Crystal structure of pharmaceutical cocrystals of 2,6-di­amino­pyridine with piracetam and theophylline

Pharmaceutical cocrystals are crystalline solids formed by an active pharmaceutical ingredient and a cocrystal former. The cocrystals 2,6-di­amino­pyridine (DAP)–piracetam [PIR; systematic name: 2-(2-oxopyrrolidin-1-yl)acetamide] (1/1), C₅H₇N₃·C₆H₁₀N₂O₂, (I), and 2,6-di­amino­pyridine–theophylline (TEO; systematic name: 1,3-dimethyl-7H-purine-2,6-dione) (1/1), C₅H₇N₃·C₇H₈N₄O₂, (II), were prepared by the solvent-assisted grinding method and were characterized by IR spectroscopy and powder X-ray diffraction. Cocrystal (I) crystallized in the ortho­rhom­bic space group Pbca and showed a 1:1 stoichiometry. The DAP and PIR molecules are linked by an N—H...O hydrogen-bond inter­action. Self-assembly of PIR mol­ecules forms a sheet of C(4) and C(7) chains. Cocrystal (II) crystallized in the monoclinic P2₁/c space group and also showed a 1:1 stoichiometry. The DAP and TEO molecules are connected by N—H...N and N—H...O hydrogen bonds, forming an R₂²(9) heterosynthon. A bidimensional supra­molecular array is formed by inter­linked DAP–TEO tetra­mers, producing a two-dimensional sheet.

Computing details

For both structures, data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SORTAV (Blessing, 1995); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

2,6-Diaminopyridine–2-(2-oxopyrrolidin-1-yl)acetamide (1/1) (nemvucol73_0ma_a)

Crystal data

C5H7N3·C6H10N2O2	F(000) = 1072
Mr = 251.3	Dx = 1.324 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 8544 reflections
a = 12.5854 (10) Å	θ = 2.6–25.7°
b = 10.0901 (7) Å	µ = 0.10 mm^−1
c = 19.8568 (16) Å	T = 293 K
V = 2521.6 (3) Å^3	Block, brown
Z = 8	0.3 × 0.2 × 0.1 mm

Data collection

Bruker APEXII diffractometer	2112 independent reflections
Radiation source: sealed x-ray tube	1916 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ or ω oscillation scans	θmax = 24.7°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −14→14
Tmin = 0.596, Tmax = 0.745	k = −11→11
9412 measured reflections	l = −23→22

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.136	w = 1/[σ^2(Fo^2) + (0.0372P)^2 + 1.9621P] where P = (Fo^2 + 2Fc^2)/3
S = 1.19	(Δ/σ)max < 0.001
2112 reflections	Δρmax = 0.23 e Å^−3
188 parameters	Δρmin = −0.23 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.075 (4)

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C2	0.15470 (18)	0.1293 (2)	0.38814 (11)	0.0408 (6)
C3	0.2301 (2)	0.2293 (3)	0.38717 (14)	0.0521 (7)
H3	0.2658	0.2514	0.3477	0.063*
C4	0.2505 (2)	0.2951 (3)	0.44659 (14)	0.0563 (7)
H4	0.3008	0.3626	0.4475	0.068*
C5	0.1969 (2)	0.2617 (3)	0.50482 (14)	0.0514 (6)
H5	0.2101	0.3061	0.545	0.062*
C6	0.12310 (19)	0.1604 (2)	0.50179 (12)	0.0440 (6)
C12	0.49435 (16)	0.3921 (2)	0.19766 (11)	0.0388 (5)
C13	0.5447 (2)	0.5128 (3)	0.16806 (13)	0.0525 (7)
H13A	0.6213	0.5097	0.1733	0.063*
H13B	0.5181	0.5923	0.1898	0.063*
C14	0.5144 (2)	0.5111 (3)	0.09418 (14)	0.0621 (8)
H14A	0.4843	0.5957	0.081	0.074*
H14B	0.5763	0.4937	0.0665	0.074*
C15	0.4337 (2)	0.4022 (2)	0.08593 (12)	0.0486 (6)
H15A	0.3642	0.4385	0.0758	0.058*
H15B	0.4542	0.3422	0.0501	0.058*
C16	0.38073 (18)	0.2096 (2)	0.16114 (12)	0.0392 (6)
H16A	0.4214	0.1596	0.1939	0.047*
H16B	0.383	0.1607	0.1191	0.047*
C17	0.26679 (17)	0.2141 (2)	0.18463 (10)	0.0333 (5)
O12	0.50567 (13)	0.34866 (18)	0.25556 (8)	0.0515 (5)
O17	0.21837 (14)	0.10905 (16)	0.19204 (9)	0.0523 (5)
N1	0.10113 (15)	0.09509 (18)	0.44420 (9)	0.0408 (5)
N2	0.1316 (2)	0.0578 (3)	0.33194 (12)	0.0593 (7)
N6	0.0664 (3)	0.1216 (3)	0.55693 (13)	0.0751 (9)
N11	0.43314 (14)	0.33441 (18)	0.15079 (9)	0.0359 (5)
N18	0.22281 (17)	0.3300 (2)	0.19661 (10)	0.0390 (5)
H2A	0.157 (2)	0.086 (3)	0.2952 (15)	0.056 (8)*
H2B	0.087 (2)	−0.004 (3)	0.3335 (12)	0.041 (7)*
H6A	0.019 (2)	0.055 (3)	0.5551 (14)	0.062 (8)*
H6B	0.080 (3)	0.157 (3)	0.5916 (18)	0.074 (10)*
H18A	0.156 (2)	0.334 (3)	0.2109 (13)	0.047 (7)*
H18B	0.256 (2)	0.404 (3)	0.1909 (12)	0.043 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2	0.0407 (12)	0.0380 (12)	0.0435 (13)	0.0055 (10)	−0.0004 (10)	0.0048 (10)
C3	0.0521 (15)	0.0476 (14)	0.0565 (15)	−0.0018 (12)	0.0073 (12)	0.0095 (12)
C4	0.0537 (15)	0.0425 (14)	0.0727 (18)	−0.0158 (12)	−0.0074 (13)	0.0090 (13)
C5	0.0571 (15)	0.0458 (14)	0.0511 (14)	−0.0073 (12)	−0.0139 (12)	0.0016 (11)
C6	0.0484 (13)	0.0417 (13)	0.0419 (13)	−0.0025 (10)	−0.0083 (10)	0.0040 (10)
C12	0.0289 (11)	0.0468 (13)	0.0407 (13)	0.0062 (9)	0.0017 (9)	−0.0038 (10)
C13	0.0468 (14)	0.0510 (15)	0.0598 (16)	−0.0075 (12)	0.0021 (12)	−0.0036 (12)
C14	0.0673 (18)	0.0609 (17)	0.0580 (17)	−0.0095 (14)	0.0066 (14)	0.0137 (13)
C15	0.0603 (15)	0.0509 (14)	0.0346 (12)	0.0009 (12)	0.0017 (11)	0.0045 (10)
C16	0.0418 (12)	0.0333 (11)	0.0425 (12)	0.0049 (9)	−0.0013 (10)	0.0005 (9)
C17	0.0421 (12)	0.0299 (11)	0.0278 (10)	−0.0017 (9)	0.0001 (9)	0.0007 (8)
O12	0.0499 (10)	0.0661 (11)	0.0385 (9)	0.0027 (8)	−0.0093 (7)	0.0042 (8)
O17	0.0598 (11)	0.0326 (9)	0.0645 (11)	−0.0086 (8)	0.0149 (8)	−0.0009 (8)
N1	0.0434 (10)	0.0389 (10)	0.0402 (11)	−0.0040 (8)	−0.0027 (8)	0.0032 (8)
N2	0.0746 (17)	0.0612 (15)	0.0422 (13)	−0.0162 (13)	0.0096 (12)	−0.0024 (11)
N6	0.097 (2)	0.091 (2)	0.0377 (13)	−0.0467 (17)	0.0010 (13)	−0.0065 (13)
N11	0.0359 (10)	0.0388 (10)	0.0329 (10)	0.0011 (8)	0.0005 (7)	0.0019 (8)
N18	0.0379 (11)	0.0312 (11)	0.0478 (12)	−0.0012 (9)	0.0086 (8)	−0.0001 (8)

Geometric parameters (Å, º)

C2—N1	1.346 (3)	C14—H14A	0.97
C2—N2	1.360 (3)	C14—H14B	0.97
C2—C3	1.386 (3)	C15—N11	1.459 (3)
C3—C4	1.378 (4)	C15—H15A	0.97
C3—H3	0.93	C15—H15B	0.97
C4—C5	1.381 (4)	C16—N11	1.436 (3)
C4—H4	0.93	C16—C17	1.509 (3)
C5—C6	1.383 (3)	C16—H16A	0.97
C5—H5	0.93	C16—H16B	0.97
C6—N1	1.348 (3)	C17—O17	1.232 (3)
C6—N6	1.364 (3)	C17—N18	1.315 (3)
C12—O12	1.239 (3)	N2—H2A	0.85 (3)
C12—N11	1.341 (3)	N2—H2B	0.84 (3)
C12—C13	1.493 (3)	N6—H6A	0.90 (3)
C13—C14	1.516 (4)	N6—H6B	0.79 (4)
C13—H13A	0.97	N18—H18A	0.88 (3)
C13—H13B	0.97	N18—H18B	0.87 (3)
C14—C15	1.505 (4)
N1—C2—N2	115.8 (2)	H14A—C14—H14B	108.6
N1—C2—C3	122.8 (2)	N11—C15—C14	104.4 (2)
N2—C2—C3	121.4 (2)	N11—C15—H15A	110.9
C4—C3—C2	117.8 (2)	C14—C15—H15A	110.9
C4—C3—H3	121.1	N11—C15—H15B	110.9
C2—C3—H3	121.1	C14—C15—H15B	110.9
C3—C4—C5	120.6 (2)	H15A—C15—H15B	108.9
C3—C4—H4	119.7	N11—C16—C17	117.03 (17)
C5—C4—H4	119.7	N11—C16—H16A	108
C4—C5—C6	118.2 (2)	C17—C16—H16A	108
C4—C5—H5	120.9	N11—C16—H16B	108
C6—C5—H5	120.9	C17—C16—H16B	108
N1—C6—N6	115.7 (2)	H16A—C16—H16B	107.3
N1—C6—C5	122.4 (2)	O17—C17—N18	122.4 (2)
N6—C6—C5	121.9 (2)	O17—C17—C16	118.77 (19)
O12—C12—N11	123.8 (2)	N18—C17—C16	118.86 (19)
O12—C12—C13	127.2 (2)	C2—N1—C6	118.3 (2)
N11—C12—C13	108.9 (2)	C2—N2—H2A	116.8 (19)
C12—C13—C14	105.3 (2)	C2—N2—H2B	120.3 (17)
C12—C13—H13A	110.7	H2A—N2—H2B	122 (3)
C14—C13—H13A	110.7	C6—N6—H6A	121.9 (19)
C12—C13—H13B	110.7	C6—N6—H6B	117 (2)
C14—C13—H13B	110.7	H6A—N6—H6B	121 (3)
H13A—C13—H13B	108.8	C12—N11—C16	123.03 (18)
C15—C14—C13	106.5 (2)	C12—N11—C15	113.98 (19)
C15—C14—H14A	110.4	C16—N11—C15	122.68 (18)
C13—C14—H14A	110.4	C17—N18—H18A	119.8 (17)
C15—C14—H14B	110.4	C17—N18—H18B	122.6 (17)
C13—C14—H14B	110.4	H18A—N18—H18B	118 (2)
N1—C2—C3—C4	0.3 (4)	N2—C2—N1—C6	178.2 (2)
N2—C2—C3—C4	−178.6 (2)	C3—C2—N1—C6	−0.8 (3)
C2—C3—C4—C5	−0.1 (4)	N6—C6—N1—C2	180.0 (2)
C3—C4—C5—C6	0.4 (4)	C5—C6—N1—C2	1.1 (3)
C4—C5—C6—N1	−0.9 (4)	O12—C12—N11—C16	−5.2 (3)
C4—C5—C6—N6	−179.7 (3)	C13—C12—N11—C16	174.40 (19)
O12—C12—C13—C14	173.6 (2)	O12—C12—N11—C15	−178.9 (2)
N11—C12—C13—C14	−6.0 (3)	C13—C12—N11—C15	0.7 (3)
C12—C13—C14—C15	8.8 (3)	C17—C16—N11—C12	95.4 (2)
C13—C14—C15—N11	−8.4 (3)	C17—C16—N11—C15	−91.4 (2)
N11—C16—C17—O17	177.80 (19)	C14—C15—N11—C12	5.0 (3)
N11—C16—C17—N18	−2.3 (3)	C14—C15—N11—C16	−168.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O17	0.85 (3)	2.20 (3)	3.029 (3)	166 (3)
N2—H2B···O12^i	0.84 (3)	2.44 (3)	3.121 (3)	138 (2)
N6—H6A···N1^ii	0.90 (3)	2.14 (3)	3.038 (4)	176 (3)
N18—H18A···O12^iii	0.89 (3)	2.01 (3)	2.899 (3)	178 (3)
N18—H18B···N11	0.86 (3)	2.47 (3)	2.799 (3)	104 (2)
N18—H18B···O17^iv	0.86 (3)	2.09 (3)	2.913 (3)	158 (2)

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

2,6-Diaminopyridine–1,3-dimethyl-7H-purine-2,6-dione (1/1) (monop21c_a)

Crystal data

C5H7N3·C7H8N4O2	F(000) = 608
Mr = 289.31	Dx = 1.441 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9001 reflections
a = 9.5439 (3) Å	θ = 2.6–25.8°
b = 15.6588 (5) Å	µ = 0.11 mm^−1
c = 9.4887 (3) Å	T = 293 K
β = 109.927 (1)°	Prism, grey
V = 1333.15 (7) Å^3	0.3 × 0.2 × 0.1 mm
Z = 4

Data collection

Bruker APEX-II diffractometer	2564 independent reflections
Radiation source: sealed x-ray tube	2381 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
φ or ω oscillation scans	θmax = 25.8°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −11→11
Tmin = 0.704, Tmax = 0.745	k = −19→19
30803 measured reflections	l = −11→11

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0555P)^2 + 0.4344P] where P = (Fo^2 + 2Fc^2)/3
2564 reflections	(Δ/σ)max = 0.001
216 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C2	0.21247 (15)	0.81387 (9)	0.54567 (15)	0.0368 (3)
C3	0.10890 (18)	0.87773 (10)	0.54065 (18)	0.0467 (4)
H3	0.1215	0.933	0.5111	0.056*
C4	−0.01177 (18)	0.85673 (11)	0.5805 (2)	0.0546 (4)
H4	−0.0822	0.8983	0.5778	0.066*
C5	−0.03043 (18)	0.77507 (11)	0.6245 (2)	0.0523 (4)
H5	−0.1118	0.7609	0.6527	0.063*
C6	0.07612 (15)	0.71453 (9)	0.62537 (15)	0.0382 (3)
C11	0.72267 (17)	0.63726 (11)	0.3094 (2)	0.0511 (4)
H11A	0.8031	0.5984	0.3187	0.077*
H11B	0.753	0.6781	0.3895	0.077*
H11C	0.6967	0.6665	0.215	0.077*
C12	0.56570 (15)	0.51097 (9)	0.24475 (15)	0.0366 (3)
C13	0.41450 (19)	0.38156 (10)	0.1791 (2)	0.0523 (4)
H13A	0.3956	0.3853	0.0732	0.079*
H13B	0.3296	0.3569	0.1962	0.079*
H13C	0.5004	0.3463	0.2246	0.079*
C14	0.34892 (14)	0.50266 (8)	0.31251 (14)	0.0334 (3)
C15	0.37949 (14)	0.58001 (8)	0.38233 (14)	0.0333 (3)
C16	0.50554 (14)	0.62997 (8)	0.38947 (15)	0.0351 (3)
C18	0.17543 (16)	0.52711 (9)	0.39562 (17)	0.0416 (3)
N1	0.19525 (12)	0.73342 (7)	0.58614 (12)	0.0358 (3)
N2	0.33778 (15)	0.83020 (9)	0.51273 (16)	0.0481 (3)
N6	0.06279 (16)	0.63045 (9)	0.65948 (16)	0.0463 (3)
N11	0.59354 (12)	0.58973 (7)	0.31676 (13)	0.0364 (3)
N13	0.44179 (12)	0.46717 (7)	0.24499 (13)	0.0371 (3)
N17	0.26514 (12)	0.59486 (7)	0.43666 (13)	0.0375 (3)
N19	0.22118 (13)	0.46826 (7)	0.32006 (14)	0.0403 (3)
O12	0.65115 (12)	0.48205 (7)	0.18507 (13)	0.0497 (3)
O16	0.54008 (12)	0.69939 (6)	0.45042 (13)	0.0491 (3)
H2A	0.341 (2)	0.8797 (13)	0.462 (2)	0.060 (5)*
H2B	0.392 (2)	0.7878 (13)	0.503 (2)	0.061 (5)*
H6A	0.148 (2)	0.5994 (12)	0.700 (2)	0.060 (5)*
H6B	−0.002 (2)	0.6222 (12)	0.698 (2)	0.061 (5)*
H17	0.249 (2)	0.6465 (12)	0.488 (2)	0.056 (5)*
H18	0.0839 (19)	0.5229 (11)	0.4224 (19)	0.051 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2	0.0393 (7)	0.0370 (7)	0.0349 (6)	−0.0027 (5)	0.0139 (5)	−0.0032 (5)
C3	0.0539 (9)	0.0366 (7)	0.0513 (8)	0.0035 (6)	0.0199 (7)	−0.0020 (6)
C4	0.0481 (9)	0.0485 (9)	0.0704 (11)	0.0106 (7)	0.0244 (8)	−0.0101 (8)
C5	0.0428 (8)	0.0535 (9)	0.0710 (11)	0.0003 (7)	0.0329 (8)	−0.0113 (8)
C6	0.0369 (7)	0.0421 (7)	0.0405 (7)	−0.0044 (6)	0.0193 (6)	−0.0078 (6)
C11	0.0424 (8)	0.0516 (9)	0.0699 (10)	−0.0094 (7)	0.0328 (8)	−0.0061 (8)
C12	0.0359 (7)	0.0371 (7)	0.0406 (7)	0.0047 (5)	0.0178 (6)	0.0015 (5)
C13	0.0563 (9)	0.0411 (8)	0.0677 (10)	−0.0049 (7)	0.0315 (8)	−0.0165 (7)
C14	0.0342 (6)	0.0320 (6)	0.0371 (7)	0.0024 (5)	0.0163 (5)	0.0029 (5)
C15	0.0334 (6)	0.0326 (6)	0.0384 (7)	0.0027 (5)	0.0181 (5)	0.0012 (5)
C16	0.0348 (7)	0.0328 (7)	0.0409 (7)	0.0023 (5)	0.0170 (5)	0.0012 (5)
C18	0.0396 (7)	0.0393 (7)	0.0543 (8)	−0.0030 (6)	0.0270 (6)	0.0003 (6)
N1	0.0351 (6)	0.0369 (6)	0.0398 (6)	−0.0006 (4)	0.0185 (5)	−0.0027 (5)
N2	0.0501 (8)	0.0409 (7)	0.0629 (8)	−0.0012 (6)	0.0315 (6)	0.0052 (6)
N6	0.0450 (7)	0.0454 (7)	0.0588 (8)	−0.0053 (6)	0.0311 (7)	−0.0001 (6)
N11	0.0325 (6)	0.0362 (6)	0.0455 (6)	−0.0005 (4)	0.0197 (5)	−0.0002 (5)
N13	0.0388 (6)	0.0327 (6)	0.0451 (6)	0.0005 (4)	0.0210 (5)	−0.0048 (5)
N17	0.0385 (6)	0.0353 (6)	0.0466 (6)	0.0005 (5)	0.0246 (5)	−0.0016 (5)
N19	0.0399 (6)	0.0363 (6)	0.0506 (7)	−0.0040 (5)	0.0233 (5)	−0.0009 (5)
O12	0.0476 (6)	0.0506 (6)	0.0624 (7)	0.0042 (5)	0.0338 (5)	−0.0080 (5)
O16	0.0482 (6)	0.0366 (6)	0.0702 (7)	−0.0071 (4)	0.0301 (5)	−0.0124 (5)

Geometric parameters (Å, º)

C2—N1	1.3434 (18)	C13—H13A	0.96
C2—N2	1.3594 (18)	C13—H13B	0.96
C2—C3	1.395 (2)	C13—H13C	0.96
C3—C4	1.369 (2)	C14—N19	1.3569 (16)
C3—H3	0.93	C14—C15	1.3636 (18)
C4—C5	1.375 (2)	C14—N13	1.3756 (16)
C4—H4	0.93	C15—N17	1.3764 (16)
C5—C6	1.388 (2)	C15—C16	1.4170 (18)
C5—H5	0.93	C16—O16	1.2227 (17)
C6—N1	1.3444 (17)	C16—N11	1.4048 (16)
C6—N6	1.372 (2)	C18—N19	1.3294 (18)
C11—N11	1.4617 (17)	C18—N17	1.3354 (18)
C11—H11A	0.96	C18—H18	0.992 (17)
C11—H11B	0.96	N2—H2A	0.92 (2)
C11—H11C	0.96	N2—H2B	0.86 (2)
C12—O12	1.2272 (16)	N6—H6A	0.91 (2)
C12—N13	1.3677 (17)	N6—H6B	0.83 (2)
C12—N11	1.3908 (18)	N17—H17	0.982 (18)
C13—N13	1.4645 (18)
N1—C2—N2	116.42 (13)	N19—C14—C15	111.98 (11)
N1—C2—C3	121.84 (13)	N19—C14—N13	126.68 (12)
N2—C2—C3	121.72 (14)	C15—C14—N13	121.33 (12)
C4—C3—C2	118.12 (14)	C14—C15—N17	105.45 (11)
C4—C3—H3	120.9	C14—C15—C16	123.45 (12)
C2—C3—H3	120.9	N17—C15—C16	131.10 (12)
C3—C4—C5	121.01 (14)	O16—C16—N11	121.41 (12)
C3—C4—H4	119.5	O16—C16—C15	126.94 (12)
C5—C4—H4	119.5	N11—C16—C15	111.64 (11)
C4—C5—C6	117.81 (14)	N19—C18—N17	114.34 (12)
C4—C5—H5	121.1	N19—C18—H18	124.9 (10)
C6—C5—H5	121.1	N17—C18—H18	120.7 (10)
N1—C6—N6	115.57 (12)	C2—N1—C6	118.87 (12)
N1—C6—C5	122.34 (14)	C2—N2—H2A	118.1 (12)
N6—C6—C5	122.02 (13)	C2—N2—H2B	118.8 (13)
N11—C11—H11A	109.5	H2A—N2—H2B	117.7 (17)
N11—C11—H11B	109.5	C6—N6—H6A	118.1 (12)
H11A—C11—H11B	109.5	C6—N6—H6B	113.3 (14)
N11—C11—H11C	109.5	H6A—N6—H6B	115.1 (18)
H11A—C11—H11C	109.5	C12—N11—C16	126.36 (11)
H11B—C11—H11C	109.5	C12—N11—C11	116.81 (11)
O12—C12—N13	121.78 (13)	C16—N11—C11	116.75 (12)
O12—C12—N11	120.54 (12)	C12—N13—C14	119.53 (11)
N13—C12—N11	117.67 (11)	C12—N13—C13	119.10 (11)
N13—C13—H13A	109.5	C14—N13—C13	121.31 (12)
N13—C13—H13B	109.5	C18—N17—C15	105.54 (11)
H13A—C13—H13B	109.5	C18—N17—H17	127.2 (11)
N13—C13—H13C	109.5	C15—N17—H17	127.1 (11)
H13A—C13—H13C	109.5	C18—N19—C14	102.68 (11)
H13B—C13—H13C	109.5
N1—C2—C3—C4	0.9 (2)	O12—C12—N11—C11	3.6 (2)
N2—C2—C3—C4	−177.74 (14)	N13—C12—N11—C11	−177.30 (13)
C2—C3—C4—C5	0.1 (2)	O16—C16—N11—C12	179.63 (13)
C3—C4—C5—C6	−0.7 (3)	C15—C16—N11—C12	0.14 (19)
C4—C5—C6—N1	0.5 (2)	O16—C16—N11—C11	−3.8 (2)
C4—C5—C6—N6	−176.32 (15)	C15—C16—N11—C11	176.72 (12)
N19—C14—C15—N17	0.08 (15)	O12—C12—N13—C14	−179.53 (13)
N13—C14—C15—N17	−179.70 (12)	N11—C12—N13—C14	1.33 (19)
N19—C14—C15—C16	−179.33 (12)	O12—C12—N13—C13	3.2 (2)
N13—C14—C15—C16	0.9 (2)	N11—C12—N13—C13	−175.92 (13)
C14—C15—C16—O16	−179.67 (14)	N19—C14—N13—C12	178.80 (12)
N17—C15—C16—O16	1.1 (2)	C15—C14—N13—C12	−1.5 (2)
C14—C15—C16—N11	−0.21 (19)	N19—C14—N13—C13	−4.0 (2)
N17—C15—C16—N11	−179.47 (13)	C15—C14—N13—C13	175.74 (13)
N2—C2—N1—C6	177.52 (12)	N19—C18—N17—C15	0.62 (17)
C3—C2—N1—C6	−1.2 (2)	C14—C15—N17—C18	−0.40 (15)
N6—C6—N1—C2	177.48 (12)	C16—C15—N17—C18	178.95 (14)
C5—C6—N1—C2	0.5 (2)	N17—C18—N19—C14	−0.56 (17)
O12—C12—N11—C16	−179.86 (13)	C15—C14—N19—C18	0.27 (15)
N13—C12—N11—C16	−0.7 (2)	N13—C14—N19—C18	−179.96 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O12^i	0.92 (2)	2.14 (2)	3.0533 (18)	170.8 (17)
N2—H2B···O16	0.87 (2)	2.16 (2)	3.0085 (18)	168.6 (18)
N6—H6A···O12^ii	0.91 (2)	2.251 (19)	3.1603 (19)	174.8 (17)
N6—H6B···N19^iii	0.83 (2)	2.48 (2)	3.183 (2)	142.8 (16)
N17—H17···N1	0.98 (2)	1.819 (19)	2.7945 (16)	171.3 (18)

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