4-(2-Meth­­oxy­phen­yl)piperazin-1-ium 6-chloro-5-iso­propyl-2,4-dioxopyrimidin-1-ide

In the cation of the title salt, C₁₁H₁₇N₂O⁺·C₇H₈ClN₂O₂⁻, the piperazine ring adopts a distorted chair conformation and contains a positively charged N atom with quaternary character. Its mean plane makes a dihedral angle of 42.36 (8)° with the phenyl ring of its 2-meth­oxy­phenyl substituent. The 2,4-dioxopyrimidin-1-ide anion is generated by deprotonation of the N atom at the 1-position of the pyrimidine­dione ring. Intra­molecular C—H⋯O hydrogen bonds generate S(6) ring motifs in both the cation and the anion. In the crystal, N—H⋯O, N—H⋯N and C—H⋯O hydrogen bonds are also observed, resulting in a two-dimensional network parallel to the ab plane. The crystal stability is further consolidated by weak C—H⋯π inter­actions.

Related literature

For the chemotherapeutic activity of pyrimidine-2,4-dione derivatives, see: Ghoshal & Jacob (1997); Spacilova et al. (2007); Blokhina et al. (1972); Tanaka et al. (1995); El-Emam et al. (2004); Al-Turkistani et al. (2011). For the acidity of pyrim­idine-2,4-dione derivatives, see: Kurinovich & Lee (2002); Jang et al. (2001); Nguyen et al. (1998). For the structures of other piperazinium salts, see: Craig et al. (2012); Dayananda et al. (2012); Fun et al. (2010). For reference bond lengths, see: Allen et al. (1987) and for hydrogen-bond motifs, see: Bernstein et al. (1995). For ring conformations and ring puckering analysis, see: Cremer & Pople (1975).

Experimental

Crystal data

• C₁₁H₁₇N₂O⁺·C₇H₈ClN₂O₂⁻

• M_r = 380.87

• Monoclinic, P 2₁ /n

• a = 8.9416 (2) Å

• b = 10.5152 (3) Å

• c = 20.5626 (5) Å

• β = 98.832 (1)°

• V = 1910.43 (8) ų

• Z = 4

• Cu Kα radiation

• μ = 1.99 mm⁻¹

• T = 296 K

• 0.81 × 0.13 × 0.05 mm

Data collection

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009) T_min = 0.296, T_max = 0.907

• 11481 measured reflections

• 3531 independent reflections

• 3204 reflections with I > 2σ(I)

• R_int = 0.033

Refinement

• R[F² > 2σ(F²)] = 0.045

• wR(F²) = 0.118

• S = 1.06

• 3531 reflections

• 251 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is centroid of the C1—C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N2⋯O2^i	0.892 (19)	1.881 (19)	2.7713 (18)	176 (2)
N2—H1N2⋯N4^ii	0.92 (2)	1.987 (19)	2.8923 (19)	166.2 (18)
N3—H1N3⋯O2^iii	0.87 (2)	2.02 (3)	2.8799 (18)	177 (2)
C8—H8B⋯O1	0.97	2.37	2.968 (2)	119
C9—H9B⋯O3^iv	0.97	2.38	3.234 (2)	146
C17—H17C⋯O3	0.96	2.38	3.015 (3)	123
C10—H10B⋯Cg2^i	0.97	2.65	3.4041 (17)	134
Symmetry codes: (i) -x+1, -y+2, -z; (ii) x, y+1, z; (iii) -x, -y+1, -z; (iv) x+1, y+1, z.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).

Supporting information

S1. Comment

Pyrimidine-2,4-diones (uracils) and their derivatives have been known from much earlier times for their diverse chemotherapeutic properties including anticancer (Ghoshal & Jacob, 1997; Spacilova et al., 2007; Blokhina et al., 1972), anti-HIV (Tanaka et al., 1995; El-Emam et al., 2004) and antibacterial activities (Al-Turkistani et al., 2011). The title piperazinium salt (I) was isolated as a minor by-product during the reaction of 6-chloro-5-isopropyluracil with 1-(2-methoxyphenyl)piperazine.

The asymmetric unit of (I) consists of a 4-(2-methoxyphenyl)piperazin-1-ium 6-chloro-5-isopropylpyrimidin-1-ide-2,4-dione cation-anion pair (Fig. 1). The 2,4-dioxopyrimidin-1-ide anion is generated by deprotonation of the N4 atom at the 1 position of the pyrimidine-dione ring (Kurinovich & Lee 2002; Jang et al., 2001; Nguyen et al., 1998). The six-membered piperazine ring (N1/C8/C9/N2/C10/C11) in the cation fragement adopts a slightly distorted chair conformation with puckering parameters: Q = 0.5774 (17) Å, θ = 177.86 (17) °, and φ = 129 (4) ° (Cremer & Pople, 1975) and contains a positively charged N atom (N2) with quaternary character. For an ideal chair configuration, θ has a value of 0 or 180°. The dihedral angle between the mean plane of the piperazine ring of the cation and the adjacent phenyl ring is 42.36 (8)°. Bond lengths (Allen et al., 1987) and angles in the title compound are within normal ranges and are comparable with those reported earlier (Craig et al. 2012; Dayananda et al., (2012); Fun et al., 2010). Intramolecular C17–H17C···O3 and C8–H8B···O1 hydrogen bonds generate S(6) ring motifs in both the cation and anion (Fig 1), while a strong intermolecular N2–H1N2···N4_pyrimidine hydrogen bond links the two moieties. In the crystal, adjacent anionic species are interconnected via N2–H2N2···O2 and N3–H1N3···O2 hydrogen bonds (Table 1) with one bifurcated O acceptor atom on the anion resulting in R₂²(9) and R₂²(8) ring motifs (Bernstein et al., 1995) respectively. The crystal structure features an intermolecular C9–H9B···O3 hydrogen bond (Fig. 2) which links the entities into a two-dimensional structure. The crystal packing is further stabilized by a weak intermolecular C10–H10B···Cg2ⁱ interaction (Table 1) involving the centroid of the C1—C6 benzene ring.

Related literature

For the chemotherapeutic activity of pyrimidine-2,4-dione derivatives, see: Ghoshal & Jacob (1997); Spacilova et al. (2007); Blokhina et al. (1972); Tanaka et al. (1995); El-Emam et al. (2004); Al-Turkistani et al. (2011). For the acidity of pyrimidine-2,4-dione derivatives, see: Kurinovich & Lee (2002); Jang et al. (2001); Nguyen et al. (1998). For the structures of other piperazinium salts, see: Craig et al. (2012); Dayananda et al. (2012); Fun et al. (2010). For reference bond lengths, see: Allen et al. (1987) and for hydrogen-bond motifs, see: Bernstein et al. (1995). For ring conformations and ring puckering analysis, see: Cremer & Pople (1975).

S2. Experimental

A mixture of 6-chloro-5-isopropyluracil (377 mg, 2.0 mmol), 1-(2-methoxyphenyl) piperazine (385 mg, 2.0 mmol) and anhydrous potassium carbonate (276 mg, 2.0 mmol), in ethanol (8 ml), was heated under reflux for 6 h. On cooling, the precipitate, thus formed was separated by filtration to yield 627 mg (91%) of 6-[4-(2-methoxyphenyl)-1-piperazinyl)]-5-isopropyluracil. The filtrate was concentrated by vacuum distillation to 5 ml and allowed to stand at room temperature overnight to yield 46 mg (6%) of the title salt (C₁₈H₂₅ClN₄O₃) as colourless plate-shaped crystals. M·P.: 517–519 K.

¹H NMR (DMSO-d₆, 500.13 MHz): δ 1.13 (d, 6H, CH₃, J = 7.2 Hz), 2.53–2.56 (m, 1H, CH), 3.22–3.24 (m, 4H, Piperazine-H), 3.77 (s, 3H, OCH₃), 3.42–3.45 (m, 4H, Piperazine-H), 6.78–7.02 (m, 4H, Ar—H), 8.02–8.14 (m, 2H, NH₂), 10.88 (s, 1H, NH). ¹³C (DMSO-d₆, 125.76 MHz): δ 19.50 (CH₃), 26.90 (CH), 46.12, 49.86 (Piperazine-C), 56.80 (OCH3), 113.86, 119.12, 122.02, 122.98, 141.70, 148.28 (Ar—C), 123.90, 158.98, 162.82 (Pyrimidine-C),

S3. Refinement

The nitrogen-bound H-atoms were located in a difference Fourier map and were refined freely. Other H atoms were positioned geometrically (C=H 0.93–0.98 Å) and refined using a riding model with U_iso(H) = 1.2 U_eq(C) or 1.5 U_eq(C) for methyl H atoms. A rotating group model was used for the methyl group.

Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of the title compound with atom labels and 50% probability displacement ellipsoids. Intramolecular hydrogen bonds are drawn as dashed lines.
	Fig. 2. Crystal packing of the title compound, showing the hydrogen bonding interactions as dashed lines. H-atoms not involved in the hydrogen bonding are omited for clarity.

4-(2-Methoxyphenyl)piperazin-1-ium 6-chloro-5-isopropyl-2,4-dioxopyrimidin-1-ide

Crystal data

C11H17N2O^+·C7H8ClN2O2^−	F(000) = 808
Mr = 380.87	Dx = 1.324 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 3769 reflections
a = 8.9416 (2) Å	θ = 4.2–69.6°
b = 10.5152 (3) Å	µ = 1.99 mm^−1
c = 20.5626 (5) Å	T = 296 K
β = 98.832 (1)°	Plate, colourless
V = 1910.43 (8) Å^3	0.81 × 0.13 × 0.05 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	3531 independent reflections
Radiation source: fine-focus sealed tube	3204 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
φ and ω scans	θmax = 69.8°, θmin = 4.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.296, Tmax = 0.907	k = −12→9
11481 measured reflections	l = −24→24

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.118	w = 1/[σ^2(Fo^2) + (0.0615P)^2 + 0.5789P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
3531 reflections	Δρmax = 0.33 e Å^−3
251 parameters	Δρmin = −0.32 e Å^−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0081 (5)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cl1	0.50958 (5)	0.52933 (5)	0.21770 (2)	0.05543 (19)
O2	0.20219 (13)	0.51968 (11)	0.00176 (5)	0.0368 (3)
N4	0.34035 (14)	0.51859 (13)	0.10447 (7)	0.0340 (3)
C14	0.20877 (17)	0.51323 (14)	0.06313 (7)	0.0300 (3)
N3	0.07667 (15)	0.50064 (14)	0.08862 (7)	0.0347 (3)
C15	0.0644 (2)	0.49113 (17)	0.15482 (8)	0.0387 (4)
O3	−0.06114 (16)	0.47528 (17)	0.17059 (7)	0.0623 (4)
C12	0.33057 (18)	0.51541 (15)	0.16938 (8)	0.0347 (3)
C13	0.2058 (2)	0.50286 (16)	0.19945 (8)	0.0370 (4)
C16	0.2061 (2)	0.49421 (19)	0.27315 (9)	0.0478 (4)
H16A	0.3083	0.5163	0.2947	0.057*
C17	0.0969 (3)	0.5878 (2)	0.29765 (10)	0.0591 (5)
H17A	0.1235	0.6729	0.2871	0.089*
H17B	0.1029	0.5796	0.3445	0.089*
H17C	−0.0044	0.5697	0.2768	0.089*
C18	0.1753 (4)	0.3582 (2)	0.29280 (12)	0.0783 (8)
H18A	0.2574	0.3045	0.2849	0.118*
H18B	0.0829	0.3287	0.2672	0.118*
H18C	0.1661	0.3556	0.3387	0.118*
O1	0.73479 (17)	0.92628 (13)	0.14090 (7)	0.0524 (3)
N2	0.57634 (15)	1.36876 (13)	0.05996 (7)	0.0347 (3)
N1	0.66629 (14)	1.10889 (13)	0.04804 (6)	0.0343 (3)
C11	0.59845 (18)	1.18107 (15)	−0.00956 (8)	0.0359 (3)
H11A	0.5429	1.1240	−0.0416	0.043*
H11B	0.6774	1.2216	−0.0297	0.043*
C5	0.79466 (19)	0.97928 (16)	−0.02689 (9)	0.0393 (4)
H5A	0.7690	1.0388	−0.0602	0.047*
C10	0.49247 (17)	1.28106 (16)	0.01019 (9)	0.0384 (4)
H10A	0.4484	1.3291	−0.0283	0.046*
H10B	0.4109	1.2403	0.0285	0.046*
C8	0.75164 (18)	1.19407 (16)	0.09704 (8)	0.0375 (4)
H8A	0.8336	1.2332	0.0784	0.045*
H8B	0.7956	1.1449	0.1351	0.045*
C3	0.9169 (2)	0.78466 (17)	0.00959 (10)	0.0485 (5)
H3A	0.9744	0.7141	0.0018	0.058*
C1	0.78835 (18)	0.90656 (16)	0.08317 (9)	0.0395 (4)
C9	0.65130 (19)	1.29640 (16)	0.11833 (8)	0.0374 (4)
H9A	0.5750	1.2581	0.1409	0.045*
H9B	0.7114	1.3539	0.1487	0.045*
C4	0.87617 (19)	0.87161 (18)	−0.03948 (10)	0.0457 (4)
H4A	0.9028	0.8588	−0.0810	0.055*
C6	0.75084 (17)	0.99994 (15)	0.03383 (8)	0.0344 (3)
C2	0.8731 (2)	0.80127 (17)	0.07064 (10)	0.0473 (4)
H2A	0.9005	0.7414	0.1036	0.057*
C7	0.7453 (3)	0.8242 (2)	0.18654 (11)	0.0666 (6)
H7A	0.6991	0.8485	0.2238	0.100*
H7B	0.8499	0.8039	0.2008	0.100*
H7C	0.6942	0.7511	0.1658	0.100*
H2N2	0.646 (2)	1.408 (2)	0.0405 (10)	0.040 (5)*
H1N2	0.511 (2)	1.428 (2)	0.0733 (10)	0.043 (5)*
H1N3	−0.006 (3)	0.4964 (19)	0.0606 (11)	0.042 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0362 (3)	0.0756 (4)	0.0511 (3)	0.0075 (2)	−0.00393 (18)	−0.0107 (2)
O2	0.0322 (5)	0.0468 (7)	0.0329 (6)	−0.0035 (5)	0.0101 (4)	0.0021 (4)
N4	0.0269 (6)	0.0386 (7)	0.0378 (7)	0.0026 (5)	0.0087 (5)	−0.0008 (5)
C14	0.0288 (7)	0.0278 (7)	0.0351 (8)	0.0002 (5)	0.0105 (6)	0.0000 (5)
N3	0.0263 (7)	0.0453 (8)	0.0335 (7)	−0.0026 (5)	0.0077 (6)	−0.0013 (5)
C15	0.0376 (8)	0.0440 (9)	0.0371 (9)	−0.0034 (7)	0.0142 (7)	−0.0024 (7)
O3	0.0402 (7)	0.1034 (12)	0.0476 (8)	−0.0184 (7)	0.0209 (6)	−0.0075 (7)
C12	0.0319 (8)	0.0338 (8)	0.0379 (8)	0.0042 (6)	0.0038 (6)	−0.0034 (6)
C13	0.0396 (9)	0.0373 (8)	0.0353 (8)	0.0021 (6)	0.0098 (7)	−0.0021 (6)
C16	0.0551 (11)	0.0542 (11)	0.0350 (9)	0.0060 (9)	0.0101 (8)	−0.0027 (7)
C17	0.0753 (14)	0.0635 (13)	0.0417 (10)	0.0122 (11)	0.0194 (9)	−0.0062 (9)
C18	0.130 (2)	0.0601 (14)	0.0516 (12)	0.0141 (15)	0.0340 (14)	0.0112 (10)
O1	0.0662 (8)	0.0449 (7)	0.0478 (7)	0.0088 (6)	0.0147 (6)	0.0087 (6)
N2	0.0304 (6)	0.0304 (7)	0.0467 (8)	0.0003 (5)	0.0164 (6)	0.0005 (5)
N1	0.0326 (6)	0.0310 (7)	0.0383 (7)	0.0024 (5)	0.0029 (5)	−0.0018 (5)
C11	0.0347 (7)	0.0346 (8)	0.0379 (8)	0.0010 (6)	0.0037 (6)	−0.0005 (6)
C5	0.0348 (8)	0.0388 (9)	0.0442 (9)	−0.0001 (6)	0.0054 (7)	−0.0022 (7)
C10	0.0315 (8)	0.0360 (8)	0.0472 (9)	0.0024 (6)	0.0044 (7)	0.0029 (7)
C8	0.0348 (8)	0.0355 (8)	0.0410 (8)	0.0023 (6)	0.0019 (6)	−0.0025 (6)
C3	0.0374 (8)	0.0347 (9)	0.0734 (13)	0.0048 (7)	0.0090 (8)	−0.0090 (8)
C1	0.0364 (8)	0.0345 (8)	0.0464 (9)	−0.0008 (7)	0.0025 (7)	−0.0001 (7)
C9	0.0387 (8)	0.0359 (8)	0.0391 (8)	−0.0022 (7)	0.0107 (7)	−0.0021 (6)
C4	0.0378 (8)	0.0449 (10)	0.0558 (11)	0.0000 (7)	0.0112 (8)	−0.0123 (8)
C6	0.0278 (7)	0.0297 (8)	0.0449 (9)	−0.0005 (6)	0.0034 (6)	−0.0025 (6)
C2	0.0440 (9)	0.0333 (9)	0.0627 (11)	0.0052 (7)	0.0020 (8)	0.0044 (8)
C7	0.0879 (16)	0.0568 (13)	0.0546 (12)	−0.0033 (12)	0.0087 (11)	0.0155 (10)

Geometric parameters (Å, º)

Cl1—C12	1.7557 (17)	N1—C6	1.427 (2)
O2—C14	1.2561 (19)	N1—C11	1.458 (2)
N4—C14	1.343 (2)	N1—C8	1.471 (2)
N4—C12	1.351 (2)	C11—C10	1.512 (2)
C14—N3	1.3702 (19)	C11—H11A	0.9700
N3—C15	1.386 (2)	C11—H11B	0.9700
N3—H1N3	0.86 (3)	C5—C6	1.382 (2)
C15—O3	1.226 (2)	C5—C4	1.392 (2)
C15—C13	1.449 (3)	C5—H5A	0.9300
C12—C13	1.362 (2)	C10—H10A	0.9700
C13—C16	1.518 (2)	C10—H10B	0.9700
C16—C18	1.523 (3)	C8—C9	1.508 (2)
C16—C17	1.526 (3)	C8—H8A	0.9700
C16—H16A	0.9800	C8—H8B	0.9700
C17—H17A	0.9600	C3—C4	1.369 (3)
C17—H17B	0.9600	C3—C2	1.383 (3)
C17—H17C	0.9600	C3—H3A	0.9300
C18—H18A	0.9600	C1—C2	1.388 (2)
C18—H18B	0.9600	C1—C6	1.415 (2)
C18—H18C	0.9600	C9—H9A	0.9700
O1—C1	1.362 (2)	C9—H9B	0.9700
O1—C7	1.419 (2)	C4—H4A	0.9300
N2—C9	1.491 (2)	C2—H2A	0.9300
N2—C10	1.491 (2)	C7—H7A	0.9600
N2—H2N2	0.89 (2)	C7—H7B	0.9600
N2—H1N2	0.93 (2)	C7—H7C	0.9600
C14—N4—C12	116.17 (13)	C10—C11—H11A	109.6
O2—C14—N4	122.35 (13)	N1—C11—H11B	109.6
O2—C14—N3	118.64 (14)	C10—C11—H11B	109.6
N4—C14—N3	119.00 (14)	H11A—C11—H11B	108.2
C14—N3—C15	125.85 (15)	C6—C5—C4	121.67 (17)
C14—N3—H1N3	116.7 (14)	C6—C5—H5A	119.2
C15—N3—H1N3	117.5 (14)	C4—C5—H5A	119.2
O3—C15—N3	118.90 (17)	N2—C10—C11	110.14 (13)
O3—C15—C13	126.11 (16)	N2—C10—H10A	109.6
N3—C15—C13	114.99 (14)	C11—C10—H10A	109.6
N4—C12—C13	129.23 (16)	N2—C10—H10B	109.6
N4—C12—Cl1	111.43 (12)	C11—C10—H10B	109.6
C13—C12—Cl1	119.34 (13)	H10A—C10—H10B	108.1
C12—C13—C15	114.63 (15)	N1—C8—C9	111.34 (13)
C12—C13—C16	125.66 (17)	N1—C8—H8A	109.4
C15—C13—C16	119.64 (15)	C9—C8—H8A	109.4
C13—C16—C18	110.40 (16)	N1—C8—H8B	109.4
C13—C16—C17	112.83 (16)	C9—C8—H8B	109.4
C18—C16—C17	111.53 (18)	H8A—C8—H8B	108.0
C13—C16—H16A	107.3	C4—C3—C2	120.27 (16)
C18—C16—H16A	107.3	C4—C3—H3A	119.9
C17—C16—H16A	107.3	C2—C3—H3A	119.9
C16—C17—H17A	109.5	O1—C1—C2	123.92 (16)
C16—C17—H17B	109.5	O1—C1—C6	116.29 (15)
H17A—C17—H17B	109.5	C2—C1—C6	119.78 (16)
C16—C17—H17C	109.5	N2—C9—C8	110.15 (13)
H17A—C17—H17C	109.5	N2—C9—H9A	109.6
H17B—C17—H17C	109.5	C8—C9—H9A	109.6
C16—C18—H18A	109.5	N2—C9—H9B	109.6
C16—C18—H18B	109.5	C8—C9—H9B	109.6
H18A—C18—H18B	109.5	H9A—C9—H9B	108.1
C16—C18—H18C	109.5	C3—C4—C5	119.60 (17)
H18A—C18—H18C	109.5	C3—C4—H4A	120.2
H18B—C18—H18C	109.5	C5—C4—H4A	120.2
C1—O1—C7	117.67 (16)	C5—C6—C1	118.03 (15)
C9—N2—C10	110.69 (13)	C5—C6—N1	122.93 (15)
C9—N2—H2N2	109.9 (13)	C1—C6—N1	119.01 (15)
C10—N2—H2N2	106.8 (13)	C3—C2—C1	120.56 (18)
C9—N2—H1N2	109.4 (13)	C3—C2—H2A	119.7
C10—N2—H1N2	110.2 (13)	C1—C2—H2A	119.7
H2N2—N2—H1N2	109.8 (18)	O1—C7—H7A	109.5
C6—N1—C11	114.77 (13)	O1—C7—H7B	109.5
C6—N1—C8	113.17 (12)	H7A—C7—H7B	109.5
C11—N1—C8	110.29 (13)	O1—C7—H7C	109.5
N1—C11—C10	110.09 (13)	H7A—C7—H7C	109.5
N1—C11—H11A	109.6	H7B—C7—H7C	109.5
C12—N4—C14—O2	177.57 (14)	N1—C11—C10—N2	58.83 (17)
C12—N4—C14—N3	−2.2 (2)	C6—N1—C8—C9	−171.18 (13)
O2—C14—N3—C15	179.40 (15)	C11—N1—C8—C9	58.72 (17)
N4—C14—N3—C15	−0.8 (2)	C7—O1—C1—C2	−10.5 (3)
C14—N3—C15—O3	−177.21 (17)	C7—O1—C1—C6	168.37 (18)
C14—N3—C15—C13	3.5 (2)	C10—N2—C9—C8	55.06 (16)
C14—N4—C12—C13	2.6 (2)	N1—C8—C9—N2	−56.08 (18)
C14—N4—C12—Cl1	−177.68 (11)	C2—C3—C4—C5	2.2 (3)
N4—C12—C13—C15	0.1 (3)	C6—C5—C4—C3	−1.3 (3)
Cl1—C12—C13—C15	−179.54 (12)	C4—C5—C6—C1	−1.4 (2)
N4—C12—C13—C16	177.04 (17)	C4—C5—C6—N1	−179.53 (15)
Cl1—C12—C13—C16	−2.6 (2)	O1—C1—C6—C5	−175.88 (15)
O3—C15—C13—C12	177.77 (18)	C2—C1—C6—C5	3.0 (2)
N3—C15—C13—C12	−3.0 (2)	O1—C1—C6—N1	2.4 (2)
O3—C15—C13—C16	0.7 (3)	C2—C1—C6—N1	−178.73 (15)
N3—C15—C13—C16	179.89 (15)	C11—N1—C6—C5	14.0 (2)
C12—C13—C16—C18	−105.4 (2)	C8—N1—C6—C5	−113.80 (17)
C15—C13—C16—C18	71.4 (2)	C11—N1—C6—C1	−164.14 (14)
C12—C13—C16—C17	129.0 (2)	C8—N1—C6—C1	68.06 (18)
C15—C13—C16—C17	−54.2 (2)	C4—C3—C2—C1	−0.5 (3)
C6—N1—C11—C10	171.16 (13)	O1—C1—C2—C3	176.69 (17)
C8—N1—C11—C10	−59.59 (16)	C6—C1—C2—C3	−2.1 (3)
C9—N2—C10—C11	−56.62 (16)

Hydrogen-bond geometry (Å, º)

Cg2 is centroid of the C1—C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N2···O2^i	0.892 (19)	1.881 (19)	2.7713 (18)	176 (2)
N2—H1N2···N4^ii	0.92 (2)	1.987 (19)	2.8923 (19)	166.2 (18)
N3—H1N3···O2^iii	0.87 (2)	2.02 (3)	2.8799 (18)	177 (2)
C8—H8B···O1	0.97	2.37	2.968 (2)	119
C9—H9B···O3^iv	0.97	2.38	3.234 (2)	146
C17—H17C···O3	0.96	2.38	3.015 (3)	123
C10—H10B···Cg2^i	0.97	2.65	3.4041 (17)	134

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

 

Footnotes

‡Additional correspondence author, e-mail: [e-mail].

§Thomson Reuters ResearcherID: C-3194-2011.

¶Thomson Reuters ResearcherID: A-3561-2009.