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The crystal structures of two NH-pyrazole derivatives forming intermolecular N—H
N hydrogen bonds are reported: 5-methyl-4-(3-methylpyrazol-5-yl)pyrazol-3-ol, C8H10N4O (P1), and 3-methyl-5-dihydro-1H-naphtho[1,2-d]pyrazole hemihydrochloride, C12H12N2.-C12H13N
.Cl− (P2). 26 other structures are surveyed in order to obtain a deeper insight into the ways NH-pyrazoles self-assemble by means of intermolecular N—HN hydrogen bonds in molecular crystals. A limited number of compounds form chains or dimers via homonuclear N+—HN positive-charge-assisted hydrogen bonds, typical of proton sponges, which can be remarkably short [e.g. NN 2.714 (3), N—H 1.09 (3), HN 1.63 (3) Å, N—HN 169 (3)° in (P2)]. Most pyrazoles, however, pack via neutral N—HN bonds which are formally assisted by resonance (resonance-assisted hydrogen bond, RAHB) through the N=C—C=C—NH iminoenamine fragment, contained in the ring, giving rise to dimers, trimers, tetramers and infinite chains of pyrazole molecules. Surprisingly, the resonance does not appear to shorten the N—HN bond with respect to the accepted mean value NN 2.97 (10) Å for non-resonant N—HN bonds. It is shown that this is due to the internal π-delocalization of the pyrazole ring, which can be hardly increased by the hydrogen-bond interaction, except in symmetrically 3,5-substituted pyrazoles which display NN distances as short as 2.82 Å, identical C—C and C—N distances in the two halves of the pyrazole molecule, and typical phenomena of N—HN dynamical proton disorder, detectable by 15N-CP/MAS solid-state NMR.
N hydrogen bonds are reported: 5-methyl-4-(3-methylpyrazol-5-yl)pyrazol-3-ol, C8H10N4O (P1), and 3-methyl-5-dihydro-1H-naphtho[1,2-d]pyrazole hemihydrochloride, C12H12N2.-C12H13N
.Cl− (P2). 26 other structures are surveyed in order to obtain a deeper insight into the ways NH-pyrazoles self-assemble by means of intermolecular N—HN hydrogen bonds in molecular crystals. A limited number of compounds form chains or dimers via homonuclear N+—HN positive-charge-assisted hydrogen bonds, typical of proton sponges, which can be remarkably short [e.g. NN 2.714 (3), N—H 1.09 (3), HN 1.63 (3) Å, N—HN 169 (3)° in (P2)]. Most pyrazoles, however, pack via neutral N—HN bonds which are formally assisted by resonance (resonance-assisted hydrogen bond, RAHB) through the N=C—C=C—NH iminoenamine fragment, contained in the ring, giving rise to dimers, trimers, tetramers and infinite chains of pyrazole molecules. Surprisingly, the resonance does not appear to shorten the N—HN bond with respect to the accepted mean value NN 2.97 (10) Å for non-resonant N—HN bonds. It is shown that this is due to the internal π-delocalization of the pyrazole ring, which can be hardly increased by the hydrogen-bond interaction, except in symmetrically 3,5-substituted pyrazoles which display NN distances as short as 2.82 Å, identical C—C and C—N distances in the two halves of the pyrazole molecule, and typical phenomena of N—HN dynamical proton disorder, detectable by 15N-CP/MAS solid-state NMR.Supporting information
 | Crystallographic Information File (CIF) |
 | Structure factor file (CIF format) |
| Structure factor file (CIF format) |
CCDC references: 138558; 138559
Computing details top
For both compounds, data collection: CAD4 Enraf-Nonius, 1984; cell refinement: CAD4 Enraf-Nonius, 1984; data reduction: MolEN, C.K. Fair, Enraf-Nonius, 1990; program(s) used to solve structure: SIR92, Altomare et al., 1994; program(s) used to refine structure: SHELX97, Sheldrick, 1997; molecular graphics: ORTEPII, Johnson, 1976; software used to prepare material for publication: PARST (Nardelli, 1983, 1995), SHELX97 (Sheldrick, 1997).
(P1) 3-hydroxy-5-methyl-4-(3'-methylpyrazol-5'-yl)pyrazole top
Crystal data top
| C8H10N4O | F(000) = 752 |
| Mr = 178.20 | Dx = 1.398 Mg m−3 |
| Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2n 2ab | Cell parameters from 25 reflections |
| a = 16.409 (3) Å | θ = 9–13° |
| b = 7.619 (1) Å | µ = 0.10 mm−1 |
| c = 13.544 (6) Å | T = 293 K |
| V = 1693.3 (8) Å3 | Prism, colourless |
| Z = 8 | 0.33 × 0.26 × 0.23 mm |
Data collection top
| Enraf Nonius CAD-4 diffractometer | Rint = 0.000 |
| Radiation source: fine-focus sealed tube | θmax = 27.0°, θmin = 2.5° |
| Graphite monochromator | h = 0→20 |
| ω/2θ scans | k = 0→9 |
| 1841 measured reflections | l = 0→17 |
| 1841 independent reflections | 3 standard reflections every 120 min |
| 1100 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.070 | Hydrogen site location: difference Fourier map |
| wR(F2) = 0.186 | All H-atom parameters refined |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.1089P)2] where P = (Fo2 + 2Fc2)/3 |
| 1841 reflections | (Δ/σ)max = 0.010 |
| 158 parameters | Δρmax = 0.27 e Å−3 |
| 0 restraints | Δρmin = −0.38 e Å−3 |
Special details top
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 (Å2) top
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.09348 (11) | 0.1782 (3) | −0.17183 (16) | 0.0522 (6) | |
| N1 | −0.09304 (14) | 0.1704 (3) | −0.05922 (17) | 0.0391 (6) | |
| N2 | −0.04603 (13) | 0.1409 (3) | −0.14028 (16) | 0.0413 (6) | |
| N3 | 0.23325 (14) | 0.3781 (4) | 0.05880 (19) | 0.0481 (7) | |
| N4 | 0.17569 (13) | 0.3032 (4) | 0.0006 (2) | 0.0467 (7) | |
| C1 | 0.02949 (15) | 0.1891 (4) | −0.1115 (2) | 0.0382 (7) | |
| C2 | 0.03050 (15) | 0.2453 (4) | −0.01439 (19) | 0.0343 (6) | |
| C3 | −0.05044 (17) | 0.2328 (4) | 0.0167 (2) | 0.0370 (7) | |
| C4 | −0.0897 (2) | 0.2740 (6) | 0.1127 (3) | 0.0537 (9) | |
| C5 | 0.09975 (15) | 0.3153 (4) | 0.0401 (2) | 0.0354 (6) | |
| C6 | 0.10917 (15) | 0.4001 (4) | 0.1266 (2) | 0.0370 (6) | |
| C7 | 0.19287 (15) | 0.4383 (4) | 0.1362 (2) | 0.0371 (6) | |
| C8 | 0.2364 (2) | 0.5280 (5) | 0.2180 (3) | 0.0491 (8) | |
| H1 | 0.077 (2) | 0.164 (5) | −0.254 (3) | 0.073 (11)* | |
| H4 | 0.1842 (17) | 0.256 (4) | −0.063 (2) | 0.042 (8)* | |
| H6 | 0.0712 (17) | 0.439 (4) | 0.176 (2) | 0.041 (8)* | |
| H10 | −0.149 (3) | 0.137 (6) | −0.058 (3) | 0.094 (14)* | |
| H41 | −0.067 (3) | 0.229 (5) | 0.171 (3) | 0.077 (13)* | |
| H42 | −0.086 (2) | 0.394 (6) | 0.121 (3) | 0.070 (12)* | |
| H43 | −0.150 (4) | 0.244 (7) | 0.105 (4) | 0.113 (17)* | |
| H81 | 0.242 (3) | 0.441 (7) | 0.261 (3) | 0.098 (16)* | |
| H82 | 0.208 (3) | 0.635 (6) | 0.241 (3) | 0.087 (13)* | |
| H83 | 0.283 (3) | 0.587 (7) | 0.198 (4) | 0.102 (16)* |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0277 (10) | 0.0873 (17) | 0.0416 (12) | −0.0052 (10) | 0.0052 (8) | −0.0091 (11) |
| N1 | 0.0277 (11) | 0.0490 (14) | 0.0405 (13) | −0.0023 (10) | 0.0007 (9) | 0.0009 (11) |
| N2 | 0.0253 (11) | 0.0592 (16) | 0.0393 (12) | −0.0049 (10) | 0.0001 (9) | 0.0014 (11) |
| N3 | 0.0261 (12) | 0.0608 (17) | 0.0573 (15) | −0.0038 (10) | −0.0006 (10) | −0.0116 (13) |
| N4 | 0.0243 (11) | 0.0694 (18) | 0.0463 (14) | 0.0000 (11) | −0.0021 (10) | −0.0133 (14) |
| C1 | 0.0270 (12) | 0.0501 (16) | 0.0376 (14) | −0.0014 (12) | 0.0018 (11) | 0.0014 (12) |
| C2 | 0.0245 (12) | 0.0413 (14) | 0.0372 (15) | 0.0014 (10) | −0.0003 (10) | 0.0034 (12) |
| C3 | 0.0274 (12) | 0.0425 (16) | 0.0412 (16) | 0.0014 (11) | 0.0020 (11) | 0.0044 (12) |
| C4 | 0.0381 (17) | 0.073 (3) | 0.050 (2) | −0.0015 (16) | 0.0086 (14) | −0.0069 (18) |
| C5 | 0.0250 (12) | 0.0418 (15) | 0.0395 (14) | 0.0009 (11) | 0.0005 (11) | 0.0057 (12) |
| C6 | 0.0260 (13) | 0.0463 (15) | 0.0389 (15) | 0.0035 (11) | 0.0014 (11) | 0.0004 (12) |
| C7 | 0.0281 (12) | 0.0340 (14) | 0.0493 (16) | 0.0005 (11) | −0.0021 (11) | 0.0032 (12) |
| C8 | 0.0440 (18) | 0.0442 (19) | 0.0589 (19) | −0.0045 (15) | −0.0086 (15) | −0.0031 (16) |
Geometric parameters (Å, º) top
| N1—N2 | 1.360 (3) | O1—H1 | 1.15 (4) |
| N1—C3 | 1.331 (4) | N1—H10 | 0.96 (5) |
| N2—C1 | 1.350 (3) | N4—H4 | 0.94 (3) |
| O1—C1 | 1.333 (3) | C3—C4 | 1.485 (4) |
| C1—C2 | 1.383 (4) | C4—H41 | 0.93 (4) |
| C2—C3 | 1.397 (4) | C4—H42 | 0.92 (4) |
| C2—C5 | 1.456 (4) | C4—H43 | 1.03 (6) |
| C5—C6 | 1.347 (4) | C6—H6 | 0.96 (3) |
| N4—C5 | 1.359 (3) | C7—C8 | 1.485 (4) |
| N3—N4 | 1.356 (3) | C8—H81 | 0.89 (5) |
| N3—C7 | 1.322 (4) | C8—H82 | 0.99 (5) |
| C6—C7 | 1.410 (4) | C8—H83 | 0.93 (5) |
| C1—O1—H1 | 114.4 (18) | H41—C4—H42 | 104 (3) |
| C3—N1—N2 | 112.6 (2) | C3—C4—H43 | 107 (3) |
| C3—N1—H10 | 126 (3) | H41—C4—H43 | 113 (4) |
| N2—N1—H10 | 121 (3) | H42—C4—H43 | 107 (4) |
| C1—N2—N1 | 104.0 (2) | C6—C5—N4 | 105.6 (2) |
| C7—N3—N4 | 104.9 (2) | C6—C5—C2 | 134.9 (2) |
| N3—N4—C5 | 112.4 (2) | N4—C5—C2 | 119.4 (3) |
| N3—N4—H4 | 126.0 (18) | C5—C6—C7 | 106.9 (2) |
| C5—N4—H4 | 121.4 (18) | C5—C6—H6 | 132.9 (17) |
| O1—C1—N2 | 121.9 (2) | C7—C6—H6 | 120.2 (16) |
| O1—C1—C2 | 126.4 (2) | N3—C7—C6 | 110.1 (2) |
| N2—C1—C2 | 111.7 (2) | N3—C7—C8 | 120.7 (3) |
| C1—C2—C3 | 104.7 (2) | C6—C7—C8 | 129.2 (3) |
| C1—C2—C5 | 127.2 (2) | C7—C8—H81 | 101 (3) |
| C3—C2—C5 | 127.9 (2) | C7—C8—H82 | 113 (3) |
| N1—C3—C2 | 106.9 (2) | H81—C8—H82 | 118 (4) |
| N1—C3—C4 | 121.6 (3) | C7—C8—H83 | 113 (3) |
| C2—C3—C4 | 131.5 (3) | H81—C8—H83 | 118 (4) |
| C3—C4—H41 | 119 (2) | H82—C8—H83 | 94 (4) |
| C3—C4—H42 | 107 (2) |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H4···O1 | 0.94 (3) | 2.18 (3) | 2.860 (3) | 128 (2) |
| O1—H1···N2i | 1.15 (4) | 1.53 (4) | 2.676 (3) | 174 (3) |
| N1—H10···N3ii | 0.95 (5) | 1.94 (5) | 2.874 (3) | 168 (4) |
| Symmetry codes: (i) −x, y, −z−1/2; (ii) x−1/2, −y+1/2, −z. |
(P2) 4,5-dihydronaphto[1,2-d]-1H,3-methylpyrazole hemihydrochloride top
Crystal data top
| C12H12N2·C12H13N2+·Cl− | F(000) = 856 |
| Mr = 404.93 | Dx = 1.261 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
| a = 8.190 (1) Å | θ = 9–14° |
| b = 14.463 (2) Å | µ = 0.20 mm−1 |
| c = 18.115 (3) Å | T = 293 K |
| β = 96.20 (1)° | Irregular, colourless |
| V = 2133.2 (5) Å3 | 0.55 × 0.19 × 0.12 mm |
| Z = 4 |
Data collection top
| Enraf Nonius CAD-4 diffractometer | Rint = 0.018 |
| Radiation source: fine-focus sealed tube | θmax = 27.0°, θmin = 2.3° |
| Graphite monochromator | h = 0→10 |
| ω/2θ scans | k = 0→18 |
| 4977 measured reflections | l = −23→22 |
| 4643 independent reflections | 3 standard reflections every 120 min |
| 2168 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.056 | All H-atom parameters refined |
| wR(F2) = 0.126 | w = 1/[σ2(Fo2) + (0.0484P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 0.97 | (Δ/σ)max = 0.027 |
| 4643 reflections | Δρmax = 0.19 e Å−3 |
| 363 parameters | Δρmin = −0.17 e Å−3 |
| 0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0011 (6) |
Special details top
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 (Å2) top
| x | y | z | Uiso*/Ueq | ||
| Cl | 0.36703 (9) | −0.12467 (5) | 0.36324 (3) | 0.0665 (3) | |
| N21 | 0.2388 (3) | 0.03276 (16) | 0.52045 (12) | 0.0537 (6) | |
| N11 | 0.2104 (3) | 0.03301 (16) | 0.44568 (12) | 0.0533 (6) | |
| C11 | 0.1113 (3) | 0.10410 (18) | 0.42360 (14) | 0.0501 (6) | |
| C21 | 0.0739 (3) | 0.14976 (18) | 0.48611 (15) | 0.0540 (7) | |
| C31 | 0.1559 (3) | 0.10331 (19) | 0.54616 (15) | 0.0545 (7) | |
| C41 | 0.1607 (6) | 0.1214 (4) | 0.6273 (2) | 0.0798 (11) | |
| C51 | −0.0409 (4) | 0.2302 (2) | 0.4810 (2) | 0.0724 (9) | |
| C61 | −0.0496 (5) | 0.2753 (3) | 0.4049 (2) | 0.0825 (11) | |
| C71 | −0.0388 (3) | 0.2116 (2) | 0.34005 (17) | 0.0651 (8) | |
| C81 | 0.0476 (3) | 0.12776 (19) | 0.34814 (15) | 0.0554 (7) | |
| C91 | 0.0665 (4) | 0.0721 (2) | 0.28737 (16) | 0.0637 (8) | |
| C101 | −0.0027 (4) | 0.0996 (3) | 0.21711 (19) | 0.0791 (10) | |
| C111 | −0.0883 (4) | 0.1812 (3) | 0.2094 (2) | 0.0884 (12) | |
| C121 | −0.1074 (4) | 0.2362 (3) | 0.2688 (2) | 0.0808 (10) | |
| N12 | 0.4670 (3) | −0.17333 (15) | 0.52867 (13) | 0.0513 (6) | |
| N22 | 0.4279 (3) | −0.10916 (14) | 0.57844 (11) | 0.0541 (6) | |
| C12 | 0.5353 (3) | −0.24820 (18) | 0.56344 (14) | 0.0496 (6) | |
| C22 | 0.5406 (3) | −0.2321 (2) | 0.63869 (14) | 0.0548 (7) | |
| C32 | 0.4739 (3) | −0.1447 (2) | 0.64561 (14) | 0.0563 (7) | |
| C42 | 0.4526 (6) | −0.0899 (4) | 0.71348 (19) | 0.0815 (11) | |
| C52 | 0.6164 (5) | −0.3018 (2) | 0.69306 (17) | 0.0722 (9) | |
| C62 | 0.6022 (6) | −0.3975 (3) | 0.6580 (2) | 0.0883 (11) | |
| C72 | 0.6427 (4) | −0.4026 (2) | 0.57911 (19) | 0.0707 (8) | |
| C82 | 0.6001 (3) | −0.32949 (19) | 0.53042 (16) | 0.0554 (7) | |
| C92 | 0.6260 (4) | −0.3354 (2) | 0.45573 (18) | 0.0647 (8) | |
| C102 | 0.6970 (4) | −0.4132 (3) | 0.4293 (3) | 0.0870 (11) | |
| C112 | 0.7424 (5) | −0.4845 (3) | 0.4770 (3) | 0.1061 (14) | |
| C122 | 0.7145 (5) | −0.4807 (3) | 0.5503 (3) | 0.0960 (13) | |
| H11 | 0.258 (3) | −0.0071 (17) | 0.4178 (13) | 0.052 (8)* | |
| H21 | 0.313 (4) | −0.021 (2) | 0.5502 (16) | 0.090 (10)* | |
| H91 | 0.124 (3) | 0.0127 (18) | 0.2939 (13) | 0.062 (8)* | |
| H101 | 0.013 (4) | 0.0585 (19) | 0.1789 (16) | 0.078 (10)* | |
| H111 | −0.129 (4) | 0.193 (2) | 0.1640 (19) | 0.088 (11)* | |
| H121 | −0.172 (4) | 0.298 (2) | 0.2650 (18) | 0.103 (11)* | |
| H411 | 0.061 (7) | 0.101 (3) | 0.647 (3) | 0.20 (2)* | |
| H421 | 0.242 (5) | 0.093 (3) | 0.654 (2) | 0.136 (18)* | |
| H431 | 0.144 (5) | 0.179 (3) | 0.635 (2) | 0.123 (17)* | |
| H511 | −0.009 (3) | 0.2741 (19) | 0.5158 (16) | 0.070 (9)* | |
| H521 | −0.149 (4) | 0.207 (2) | 0.4938 (17) | 0.097 (10)* | |
| H611 | −0.144 (4) | 0.316 (2) | 0.3957 (18) | 0.108 (12)* | |
| H621 | 0.045 (4) | 0.316 (2) | 0.4043 (16) | 0.090 (11)* | |
| H12 | 0.448 (3) | −0.1653 (16) | 0.4767 (14) | 0.052 (7)* | |
| H92 | 0.594 (3) | −0.2827 (18) | 0.4213 (14) | 0.064 (8)* | |
| H102 | 0.709 (4) | −0.420 (2) | 0.3768 (18) | 0.090 (11)* | |
| H112 | 0.792 (4) | −0.545 (3) | 0.4611 (18) | 0.105 (12)* | |
| H122 | 0.738 (4) | −0.523 (2) | 0.5841 (18) | 0.093 (12)* | |
| H412 | 0.471 (4) | −0.130 (2) | 0.753 (2) | 0.115 (14)* | |
| H422 | 0.538 (7) | −0.054 (4) | 0.727 (3) | 0.20 (3)* | |
| H432 | 0.345 (6) | −0.068 (3) | 0.714 (2) | 0.141 (18)* | |
| H512 | 0.563 (3) | −0.3009 (16) | 0.7378 (14) | 0.054 (7)* | |
| H522 | 0.743 (4) | −0.281 (2) | 0.7087 (16) | 0.089 (9)* | |
| H612 | 0.480 (4) | −0.416 (2) | 0.6583 (16) | 0.087 (10)* | |
| H622 | 0.674 (4) | −0.440 (2) | 0.6878 (16) | 0.087 (10)* |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl | 0.0797 (5) | 0.0711 (5) | 0.0473 (4) | 0.0027 (4) | 0.0002 (3) | −0.0086 (4) |
| N21 | 0.0580 (15) | 0.0569 (15) | 0.0452 (13) | −0.0029 (12) | 0.0019 (11) | −0.0013 (11) |
| N11 | 0.0530 (14) | 0.0543 (15) | 0.0526 (14) | −0.0006 (12) | 0.0059 (11) | −0.0065 (12) |
| C11 | 0.0392 (14) | 0.0489 (16) | 0.0618 (17) | −0.0050 (13) | 0.0040 (12) | −0.0005 (13) |
| C21 | 0.0422 (15) | 0.0496 (16) | 0.0699 (18) | −0.0069 (13) | 0.0043 (13) | −0.0066 (14) |
| C31 | 0.0461 (15) | 0.0581 (18) | 0.0603 (17) | −0.0098 (13) | 0.0110 (13) | −0.0097 (14) |
| C41 | 0.084 (3) | 0.094 (3) | 0.064 (2) | −0.006 (3) | 0.017 (2) | −0.019 (2) |
| C51 | 0.0493 (19) | 0.068 (2) | 0.098 (3) | 0.0016 (17) | 0.0031 (18) | −0.019 (2) |
| C61 | 0.068 (2) | 0.063 (2) | 0.112 (3) | 0.006 (2) | −0.013 (2) | 0.001 (2) |
| C71 | 0.0475 (17) | 0.063 (2) | 0.082 (2) | −0.0069 (15) | −0.0018 (15) | 0.0095 (17) |
| C81 | 0.0427 (15) | 0.0624 (18) | 0.0600 (17) | −0.0098 (14) | 0.0005 (12) | 0.0029 (15) |
| C91 | 0.0510 (18) | 0.081 (2) | 0.0598 (19) | −0.0003 (17) | 0.0062 (14) | 0.0103 (17) |
| C101 | 0.064 (2) | 0.113 (3) | 0.062 (2) | −0.010 (2) | 0.0102 (17) | 0.006 (2) |
| C111 | 0.068 (2) | 0.121 (4) | 0.073 (3) | −0.012 (2) | −0.009 (2) | 0.037 (3) |
| C121 | 0.061 (2) | 0.079 (3) | 0.098 (3) | −0.0074 (19) | −0.0103 (19) | 0.024 (2) |
| N12 | 0.0542 (14) | 0.0567 (15) | 0.0420 (12) | −0.0034 (11) | 0.0008 (10) | 0.0015 (12) |
| N22 | 0.0557 (14) | 0.0599 (14) | 0.0468 (12) | −0.0031 (12) | 0.0052 (10) | −0.0039 (11) |
| C12 | 0.0444 (15) | 0.0537 (17) | 0.0500 (16) | −0.0059 (13) | 0.0016 (12) | 0.0072 (13) |
| C22 | 0.0465 (16) | 0.069 (2) | 0.0482 (16) | −0.0126 (14) | 0.0028 (12) | 0.0120 (14) |
| C32 | 0.0540 (16) | 0.068 (2) | 0.0468 (16) | −0.0138 (15) | 0.0055 (12) | −0.0016 (14) |
| C42 | 0.086 (3) | 0.106 (3) | 0.053 (2) | −0.016 (3) | 0.0128 (19) | −0.013 (2) |
| C52 | 0.072 (2) | 0.094 (3) | 0.0493 (18) | −0.0105 (19) | 0.0010 (16) | 0.0199 (17) |
| C62 | 0.090 (3) | 0.078 (3) | 0.092 (3) | 0.001 (2) | −0.011 (2) | 0.034 (2) |
| C72 | 0.0636 (19) | 0.060 (2) | 0.085 (2) | −0.0026 (16) | −0.0093 (16) | 0.0110 (17) |
| C82 | 0.0430 (15) | 0.0570 (18) | 0.0648 (18) | −0.0066 (14) | −0.0015 (13) | 0.0048 (15) |
| C92 | 0.0602 (19) | 0.062 (2) | 0.072 (2) | −0.0029 (16) | 0.0088 (15) | −0.0083 (18) |
| C102 | 0.074 (2) | 0.088 (3) | 0.100 (3) | −0.007 (2) | 0.011 (2) | −0.024 (3) |
| C112 | 0.088 (3) | 0.083 (3) | 0.143 (4) | 0.014 (2) | −0.007 (3) | −0.028 (3) |
| C122 | 0.094 (3) | 0.062 (3) | 0.124 (4) | 0.008 (2) | −0.024 (3) | 0.010 (3) |
Geometric parameters (Å, º) top
| N11—N21 | 1.349 (3) | C101—C111 | 1.372 (5) |
| N11—C11 | 1.344 (3) | C101—H101 | 0.93 (3) |
| N21—C31 | 1.337 (3) | C111—C121 | 1.361 (5) |
| C11—C21 | 1.374 (3) | C111—H111 | 0.87 (3) |
| C21—C31 | 1.388 (4) | C121—H121 | 1.03 (3) |
| N12—N22 | 1.356 (3) | N12—H12 | 0.94 (2) |
| N12—C12 | 1.344 (3) | C12—C82 | 1.446 (4) |
| N22—C32 | 1.337 (3) | C22—C52 | 1.496 (4) |
| C12—C22 | 1.379 (3) | C32—C42 | 1.489 (4) |
| C22—C32 | 1.388 (4) | C42—H412 | 0.92 (4) |
| N21—H21 | 1.09 (3) | C42—H422 | 0.88 (6) |
| N11—H11 | 0.89 (2) | C42—H432 | 0.94 (4) |
| C11—C81 | 1.450 (3) | C52—C62 | 1.523 (5) |
| C21—C51 | 1.493 (4) | C52—H512 | 0.96 (2) |
| C31—C41 | 1.490 (4) | C52—H522 | 1.09 (3) |
| C41—H411 | 0.97 (5) | C62—C72 | 1.504 (5) |
| C41—H421 | 0.88 (4) | C62—H612 | 1.03 (3) |
| C41—H431 | 0.86 (4) | C62—H622 | 0.97 (3) |
| C51—C61 | 1.519 (5) | C72—C82 | 1.397 (4) |
| C51—H511 | 0.91 (3) | C72—C122 | 1.400 (5) |
| C51—H521 | 1.00 (3) | C82—C92 | 1.395 (4) |
| C61—C71 | 1.503 (4) | C92—C102 | 1.375 (5) |
| C61—H611 | 0.97 (4) | C92—H92 | 1.00 (3) |
| C61—H621 | 0.97 (3) | C102—C112 | 1.370 (6) |
| C71—C121 | 1.397 (4) | C102—H102 | 0.97 (3) |
| C71—C81 | 1.403 (4) | C112—C122 | 1.371 (6) |
| C81—C91 | 1.386 (4) | C112—H112 | 1.02 (4) |
| C91—C101 | 1.394 (4) | C122—H122 | 0.87 (3) |
| C91—H91 | 0.98 (3) | ||
| C31—N21—N11 | 108.0 (2) | C71—C121—H121 | 115.7 (19) |
| C31—N21—H21 | 130.2 (15) | C12—N12—N22 | 110.9 (2) |
| N11—N21—H21 | 121.7 (15) | C12—N12—H12 | 125.5 (14) |
| C11—N11—N21 | 109.5 (2) | N22—N12—H12 | 123.7 (14) |
| C11—N11—H11 | 128.2 (16) | C32—N22—N12 | 106.2 (2) |
| N21—N11—H11 | 122.2 (16) | N12—C12—C22 | 107.1 (2) |
| N11—C11—C21 | 107.7 (2) | N12—C12—C82 | 127.9 (2) |
| N11—C11—C81 | 127.2 (2) | C22—C12—C82 | 124.9 (3) |
| C21—C11—C81 | 125.0 (3) | C12—C22—C32 | 105.8 (2) |
| C11—C21—C31 | 106.3 (2) | C12—C22—C52 | 120.2 (3) |
| C11—C21—C51 | 121.2 (3) | C32—C22—C52 | 133.9 (3) |
| C31—C21—C51 | 132.4 (3) | N22—C32—C22 | 110.1 (2) |
| N21—C31—C21 | 108.5 (2) | N22—C32—C42 | 120.0 (3) |
| N21—C31—C41 | 121.2 (3) | C22—C32—C42 | 129.9 (3) |
| C21—C31—C41 | 130.3 (3) | C32—C42—H412 | 107 (2) |
| C31—C41—H411 | 112 (3) | C32—C42—H422 | 112 (3) |
| C31—C41—H421 | 114 (3) | H412—C42—H422 | 96 (4) |
| H411—C41—H421 | 106 (4) | C32—C42—H432 | 112 (2) |
| C31—C41—H431 | 111 (3) | H412—C42—H432 | 106 (3) |
| H411—C41—H431 | 94 (4) | H422—C42—H432 | 121 (4) |
| H421—C41—H431 | 119 (4) | C22—C52—C62 | 109.3 (3) |
| C21—C51—C61 | 111.0 (3) | C22—C52—H512 | 110.5 (15) |
| C21—C51—H511 | 111.6 (17) | C62—C52—H512 | 110.0 (15) |
| C61—C51—H511 | 108.1 (17) | C22—C52—H522 | 107.4 (15) |
| C21—C51—H521 | 107.1 (18) | C62—C52—H522 | 112.9 (15) |
| C61—C51—H521 | 113.5 (18) | H512—C52—H522 | 107 (2) |
| H511—C51—H521 | 106 (2) | C72—C62—C52 | 115.2 (3) |
| C71—C61—C51 | 116.5 (3) | C72—C62—H612 | 107.8 (16) |
| C71—C61—H611 | 111 (2) | C52—C62—H612 | 105.1 (17) |
| C51—C61—H611 | 112 (2) | C72—C62—H622 | 108.5 (17) |
| C71—C61—H621 | 104.2 (18) | C52—C62—H622 | 109.1 (17) |
| C51—C61—H621 | 108.0 (18) | H612—C62—H622 | 111 (2) |
| H611—C61—H621 | 104 (3) | C82—C72—C122 | 117.5 (4) |
| C121—C71—C81 | 117.7 (3) | C82—C72—C62 | 119.9 (3) |
| C121—C71—C61 | 120.9 (3) | C122—C72—C62 | 122.6 (3) |
| C81—C71—C61 | 121.3 (3) | C92—C82—C72 | 120.8 (3) |
| C91—C81—C71 | 121.1 (3) | C92—C82—C12 | 123.5 (3) |
| C91—C81—C11 | 123.5 (3) | C72—C82—C12 | 115.6 (3) |
| C71—C81—C11 | 115.4 (3) | C102—C92—C82 | 120.1 (4) |
| C81—C91—C101 | 119.3 (3) | C102—C92—H92 | 120.0 (15) |
| C81—C91—H91 | 120.4 (14) | C82—C92—H92 | 119.9 (15) |
| C101—C91—H91 | 120.2 (15) | C112—C102—C92 | 119.5 (4) |
| C111—C101—C91 | 119.4 (4) | C112—C102—H102 | 119.3 (19) |
| C111—C101—H101 | 125.5 (19) | C92—C102—H102 | 121.1 (19) |
| C91—C101—H101 | 115.0 (19) | C102—C112—C122 | 121.2 (4) |
| C121—C111—C101 | 121.5 (4) | C102—C112—H112 | 123.8 (19) |
| C121—C111—H111 | 124 (2) | C122—C112—H112 | 115.0 (19) |
| C101—C111—H111 | 114 (2) | C112—C122—C72 | 120.9 (4) |
| C111—C121—C71 | 120.8 (4) | C112—C122—H122 | 127 (2) |
| C111—C121—H121 | 123.5 (19) | C72—C122—H122 | 112 (2) |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N11—H11···Cl | 3.081 (2) | 0.89 (2) | 2.20 (2) | 170 (2) |
| N21—H21···N22 | 2.714 (3) | 1.09 (3) | 1.63 (3) | 169 (3) |
| N12—H12···Cl | 3.101 (3) | 0.94 (2) | 2.17 (2) | 168 (2) |
