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), C
5H
7N
3·C
6H
10N
2O
2, (I), and 2,6-diaminopyridine–theophylline (TEO; systematic name: 1,3-dimethyl-7
H-purine-2,6-dione) (1/1), C
5H
7N
3·C
7H
8N
4O
2, (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
P2
1/
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.
Supporting information
CCDC references: 1570704; 1570703
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)
top
Crystal data top
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) Å3 | Block, brown |
Z = 8 | 0.3 × 0.2 × 0.1 mm |
Data collection top
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 top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.056 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.136 | w = 1/[σ2(Fo2) + (0.0372P)2 + 1.9621P] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.075 (4) |
Special details top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
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···O12i | 0.84 (3) | 2.44 (3) | 3.121 (3) | 138 (2) |
N6—H6A···N1ii | 0.90 (3) | 2.14 (3) | 3.038 (4) | 176 (3) |
N18—H18A···O12iii | 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···O17iv | 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-7
H-purine-2,6-dione (1/1) (monop21c_a)
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Crystal data top
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) Å3 | 0.3 × 0.2 × 0.1 mm |
Z = 4 | |
Data collection top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0555P)2 + 0.4344P] where P = (Fo2 + 2Fc2)/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 top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O12i | 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···O12ii | 0.91 (2) | 2.251 (19) | 3.1603 (19) | 174.8 (17) |
N6—H6B···N19iii | 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. |