The 1,10-phenanthrolinium cation and 3-hydroxy-2,4,6-trinitrophenolate anion are held together through an N—H⋯O hydrogen bond. In the crystal, cation–anion pairs are connected by C—H⋯O hydrogen bonds, forming a chain structure along [101]. Spectroscopic data also support the formation of a molecular salt. Sensitivity tests and thermal testing indicate that it is an insensitive high energy density material (IHEDM).
Keywords: crystal structure, spectroscopic characterization, sensitivity test, thermal testing, high energy density material, IHDEM
Abstract
In the title molecular salt, C12H9N2 +·C6H2N3O8 −, the cation and anion are connected by an N—H⋯O hydrogen bond. In the anion, an intramolecular O—H⋯O hydrogen bond with an S(6) ring motif is observed. The planes of two of the nitro groups are approximately parallel to the plane of the benzene ring, making dihedral angles of 3.9 (2) and 15.3 (2)°, while the third nitro group is almost perpendicular to the benzene ring, with a dihedral angle of 78.6 (3)°. In the crystal, cation–anion pairs related by an n-glide plane are connected by C—H⋯O hydrogen bonds, forming a chain structure along [101]. Sensitivity tests and thermal testing indicate that the title salt is an insensitive high-energy-density material (IHEDM).
Chemical context
2,4,6-Trinitrobenzene-1,3-diol (styphnic acid) is an energetic molecule, which forms complexes with metal ions (Liu et al., 2009 ▸; Zhang et al., 2011 ▸; Zhu et al., 2009 ▸) and salts with organic amines (Kalaivani & Malarvizhi, 2010 ▸; Kalaivani et al., 2011 ▸; Muthulakshmi & Kalaivani, 2015 ▸; Srinivas et al., 2014 ▸). 1,10-Phenanthroline is a well-known heterocyclic chelating agent (Goel & Singh, 2013 ▸; MacDonnell et al., 1999 ▸). It also shows good anticancer activity (Sastri et al., 2003 ▸). It is observed in the present study that although styphnic acid contains two acidic phenolic hydrogen atoms and 1,10-phenanthroline contains two basic tertiary nitrogen atoms, they form only the monoprotonated title molecular salt with 1:1 stoichiometry upon mixing of their ethanolic solutions. 
Structural commentary
The molecular structure of the title molecular salt is depicted in Fig. 1 ▸. The acidic hydrogen atom of the phenolic group in styphnic acid protonates the nitrogen atom of 1,10-phenanthroline, making it a cation. An S(6) ring motif is formed in the anion by an intramolecular O—H⋯O hydrogen bond (Table 1 ▸). Of the three nitro groups present in the anion, the plane of the one which is involved in the intramolecular hydrogen bond deviates only slightly from the plane of benzene ring [dihedral angle 3.94 (8)°] to which it is attached. The nitro group flanked between the C—O− group and the O—H group deviates to a greater extent [dihedral angle 78.62 (1)°] than the remaining nitro group which is oriented between the C—H and C—O− groups [dihedral angle 15.27 (7)°].
Figure 1.
A view of the molecular structure of the title molecular salt, with the atom labelling. Displacement ellipsoids are drawn at the 40% probability level. The N—H⋯O hydrogen bond is shown as a dashed line.
Table 1. Hydrogen-bond geometry (, ).
| DHA | DH | HA | D A | DHA |
|---|---|---|---|---|
| C10H10O7i | 0.93 | 2.52 | 3.398(2) | 158 |
| N2H2AO7 | 0.94(2) | 1.87(2) | 2.702(2) | 146.7(17) |
| O8H8AO5 | 0.82 | 1.88 | 2.579(2) | 143 |
Symmetry code: (i) 
.
Supramolecular features
In the crystal, the C—O− (acceptor) group of the phenolate anion and the N—H (donor) of the cation form an N—H⋯O hydrogen bond (Table 1 ▸ and Fig. 1 ▸). A weak C—H⋯O hydrogen bond is also observed in the crystal, forming a chain structure along [101] (Table 1 ▸ and Figs. 2 ▸ and 3 ▸).
Figure 2.
The crystal packing of the title molecular salt viewed along the a axis. Hydrogen bonds are shown as dotted lines.
Figure 3.
The crystal packing of the title molecular salt viewed along the b axis. Hydrogen bonds are shown as dotted lines.
Database survey
A search of the Cambridge Structural Database (Version 5.35, May 2014; Groom & Allen, 2014 ▸) for 3-hydroxy-2,4,6-trinitrophenolates gave 14 hits. Six concern metal-complex cations and eight organic cations. Amongst the latter are two compounds, referred to above in §1 for their high thermal stability, viz. 2-methoxyanilinium 3-hydroxy-2,4,6-trinitrophenolate (Kalaivani et al., 2011 ▸), morpholinium 3-hydroxy-2,4,6-trinitrophenolate (Kalaivani & Malarvizhi, 2010 ▸) while the crystal structure and thermal behaviour of pyridinium styphnate is reported by Muthulakshmi & Kalaivani (2015 ▸).
Synthesis and crystallization
Equimolar solutions of each of styphnic acid (2.45 g, 0.01 mol, 40 mL) and 1,10-phenanthroline monohydrate (1.98 g, 0.01 mol, 30 mL) in ethanol were mixed and shaken well for 3 h. On standing at 298 K for two h, the mixture yielded a yellow solid which was ground, washed well with dry ether and recrystallized from a ethanol–water mixture. Shining yellow single crystals were obtained from the mother liquor by slow evaporation (m.p. 395 K, yield 80%). Although the monoprotonated salt is obtained in good yield, several attempts to prepare the diprotonated salt from styphnic acid and 1,10-phenanthroline by mixing them in different concentrations in solvents of different polarity were not successful. The title molecular salt is produced due to a proton-transfer reaction in which one of the two phenolic group hydrogen atoms is transferred to one of the tertiary nitrogen atoms of 1,10-phenanthroline. This type of interaction is also evidenced by the spectroscopic data [IR: 1532 (N—O asym. str.), 1297 (N—O sym. str.), 2200–3500, 461 (amine salt) cm−1 (Silverstein & Webster, 2004 ▸; Ramachandran et al. 2007 ▸); 1H NMR: δ 8.52 p.p.m. (s, C—H proton of phenolate moiety), 9.28–8.19 p.p.m. (m, ring proton of cation), 7.0–5.5 p.p.m. (broad, time-averaged signal of OH and NH protons); 13C NMR: δ 156.0, 148.1, 142.2, 138.0, 135.3, 129.9, 127.9, 126.1 and 126.0 p.p.m.].
Sensitivity testing and thermal studies
The title molecular salt has three nitro groups attached to the benzene ring and hence it was subjected to sensitivity testing (impact sensitivity and friction sensitivity) and thermal studies (TGA/DTA). The molecular salt is insensitive towards impact and friction (Meyer et al., 2007 ▸). The activation energy for the decomposition of the title molecular salt was determined from TGA/DTA curves obtained at four different heating rates (5, 10, 15 and 20 K min−1) applying Ozawa and Kissinger methods (Kissinger, 1957 ▸; Ozawa, 1965 ▸). The activation energy determined was 459 kJ mol−1 from the Ozawa plot and 478 kcal mol−1 from the Kissinger plot. The sensitivity tests and thermal studies indicate that this molecular salt is an insensitive high-energy-density material (IHEDM).
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. C- and O-bound H atoms were positioned geometrically with C—H = 0.93 Å and O—H = 0.82 Å, and were refined as riding with U iso(H) = 1.2U eq(C) and 1.5U eq(O). The N-bound H atom was located in a difference Fourier map and refined freely [N—H = 0.94 (2) Å].
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C12H9N2 +C6H2N3O8 |
| M r | 425.32 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 296 |
| a, b, c () | 10.0984(7), 19.0072(14), 10.5124(7) |
| () | 118.419(2) |
| V (3) | 1774.6(2) |
| Z | 4 |
| Radiation type | Mo K |
| (mm1) | 0.13 |
| Crystal size (mm) | 0.35 0.30 0.25 |
| Data collection | |
| Diffractometer | Bruker Kappa APEXII CCD |
| Absorption correction | Multi-scan (SADABS; Bruker, 2004 ▸) |
| T min, T max | 0.952, 0.970 |
| No. of measured, independent and observed [I > 2(I)] reflections | 35336, 4007, 2551 |
| R int | 0.040 |
| (sin /)max (1) | 0.648 |
| Refinement | |
| R[F 2 > 2(F 2)], wR(F 2), S | 0.042, 0.125, 1.01 |
| No. of reflections | 4007 |
| No. of parameters | 284 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| max, min (e 3) | 0.24, 0.22 |
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015010737/is5402sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010737/is5402Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015010737/is5402Isup3.cml
CCDC reference: 1050845
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors are thankful to the UGC for financial support, to the SAIF, IIT Madras, for the spectroscopic and single-crystal XRD data collection, and to B. S. Abdur, Rahman University, Chennai-46, for the TGA/DTA studies.
supplementary crystallographic information
Crystal data
| C12H9N2+·C6H2N3O8− | F(000) = 872 |
| Mr = 425.32 | Dx = 1.592 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| a = 10.0984 (7) Å | Cell parameters from 8729 reflections |
| b = 19.0072 (14) Å | θ = 2.3–26.0° |
| c = 10.5124 (7) Å | µ = 0.13 mm−1 |
| β = 118.419 (2)° | T = 296 K |
| V = 1774.6 (2) Å3 | Plate, yellow |
| Z = 4 | 0.35 × 0.30 × 0.25 mm |
Data collection
| Bruker Kappa APEXII CCD diffractometer | 4007 independent reflections |
| Radiation source: fine-focus sealed tube | 2551 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.040 |
| ω and φ scan | θmax = 27.4°, θmin = 2.1° |
| Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −13→13 |
| Tmin = 0.952, Tmax = 0.970 | k = −24→24 |
| 35336 measured reflections | l = −13→13 |
Refinement
| Refinement on F2 | 0 restraints |
| Least-squares matrix: full | Hydrogen site location: mixed |
| R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.125 | w = 1/[σ2(Fo2) + (0.0575P)2 + 0.5078P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max < 0.001 |
| 4007 reflections | Δρmax = 0.24 e Å−3 |
| 284 parameters | Δρmin = −0.22 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.7553 (2) | 0.19947 (11) | 0.2956 (2) | 0.0454 (5) | |
| H1 | 0.7460 | 0.2332 | 0.3549 | 0.054* | |
| C2 | 0.8951 (2) | 0.17090 (12) | 0.3325 (2) | 0.0528 (5) | |
| H2 | 0.9799 | 0.1855 | 0.4160 | 0.063* | |
| C3 | 0.9067 (2) | 0.12136 (12) | 0.2455 (2) | 0.0494 (5) | |
| H3 | 1.0001 | 0.1016 | 0.2703 | 0.059* | |
| C4 | 0.78005 (19) | 0.09958 (10) | 0.1189 (2) | 0.0394 (4) | |
| C5 | 0.7858 (2) | 0.04786 (11) | 0.0239 (2) | 0.0518 (5) | |
| H5 | 0.8777 | 0.0280 | 0.0436 | 0.062* | |
| C6 | 0.6600 (3) | 0.02750 (11) | −0.0938 (2) | 0.0518 (5) | |
| H6 | 0.6664 | −0.0065 | −0.1544 | 0.062* | |
| C7 | 0.5170 (2) | 0.05664 (10) | −0.1282 (2) | 0.0412 (4) | |
| C8 | 0.3825 (2) | 0.03423 (11) | −0.2468 (2) | 0.0512 (5) | |
| H8 | 0.3837 | −0.0012 | −0.3071 | 0.061* | |
| C9 | 0.2506 (2) | 0.06479 (12) | −0.2725 (2) | 0.0548 (6) | |
| H9 | 0.1604 | 0.0501 | −0.3499 | 0.066* | |
| C10 | 0.2520 (2) | 0.11849 (11) | −0.1817 (2) | 0.0518 (5) | |
| H10 | 0.1608 | 0.1394 | −0.2021 | 0.062* | |
| C11 | 0.50613 (19) | 0.10956 (9) | −0.04079 (19) | 0.0350 (4) | |
| C12 | 0.64071 (18) | 0.13032 (9) | 0.08508 (18) | 0.0331 (4) | |
| N1 | 0.37497 (16) | 0.14143 (8) | −0.06844 (17) | 0.0422 (4) | |
| N2 | 0.63483 (17) | 0.17898 (8) | 0.17614 (16) | 0.0370 (4) | |
| H2A | 0.542 (2) | 0.1997 (11) | 0.155 (2) | 0.049 (6)* | |
| C13 | 0.20014 (19) | 0.22681 (10) | 0.12247 (19) | 0.0372 (4) | |
| C14 | 0.30718 (19) | 0.28269 (10) | 0.14818 (18) | 0.0368 (4) | |
| C15 | 0.23831 (19) | 0.35056 (10) | 0.11961 (19) | 0.0391 (4) | |
| C16 | 0.0886 (2) | 0.36441 (10) | 0.06754 (19) | 0.0408 (4) | |
| C17 | −0.00782 (19) | 0.30634 (11) | 0.0441 (2) | 0.0427 (5) | |
| C18 | 0.0499 (2) | 0.23906 (11) | 0.07130 (19) | 0.0420 (4) | |
| H18 | −0.0146 | 0.2012 | 0.0545 | 0.050* | |
| N3 | 0.24894 (18) | 0.15442 (9) | 0.15365 (17) | 0.0425 (4) | |
| N4 | 0.33779 (19) | 0.41089 (9) | 0.1449 (2) | 0.0517 (4) | |
| N5 | −0.16493 (18) | 0.31559 (11) | −0.00773 (18) | 0.0539 (5) | |
| O1 | 0.15283 (17) | 0.10808 (8) | 0.10657 (19) | 0.0679 (5) | |
| O2 | 0.38275 (15) | 0.14144 (7) | 0.22911 (15) | 0.0511 (4) | |
| O3 | 0.4138 (2) | 0.43000 (11) | 0.2680 (2) | 0.0912 (6) | |
| O4 | 0.3418 (2) | 0.43695 (11) | 0.0422 (2) | 0.0951 (7) | |
| O5 | −0.21917 (15) | 0.37586 (9) | −0.04103 (16) | 0.0630 (4) | |
| O6 | −0.24439 (17) | 0.26421 (11) | −0.0213 (2) | 0.0863 (6) | |
| O7 | 0.44347 (13) | 0.27585 (7) | 0.18477 (15) | 0.0483 (4) | |
| O8 | 0.04242 (15) | 0.43111 (7) | 0.04180 (16) | 0.0577 (4) | |
| H8A | −0.0489 | 0.4327 | 0.0110 | 0.087* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0381 (10) | 0.0461 (12) | 0.0484 (11) | −0.0042 (8) | 0.0178 (9) | −0.0046 (9) |
| C2 | 0.0317 (10) | 0.0658 (14) | 0.0502 (12) | −0.0055 (9) | 0.0109 (9) | −0.0016 (11) |
| C3 | 0.0292 (9) | 0.0600 (13) | 0.0577 (12) | 0.0085 (9) | 0.0196 (9) | 0.0102 (10) |
| C4 | 0.0335 (9) | 0.0398 (10) | 0.0486 (11) | 0.0076 (8) | 0.0224 (8) | 0.0089 (9) |
| C5 | 0.0480 (12) | 0.0521 (13) | 0.0637 (13) | 0.0191 (10) | 0.0333 (11) | 0.0081 (10) |
| C6 | 0.0645 (14) | 0.0421 (12) | 0.0583 (13) | 0.0117 (10) | 0.0369 (12) | −0.0003 (10) |
| C7 | 0.0482 (11) | 0.0351 (10) | 0.0435 (10) | 0.0012 (8) | 0.0245 (9) | 0.0034 (8) |
| C8 | 0.0637 (14) | 0.0454 (12) | 0.0458 (11) | −0.0074 (10) | 0.0270 (10) | −0.0058 (9) |
| C9 | 0.0484 (12) | 0.0593 (14) | 0.0453 (12) | −0.0129 (10) | 0.0129 (10) | −0.0050 (10) |
| C10 | 0.0338 (10) | 0.0539 (13) | 0.0577 (13) | −0.0006 (9) | 0.0136 (10) | 0.0035 (10) |
| C11 | 0.0334 (9) | 0.0328 (9) | 0.0399 (10) | 0.0014 (7) | 0.0184 (8) | 0.0053 (8) |
| C12 | 0.0310 (9) | 0.0300 (9) | 0.0404 (9) | 0.0024 (7) | 0.0186 (8) | 0.0047 (8) |
| N1 | 0.0295 (8) | 0.0429 (9) | 0.0490 (9) | 0.0024 (7) | 0.0146 (7) | 0.0011 (7) |
| N2 | 0.0287 (8) | 0.0375 (9) | 0.0438 (9) | 0.0027 (7) | 0.0164 (7) | 0.0008 (7) |
| C13 | 0.0345 (9) | 0.0380 (10) | 0.0394 (10) | 0.0043 (8) | 0.0177 (8) | 0.0016 (8) |
| C14 | 0.0305 (9) | 0.0415 (10) | 0.0358 (9) | 0.0038 (8) | 0.0137 (8) | −0.0018 (8) |
| C15 | 0.0324 (9) | 0.0386 (10) | 0.0428 (10) | 0.0034 (8) | 0.0150 (8) | −0.0016 (8) |
| C16 | 0.0371 (10) | 0.0436 (11) | 0.0384 (10) | 0.0112 (8) | 0.0153 (8) | 0.0025 (8) |
| C17 | 0.0295 (9) | 0.0572 (13) | 0.0405 (10) | 0.0098 (9) | 0.0158 (8) | 0.0063 (9) |
| C18 | 0.0344 (9) | 0.0514 (12) | 0.0410 (10) | −0.0001 (8) | 0.0185 (8) | 0.0033 (9) |
| N3 | 0.0415 (9) | 0.0420 (9) | 0.0492 (9) | 0.0023 (7) | 0.0257 (8) | 0.0008 (7) |
| N4 | 0.0406 (10) | 0.0412 (10) | 0.0687 (12) | 0.0036 (8) | 0.0221 (9) | −0.0038 (9) |
| N5 | 0.0327 (9) | 0.0761 (14) | 0.0513 (10) | 0.0101 (9) | 0.0187 (8) | 0.0090 (9) |
| O1 | 0.0523 (9) | 0.0437 (9) | 0.1065 (13) | −0.0066 (7) | 0.0367 (9) | −0.0094 (8) |
| O2 | 0.0416 (8) | 0.0498 (8) | 0.0574 (8) | 0.0109 (6) | 0.0200 (7) | 0.0091 (7) |
| O3 | 0.0767 (12) | 0.0996 (15) | 0.0885 (13) | −0.0341 (11) | 0.0323 (11) | −0.0422 (11) |
| O4 | 0.0991 (15) | 0.0829 (14) | 0.0965 (14) | −0.0256 (11) | 0.0410 (12) | 0.0204 (11) |
| O5 | 0.0387 (8) | 0.0775 (12) | 0.0660 (10) | 0.0230 (8) | 0.0194 (7) | 0.0057 (8) |
| O6 | 0.0357 (8) | 0.0942 (14) | 0.1205 (16) | 0.0024 (9) | 0.0304 (9) | 0.0257 (12) |
| O7 | 0.0296 (7) | 0.0430 (8) | 0.0689 (9) | 0.0042 (6) | 0.0206 (6) | −0.0054 (7) |
| O8 | 0.0441 (8) | 0.0482 (9) | 0.0739 (10) | 0.0189 (7) | 0.0225 (7) | 0.0038 (7) |
Geometric parameters (Å, º)
| C1—N2 | 1.325 (2) | C11—C12 | 1.429 (2) |
| C1—C2 | 1.384 (3) | C12—N2 | 1.353 (2) |
| C1—H1 | 0.9300 | N2—H2A | 0.94 (2) |
| C2—C3 | 1.356 (3) | C13—C18 | 1.367 (2) |
| C2—H2 | 0.9300 | C13—N3 | 1.446 (2) |
| C3—C4 | 1.399 (3) | C13—C14 | 1.446 (3) |
| C3—H3 | 0.9300 | C14—O7 | 1.247 (2) |
| C4—C12 | 1.404 (2) | C14—C15 | 1.428 (3) |
| C4—C5 | 1.422 (3) | C15—C16 | 1.366 (2) |
| C5—C6 | 1.341 (3) | C15—N4 | 1.463 (3) |
| C5—H5 | 0.9300 | C16—O8 | 1.333 (2) |
| C6—C7 | 1.424 (3) | C16—C17 | 1.414 (3) |
| C6—H6 | 0.9300 | C17—C18 | 1.378 (3) |
| C7—C11 | 1.402 (3) | C17—N5 | 1.422 (2) |
| C7—C8 | 1.403 (3) | C18—H18 | 0.9300 |
| C8—C9 | 1.357 (3) | N3—O2 | 1.2230 (19) |
| C8—H8 | 0.9300 | N3—O1 | 1.227 (2) |
| C9—C10 | 1.393 (3) | N4—O3 | 1.204 (2) |
| C9—H9 | 0.9300 | N4—O4 | 1.207 (3) |
| C10—N1 | 1.320 (2) | N5—O6 | 1.228 (2) |
| C10—H10 | 0.9300 | N5—O5 | 1.246 (2) |
| C11—N1 | 1.356 (2) | O8—H8A | 0.8200 |
| N2—C1—C2 | 120.31 (19) | N2—C12—C11 | 120.09 (15) |
| N2—C1—H1 | 119.8 | C4—C12—C11 | 121.09 (16) |
| C2—C1—H1 | 119.8 | C10—N1—C11 | 116.72 (17) |
| C3—C2—C1 | 119.13 (18) | C1—N2—C12 | 122.82 (16) |
| C3—C2—H2 | 120.4 | C1—N2—H2A | 117.7 (12) |
| C1—C2—H2 | 120.4 | C12—N2—H2A | 119.4 (12) |
| C2—C3—C4 | 120.94 (18) | C18—C13—N3 | 116.50 (17) |
| C2—C3—H3 | 119.5 | C18—C13—C14 | 122.64 (17) |
| C4—C3—H3 | 119.5 | N3—C13—C14 | 120.85 (15) |
| C3—C4—C12 | 118.00 (18) | O7—C14—C15 | 120.97 (17) |
| C3—C4—C5 | 123.26 (17) | O7—C14—C13 | 126.74 (17) |
| C12—C4—C5 | 118.74 (17) | C15—C14—C13 | 112.22 (15) |
| C6—C5—C4 | 120.69 (18) | C16—C15—C14 | 126.41 (17) |
| C6—C5—H5 | 119.7 | C16—C15—N4 | 117.07 (16) |
| C4—C5—H5 | 119.7 | C14—C15—N4 | 116.50 (15) |
| C5—C6—C7 | 121.53 (19) | O8—C16—C15 | 118.55 (18) |
| C5—C6—H6 | 119.2 | O8—C16—C17 | 124.17 (16) |
| C7—C6—H6 | 119.2 | C15—C16—C17 | 117.28 (17) |
| C11—C7—C8 | 117.12 (18) | C18—C17—C16 | 120.00 (16) |
| C11—C7—C6 | 119.94 (18) | C18—C17—N5 | 118.63 (19) |
| C8—C7—C6 | 122.93 (19) | C16—C17—N5 | 121.37 (18) |
| C9—C8—C7 | 119.38 (19) | C13—C18—C17 | 121.38 (18) |
| C9—C8—H8 | 120.3 | C13—C18—H18 | 119.3 |
| C7—C8—H8 | 120.3 | C17—C18—H18 | 119.3 |
| C8—C9—C10 | 119.21 (19) | O2—N3—O1 | 122.31 (16) |
| C8—C9—H9 | 120.4 | O2—N3—C13 | 119.42 (16) |
| C10—C9—H9 | 120.4 | O1—N3—C13 | 118.22 (16) |
| N1—C10—C9 | 123.93 (19) | O3—N4—O4 | 124.2 (2) |
| N1—C10—H10 | 118.0 | O3—N4—C15 | 117.6 (2) |
| C9—C10—H10 | 118.0 | O4—N4—C15 | 118.16 (19) |
| N1—C11—C7 | 123.58 (17) | O6—N5—O5 | 121.52 (17) |
| N1—C11—C12 | 118.47 (16) | O6—N5—C17 | 119.63 (19) |
| C7—C11—C12 | 117.95 (16) | O5—N5—C17 | 118.84 (19) |
| N2—C12—C4 | 118.80 (16) | C16—O8—H8A | 109.5 |
| N2—C1—C2—C3 | −0.5 (3) | N3—C13—C14—O7 | 6.9 (3) |
| C1—C2—C3—C4 | 0.7 (3) | C18—C13—C14—C15 | 2.4 (3) |
| C2—C3—C4—C12 | −0.3 (3) | N3—C13—C14—C15 | −176.13 (15) |
| C2—C3—C4—C5 | −180.0 (2) | O7—C14—C15—C16 | 174.20 (18) |
| C3—C4—C5—C6 | 178.0 (2) | C13—C14—C15—C16 | −2.9 (3) |
| C12—C4—C5—C6 | −1.7 (3) | O7—C14—C15—N4 | −3.9 (3) |
| C4—C5—C6—C7 | 0.1 (3) | C13—C14—C15—N4 | 178.93 (16) |
| C5—C6—C7—C11 | 2.2 (3) | C14—C15—C16—O8 | −177.46 (17) |
| C5—C6—C7—C8 | −177.0 (2) | N4—C15—C16—O8 | 0.7 (3) |
| C11—C7—C8—C9 | 1.0 (3) | C14—C15—C16—C17 | 2.4 (3) |
| C6—C7—C8—C9 | −179.84 (19) | N4—C15—C16—C17 | −179.48 (17) |
| C7—C8—C9—C10 | 0.9 (3) | O8—C16—C17—C18 | 178.77 (17) |
| C8—C9—C10—N1 | −1.2 (3) | C15—C16—C17—C18 | −1.1 (3) |
| C8—C7—C11—N1 | −2.8 (3) | O8—C16—C17—N5 | −1.2 (3) |
| C6—C7—C11—N1 | 178.01 (17) | C15—C16—C17—N5 | 178.99 (17) |
| C8—C7—C11—C12 | 176.54 (17) | N3—C13—C18—C17 | 177.12 (16) |
| C6—C7—C11—C12 | −2.7 (3) | C14—C13—C18—C17 | −1.4 (3) |
| C3—C4—C12—N2 | −0.4 (3) | C16—C17—C18—C13 | 0.7 (3) |
| C5—C4—C12—N2 | 179.32 (17) | N5—C17—C18—C13 | −179.38 (17) |
| C3—C4—C12—C11 | −178.65 (17) | C18—C13—N3—O2 | −163.44 (16) |
| C5—C4—C12—C11 | 1.1 (3) | C14—C13—N3—O2 | 15.1 (3) |
| N1—C11—C12—N2 | 2.2 (2) | C18—C13—N3—O1 | 14.3 (2) |
| C7—C11—C12—N2 | −177.13 (16) | C14—C13—N3—O1 | −167.14 (17) |
| N1—C11—C12—C4 | −179.56 (16) | C16—C15—N4—O3 | 103.1 (2) |
| C7—C11—C12—C4 | 1.1 (2) | C14—C15—N4—O3 | −78.6 (2) |
| C9—C10—N1—C11 | −0.5 (3) | C16—C15—N4—O4 | −79.0 (2) |
| C7—C11—N1—C10 | 2.5 (3) | C14—C15—N4—O4 | 99.3 (2) |
| C12—C11—N1—C10 | −176.79 (16) | C18—C17—N5—O6 | 3.0 (3) |
| C2—C1—N2—C12 | −0.2 (3) | C16—C17—N5—O6 | −177.05 (19) |
| C4—C12—N2—C1 | 0.6 (3) | C18—C17—N5—O5 | −175.60 (17) |
| C11—C12—N2—C1 | 178.89 (17) | C16—C17—N5—O5 | 4.3 (3) |
| C18—C13—C14—O7 | −174.58 (18) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C10—H10···O7i | 0.93 | 2.52 | 3.398 (2) | 158 |
| N2—H2A···O7 | 0.94 (2) | 1.87 (2) | 2.702 (2) | 146.7 (17) |
| O8—H8A···O5 | 0.82 | 1.88 | 2.579 (2) | 143 |
Symmetry code: (i) x−1/2, −y+1/2, z−1/2.
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015010737/is5402sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010737/is5402Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015010737/is5402Isup3.cml
CCDC reference: 1050845
Additional supporting information: crystallographic information; 3D view; checkCIF report