10-Ethyl-4-oxo-2,3,4,10-tetra­hydro­pyrimido[4,5-b]quinolin-2-iminium 4-toluene­sulfonate: a polarized electronic structure in the cation and a hydrogen-bonded sheet structure

In the title compound, C₁₃H₁₃N₄O⁺·C₇H₇O₃S^-, the bond distances within the cation provide evidence for the delocalization of the positive charge in a manner reminiscent of guanidinium cations. Three independent N-H...O hydrogen bonds link the ions into centrosymmetric four-ion aggregates, and these are further linked into sheets by a single C-H...O hydrogen bond. This study shows how a single hydrogen bond can link centrosymmetric entities into a continuous sheet structure.

S1. Comment

The synthesis and study of fused pyrimidine compounds is of interest due to the wide variety of their biological and pharmacological properties. In particular, pyrimidinoquinolines have found application as antitumour agents (Chua et al., 2008; Weissman & Yang, 2007), as biocidal agents (Kumar et al., 2002) and as antiallergic agents (Althuis et al., 1980). Compounds of this type have been prepared from 5-formyl-4,6-dichloropyrimidines using a two-step sequence consisting of a monosubstitution with aromatic amines (Quiroga et al., 2008) followed by an acid-catalysed Bradsher-type cyclocondensation. The title compound, (I), was isolated in small quantity from an attempt to induce such cyclocondensation using 4-toluenesulfonic acid under microwave irradiation.

The title compound is a salt, C₁₃H₁₃N₄O⁺.C₇H₇O₃S^-, for which the asymmetric unit was selected so that the two independent ions are linked within the asymmetric unit by two N—H···O hydrogen bonds, which are both almost linear (Fig. 1, Table 2). The dihedral angle between the mean plane of the tricyclic ring system of the cation and the aryl ring of the anion is only 5.4 (2)°, so that the non-H atoms of the ring systems within the asymmetric unit are almost coplanar. The main deviations from the near-planarity are found for the O atoms of the sulfonate group and the N-ethyl group pendent from the cation, the plane of which is almost orthogonal to that of the adjacent ring (Table 1).

Within the cation, the peripheral and exocyclic bond distances (Table 1) exhibit some interesting values. Amongst the peripheral C—C distances, the bonds C4a—C5, C6—C7 and C8—C9 are all significantly shorter than the remainder, indicating a degree of double-bond fixation. Of the C—N distances, the exocyclic distance C2—N2 is the shortest by some margin, the ring distances C2—N1 and C8a—N1 [C10a—N1?] are longer than C2—N2, and fairly similar to each other, the distances C2—N3 and C8a—N10 [C10a—N10?] are longer still and are also similar to each other, the amidic bond C4—N3 is long for its type with a distance more typical of C—N bonds in bis-acyl imines (Allen et al., 1987), while C9a—N10 is the longest of all the C—N bonds. The C2—N2 distance is, in fact, rather typical of those found in guanidinium cations (Allen et al., 1987), and it is close in value to the length of 1.3195 (9) Å of the corresponding bond in the cation, (II), in its sulfate salt [Cambridge Structural Database (Allen, 2002) refcode HACDEU; Bieri et al., 1993]. This distance is also consistent with the character of the C4—N3 bond, and these observations suggest that the positive charge which is formally localized at N2 is, in fact, best described as delocalized over atoms N2, N3 and N10, as in forms (Ia)–(Ic) (see scheme). The cation can thus be regarded as a protonated iminouracil derivative.

As noted above, the two independent ions within the asymmetric unit of (I) are linked by two N—H···O hydrogen bonds, both of which are almost linear. In addition, pairs of these units are linked by a third N—H···O hydrogen bond (Table 2) to form a centrosymmetric four-ion aggregate in which the central R²₄(8) (Bernstein et al., 1995) ring is flanked by two symmetry-equivalent R²₂(8) rings (Fig. 2). These aggregates can be regarded as the basic building block for the structure as a whole and a single C—H···O hydrogen bond (Table 2) links these building blocks into sheets.

The aryl atoms C23 at (x, y, z) and (-x, 1 - y, 1 - z) are components of the aggregate centred at (0, 1/2, 1/2). These two atoms act as hydrogen-bond donors to the sulfonate atoms O21 at (1/2 + x, 1.5 - y, 1/2 + z) and (-1/2 - x, -1/2 + y, 1/2 - z), respectively, which themselves are components of the aggregates centred at (1/2, 1, 1) and (-1/2, 0, 0), respectively. Similarly, the atoms O21 at (x, y, z) and (-x, 1 - y, 1 - z) accept hydrogen bonds from the atoms C23 at (-1/2 + x, 3/2 - y, -1/2 + z) and (1/2 - x, -1/2 + y, 3/2 - z), respectively, which are components of the aggregates centred at (-1/2, 1, 0) and (1/2, 0, 1). Propagation of this interaction by the space group links the centrosymmetric four-ion aggregates into a sheet parallel to (101) and built from a combination of R²₂(8), R²₄(8) and R⁸₈(40) rings (Fig. 3). Thus, a single hydrogen bond is sufficient to link the centrosymmetric four-ion entities into a two-dimensional structure. There are no direction-specific interactions between adjacent sheets. By contrast, in HACDEU, where there are nine independent N—H bonds all participating in hydrogen-bond formation, the overall hydrogen-bonded supramolecular structure is three-dimensional.

S2. Experimental

A mixture of 2-amino-4-chloro-6-(N-ethyl-N-phenylamino)pyrimidin- 5-carbaldehyde (0.18 mmol) and 4-toluenesulfonic acid monohydrate (0.18 mmol) in ethanol (3 ml) was subjected to microwave irradiation in a sealed tube under magnetic stirring, using a CEM monomode microwave reactor (maximum power 300 W, ramp time 15 min, hold time 10 min, maximum temperature 573 K). The reaction mixture was then cooled in a refrigerator and the resulting solid, which proved to be a mixture of several products, was collected by filtration. Recrystallization from ethanol afforded a few crystals of the title compound as brown blocks, which proved to be suitable for single-crystal X-ray diffraction (m.p. 537–538 K).

S3. Refinement

The space group P2₁/n was uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aryl), 0.98 (CH₃) or 0.99 Å (CH₂), and N—H = 0.88 Å, and with U_iso(H) = kU_eq(carrier) where k = 1.5 for the methyl groups and 1.2 for all other H atoms.

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The two independent ions in the asymmetric unit of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure of compound (II), showing a centrosymmetric four-ion aggregate. For the sake of clarity, H atoms bonded to C atoms have been omitted, as has the unit-cell outline. Atoms marked with an asterisk (*) are at the symmetry position (-x, 1 - y, 1 - z).
	Fig. 3. A stereoview of part of the crystal structure of compound (I), showing the formation of a hydrogen-bonded sheet parallel to (101). For the sake of clarity, H atoms bonded to C atoms and not participating in the sheet formation have been omitted.

10-Ethyl-4-oxo-2,3,4,10-tetrahydropyrimido[4,5-b]quinolin-2-iminium 4-toluenesulfonate

Crystal data

C13H13N4O^−·C7H7O3S^−	F(000) = 864
Mr = 412.46	Dx = 1.440 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4370 reflections
a = 9.0213 (7) Å	θ = 3.0–27.5°
b = 20.2880 (18) Å	µ = 0.21 mm^−1
c = 10.3932 (6) Å	T = 120 K
β = 90.245 (5)°	Block, brown
V = 1902.2 (2) Å^3	0.41 × 0.40 × 0.39 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	4370 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	3363 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −26→26
Tmin = 0.920, Tmax = 0.924	l = −13→13
43973 measured reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0558P)^2 + 1.7964P] where P = (Fo^2 + 2Fc^2)/3
4370 reflections	(Δ/σ)max = 0.001
265 parameters	Δρmax = 0.67 e Å^−3
0 restraints	Δρmin = −0.53 e Å^−3

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

	x	y	z	Uiso*/Ueq
O4	0.64589 (16)	0.54921 (7)	0.33102 (14)	0.0266 (3)
N1	0.29440 (18)	0.43190 (8)	0.23268 (15)	0.0194 (3)
N2	0.17135 (19)	0.48063 (8)	0.39913 (16)	0.0238 (4)
N3	0.41094 (18)	0.51349 (8)	0.36439 (15)	0.0199 (3)
N10	0.42389 (18)	0.38463 (8)	0.06496 (15)	0.0203 (3)
C2	0.2930 (2)	0.47483 (9)	0.33136 (18)	0.0199 (4)
C4	0.5437 (2)	0.51338 (9)	0.29960 (18)	0.0202 (4)
C4a	0.5482 (2)	0.46738 (9)	0.19008 (17)	0.0191 (4)
C5	0.6715 (2)	0.46203 (10)	0.11567 (18)	0.0218 (4)
C5a	0.6715 (2)	0.41993 (9)	0.00712 (18)	0.0208 (4)
C6	0.7934 (2)	0.41660 (10)	−0.07698 (19)	0.0253 (4)
C7	0.7895 (2)	0.37683 (11)	−0.18338 (19)	0.0277 (5)
C8	0.6627 (3)	0.33927 (11)	−0.20807 (19)	0.0280 (5)
C9	0.5418 (2)	0.34050 (10)	−0.12797 (19)	0.0258 (4)
C9a	0.5442 (2)	0.38107 (9)	−0.01786 (18)	0.0207 (4)
C10a	0.4193 (2)	0.42838 (9)	0.16462 (17)	0.0179 (4)
C101	0.2940 (2)	0.34104 (10)	0.04370 (19)	0.0247 (4)
C102	0.1849 (3)	0.37210 (11)	−0.0497 (2)	0.0310 (5)
S21	0.21577 (5)	0.63290 (2)	0.57680 (4)	0.01933 (14)
O21	0.16066 (18)	0.67555 (8)	0.47577 (13)	0.0325 (4)
O22	0.36624 (15)	0.60961 (7)	0.55342 (13)	0.0236 (3)
O23	0.11580 (16)	0.57842 (7)	0.60677 (15)	0.0312 (4)
C21	0.2251 (2)	0.68253 (9)	0.71609 (17)	0.0180 (4)
C22	0.3549 (2)	0.71581 (10)	0.74558 (19)	0.0222 (4)
C23	0.3588 (2)	0.75895 (10)	0.84913 (19)	0.0249 (4)
C24	0.2331 (2)	0.76964 (9)	0.92384 (18)	0.0225 (4)
C25	0.1042 (2)	0.73578 (10)	0.89278 (19)	0.0241 (4)
C26	0.0988 (2)	0.69193 (10)	0.79000 (18)	0.0221 (4)
C241	0.2368 (3)	0.81646 (11)	1.0356 (2)	0.0305 (5)
H2A	0.0959	0.4547	0.3811	0.029*
H2B	0.1676	0.5059	0.4678	0.029*
H3	0.4008	0.5422	0.4272	0.024*
H5	0.7579	0.4866	0.1367	0.026*
H6	0.8793	0.4422	−0.0596	0.030*
H7	0.8719	0.3748	−0.2398	0.033*
H8	0.6600	0.3120	−0.2824	0.034*
H9	0.4572	0.3142	−0.1467	0.031*
H10a	0.2442	0.3327	0.1268	0.030*
H10B	0.3279	0.2982	0.0091	0.030*
H10C	0.1460	0.4130	−0.0127	0.047*
H10D	0.1030	0.3415	−0.0658	0.047*
H10E	0.2352	0.3819	−0.1308	0.047*
H22	0.4411	0.7091	0.6950	0.027*
H23	0.4483	0.7815	0.8694	0.030*
H25	0.0177	0.7427	0.9428	0.029*
H26	0.0100	0.6687	0.7706	0.027*
H24a	0.2238	0.7918	1.1159	0.046*
H24B	0.1566	0.8487	1.0264	0.046*
H24C	0.3323	0.8394	1.0375	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O4	0.0260 (7)	0.0255 (8)	0.0283 (7)	−0.0034 (6)	−0.0009 (6)	−0.0060 (6)
N1	0.0244 (8)	0.0147 (7)	0.0192 (7)	−0.0007 (6)	0.0020 (6)	−0.0023 (6)
N2	0.0264 (9)	0.0196 (8)	0.0254 (8)	−0.0032 (7)	0.0040 (7)	−0.0072 (7)
N3	0.0236 (8)	0.0165 (8)	0.0196 (8)	0.0016 (6)	0.0004 (6)	−0.0041 (6)
N10	0.0258 (9)	0.0159 (8)	0.0191 (8)	0.0004 (6)	0.0014 (6)	−0.0017 (6)
C2	0.0240 (10)	0.0149 (9)	0.0209 (9)	0.0007 (7)	−0.0009 (7)	0.0021 (7)
C4	0.0237 (10)	0.0167 (9)	0.0203 (9)	0.0017 (7)	−0.0011 (7)	0.0006 (7)
C4a	0.0239 (10)	0.0145 (9)	0.0189 (9)	0.0014 (7)	−0.0005 (7)	0.0013 (7)
C5	0.0235 (10)	0.0204 (9)	0.0213 (9)	0.0016 (8)	−0.0014 (7)	0.0008 (7)
C5a	0.0234 (10)	0.0199 (9)	0.0190 (9)	0.0055 (8)	0.0005 (7)	0.0020 (7)
C6	0.0257 (10)	0.0267 (10)	0.0233 (10)	0.0032 (8)	0.0019 (8)	0.0022 (8)
C7	0.0304 (11)	0.0315 (11)	0.0213 (10)	0.0094 (9)	0.0047 (8)	0.0020 (8)
C8	0.0390 (12)	0.0251 (11)	0.0199 (9)	0.0072 (9)	0.0029 (8)	−0.0027 (8)
C9	0.0349 (11)	0.0206 (10)	0.0220 (9)	0.0015 (8)	0.0009 (8)	−0.0020 (8)
C9a	0.0263 (10)	0.0174 (9)	0.0184 (9)	0.0046 (8)	0.0019 (7)	0.0008 (7)
C10a	0.0243 (10)	0.0130 (8)	0.0162 (8)	0.0025 (7)	−0.0007 (7)	0.0014 (7)
C101	0.0332 (11)	0.0177 (9)	0.0233 (9)	−0.0065 (8)	0.0043 (8)	−0.0035 (8)
C102	0.0320 (12)	0.0312 (12)	0.0299 (11)	−0.0089 (9)	−0.0033 (9)	−0.0032 (9)
S21	0.0218 (2)	0.0176 (2)	0.0186 (2)	0.00133 (18)	−0.00020 (17)	−0.00366 (17)
O21	0.0461 (9)	0.0324 (8)	0.0189 (7)	0.0144 (7)	−0.0065 (6)	−0.0030 (6)
O22	0.0223 (7)	0.0231 (7)	0.0254 (7)	0.0029 (6)	0.0011 (6)	−0.0069 (6)
O23	0.0291 (8)	0.0268 (8)	0.0377 (8)	−0.0098 (6)	0.0075 (7)	−0.0123 (6)
C21	0.0228 (9)	0.0138 (8)	0.0173 (8)	0.0013 (7)	−0.0003 (7)	0.0010 (7)
C22	0.0213 (10)	0.0222 (10)	0.0230 (9)	−0.0005 (8)	0.0023 (8)	−0.0029 (8)
C23	0.0251 (10)	0.0231 (10)	0.0264 (10)	−0.0038 (8)	−0.0027 (8)	−0.0045 (8)
C24	0.0316 (10)	0.0173 (9)	0.0185 (9)	0.0040 (8)	−0.0032 (8)	−0.0011 (7)
C25	0.0258 (10)	0.0239 (10)	0.0226 (9)	0.0015 (8)	0.0044 (8)	−0.0019 (8)
C26	0.0209 (9)	0.0221 (10)	0.0233 (9)	−0.0018 (8)	0.0008 (7)	−0.0029 (8)
C241	0.0390 (12)	0.0274 (11)	0.0250 (10)	0.0023 (9)	−0.0040 (9)	−0.0095 (9)

Geometric parameters (Å, º)

N1—C2	1.346 (2)	C9—H9	0.95
C2—N3	1.364 (2)	C101—C102	1.516 (3)
N3—C4	1.377 (2)	C101—H10a	0.99
C4—C4a	1.473 (3)	C101—H10B	0.99
C4a—C5	1.362 (3)	C102—H10C	0.98
C5—C5a	1.415 (3)	C102—H10D	0.98
C5a—C6	1.410 (3)	C102—H10E	0.98
C6—C7	1.369 (3)	S21—O21	1.4471 (15)
C7—C8	1.397 (3)	S21—O22	1.4586 (14)
C8—C9	1.376 (3)	S21—O23	1.4610 (15)
C9—C9a	1.410 (3)	S21—C21	1.7650 (18)
C9a—N10	1.390 (2)	C21—C22	1.385 (3)
N10—C10a	1.365 (2)	C21—C26	1.390 (3)
C10a—N1	1.335 (2)	C22—C23	1.387 (3)
C4a—C10a	1.430 (3)	C22—H22	0.95
C5a—C9a	1.416 (3)	C23—C24	1.395 (3)
C2—N2	1.312 (3)	C23—H23	0.95
C4—O4	1.217 (2)	C24—C25	1.387 (3)
N2—H2A	0.88	C24—C241	1.501 (3)
N2—H2B	0.88	C25—C26	1.391 (3)
N3—H3	0.88	C25—H25	0.95
N10—C101	1.484 (3)	C26—H26	0.95
C5—H5	0.95	C241—H24a	0.98
C6—H6	0.95	C241—H24B	0.98
C7—H7	0.95	C241—H24C	0.98
C8—H8	0.95
C10a—N1—C2	116.69 (16)	N10—C101—C102	110.95 (16)
C2—N2—H2A	118.7	N10—C101—H10a	109.4
C2—N2—H2B	121.6	C102—C101—H10a	109.4
H2A—N2—H2B	119.3	N10—C101—H10B	109.4
C2—N3—C4	123.72 (16)	C102—C101—H10B	109.4
C2—N3—H3	118.9	H10a—C101—H10B	108.0
C4—N3—H3	117.2	C101—C102—H10C	109.5
C10a—N10—C9a	122.03 (16)	C101—C102—H10D	109.5
C10a—N10—C101	118.30 (16)	H10C—C102—H10D	109.5
C9a—N10—C101	119.65 (16)	C101—C102—H10E	109.5
N2—C2—N1	118.54 (17)	H10C—C102—H10E	109.5
N2—C2—N3	117.81 (17)	H10D—C102—H10E	109.5
N1—C2—N3	123.65 (17)	O21—S21—O22	112.95 (9)
O4—C4—N3	121.81 (17)	O21—S21—O23	113.37 (10)
O4—C4—C4a	124.25 (18)	O22—S21—O23	111.48 (9)
N3—C4—C4a	113.93 (16)	O21—S21—C21	105.60 (9)
C5—C4a—C10a	121.09 (17)	O22—S21—C21	106.28 (9)
C5—C4a—C4	120.94 (17)	O23—S21—C21	106.49 (9)
C10a—C4a—C4	117.97 (16)	C22—C21—C26	120.34 (17)
C4a—C5—C5a	120.20 (18)	C22—C21—S21	119.78 (14)
C4a—C5—H5	119.9	C26—C21—S21	119.69 (15)
C5a—C5—H5	119.9	C21—C22—C23	119.85 (18)
C6—C5a—C5	121.70 (19)	C21—C22—H22	120.1
C6—C5a—C9a	119.61 (18)	C23—C22—H22	120.1
C5—C5a—C9a	118.68 (17)	C22—C23—C24	120.80 (18)
C7—C6—C5a	120.7 (2)	C22—C23—H23	119.6
C7—C6—H6	119.6	C24—C23—H23	119.6
C5a—C6—H6	119.6	C25—C24—C23	118.46 (18)
C6—C7—C8	119.24 (19)	C25—C24—C241	120.62 (19)
C6—C7—H7	120.4	C23—C24—C241	120.92 (19)
C8—C7—H7	120.4	C24—C25—C26	121.46 (18)
C9—C8—C7	121.99 (19)	C24—C25—H25	119.3
C9—C8—H8	119.0	C26—C25—H25	119.3
C7—C8—H8	119.0	C21—C26—C25	119.09 (18)
C8—C9—C9a	119.5 (2)	C21—C26—H26	120.5
C8—C9—H9	120.3	C25—C26—H26	120.5
C9a—C9—H9	120.3	C24—C241—H24a	109.5
N10—C9a—C9	121.59 (18)	C24—C241—H24B	109.5
N10—C9a—C5a	119.48 (17)	H24a—C241—H24B	109.5
C9—C9a—C5a	118.91 (18)	C24—C241—H24C	109.5
N1—C10a—N10	117.75 (17)	H24a—C241—H24C	109.5
N1—C10a—C4a	124.03 (17)	H24B—C241—H24C	109.5
N10—C10a—C4a	118.22 (16)
C10a—N1—C2—N2	178.75 (17)	C2—N1—C10a—N10	179.26 (16)
C10a—N1—C2—N3	−0.5 (3)	C2—N1—C10a—C4a	−0.5 (3)
C4—N3—C2—N2	−178.48 (17)	C9a—N10—C10a—N1	174.71 (17)
C4—N3—C2—N1	0.7 (3)	C101—N10—C10a—N1	−3.7 (2)
C2—N3—C4—O4	179.07 (17)	C9a—N10—C10a—C4a	−5.5 (3)
C2—N3—C4—C4a	0.0 (3)	C101—N10—C10a—C4a	176.05 (16)
O4—C4—C4a—C5	0.3 (3)	C5—C4a—C10a—N1	−179.06 (18)
N3—C4—C4a—C5	179.39 (17)	C4—C4a—C10a—N1	1.2 (3)
O4—C4—C4a—C10a	−179.91 (18)	C5—C4a—C10a—N10	1.2 (3)
N3—C4—C4a—C10a	−0.8 (2)	C4—C4a—C10a—N10	−178.60 (16)
C10a—C4a—C5—C5a	3.3 (3)	C9a—N10—C101—C102	−86.8 (2)
C4—C4a—C5—C5a	−176.96 (17)	C10a—N10—C101—C102	91.7 (2)
C4a—C5—C5a—C6	175.58 (18)	O21—S21—C21—C22	−91.58 (17)
C4a—C5—C5a—C9a	−3.5 (3)	O22—S21—C21—C22	28.64 (18)
C5—C5a—C6—C7	−178.24 (18)	O23—S21—C21—C22	147.61 (16)
C9a—C5a—C6—C7	0.8 (3)	O21—S21—C21—C26	83.54 (17)
C5a—C6—C7—C8	0.0 (3)	O22—S21—C21—C26	−156.24 (15)
C6—C7—C8—C9	−0.6 (3)	O23—S21—C21—C26	−37.27 (18)
C7—C8—C9—C9a	0.4 (3)	C26—C21—C22—C23	−0.2 (3)
C10a—N10—C9a—C9	−173.51 (18)	S21—C21—C22—C23	174.84 (15)
C101—N10—C9a—C9	4.9 (3)	C21—C22—C23—C24	−0.4 (3)
C10a—N10—C9a—C5a	5.3 (3)	C22—C23—C24—C25	0.4 (3)
C101—N10—C9a—C5a	−176.29 (17)	C22—C23—C24—C241	−179.77 (19)
C8—C9—C9a—N10	179.13 (18)	C23—C24—C25—C26	0.1 (3)
C8—C9—C9a—C5a	0.3 (3)	C241—C24—C25—C26	−179.65 (19)
C6—C5a—C9a—N10	−179.76 (17)	C22—C21—C26—C25	0.8 (3)
C5—C5a—C9a—N10	−0.7 (3)	S21—C21—C26—C25	−174.28 (15)
C6—C5a—C9a—C9	−0.9 (3)	C24—C25—C26—C21	−0.8 (3)
C5—C5a—C9a—C9	178.14 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O23^i	0.88	2.03	2.855 (2)	156
N2—H2B···O23	0.88	2.11	2.976 (2)	166
N3—H3···O22	0.88	1.92	2.799 (2)	174
C23—H23···O21^ii	0.95	2.37	3.299 (3)	164

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x+1/2, −y+3/2, z+1/2.