—C14—Br1	118.79 (11)	H19A—C19—H19B	109.5
C14—C15—C16	118.90 (13)	N6—C19—H19C	109.5
C15—C16—C11	119.35 (13)	H19A—C19—H19C	109.5
C17—N6—C19	121.65 (13)	H19B—C19—H19C	109.5

N2—N1—C2—N4	2.44 (19)	C4—C5—C6—O1	177.72 (13)
C6—N1—C2—N4	−168.95 (13)	C8—C5—C6—O1	−1.0 (2)
N2—N1—C2—N3	−176.97 (12)	C4—C5—C6—N1	−2.16 (18)
C6—N1—C2—N3	11.6 (2)	C8—C5—C6—N1	179.16 (12)
C2—N1—N2—S2	100.31 (12)	O3—S2—C11—C12	160.71 (11)
C6—N1—N2—S2	−88.07 (13)	O2—S2—C11—C12	27.34 (13)
O3—S2—N2—N1	−167.13 (9)	N2—S2—C11—C12	−88.10 (12)
O2—S2—N2—N1	−38.42 (11)	O3—S2—C11—C16	−19.99 (13)
C11—S2—N2—N1	78.98 (11)	O2—S2—C11—C16	−153.36 (11)
N4—C2—N3—C4	175.25 (13)	N2—S2—C11—C16	91.20 (12)
N1—C2—N3—C4	−5.3 (2)	C16—C11—C12—C13	0.3 (2)
C2—N3—C4—C5	−4.6 (2)	S2—C11—C12—C13	179.59 (11)
C2—N3—C4—S1	174.66 (10)	C11—C12—C13—C14	0.2 (2)
C7—S1—C4—N3	−0.12 (13)	C12—C13—C14—C15	−0.6 (2)
C7—S1—C4—C5	179.14 (12)	C12—C13—C14—Br1	179.51 (11)
N3—C4—C5—C6	8.4 (2)	C13—C14—C15—C16	0.4 (2)
S1—C4—C5—C6	−170.82 (10)	Br1—C14—C15—C16	−179.69 (11)
N3—C4—C5—C8	−172.98 (14)	C14—C15—C16—C11	0.1 (2)
S1—C4—C5—C8	7.81 (19)	C12—C11—C16—C15	−0.5 (2)
C2—N1—C6—O1	172.81 (12)	S2—C11—C16—C15	−179.77 (11)
N2—N1—C6—O1	1.68 (19)	C19—N6—C17—O4	174.49 (15)
C2—N1—C6—C5	−7.29 (18)	C18—N6—C17—O4	1.3 (2)
N2—N1—C6—C5	−178.42 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H01···O1ⁱ	0.80 (2)	2.00 (2)	2.7784 (15)	165.5 (19)
N4—H02···O4ⁱⁱ	0.86 (2)	1.98 (2)	2.8382 (16)	177.9 (19)
N4—H03···O4	0.85 (2)	2.07 (2)	2.8005 (16)	143.1 (18)
C12—H12···O2ⁱⁱⁱ	0.95	2.46	3.4096 (18)	173
C7—H7B···O3^iv	0.98	2.45	3.2848 (19)	143
C17—H17···Br1^v	0.95	3.05	3.6686 (15)	124

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

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