Crystal structure of 2-(1,3,7,9-tetra­methyl-2,4,6,8-tetra­oxo-1,2,3,4,6,7,8,9-octa­hydro­pyrido[2,3-d:6,5-d′]dipyrimidin-5-yl)benzamide di­methyl­formamide hemisolvate

In the crystal, the benzamide mol­ecules are linked by N—H...O hydrogen bonds to generate tetra­mers with an approximate square-prismatic shape, which appears to correlate with the tetra­gonal crystal symmetry.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in solvent or counterion
• R factor = 0.056
• wR factor = 0.135
• Data-to-parameter ratio = 18.3

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
STRVA01_ALERT_4_C           Flack test results are meaningless.
           From the CIF: _refine_ls_abs_structure_Flack    0.000
           From the CIF: _refine_ls_abs_structure_Flack_su    1.000
PLAT430_ALERT_2_C Short Inter D...A Contact  O29    ..  N9      ..       2.88 Ang.

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3 Note
PLAT032_ALERT_4_G Std. Uncertainty on Flack Parameter Value High .      1.000 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT302_ALERT_4_G Anion/Solvent Disorder ............ Percentage =        100 Note
PLAT432_ALERT_2_G Short Inter X...Y Contact  O29    ..  C10     ..       2.91 Ang.
PLAT850_ALERT_4_G Check Flack Parameter Exact Value 0.00 and su ..       1.00 Check
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          1 Note
PLAT916_ALERT_2_G Hooft y and Flack x Parameter values differ by .       0.20 Check
PLAT950_ALERT_5_G Calculated (ThMax) and CIF-Reported Kmax Differ          10 Units

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  10 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Chemical context

Compounds containing fused pyrimidine rings show diverse and inter­esting biological properties. In particular, the representatives of this family show anti­viral (Hossain et al., 1997), anti­bacterial (Sabnis & Rangnekar, 1990), anti-AIDS (Joseph & Burke, 1993) and anti­nociceptive (Bookser et al., 2005) activities and may serve as non-nucleoside reverse transcriptase inhibitors as well (De Clercq, 1996). Such a broad spectrum of biological properties for these compounds gives rise to inter­est in their structures and in this paper the structure of the title solvate, (I), is described.

S2. Structural commentary

The molecular structure of the title compound is depicted in Fig. 1. The molecule of (I) contains two almost planar fragments: (i) pyridodi­pyrimidine (r.m.s. deviation = 0.046 Å) and (ii) benzamide (r.m.s. deviation = 0.010 Å). The dihedral angle between them is 82.26 (11)°. The di­methyl formamide solvent molecule is disordered about a crystallographic twofold axis.

S3. Supra­molecular features

Each disordered solvent molecule is connected to an adjacent 2-(1,3,7,9-tetra­methyl-2,4,6,8-tetra­oxo-1,2,3,4,6,7,8,9-o­cta­hydro­pyrido[2,3-d:6,5-d']dipyrimidin-5-yl)benzamide molecule, related by twofold axes, via a non-classical C17–H17···O51hydrogen bond (see Fig. 2 and Table 1). The hydrogen atoms of the amide group are involved in the formation of inter­molecular N23–H23B···O31ⁱ and N23–H32A···O22ⁱⁱ hydrogen bonds, which link four molecules of the title compound into a four-membered tetra­mer with an almost square-prismatic shape (see Fig. 3). In the extended structure, the inter­actions between these telomeres have solely van der Waals character. It appears that the almost square-prismatic shape of these tetra­mers is responsible for the unusual high symmetry of this structure (space group I42d).

S4. Database survey

In the Cambridge Structural Database, just three comparable structures were found: (i) 5-(4-fluoro­phenyl)-1,3,7,9-tetra­methyl­pyrido[2,3-d:6,5-d]di­pyrimidine-2,4,6,8(1H,3H,7H,9H)-tetrone (Ghorbani & Bazgir, 2007); (ii) 5-(4-bromo­phenyl)-1,3,7,9-tetra­methyl­pyrimido[5',4':5,6]pyrido[2,3-d]pyrimidine-2,4,6,8(1H,3H,7H,9H)-tetrone (Dabiri et al., 2007); (iii) 1,3,7,9-tetra­methyl­pyrido[2,3-d:6,5-d']di­pyrimidine-2,4,6,8-tetrone (Enrique-Miron et al., 1994). The basic fragment for the title compound and compounds (i) and (ii) is the structure of compound (iii) in which the hydrogen atom of the pyridine ring is replaced by benzamide, fluoro­phenyl and bromo­phenyl respectively. There are no essential differences in the geometrical characteristics of corresponding chemical bonds, but the crystal packing of the molecules differs essentially because of various features of the inter­molecular hydrogen bonding.

S5. Synthesis and crystallization

To synthesize the title compound, a mixture of 6-amino-1,3-di­methyl-1,2,3,4-tetra­hydro-2,4-pyrimidine­dione 1.55 g (10 mM) and 1,2-benzene­dicarbonyl chloride 2.0 g (10 mM) dissolved in 10 ml DMFA was stirred under reflux for 2 h. The mixture was concentrated under reduced pressure, then 20 ml of iced water was added to it and filtered. The synthesized compound was dissolved in ethanol and crystallized by slow evaporation at room temperature (m.p. = 627–628 K, 55% yield).

S6. Refinement

Crystal data, data collection details and structure refinement details are summarized in Table 2. The solvent molecule of di­methyl­formamide is disordered about a crystallographic twofold axis. The coordinates of the H atoms of the phenyl ring and methyl groups were determined geometrically and refined using a riding model with the following restraints: for the phenyl ring, C—H = 0.93 Å, U_iso(H) = 1.2U_eq(C), and for the methyl groups, C—H = 0.96 Å, U_iso(H) = 1.5U_eq(C). Only the coordinates of the H atoms of the amide group, involved in hydrogen bonding, were determined from difference Fourier syntheses and refined freely.

Related literature

For crystal structures of related compounds, see: Ghorbani (2007), Dabiri (2007), Enrique-Miron (1994). For biological activities of fused pyrimidines, see: Hossain (1997), Sabnis (1990), Joseph (1993), Bookser (2005), De Clercq (1996).

Computing details

Data collection: CAD-4 Software (Enraf–Nonius, 1988); cell refinement: SETANG in CAD-4 Software (Enraf–Nonius, 1988); data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: enCIFer (Allen et al., 2004) and publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure with thermal displacement ellipsoids drawn at the 50% probability level (H atoms omitted for clarity).
	Fig. 2. Non-classical hydrogen bonding of disordered DMFA with molecules of 2-(1,3,7,9-tetramethyl-2,4,6,8-tetraoxo-1,2,3,4,6,7,8,9-octahydropyrido[2,3-d:6,5-d']dipyrimidin-5-yl)benzamide related by the twofold axes of the space group.
	Fig. 3. Square-prismatic telomer formed by four molecules of 2-(1,3,7,9-tetramethyl-2,4,6,8-tetraoxo-1,2,3,4,6,7,8,9-octahydropyrido[2,3-d:6,5-d']dipyrimidin-5-yl)benzamide via intermolecular hydrogen bonding.

2-(1,3,7,9-Tetramethyl-2,4,6,8-tetraoxo-1,2,3,4,6,7,8,9-octahydropyrido[2,3-d:6,5-d']dipyrimidin-5-yl)benzamide N,N-dimethylformamide hemisolvate

Crystal data

2C20H18N6O5·C3H7NO	Dx = 1.432 Mg m^−3
Mr = 917.90	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I42d	Cell parameters from 24 reflections
a = 26.173 (4) Å	θ = 12.2–17.3°
c = 12.434 (3) Å	µ = 0.11 mm^−1
V = 8517 (3) Å^3	T = 293 K
Z = 8	Spherical, colourless
F(000) = 3840	0.16 × 0.16 × 0.16 × 0.16 (radius) mm

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.015
Radiation source: fine-focus sealed tube	θmax = 30.0°, θmin = 1.6°
Graphite monochromator	h = −26→26
θ/2θ scans	k = −36→36
6734 measured reflections	l = −17→17
6216 independent reflections	1 standard reflections every 60 min
3247 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.056	w = 1/[σ^2(Fo^2) + (0.0536P)^2 + 1.2893P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.135	(Δ/σ)max = 0.006
S = 1.01	Δρmax = 0.12 e Å^−3
6216 reflections	Δρmin = −0.17 e Å^−3
339 parameters	Absolute structure: Flack x determined using 1083 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.0 (10)

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.54916 (10)	0.33509 (10)	0.1396 (2)	0.0533 (7)
C2	0.54598 (13)	0.30369 (12)	0.0506 (2)	0.0561 (8)
N3	0.49790 (10)	0.29334 (9)	0.01248 (19)	0.0564 (7)
C4	0.45404 (12)	0.31201 (11)	0.0602 (2)	0.0491 (7)
N5	0.41001 (10)	0.29570 (9)	0.01939 (18)	0.0510 (6)
C6	0.36754 (12)	0.31226 (11)	0.0642 (2)	0.0483 (7)
N7	0.32283 (10)	0.29304 (10)	0.0228 (2)	0.0572 (7)
C8	0.27519 (13)	0.30566 (13)	0.0635 (3)	0.0645 (10)
N9	0.27443 (10)	0.33727 (10)	0.1518 (2)	0.0596 (8)
C10	0.31609 (11)	0.36475 (13)	0.1894 (2)	0.0539 (8)
C11	0.36577 (11)	0.34801 (11)	0.1489 (2)	0.0460 (7)
C12	0.41230 (11)	0.36644 (10)	0.1882 (2)	0.0434 (6)
C13	0.45766 (11)	0.34605 (10)	0.1470 (2)	0.0442 (7)
C14	0.50830 (11)	0.35936 (11)	0.1884 (2)	0.0474 (7)
C15	0.41236 (10)	0.40442 (10)	0.2778 (2)	0.0414 (6)
C16	0.40476 (11)	0.38612 (11)	0.3818 (2)	0.0487 (7)
H16	0.4010	0.3512	0.3931	0.058*
C17	0.40282 (11)	0.41874 (12)	0.4672 (2)	0.0533 (8)
H17	0.3967	0.4061	0.5359	0.064*
C18	0.40994 (14)	0.47024 (12)	0.4523 (2)	0.0620 (9)
H18	0.4094	0.4924	0.5107	0.074*
C19	0.41787 (13)	0.48880 (11)	0.3495 (2)	0.0569 (8)
H19	0.4227	0.5237	0.3395	0.068*
C20	0.41875 (10)	0.45666 (10)	0.2610 (2)	0.0444 (7)
C21	0.42413 (11)	0.47689 (11)	0.1484 (2)	0.0497 (8)
O22	0.41550 (10)	0.45010 (8)	0.06982 (15)	0.0680 (6)
N23	0.43726 (14)	0.52520 (11)	0.1365 (3)	0.0786 (10)
H23A	0.4405 (14)	0.5378 (14)	0.065 (3)	0.088 (12)*
H23B	0.4487 (13)	0.5433 (12)	0.191 (2)	0.069 (10)*
O24	0.30973 (8)	0.39919 (10)	0.2537 (2)	0.0722 (7)
C25	0.22403 (12)	0.35043 (16)	0.1963 (3)	0.0811 (12)
H25A	0.2016	0.3216	0.1898	0.122*
H25B	0.2101	0.3789	0.1573	0.122*
H25C	0.2276	0.3594	0.2708	0.122*
O26	0.23650 (9)	0.28828 (12)	0.0252 (2)	0.0939 (9)
C27	0.32474 (15)	0.25925 (14)	−0.0717 (3)	0.0736 (11)
H27A	0.3295	0.2794	−0.1354	0.110*
H27B	0.2933	0.2406	−0.0772	0.110*
H27C	0.3527	0.2357	−0.0642	0.110*
C28	0.49437 (16)	0.26283 (14)	−0.0869 (3)	0.0777 (11)
H28A	0.4900	0.2274	−0.0688	0.116*
H28B	0.5251	0.2670	−0.1281	0.116*
H28C	0.4657	0.2742	−0.1285	0.116*
O29	0.58408 (9)	0.28574 (10)	0.00875 (19)	0.0769 (7)
C30	0.60084 (12)	0.34458 (14)	0.1798 (3)	0.0697 (10)
H30A	0.6183	0.3673	0.1317	0.105*
H30B	0.6191	0.3129	0.1840	0.105*
H30C	0.5990	0.3598	0.2499	0.105*
O31	0.51616 (7)	0.38890 (9)	0.26314 (18)	0.0603 (6)
N50	0.44874 (14)	0.25496 (10)	0.6322 (12)	0.0817 (17)	0.5
O51	0.4092 (3)	0.3226 (3)	0.6400 (9)	0.180 (4)	0.5
C52	0.3997 (5)	0.2778 (4)	0.6276 (15)	0.173 (6)	0.5
H52	0.3681	0.2622	0.6175	0.208*	0.5
C53	0.49626 (16)	0.2790 (3)	0.6091 (7)	0.126 (4)	0.5
H53A	0.4934	0.2979	0.5432	0.189*	0.5
H53B	0.5224	0.2534	0.6017	0.189*	0.5
H53C	0.5051	0.3018	0.6666	0.189*	0.5
C55	0.4465 (5)	0.20136 (14)	0.6134 (9)	0.141 (5)	0.5
H55A	0.4204	0.1942	0.5613	0.211*	0.5
H55B	0.4387	0.1840	0.6795	0.211*	0.5
H55C	0.4789	0.1897	0.5868	0.211*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0482 (14)	0.0619 (15)	0.0498 (14)	0.0064 (12)	0.0030 (12)	0.0018 (13)
C2	0.0662 (19)	0.0569 (18)	0.0453 (16)	0.0124 (16)	0.0074 (16)	0.0080 (15)
N3	0.0700 (16)	0.0575 (14)	0.0416 (13)	0.0034 (13)	0.0066 (14)	−0.0056 (12)
C4	0.0633 (18)	0.0438 (15)	0.0403 (15)	0.0031 (14)	0.0002 (15)	0.0008 (13)
N5	0.0650 (15)	0.0483 (12)	0.0397 (12)	−0.0029 (12)	−0.0055 (13)	−0.0051 (11)
C6	0.0606 (18)	0.0444 (15)	0.0399 (14)	−0.0080 (14)	−0.0108 (14)	0.0073 (13)
N7	0.0667 (16)	0.0580 (15)	0.0470 (14)	−0.0150 (13)	−0.0187 (13)	0.0022 (13)
C8	0.065 (2)	0.073 (2)	0.0557 (19)	−0.0204 (17)	−0.0157 (17)	0.0133 (17)
N9	0.0501 (14)	0.0730 (17)	0.0556 (16)	−0.0119 (13)	−0.0073 (13)	0.0102 (14)
C10	0.0490 (16)	0.0661 (19)	0.0466 (16)	−0.0066 (15)	−0.0070 (14)	0.0078 (16)
C11	0.0494 (16)	0.0487 (15)	0.0400 (15)	−0.0037 (13)	−0.0047 (13)	0.0051 (13)
C12	0.0491 (14)	0.0422 (13)	0.0389 (13)	−0.0061 (13)	−0.0013 (13)	0.0039 (12)
C13	0.0495 (15)	0.0412 (14)	0.0419 (15)	−0.0025 (13)	0.0004 (13)	0.0006 (13)
C14	0.0473 (15)	0.0495 (16)	0.0453 (15)	−0.0001 (13)	0.0001 (14)	0.0056 (13)
C15	0.0364 (12)	0.0481 (14)	0.0398 (13)	0.0001 (13)	−0.0021 (12)	−0.0024 (12)
C16	0.0491 (16)	0.0520 (15)	0.0452 (14)	−0.0044 (14)	−0.0024 (14)	0.0036 (13)
C17	0.0516 (16)	0.0709 (19)	0.0375 (14)	0.0023 (16)	−0.0004 (13)	0.0013 (14)
C18	0.084 (2)	0.0601 (18)	0.0417 (15)	0.0050 (18)	−0.0008 (18)	−0.0108 (14)
C19	0.074 (2)	0.0454 (16)	0.0518 (16)	0.0043 (15)	−0.0009 (17)	−0.0045 (14)
C20	0.0427 (14)	0.0495 (15)	0.0409 (13)	0.0008 (13)	−0.0007 (13)	−0.0028 (13)
C21	0.0517 (17)	0.0484 (15)	0.0491 (17)	−0.0007 (13)	0.0010 (14)	0.0021 (14)
O22	0.1034 (17)	0.0591 (12)	0.0416 (11)	−0.0127 (13)	0.0011 (12)	−0.0043 (10)
N23	0.134 (3)	0.0529 (16)	0.0484 (16)	−0.0154 (17)	0.0014 (18)	0.0023 (14)
O24	0.0514 (12)	0.0916 (17)	0.0736 (15)	0.0044 (12)	−0.0026 (12)	−0.0222 (14)
C25	0.0446 (18)	0.118 (3)	0.080 (3)	−0.010 (2)	−0.0022 (18)	0.006 (2)
O26	0.0717 (15)	0.128 (2)	0.0816 (17)	−0.0388 (15)	−0.0298 (14)	−0.0001 (17)
C27	0.094 (3)	0.071 (2)	0.056 (2)	−0.013 (2)	−0.0233 (19)	−0.0092 (18)
C28	0.099 (3)	0.082 (2)	0.0515 (19)	0.010 (2)	0.007 (2)	−0.0215 (18)
O29	0.0739 (14)	0.0908 (16)	0.0659 (14)	0.0232 (14)	0.0178 (13)	−0.0051 (13)
C30	0.0494 (18)	0.083 (2)	0.076 (2)	0.0070 (16)	−0.0015 (17)	−0.003 (2)
O31	0.0492 (12)	0.0676 (13)	0.0642 (13)	−0.0020 (10)	−0.0057 (10)	−0.0177 (12)
N50	0.120 (4)	0.047 (3)	0.078 (4)	0.001 (5)	−0.009 (8)	−0.005 (3)
O51	0.164 (7)	0.124 (5)	0.252 (10)	0.065 (5)	0.057 (7)	0.065 (6)
C52	0.126 (9)	0.101 (7)	0.291 (17)	0.034 (7)	0.034 (11)	0.057 (10)
C53	0.149 (8)	0.140 (8)	0.089 (6)	−0.054 (7)	−0.002 (7)	−0.026 (7)
C55	0.193 (12)	0.091 (7)	0.138 (9)	−0.033 (8)	−0.025 (10)	0.031 (7)

Geometric parameters (Å, º)

N1—C2	1.380 (4)	C18—H18	0.9300
N1—C14	1.384 (4)	C19—C20	1.385 (4)
N1—C30	1.463 (4)	C19—H19	0.9300
C2—O29	1.219 (4)	C20—C21	1.503 (4)
C2—N3	1.372 (4)	C21—O22	1.224 (3)
N3—C4	1.382 (4)	C21—N23	1.319 (4)
N3—C28	1.474 (4)	N23—H23A	0.96 (4)
C4—N5	1.330 (4)	N23—H23B	0.88 (3)
C4—C13	1.402 (4)	C25—H25A	0.9600
N5—C6	1.317 (4)	C25—H25B	0.9600
C6—N7	1.374 (4)	C25—H25C	0.9600
C6—C11	1.409 (4)	C27—H27A	0.9600
N7—C8	1.386 (4)	C27—H27B	0.9600
N7—C27	1.471 (4)	C27—H27C	0.9600
C8—O26	1.207 (4)	C28—H28A	0.9600
C8—N9	1.375 (4)	C28—H28B	0.9600
N9—C10	1.388 (4)	C28—H28C	0.9600
N9—C25	1.471 (4)	C30—H30A	0.9600
C10—O24	1.216 (4)	C30—H30B	0.9600
C10—C11	1.462 (4)	C30—H30C	0.9600
C11—C12	1.398 (4)	N50—C52	1.417 (13)
C12—C13	1.399 (4)	N50—C53	1.423 (5)
C12—C15	1.493 (4)	N50—C55	1.423 (5)
C13—C14	1.464 (4)	O51—C52	1.207 (14)
O31—C14	1.226 (3)	C52—H52	0.9300
C15—C16	1.393 (4)	C53—H53A	0.9600
C15—C20	1.393 (4)	C53—H53B	0.9600
C16—C17	1.364 (4)	C53—H53C	0.9600
C16—H16	0.9300	C55—H55A	0.9600
C17—C18	1.373 (4)	C55—H55B	0.9600
C17—H17	0.9300	C55—H55C	0.9600
C18—C19	1.383 (4)
C2—N1—C14	125.3 (3)	C18—C19—H19	119.2
C2—N1—C30	115.5 (3)	C20—C19—H19	119.2
C14—N1—C30	119.1 (3)	C19—C20—C15	118.3 (3)
O29—C2—N3	121.8 (3)	C19—C20—C21	121.8 (3)
O29—C2—N1	121.5 (3)	C15—C20—C21	119.8 (2)
N3—C2—N1	116.7 (3)	O22—C21—N23	120.5 (3)
C2—N3—C4	122.9 (3)	O22—C21—C20	121.6 (3)
C2—N3—C28	117.0 (3)	N23—C21—C20	117.8 (3)
C4—N3—C28	120.0 (3)	C21—N23—H23A	117 (2)
N5—C4—N3	116.2 (3)	C21—N23—H23B	121 (2)
N5—C4—C13	123.8 (3)	H23A—N23—H23B	120 (3)
N3—C4—C13	119.9 (3)	N9—C25—H25A	109.5
C6—N5—C4	117.6 (2)	N9—C25—H25B	109.5
N5—C6—N7	116.1 (3)	H25A—C25—H25B	109.5
N5—C6—C11	124.2 (3)	N9—C25—H25C	109.5
N7—C6—C11	119.7 (3)	H25A—C25—H25C	109.5
C6—N7—C8	122.8 (3)	H25B—C25—H25C	109.5
C6—N7—C27	119.4 (3)	N7—C27—H27A	109.5
C8—N7—C27	117.7 (3)	N7—C27—H27B	109.5
O26—C8—N9	121.9 (3)	H27A—C27—H27B	109.5
O26—C8—N7	121.4 (3)	N7—C27—H27C	109.5
N9—C8—N7	116.6 (3)	H27A—C27—H27C	109.5
C8—N9—C10	124.7 (3)	H27B—C27—H27C	109.5
C8—N9—C25	117.0 (3)	N3—C28—H28A	109.5
C10—N9—C25	117.1 (3)	N3—C28—H28B	109.5
O24—C10—N9	119.9 (3)	H28A—C28—H28B	109.5
O24—C10—C11	124.8 (3)	N3—C28—H28C	109.5
N9—C10—C11	115.3 (3)	H28A—C28—H28C	109.5
C12—C11—C6	117.5 (3)	H28B—C28—H28C	109.5
C12—C11—C10	123.4 (3)	N1—C30—H30A	109.5
C6—C11—C10	119.1 (3)	N1—C30—H30B	109.5
C11—C12—C13	118.6 (2)	H30A—C30—H30B	109.5
C11—C12—C15	119.5 (3)	N1—C30—H30C	109.5
C13—C12—C15	121.8 (3)	H30A—C30—H30C	109.5
C12—C13—C4	117.8 (3)	H30B—C30—H30C	109.5
C12—C13—C14	123.3 (3)	C52—N50—C53	126.6 (7)
C4—C13—C14	118.9 (3)	C52—N50—C55	111.9 (9)
O31—C14—N1	119.5 (3)	C53—N50—C55	116.0 (8)
O31—C14—C13	124.7 (3)	O51—C52—N50	102.6 (11)
N1—C14—C13	115.8 (3)	O51—C52—H52	128.7
C16—C15—C20	119.6 (2)	N50—C52—H52	128.7
C16—C15—C12	117.6 (2)	N50—C53—H53A	109.5
C20—C15—C12	122.8 (2)	N50—C53—H53B	109.5
C17—C16—C15	120.9 (3)	H53A—C53—H53B	109.5
C17—C16—H16	119.6	N50—C53—H53C	109.5
C15—C16—H16	119.6	H53A—C53—H53C	109.5
C16—C17—C18	120.3 (3)	H53B—C53—H53C	109.5
C16—C17—H17	119.9	N50—C55—H55A	109.5
C18—C17—H17	119.9	N50—C55—H55B	109.5
C17—C18—C19	119.3 (3)	H55A—C55—H55B	109.5
C17—C18—H18	120.3	N50—C55—H55C	109.5
C19—C18—H18	120.3	H55A—C55—H55C	109.5
C18—C19—C20	121.6 (3)	H55B—C55—H55C	109.5
C14—N1—C2—O29	176.2 (3)	C10—C11—C12—C13	177.1 (3)
C30—N1—C2—O29	−0.6 (4)	C6—C11—C12—C15	180.0 (2)
C14—N1—C2—N3	−4.4 (4)	C10—C11—C12—C15	1.3 (4)
C30—N1—C2—N3	178.8 (3)	C11—C12—C13—C4	6.6 (4)
O29—C2—N3—C4	178.1 (3)	C15—C12—C13—C4	−177.8 (2)
N1—C2—N3—C4	−1.3 (4)	C11—C12—C13—C14	−174.8 (3)
O29—C2—N3—C28	−4.8 (4)	C15—C12—C13—C14	0.9 (4)
N1—C2—N3—C28	175.8 (3)	N5—C4—C13—C12	−4.2 (4)
C2—N3—C4—N5	−175.1 (3)	N3—C4—C13—C12	176.0 (3)
C28—N3—C4—N5	7.9 (4)	N5—C4—C13—C14	177.0 (3)
C2—N3—C4—C13	4.7 (4)	N3—C4—C13—C14	−2.7 (4)
C28—N3—C4—C13	−172.3 (3)	C2—N1—C14—O31	−175.5 (3)
N3—C4—N5—C6	179.1 (3)	C30—N1—C14—O31	1.2 (4)
C13—C4—N5—C6	−0.7 (4)	C2—N1—C14—C13	6.1 (4)
C4—N5—C6—N7	−177.5 (3)	C30—N1—C14—C13	−177.2 (3)
C4—N5—C6—C11	3.3 (4)	C12—C13—C14—O31	0.7 (5)
N5—C6—N7—C8	178.1 (3)	C4—C13—C14—O31	179.4 (3)
C11—C6—N7—C8	−2.7 (4)	C12—C13—C14—N1	179.0 (3)
N5—C6—N7—C27	−4.6 (4)	C4—C13—C14—N1	−2.3 (4)
C11—C6—N7—C27	174.7 (3)	C11—C12—C15—C16	79.1 (3)
C6—N7—C8—O26	179.8 (3)	C13—C12—C15—C16	−96.6 (3)
C27—N7—C8—O26	2.4 (5)	C11—C12—C15—C20	−99.8 (3)
C6—N7—C8—N9	−2.6 (4)	C13—C12—C15—C20	84.6 (4)
C27—N7—C8—N9	180.0 (3)	C20—C15—C16—C17	0.9 (4)
O26—C8—N9—C10	−169.4 (3)	C12—C15—C16—C17	−178.0 (3)
N7—C8—N9—C10	13.0 (5)	C15—C16—C17—C18	−2.0 (5)
O26—C8—N9—C25	−1.8 (5)	C16—C17—C18—C19	1.5 (5)
N7—C8—N9—C25	−179.4 (3)	C17—C18—C19—C20	0.1 (5)
C8—N9—C10—O24	165.2 (3)	C18—C19—C20—C15	−1.2 (5)
C25—N9—C10—O24	−2.4 (4)	C18—C19—C20—C21	176.2 (3)
C8—N9—C10—C11	−16.6 (4)	C16—C15—C20—C19	0.7 (4)
C25—N9—C10—C11	175.8 (3)	C12—C15—C20—C19	179.6 (3)
N5—C6—C11—C12	−0.8 (4)	C16—C15—C20—C21	−176.7 (3)
N7—C6—C11—C12	−180.0 (3)	C12—C15—C20—C21	2.1 (4)
N5—C6—C11—C10	177.9 (3)	C19—C20—C21—O22	−166.2 (3)
N7—C6—C11—C10	−1.3 (4)	C15—C20—C21—O22	11.1 (4)
O24—C10—C11—C12	6.9 (5)	C19—C20—C21—N23	12.0 (4)
N9—C10—C11—C12	−171.3 (3)	C15—C20—C21—N23	−170.6 (3)
O24—C10—C11—C6	−171.7 (3)	C53—N50—C52—O51	−25 (2)
N9—C10—C11—C6	10.1 (4)	C55—N50—C52—O51	−176.9 (13)
C6—C11—C12—C13	−4.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N23—H23B···O31^i	0.88 (3)	2.19 (3)	3.003 (4)	153 (3)
N23—H23A···O22^ii	0.96 (4)	2.09 (4)	3.017 (4)	164 (3)
C17—H17···O51	0.93	2.56	3.313 (10)	138

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