Supra­molecular patterns in benzyl­adeninium p-toluene­sulfonate

In the title compound (systematic name: 6-benzylamino-7H-purin-3-ium p-toluene­sulfonate), C₁₂H₁₂N₅⁺·C₇H₇O₃S⁻, the adenine moiety exists as the N³-protonated N⁷—H tautomer. The dihedral angle between the adenine ring system and the phenyl ring is 82.76 (11)°. Two of the sulfonate O atoms form C—H...O and N—H...O hydrogen bonds with the H atoms on the N and C atoms in the 3- and 8-positions, respectively, of the adenine moiety, leading to a zigzag chain. Two anti­parallel zigzag chains are linked by the remaining sulfonate O atom through Hoogsteen-site H atoms (i.e. those on the N atoms in the 6- and 7-positions) of the adenine moiety, leading to a double chain. An annulus formed by a pair of inversion-related anions and cations has been identified. An intra­molecular toluene­sulfonate–phenyl C—H...π inter­action is also present.

S1. Comment

N⁶-Substituted aminopurine compounds such as N⁶-furfuryladenine (FA), N⁶-benzyladenine (BA) and trans-zeatin are plant hormones classified under the name of cytokinins. They are responsible for proliferation, growth regulation, antioxidance, mutation, enzyme inhibition etc. in plant cells (Francis & Sorrell, 2001). The cyclin-dependent kinases (CDK) are important functional enzymes controlled by cytokinins during apoptosis, neuronal stimulations and transcription. These kinases are influenced particularly by 2,9-substituted cytokinins (Trávníček & Kryštof, 2004). BA enhances the apical dominance, flowering and sometimes causes heterogeneity and inhibition of rooting and growth (Trávníček et al., 2004). BA derivatives are used in neurological, antitumour and parasitic treatments (Bressi et al., 2000; Haung et al., 2007). Some of the bimetallic BA compounds mimic superoxide dismutase (SOD) and have antidiabetic activity (Dvorák et al., 2010).

The asymmetric unit of the title compound, (I), consists of one benzyladeninium cation (BAH⁺) and one toluenesulfonate anion (Fig. 1, Table 1). BAH⁺ exists as the N3-protonated N7—H tautomer as reported earlier (Umadevi et al., 2001; Nirmalram et al., 2011; Balasubramanian et al., 1996), in contrast to adenine systems where the N9—H tautomer predominates and the protonation site is N1 (Ślósarek et al., 2006). The N3 protonation of the base is confirmed from the C2—N3—C4 bond angle of 116.9 (2)°, which is wider than the value of 110.7 (2)° in neutral BA (Raghunathan et al., 1983). The dihedral angle between the benzyl substituent and the adenine ring system is 82.76 (11)°. The free N1 position, the dihedral angle of ca 80° and the distal orientation of the N6 substituent with respect to N7 are important requisites for cytokinin activity, and these features also occur in the title crystal structure.

The crystal structure of (I) comprises a three-dimensional network of N—H···O, C—H···O, C—H···π and π–π interactions which gives rise to the following supramolecular patterns. In the toluenesulfonate anion, all sulfonate O atoms act as hydrogen-bond acceptors: one (O3) forms an N—H···O hydrogen bond with the protonated N3 hydrogen of a BAH⁺ cation; O2 forms a C—H···O hydrogen bond with the acidic C8 hydrogen of adjacent BAH⁺, leading to a zigzag supramolecular chain of graph-set notation C₂²(9) (Fig. 2). This chain is crosslinked with an antiparallel one: the remaining oxygen of the sulfonate (O1) forms N—H···O hydrogen bonds to the Hoogsteen-site H atoms of adenine (N6—H and N7—H), forming a double chain (Fig. 3) and an R₂¹(7) motif. This motif has been recently identified in cobalt complexes of the N6-furfuryladenine cation and N6-benzyladenine cation (Tamilselvi & Muthiah, 2010).

Because of the interplay of double chains, two inversion-related BAH⁺ cations and two inversion-related sulfonate anions a supramolecular annulus (Fig. 4) is formed. In this annulus the inversion-related purine rings (N1, C2, N3, C4, C5, C6, N7, C8 and N9) and [N1ⁱ–N9ⁱ; symmetry code: (i) -x+1, -y, -z+1] adopt an antiparallel stacking arrangment through face-to-face (π–π) interaction with the corresponding Cg···Cg distance of 3.377 (s.u.??) Å. The interplanar distance between stacked purine rings is 3.330 (s.u.??) Å. These values are well within the range reported earlier (Garcia-Teran et al., 2004; [##AUTHOR: Add reference to list] Verma et al., 2010). Two annuli are connected by an R₄⁴(14) motif. An edge-to-face (C—H···π) interaction is observed between C18—H18 of the toluenesulfonate and the C11–C16 phenyl ring of BAH⁺, with a H18···Cg distance of 2.86 Å and an C18—H18···Cg angle of 162° (Wang et al., 2007). The double chains are linked by a π–π stacking interaction between the toluenesulfonate phenyl ring and the pyrimidine ring with a Cg···Cg distance of 3.6127 (15) Å (Verma et al., 2010). [##AUTHOR: Are "Verma et al., 2009" and "Verma et al., 2010" different references, or is this a simple mistake?]

Related literature

For related literature, see: Tamilselvi & Muthiah (2010); Balasubramanian et al. (1996); Bressi et al. (2000); Dvorák et al. (2010); Haung et al. (2007); Nirmalram et al. (2011); Raghunathan et al. (1983); Trávníček & Kryštof (2004); Trávníček et al. (2004); Umadevi et al. (2001); Verma et al. (2010); Wang et al. (2007).

S2. Experimental

N⁶-Benzyladenine (56.3 mg, 0.25 mmol) was dissolved in methanol (20 ml). p-Toluenesulfonic acid (47.4 mg, 0.25 mmol) was dissolved in ethanol (20 ml). The solutions were mixed and heated for 30 min over a water bath. Colourless, needle-shaped crystals of (I) appeared after a few days of evaporation at room temperature.

S3. Refinement

##AUTHOR: Please check rewording. Methyl H atoms were located in a difference Fourier synthesis and subsequently idealized and refined as a rigid rotating group, with C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C). Other C-bonded H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 (aromatic) and 0.97Å (methylene), and with U_iso(H) = 1.2U_eq(C). All N-bonded H atoms were placed in idealized positions and constrained to ride 0.86 Å from their parent atoms, with U_iso(H) = 1.2U_eq(N).

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. A view of the components of (I), with ellipsoids drawn at the 50% probability level.
	Fig. 2. A view of the structure of (I), showing the double chains formed by two C2^2(9) chains. H atoms not involved in hydrogen bonding have been omitted for clarity.
	Fig. 3. A view of a double chain illustrating the R4^4(14) motif and C—H···π interaction.
	Fig. 4. A view of one annulus showing the antiparallel stacking of purine moieties. ##AUTHOR: Please check slightly changed Figure captions. Having the Scheme in the same orientation as Figure 1 would be beneficial.

6-benzylamino-7H-purin-3-ium p-toluenesulfonate

Crystal data

C12H12N5^+·C7H7O3S^−	Z = 2
Mr = 397.46	F(000) = 416
Triclinic, P1	Dx = 1.401 Mg m^−3 Dm = 1.40 Mg m^−3 Dm measured by ?
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5741 (10) Å	Cell parameters from 6129 reflections
b = 9.9089 (11) Å	θ = 1.8–32.6°
c = 11.3324 (12) Å	µ = 0.20 mm^−1
α = 99.957 (6)°	T = 296 K
β = 90.886 (7)°	Needle, colourless
γ = 116.562 (6)°	0.12 × 0.10 × 0.08 mm
V = 941.87 (18) Å^3

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	6129 independent reflections
Radiation source: fine-focus sealed tube	3345 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.063
ϕ and ω scans	θmax = 32.6°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→14
Tmin = 0.976, Tmax = 0.984	k = −14→14
17454 measured reflections	l = −16→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.210	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.1215P)^2] where P = (Fo^2 + 2Fc^2)/3
6129 reflections	(Δ/σ)max < 0.001
254 parameters	Δρmax = 0.65 e Å^−3
0 restraints	Δρmin = −0.65 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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

	x	y	z	Uiso*/Ueq
N1	0.2288 (2)	−0.0368 (2)	0.42733 (18)	0.0461 (6)
N3	0.3802 (2)	−0.1331 (2)	0.31236 (17)	0.0454 (6)
N6	0.3323 (2)	0.2193 (2)	0.52475 (16)	0.0435 (5)
N7	0.63621 (19)	0.2555 (2)	0.40766 (16)	0.0418 (5)
N9	0.6483 (2)	0.0534 (2)	0.29301 (17)	0.0487 (6)
C2	0.2491 (3)	−0.1469 (3)	0.3612 (2)	0.0498 (7)
C4	0.5046 (2)	0.0095 (2)	0.33370 (18)	0.0383 (6)
C5	0.4926 (2)	0.1308 (2)	0.40451 (17)	0.0365 (6)
C6	0.3506 (2)	0.1085 (2)	0.45389 (17)	0.0370 (6)
C8	0.7234 (3)	0.2026 (3)	0.3408 (2)	0.0485 (7)
C10	0.1829 (2)	0.1985 (3)	0.5686 (2)	0.0533 (7)
C11	0.2069 (2)	0.2994 (2)	0.69131 (19)	0.0420 (6)
C12	0.2777 (3)	0.2814 (3)	0.7901 (2)	0.0551 (8)
C13	0.2901 (3)	0.3676 (4)	0.9033 (2)	0.0677 (10)
C14	0.2287 (4)	0.4700 (3)	0.9185 (3)	0.0678 (10)
C15	0.1586 (3)	0.4889 (3)	0.8214 (2)	0.0605 (9)
C16	0.1493 (3)	0.4058 (3)	0.7077 (2)	0.0482 (7)
S1	0.75070 (6)	0.54293 (6)	0.68482 (5)	0.0417 (2)
O1	0.64140 (19)	0.49619 (18)	0.57668 (14)	0.0533 (5)
O2	0.90639 (19)	0.5751 (2)	0.65570 (18)	0.0692 (7)
O3	0.6900 (3)	0.4334 (2)	0.76371 (17)	0.0684 (7)
C17	0.7570 (2)	0.7154 (2)	0.76547 (17)	0.0375 (6)
C18	0.6204 (3)	0.7118 (3)	0.8061 (2)	0.0475 (7)
C19	0.6254 (3)	0.8448 (3)	0.8732 (2)	0.0555 (9)
C20	0.7627 (4)	0.9811 (3)	0.9006 (2)	0.0562 (9)
C21	0.8965 (4)	0.9819 (3)	0.8572 (3)	0.0695 (9)
C22	0.8957 (3)	0.8505 (3)	0.7899 (2)	0.0552 (8)
C23	0.7662 (5)	1.1244 (4)	0.9762 (3)	0.0905 (14)
H2	0.16410	−0.24480	0.34660	0.0600*
H3	0.38530	−0.21100	0.26940	0.0550*
H6	0.41270	0.30810	0.54610	0.0520*
H7	0.66480	0.34870	0.44480	0.0500*
H8	0.82690	0.26510	0.32930	0.0580*
H10A	0.12030	0.09140	0.57350	0.0640*
H10B	0.12570	0.22370	0.51190	0.0640*
H12	0.31760	0.21050	0.78070	0.0660*
H13	0.34020	0.35620	0.96910	0.0810*
H14	0.23490	0.52630	0.99480	0.0810*
H15	0.11680	0.55820	0.83180	0.0730*
H16	0.10380	0.42170	0.64170	0.0580*
H18	0.52640	0.62120	0.78870	0.0570*
H19	0.53340	0.84230	0.90060	0.0670*
H21	0.99000	1.07310	0.87340	0.0830*
H22	0.98750	0.85350	0.76170	0.0660*
H23A	0.86350	1.21210	0.97110	0.1360*
H23B	0.75710	1.11310	1.05860	0.1360*
H23C	0.68030	1.13890	0.94700	0.1360*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0402 (9)	0.0340 (9)	0.0549 (11)	0.0115 (7)	0.0039 (8)	0.0019 (8)
N3	0.0544 (11)	0.0292 (9)	0.0493 (10)	0.0192 (8)	0.0011 (8)	−0.0004 (7)
N6	0.0390 (9)	0.0341 (9)	0.0487 (10)	0.0122 (7)	0.0096 (7)	−0.0012 (7)
N7	0.0409 (9)	0.0301 (8)	0.0485 (10)	0.0127 (7)	0.0098 (7)	0.0030 (7)
N9	0.0562 (11)	0.0407 (10)	0.0505 (11)	0.0244 (9)	0.0127 (9)	0.0057 (8)
C2	0.0474 (12)	0.0313 (11)	0.0589 (14)	0.0105 (9)	−0.0012 (10)	0.0014 (9)
C4	0.0474 (11)	0.0316 (10)	0.0363 (10)	0.0189 (8)	0.0038 (8)	0.0053 (8)
C5	0.0410 (10)	0.0307 (10)	0.0352 (10)	0.0149 (8)	0.0033 (8)	0.0046 (7)
C6	0.0388 (10)	0.0317 (9)	0.0363 (10)	0.0132 (7)	0.0017 (8)	0.0046 (7)
C8	0.0472 (12)	0.0415 (12)	0.0554 (13)	0.0193 (10)	0.0162 (10)	0.0078 (10)
C10	0.0369 (11)	0.0501 (13)	0.0595 (14)	0.0140 (9)	0.0074 (10)	−0.0060 (11)
C11	0.0324 (9)	0.0365 (11)	0.0501 (12)	0.0115 (8)	0.0098 (8)	0.0030 (9)
C12	0.0530 (13)	0.0518 (14)	0.0645 (16)	0.0268 (11)	0.0092 (11)	0.0136 (12)
C13	0.0725 (18)	0.075 (2)	0.0500 (15)	0.0274 (15)	0.0013 (12)	0.0170 (13)
C14	0.0821 (19)	0.0573 (17)	0.0495 (15)	0.0239 (14)	0.0149 (13)	−0.0032 (12)
C15	0.0688 (16)	0.0466 (14)	0.0652 (17)	0.0298 (12)	0.0124 (13)	−0.0009 (12)
C16	0.0460 (12)	0.0448 (12)	0.0515 (13)	0.0201 (10)	0.0053 (10)	0.0060 (10)
S1	0.0430 (3)	0.0298 (3)	0.0471 (3)	0.0162 (2)	−0.0001 (2)	−0.0037 (2)
O1	0.0569 (10)	0.0430 (9)	0.0503 (9)	0.0219 (7)	−0.0095 (7)	−0.0110 (7)
O2	0.0451 (9)	0.0602 (12)	0.0951 (14)	0.0284 (8)	0.0039 (9)	−0.0146 (10)
O3	0.1106 (15)	0.0331 (9)	0.0596 (11)	0.0332 (9)	0.0112 (10)	0.0032 (8)
C17	0.0426 (10)	0.0307 (10)	0.0361 (10)	0.0163 (8)	−0.0007 (8)	0.0006 (7)
C18	0.0473 (12)	0.0414 (12)	0.0547 (13)	0.0223 (10)	0.0047 (10)	0.0059 (10)
C19	0.0712 (16)	0.0576 (16)	0.0533 (14)	0.0433 (13)	0.0132 (12)	0.0098 (12)
C20	0.0911 (19)	0.0431 (13)	0.0402 (12)	0.0387 (13)	0.0078 (12)	−0.0003 (9)
C21	0.0762 (18)	0.0341 (12)	0.0686 (17)	0.0069 (11)	0.0080 (14)	−0.0109 (11)
C22	0.0485 (12)	0.0369 (12)	0.0626 (15)	0.0106 (9)	0.0086 (11)	−0.0088 (10)
C23	0.152 (3)	0.060 (2)	0.0673 (19)	0.062 (2)	0.016 (2)	−0.0067 (15)

Geometric parameters (Å, º)

S1—O1	1.4636 (18)	C15—C16	1.382 (3)
S1—O2	1.435 (2)	C2—H2	0.9300
S1—O3	1.4500 (19)	C8—H8	0.9300
S1—C17	1.768 (2)	C10—H10A	0.9700
N1—C6	1.364 (3)	C10—H10B	0.9700
N1—C2	1.304 (3)	C12—H12	0.9300
N3—C2	1.340 (4)	C13—H13	0.9300
N3—C4	1.357 (3)	C14—H14	0.9300
N6—C10	1.459 (3)	C15—H15	0.9300
N6—C6	1.324 (3)	C16—H16	0.9300
N7—C8	1.349 (3)	C17—C18	1.381 (4)
N7—C5	1.372 (3)	C17—C22	1.379 (3)
N9—C4	1.360 (3)	C18—C19	1.383 (4)
N9—C8	1.325 (3)	C19—C20	1.380 (4)
N3—H3	0.8600	C20—C21	1.377 (6)
N6—H6	0.8600	C20—C23	1.512 (5)
N7—H7	0.8600	C21—C22	1.387 (4)
C4—C5	1.377 (3)	C18—H18	0.9300
C5—C6	1.417 (3)	C19—H19	0.9300
C10—C11	1.513 (3)	C21—H21	0.9300
C11—C16	1.380 (4)	C22—H22	0.9300
C11—C12	1.378 (3)	C23—H23A	0.9600
C12—C13	1.384 (3)	C23—H23B	0.9600
C13—C14	1.372 (5)	C23—H23C	0.9600
C14—C15	1.363 (4)
S1···H6	3.1900	C8···C15^ii	3.594 (4)
S1···H7	2.9100	C15···C8^ii	3.594 (4)
S1···H3^i	3.0900	C16···C2^vii	3.493 (4)
O1···N7	2.770 (2)	C18···C5^ii	3.466 (3)
O1···O1^ii	3.231 (3)	C19···C5^ii	3.411 (3)
O1···N6^ii	3.135 (2)	C19···C4^ii	3.438 (3)
O1···N6	2.959 (3)	C12···H21^viii	2.9000
O2···C8^iii	3.225 (4)	C12···H6	3.0700
O3···N3^i	2.712 (3)	C13···H21^viii	3.0000
O3···C2^i	3.243 (4)	C13···H18	3.0400
O1···H7	1.9900	C14···H18	3.1000
O1···H6	2.1200	C16···H2^vii	2.6900
O1···H6^ii	2.7900	C18···H13^v	2.8100
O2···H8^iii	2.3100	C19···H13^v	3.0100
O2···H16^iv	2.9000	H2···C16^vii	2.6900
O2···H22	2.5600	H2···H16^vii	2.4000
O2···H15^iv	2.8900	H3···O3^i	1.9500
O3···H14^v	2.7300	H3···S1^i	3.0900
O3···H18	2.9000	H6···O1	2.1200
O3···H3^i	1.9500	H6···N7	2.8500
N3···O3^i	2.712 (3)	H6···H7	2.5900
N3···C5^i	3.407 (3)	H6···O1^ii	2.7900
N6···N7	3.116 (3)	H6···C12	3.0700
N6···O1^ii	3.135 (2)	H6···S1	3.1900
N6···O1	2.959 (3)	H7···O1	1.9900
N7···O1	2.770 (2)	H7···H6	2.5900
N7···N9	2.241 (3)	H7···S1	2.9100
N7···N6	3.116 (3)	H8···O2^iii	2.3100
N7···C2^i	3.342 (3)	H10A···H10A^vii	2.5400
N9···N7	2.241 (3)	H10A···N1	2.4400
N1···H10A	2.4400	H10B···H16	2.3300
N6···H12	2.9200	H12···N9^i	2.7700
N7···H6	2.8500	H12···N6	2.9200
N9···H12^i	2.7700	H13···C18^v	2.8100
N9···H23B^vi	2.9300	H13···C19^v	3.0100
C2···O3^i	3.243 (4)	H14···O3^v	2.7300
C2···N7^i	3.342 (3)	H15···O2^ix	2.8900
C2···C5^i	3.534 (3)	H16···O2^ix	2.9000
C2···C16^vii	3.493 (4)	H16···H10B	2.3300
C2···C8^i	3.539 (3)	H16···H2^vii	2.4000
C4···C6^i	3.377 (3)	H18···O3	2.9000
C4···C19^ii	3.438 (3)	H18···C13	3.0400
C4···C5^i	3.492 (3)	H18···C14	3.1000
C5···C4^i	3.492 (3)	H19···H23C	2.5800
C5···C18^ii	3.466 (3)	H21···C12^x	2.9000
C5···C19^ii	3.411 (3)	H21···C13^x	3.0000
C5···C2^i	3.534 (3)	H21···H23A	2.3700
C5···N3^i	3.407 (3)	H22···O2	2.5600
C6···C4^i	3.377 (3)	H23A···H21	2.3700
C8···O2^iii	3.225 (4)	H23B···N9^xi	2.9300
C8···C2^i	3.539 (3)	H23C···H19	2.5800
O2—S1—O3	113.68 (15)	N7—C8—H8	123.00
O2—S1—C17	108.10 (10)	N6—C10—H10B	109.00
O3—S1—C17	105.49 (11)	C11—C10—H10A	109.00
O1—S1—C17	105.96 (10)	N6—C10—H10A	109.00
O1—S1—O2	111.84 (11)	H10A—C10—H10B	108.00
O1—S1—O3	111.22 (12)	C11—C10—H10B	109.00
C2—N1—C6	119.3 (2)	C11—C12—H12	120.00
C2—N3—C4	116.9 (2)	C13—C12—H12	120.00
C6—N6—C10	123.38 (19)	C12—C13—H13	120.00
C5—N7—C8	106.15 (19)	C14—C13—H13	120.00
C4—N9—C8	103.0 (2)	C15—C14—H14	120.00
C2—N3—H3	122.00	C13—C14—H14	120.00
C4—N3—H3	122.00	C14—C15—H15	120.00
C10—N6—H6	118.00	C16—C15—H15	120.00
C6—N6—H6	118.00	C15—C16—H16	120.00
C5—N7—H7	127.00	C11—C16—H16	120.00
C8—N7—H7	127.00	S1—C17—C18	118.62 (16)
N1—C2—N3	126.5 (2)	S1—C17—C22	121.04 (18)
N3—C4—N9	128.11 (19)	C18—C17—C22	120.3 (2)
N9—C4—C5	112.12 (17)	C17—C18—C19	119.0 (2)
N3—C4—C5	119.77 (19)	C18—C19—C20	122.0 (3)
N7—C5—C4	104.87 (18)	C19—C20—C21	117.7 (3)
N7—C5—C6	134.58 (18)	C19—C20—C23	121.1 (3)
C4—C5—C6	120.54 (17)	C21—C20—C23	121.2 (3)
N1—C6—N6	119.44 (19)	C20—C21—C22	121.8 (3)
N1—C6—C5	116.95 (18)	C17—C22—C21	119.2 (3)
N6—C6—C5	123.60 (18)	C17—C18—H18	120.00
N7—C8—N9	113.9 (2)	C19—C18—H18	120.00
N6—C10—C11	111.51 (19)	C18—C19—H19	119.00
C10—C11—C16	120.2 (2)	C20—C19—H19	119.00
C10—C11—C12	121.2 (2)	C20—C21—H21	119.00
C12—C11—C16	118.5 (2)	C22—C21—H21	119.00
C11—C12—C13	120.7 (3)	C17—C22—H22	120.00
C12—C13—C14	120.0 (3)	C21—C22—H22	120.00
C13—C14—C15	119.8 (3)	C20—C23—H23A	109.00
C14—C15—C16	120.4 (3)	C20—C23—H23B	109.00
C11—C16—C15	120.5 (2)	C20—C23—H23C	109.00
N1—C2—H2	117.00	H23A—C23—H23B	109.00
N3—C2—H2	117.00	H23A—C23—H23C	109.00
N9—C8—H8	123.00	H23B—C23—H23C	109.00
O3—S1—C17—C22	122.2 (2)	N7—C5—C6—N1	178.5 (2)
O3—S1—C17—C18	−56.4 (2)	N7—C5—C6—N6	−2.8 (4)
O1—S1—C17—C18	61.60 (19)	C4—C5—C6—N6	178.47 (19)
O2—S1—C17—C18	−178.37 (18)	C4—C5—C6—N1	−0.3 (3)
O1—S1—C17—C22	−119.77 (19)	N6—C10—C11—C12	−62.6 (3)
O2—S1—C17—C22	0.3 (2)	N6—C10—C11—C16	121.3 (2)
C2—N1—C6—N6	−177.4 (2)	C10—C11—C12—C13	−175.9 (3)
C6—N1—C2—N3	−1.3 (4)	C12—C11—C16—C15	−1.9 (4)
C2—N1—C6—C5	1.4 (3)	C16—C11—C12—C13	0.3 (4)
C4—N3—C2—N1	0.0 (4)	C10—C11—C16—C15	174.3 (2)
C2—N3—C4—N9	−178.8 (2)	C11—C12—C13—C14	1.4 (5)
C2—N3—C4—C5	1.1 (3)	C12—C13—C14—C15	−1.4 (5)
C10—N6—C6—C5	175.60 (19)	C13—C14—C15—C16	−0.1 (5)
C6—N6—C10—C11	149.0 (2)	C14—C15—C16—C11	1.8 (4)
C10—N6—C6—N1	−5.7 (3)	S1—C17—C18—C19	177.57 (18)
C8—N7—C5—C6	−179.2 (2)	C22—C17—C18—C19	−1.1 (3)
C8—N7—C5—C4	−0.3 (2)	S1—C17—C22—C21	−177.7 (2)
C5—N7—C8—N9	0.6 (3)	C18—C17—C22—C21	0.9 (4)
C8—N9—C4—C5	0.4 (2)	C17—C18—C19—C20	0.1 (4)
C8—N9—C4—N3	−179.7 (2)	C18—C19—C20—C21	0.9 (4)
C4—N9—C8—N7	−0.6 (3)	C18—C19—C20—C23	−178.8 (3)
N9—C4—C5—N7	−0.1 (2)	C19—C20—C21—C22	−1.1 (4)
N3—C4—C5—N7	180.00 (19)	C23—C20—C21—C22	178.6 (3)
N3—C4—C5—C6	−0.9 (3)	C20—C21—C22—C17	0.2 (4)
N9—C4—C5—C6	178.99 (18)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O3^i	0.86	1.95	2.712 (3)	147
N6—H6···O1	0.86	2.12	2.959 (3)	165
N7—H7···O1	0.86	1.99	2.770 (2)	150
C8—H8···O2^iii	0.93	2.31	3.225 (4)	168
C10—H10A···N1	0.97	2.44	2.800 (3)	102
C22—H22···O2	0.93	2.56	2.931 (3)	104

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