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3-Aminocarbonyl-1-benzylpyridinium bromide (N-benzylnicotinamide, BNA), C13H13N2O+·Br−, (I), and 1-benzyl-1,4-dihydropyridine-3-carboxamide (N-benzyl-1,4-dihydronicotinamide, rBNA), C13H14N2O, (II), are valuable model compounds used to study the enzymatic cofactors NAD(P)+ and NAD(P)H. BNA was crystallized successfully and its structure determined for the first time, while a low-temperature high-resolution structure of rBNA was obtained. Together, these structures provide the most detailed view of the reactive portions of NAD(P)+ and NAD(P)H. The amide group in BNA is rotated 8.4 (4)° out of the plane of the pyridine ring, while the two rings display a dihedral angle of 70.48 (17)°. In the rBNA structure, the dihydropyridine ring is essentially planar, indicating significant delocalization of the formal double bonds, and the amide group is coplanar with the ring [dihedral angle = 4.35 (9)°]. This rBNA conformation may lower the transition-state energy of an ene reaction between a substrate double bond and the dihydropyridine ring. The transition state would involve one atom of the double bond binding to the carbon ortho to both the ring N atom and the amide substituent of the dihydropyridine ring, while the other end of the double bond accepts an H atom from the methylene group para to the N atom.
Keywords: NAD(P)+; NAD(P)H; dinucleotide; enzymatic cofactor; crystal structure; pyridinium; salt; nicotinamide; ene reaction.
Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229617008877/sk3659sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S2053229617008877/sk3659BNAsup2.hkl |
| Structure factor file (CIF format) https://doi.org/10.1107/S2053229617008877/sk3659rBNAsup3.hkl |
 | Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229617008877/sk3659BNAsup4.cml |
| Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229617008877/sk3659rBNAsup5.cml |
CCDC references: 1556091; 1556090
Computing details top
Data collection: APEX2 (Bruker, 2005) for BNA; APEX3 (Bruker, 2015) for rBNA. Cell refinement: SAINT (Bruker, 2005) for BNA; SAINT (Bruker, 2015) for rBNA. Data reduction: SAINT (Bruker, 2005) for BNA; SAINT (Bruker, 2015) for rBNA. Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for BNA; SHELXT2014 (Sheldrick 2015a) for rBNA. For both compounds, program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: CrystalMaker (Palmer, 2014); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).
(BNA) 3-Aminocarbonyl-1-benzylpyridinium bromide top
Crystal data top
| C13H13N2O+·Br− | F(000) = 592 |
| Mr = 293.16 | Dx = 1.572 Mg m−3 |
| Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
| a = 4.7443 (3) Å | Cell parameters from 3782 reflections |
| b = 39.332 (2) Å | θ = 2.2–66.7° |
| c = 6.7618 (4) Å | µ = 4.40 mm−1 |
| β = 100.990 (3)° | T = 140 K |
| V = 1238.64 (13) Å3 | Triangular plate, colorless |
| Z = 4 | 0.22 × 0.12 × 0.03 mm |
Data collection top
| Bruker APEX DUO diffractometer | 2094 reflections with I > 2σ(I) |
| Radiation source: ImuS | Rint = 0.030 |
| ω and phi scans | θmax = 68.3°, θmin = 2.3° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −5→5 |
| Tmin = 0.593, Tmax = 0.753 | k = −46→46 |
| 6573 measured reflections | l = −6→7 |
| 2131 independent reflections |
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: difference Fourier map |
| wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.26 | w = 1/[σ2(Fo2) + 2.818P] where P = (Fo2 + 2Fc2)/3 |
| 2131 reflections | (Δ/σ)max < 0.001 |
| 204 parameters | Δρmax = 0.36 e Å−3 |
| 0 restraints | Δρmin = −0.50 e Å−3 |
Special details top
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) top
| x | y | z | Uiso*/Ueq | ||
| Br1 | 0.92360 (8) | 0.11798 (2) | 0.08674 (6) | 0.02633 (14) | |
| O1 | 0.3053 (6) | 0.00339 (6) | 0.2210 (4) | 0.0330 (6) | |
| N1 | 0.4460 (6) | 0.10865 (6) | 0.5640 (4) | 0.0181 (6) | |
| N2 | 0.6147 (7) | 0.04037 (9) | 0.1223 (5) | 0.0306 (7) | |
| C1 | 0.5786 (8) | 0.14361 (8) | 0.5789 (6) | 0.0230 (7) | |
| H1A | 0.671 (9) | 0.1466 (10) | 0.462 (7) | 0.028* | |
| H1B | 0.736 (9) | 0.1425 (10) | 0.694 (6) | 0.028* | |
| C2 | 0.4891 (7) | 0.08803 (8) | 0.4139 (5) | 0.0191 (7) | |
| C3 | 0.3832 (7) | 0.05515 (8) | 0.4013 (5) | 0.0220 (7) | |
| C4 | 0.2245 (8) | 0.04447 (8) | 0.5418 (6) | 0.0234 (8) | |
| C5 | 0.1789 (8) | 0.06634 (9) | 0.6937 (6) | 0.0258 (8) | |
| C6 | 0.2949 (7) | 0.09852 (8) | 0.7028 (5) | 0.0213 (7) | |
| C7 | 0.3656 (7) | 0.17122 (8) | 0.5994 (5) | 0.0213 (7) | |
| C8 | 0.2115 (9) | 0.18709 (9) | 0.4293 (7) | 0.0290 (8) | |
| C9 | 0.0158 (9) | 0.21245 (10) | 0.4488 (7) | 0.0370 (10) | |
| C10 | −0.0290 (9) | 0.22193 (9) | 0.6364 (8) | 0.0387 (11) | |
| C11 | 0.1230 (9) | 0.20634 (9) | 0.8055 (7) | 0.0347 (10) | |
| C12 | 0.3247 (8) | 0.18127 (8) | 0.7893 (6) | 0.0268 (8) | |
| C13 | 0.4302 (8) | 0.03091 (8) | 0.2379 (6) | 0.0257 (8) | |
| H1N | 0.691 (9) | 0.0595 (11) | 0.122 (6) | 0.023 (10)* | |
| H2N | 0.654 (9) | 0.0263 (11) | 0.035 (7) | 0.026 (11)* | |
| H2 | 0.597 (8) | 0.0974 (9) | 0.329 (6) | 0.013 (9)* | |
| H4 | 0.144 (9) | 0.0216 (10) | 0.534 (6) | 0.030 (11)* | |
| H5 | 0.066 (8) | 0.0582 (9) | 0.788 (6) | 0.016 (9)* | |
| H6 | 0.275 (10) | 0.1149 (11) | 0.818 (7) | 0.038 (12)* | |
| H8 | 0.238 (9) | 0.1808 (10) | 0.309 (7) | 0.029 (11)* | |
| H9 | −0.081 (10) | 0.2234 (11) | 0.329 (7) | 0.034 (11)* | |
| H10 | −0.164 (10) | 0.2391 (11) | 0.639 (7) | 0.042 (13)* | |
| H11 | 0.098 (9) | 0.2121 (10) | 0.931 (7) | 0.033 (12)* | |
| H12 | 0.443 (10) | 0.1713 (11) | 0.913 (7) | 0.041 (12)* |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.0270 (2) | 0.0300 (2) | 0.0230 (2) | −0.00053 (14) | 0.00731 (15) | 0.00040 (14) |
| O1 | 0.0408 (16) | 0.0213 (12) | 0.0385 (17) | −0.0028 (11) | 0.0118 (13) | −0.0089 (11) |
| N1 | 0.0183 (14) | 0.0174 (13) | 0.0190 (16) | −0.0001 (10) | 0.0045 (11) | −0.0003 (10) |
| N2 | 0.0367 (19) | 0.0230 (16) | 0.033 (2) | −0.0010 (14) | 0.0090 (15) | −0.0098 (14) |
| C1 | 0.0221 (17) | 0.0169 (16) | 0.032 (2) | −0.0041 (13) | 0.0107 (16) | −0.0028 (14) |
| C2 | 0.0209 (17) | 0.0206 (16) | 0.0152 (18) | 0.0028 (13) | 0.0024 (14) | 0.0003 (13) |
| C3 | 0.0209 (17) | 0.0200 (16) | 0.023 (2) | 0.0035 (13) | 0.0002 (14) | −0.0012 (13) |
| C4 | 0.0252 (18) | 0.0185 (16) | 0.025 (2) | −0.0020 (13) | 0.0010 (15) | 0.0000 (13) |
| C5 | 0.0266 (19) | 0.0232 (17) | 0.028 (2) | −0.0030 (14) | 0.0059 (16) | 0.0026 (14) |
| C6 | 0.0188 (17) | 0.0227 (16) | 0.024 (2) | 0.0012 (13) | 0.0086 (14) | −0.0009 (14) |
| C7 | 0.0207 (17) | 0.0152 (15) | 0.028 (2) | −0.0053 (12) | 0.0059 (15) | −0.0028 (13) |
| C8 | 0.035 (2) | 0.0235 (18) | 0.029 (2) | −0.0034 (15) | 0.0063 (17) | 0.0013 (15) |
| C9 | 0.035 (2) | 0.0263 (19) | 0.047 (3) | 0.0028 (16) | 0.001 (2) | 0.0090 (18) |
| C10 | 0.035 (2) | 0.0198 (18) | 0.063 (3) | 0.0044 (16) | 0.015 (2) | −0.0012 (18) |
| C11 | 0.045 (2) | 0.0232 (18) | 0.042 (3) | −0.0051 (16) | 0.023 (2) | −0.0116 (17) |
| C12 | 0.031 (2) | 0.0176 (16) | 0.031 (2) | −0.0040 (14) | 0.0060 (17) | −0.0044 (14) |
| C13 | 0.0287 (19) | 0.0200 (17) | 0.027 (2) | 0.0056 (14) | 0.0017 (16) | −0.0027 (14) |
Geometric parameters (Å, º) top
| O1—C13 | 1.229 (4) | C4—H4 | 0.98 (4) |
| N1—C2 | 1.345 (4) | C5—C6 | 1.377 (5) |
| N1—C6 | 1.346 (4) | C5—H5 | 0.96 (4) |
| N1—C1 | 1.507 (4) | C6—H6 | 1.03 (4) |
| N2—C13 | 1.333 (5) | C7—C8 | 1.388 (5) |
| N2—H1N | 0.83 (4) | C7—C12 | 1.392 (5) |
| N2—H2N | 0.86 (4) | C8—C9 | 1.386 (6) |
| C1—C7 | 1.508 (5) | C8—H8 | 0.88 (4) |
| C1—H1A | 0.98 (4) | C9—C10 | 1.377 (7) |
| C1—H1B | 0.97 (4) | C9—H9 | 0.96 (4) |
| C2—C3 | 1.384 (5) | C10—C11 | 1.375 (6) |
| C2—H2 | 0.91 (4) | C10—H10 | 0.93 (5) |
| C3—C4 | 1.385 (5) | C11—C12 | 1.393 (5) |
| C3—C13 | 1.508 (5) | C11—H11 | 0.91 (4) |
| C4—C5 | 1.388 (5) | C12—H12 | 1.00 (5) |
| C2—N1—C6 | 121.7 (3) | N1—C6—C5 | 120.2 (3) |
| C2—N1—C1 | 118.6 (3) | N1—C6—H6 | 119 (2) |
| C6—N1—C1 | 119.6 (3) | C5—C6—H6 | 121 (2) |
| C13—N2—H1N | 126 (3) | C8—C7—C12 | 119.5 (3) |
| C13—N2—H2N | 119 (3) | C8—C7—C1 | 120.3 (3) |
| H1N—N2—H2N | 115 (4) | C12—C7—C1 | 120.2 (3) |
| N1—C1—C7 | 112.6 (3) | C9—C8—C7 | 120.1 (4) |
| N1—C1—H1A | 108 (2) | C9—C8—H8 | 120 (3) |
| C7—C1—H1A | 113 (2) | C7—C8—H8 | 120 (3) |
| N1—C1—H1B | 105 (2) | C10—C9—C8 | 120.4 (4) |
| C7—C1—H1B | 113 (2) | C10—C9—H9 | 122 (3) |
| H1A—C1—H1B | 105 (3) | C8—C9—H9 | 118 (3) |
| N1—C2—C3 | 120.3 (3) | C11—C10—C9 | 119.8 (4) |
| N1—C2—H2 | 114 (2) | C11—C10—H10 | 124 (3) |
| C3—C2—H2 | 125 (2) | C9—C10—H10 | 116 (3) |
| C2—C3—C4 | 118.6 (3) | C10—C11—C12 | 120.6 (4) |
| C2—C3—C13 | 122.2 (3) | C10—C11—H11 | 122 (3) |
| C4—C3—C13 | 119.1 (3) | C12—C11—H11 | 118 (3) |
| C3—C4—C5 | 120.1 (3) | C7—C12—C11 | 119.5 (4) |
| C3—C4—H4 | 120 (2) | C7—C12—H12 | 121 (3) |
| C5—C4—H4 | 120 (2) | C11—C12—H12 | 120 (3) |
| C6—C5—C4 | 119.0 (4) | O1—C13—N2 | 123.4 (3) |
| C6—C5—H5 | 123 (2) | O1—C13—C3 | 119.3 (3) |
| C4—C5—H5 | 118 (2) | N2—C13—C3 | 117.3 (3) |
| C2—N1—C1—C7 | 130.0 (3) | N1—C1—C7—C12 | 89.8 (4) |
| C6—N1—C1—C7 | −51.8 (4) | C12—C7—C8—C9 | −0.8 (5) |
| C6—N1—C2—C3 | −1.5 (5) | C1—C7—C8—C9 | 180.0 (3) |
| C1—N1—C2—C3 | 176.7 (3) | C7—C8—C9—C10 | −0.5 (6) |
| N1—C2—C3—C4 | 2.2 (5) | C8—C9—C10—C11 | 0.6 (6) |
| N1—C2—C3—C13 | −179.0 (3) | C9—C10—C11—C12 | 0.7 (6) |
| C2—C3—C4—C5 | −1.3 (5) | C8—C7—C12—C11 | 2.0 (5) |
| C13—C3—C4—C5 | 179.9 (3) | C1—C7—C12—C11 | −178.7 (3) |
| C3—C4—C5—C6 | −0.4 (5) | C10—C11—C12—C7 | −2.0 (6) |
| C2—N1—C6—C5 | −0.2 (5) | C2—C3—C13—O1 | −172.1 (3) |
| C1—N1—C6—C5 | −178.4 (3) | C4—C3—C13—O1 | 6.7 (5) |
| C4—C5—C6—N1 | 1.1 (5) | C2—C3—C13—N2 | 9.9 (5) |
| N1—C1—C7—C8 | −91.0 (4) | C4—C3—C13—N2 | −171.3 (3) |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2···Br1 | 0.91 (4) | 2.59 (4) | 3.503 (4) | 174 (3) |
| N2—H1N···Br1 | 0.83 (4) | 2.58 (4) | 3.414 (4) | 175 (4) |
| C1—H1B···Br1i | 0.97 (4) | 2.81 (4) | 3.653 (4) | 146 (3) |
| N2—H2N···O1ii | 0.86 (4) | 2.12 (5) | 2.972 (4) | 169 (4) |
| C6—H6···Br1iii | 1.03 (4) | 2.69 (5) | 3.489 (4) | 134 (3) |
| Symmetry codes: (i) x, y, z+1; (ii) −x+1, −y, −z; (iii) x−1, y, z+1. |
(rBNA) 1-Benzyl-1,4-dihydropyridine-3-carboxamide top
Crystal data top
| C13H14N2O | F(000) = 456 |
| Mr = 214.26 | Dx = 1.283 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| a = 12.0186 (8) Å | Cell parameters from 9967 reflections |
| b = 5.7435 (4) Å | θ = 2.2–32.9° |
| c = 16.1124 (11) Å | µ = 0.08 mm−1 |
| β = 94.474 (1)° | T = 120 K |
| V = 1108.83 (13) Å3 | Irregular, yellow |
| Z = 4 | 0.58 × 0.25 × 0.15 mm |
Data collection top
| Bruker APEX DUO diffractometer | 3493 reflections with I > 2σ(I) |
| Radiation source: sealed tube | Rint = 0.018 |
| ω scans | θmax = 33.0°, θmin = 2.0° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −17→18 |
| Tmin = 0.649, Tmax = 0.746 | k = −8→8 |
| 18636 measured reflections | l = −24→24 |
| 3990 independent reflections |
Refinement top
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: notdet |
| R[F2 > 2σ(F2)] = 0.044 | Hydrogen site location: difference Fourier map |
| wR(F2) = 0.118 | All H-atom parameters refined |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.0606P)2 + 0.3527P] where P = (Fo2 + 2Fc2)/3 |
| 3990 reflections | (Δ/σ)max = 0.001 |
| 201 parameters | Δρmax = 0.46 e Å−3 |
| 0 restraints | Δρmin = −0.21 e Å−3 |
Special details top
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) top
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.89767 (6) | 0.50377 (12) | 0.57312 (4) | 0.02467 (15) | |
| N1 | 0.64579 (6) | 0.87267 (13) | 0.67126 (4) | 0.01799 (14) | |
| N2 | 0.91027 (7) | 0.75546 (15) | 0.46691 (5) | 0.02322 (16) | |
| C1 | 0.59976 (7) | 0.78251 (16) | 0.74587 (5) | 0.01867 (16) | |
| C2 | 0.72644 (6) | 0.75304 (14) | 0.63397 (5) | 0.01599 (15) | |
| C3 | 0.77070 (6) | 0.82373 (14) | 0.56338 (5) | 0.01580 (15) | |
| C4 | 0.73028 (8) | 1.04139 (16) | 0.51711 (6) | 0.02220 (17) | |
| C5 | 0.64308 (8) | 1.16257 (16) | 0.56385 (6) | 0.02323 (18) | |
| C6 | 0.60583 (7) | 1.08005 (15) | 0.63390 (6) | 0.02056 (16) | |
| C7 | 0.50365 (6) | 0.61407 (14) | 0.72984 (5) | 0.01598 (15) | |
| C8 | 0.48033 (7) | 0.45594 (16) | 0.79211 (5) | 0.01969 (16) | |
| C9 | 0.39102 (8) | 0.30213 (17) | 0.78060 (6) | 0.02391 (18) | |
| C10 | 0.32334 (8) | 0.30488 (17) | 0.70625 (6) | 0.02567 (19) | |
| C11 | 0.34655 (8) | 0.46045 (17) | 0.64384 (6) | 0.02439 (18) | |
| C12 | 0.43627 (7) | 0.61424 (16) | 0.65527 (5) | 0.01973 (16) | |
| C13 | 0.86313 (6) | 0.68262 (15) | 0.53561 (5) | 0.01651 (15) | |
| H1N | 0.9703 (14) | 0.670 (3) | 0.4505 (9) | 0.041 (4)* | |
| H2N | 0.8876 (13) | 0.888 (3) | 0.4416 (9) | 0.038 (4)* | |
| H1A | 0.6600 (12) | 0.703 (2) | 0.7803 (8) | 0.028 (3)* | |
| H1B | 0.5748 (12) | 0.917 (3) | 0.7777 (8) | 0.031 (3)* | |
| H2 | 0.7528 (10) | 0.612 (2) | 0.6625 (8) | 0.021 (3)* | |
| H5 | 0.6140 (13) | 1.311 (3) | 0.5437 (9) | 0.037 (4)* | |
| H4A | 0.7937 (13) | 1.151 (3) | 0.5127 (9) | 0.039 (4)* | |
| H4B | 0.6989 (12) | 1.001 (3) | 0.4589 (9) | 0.032 (4)* | |
| H6 | 0.5501 (12) | 1.163 (2) | 0.6639 (9) | 0.032 (4)* | |
| H8 | 0.5297 (12) | 0.455 (3) | 0.8433 (9) | 0.030 (3)* | |
| H9 | 0.3778 (12) | 0.194 (3) | 0.8240 (9) | 0.034 (4)* | |
| H10 | 0.2612 (12) | 0.191 (3) | 0.6987 (9) | 0.033 (4)* | |
| H11 | 0.2998 (13) | 0.460 (3) | 0.5899 (9) | 0.037 (4)* | |
| H12 | 0.4520 (12) | 0.723 (2) | 0.6110 (8) | 0.029 (3)* |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0264 (3) | 0.0255 (3) | 0.0232 (3) | 0.0096 (3) | 0.0094 (2) | 0.0065 (2) |
| N1 | 0.0172 (3) | 0.0175 (3) | 0.0198 (3) | 0.0023 (2) | 0.0048 (2) | 0.0000 (2) |
| N2 | 0.0225 (3) | 0.0258 (4) | 0.0224 (3) | 0.0047 (3) | 0.0089 (3) | 0.0060 (3) |
| C1 | 0.0170 (3) | 0.0235 (4) | 0.0157 (3) | −0.0008 (3) | 0.0024 (3) | −0.0025 (3) |
| C2 | 0.0144 (3) | 0.0162 (3) | 0.0174 (3) | 0.0008 (2) | 0.0015 (2) | −0.0011 (3) |
| C3 | 0.0158 (3) | 0.0153 (3) | 0.0162 (3) | 0.0001 (3) | 0.0013 (2) | −0.0008 (3) |
| C4 | 0.0279 (4) | 0.0172 (4) | 0.0220 (4) | 0.0037 (3) | 0.0054 (3) | 0.0034 (3) |
| C5 | 0.0289 (4) | 0.0156 (4) | 0.0253 (4) | 0.0058 (3) | 0.0029 (3) | 0.0002 (3) |
| C6 | 0.0217 (4) | 0.0160 (4) | 0.0240 (4) | 0.0037 (3) | 0.0021 (3) | −0.0033 (3) |
| C7 | 0.0149 (3) | 0.0169 (3) | 0.0164 (3) | 0.0033 (2) | 0.0024 (2) | −0.0017 (3) |
| C8 | 0.0189 (3) | 0.0225 (4) | 0.0180 (3) | 0.0044 (3) | 0.0037 (3) | 0.0017 (3) |
| C9 | 0.0237 (4) | 0.0216 (4) | 0.0273 (4) | 0.0010 (3) | 0.0075 (3) | 0.0038 (3) |
| C10 | 0.0226 (4) | 0.0223 (4) | 0.0324 (5) | −0.0038 (3) | 0.0038 (3) | −0.0018 (3) |
| C11 | 0.0223 (4) | 0.0247 (4) | 0.0253 (4) | −0.0030 (3) | −0.0036 (3) | −0.0017 (3) |
| C12 | 0.0205 (3) | 0.0197 (4) | 0.0187 (3) | −0.0002 (3) | −0.0011 (3) | 0.0008 (3) |
| C13 | 0.0157 (3) | 0.0184 (4) | 0.0155 (3) | −0.0006 (3) | 0.0017 (2) | −0.0015 (3) |
Geometric parameters (Å, º) top
| O1—C13 | 1.2464 (10) | C4—H4B | 1.010 (14) |
| N1—C2 | 1.3651 (10) | C5—C6 | 1.3333 (13) |
| N1—C6 | 1.4024 (11) | C5—H5 | 0.967 (16) |
| N1—C1 | 1.4571 (11) | C6—H6 | 0.979 (14) |
| N2—C13 | 1.3487 (11) | C7—C12 | 1.3955 (11) |
| N2—H1N | 0.928 (17) | C7—C8 | 1.3978 (12) |
| N2—H2N | 0.897 (16) | C8—C9 | 1.3913 (13) |
| C1—C7 | 1.5134 (12) | C8—H8 | 0.978 (14) |
| C1—H1A | 0.989 (14) | C9—C10 | 1.3947 (14) |
| C1—H1B | 0.988 (15) | C9—H9 | 0.959 (15) |
| C2—C3 | 1.3550 (11) | C10—C11 | 1.3896 (14) |
| C2—H2 | 0.971 (13) | C10—H10 | 0.994 (15) |
| C3—C13 | 1.4727 (11) | C11—C12 | 1.3950 (12) |
| C3—C4 | 1.5159 (12) | C11—H11 | 0.998 (15) |
| C4—C5 | 1.5076 (13) | C12—H12 | 0.978 (14) |
| C4—H4A | 0.997 (16) | ||
| C2—N1—C6 | 118.01 (7) | C4—C5—H5 | 119.1 (9) |
| C2—N1—C1 | 120.84 (7) | C5—C6—N1 | 122.62 (8) |
| C6—N1—C1 | 121.11 (7) | C5—C6—H6 | 122.3 (8) |
| C13—N2—H1N | 117.0 (10) | N1—C6—H6 | 115.1 (8) |
| C13—N2—H2N | 120.3 (10) | C12—C7—C8 | 118.88 (8) |
| H1N—N2—H2N | 122.4 (14) | C12—C7—C1 | 122.04 (7) |
| N1—C1—C7 | 114.85 (7) | C8—C7—C1 | 119.07 (7) |
| N1—C1—H1A | 108.6 (8) | C9—C8—C7 | 120.84 (8) |
| C7—C1—H1A | 108.5 (8) | C9—C8—H8 | 121.3 (9) |
| N1—C1—H1B | 107.5 (8) | C7—C8—H8 | 117.8 (9) |
| C7—C1—H1B | 109.3 (8) | C8—C9—C10 | 119.97 (8) |
| H1A—C1—H1B | 107.9 (11) | C8—C9—H9 | 119.0 (9) |
| C3—C2—N1 | 123.88 (8) | C10—C9—H9 | 121.0 (9) |
| C3—C2—H2 | 120.8 (7) | C11—C10—C9 | 119.49 (9) |
| N1—C2—H2 | 115.3 (7) | C11—C10—H10 | 121.8 (8) |
| C2—C3—C13 | 116.42 (7) | C9—C10—H10 | 118.7 (8) |
| C2—C3—C4 | 121.88 (7) | C10—C11—C12 | 120.55 (8) |
| C13—C3—C4 | 121.66 (7) | C10—C11—H11 | 119.8 (9) |
| C5—C4—C3 | 110.10 (7) | C12—C11—H11 | 119.6 (9) |
| C5—C4—H4A | 108.0 (9) | C11—C12—C7 | 120.26 (8) |
| C3—C4—H4A | 109.9 (9) | C11—C12—H12 | 120.0 (8) |
| C5—C4—H4B | 110.2 (8) | C7—C12—H12 | 119.8 (8) |
| C3—C4—H4B | 110.5 (9) | O1—C13—N2 | 120.55 (8) |
| H4A—C4—H4B | 108.2 (12) | O1—C13—C3 | 122.47 (7) |
| C6—C5—C4 | 123.44 (8) | N2—C13—C3 | 116.98 (7) |
| C6—C5—H5 | 117.5 (9) | ||
| C2—N1—C1—C7 | −86.06 (9) | N1—C1—C7—C8 | 156.84 (7) |
| C6—N1—C1—C7 | 91.57 (9) | C12—C7—C8—C9 | −0.52 (12) |
| C6—N1—C2—C3 | 0.50 (12) | C1—C7—C8—C9 | 178.40 (8) |
| C1—N1—C2—C3 | 178.21 (7) | C7—C8—C9—C10 | −0.13 (13) |
| N1—C2—C3—C13 | 175.34 (7) | C8—C9—C10—C11 | 0.60 (14) |
| N1—C2—C3—C4 | −2.46 (13) | C9—C10—C11—C12 | −0.43 (15) |
| C2—C3—C4—C5 | 3.16 (12) | C10—C11—C12—C7 | −0.23 (14) |
| C13—C3—C4—C5 | −174.52 (8) | C8—C7—C12—C11 | 0.70 (12) |
| C3—C4—C5—C6 | −2.39 (13) | C1—C7—C12—C11 | −178.20 (8) |
| C4—C5—C6—N1 | 0.80 (15) | C2—C3—C13—O1 | 1.90 (12) |
| C2—N1—C6—C5 | 0.36 (13) | C4—C3—C13—O1 | 179.70 (8) |
| C1—N1—C6—C5 | −177.34 (8) | C2—C3—C13—N2 | −177.93 (8) |
| N1—C1—C7—C12 | −24.27 (11) | C4—C3—C13—N2 | −0.13 (12) |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H1N···O1i | 0.928 (17) | 1.937 (17) | 2.8625 (10) | 174.6 (14) |
| C1—H1B···O1ii | 0.988 (15) | 2.451 (14) | 3.1792 (10) | 130.2 (11) |
| Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+3/2, y+1/2, −z+3/2. |
