Three solvates of a bis-mesoionic fluorescent yellow pigment

p-Phenyl­enebis(2-oxo-3-phenyl-1,2-dihydro­pyrido[1,2-a]pyrimidin-5-ium-4-olate), C₃₄H₂₂N₄O₄, is a bis-mesoionic yellow pigment that shows fluorescence in the solid state. During a polymorph screening, single crystals of three solvates were grown and their crystal structures determined. Solvent-free crystals were not obtained. A solvate with N-methyl­pyrroli­done (NMP) and propan-2-ol, C₃₄H₂₂N₄O₄·2C₅H₉NO·C₃H₈O, (Ia), and an NMP tri­solvate, C₃₄H₂₂N₄O₄·3C₅H₉NO, (Ib), crystallize with pigment mol­ecules on inversion centres. The NMP/propan-2-ol mixed solvate (Ia) forms O—H...O hydrogen bonds between the different solvent mol­ecules. In both structures, at least one of the solvent mol­ecules is disordered. A third solvate structure, C₃₄H₂₂N₄O₄·0.5C₅H₉NO·C₄H₁₀O, (Ic), was obtained by crystallization from NMP and butan-1-ol. In this case, there are two symmetry-independent pigment mol­ecules, both situated on inversion centres. The solvent mol­ecules are heavily disordered and their contribution to the scattering was suppressed. This solvate displays a channel structure, whereas the other two solvates form layer structures.

S1. Comment

Mesoionic compounds are `dipolar five- (possibly six-) membered heterocyclic compounds in which both the negative and the positive charge are delocalized, for which a totally covalent structure cannot be written, and which cannot be represented satisfactorily by any one polar structure' (IUPAC, 1995). These substances represent a small class of compounds. Pyridopyrimidinium olates based on 2,4-dioxopyrimidine are mesoionic (Friedrichsen et al., 1982; Schober & Kappe, 1988; Kappe, 1998; Fiksdahl et al., 2000). Moreover, some of them exhibit yellow solid-state fluorescence. Fluorescence in the solid state is a rather unusual property since most compounds that fluoresce in solution lose this property when they are crystallized. Recently, the phenomenon of solid-state fluorescence in an organic pigment was explained by time-dependent density functional theory (TD-DFT) calculations (Dreuw et al., 2005).

2-Oxo-3-phenyl-1,2-dihydro-pyrido[1,2-a]pyrimidin-5-ium-4-olate, (II), being a derivative of Chichibabin's malonyl α-aminopyridine (Reference?), is a mesoionic yellow compound [Plüg et al., 2000; Cambridge Structural Database (CSD; Allen, 2002) refcode XAKZEO]. It shows a high solubility in most organic solvents and it is therefore not feasible to use it as an industrially produced pigment. To enhance the insolubility, the title compound, (I), was synthesized. This compound actually shows a lower solubility and a strong yellow fluorescence (Metz & Plüg, 2005). Compound (I) is not industrially produced, either.

In order to search for different crystallographic phases, hydrates or solvates of (I), a polymorph screening was launched. Different crystallization methods used included recrystallization from various solvents and solvent mixtures by heating and subsequent slow cooling, overlaying a solution of the compound with an anti-solvent (Fock, 1888), and diffusion of an anti-solvent into a solution of the compound via the gas phase. The solvents used included the most common organic solvents, e.g. dimethylsulfoxide, N-methylpyrrolidone (NMP), N,N'-dimethylformamide, different ethers and esters, propan-2-ol (ⁱPrOH), butan-1-ol (1-BuOH) and other alcohols, and water.

In several experiments, single crystals could be grown, and the crystal structures could be determined for three solvates, namely (I).2NMP.ⁱPrOH, (Ia), (I).3NMP, (Ib), and a solvate with 1-BuOH and NMP, (Ic).

Compounds (Ia) and (Ib) crystallize in space group P1 with Z = 1 (Figs. 1 and 2), whereas (Ic) crystallizes in space group P1 with Z = 2. In (Ia) and (Ib) the pigment molecules (I) are situated on crystallographic inversion centres. In (Ic), there are two symmetry-independent pigment molecules, both on inversion centres (Fig. 3). The refinement of the pigment molecules of (Ic) could be performed without any difficulties, but the solvent molecules are heavily disordered. In the difference Fourier synthesis there are six peaks with electron densities of 1.0 to 2.3 e Å^-3. No reasonable model could be found for a successful refinement with either NMP or butan-1-ol as solvent. A comparison with the crystal structures of (Ia) and (Ib) showed that the solvent molecules should occupy a volume of 374 ų per unit cell. According to Hofmann's volume increments (Hofmann, 2002), an NMP molecule has a volume of 147 ų and butan-1-ol one of 117 ų. Hence, the unit cell may contain e.g. two molecules of butan-1-ol and one molecule of NMP (sum 381 ų), or two molecules of NMP and a partial molecule of butan-1-ol. In the former case, the crystal would have a composition of 2C₃₄H₂₂N₄O₄.C₅H₉NO.2C₄H₁₀O. Lattice energy minimizations were performed with the aim of obtaining possible positions for the solvent molecules but the results were inconclusive. Thus, in (Ic) the contribution of the solvent molecules to the scattering was suppressed using the SQUEEZE procedure in PLATON (van der Sluis & Spek, 1990; Spek, 2009; see Experimental). By this means the void is calculated to contain about 48 electrons, which is much less than assumed by the formula 2C₃₄H₂₂N₄O₄.C₅H₉NO.2C₄H₁₀O (138 electrons). This indicates that the solvent positions might be only partially occupied.

The structures of (Ia) and (Ib) are pseudo-isomorphic. The lattice parameters are similar and the pigment molecules and two NMP molecules have similar arrangements in both structures, but the disordered propan-2-ol molecule in (Ia) is replaced by a disordered NMP molecule in (Ib). Correspondingly, the unit-cell volume of (Ia) is 52 ų smaller than that of (Ib). In all three structures, the pigment molecules are essentially planar except for the linking phenylene moieties, which are rotated out of the pyrido[1,2-a]pyrimidin-1-ium plane by 82.17 (6)° in (Ia), 79.51 (8)° in (Ib), and 88.16 (12) and 79.07 (10)° for the two independent molecules in (Ic). Thus, the phenylene moieties are oriented nearly orthogonal to the rest of the molecule, to avoid steric hindrance between the phenylene H atom and the atoms of the heterocyclic system. The terminal phenyl ring is also rotated out of the pyrido[1,2-a]pyrimidin-1-ium plane. The dihedral angles are 23.24 (7)° in (Ia), 28.76 (10)° in (Ib), and 44.79 (15) and 35.68 (15)° in (Ic). Apparently this dihedral angle can be easily influenced by the molecular packing. In (Ia) only the propan-2-ol is disordered (see Fig. 4), whereas in (Ib) all NMP molecules are disordered (Fig. 2). In one NMP molecule, the N—CH₃ group (atoms N41 and C41) is disordered with a CH₂ group (atom C43), whereas the C═O group maintains its position. The other NMP molecule is located on a crystallographic inversion centre between the N atom and the carbonyl C atom, which leads to a disorder of all atoms. In (Ia), the propan-2-ol molecule forms a hydrogen bond to an NMP molecule (Fig. 4, Table 1). Compounds (Ia) and (Ib) display layer structures in which the pigment and solvent molecules are arranged in alternating layers (Figs. 5 and 6). In compound (Ic), the molecules form columns in the [100] direction; the solvent molecules are embedded in channels situated between the columns (Fig. 7).

In all structures, the out-of-plane rotation of the central phenylene ring results in a cross-shaped molecular conformation which hinders efficient molecular packing (as for several spiro compounds). This may be the reason that the solvent molecules are incorporated into the crystals.

The bond lengths in the mesoionic ring system (see Table 2 and Fig. 8) are in agreement with the values found for (II). The bond lengths show that the positive charge is delocalized over the N1/C6/N5 fragment and the adjacent pyridine ring, whereas the negative charge is distributed over the O2/C2–C4/O4 fragment. Between these two fragments the conjugation is weak, as can be seen from the long N1—C2 and C4—N5 bond lengths.

Solvent-free single crystals of (I) could not be obtained. All crystals of (I) collapse when they are dried at room temperature, resulting in powders of such low crystallinity that crystal structure solution from the powder data, which nowadays can be done routinely (David et al., 1998; Nowell et al., 2002; van de Streek et al., 2009), failed. None of the powder patterns could be indexed in a reasonable way [DIVCOL06 (Boultif & Louër, 2004); MCMAILLE (Version 4.0; Bergmann et al., 2004)]. The powder patterns of (I) were unrelated to the simulated powder patterns of (Ia), (Ib) or (Ic). Therefore, the crystal structure of solvent-free compound (I) could not be determined.

S2. Experimental

Compound (I) was synthesized according to the method of Metz & Plüg (2005) (see scheme). The obtained powder was stirred in dimethylformamide for 30–60 min, filtered, and dried at 353–373 K, giving 10 g of (I).

For crystals of (Ia), a suspension of compound (I) (10 mg) in N-methylpyrrolidone (2 ml) was heated in a beaker to 477 K, then cooled down to room temperature. The beaker was placed into a larger beaker and next to the smaller beaker propan-2-ol (4 ml) was added. The larger beaker was sealed and kept for 3 d. Yellow fluorescent crystals of (Ia) were obtained, with sizes up to 0.8 × 0.4 × 0.4 mm.

For crystals of (Ib), the crystallization was carried out as for (Ia), but butan-1-ol (2 ml) was used instead of propan-2-ol. After 2 d, yellow fluorescent crystals of (Ib) were obtained, with sizes up to 1.2 × 1.2 × 0.4 mm.

For crystals of (Ic), the crystallization was carried out as for (Ia), but using butan-1-ol (4 ml) instead of propan-2-ol. Yellow fluorescent crystals of (Ic) were obtained, with sizes up to 1.8 × 0.9 × 0.9 mm.

For the phase analysis the powder samples were measured on a Stoe STADI-P powder diffractometer [curved Ge(111) primary monochromator, Cu Kα₁ radiation, λ = 1.5406 Å] in transmission geometry from 2 to 74° in 2θ. All samples were prepared between two polyacetate films. An image-plate position-sensitive detector (IPPSD) was used. For data acquisition the Stoe software WinXPOW (Reference?) was used.

S3. Refinement

In (Ia) the propan-2-ol molecule is disordered across a centre of inversion over two equally occupied sites. The C—C bonds and C—C—O angles in this molecule were restrained to be equal with effective s.u.s of 0.02 and 0.04, respectively. The highest peak in the final difference density map (0.72 e Å^-3) is located 0.93 Å from atom H41B.

Both N-methylpyrrolidone molecules of (Ib) are disordered over two equally occupied sites. One is located on a centre of inversion, the other on a general position. In both of them, the atoms sharing the same site were refined with coordinates and displacement parameters constrained to the same values. The bonds between the methylene C atoms were restrained to 1.500 (1) Å. The highest peak in the final difference density map (0.90 e Å^-3) is located 0.43 Å from atom C54.

From the enlarged atomic displacement parameters for some atoms of the solvent molecules in (Ia) and (Ib), it is evident that the solvent molecules are highly disordered and that the best refined models only approximate the true average arrangement. The geometric parameters of the solvent molecules should therefore be considered to be only approximate.

The H atoms for (Ia), (Ib) and (Ic) were located in difference maps, but were geometrically positioned and refined using a riding model with fixed individual displacement parameters [U_iso(H) = 1.2U_eq(C,O) or 1.5 U_eq(C_methyl)] and with O—H = 0.84 Å, C_aromatic—H = 0.95 Å, C_methylene—H = 0.99 Å or C_methyl—H = 0.98 Å. The methyl groups were allowed to rotate but not to tip. The torsion angle about the C—O bond of each hydroxyl group was refined.

The solvent molecules in (Ic) are severely disordered and could not be modelled. The contribution of the disordered solvent to the calculated structure factors was taken into account following the BYPASS algorithm (van der Sluis & Spek, 1990), implemented as the SQUEEZE option in PLATON (Spek, 2009). The final F_o²/F_c² data were calculated with the FCF routine of PLATON and include the disordered solvent contribution. PLATON found one void (volume 386 ų) in the unit cell (located at x = -0.053, y = 0.000, z = 1/2) and estimated that there are approximately 48 electrons in this void. For calculating M_r, µ, ρ etc. we assumed a composition of C₃₄H₂₂N₄O₄.0.5C₅H₉NO.C₄H₁₀O. Although we had suppressed the contribution of the solvent to the scattering power for (Ic), the figures of merit remain rather high. This is most probably due to the low quality of the crystal [expressed in R(int) = 0.0875 and R(σ) = 0.1178]. However, this crystal was the best we could obtain.

Computing details

For all compounds, data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Version 2.0; Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures

	Fig. 1. Molecular structure of (Ia), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Molecular structure of (Ib), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. Molecular structure of (Ic), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. The disorder of one propan-2-ol molecule between two NMP molecules in (Ia). The crystallographic inversion centre is shown as a small circle.
	Fig. 5. The packing of (Ia). Molecules of (I) are shaded light and solvent molecules are dark (yellow and blue, respectively, in the electronic version of the journal).
	Fig. 6. The packing of (Ib). Molecules of (I) are shaded light and solvent molecules are dark (yellow and blue, respectively, in the electronic version of the journal).
	Fig. 7. The packing of (Ic), viewed along [100]. The channels are filled by disordered solvent molecules, which were omitted from the model.
	Fig. 8. Charge delocalization and atom numbering in the mesoionic heterocycle of (I).

(Ia) p-phenylenebis(2-oxo-3-phenyl-1,2-dihydropyrido[1,2- a]pyrimidin-5-ium-4-olate)–N-methylpyrrolidone–propan-2-ol (1/2/1)

Crystal data

C34H22N4O4·2C5H9NO·C3H8O	Z = 1
Mr = 808.91	F(000) = 428
Triclinic, P1	Dx = 1.334 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7737 (10) Å	Cell parameters from 21638 reflections
b = 10.4982 (11) Å	θ = 3.7–26.4°
c = 11.7877 (12) Å	µ = 0.09 mm^−1
α = 98.463 (8)°	T = 173 K
β = 101.314 (8)°	Block, yellow
γ = 104.750 (8)°	0.53 × 0.32 × 0.26 mm
V = 1007.07 (19) Å^3

Data collection

Stoe IPDS II two-circle diffractometer	3305 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.053
Graphite monochromator	θmax = 26.5°, θmin = 3.7°
ω scans	h = −10→10
19547 measured reflections	k = −13→13
4103 independent reflections	l = −14→13

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.181	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.111P)^2 + 0.3234P] where P = (Fo^2 + 2Fc^2)/3
4103 reflections	(Δ/σ)max < 0.001
290 parameters	Δρmax = 0.72 e Å^−3
2 restraints	Δρmin = −0.33 e Å^−3

Special details

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.

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	Occ. (<1)
N1	0.55844 (17)	0.74906 (13)	0.44080 (13)	0.0262 (3)
C2	0.4219 (2)	0.64036 (16)	0.37141 (16)	0.0274 (4)
O2	0.29201 (16)	0.66674 (13)	0.34789 (14)	0.0408 (4)
C3	0.4507 (2)	0.51325 (16)	0.33708 (15)	0.0256 (4)
C4	0.6071 (2)	0.49768 (16)	0.36619 (15)	0.0272 (4)
O4	0.65244 (16)	0.39656 (12)	0.34775 (14)	0.0392 (4)
N5	0.74065 (17)	0.62329 (13)	0.42715 (13)	0.0253 (3)
C6	0.7133 (2)	0.74179 (16)	0.46615 (15)	0.0252 (4)
C7	0.8456 (2)	0.85140 (17)	0.53172 (17)	0.0312 (4)
H7	0.8275	0.9332	0.5637	0.037*
C8	1.0004 (2)	0.84065 (19)	0.54965 (18)	0.0350 (4)
H8	1.0895	0.9143	0.5952	0.042*
C9	1.0273 (2)	0.71982 (19)	0.50034 (19)	0.0356 (4)
H9	1.1345	0.7128	0.5079	0.043*
C10	0.8970 (2)	0.61409 (18)	0.44203 (17)	0.0315 (4)
H10	0.9138	0.5315	0.4106	0.038*
C11	0.52830 (19)	0.87812 (16)	0.47173 (16)	0.0257 (4)
C12	0.4773 (2)	0.90745 (16)	0.57391 (16)	0.0285 (4)
H12	0.4622	0.8442	0.6236	0.034*
C13	0.4485 (2)	1.03164 (17)	0.60257 (16)	0.0285 (4)
H13	0.4135	1.0540	0.6722	0.034*
C31	0.3120 (2)	0.39662 (16)	0.26643 (15)	0.0276 (4)
C32	0.1515 (2)	0.38518 (18)	0.27442 (17)	0.0328 (4)
H32	0.1305	0.4533	0.3263	0.039*
C33	0.0231 (2)	0.2760 (2)	0.20777 (19)	0.0397 (5)
H33	−0.0844	0.2702	0.2148	0.048*
C34	0.0504 (3)	0.17544 (19)	0.13120 (19)	0.0436 (5)
H34	−0.0375	0.1006	0.0861	0.052*
C35	0.2072 (3)	0.1853 (2)	0.1212 (2)	0.0454 (5)
H35	0.2265	0.1173	0.0681	0.055*
C36	0.3371 (3)	0.29388 (18)	0.18798 (18)	0.0364 (4)
H36	0.4441	0.2985	0.1804	0.044*
N41	0.9436 (3)	0.7366 (2)	0.1713 (2)	0.0613 (6)
C41	1.0889 (4)	0.8517 (3)	0.2230 (3)	0.0619 (7)
H41A	1.0565	0.9338	0.2398	0.093*
H41B	1.1584	0.8615	0.1671	0.093*
H41C	1.1491	0.8365	0.2966	0.093*
C42	0.8000 (5)	0.7416 (4)	0.1798 (3)	0.0768 (10)
O42	0.7721 (4)	0.8386 (3)	0.2386 (2)	0.0939 (9)
C43	0.6787 (4)	0.6104 (4)	0.1064 (3)	0.0710 (8)
H43A	0.6001	0.5714	0.1509	0.085*
H43B	0.6182	0.6252	0.0317	0.085*
C44	0.7815 (5)	0.5195 (4)	0.0821 (4)	0.0870 (10)
H44A	0.7411	0.4657	0.0002	0.104*
H44B	0.7817	0.4576	0.1378	0.104*
C45	0.9556 (4)	0.6180 (3)	0.1003 (2)	0.0575 (6)
H45A	1.0404	0.5833	0.1425	0.069*
H45B	0.9786	0.6349	0.0241	0.069*
C51	0.4168 (8)	0.8510 (8)	0.0339 (8)	0.080 (2)	0.50
H51A	0.4204	0.8097	0.1033	0.120*	0.50
H51B	0.4618	0.8039	−0.0233	0.120*	0.50
H51C	0.3040	0.8445	−0.0027	0.120*	0.50
C52	0.5135 (14)	0.9936 (11)	0.0704 (10)	0.077 (2)	0.50
H52A	0.4716	1.0404	0.1323	0.092*	0.50
O52	0.6812 (5)	1.0130 (5)	0.1134 (5)	0.0825 (13)	0.50
H52	0.6984	0.9380	0.1142	0.099*	0.50
C53	0.498 (3)	1.055 (3)	−0.0312 (16)	0.209 (15)	0.50
H53A	0.5623	1.1501	−0.0080	0.313*	0.50
H53B	0.3835	1.0484	−0.0623	0.313*	0.50
H53C	0.5377	1.0085	−0.0923	0.313*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0244 (7)	0.0194 (7)	0.0354 (8)	0.0099 (5)	0.0066 (6)	0.0023 (5)
C2	0.0260 (8)	0.0224 (8)	0.0334 (9)	0.0090 (6)	0.0063 (7)	0.0028 (6)
O2	0.0267 (7)	0.0288 (7)	0.0619 (9)	0.0136 (5)	0.0010 (6)	−0.0024 (6)
C3	0.0294 (8)	0.0206 (7)	0.0283 (8)	0.0093 (6)	0.0082 (7)	0.0044 (6)
C4	0.0327 (9)	0.0202 (7)	0.0312 (9)	0.0109 (6)	0.0096 (7)	0.0051 (6)
O4	0.0380 (7)	0.0236 (6)	0.0575 (9)	0.0170 (5)	0.0089 (6)	0.0026 (6)
N5	0.0262 (7)	0.0223 (7)	0.0314 (7)	0.0122 (5)	0.0085 (6)	0.0063 (5)
C6	0.0262 (8)	0.0229 (8)	0.0300 (8)	0.0113 (6)	0.0084 (6)	0.0069 (6)
C7	0.0294 (9)	0.0238 (8)	0.0398 (10)	0.0097 (7)	0.0057 (7)	0.0052 (7)
C8	0.0264 (9)	0.0295 (9)	0.0471 (11)	0.0071 (7)	0.0048 (8)	0.0089 (8)
C9	0.0245 (8)	0.0375 (10)	0.0494 (11)	0.0142 (7)	0.0101 (8)	0.0129 (8)
C10	0.0302 (9)	0.0313 (9)	0.0396 (10)	0.0176 (7)	0.0112 (7)	0.0090 (7)
C11	0.0215 (7)	0.0192 (7)	0.0357 (9)	0.0091 (6)	0.0047 (6)	0.0012 (6)
C12	0.0294 (8)	0.0231 (8)	0.0353 (9)	0.0105 (6)	0.0086 (7)	0.0070 (6)
C13	0.0291 (8)	0.0249 (8)	0.0338 (9)	0.0117 (6)	0.0102 (7)	0.0028 (6)
C31	0.0330 (9)	0.0221 (8)	0.0280 (8)	0.0088 (7)	0.0067 (7)	0.0064 (6)
C32	0.0339 (9)	0.0278 (8)	0.0354 (9)	0.0077 (7)	0.0073 (7)	0.0060 (7)
C33	0.0336 (10)	0.0350 (10)	0.0461 (11)	0.0044 (8)	0.0046 (8)	0.0117 (8)
C34	0.0448 (11)	0.0279 (9)	0.0441 (11)	0.0015 (8)	−0.0054 (9)	0.0024 (8)
C35	0.0553 (13)	0.0288 (9)	0.0431 (11)	0.0103 (9)	0.0035 (9)	−0.0054 (8)
C36	0.0414 (10)	0.0275 (9)	0.0383 (10)	0.0108 (8)	0.0088 (8)	0.0009 (7)
N41	0.0817 (16)	0.0693 (14)	0.0526 (12)	0.0466 (12)	0.0241 (11)	0.0199 (10)
C41	0.0725 (17)	0.0473 (13)	0.0646 (16)	0.0244 (12)	0.0064 (13)	0.0094 (12)
C42	0.103 (2)	0.119 (3)	0.0499 (15)	0.076 (2)	0.0379 (16)	0.0416 (17)
O42	0.135 (2)	0.129 (2)	0.0654 (13)	0.0988 (19)	0.0513 (14)	0.0255 (13)
C43	0.0662 (17)	0.099 (2)	0.0485 (15)	0.0157 (16)	0.0180 (13)	0.0271 (15)
C44	0.086 (2)	0.075 (2)	0.088 (2)	0.0153 (18)	0.0072 (19)	0.0162 (18)
C45	0.0821 (18)	0.0527 (14)	0.0486 (13)	0.0366 (13)	0.0191 (12)	0.0099 (11)
C51	0.052 (3)	0.103 (6)	0.091 (5)	0.031 (4)	0.029 (3)	0.005 (4)
C52	0.075 (5)	0.124 (6)	0.077 (5)	0.072 (5)	0.046 (4)	0.048 (5)
O52	0.053 (2)	0.074 (3)	0.120 (4)	0.020 (2)	0.013 (2)	0.026 (3)
C53	0.171 (18)	0.46 (5)	0.153 (17)	0.23 (3)	0.141 (16)	0.18 (2)

Geometric parameters (Å, º)

N1—C6	1.357 (2)	C34—H34	0.9500
N1—C2	1.432 (2)	C35—C36	1.393 (3)
N1—C11	1.454 (2)	C35—H35	0.9500
C2—O2	1.230 (2)	C36—H36	0.9500
C2—C3	1.436 (2)	N41—C42	1.297 (4)
C3—C4	1.404 (2)	N41—C45	1.433 (3)
C3—C31	1.489 (2)	N41—C41	1.467 (4)
C4—O4	1.230 (2)	C41—H41A	0.9800
C4—N5	1.494 (2)	C41—H41B	0.9800
N5—C6	1.358 (2)	C41—H41C	0.9800
N5—C10	1.379 (2)	C42—O42	1.250 (4)
C6—C7	1.405 (2)	C42—C43	1.524 (5)
C7—C8	1.370 (3)	C43—C44	1.505 (5)
C7—H7	0.9500	C43—H43A	0.9900
C8—C9	1.411 (3)	C43—H43B	0.9900
C8—H8	0.9500	C44—C45	1.565 (5)
C9—C10	1.354 (3)	C44—H44A	0.9900
C9—H9	0.9500	C44—H44B	0.9900
C10—H10	0.9500	C45—H45A	0.9900
C11—C12	1.385 (3)	C45—H45B	0.9900
C11—C13^i	1.386 (3)	C51—C52	1.472 (15)
C12—C13	1.396 (2)	C51—H51A	0.9800
C12—H12	0.9500	C51—H51B	0.9800
C13—C11^i	1.386 (3)	C51—H51C	0.9800
C13—H13	0.9500	C52—O52	1.410 (12)
C31—C32	1.405 (3)	C52—C53	1.440 (12)
C31—C36	1.405 (3)	C52—H52A	1.0000
C32—C33	1.390 (3)	O52—H52	0.8400
C32—H32	0.9500	C53—H53A	0.9800
C33—C34	1.385 (3)	C53—H53B	0.9800
C33—H33	0.9500	C53—H53C	0.9800
C34—C35	1.383 (3)
C6—N1—C2	123.90 (14)	C36—C35—H35	119.6
C6—N1—C11	119.28 (13)	C35—C36—C31	120.84 (19)
C2—N1—C11	116.34 (13)	C35—C36—H36	119.6
O2—C2—N1	115.85 (15)	C31—C36—H36	119.6
O2—C2—C3	127.11 (16)	C42—N41—C45	117.8 (3)
N1—C2—C3	117.04 (15)	C42—N41—C41	122.0 (3)
C4—C3—C2	121.45 (15)	C45—N41—C41	120.0 (2)
C4—C3—C31	119.53 (14)	N41—C41—H41A	109.5
C2—C3—C31	119.00 (15)	N41—C41—H41B	109.5
O4—C4—C3	130.07 (16)	H41A—C41—H41B	109.5
O4—C4—N5	114.36 (15)	N41—C41—H41C	109.5
C3—C4—N5	115.56 (14)	H41A—C41—H41C	109.5
C6—N5—C10	120.50 (15)	H41B—C41—H41C	109.5
C6—N5—C4	123.06 (14)	O42—C42—N41	124.5 (4)
C10—N5—C4	116.44 (14)	O42—C42—C43	128.2 (3)
N1—C6—N5	118.40 (15)	N41—C42—C43	107.3 (3)
N1—C6—C7	122.63 (15)	C44—C43—C42	104.5 (3)
N5—C6—C7	118.97 (15)	C44—C43—H43A	110.9
C8—C7—C6	120.20 (17)	C42—C43—H43A	110.9
C8—C7—H7	119.9	C44—C43—H43B	110.9
C6—C7—H7	119.9	C42—C43—H43B	110.9
C7—C8—C9	119.82 (17)	H43A—C43—H43B	108.9
C7—C8—H8	120.1	C43—C44—C45	104.4 (3)
C9—C8—H8	120.1	C43—C44—H44A	110.9
C10—C9—C8	118.58 (17)	C45—C44—H44A	110.9
C10—C9—H9	120.7	C43—C44—H44B	110.9
C8—C9—H9	120.7	C45—C44—H44B	110.9
C9—C10—N5	121.63 (16)	H44A—C44—H44B	108.9
C9—C10—H10	119.2	N41—C45—C44	101.2 (2)
N5—C10—H10	119.2	N41—C45—H45A	111.5
C12—C11—C13^i	121.92 (15)	C44—C45—H45A	111.5
C12—C11—N1	119.37 (15)	N41—C45—H45B	111.5
C13^i—C11—N1	118.71 (15)	C44—C45—H45B	111.5
C11—C12—C13	118.83 (16)	H45A—C45—H45B	109.3
C11—C12—H12	120.6	C52—C51—H51A	109.5
C13—C12—H12	120.6	C52—C51—H51B	109.5
C11^i—C13—C12	119.25 (16)	H51A—C51—H51B	109.5
C11^i—C13—H13	120.4	C52—C51—H51C	109.5
C12—C13—H13	120.4	H51A—C51—H51C	109.5
C32—C31—C36	117.41 (16)	H51B—C51—H51C	109.5
C32—C31—C3	121.75 (16)	O52—C52—C53	106.1 (7)
C36—C31—C3	120.84 (16)	O52—C52—C51	113.6 (7)
C33—C32—C31	121.17 (18)	C53—C52—C51	108.7 (14)
C33—C32—H32	119.4	O52—C52—H52A	109.4
C31—C32—H32	119.4	C53—C52—H52A	109.4
C34—C33—C32	120.57 (19)	C51—C52—H52A	109.4
C34—C33—H33	119.7	C52—O52—H52	109.5
C32—C33—H33	119.7	C52—C53—H53A	109.5
C35—C34—C33	119.21 (17)	C52—C53—H53B	109.5
C35—C34—H34	120.4	H53A—C53—H53B	109.5
C33—C34—H34	120.4	C52—C53—H53C	109.5
C34—C35—C36	120.80 (19)	H53A—C53—H53C	109.5
C34—C35—H35	119.6	H53B—C53—H53C	109.5
C6—N1—C2—O2	−173.91 (17)	C4—N5—C10—C9	−177.21 (16)
C11—N1—C2—O2	−1.9 (2)	C6—N1—C11—C12	−99.30 (19)
C6—N1—C2—C3	6.2 (2)	C2—N1—C11—C12	88.33 (19)
C11—N1—C2—C3	178.17 (15)	C6—N1—C11—C13^i	80.8 (2)
O2—C2—C3—C4	177.59 (18)	C2—N1—C11—C13^i	−91.59 (19)
N1—C2—C3—C4	−2.5 (2)	C13^i—C11—C12—C13	0.0 (3)
O2—C2—C3—C31	−0.8 (3)	N1—C11—C12—C13	−179.90 (15)
N1—C2—C3—C31	179.06 (14)	C11—C12—C13—C11^i	0.0 (3)
C2—C3—C4—O4	177.25 (18)	C4—C3—C31—C32	153.47 (17)
C31—C3—C4—O4	−4.3 (3)	C2—C3—C31—C32	−28.1 (2)
C2—C3—C4—N5	−4.0 (2)	C4—C3—C31—C36	−27.1 (2)
C31—C3—C4—N5	174.41 (14)	C2—C3—C31—C36	151.36 (17)
O4—C4—N5—C6	−172.88 (16)	C36—C31—C32—C33	0.4 (3)
C3—C4—N5—C6	8.2 (2)	C3—C31—C32—C33	179.84 (16)
O4—C4—N5—C10	7.5 (2)	C31—C32—C33—C34	−0.2 (3)
C3—C4—N5—C10	−171.44 (15)	C32—C33—C34—C35	−0.4 (3)
C2—N1—C6—N5	−2.4 (3)	C33—C34—C35—C36	0.8 (3)
C11—N1—C6—N5	−174.14 (15)	C34—C35—C36—C31	−0.6 (3)
C2—N1—C6—C7	178.16 (16)	C32—C31—C36—C35	0.0 (3)
C11—N1—C6—C7	6.4 (3)	C3—C31—C36—C35	−179.48 (18)
C10—N5—C6—N1	174.54 (16)	C45—N41—C42—O42	180.0 (3)
C4—N5—C6—N1	−5.1 (2)	C41—N41—C42—O42	−5.3 (4)
C10—N5—C6—C7	−6.0 (2)	C45—N41—C42—C43	−0.1 (3)
C4—N5—C6—C7	174.42 (15)	C41—N41—C42—C43	174.7 (2)
N1—C6—C7—C8	−176.68 (17)	O42—C42—C43—C44	−166.1 (3)
N5—C6—C7—C8	3.9 (3)	N41—C42—C43—C44	14.0 (3)
C6—C7—C8—C9	1.1 (3)	C42—C43—C44—C45	−20.9 (3)
C7—C8—C9—C10	−3.9 (3)	C42—N41—C45—C44	−13.1 (3)
C8—C9—C10—N5	1.9 (3)	C41—N41—C45—C44	172.0 (2)
C6—N5—C10—C9	3.2 (3)	C43—C44—C45—N41	20.3 (3)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O52—H52···O42	0.84	2.02	2.691 (5)	137

(Ib) p-phenylenebis(2-oxo-3-phenyl-1,2-dihydropyrido[1,2- a]pyrimidin-5-ium-4-olate)–N-methylpyrrolidone (1/3)

Crystal data

C34H22N4O4·3C5H9NO	Z = 1
Mr = 847.95	F(000) = 448
Triclinic, P1	Dx = 1.329 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8137 (8) Å	Cell parameters from 14799 reflections
b = 10.1565 (9) Å	θ = 3.7–26.4°
c = 12.7300 (11) Å	µ = 0.09 mm^−1
α = 99.212 (7)°	T = 173 K
β = 99.567 (7)°	Plate, yellow
γ = 105.102 (7)°	0.24 × 0.23 × 0.13 mm
V = 1059.84 (16) Å^3

Data collection

Stoe IPDS II two-circle diffractometer	3513 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.035
Graphite monochromator	θmax = 26.4°, θmin = 3.6°
ω scans	h = −10→10
15396 measured reflections	k = −12→12
4290 independent reflections	l = −15→15

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)] = 0.080	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.223	H-atom parameters constrained
S = 1.20	w = 1/[σ^2(Fo^2) + (0.0957P)^2 + 0.9685P] where P = (Fo^2 + 2Fc^2)/3
4290 reflections	(Δ/σ)max < 0.001
298 parameters	Δρmax = 0.90 e Å^−3
2 restraints	Δρmin = −1.05 e Å^−3

Special details

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.

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	Occ. (<1)
N1	0.4405 (2)	0.26030 (19)	0.55528 (17)	0.0242 (4)
C2	0.5747 (3)	0.3720 (2)	0.6210 (2)	0.0265 (5)
O2	0.7048 (2)	0.3471 (2)	0.63636 (19)	0.0446 (6)
C3	0.5429 (3)	0.5000 (2)	0.66306 (19)	0.0237 (5)
C4	0.3872 (3)	0.5144 (2)	0.6418 (2)	0.0249 (5)
O4	0.3401 (2)	0.61624 (17)	0.66966 (17)	0.0354 (5)
N5	0.2570 (2)	0.38703 (19)	0.57638 (17)	0.0234 (4)
C6	0.2858 (3)	0.2665 (2)	0.5333 (2)	0.0232 (5)
C7	0.1571 (3)	0.1546 (2)	0.4680 (2)	0.0295 (5)
H7	0.1771	0.0720	0.4346	0.035*
C8	0.0032 (3)	0.1644 (3)	0.4526 (2)	0.0339 (6)
H8	−0.0834	0.0894	0.4076	0.041*
C9	−0.0260 (3)	0.2863 (3)	0.5039 (3)	0.0366 (6)
H9	−0.1327	0.2926	0.4971	0.044*
C10	0.1013 (3)	0.3949 (3)	0.5634 (2)	0.0303 (6)
H10	0.0825	0.4781	0.5967	0.036*
C11	0.4702 (3)	0.1259 (2)	0.5251 (2)	0.0235 (5)
C12	0.5351 (3)	0.0990 (2)	0.4350 (2)	0.0260 (5)
H12	0.5584	0.1661	0.3913	0.031*
C13	0.5654 (3)	−0.0295 (2)	0.4099 (2)	0.0263 (5)
H13	0.6102	−0.0507	0.3487	0.032*
C31	0.6781 (3)	0.6165 (2)	0.7364 (2)	0.0271 (5)
C32	0.8374 (3)	0.6368 (3)	0.7251 (2)	0.0369 (6)
H32	0.8596	0.5779	0.6675	0.044*
C33	0.9645 (3)	0.7421 (3)	0.7970 (3)	0.0475 (8)
H33	1.0717	0.7535	0.7881	0.057*
C34	0.9348 (4)	0.8297 (3)	0.8811 (3)	0.0501 (8)
H34	1.0211	0.9010	0.9301	0.060*
C35	0.7779 (4)	0.8121 (3)	0.8931 (3)	0.0492 (8)
H35	0.7566	0.8722	0.9505	0.059*
C36	0.6508 (3)	0.7070 (3)	0.8219 (2)	0.0380 (6)
H36	0.5440	0.6966	0.8313	0.046*
N41	−0.0022 (13)	0.2372 (9)	0.8047 (6)	0.167 (4)	0.50
C41"	−0.0022 (13)	0.2372 (9)	0.8047 (6)	0.167 (4)	0.50
H41G	−0.0502	0.1586	0.8344	0.200*	0.50
H41H	−0.0680	0.2354	0.7365	0.200*	0.50
C41	−0.1115 (13)	0.1371 (9)	0.7618 (9)	0.085 (4)	0.50
H41A	−0.0719	0.0735	0.7148	0.127*	0.50
H41B	−0.1519	0.0915	0.8181	0.127*	0.50
H41C	−0.1986	0.1610	0.7179	0.127*	0.50
C42	0.1350 (6)	0.2248 (5)	0.7862 (4)	0.0705 (12)
O42	0.1821 (3)	0.1443 (3)	0.7287 (2)	0.0644 (7)
C43	0.2518 (9)	0.3502 (8)	0.8621 (4)	0.118 (2)	0.50
H43A	0.3205	0.4042	0.8203	0.142*	0.50
H43B	0.3223	0.3196	0.9161	0.142*	0.50
N43	0.2518 (9)	0.3502 (8)	0.8621 (4)	0.118 (2)	0.50
C41'	0.4066 (11)	0.3595 (9)	0.8789 (7)	0.075 (3)	0.50
H41D	0.4684	0.4471	0.9304	0.112*	0.50
H41E	0.4243	0.2805	0.9092	0.112*	0.50
H41F	0.4417	0.3577	0.8097	0.112*	0.50
C44	0.1726 (11)	0.4372 (10)	0.9177 (6)	0.141 (3)
H44A	0.1995	0.5305	0.8986	0.170*
H44B	0.2084	0.4498	0.9976	0.170*
C45	−0.0004 (8)	0.3647 (6)	0.8815 (4)	0.0900 (16)
H45A	−0.0491	0.3407	0.9433	0.108*
H45B	−0.0582	0.4218	0.8445	0.108*
N51	0.4449 (4)	0.9521 (5)	0.9636 (3)	0.0671 (10)	0.50
C52	0.4449 (4)	0.9521 (5)	0.9636 (3)	0.0671 (10)	0.50
C51	0.3660 (6)	0.8360 (5)	0.9988 (4)	0.0997 (14)	0.50
H51A	0.2868	0.7734	0.9354	0.149*	0.50
H51B	0.4422	0.7882	1.0269	0.149*	0.50
H51C	0.3105	0.8625	1.0557	0.149*	0.50
O52	0.3660 (6)	0.8360 (5)	0.9988 (4)	0.0997 (14)	0.50
C55	0.4162 (4)	0.9703 (4)	0.8517 (3)	0.0587 (9)
H55A	0.3115	0.9881	0.8298	0.070*
H55B	0.4222	0.8888	0.8000	0.070*
C54	0.5553 (9)	1.1015 (7)	0.8832 (5)	0.092 (3)	0.50
H54A	0.5189	1.1711	0.8477	0.110*	0.50
H54B	0.6376	1.0754	0.8472	0.110*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0184 (9)	0.0166 (9)	0.0358 (11)	0.0063 (7)	0.0041 (8)	0.0004 (8)
C2	0.0200 (11)	0.0211 (11)	0.0346 (13)	0.0053 (9)	0.0029 (9)	−0.0005 (9)
O2	0.0212 (9)	0.0352 (10)	0.0668 (14)	0.0123 (8)	−0.0029 (8)	−0.0127 (9)
C3	0.0231 (11)	0.0174 (10)	0.0280 (12)	0.0034 (8)	0.0048 (9)	0.0023 (9)
C4	0.0255 (11)	0.0158 (10)	0.0322 (12)	0.0051 (8)	0.0061 (9)	0.0041 (9)
O4	0.0317 (9)	0.0196 (8)	0.0531 (12)	0.0117 (7)	0.0058 (8)	−0.0003 (8)
N5	0.0189 (9)	0.0172 (9)	0.0339 (11)	0.0062 (7)	0.0045 (8)	0.0043 (8)
C6	0.0187 (10)	0.0183 (10)	0.0323 (12)	0.0060 (8)	0.0043 (9)	0.0049 (9)
C7	0.0241 (12)	0.0193 (11)	0.0408 (14)	0.0053 (9)	0.0016 (10)	0.0022 (10)
C8	0.0213 (11)	0.0248 (12)	0.0496 (16)	0.0025 (9)	−0.0008 (10)	0.0073 (11)
C9	0.0193 (11)	0.0325 (13)	0.0583 (18)	0.0102 (10)	0.0044 (11)	0.0106 (12)
C10	0.0236 (12)	0.0251 (12)	0.0453 (15)	0.0126 (9)	0.0075 (10)	0.0081 (10)
C11	0.0167 (10)	0.0171 (10)	0.0340 (12)	0.0062 (8)	0.0021 (9)	−0.0003 (9)
C12	0.0243 (11)	0.0201 (11)	0.0336 (13)	0.0069 (9)	0.0070 (9)	0.0046 (9)
C13	0.0239 (11)	0.0233 (11)	0.0318 (12)	0.0084 (9)	0.0082 (9)	0.0016 (9)
C31	0.0281 (12)	0.0191 (10)	0.0303 (13)	0.0033 (9)	0.0023 (9)	0.0042 (9)
C32	0.0288 (13)	0.0332 (13)	0.0388 (15)	−0.0018 (10)	0.0070 (11)	−0.0021 (11)
C33	0.0284 (14)	0.0453 (17)	0.0532 (19)	−0.0052 (12)	0.0042 (12)	−0.0019 (14)
C34	0.0401 (16)	0.0365 (15)	0.0507 (19)	−0.0056 (12)	−0.0079 (13)	−0.0086 (13)
C35	0.0484 (17)	0.0360 (15)	0.0478 (18)	0.0052 (13)	0.0011 (14)	−0.0131 (13)
C36	0.0340 (14)	0.0294 (13)	0.0424 (16)	0.0059 (11)	0.0042 (11)	−0.0058 (11)
N41	0.311 (11)	0.200 (8)	0.156 (6)	0.224 (8)	0.176 (7)	0.133 (6)
C41"	0.311 (11)	0.200 (8)	0.156 (6)	0.224 (8)	0.176 (7)	0.133 (6)
C41	0.090 (7)	0.047 (5)	0.092 (7)	0.019 (4)	−0.028 (6)	−0.002 (5)
C42	0.115 (4)	0.068 (3)	0.063 (2)	0.055 (3)	0.048 (3)	0.036 (2)
O42	0.0692 (17)	0.0665 (16)	0.0702 (17)	0.0340 (14)	0.0281 (14)	0.0141 (13)
C43	0.190 (7)	0.171 (6)	0.076 (3)	0.132 (6)	0.081 (4)	0.076 (4)
N43	0.190 (7)	0.171 (6)	0.076 (3)	0.132 (6)	0.081 (4)	0.076 (4)
C41'	0.068 (5)	0.067 (5)	0.058 (5)	−0.026 (4)	−0.003 (4)	0.016 (4)
C44	0.166 (8)	0.180 (8)	0.105 (5)	0.107 (7)	0.026 (5)	0.018 (5)
C45	0.132 (5)	0.095 (4)	0.083 (3)	0.077 (4)	0.055 (3)	0.029 (3)
N51	0.069 (2)	0.108 (3)	0.0426 (18)	0.055 (2)	0.0138 (14)	0.0187 (18)
C52	0.069 (2)	0.108 (3)	0.0426 (18)	0.055 (2)	0.0138 (14)	0.0187 (18)
C51	0.119 (4)	0.098 (3)	0.109 (3)	0.036 (3)	0.055 (3)	0.059 (3)
O52	0.119 (4)	0.098 (3)	0.109 (3)	0.036 (3)	0.055 (3)	0.059 (3)
C55	0.063 (2)	0.069 (2)	0.0403 (18)	0.0228 (18)	0.0023 (15)	0.0072 (16)
C54	0.053 (5)	0.115 (8)	0.098 (8)	0.004 (5)	0.002 (5)	0.047 (6)

Geometric parameters (Å, º)

N1—C6	1.366 (3)	N41—C45	1.487 (9)
N1—C2	1.433 (3)	N41—H41G	0.9649
N1—C11	1.460 (3)	N41—H41H	0.9554
C2—O2	1.229 (3)	C41—H41G	0.9486
C2—C3	1.440 (3)	C41—H41H	1.0920
C3—C4	1.405 (3)	C41—H41A	0.9800
C3—C31	1.494 (3)	C41—H41B	0.9800
C4—O4	1.234 (3)	C41—H41C	0.9800
C4—N5	1.500 (3)	C42—O42	1.209 (5)
N5—C6	1.363 (3)	C42—C43	1.486 (9)
N5—C10	1.379 (3)	C43—C44	1.433 (8)
C6—C7	1.407 (3)	C43—H43A	0.9900
C7—C8	1.370 (3)	C43—H43B	0.9900
C7—H7	0.9500	C41'—H43A	1.1992
C8—C9	1.411 (4)	C41'—H43B	0.9804
C8—H8	0.9500	C41'—H41D	0.9800
C9—C10	1.362 (4)	C41'—H41E	0.9799
C9—H9	0.9500	C41'—H41F	0.9800
C10—H10	0.9500	C44—C45	1.467 (10)
C11—C12	1.384 (3)	C44—H44A	0.9941
C11—C13^i	1.388 (3)	C44—H44B	0.9905
C12—C13	1.397 (3)	C45—H45A	0.9909
C12—H12	0.9500	C45—H45B	0.9895
C13—C11^i	1.388 (3)	N51—C52^ii	1.292 (8)
C13—H13	0.9500	N51—N51^ii	1.292 (8)
C31—C32	1.400 (4)	N51—C51	1.386 (6)
C31—C36	1.403 (4)	N51—C55	1.454 (5)
C32—C33	1.399 (4)	C51—C54^ii	1.5028 (11)
C32—H32	0.9500	C51—H51A	0.9800
C33—C34	1.384 (5)	C51—H51B	0.9800
C33—H33	0.9500	C51—H51C	0.9800
C34—C35	1.385 (5)	C55—C54	1.5009 (11)
C34—H34	0.9500	C55—H55A	0.9900
C35—C36	1.395 (4)	C55—H55B	0.9900
C35—H35	0.9500	C54—O52^ii	1.5028 (10)
C36—H36	0.9500	C54—C51^ii	1.5028 (10)
N41—C41	1.181 (13)	C54—H54A	0.9900
N41—C42	1.303 (8)	C54—H54B	0.9900
C6—N1—C2	124.38 (19)	H41H—C41—H41A	102.1
C6—N1—C11	118.70 (18)	N41—C41—H41B	108.7
C2—N1—C11	116.23 (17)	H41G—C41—H41B	58.4
O2—C2—N1	116.1 (2)	H41H—C41—H41B	146.7
O2—C2—C3	126.9 (2)	H41A—C41—H41B	109.5
N1—C2—C3	116.99 (19)	N41—C41—H41C	111.6
C4—C3—C2	121.6 (2)	H41G—C41—H41C	140.5
C4—C3—C31	119.7 (2)	H41H—C41—H41C	68.0
C2—C3—C31	118.6 (2)	H41A—C41—H41C	109.5
O4—C4—C3	129.8 (2)	H41B—C41—H41C	109.5
O4—C4—N5	114.5 (2)	O42—C42—N41	137.8 (7)
C3—C4—N5	115.73 (19)	O42—C42—C43	120.2 (5)
C6—N5—C10	120.07 (19)	N41—C42—C43	102.0 (6)
C6—N5—C4	123.32 (18)	C44—C43—C42	111.9 (6)
C10—N5—C4	116.58 (19)	C44—C43—H43A	109.5
N5—C6—N1	117.89 (19)	C42—C43—H43A	108.9
N5—C6—C7	119.4 (2)	C44—C43—H43B	109.7
N1—C6—C7	122.7 (2)	C42—C43—H43B	108.9
C8—C7—C6	120.1 (2)	H43A—C43—H43B	107.9
C8—C7—H7	119.9	H43A—C41'—H43B	93.9
C6—C7—H7	119.9	H43A—C41'—H41D	98.7
C7—C8—C9	119.7 (2)	H43B—C41'—H41D	102.8
C7—C8—H8	120.2	H43A—C41'—H41E	148.7
C9—C8—H8	120.2	H43B—C41'—H41E	67.2
C10—C9—C8	118.9 (2)	H41D—C41'—H41E	109.5
C10—C9—H9	120.6	H43A—C41'—H41F	72.0
C8—C9—H9	120.6	H43B—C41'—H41F	146.3
C9—C10—N5	121.6 (2)	H41D—C41'—H41F	109.5
C9—C10—H10	119.2	H41E—C41'—H41F	109.5
N5—C10—H10	119.2	C43—C44—C45	106.0 (7)
C12—C11—C13^i	122.0 (2)	C43—C44—H44A	110.1
C12—C11—N1	119.8 (2)	C45—C44—H44A	111.2
C13^i—C11—N1	118.2 (2)	C43—C44—H44B	110.0
C11—C12—C13	118.3 (2)	C45—C44—H44B	111.0
C11—C12—H12	120.8	H44A—C44—H44B	108.6
C13—C12—H12	120.8	C44—C45—N41	101.9 (6)
C11^i—C13—C12	119.7 (2)	C44—C45—H45A	111.6
C11^i—C13—H13	120.2	N41—C45—H45A	111.3
C12—C13—H13	120.2	C44—C45—H45B	111.3
C32—C31—C36	117.3 (2)	N41—C45—H45B	111.6
C32—C31—C3	121.5 (2)	H45A—C45—H45B	109.0
C36—C31—C3	121.1 (2)	C52^ii—N51—C51	116.2 (5)
C33—C32—C31	121.3 (3)	N51^ii—N51—C51	116.2 (5)
C33—C32—H32	119.3	C52^ii—N51—C55	118.8 (5)
C31—C32—H32	119.3	N51^ii—N51—C55	118.8 (5)
C34—C33—C32	120.3 (3)	C51—N51—C55	124.9 (4)
C34—C33—H33	119.8	N51—C51—C54^ii	93.6 (4)
C32—C33—H33	119.8	N51—C51—H51A	106.9
C33—C34—C35	119.3 (3)	C54^ii—C51—H51A	158.3
C33—C34—H34	120.4	N51—C51—H51B	110.6
C35—C34—H34	120.4	C54^ii—C51—H51B	68.4
C34—C35—C36	120.6 (3)	H51A—C51—H51B	109.5
C34—C35—H35	119.7	N51—C51—H51C	110.9
C36—C35—H35	119.7	C54^ii—C51—H51C	54.7
C35—C36—C31	121.1 (3)	H51A—C51—H51C	109.5
C35—C36—H36	119.4	H51B—C51—H51C	109.5
C31—C36—H36	119.4	N51—C55—C54	89.8 (4)
C41—N41—C42	112.8 (8)	N51—C55—H55A	112.0
C41—N41—C45	129.0 (9)	C54—C55—H55A	112.7
C42—N41—C45	118.0 (9)	N51—C55—H55B	111.6
C41—N41—H41G	51.3	C54—C55—H55B	119.5
C42—N41—H41G	107.4	H55A—C55—H55B	109.9
C45—N41—H41G	106.7	C55—C54—O52^ii	120.4 (5)
C41—N41—H41H	60.4	C55—C54—C51^ii	120.4 (5)
C42—N41—H41H	107.4	C55—C54—H54A	106.3
C45—N41—H41H	106.6	O52^ii—C54—H54A	110.4
H41G—N41—H41H	110.7	C51^ii—C54—H54A	110.4
N41—C41—H41G	52.5	C55—C54—H54B	103.4
N41—C41—H41H	49.5	O52^ii—C54—H54B	107.3
H41G—C41—H41H	101.2	C51^ii—C54—H54B	107.3
N41—C41—H41A	108.1	H54A—C54—H54B	108.2
H41G—C41—H41A	110.0
C6—N1—C2—O2	177.1 (2)	C2—N1—C11—C13^i	94.4 (3)
C11—N1—C2—O2	6.8 (3)	C13^i—C11—C12—C13	−0.2 (4)
C6—N1—C2—C3	−2.0 (4)	N1—C11—C12—C13	178.6 (2)
C11—N1—C2—C3	−172.3 (2)	C11—C12—C13—C11^i	0.2 (4)
O2—C2—C3—C4	−178.4 (3)	C4—C3—C31—C32	−152.0 (2)
N1—C2—C3—C4	0.7 (4)	C2—C3—C31—C32	31.6 (4)
O2—C2—C3—C31	−2.0 (4)	C4—C3—C31—C36	30.2 (4)
N1—C2—C3—C31	177.0 (2)	C2—C3—C31—C36	−146.2 (3)
C2—C3—C4—O4	−178.7 (3)	C36—C31—C32—C33	0.8 (4)
C31—C3—C4—O4	5.0 (4)	C3—C31—C32—C33	−177.1 (3)
C2—C3—C4—N5	2.1 (3)	C31—C32—C33—C34	−0.4 (5)
C31—C3—C4—N5	−174.2 (2)	C32—C33—C34—C35	−0.1 (5)
O4—C4—N5—C6	176.5 (2)	C33—C34—C35—C36	0.3 (5)
C3—C4—N5—C6	−4.2 (3)	C34—C35—C36—C31	0.0 (5)
O4—C4—N5—C10	−5.3 (3)	C32—C31—C36—C35	−0.6 (4)
C3—C4—N5—C10	174.1 (2)	C3—C31—C36—C35	177.3 (3)
C10—N5—C6—N1	−175.1 (2)	C41—N41—C42—O42	8.8 (11)
C4—N5—C6—N1	3.1 (3)	C45—N41—C42—O42	−176.1 (5)
C10—N5—C6—C7	5.2 (4)	C41—N41—C42—C43	−170.9 (8)
C4—N5—C6—C7	−176.6 (2)	C45—N41—C42—C43	4.2 (6)
C2—N1—C6—N5	0.1 (4)	O42—C42—C43—C44	176.1 (5)
C11—N1—C6—N5	170.2 (2)	N41—C42—C43—C44	−4.1 (6)
C2—N1—C6—C7	179.8 (2)	C42—C43—C44—C45	2.6 (7)
C11—N1—C6—C7	−10.1 (4)	C43—C44—C45—N41	−0.2 (7)
N5—C6—C7—C8	−3.3 (4)	C41—N41—C45—C44	171.4 (10)
N1—C6—C7—C8	177.1 (2)	C42—N41—C45—C44	−2.8 (7)
C6—C7—C8—C9	−1.0 (4)	C52^ii—N51—C51—C54^ii	7.2 (7)
C7—C8—C9—C10	3.3 (4)	N51^ii—N51—C51—C54^ii	7.2 (7)
C8—C9—C10—N5	−1.4 (4)	C55—N51—C51—C54^ii	−175.0 (5)
C6—N5—C10—C9	−2.9 (4)	C52^ii—N51—C55—C54	4.5 (6)
C4—N5—C10—C9	178.8 (2)	N51^ii—N51—C55—C54	4.5 (6)
C6—N1—C11—C12	104.7 (3)	C51—N51—C55—C54	−173.3 (6)
C2—N1—C11—C12	−84.5 (3)	N51—C55—C54—O52^ii	−9.8 (8)
C6—N1—C11—C13^i	−76.5 (3)	N51—C55—C54—C51^ii	−9.8 (8)

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

(Ic) p-phenylenebis(2-oxo-3-phenyl-1,2-dihydropyrido[1,2- a]pyrimidin-5-ium-4-olate)-N-methylpyrrolidone–butan-1-ol (2/1/2)

Crystal data

C34H22N4O4·0.5C5H9NO·C4H10O	Z = 2
Mr = 674.24	F(000) = 710
Triclinic, P1	Dx = 1.375 Mg m^−3
a = 5.7853 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 15.2219 (17) Å	Cell parameters from 8048 reflections
c = 19.198 (2) Å	θ = 3.6–52.5°
α = 75.321 (9)°	µ = 0.09 mm^−1
β = 87.393 (8)°	T = 173 K
γ = 84.740 (9)°	Needle, yellow
V = 1628.1 (3) Å^3	0.21 × 0.09 × 0.09 mm

Data collection

Stoe IPDS II two-circle diffractometer	3364 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.088
Graphite monochromator	θmax = 26.4°, θmin = 3.5°
ω scans	h = −7→7
23578 measured reflections	k = −18→19
6641 independent reflections	l = −23→23

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)] = 0.081	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.218	H-atom parameters constrained
S = 0.95	w = 1/[σ^2(Fo^2) + (0.1056P)^2] where P = (Fo^2 + 2Fc^2)/3
6641 reflections	(Δ/σ)max < 0.001
379 parameters	Δρmax = 0.64 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

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
N1	0.2982 (5)	0.5182 (2)	0.36513 (15)	0.0295 (7)
C2	0.1188 (6)	0.5895 (3)	0.34382 (19)	0.0300 (8)
O2	0.0731 (5)	0.64010 (19)	0.38436 (14)	0.0375 (6)
C3	0.0042 (7)	0.5936 (2)	0.27836 (18)	0.0302 (8)
C4	0.0678 (7)	0.5334 (2)	0.23518 (19)	0.0323 (8)
O4	−0.0094 (6)	0.5303 (2)	0.17716 (15)	0.0468 (8)
N5	0.2659 (6)	0.4651 (2)	0.26185 (16)	0.0346 (8)
C6	0.3801 (7)	0.4605 (3)	0.32395 (19)	0.0337 (9)
C7	0.5792 (8)	0.3992 (3)	0.3412 (2)	0.0451 (10)
H7	0.6619	0.3962	0.3835	0.054*
C8	0.6532 (10)	0.3441 (4)	0.2969 (3)	0.0575 (13)
H8	0.7878	0.3030	0.3084	0.069*
C9	0.5313 (11)	0.3481 (3)	0.2351 (3)	0.0612 (15)
H9	0.5811	0.3091	0.2048	0.073*
C10	0.3421 (9)	0.4077 (3)	0.2183 (2)	0.0488 (12)
H10	0.2600	0.4103	0.1760	0.059*
C11	0.4026 (6)	0.5091 (3)	0.43449 (18)	0.0282 (8)
C12	0.6821 (7)	0.5520 (3)	0.5055 (2)	0.0346 (9)
H12	0.8061	0.5870	0.5097	0.042*
C13	0.5822 (7)	0.5613 (3)	0.43847 (19)	0.0345 (9)
H13	0.6371	0.6028	0.3966	0.041*
C31	−0.1790 (7)	0.6692 (3)	0.25192 (18)	0.0319 (8)
C32	−0.3799 (7)	0.6528 (3)	0.2207 (2)	0.0400 (10)
H32	−0.4018	0.5927	0.2181	0.048*
C33	−0.5487 (7)	0.7237 (3)	0.1935 (2)	0.0456 (11)
H33	−0.6858	0.7107	0.1739	0.055*
C34	−0.5181 (8)	0.8129 (4)	0.1946 (3)	0.0545 (13)
H34	−0.6301	0.8613	0.1744	0.065*
C35	−0.3194 (9)	0.8296 (4)	0.2260 (3)	0.0597 (14)
H35	−0.2959	0.8901	0.2276	0.072*
C36	−0.1545 (7)	0.7584 (3)	0.2550 (2)	0.0431 (10)
H36	−0.0226	0.7710	0.2775	0.052*
N1A	0.5020 (5)	0.30686 (18)	0.03210 (16)	0.0269 (6)
C2A	0.3202 (6)	0.2677 (2)	0.08122 (19)	0.0271 (8)
O2A	0.1792 (5)	0.32191 (17)	0.10197 (15)	0.0341 (6)
C3A	0.3255 (6)	0.1707 (2)	0.10185 (19)	0.0274 (8)
C4A	0.4819 (7)	0.1153 (2)	0.06960 (19)	0.0316 (8)
O4A	0.4962 (6)	0.03164 (17)	0.07797 (17)	0.0490 (8)
N5A	0.6570 (6)	0.16488 (19)	0.01797 (16)	0.0288 (7)
C6A	0.6726 (6)	0.2570 (2)	0.00309 (18)	0.0250 (7)
C7A	0.8570 (7)	0.2956 (2)	−0.04070 (19)	0.0288 (8)
H7A	0.8687	0.3595	−0.0514	0.035*
C8A	1.0205 (7)	0.2414 (2)	−0.06809 (19)	0.0305 (8)
H8A	1.1477	0.2673	−0.0965	0.037*
C9A	0.9987 (8)	0.1469 (3)	−0.0539 (2)	0.0371 (9)
H9A	1.1098	0.1089	−0.0731	0.045*
C10A	0.8185 (8)	0.1114 (2)	−0.0128 (2)	0.0372 (10)
H10A	0.8011	0.0481	−0.0047	0.045*
C11A	0.5049 (6)	0.4063 (2)	0.01474 (19)	0.0265 (7)
C12A	0.3504 (7)	0.4594 (2)	−0.0352 (2)	0.0304 (8)
H12A	0.2492	0.4314	−0.0590	0.037*
C13A	0.3447 (6)	0.5547 (2)	−0.05015 (19)	0.0276 (8)
H13A	0.2393	0.5920	−0.0840	0.033*
C31A	0.1641 (6)	0.1251 (2)	0.1598 (2)	0.0299 (8)
C32A	0.2385 (9)	0.0396 (3)	0.2084 (2)	0.0465 (11)
H32A	0.3889	0.0120	0.2015	0.056*
C33A	0.0982 (10)	−0.0044 (3)	0.2656 (3)	0.0560 (13)
H33A	0.1529	−0.0606	0.2972	0.067*
C34A	−0.1261 (9)	0.0363 (3)	0.2754 (3)	0.0553 (13)
H34A	−0.2261	0.0068	0.3130	0.066*
C35A	−0.1974 (9)	0.1166 (4)	0.2316 (3)	0.0552 (13)
H35A	−0.3476	0.1438	0.2394	0.066*
C36A	−0.0585 (8)	0.1619 (3)	0.1747 (2)	0.0443 (10)
H36A	−0.1162	0.2192	0.1454	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0302 (17)	0.0412 (17)	0.0189 (14)	−0.0020 (14)	−0.0076 (12)	−0.0098 (12)
C2	0.0254 (19)	0.043 (2)	0.0242 (17)	−0.0073 (16)	−0.0014 (15)	−0.0117 (15)
O2	0.0324 (15)	0.0540 (17)	0.0302 (14)	0.0019 (13)	−0.0071 (11)	−0.0191 (12)
C3	0.031 (2)	0.0366 (19)	0.0230 (17)	−0.0071 (16)	−0.0037 (15)	−0.0062 (15)
C4	0.041 (2)	0.0333 (19)	0.0223 (17)	−0.0058 (16)	−0.0132 (16)	−0.0032 (14)
O4	0.069 (2)	0.0453 (16)	0.0286 (14)	0.0019 (15)	−0.0264 (14)	−0.0124 (12)
N5	0.048 (2)	0.0326 (16)	0.0242 (15)	−0.0043 (15)	−0.0082 (14)	−0.0073 (13)
C6	0.039 (2)	0.042 (2)	0.0214 (17)	−0.0069 (18)	−0.0066 (16)	−0.0083 (15)
C7	0.046 (3)	0.059 (3)	0.030 (2)	0.008 (2)	−0.0095 (19)	−0.0156 (19)
C8	0.066 (3)	0.060 (3)	0.046 (3)	0.018 (3)	−0.013 (2)	−0.020 (2)
C9	0.094 (4)	0.052 (3)	0.042 (3)	0.021 (3)	−0.023 (3)	−0.026 (2)
C10	0.082 (4)	0.037 (2)	0.031 (2)	0.002 (2)	−0.016 (2)	−0.0148 (17)
C11	0.0239 (19)	0.045 (2)	0.0161 (15)	−0.0013 (16)	−0.0045 (13)	−0.0088 (14)
C12	0.029 (2)	0.050 (2)	0.0261 (18)	−0.0127 (17)	−0.0063 (15)	−0.0075 (16)
C13	0.031 (2)	0.051 (2)	0.0209 (17)	−0.0090 (18)	−0.0060 (15)	−0.0046 (16)
C31	0.028 (2)	0.048 (2)	0.0193 (17)	0.0002 (17)	−0.0025 (15)	−0.0080 (15)
C32	0.035 (2)	0.052 (2)	0.031 (2)	−0.0102 (19)	−0.0118 (17)	−0.0014 (17)
C33	0.027 (2)	0.072 (3)	0.031 (2)	−0.007 (2)	−0.0092 (17)	0.001 (2)
C34	0.036 (3)	0.079 (3)	0.049 (3)	0.023 (2)	−0.012 (2)	−0.025 (2)
C35	0.052 (3)	0.064 (3)	0.072 (3)	0.028 (2)	−0.024 (3)	−0.042 (3)
C36	0.032 (2)	0.055 (3)	0.051 (3)	0.0081 (19)	−0.0149 (19)	−0.032 (2)
N1A	0.0280 (16)	0.0193 (13)	0.0341 (16)	0.0039 (12)	−0.0085 (13)	−0.0089 (12)
C2A	0.029 (2)	0.0259 (17)	0.0286 (18)	0.0045 (15)	−0.0099 (15)	−0.0127 (14)
O2A	0.0354 (15)	0.0278 (13)	0.0423 (15)	0.0057 (11)	−0.0027 (12)	−0.0170 (11)
C3A	0.027 (2)	0.0256 (17)	0.0303 (18)	0.0017 (14)	−0.0058 (15)	−0.0093 (14)
C4A	0.038 (2)	0.0281 (18)	0.0265 (18)	−0.0028 (16)	0.0036 (16)	−0.0040 (14)
O4A	0.068 (2)	0.0189 (13)	0.0566 (18)	−0.0024 (13)	0.0242 (16)	−0.0075 (12)
N5A	0.0347 (18)	0.0218 (14)	0.0280 (15)	0.0049 (12)	−0.0012 (13)	−0.0055 (12)
C6A	0.034 (2)	0.0171 (15)	0.0237 (16)	0.0018 (14)	−0.0069 (15)	−0.0053 (13)
C7A	0.033 (2)	0.0271 (17)	0.0258 (17)	0.0033 (15)	−0.0078 (15)	−0.0064 (14)
C8A	0.035 (2)	0.0309 (18)	0.0242 (17)	0.0000 (16)	−0.0036 (15)	−0.0040 (14)
C9A	0.047 (3)	0.0289 (18)	0.0307 (19)	0.0064 (17)	0.0101 (18)	−0.0037 (15)
C10A	0.053 (3)	0.0214 (17)	0.034 (2)	0.0095 (17)	0.0083 (19)	−0.0064 (15)
C11A	0.0281 (19)	0.0219 (16)	0.0295 (18)	0.0003 (14)	−0.0052 (15)	−0.0068 (13)
C12A	0.035 (2)	0.0248 (17)	0.0337 (19)	0.0032 (15)	−0.0146 (16)	−0.0114 (15)
C13A	0.030 (2)	0.0237 (17)	0.0305 (18)	0.0007 (14)	−0.0109 (15)	−0.0087 (14)
C31A	0.027 (2)	0.0273 (18)	0.038 (2)	−0.0042 (15)	0.0008 (16)	−0.0126 (15)
C32A	0.050 (3)	0.037 (2)	0.047 (2)	−0.004 (2)	0.004 (2)	−0.0004 (18)
C33A	0.068 (4)	0.040 (2)	0.054 (3)	−0.008 (2)	0.011 (3)	−0.001 (2)
C34A	0.056 (3)	0.049 (3)	0.061 (3)	−0.015 (2)	0.027 (3)	−0.014 (2)
C35A	0.044 (3)	0.067 (3)	0.055 (3)	0.004 (2)	0.015 (2)	−0.020 (2)
C36A	0.043 (3)	0.040 (2)	0.049 (2)	0.0006 (19)	0.001 (2)	−0.0119 (19)

Geometric parameters (Å, º)

N1—C6	1.365 (5)	N1A—C6A	1.373 (5)
N1—C2	1.424 (5)	N1A—C2A	1.446 (5)
N1—C11	1.457 (4)	N1A—C11A	1.467 (4)
C2—O2	1.232 (4)	C2A—O2A	1.232 (4)
C2—C3	1.432 (5)	C2A—C3A	1.426 (5)
C3—C4	1.399 (5)	C3A—C4A	1.409 (5)
C3—C31	1.495 (5)	C3A—C31A	1.491 (5)
C4—O4	1.232 (4)	C4A—O4A	1.238 (4)
C4—N5	1.491 (5)	C4A—N5A	1.499 (5)
N5—C6	1.372 (5)	N5A—C6A	1.370 (4)
N5—C10	1.387 (5)	N5A—C10A	1.393 (5)
C6—C7	1.410 (6)	C6A—C7A	1.405 (5)
C7—C8	1.368 (6)	C7A—C8A	1.373 (5)
C7—H7	0.9500	C7A—H7A	0.9500
C8—C9	1.393 (7)	C8A—C9A	1.410 (5)
C8—H8	0.9500	C8A—H8A	0.9500
C9—C10	1.351 (7)	C9A—C10A	1.347 (6)
C9—H9	0.9500	C9A—H9A	0.9500
C10—H10	0.9500	C10A—H10A	0.9500
C11—C13	1.380 (5)	C11A—C12A	1.386 (5)
C11—C12^i	1.386 (5)	C11A—C13A^ii	1.387 (5)
C12—C11^i	1.386 (5)	C12A—C13A	1.403 (5)
C12—C13	1.403 (5)	C12A—H12A	0.9500
C12—H12	0.9500	C13A—C11A^ii	1.387 (5)
C13—H13	0.9500	C13A—H13A	0.9500
C31—C36	1.395 (6)	C31A—C36A	1.404 (6)
C31—C32	1.401 (5)	C31A—C32A	1.438 (6)
C32—C33	1.400 (6)	C32A—C33A	1.400 (6)
C32—H32	0.9500	C32A—H32A	0.9500
C33—C34	1.391 (7)	C33A—C34A	1.412 (7)
C33—H33	0.9500	C33A—H33A	0.9500
C34—C35	1.395 (7)	C34A—C35A	1.339 (7)
C34—H34	0.9500	C34A—H34A	0.9500
C35—C36	1.396 (6)	C35A—C36A	1.398 (7)
C35—H35	0.9500	C35A—H35A	0.9500
C36—H36	0.9500	C36A—H36A	0.9500
C6—N1—C2	124.1 (3)	C6A—N1A—C2A	124.3 (3)
C6—N1—C11	118.9 (3)	C6A—N1A—C11A	119.0 (3)
C2—N1—C11	117.0 (3)	C2A—N1A—C11A	116.7 (3)
O2—C2—N1	116.9 (3)	O2A—C2A—C3A	126.8 (3)
O2—C2—C3	126.3 (4)	O2A—C2A—N1A	116.3 (3)
N1—C2—C3	116.7 (3)	C3A—C2A—N1A	116.9 (3)
C4—C3—C2	122.6 (4)	C4A—C3A—C2A	122.0 (3)
C4—C3—C31	118.2 (3)	C4A—C3A—C31A	118.1 (3)
C2—C3—C31	119.0 (3)	C2A—C3A—C31A	119.9 (3)
O4—C4—C3	129.8 (4)	O4A—C4A—C3A	129.4 (3)
O4—C4—N5	115.0 (3)	O4A—C4A—N5A	115.3 (3)
C3—C4—N5	115.1 (3)	C3A—C4A—N5A	115.3 (3)
C6—N5—C10	120.0 (4)	C6A—N5A—C10A	119.6 (3)
C6—N5—C4	123.4 (3)	C6A—N5A—C4A	123.9 (3)
C10—N5—C4	116.6 (3)	C10A—N5A—C4A	116.4 (3)
N1—C6—N5	117.8 (4)	N5A—C6A—N1A	117.0 (3)
N1—C6—C7	123.1 (3)	N5A—C6A—C7A	119.4 (3)
N5—C6—C7	119.1 (4)	N1A—C6A—C7A	123.6 (3)
C8—C7—C6	119.9 (4)	C8A—C7A—C6A	120.3 (3)
C8—C7—H7	120.0	C8A—C7A—H7A	119.9
C6—C7—H7	120.0	C6A—C7A—H7A	119.9
C7—C8—C9	120.1 (5)	C7A—C8A—C9A	119.7 (4)
C7—C8—H8	120.0	C7A—C8A—H8A	120.1
C9—C8—H8	120.0	C9A—C8A—H8A	120.1
C10—C9—C8	119.9 (4)	C10A—C9A—C8A	119.1 (4)
C10—C9—H9	120.1	C10A—C9A—H9A	120.4
C8—C9—H9	120.1	C8A—C9A—H9A	120.4
C9—C10—N5	121.0 (4)	C9A—C10A—N5A	121.8 (3)
C9—C10—H10	119.5	C9A—C10A—H10A	119.1
N5—C10—H10	119.5	N5A—C10A—H10A	119.1
C13—C11—C12^i	122.1 (3)	C12A—C11A—C13A^ii	121.5 (3)
C13—C11—N1	119.2 (3)	C12A—C11A—N1A	118.9 (3)
C12^i—C11—N1	118.7 (3)	C13A^ii—C11A—N1A	119.6 (3)
C11^i—C12—C13	119.1 (4)	C11A—C12A—C13A	119.5 (3)
C11^i—C12—H12	120.5	C11A—C12A—H12A	120.3
C13—C12—H12	120.5	C13A—C12A—H12A	120.3
C11—C13—C12	118.8 (3)	C11A^ii—C13A—C12A	119.0 (3)
C11—C13—H13	120.6	C11A^ii—C13A—H13A	120.5
C12—C13—H13	120.6	C12A—C13A—H13A	120.5
C36—C31—C32	117.6 (4)	C36A—C31A—C32A	114.9 (4)
C36—C31—C3	121.9 (3)	C36A—C31A—C3A	124.9 (4)
C32—C31—C3	120.5 (4)	C32A—C31A—C3A	120.1 (3)
C33—C32—C31	121.0 (4)	C33A—C32A—C31A	122.6 (4)
C33—C32—H32	119.5	C33A—C32A—H32A	118.7
C31—C32—H32	119.5	C31A—C32A—H32A	118.7
C34—C33—C32	120.8 (4)	C32A—C33A—C34A	118.6 (4)
C34—C33—H33	119.6	C32A—C33A—H33A	120.7
C32—C33—H33	119.6	C34A—C33A—H33A	120.7
C33—C34—C35	118.4 (4)	C35A—C34A—C33A	119.7 (4)
C33—C34—H34	120.8	C35A—C34A—H34A	120.1
C35—C34—H34	120.8	C33A—C34A—H34A	120.1
C34—C35—C36	120.6 (5)	C34A—C35A—C36A	122.3 (5)
C34—C35—H35	119.7	C34A—C35A—H35A	118.9
C36—C35—H35	119.7	C36A—C35A—H35A	118.9
C31—C36—C35	121.5 (4)	C35A—C36A—C31A	121.7 (4)
C31—C36—H36	119.2	C35A—C36A—H36A	119.1
C35—C36—H36	119.2	C31A—C36A—H36A	119.1
C6—N1—C2—O2	−175.3 (3)	C6A—N1A—C2A—O2A	−179.5 (3)
C11—N1—C2—O2	3.0 (5)	C11A—N1A—C2A—O2A	2.5 (4)
C6—N1—C2—C3	6.5 (5)	C6A—N1A—C2A—C3A	1.9 (5)
C11—N1—C2—C3	−175.2 (3)	C11A—N1A—C2A—C3A	−176.1 (3)
O2—C2—C3—C4	179.8 (4)	O2A—C2A—C3A—C4A	173.9 (4)
N1—C2—C3—C4	−2.3 (5)	N1A—C2A—C3A—C4A	−7.6 (5)
O2—C2—C3—C31	4.4 (6)	O2A—C2A—C3A—C31A	−6.8 (6)
N1—C2—C3—C31	−177.6 (3)	N1A—C2A—C3A—C31A	171.6 (3)
C2—C3—C4—O4	−177.7 (4)	C2A—C3A—C4A—O4A	−174.4 (4)
C31—C3—C4—O4	−2.3 (6)	C31A—C3A—C4A—O4A	6.4 (6)
C2—C3—C4—N5	−0.7 (5)	C2A—C3A—C4A—N5A	6.0 (5)
C31—C3—C4—N5	174.7 (3)	C31A—C3A—C4A—N5A	−173.3 (3)
O4—C4—N5—C6	177.4 (4)	O4A—C4A—N5A—C6A	−178.3 (4)
C3—C4—N5—C6	−0.1 (5)	C3A—C4A—N5A—C6A	1.4 (5)
O4—C4—N5—C10	1.0 (5)	O4A—C4A—N5A—C10A	−1.7 (5)
C3—C4—N5—C10	−176.5 (4)	C3A—C4A—N5A—C10A	177.9 (3)
C2—N1—C6—N5	−7.3 (5)	C10A—N5A—C6A—N1A	176.9 (3)
C11—N1—C6—N5	174.4 (3)	C4A—N5A—C6A—N1A	−6.7 (5)
C2—N1—C6—C7	170.6 (4)	C10A—N5A—C6A—C7A	−2.6 (5)
C11—N1—C6—C7	−7.7 (6)	C4A—N5A—C6A—C7A	173.8 (3)
C10—N5—C6—N1	−179.8 (4)	C2A—N1A—C6A—N5A	5.0 (5)
C4—N5—C6—N1	3.9 (5)	C11A—N1A—C6A—N5A	−177.0 (3)
C10—N5—C6—C7	2.2 (6)	C2A—N1A—C6A—C7A	−175.5 (3)
C4—N5—C6—C7	−174.1 (4)	C11A—N1A—C6A—C7A	2.4 (5)
N1—C6—C7—C8	−179.2 (4)	N5A—C6A—C7A—C8A	−0.2 (5)
N5—C6—C7—C8	−1.3 (7)	N1A—C6A—C7A—C8A	−179.7 (3)
C6—C7—C8—C9	−0.4 (8)	C6A—C7A—C8A—C9A	1.9 (5)
C7—C8—C9—C10	1.1 (9)	C7A—C8A—C9A—C10A	−0.8 (6)
C8—C9—C10—N5	−0.2 (8)	C8A—C9A—C10A—N5A	−2.1 (6)
C6—N5—C10—C9	−1.5 (7)	C6A—N5A—C10A—C9A	3.8 (6)
C4—N5—C10—C9	175.0 (4)	C4A—N5A—C10A—C9A	−172.8 (4)
C6—N1—C11—C13	93.3 (4)	C6A—N1A—C11A—C12A	103.1 (4)
C2—N1—C11—C13	−85.1 (4)	C2A—N1A—C11A—C12A	−78.8 (4)
C6—N1—C11—C12^i	−86.7 (4)	C6A—N1A—C11A—C13A^ii	−79.1 (4)
C2—N1—C11—C12^i	94.9 (4)	C2A—N1A—C11A—C13A^ii	99.0 (4)
C12^i—C11—C13—C12	0.1 (7)	C13A^ii—C11A—C12A—C13A	−0.3 (6)
N1—C11—C13—C12	−179.9 (4)	N1A—C11A—C12A—C13A	177.5 (3)
C11^i—C12—C13—C11	−0.1 (7)	C11A—C12A—C13A—C11A^ii	0.3 (6)
C4—C3—C31—C36	−134.5 (4)	C4A—C3A—C31A—C36A	−149.8 (4)
C2—C3—C31—C36	41.0 (5)	C2A—C3A—C31A—C36A	30.9 (6)
C4—C3—C31—C32	43.4 (5)	C4A—C3A—C31A—C32A	34.4 (5)
C2—C3—C31—C32	−141.1 (4)	C2A—C3A—C31A—C32A	−144.9 (4)
C36—C31—C32—C33	0.3 (6)	C36A—C31A—C32A—C33A	1.1 (6)
C3—C31—C32—C33	−177.7 (4)	C3A—C31A—C32A—C33A	177.3 (4)
C31—C32—C33—C34	2.0 (6)	C31A—C32A—C33A—C34A	0.7 (7)
C32—C33—C34—C35	−2.4 (7)	C32A—C33A—C34A—C35A	−1.8 (8)
C33—C34—C35—C36	0.5 (8)	C33A—C34A—C35A—C36A	1.2 (8)
C32—C31—C36—C35	−2.2 (6)	C34A—C35A—C36A—C31A	0.7 (8)
C3—C31—C36—C35	175.8 (4)	C32A—C31A—C36A—C35A	−1.8 (6)
C34—C35—C36—C31	1.9 (8)	C3A—C31A—C36A—C35A	−177.7 (4)

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