Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109018964/sk3324sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109018964/sk3324Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109018964/sk3324IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109018964/sk3324IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109018964/sk3324IVsup5.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109018964/sk3324Vsup6.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109018964/sk3324VIsup7.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109018964/sk3324VIIsup8.hkl |
CCDC references: 742188; 742189; 742190; 742191; 742192; 742193; 742194
To a solution of the appropriate (E)-5-arylidenamino-3-tert-butyl-1-phenyl-1H-pyrazole (100 mg) in methanol (3–4 ml) solid sodium borohydride (2.5 mmol) was added portionwise with stirring during 5 min, and after 1 h at ambient temperature, the volume of the reaction mixture was reduced under reduced pressure to 1 ml, followed by the addition of 5 ml of water. The aqueous solution was extracted with ethyl acetate (2 × 5 ml), and the combined organic extracts were dried over anhydrous sodium sulfate; after removal of the solvent the resulting products were crystallized from ethanol, except for (I) which was crystallized from hexane. (I): colourless, 91% yield, m.p. 351 K; MS (70 eV) m/z (%): 305 (100) [M+], 290 (59) [M-15], 263 (69) [M-42], 91 (34), 77 (13) [Ph]; analysis found: C 78.5, H 7.8, N 13.7%; C20H23N3 requires C 78.7, H 7.6, N 13.8%. (II): colourless, 85% yield, m.p. 372–373 K; MS (70 eV) m/z (%): 319 (76) [M+], 304 (18) [M-15], 277 (30) [M-42], 105 (100) [C8H9], 77 (8) [Ph]; analysis found: C 78.7, H 8.1, N 12.9%; C21H25N3 requires C 79.0, H 7.9, N 13.2%. (III): yellow, 77% yield, m.p. 370–371 K; MS 70 (eV) m/z (%): 373 (100) [M+], 358 (84) [M-15], 331 (98) [M-42], 214 (19), 159 (38) [C8H6F3], 77 (10); analysis found: C 67.4, H 5.9, N 11.2%; C21H22F3N3 requires C 67.6, H 5.9, N 11.3%. (IV) colourless, 89% yield, m.p. 386–388 K; MS (70 eV) m/z (%): 341/339 (28/84) [M+], 326/324 (13/35) [M-15], 299/297 (20/58) [M-42], 214 (37), 158 (38), 127/125 (29/100) [C7H6Cl], 77 (63) [Ph]; analysis found: C 70.5, H 6.7, N 12.3%; C20H22ClN3 requires C 70.7, H 6.5, N 12.4%. (V): yellow, 83% yield, m.p. 365–366 K; MS (70 eV) m/z (%): 385/383 (96/100) [M+], 370/368 (45/44) [M-15], 343/341 (70/73) [M-42], 214 (70), 171/169 (72/67) [C7H6Br]; analysis found: C 62.3, H 5.9, N 11.0%; C20H22BrN3 requires C 62.5, H 5.8, N 10.9%. (VI): yellow, 84% yield, m.p. 375–377 K; MS (70 eV) m/z (%): 350 (95) [M+], 335 (85) [M-15], 308 (100) [M-42], 214 (15), 158 (15); analysis found: C 68.2, H 6.3, N 16.0%; C20H22N4O2 requires C 68.6, H 6.3, N 16.0%. (VII): colourless, 83% yield, m.p. 392–394 K; MS 70 (eV) m/z (%): 395 (8) [M+], 181 (100) [C10H13O3]; analysis found: C 69.9, H 7.3, N 10.7%; C23H29N3O3 requires C 69.9, H 7.4, N 10.6%.
All H atoms were located in difference maps and then treated as riding atoms with distances C—H = 0.95 (aromatic and pyrazole), 0.98 (CH3) or 0.99Å (CH2) and N—H = 0.88Å, with Uiso(H) = kUeq(carrier), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and k = 1.2 for all other H atoms. For the compounds which crystallize in centrosymmetric space groups, the reference molecules were all selected to have the same orientation of the 1-phenyl group, as defined by the sign of the torsion angle N2—N1—C11—C12. In the absence of significant resonant scattering, it was not possible, for compound (II), to distinguish between the possible enantiomeric space groups P41212 and P43212; for consistency of configuration, P43212 was selected and the Friedel-equivalent reflections were merged prior to the final refinements. In compound (VI), the largest maxima in the final difference maps, with heights 0.65, 0.62 and 0.40 e Å-3 were located, respectively, 1.37Å from C33, 1.07Å from C34 and 1.12Å from C32, consistent with some librational motion of this group about the C3—C31 bond.
For all compounds, data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
C20H23N3 | F(000) = 1312 |
Mr = 305.41 | Dx = 1.219 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 3813 reflections |
a = 20.038 (4) Å | θ = 3.0–27.5° |
b = 7.3732 (12) Å | µ = 0.07 mm−1 |
c = 23.444 (3) Å | T = 120 K |
β = 106.007 (13)° | Block, colourless |
V = 3329.4 (10) Å3 | 0.31 × 0.26 × 0.21 mm |
Z = 8 |
Bruker–Nonius KappaCCD diffractometer | 3813 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 2464 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.075 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ and ω scans | h = −25→26 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −9→8 |
Tmin = 0.967, Tmax = 0.985 | l = −30→30 |
30597 measured reflections |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0479P)2 + 3.306P] where P = (Fo2 + 2Fc2)/3 |
3813 reflections | (Δ/σ)max = 0.001 |
211 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C20H23N3 | V = 3329.4 (10) Å3 |
Mr = 305.41 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.038 (4) Å | µ = 0.07 mm−1 |
b = 7.3732 (12) Å | T = 120 K |
c = 23.444 (3) Å | 0.31 × 0.26 × 0.21 mm |
β = 106.007 (13)° |
Bruker–Nonius KappaCCD diffractometer | 3813 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2464 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 0.985 | Rint = 0.075 |
30597 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.21 e Å−3 |
3813 reflections | Δρmin = −0.36 e Å−3 |
211 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.80088 (7) | 0.5329 (2) | 0.26985 (6) | 0.0230 (3) | |
N2 | 0.84668 (7) | 0.5054 (2) | 0.32481 (6) | 0.0241 (3) | |
C3 | 0.80690 (9) | 0.4923 (2) | 0.36096 (7) | 0.0233 (4) | |
C4 | 0.73622 (9) | 0.5123 (2) | 0.33111 (8) | 0.0252 (4) | |
H4 | 0.6980 | 0.5071 | 0.3477 | 0.030* | |
C5 | 0.73429 (9) | 0.5410 (2) | 0.27302 (7) | 0.0225 (4) | |
C11 | 0.82814 (9) | 0.5552 (2) | 0.22082 (7) | 0.0223 (4) | |
C12 | 0.79363 (9) | 0.4875 (2) | 0.16575 (7) | 0.0234 (4) | |
H12 | 0.7509 | 0.4249 | 0.1602 | 0.028* | |
C13 | 0.82168 (10) | 0.5117 (2) | 0.11892 (8) | 0.0271 (4) | |
H13 | 0.7977 | 0.4666 | 0.0808 | 0.033* | |
C14 | 0.88396 (10) | 0.6003 (3) | 0.12662 (8) | 0.0292 (4) | |
H14 | 0.9029 | 0.6167 | 0.0940 | 0.035* | |
C15 | 0.91864 (10) | 0.6648 (3) | 0.18190 (8) | 0.0306 (4) | |
H15 | 0.9618 | 0.7253 | 0.1875 | 0.037* | |
C16 | 0.89114 (9) | 0.6424 (3) | 0.22916 (8) | 0.0277 (4) | |
H16 | 0.9154 | 0.6867 | 0.2673 | 0.033* | |
C31 | 0.83925 (9) | 0.4710 (2) | 0.42670 (7) | 0.0251 (4) | |
C32 | 0.91643 (10) | 0.4319 (3) | 0.44016 (8) | 0.0335 (5) | |
H32A | 0.9233 | 0.3150 | 0.4227 | 0.050* | |
H32B | 0.9369 | 0.4274 | 0.4832 | 0.050* | |
H32C | 0.9389 | 0.5280 | 0.4232 | 0.050* | |
C33 | 0.82778 (11) | 0.6468 (3) | 0.45687 (8) | 0.0349 (5) | |
H33A | 0.8476 | 0.7483 | 0.4400 | 0.052* | |
H33B | 0.8505 | 0.6384 | 0.4995 | 0.052* | |
H33C | 0.7779 | 0.6666 | 0.4504 | 0.052* | |
C34 | 0.80419 (11) | 0.3155 (3) | 0.45023 (9) | 0.0394 (5) | |
H34A | 0.7543 | 0.3398 | 0.4417 | 0.059* | |
H34B | 0.8243 | 0.3046 | 0.4932 | 0.059* | |
H34C | 0.8114 | 0.2021 | 0.4310 | 0.059* | |
N51 | 0.67992 (7) | 0.5687 (2) | 0.22328 (6) | 0.0246 (4) | |
H51 | 0.6899 | 0.6431 | 0.1975 | 0.029* | |
C51 | 0.55559 (9) | 0.5726 (2) | 0.17444 (7) | 0.0227 (4) | |
C52 | 0.49507 (9) | 0.6717 (3) | 0.16277 (8) | 0.0279 (4) | |
H52 | 0.4897 | 0.7611 | 0.1904 | 0.034* | |
C53 | 0.44235 (10) | 0.6436 (3) | 0.11191 (9) | 0.0340 (5) | |
H53 | 0.4005 | 0.7111 | 0.1051 | 0.041* | |
C54 | 0.44987 (10) | 0.5183 (3) | 0.07089 (8) | 0.0318 (5) | |
H54 | 0.4136 | 0.4999 | 0.0355 | 0.038* | |
C55 | 0.51016 (10) | 0.4197 (3) | 0.08137 (8) | 0.0298 (4) | |
H55 | 0.5159 | 0.3343 | 0.0528 | 0.036* | |
C56 | 0.56229 (9) | 0.4441 (2) | 0.13307 (8) | 0.0261 (4) | |
H56 | 0.6032 | 0.3724 | 0.1405 | 0.031* | |
C57 | 0.61154 (9) | 0.6008 (3) | 0.23129 (8) | 0.0253 (4) | |
H571 | 0.6090 | 0.7265 | 0.2454 | 0.030* | |
H572 | 0.6039 | 0.5172 | 0.2619 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0215 (8) | 0.0296 (8) | 0.0167 (7) | 0.0000 (6) | 0.0032 (6) | 0.0011 (6) |
N2 | 0.0247 (8) | 0.0283 (8) | 0.0167 (7) | −0.0008 (7) | 0.0013 (6) | 0.0002 (6) |
C3 | 0.0261 (9) | 0.0221 (9) | 0.0207 (9) | −0.0029 (8) | 0.0050 (7) | −0.0008 (7) |
C4 | 0.0253 (10) | 0.0275 (10) | 0.0228 (9) | −0.0043 (8) | 0.0069 (7) | −0.0003 (7) |
C5 | 0.0237 (9) | 0.0203 (9) | 0.0227 (9) | −0.0009 (7) | 0.0047 (7) | −0.0016 (7) |
C11 | 0.0231 (9) | 0.0235 (9) | 0.0203 (8) | 0.0039 (7) | 0.0060 (7) | 0.0036 (7) |
C12 | 0.0228 (9) | 0.0241 (9) | 0.0227 (9) | 0.0008 (8) | 0.0053 (7) | 0.0005 (7) |
C13 | 0.0296 (10) | 0.0306 (10) | 0.0199 (9) | 0.0047 (8) | 0.0051 (7) | −0.0010 (7) |
C14 | 0.0298 (10) | 0.0358 (11) | 0.0245 (9) | 0.0041 (9) | 0.0119 (8) | 0.0032 (8) |
C15 | 0.0247 (10) | 0.0344 (11) | 0.0322 (10) | −0.0023 (8) | 0.0070 (8) | 0.0022 (8) |
C16 | 0.0258 (10) | 0.0319 (10) | 0.0235 (9) | −0.0007 (8) | 0.0037 (8) | 0.0002 (8) |
C31 | 0.0273 (10) | 0.0281 (10) | 0.0178 (8) | −0.0052 (8) | 0.0029 (7) | 0.0008 (7) |
C32 | 0.0334 (11) | 0.0392 (12) | 0.0240 (10) | −0.0012 (9) | 0.0014 (8) | 0.0011 (8) |
C33 | 0.0435 (12) | 0.0370 (12) | 0.0233 (10) | −0.0016 (9) | 0.0076 (9) | −0.0034 (8) |
C34 | 0.0456 (12) | 0.0427 (13) | 0.0247 (10) | −0.0158 (10) | 0.0008 (9) | 0.0055 (9) |
N51 | 0.0204 (8) | 0.0326 (9) | 0.0201 (7) | 0.0003 (7) | 0.0047 (6) | 0.0040 (6) |
C51 | 0.0224 (9) | 0.0243 (9) | 0.0219 (9) | −0.0005 (8) | 0.0068 (7) | 0.0043 (7) |
C52 | 0.0280 (10) | 0.0294 (10) | 0.0277 (10) | 0.0042 (8) | 0.0099 (8) | −0.0004 (8) |
C53 | 0.0261 (10) | 0.0369 (12) | 0.0371 (11) | 0.0069 (9) | 0.0056 (9) | 0.0045 (9) |
C54 | 0.0265 (10) | 0.0362 (11) | 0.0276 (10) | −0.0014 (9) | −0.0012 (8) | 0.0014 (8) |
C55 | 0.0334 (11) | 0.0273 (10) | 0.0265 (10) | 0.0000 (9) | 0.0046 (8) | −0.0031 (8) |
C56 | 0.0248 (9) | 0.0279 (10) | 0.0247 (9) | 0.0012 (8) | 0.0056 (8) | 0.0008 (8) |
C57 | 0.0241 (9) | 0.0296 (10) | 0.0231 (9) | −0.0005 (8) | 0.0081 (7) | −0.0023 (7) |
N1—C5 | 1.358 (2) | C32—H32B | 0.9800 |
N1—N2 | 1.3752 (19) | C32—H32C | 0.9800 |
N1—C11 | 1.412 (2) | C33—H33A | 0.9800 |
N2—C3 | 1.318 (2) | C33—H33B | 0.9800 |
C3—C4 | 1.404 (2) | C33—H33C | 0.9800 |
C3—C31 | 1.506 (2) | C34—H34A | 0.9800 |
C4—C5 | 1.368 (2) | C34—H34B | 0.9800 |
C4—H4 | 0.9500 | C34—H34C | 0.9800 |
C5—N51 | 1.374 (2) | N51—C57 | 1.453 (2) |
C11—C12 | 1.379 (2) | N51—H51 | 0.8799 |
C11—C16 | 1.382 (2) | C57—C51 | 1.501 (2) |
C12—C13 | 1.376 (2) | C57—H571 | 0.9900 |
C12—H12 | 0.9500 | C57—H572 | 0.9900 |
C13—C14 | 1.376 (3) | C51—C52 | 1.377 (2) |
C13—H13 | 0.9500 | C51—C56 | 1.388 (3) |
C14—C15 | 1.376 (3) | C52—C53 | 1.373 (3) |
C14—H14 | 0.9500 | C52—H52 | 0.9500 |
C15—C16 | 1.377 (3) | C53—C54 | 1.371 (3) |
C15—H15 | 0.9500 | C53—H53 | 0.9500 |
C16—H16 | 0.9500 | C54—C55 | 1.373 (3) |
C31—C32 | 1.518 (3) | C54—H54 | 0.9500 |
C31—C33 | 1.524 (3) | C55—C56 | 1.376 (2) |
C31—C34 | 1.525 (3) | C55—H55 | 0.9500 |
C32—H32A | 0.9800 | C56—H56 | 0.9500 |
C5—N1—N2 | 111.53 (13) | H32A—C32—H32C | 109.5 |
C5—N1—C11 | 130.25 (14) | H32B—C32—H32C | 109.5 |
N2—N1—C11 | 118.16 (14) | C31—C33—H33A | 109.5 |
C3—N2—N1 | 104.34 (14) | C31—C33—H33B | 109.5 |
N2—C3—C4 | 112.19 (15) | H33A—C33—H33B | 109.5 |
N2—C3—C31 | 119.99 (16) | C31—C33—H33C | 109.5 |
C4—C3—C31 | 127.69 (16) | H33A—C33—H33C | 109.5 |
C5—C4—C3 | 105.09 (16) | H33B—C33—H33C | 109.5 |
C5—C4—H4 | 127.5 | C31—C34—H34A | 109.5 |
C3—C4—H4 | 127.5 | C31—C34—H34B | 109.5 |
N1—C5—C4 | 106.81 (15) | H34A—C34—H34B | 109.5 |
N1—C5—N51 | 121.40 (15) | C31—C34—H34C | 109.5 |
C4—C5—N51 | 131.77 (17) | H34A—C34—H34C | 109.5 |
C12—C11—C16 | 120.23 (16) | H34B—C34—H34C | 109.5 |
C12—C11—N1 | 120.89 (16) | C5—N51—C57 | 118.02 (14) |
C16—C11—N1 | 118.86 (16) | C5—N51—H51 | 113.5 |
C13—C12—C11 | 119.37 (17) | C57—N51—H51 | 112.9 |
C13—C12—H12 | 120.3 | N51—C57—C51 | 111.28 (14) |
C11—C12—H12 | 120.3 | N51—C57—H571 | 109.4 |
C14—C13—C12 | 120.81 (17) | C51—C57—H571 | 109.4 |
C14—C13—H13 | 119.6 | N51—C57—H572 | 109.4 |
C12—C13—H13 | 119.6 | C51—C57—H572 | 109.4 |
C13—C14—C15 | 119.49 (17) | H571—C57—H572 | 108.0 |
C13—C14—H14 | 120.3 | C52—C51—C56 | 118.22 (16) |
C15—C14—H14 | 120.3 | C52—C51—C57 | 120.26 (16) |
C14—C15—C16 | 120.41 (18) | C56—C51—C57 | 121.50 (16) |
C14—C15—H15 | 119.8 | C53—C52—C51 | 121.10 (18) |
C16—C15—H15 | 119.8 | C53—C52—H52 | 119.5 |
C15—C16—C11 | 119.67 (17) | C51—C52—H52 | 119.5 |
C15—C16—H16 | 120.2 | C54—C53—C52 | 120.25 (18) |
C11—C16—H16 | 120.2 | C54—C53—H53 | 119.9 |
C3—C31—C32 | 111.01 (15) | C52—C53—H53 | 119.9 |
C3—C31—C33 | 107.99 (15) | C53—C54—C55 | 119.51 (18) |
C32—C31—C33 | 109.91 (16) | C53—C54—H54 | 120.2 |
C3—C31—C34 | 109.70 (15) | C55—C54—H54 | 120.2 |
C32—C31—C34 | 109.05 (16) | C54—C55—C56 | 120.34 (18) |
C33—C31—C34 | 109.15 (16) | C54—C55—H55 | 119.8 |
C31—C32—H32A | 109.5 | C56—C55—H55 | 119.8 |
C31—C32—H32B | 109.5 | C55—C56—C51 | 120.55 (17) |
H32A—C32—H32B | 109.5 | C55—C56—H56 | 119.7 |
C31—C32—H32C | 109.5 | C51—C56—H56 | 119.7 |
C5—N1—N2—C3 | 1.60 (19) | C12—C11—C16—C15 | 1.4 (3) |
C11—N1—N2—C3 | 179.13 (15) | N1—C11—C16—C15 | 179.77 (17) |
N1—N2—C3—C4 | −0.62 (19) | N2—C3—C31—C32 | −10.9 (2) |
N1—N2—C3—C31 | −176.80 (15) | C4—C3—C31—C32 | 173.57 (18) |
N2—C3—C4—C5 | −0.5 (2) | N2—C3—C31—C33 | 109.65 (19) |
C31—C3—C4—C5 | 175.30 (17) | C4—C3—C31—C33 | −65.9 (2) |
N2—N1—C5—C4 | −2.0 (2) | N2—C3—C31—C34 | −131.50 (18) |
C11—N1—C5—C4 | −179.10 (17) | C4—C3—C31—C34 | 53.0 (2) |
N2—N1—C5—N51 | 179.60 (15) | N1—C5—N51—C57 | −171.61 (16) |
C11—N1—C5—N51 | 2.5 (3) | C4—C5—N51—C57 | 10.4 (3) |
C3—C4—C5—N1 | 1.46 (19) | C5—N51—C57—C51 | −162.80 (15) |
C3—C4—C5—N51 | 179.68 (18) | N51—C57—C51—C52 | −148.74 (17) |
C5—N1—C11—C12 | −38.7 (3) | N51—C57—C51—C56 | 32.9 (2) |
N2—N1—C11—C12 | 144.31 (16) | C56—C51—C52—C53 | 0.6 (3) |
C5—N1—C11—C16 | 142.90 (19) | C57—C51—C52—C53 | −177.82 (17) |
N2—N1—C11—C16 | −34.1 (2) | C51—C52—C53—C54 | −1.6 (3) |
C16—C11—C12—C13 | −1.6 (3) | C52—C53—C54—C55 | 0.8 (3) |
N1—C11—C12—C13 | −179.98 (16) | C53—C54—C55—C56 | 1.1 (3) |
C11—C12—C13—C14 | 0.8 (3) | C54—C55—C56—C51 | −2.1 (3) |
C12—C13—C14—C15 | 0.2 (3) | C52—C51—C56—C55 | 1.2 (3) |
C13—C14—C15—C16 | −0.5 (3) | C57—C51—C56—C55 | 179.63 (17) |
C14—C15—C16—C11 | −0.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···N51 | 0.95 | 2.55 | 3.011 (2) | 110 |
N51—H51···Cg1i | 0.88 | 2.82 | 3.523 (2) | 138 |
Symmetry code: (i) −x+3/2, y+1/2, −z+1/2. |
C21H25N3 | Dx = 1.184 Mg m−3 |
Mr = 319.44 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P43212 | Cell parameters from 2412 reflections |
Hall symbol: P 4nw 2abw | θ = 3.0–27.5° |
a = 10.7749 (13) Å | µ = 0.07 mm−1 |
c = 30.868 (3) Å | T = 120 K |
V = 3583.6 (7) Å3 | Block, colourless |
Z = 8 | 0.37 × 0.27 × 0.24 mm |
F(000) = 1376 |
Bruker–Nonius KappaCCD diffractometer | 2412 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 1598 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.075 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ and ω scans | h = −13→13 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→12 |
Tmin = 0.949, Tmax = 0.983 | l = −27→40 |
22266 measured reflections |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0473P)2 + 0.8586P] where P = (Fo2 + 2Fc2)/3 |
2412 reflections | (Δ/σ)max = 0.001 |
221 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C21H25N3 | Z = 8 |
Mr = 319.44 | Mo Kα radiation |
Tetragonal, P43212 | µ = 0.07 mm−1 |
a = 10.7749 (13) Å | T = 120 K |
c = 30.868 (3) Å | 0.37 × 0.27 × 0.24 mm |
V = 3583.6 (7) Å3 |
Bruker–Nonius KappaCCD diffractometer | 2412 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1598 reflections with I > 2σ(I) |
Tmin = 0.949, Tmax = 0.983 | Rint = 0.075 |
22266 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.20 e Å−3 |
2412 reflections | Δρmin = −0.30 e Å−3 |
221 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.6755 (2) | 0.1622 (2) | 0.46533 (7) | 0.0207 (6) | |
N2 | 0.7693 (2) | 0.0822 (2) | 0.45423 (7) | 0.0206 (6) | |
C3 | 0.7206 (3) | 0.0090 (3) | 0.42443 (8) | 0.0202 (7) | |
C4 | 0.5959 (3) | 0.0387 (3) | 0.41657 (9) | 0.0221 (7) | |
H4 | 0.5414 | −0.0005 | 0.3966 | 0.026* | |
C5 | 0.5690 (3) | 0.1356 (3) | 0.44345 (8) | 0.0190 (6) | |
C11 | 0.6954 (3) | 0.2449 (3) | 0.50004 (8) | 0.0197 (7) | |
C12 | 0.6366 (3) | 0.3584 (3) | 0.50237 (9) | 0.0234 (7) | |
H12 | 0.5832 | 0.3848 | 0.4797 | 0.028* | |
C13 | 0.6562 (3) | 0.4331 (3) | 0.53798 (9) | 0.0291 (8) | |
H13 | 0.6145 | 0.5106 | 0.5400 | 0.035* | |
C14 | 0.7349 (3) | 0.3968 (3) | 0.57046 (9) | 0.0300 (8) | |
H14 | 0.7471 | 0.4485 | 0.5950 | 0.036* | |
C15 | 0.7958 (3) | 0.2859 (3) | 0.56735 (9) | 0.0293 (8) | |
H15 | 0.8514 | 0.2613 | 0.5897 | 0.035* | |
C16 | 0.7774 (3) | 0.2094 (3) | 0.53224 (8) | 0.0256 (7) | |
H16 | 0.8207 | 0.1328 | 0.5301 | 0.031* | |
C31 | 0.8006 (3) | −0.0872 (3) | 0.40309 (8) | 0.0218 (7) | |
C32 | 0.7220 (3) | −0.1920 (3) | 0.38577 (11) | 0.0366 (9) | |
H32A | 0.6773 | −0.2315 | 0.4097 | 0.055* | |
H32B | 0.7754 | −0.2533 | 0.3716 | 0.055* | |
H32C | 0.6622 | −0.1591 | 0.3648 | 0.055* | |
C33 | 0.8954 (4) | −0.1373 (4) | 0.43462 (10) | 0.0441 (10) | |
H33A | 0.9448 | −0.0685 | 0.4463 | 0.066* | |
H33B | 0.9502 | −0.1959 | 0.4197 | 0.066* | |
H33C | 0.8528 | −0.1798 | 0.4584 | 0.066* | |
C34 | 0.8705 (3) | −0.0266 (3) | 0.36534 (10) | 0.0383 (9) | |
H34A | 0.8107 | 0.0076 | 0.3446 | 0.057* | |
H34B | 0.9222 | −0.0890 | 0.3509 | 0.057* | |
H34C | 0.9234 | 0.0403 | 0.3764 | 0.057* | |
N51 | 0.4617 (2) | 0.2027 (2) | 0.44928 (7) | 0.0221 (6) | |
H51 | 0.4505 | 0.2182 | 0.4770 | 0.027* | |
C51 | 0.2467 (3) | 0.2452 (3) | 0.43416 (9) | 0.0228 (7) | |
C52 | 0.1322 (3) | 0.2013 (3) | 0.44692 (9) | 0.0281 (8) | |
H52 | 0.1201 | 0.1146 | 0.4505 | 0.034* | |
C53 | 0.0347 (3) | 0.2821 (3) | 0.45460 (9) | 0.0292 (8) | |
H53 | −0.0434 | 0.2500 | 0.4634 | 0.035* | |
C54 | 0.0491 (3) | 0.4084 (3) | 0.44962 (9) | 0.0255 (8) | |
C55 | 0.1625 (3) | 0.4516 (3) | 0.43583 (8) | 0.0246 (7) | |
H55 | 0.1738 | 0.5381 | 0.4314 | 0.030* | |
C56 | 0.2606 (3) | 0.3714 (3) | 0.42826 (9) | 0.0257 (8) | |
H56 | 0.3382 | 0.4036 | 0.4189 | 0.031* | |
C57 | 0.3535 (3) | 0.1596 (3) | 0.42651 (10) | 0.0286 (8) | |
H571 | 0.3318 | 0.0752 | 0.4366 | 0.034* | |
H572 | 0.3716 | 0.1553 | 0.3951 | 0.034* | |
C58 | −0.0538 (3) | 0.4969 (4) | 0.46037 (11) | 0.0385 (9) | |
H58A | −0.0282 | 0.5503 | 0.4845 | 0.058* | |
H58B | −0.1280 | 0.4500 | 0.4687 | 0.058* | |
H58C | −0.0723 | 0.5483 | 0.4350 | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0201 (15) | 0.0219 (14) | 0.0200 (11) | 0.0023 (12) | −0.0001 (11) | −0.0044 (11) |
N2 | 0.0201 (14) | 0.0200 (14) | 0.0218 (11) | 0.0045 (12) | 0.0013 (11) | −0.0034 (11) |
C3 | 0.0248 (18) | 0.0164 (16) | 0.0193 (12) | 0.0008 (14) | −0.0010 (13) | 0.0012 (12) |
C4 | 0.0222 (17) | 0.0239 (18) | 0.0201 (13) | −0.0012 (15) | −0.0010 (13) | 0.0017 (14) |
C5 | 0.0192 (17) | 0.0184 (17) | 0.0193 (12) | 0.0012 (14) | −0.0004 (13) | 0.0016 (13) |
C11 | 0.0211 (16) | 0.0203 (16) | 0.0177 (12) | −0.0019 (14) | 0.0025 (13) | −0.0019 (13) |
C12 | 0.0215 (18) | 0.0265 (19) | 0.0223 (14) | 0.0005 (14) | 0.0008 (14) | −0.0009 (14) |
C13 | 0.0313 (19) | 0.0220 (18) | 0.0339 (16) | −0.0005 (16) | 0.0039 (16) | −0.0082 (15) |
C14 | 0.030 (2) | 0.034 (2) | 0.0264 (14) | −0.0061 (17) | 0.0012 (15) | −0.0131 (16) |
C15 | 0.0271 (19) | 0.041 (2) | 0.0197 (13) | −0.0043 (17) | −0.0018 (14) | −0.0034 (15) |
C16 | 0.0217 (18) | 0.0305 (19) | 0.0245 (14) | 0.0037 (15) | 0.0030 (14) | 0.0002 (15) |
C31 | 0.0228 (18) | 0.0177 (17) | 0.0247 (13) | 0.0031 (15) | 0.0009 (13) | 0.0006 (13) |
C32 | 0.032 (2) | 0.028 (2) | 0.0492 (19) | −0.0014 (17) | 0.0068 (17) | −0.0153 (17) |
C33 | 0.050 (2) | 0.046 (2) | 0.0363 (18) | 0.027 (2) | −0.0096 (18) | −0.0141 (18) |
C34 | 0.038 (2) | 0.036 (2) | 0.0410 (18) | 0.0035 (18) | 0.0176 (18) | −0.0029 (17) |
N51 | 0.0196 (14) | 0.0258 (15) | 0.0208 (11) | 0.0022 (12) | 0.0003 (11) | −0.0052 (11) |
C51 | 0.0196 (17) | 0.0254 (18) | 0.0234 (13) | 0.0007 (14) | −0.0035 (13) | −0.0023 (14) |
C52 | 0.028 (2) | 0.0236 (19) | 0.0330 (16) | −0.0048 (16) | −0.0043 (15) | 0.0029 (15) |
C53 | 0.0192 (18) | 0.038 (2) | 0.0302 (15) | −0.0023 (17) | 0.0010 (14) | 0.0012 (16) |
C54 | 0.0202 (18) | 0.037 (2) | 0.0192 (13) | 0.0052 (16) | −0.0027 (13) | −0.0060 (15) |
C55 | 0.0270 (19) | 0.0241 (18) | 0.0227 (13) | 0.0001 (16) | −0.0031 (14) | −0.0049 (14) |
C56 | 0.0233 (18) | 0.034 (2) | 0.0201 (13) | −0.0031 (16) | −0.0007 (14) | −0.0065 (14) |
C57 | 0.0249 (18) | 0.0279 (19) | 0.0330 (16) | 0.0030 (16) | −0.0061 (15) | −0.0092 (16) |
C58 | 0.024 (2) | 0.053 (2) | 0.0382 (18) | 0.0081 (18) | −0.0015 (16) | −0.0089 (18) |
N1—C5 | 1.362 (4) | C33—H33A | 0.9800 |
N1—N2 | 1.371 (3) | C33—H33B | 0.9800 |
N1—C11 | 1.410 (3) | C33—H33C | 0.9800 |
N2—C3 | 1.320 (3) | C34—H34A | 0.9800 |
C3—C4 | 1.402 (4) | C34—H34B | 0.9800 |
C3—C31 | 1.501 (4) | C34—H34C | 0.9800 |
C4—C5 | 1.365 (4) | N51—C57 | 1.438 (4) |
C4—H4 | 0.9500 | N51—H51 | 0.8800 |
C5—N51 | 1.376 (4) | C57—C51 | 1.493 (4) |
C11—C12 | 1.379 (4) | C57—H571 | 0.9900 |
C11—C16 | 1.384 (4) | C57—H572 | 0.9900 |
C12—C13 | 1.378 (4) | C51—C52 | 1.379 (4) |
C12—H12 | 0.9500 | C51—C56 | 1.380 (4) |
C13—C14 | 1.370 (4) | C52—C53 | 1.385 (5) |
C13—H13 | 0.9500 | C52—H52 | 0.9500 |
C14—C15 | 1.367 (5) | C53—C54 | 1.378 (4) |
C14—H14 | 0.9500 | C53—H53 | 0.9500 |
C15—C16 | 1.376 (4) | C54—C55 | 1.375 (4) |
C15—H15 | 0.9500 | C54—C58 | 1.500 (4) |
C16—H16 | 0.9500 | C55—C56 | 1.385 (4) |
C31—C32 | 1.509 (4) | C55—H55 | 0.9500 |
C31—C33 | 1.510 (4) | C56—H56 | 0.9500 |
C31—C34 | 1.534 (4) | C58—H58A | 0.9800 |
C32—H32A | 0.9800 | C58—H58B | 0.9800 |
C32—H32B | 0.9800 | C58—H58C | 0.9800 |
C32—H32C | 0.9800 | ||
C5—N1—N2 | 111.4 (2) | C31—C33—H33B | 109.5 |
C5—N1—C11 | 129.6 (2) | H33A—C33—H33B | 109.5 |
N2—N1—C11 | 118.3 (2) | C31—C33—H33C | 109.5 |
C3—N2—N1 | 104.9 (2) | H33A—C33—H33C | 109.5 |
N2—C3—C4 | 111.4 (3) | H33B—C33—H33C | 109.5 |
N2—C3—C31 | 119.4 (3) | C31—C34—H34A | 109.5 |
C4—C3—C31 | 129.2 (3) | C31—C34—H34B | 109.5 |
C5—C4—C3 | 105.8 (3) | H34A—C34—H34B | 109.5 |
C5—C4—H4 | 127.1 | C31—C34—H34C | 109.5 |
C3—C4—H4 | 127.1 | H34A—C34—H34C | 109.5 |
N1—C5—C4 | 106.4 (3) | H34B—C34—H34C | 109.5 |
N1—C5—N51 | 122.2 (2) | C5—N51—C57 | 116.6 (2) |
C4—C5—N51 | 131.3 (3) | C5—N51—H51 | 110.0 |
C12—C11—C16 | 120.1 (3) | C57—N51—H51 | 115.2 |
C12—C11—N1 | 122.0 (3) | N51—C57—C51 | 110.4 (2) |
C16—C11—N1 | 117.9 (3) | N51—C57—H571 | 109.6 |
C11—C12—C13 | 119.3 (3) | C51—C57—H571 | 109.6 |
C11—C12—H12 | 120.4 | N51—C57—H572 | 109.6 |
C13—C12—H12 | 120.4 | C51—C57—H572 | 109.6 |
C14—C13—C12 | 120.8 (3) | H571—C57—H572 | 108.1 |
C14—C13—H13 | 119.6 | C52—C51—C56 | 118.2 (3) |
C12—C13—H13 | 119.6 | C52—C51—C57 | 121.5 (3) |
C15—C14—C13 | 119.7 (3) | C56—C51—C57 | 120.3 (3) |
C15—C14—H14 | 120.2 | C51—C52—C53 | 120.8 (3) |
C13—C14—H14 | 120.2 | C51—C52—H52 | 119.6 |
C14—C15—C16 | 120.7 (3) | C53—C52—H52 | 119.6 |
C14—C15—H15 | 119.7 | C54—C53—C52 | 121.0 (3) |
C16—C15—H15 | 119.7 | C54—C53—H53 | 119.5 |
C15—C16—C11 | 119.5 (3) | C52—C53—H53 | 119.5 |
C15—C16—H16 | 120.3 | C55—C54—C53 | 118.0 (3) |
C11—C16—H16 | 120.3 | C55—C54—C58 | 120.6 (3) |
C3—C31—C32 | 110.5 (3) | C53—C54—C58 | 121.3 (3) |
C3—C31—C33 | 110.6 (2) | C54—C55—C56 | 121.3 (3) |
C32—C31—C33 | 109.9 (3) | C54—C55—H55 | 119.4 |
C3—C31—C34 | 108.8 (2) | C56—C55—H55 | 119.4 |
C32—C31—C34 | 109.0 (2) | C51—C56—C55 | 120.7 (3) |
C33—C31—C34 | 108.0 (3) | C51—C56—H56 | 119.7 |
C31—C32—H32A | 109.5 | C55—C56—H56 | 119.7 |
C31—C32—H32B | 109.5 | C54—C58—H58A | 109.5 |
H32A—C32—H32B | 109.5 | C54—C58—H58B | 109.5 |
C31—C32—H32C | 109.5 | H58A—C58—H58B | 109.5 |
H32A—C32—H32C | 109.5 | C54—C58—H58C | 109.5 |
H32B—C32—H32C | 109.5 | H58A—C58—H58C | 109.5 |
C31—C33—H33A | 109.5 | H58B—C58—H58C | 109.5 |
C5—N1—N2—C3 | 1.9 (3) | N1—C11—C16—C15 | −177.7 (3) |
C11—N1—N2—C3 | 173.7 (2) | N2—C3—C31—C32 | 155.9 (3) |
N1—N2—C3—C4 | −1.1 (3) | C4—C3—C31—C32 | −26.5 (4) |
N1—N2—C3—C31 | 176.9 (2) | N2—C3—C31—C33 | 33.9 (4) |
N2—C3—C4—C5 | −0.1 (3) | C4—C3—C31—C33 | −148.5 (3) |
C31—C3—C4—C5 | −177.8 (3) | N2—C3—C31—C34 | −84.6 (3) |
N2—N1—C5—C4 | −1.9 (3) | C4—C3—C31—C34 | 93.0 (4) |
C11—N1—C5—C4 | −172.6 (3) | N1—C5—N51—C57 | −175.7 (3) |
N2—N1—C5—N51 | 179.7 (2) | C4—C5—N51—C57 | 6.3 (4) |
C11—N1—C5—N51 | 9.0 (4) | C5—N51—C57—C51 | −177.0 (3) |
C3—C4—C5—N1 | 1.2 (3) | N51—C57—C51—C52 | −130.1 (3) |
C3—C4—C5—N51 | 179.4 (3) | N51—C57—C51—C56 | 50.4 (4) |
C5—N1—C11—C12 | −38.2 (4) | C56—C51—C52—C53 | −1.5 (5) |
N2—N1—C11—C12 | 151.7 (3) | C57—C51—C52—C53 | 178.9 (3) |
C5—N1—C11—C16 | 142.2 (3) | C51—C52—C53—C54 | 0.2 (5) |
N2—N1—C11—C16 | −28.0 (4) | C52—C53—C54—C55 | 1.5 (5) |
C16—C11—C12—C13 | −2.9 (4) | C52—C53—C54—C58 | −176.4 (3) |
N1—C11—C12—C13 | 177.4 (3) | C53—C54—C55—C56 | −1.7 (4) |
C11—C12—C13—C14 | 1.3 (5) | C58—C54—C55—C56 | 176.1 (3) |
C12—C13—C14—C15 | 0.7 (5) | C52—C51—C56—C55 | 1.3 (4) |
C13—C14—C15—C16 | −1.0 (5) | C57—C51—C56—C55 | −179.2 (2) |
C14—C15—C16—C11 | −0.7 (5) | C54—C55—C56—C51 | 0.4 (4) |
C12—C11—C16—C15 | 2.6 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···N51 | 0.95 | 2.54 | 3.009 (4) | 111 |
N51—H51···Cg3i | 0.88 | 2.95 | 3.718 (2) | 147 |
C55—H55···Cg2i | 0.95 | 2.70 | 3.444 (3) | 136 |
Symmetry code: (i) y, x, −z+1. |
C21H22F3N3 | F(000) = 1568 |
Mr = 373.42 | Dx = 1.350 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 4218 reflections |
a = 20.824 (3) Å | θ = 2.9–27.5° |
b = 7.3429 (11) Å | µ = 0.10 mm−1 |
c = 24.225 (4) Å | T = 120 K |
β = 97.275 (11)° | Needle, colourless |
V = 3674.3 (10) Å3 | 0.36 × 0.09 × 0.04 mm |
Z = 8 |
Bruker–Nonius KappaCCD diffractometer | 4218 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 2014 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.151 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ and ω scans | h = −26→26 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −9→9 |
Tmin = 0.946, Tmax = 0.996 | l = −31→31 |
21869 measured reflections |
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)] = 0.083 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.196 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0791P)2] where P = (Fo2 + 2Fc2)/3 |
4218 reflections | (Δ/σ)max = 0.001 |
247 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
C21H22F3N3 | V = 3674.3 (10) Å3 |
Mr = 373.42 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.824 (3) Å | µ = 0.10 mm−1 |
b = 7.3429 (11) Å | T = 120 K |
c = 24.225 (4) Å | 0.36 × 0.09 × 0.04 mm |
β = 97.275 (11)° |
Bruker–Nonius KappaCCD diffractometer | 4218 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2014 reflections with I > 2σ(I) |
Tmin = 0.946, Tmax = 0.996 | Rint = 0.151 |
21869 measured reflections |
R[F2 > 2σ(F2)] = 0.083 | 0 restraints |
wR(F2) = 0.196 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.29 e Å−3 |
4218 reflections | Δρmin = −0.47 e Å−3 |
247 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.80598 (14) | 0.5223 (4) | 0.26474 (12) | 0.0208 (7) | |
N2 | 0.84366 (14) | 0.5000 (4) | 0.31528 (11) | 0.0214 (7) | |
C3 | 0.80213 (17) | 0.4853 (4) | 0.35142 (14) | 0.0202 (8) | |
C4 | 0.73816 (17) | 0.5000 (5) | 0.32628 (14) | 0.0224 (8) | |
H4 | 0.6999 | 0.4927 | 0.3438 | 0.027* | |
C5 | 0.74238 (17) | 0.5270 (5) | 0.27133 (14) | 0.0204 (8) | |
C11 | 0.83698 (18) | 0.5484 (4) | 0.21710 (14) | 0.0211 (8) | |
C12 | 0.80881 (17) | 0.4881 (5) | 0.16545 (14) | 0.0231 (8) | |
H12 | 0.7684 | 0.4266 | 0.1619 | 0.028* | |
C13 | 0.83955 (19) | 0.5176 (5) | 0.11938 (15) | 0.0280 (9) | |
H13 | 0.8198 | 0.4790 | 0.0838 | 0.034* | |
C14 | 0.8991 (2) | 0.6031 (5) | 0.12449 (17) | 0.0313 (10) | |
H14 | 0.9202 | 0.6252 | 0.0926 | 0.038* | |
C15 | 0.92733 (19) | 0.6554 (5) | 0.17605 (17) | 0.0296 (10) | |
H15 | 0.9687 | 0.7120 | 0.1799 | 0.036* | |
C16 | 0.89719 (18) | 0.6278 (5) | 0.22198 (16) | 0.0260 (9) | |
H16 | 0.9178 | 0.6636 | 0.2576 | 0.031* | |
C31 | 0.82464 (17) | 0.4647 (5) | 0.41273 (14) | 0.0230 (8) | |
C32 | 0.89773 (17) | 0.4476 (5) | 0.42395 (15) | 0.0264 (9) | |
H32A | 0.9114 | 0.3355 | 0.4069 | 0.040* | |
H32B | 0.9111 | 0.4435 | 0.4642 | 0.040* | |
H32C | 0.9178 | 0.5527 | 0.4080 | 0.040* | |
C33 | 0.80282 (19) | 0.6331 (5) | 0.44218 (16) | 0.0303 (10) | |
H33A | 0.8228 | 0.7418 | 0.4282 | 0.045* | |
H33B | 0.8160 | 0.6219 | 0.4823 | 0.045* | |
H33C | 0.7556 | 0.6439 | 0.4349 | 0.045* | |
C34 | 0.7936 (2) | 0.2971 (5) | 0.43503 (17) | 0.0360 (11) | |
H34A | 0.7464 | 0.3087 | 0.4283 | 0.054* | |
H34B | 0.8074 | 0.2862 | 0.4751 | 0.054* | |
H34C | 0.8070 | 0.1883 | 0.4160 | 0.054* | |
N51 | 0.69471 (13) | 0.5515 (4) | 0.22687 (12) | 0.0229 (7) | |
H51 | 0.7091 | 0.6275 | 0.2032 | 0.027* | |
C51 | 0.57982 (17) | 0.5726 (5) | 0.19126 (14) | 0.0197 (8) | |
C52 | 0.52900 (18) | 0.6943 (5) | 0.18628 (16) | 0.0256 (9) | |
H52 | 0.5278 | 0.7873 | 0.2134 | 0.031* | |
C53 | 0.48006 (18) | 0.6831 (5) | 0.14272 (16) | 0.0271 (9) | |
H53 | 0.4444 | 0.7645 | 0.1406 | 0.033* | |
C54 | 0.48295 (17) | 0.5532 (5) | 0.10209 (15) | 0.0230 (8) | |
C55 | 0.53430 (17) | 0.4343 (5) | 0.10571 (15) | 0.0231 (8) | |
H55 | 0.5368 | 0.3466 | 0.0772 | 0.028* | |
C56 | 0.58201 (17) | 0.4420 (5) | 0.15044 (14) | 0.0217 (8) | |
H56 | 0.6167 | 0.3571 | 0.1533 | 0.026* | |
C57 | 0.63008 (16) | 0.5817 (5) | 0.24123 (14) | 0.0207 (8) | |
H571 | 0.6283 | 0.7027 | 0.2590 | 0.025* | |
H572 | 0.6204 | 0.4886 | 0.2686 | 0.025* | |
C58 | 0.43125 (19) | 0.5515 (5) | 0.05461 (16) | 0.0298 (9) | |
F1 | 0.37230 (10) | 0.5426 (4) | 0.07037 (10) | 0.0488 (7) | |
F2 | 0.43146 (12) | 0.7029 (3) | 0.02396 (10) | 0.0433 (7) | |
F3 | 0.43564 (11) | 0.4136 (3) | 0.02004 (9) | 0.0388 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0201 (17) | 0.0217 (16) | 0.0195 (17) | 0.0011 (13) | −0.0011 (13) | 0.0019 (13) |
N2 | 0.0204 (17) | 0.0239 (17) | 0.0185 (17) | 0.0017 (13) | −0.0027 (13) | 0.0025 (13) |
C3 | 0.023 (2) | 0.0175 (19) | 0.0202 (19) | −0.0021 (15) | 0.0018 (16) | 0.0007 (15) |
C4 | 0.020 (2) | 0.026 (2) | 0.022 (2) | −0.0027 (16) | 0.0051 (15) | −0.0011 (16) |
C5 | 0.021 (2) | 0.0174 (19) | 0.022 (2) | −0.0004 (15) | −0.0005 (15) | −0.0008 (15) |
C11 | 0.026 (2) | 0.0177 (18) | 0.020 (2) | 0.0097 (16) | 0.0038 (16) | 0.0047 (15) |
C12 | 0.023 (2) | 0.020 (2) | 0.025 (2) | 0.0041 (16) | −0.0003 (16) | 0.0033 (16) |
C13 | 0.038 (2) | 0.026 (2) | 0.021 (2) | 0.0126 (18) | 0.0053 (18) | 0.0047 (16) |
C14 | 0.034 (3) | 0.034 (2) | 0.028 (2) | 0.0079 (19) | 0.0140 (19) | 0.0083 (18) |
C15 | 0.025 (2) | 0.030 (2) | 0.036 (3) | 0.0019 (17) | 0.0116 (19) | 0.0048 (18) |
C16 | 0.025 (2) | 0.023 (2) | 0.030 (2) | 0.0008 (16) | 0.0011 (18) | 0.0041 (17) |
C31 | 0.022 (2) | 0.026 (2) | 0.020 (2) | −0.0042 (16) | −0.0020 (15) | −0.0003 (16) |
C32 | 0.026 (2) | 0.028 (2) | 0.024 (2) | −0.0056 (17) | −0.0030 (16) | 0.0008 (17) |
C33 | 0.026 (2) | 0.042 (2) | 0.023 (2) | −0.0038 (18) | 0.0009 (17) | −0.0073 (18) |
C34 | 0.036 (3) | 0.040 (2) | 0.030 (2) | −0.009 (2) | −0.001 (2) | 0.0087 (19) |
N51 | 0.0170 (17) | 0.0307 (17) | 0.0202 (16) | −0.0008 (13) | −0.0003 (13) | 0.0053 (13) |
C51 | 0.0172 (19) | 0.0211 (19) | 0.022 (2) | −0.0009 (15) | 0.0060 (15) | 0.0054 (16) |
C52 | 0.027 (2) | 0.022 (2) | 0.028 (2) | 0.0025 (17) | 0.0025 (18) | −0.0041 (16) |
C53 | 0.017 (2) | 0.030 (2) | 0.035 (2) | 0.0081 (16) | 0.0049 (18) | 0.0028 (18) |
C54 | 0.018 (2) | 0.026 (2) | 0.024 (2) | 0.0005 (16) | 0.0002 (16) | 0.0047 (16) |
C55 | 0.027 (2) | 0.0209 (19) | 0.021 (2) | −0.0036 (17) | 0.0019 (16) | −0.0009 (16) |
C56 | 0.0159 (19) | 0.025 (2) | 0.025 (2) | 0.0032 (16) | 0.0034 (16) | 0.0010 (16) |
C57 | 0.020 (2) | 0.0208 (19) | 0.021 (2) | −0.0046 (15) | 0.0003 (15) | 0.0001 (15) |
C58 | 0.024 (2) | 0.037 (2) | 0.028 (2) | 0.0015 (18) | 0.0003 (17) | 0.005 (2) |
F1 | 0.0160 (13) | 0.0835 (19) | 0.0454 (16) | 0.0012 (12) | −0.0018 (11) | 0.0038 (13) |
F2 | 0.0476 (16) | 0.0418 (14) | 0.0362 (15) | 0.0078 (11) | −0.0111 (12) | 0.0145 (11) |
F3 | 0.0352 (14) | 0.0436 (14) | 0.0335 (13) | −0.0014 (11) | −0.0116 (10) | −0.0036 (11) |
N1—C5 | 1.354 (4) | C33—H33A | 0.9800 |
N1—N2 | 1.378 (4) | C33—H33B | 0.9800 |
N1—C11 | 1.405 (4) | C33—H33C | 0.9800 |
N2—C3 | 1.311 (4) | C34—H34A | 0.9800 |
C3—C4 | 1.397 (5) | C34—H34B | 0.9800 |
C3—C31 | 1.507 (5) | C34—H34C | 0.9800 |
C4—C5 | 1.360 (5) | N51—C57 | 1.449 (4) |
C4—H4 | 0.9500 | N51—H51 | 0.8797 |
C5—N51 | 1.381 (4) | C57—C51 | 1.498 (5) |
C11—C16 | 1.374 (5) | C57—H571 | 0.9900 |
C11—C12 | 1.386 (5) | C57—H572 | 0.9900 |
C12—C13 | 1.372 (5) | C51—C52 | 1.378 (5) |
C12—H12 | 0.9500 | C51—C56 | 1.382 (5) |
C13—C14 | 1.382 (5) | C52—C53 | 1.373 (5) |
C13—H13 | 0.9500 | C52—H52 | 0.9500 |
C14—C15 | 1.366 (5) | C53—C54 | 1.377 (5) |
C14—H14 | 0.9500 | C53—H53 | 0.9500 |
C15—C16 | 1.360 (5) | C54—C55 | 1.375 (5) |
C15—H15 | 0.9500 | C54—C58 | 1.473 (5) |
C16—H16 | 0.9500 | C55—C56 | 1.375 (5) |
C31—C32 | 1.517 (5) | C55—H55 | 0.9500 |
C31—C34 | 1.521 (5) | C56—H56 | 0.9500 |
C31—C33 | 1.525 (5) | C58—F3 | 1.324 (4) |
C32—H32A | 0.9800 | C58—F1 | 1.332 (4) |
C32—H32B | 0.9800 | C58—F2 | 1.337 (4) |
C32—H32C | 0.9800 | ||
C5—N1—N2 | 110.7 (3) | C31—C33—H33B | 109.5 |
C5—N1—C11 | 130.6 (3) | H33A—C33—H33B | 109.5 |
N2—N1—C11 | 118.5 (3) | C31—C33—H33C | 109.5 |
C3—N2—N1 | 104.7 (3) | H33A—C33—H33C | 109.5 |
N2—C3—C4 | 112.1 (3) | H33B—C33—H33C | 109.5 |
N2—C3—C31 | 121.1 (3) | C31—C34—H34A | 109.5 |
C4—C3—C31 | 126.7 (3) | C31—C34—H34B | 109.5 |
C5—C4—C3 | 105.2 (3) | H34A—C34—H34B | 109.5 |
C5—C4—H4 | 127.4 | C31—C34—H34C | 109.5 |
C3—C4—H4 | 127.4 | H34A—C34—H34C | 109.5 |
N1—C5—C4 | 107.3 (3) | H34B—C34—H34C | 109.5 |
N1—C5—N51 | 121.9 (3) | C5—N51—C57 | 115.5 (3) |
C4—C5—N51 | 130.8 (3) | C5—N51—H51 | 108.7 |
C16—C11—C12 | 119.4 (3) | C57—N51—H51 | 117.6 |
C16—C11—N1 | 119.8 (3) | N51—C57—C51 | 112.0 (3) |
C12—C11—N1 | 120.8 (3) | N51—C57—H571 | 109.2 |
C13—C12—C11 | 119.8 (4) | C51—C57—H571 | 109.2 |
C13—C12—H12 | 120.1 | N51—C57—H572 | 109.2 |
C11—C12—H12 | 120.1 | C51—C57—H572 | 109.2 |
C12—C13—C14 | 120.3 (4) | H571—C57—H572 | 107.9 |
C12—C13—H13 | 119.8 | C52—C51—C56 | 118.8 (3) |
C14—C13—H13 | 119.8 | C52—C51—C57 | 119.5 (3) |
C15—C14—C13 | 119.1 (4) | C56—C51—C57 | 121.7 (3) |
C15—C14—H14 | 120.4 | C53—C52—C51 | 121.0 (4) |
C13—C14—H14 | 120.4 | C53—C52—H52 | 119.5 |
C16—C15—C14 | 121.1 (4) | C51—C52—H52 | 119.5 |
C16—C15—H15 | 119.5 | C52—C53—C54 | 119.7 (3) |
C14—C15—H15 | 119.5 | C52—C53—H53 | 120.2 |
C15—C16—C11 | 120.2 (4) | C54—C53—H53 | 120.2 |
C15—C16—H16 | 119.9 | C55—C54—C53 | 119.9 (3) |
C11—C16—H16 | 119.9 | C55—C54—C58 | 122.0 (3) |
C3—C31—C32 | 111.4 (3) | C53—C54—C58 | 118.0 (3) |
C3—C31—C34 | 109.7 (3) | C54—C55—C56 | 120.2 (3) |
C32—C31—C34 | 109.3 (3) | C54—C55—H55 | 119.9 |
C3—C31—C33 | 107.8 (3) | C56—C55—H55 | 119.9 |
C32—C31—C33 | 109.6 (3) | C55—C56—C51 | 120.4 (3) |
C34—C31—C33 | 108.9 (3) | C55—C56—H56 | 119.8 |
C31—C32—H32A | 109.5 | C51—C56—H56 | 119.8 |
C31—C32—H32B | 109.5 | F3—C58—F1 | 106.5 (3) |
H32A—C32—H32B | 109.5 | F3—C58—F2 | 106.2 (3) |
C31—C32—H32C | 109.5 | F1—C58—F2 | 105.5 (3) |
H32A—C32—H32C | 109.5 | F3—C58—C54 | 113.5 (3) |
H32B—C32—H32C | 109.5 | F1—C58—C54 | 112.7 (3) |
C31—C33—H33A | 109.5 | F2—C58—C54 | 111.9 (3) |
C5—N1—N2—C3 | 2.1 (3) | N2—C3—C31—C34 | −126.2 (3) |
C11—N1—N2—C3 | 177.9 (3) | C4—C3—C31—C34 | 57.2 (5) |
N1—N2—C3—C4 | −0.9 (4) | N2—C3—C31—C33 | 115.3 (3) |
N1—N2—C3—C31 | −178.0 (3) | C4—C3—C31—C33 | −61.4 (4) |
N2—C3—C4—C5 | −0.6 (4) | N1—C5—N51—C57 | −170.8 (3) |
C31—C3—C4—C5 | 176.4 (3) | C4—C5—N51—C57 | 10.9 (5) |
N2—N1—C5—C4 | −2.5 (4) | C5—N51—C57—C51 | −169.5 (3) |
C11—N1—C5—C4 | −177.6 (3) | N51—C57—C51—C52 | −140.2 (3) |
N2—N1—C5—N51 | 178.8 (3) | N51—C57—C51—C56 | 41.6 (5) |
C11—N1—C5—N51 | 3.7 (5) | C56—C51—C52—C53 | 2.2 (5) |
C3—C4—C5—N1 | 1.8 (4) | C57—C51—C52—C53 | −176.1 (3) |
C3—C4—C5—N51 | −179.7 (3) | C51—C52—C53—C54 | −2.7 (6) |
C5—N1—C11—C16 | 146.7 (3) | C52—C53—C54—C55 | 0.8 (6) |
N2—N1—C11—C16 | −28.1 (4) | C52—C53—C54—C58 | −177.0 (3) |
C5—N1—C11—C12 | −36.0 (5) | C53—C54—C55—C56 | 1.5 (5) |
N2—N1—C11—C12 | 149.2 (3) | C58—C54—C55—C56 | 179.2 (3) |
C16—C11—C12—C13 | −3.7 (5) | C54—C55—C56—C51 | −1.9 (5) |
N1—C11—C12—C13 | 179.0 (3) | C52—C51—C56—C55 | 0.1 (5) |
C11—C12—C13—C14 | 1.6 (5) | C57—C51—C56—C55 | 178.4 (3) |
C12—C13—C14—C15 | 0.9 (5) | C55—C54—C58—F3 | 7.1 (5) |
C13—C14—C15—C16 | −1.3 (6) | C53—C54—C58—F3 | −175.2 (3) |
C14—C15—C16—C11 | −0.9 (6) | C55—C54—C58—F1 | 128.2 (4) |
C12—C11—C16—C15 | 3.4 (5) | C53—C54—C58—F1 | −54.1 (5) |
N1—C11—C16—C15 | −179.3 (3) | C55—C54—C58—F2 | −113.1 (4) |
N2—C3—C31—C32 | −4.9 (4) | C53—C54—C58—F2 | 64.6 (5) |
C4—C3—C31—C32 | 178.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···N51 | 0.95 | 2.51 | 2.995 (5) | 112 |
N51—H51···Cg1i | 0.88 | 2.80 | 3.470 (3) | 134 |
C53—H53···Cg2ii | 0.95 | 2.91 | 3.809 (4) | 157 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x−1/2, y+1/2, z. |
C20H22ClN3 | Z = 2 |
Mr = 339.86 | F(000) = 360 |
Triclinic, P1 | Dx = 1.298 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.385 (3) Å | Cell parameters from 3991 reflections |
b = 9.7584 (19) Å | θ = 2.8–27.5° |
c = 10.6014 (17) Å | µ = 0.23 mm−1 |
α = 112.459 (13)° | T = 120 K |
β = 95.721 (18)° | Lath, colourless |
γ = 99.735 (19)° | 0.25 × 0.10 × 0.05 mm |
V = 869.8 (4) Å3 |
Bruker–Nonius KappaCCD diffractometer | 3991 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 2811 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ and ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→12 |
Tmin = 0.958, Tmax = 0.989 | l = −13→13 |
25011 measured reflections |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0483P)2 + 0.3135P] where P = (Fo2 + 2Fc2)/3 |
3991 reflections | (Δ/σ)max = 0.001 |
220 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C20H22ClN3 | γ = 99.735 (19)° |
Mr = 339.86 | V = 869.8 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.385 (3) Å | Mo Kα radiation |
b = 9.7584 (19) Å | µ = 0.23 mm−1 |
c = 10.6014 (17) Å | T = 120 K |
α = 112.459 (13)° | 0.25 × 0.10 × 0.05 mm |
β = 95.721 (18)° |
Bruker–Nonius KappaCCD diffractometer | 3991 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2811 reflections with I > 2σ(I) |
Tmin = 0.958, Tmax = 0.989 | Rint = 0.059 |
25011 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.23 e Å−3 |
3991 reflections | Δρmin = −0.28 e Å−3 |
220 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.46276 (16) | 0.21931 (17) | 0.40900 (15) | 0.0211 (3) | |
N2 | 0.34863 (16) | 0.13933 (17) | 0.29828 (15) | 0.0222 (3) | |
C3 | 0.25146 (19) | 0.0681 (2) | 0.34731 (19) | 0.0213 (4) | |
C4 | 0.3010 (2) | 0.0982 (2) | 0.48675 (19) | 0.0231 (4) | |
H4 | 0.2510 | 0.0596 | 0.5440 | 0.028* | |
C5 | 0.43605 (19) | 0.1942 (2) | 0.52260 (18) | 0.0203 (4) | |
C11 | 0.59165 (19) | 0.3020 (2) | 0.39085 (18) | 0.0206 (4) | |
C12 | 0.66041 (19) | 0.4440 (2) | 0.49181 (18) | 0.0224 (4) | |
H12 | 0.6205 | 0.4867 | 0.5733 | 0.027* | |
C13 | 0.7868 (2) | 0.5232 (2) | 0.4738 (2) | 0.0272 (4) | |
H13 | 0.8346 | 0.6204 | 0.5436 | 0.033* | |
C14 | 0.8447 (2) | 0.4632 (2) | 0.3558 (2) | 0.0286 (4) | |
H14 | 0.9322 | 0.5183 | 0.3440 | 0.034* | |
C15 | 0.7745 (2) | 0.3225 (2) | 0.2549 (2) | 0.0279 (4) | |
H15 | 0.8137 | 0.2810 | 0.1727 | 0.033* | |
C16 | 0.6484 (2) | 0.2413 (2) | 0.27166 (18) | 0.0238 (4) | |
H16 | 0.6007 | 0.1441 | 0.2016 | 0.029* | |
C31 | 0.1061 (2) | −0.0262 (2) | 0.25749 (19) | 0.0254 (4) | |
C32 | 0.0479 (2) | −0.1502 (2) | 0.3052 (2) | 0.0336 (5) | |
H32A | 0.1201 | −0.2127 | 0.3017 | 0.050* | |
H32B | −0.0446 | −0.2143 | 0.2441 | 0.050* | |
H32C | 0.0309 | −0.1034 | 0.4006 | 0.050* | |
C33 | 0.1222 (2) | −0.0981 (2) | 0.1058 (2) | 0.0326 (5) | |
H33A | 0.1631 | −0.0182 | 0.0765 | 0.049* | |
H33B | 0.0257 | −0.1545 | 0.0483 | 0.049* | |
H33C | 0.1883 | −0.1680 | 0.0951 | 0.049* | |
C34 | −0.0037 (2) | 0.0753 (2) | 0.2703 (2) | 0.0353 (5) | |
H34A | −0.0156 | 0.1220 | 0.3674 | 0.053* | |
H34B | −0.0987 | 0.0139 | 0.2125 | 0.053* | |
H34C | 0.0328 | 0.1553 | 0.2395 | 0.053* | |
N51 | 0.53524 (17) | 0.25935 (18) | 0.64426 (15) | 0.0245 (4) | |
H51 | 0.6259 | 0.2972 | 0.6406 | 0.029* | |
C51 | 0.42418 (19) | 0.2693 (2) | 0.84934 (18) | 0.0209 (4) | |
C52 | 0.35845 (19) | 0.3835 (2) | 0.84378 (18) | 0.0218 (4) | |
H52 | 0.3723 | 0.4197 | 0.7734 | 0.026* | |
C53 | 0.2726 (2) | 0.4458 (2) | 0.93988 (18) | 0.0236 (4) | |
H53 | 0.2263 | 0.5236 | 0.9353 | 0.028* | |
C54 | 0.2552 (2) | 0.3938 (2) | 1.04165 (18) | 0.0251 (4) | |
Cl54 | 0.14512 (6) | 0.47041 (6) | 1.16049 (5) | 0.03495 (16) | |
C55 | 0.3209 (2) | 0.2817 (2) | 1.05116 (19) | 0.0266 (4) | |
H55 | 0.3088 | 0.2477 | 1.1231 | 0.032* | |
C56 | 0.4045 (2) | 0.2202 (2) | 0.95394 (19) | 0.0257 (4) | |
H56 | 0.4499 | 0.1419 | 0.9587 | 0.031* | |
C57 | 0.5197 (2) | 0.1986 (2) | 0.74782 (18) | 0.0257 (4) | |
H571 | 0.6186 | 0.2134 | 0.8001 | 0.031* | |
H572 | 0.4777 | 0.0877 | 0.7004 | 0.031* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0201 (8) | 0.0217 (8) | 0.0182 (7) | 0.0007 (6) | 0.0008 (6) | 0.0068 (6) |
N2 | 0.0210 (8) | 0.0197 (8) | 0.0189 (8) | 0.0008 (6) | −0.0026 (6) | 0.0036 (6) |
C3 | 0.0202 (9) | 0.0180 (9) | 0.0243 (9) | 0.0048 (7) | 0.0026 (7) | 0.0069 (7) |
C4 | 0.0213 (9) | 0.0231 (10) | 0.0234 (9) | 0.0039 (8) | 0.0042 (7) | 0.0081 (8) |
C5 | 0.0199 (9) | 0.0215 (9) | 0.0178 (9) | 0.0046 (7) | 0.0032 (7) | 0.0062 (7) |
C11 | 0.0190 (9) | 0.0215 (9) | 0.0216 (9) | 0.0055 (7) | 0.0022 (7) | 0.0091 (7) |
C12 | 0.0207 (9) | 0.0237 (10) | 0.0201 (9) | 0.0049 (8) | 0.0041 (7) | 0.0058 (7) |
C13 | 0.0250 (10) | 0.0241 (10) | 0.0281 (10) | 0.0007 (8) | −0.0002 (8) | 0.0089 (8) |
C14 | 0.0202 (9) | 0.0360 (11) | 0.0364 (11) | 0.0059 (8) | 0.0075 (8) | 0.0217 (9) |
C15 | 0.0296 (10) | 0.0353 (11) | 0.0268 (10) | 0.0144 (9) | 0.0121 (8) | 0.0165 (9) |
C16 | 0.0281 (10) | 0.0221 (10) | 0.0202 (9) | 0.0070 (8) | 0.0041 (8) | 0.0070 (8) |
C31 | 0.0213 (9) | 0.0220 (10) | 0.0257 (10) | 0.0020 (8) | −0.0013 (8) | 0.0045 (8) |
C32 | 0.0300 (11) | 0.0266 (11) | 0.0348 (11) | −0.0046 (9) | 0.0006 (9) | 0.0083 (9) |
C33 | 0.0273 (10) | 0.0339 (11) | 0.0250 (10) | 0.0014 (9) | −0.0048 (8) | 0.0040 (9) |
C34 | 0.0233 (10) | 0.0297 (11) | 0.0411 (12) | 0.0041 (9) | −0.0043 (9) | 0.0050 (9) |
N51 | 0.0189 (8) | 0.0330 (9) | 0.0185 (8) | 0.0013 (7) | 0.0013 (6) | 0.0094 (7) |
C51 | 0.0190 (9) | 0.0210 (9) | 0.0176 (9) | −0.0006 (7) | −0.0005 (7) | 0.0055 (7) |
C52 | 0.0211 (9) | 0.0230 (10) | 0.0183 (9) | 0.0009 (8) | 0.0007 (7) | 0.0074 (7) |
C53 | 0.0235 (9) | 0.0215 (9) | 0.0218 (9) | 0.0030 (8) | −0.0002 (7) | 0.0065 (8) |
C54 | 0.0217 (9) | 0.0251 (10) | 0.0185 (9) | −0.0026 (8) | 0.0027 (7) | 0.0017 (8) |
Cl54 | 0.0308 (3) | 0.0383 (3) | 0.0251 (3) | 0.0021 (2) | 0.0100 (2) | 0.0027 (2) |
C55 | 0.0317 (10) | 0.0252 (10) | 0.0195 (9) | −0.0015 (8) | 0.0024 (8) | 0.0093 (8) |
C56 | 0.0289 (10) | 0.0231 (10) | 0.0248 (10) | 0.0038 (8) | 0.0003 (8) | 0.0113 (8) |
C57 | 0.0267 (10) | 0.0322 (11) | 0.0193 (9) | 0.0092 (8) | 0.0024 (8) | 0.0111 (8) |
N1—C5 | 1.356 (2) | C32—H32B | 0.9800 |
N1—N2 | 1.379 (2) | C32—H32C | 0.9800 |
N1—C11 | 1.410 (2) | C33—H33A | 0.9800 |
N2—C3 | 1.319 (2) | C33—H33B | 0.9800 |
C3—C4 | 1.405 (3) | C33—H33C | 0.9800 |
C3—C31 | 1.504 (2) | C34—H34A | 0.9800 |
C4—C5 | 1.363 (3) | C34—H34B | 0.9800 |
C4—H4 | 0.9500 | C34—H34C | 0.9800 |
C5—N51 | 1.367 (2) | N51—C57 | 1.441 (2) |
C11—C16 | 1.378 (3) | N51—H51 | 0.8796 |
C11—C12 | 1.382 (3) | C57—C51 | 1.507 (3) |
C12—C13 | 1.374 (3) | C57—H571 | 0.9900 |
C12—H12 | 0.9500 | C57—H572 | 0.9900 |
C13—C14 | 1.373 (3) | C51—C52 | 1.379 (3) |
C13—H13 | 0.9500 | C51—C56 | 1.382 (3) |
C14—C15 | 1.377 (3) | C52—C53 | 1.383 (3) |
C14—H14 | 0.9500 | C52—H52 | 0.9500 |
C15—C16 | 1.376 (3) | C53—C54 | 1.369 (3) |
C15—H15 | 0.9500 | C53—H53 | 0.9500 |
C16—H16 | 0.9500 | C54—C55 | 1.374 (3) |
C31—C32 | 1.523 (3) | C54—Cl54 | 1.7361 (19) |
C31—C33 | 1.524 (3) | C55—C56 | 1.374 (3) |
C31—C34 | 1.526 (3) | C55—H55 | 0.9500 |
C32—H32A | 0.9800 | C56—H56 | 0.9500 |
C5—N1—N2 | 111.43 (14) | H32A—C32—H32C | 109.5 |
C5—N1—C11 | 128.43 (15) | H32B—C32—H32C | 109.5 |
N2—N1—C11 | 119.89 (14) | C31—C33—H33A | 109.5 |
C3—N2—N1 | 104.48 (14) | C31—C33—H33B | 109.5 |
N2—C3—C4 | 111.68 (16) | H33A—C33—H33B | 109.5 |
N2—C3—C31 | 120.28 (16) | C31—C33—H33C | 109.5 |
C4—C3—C31 | 128.00 (17) | H33A—C33—H33C | 109.5 |
C5—C4—C3 | 105.55 (16) | H33B—C33—H33C | 109.5 |
C5—C4—H4 | 127.2 | C31—C34—H34A | 109.5 |
C3—C4—H4 | 127.2 | C31—C34—H34B | 109.5 |
N1—C5—C4 | 106.84 (15) | H34A—C34—H34B | 109.5 |
N1—C5—N51 | 121.89 (16) | C31—C34—H34C | 109.5 |
C4—C5—N51 | 131.27 (17) | H34A—C34—H34C | 109.5 |
C16—C11—C12 | 120.09 (17) | H34B—C34—H34C | 109.5 |
C16—C11—N1 | 119.81 (16) | C5—N51—C57 | 119.01 (15) |
C12—C11—N1 | 120.10 (16) | C5—N51—H51 | 117.2 |
C13—C12—C11 | 119.68 (17) | C57—N51—H51 | 115.6 |
C13—C12—H12 | 120.2 | N51—C57—C51 | 114.45 (16) |
C11—C12—H12 | 120.2 | N51—C57—H571 | 108.6 |
C14—C13—C12 | 120.66 (18) | C51—C57—H571 | 108.6 |
C14—C13—H13 | 119.7 | N51—C57—H572 | 108.6 |
C12—C13—H13 | 119.7 | C51—C57—H572 | 108.6 |
C13—C14—C15 | 119.34 (18) | H571—C57—H572 | 107.6 |
C13—C14—H14 | 120.3 | C52—C51—C56 | 118.76 (17) |
C15—C14—H14 | 120.3 | C52—C51—C57 | 122.52 (16) |
C16—C15—C14 | 120.75 (18) | C56—C51—C57 | 118.71 (17) |
C16—C15—H15 | 119.6 | C51—C52—C53 | 120.49 (17) |
C14—C15—H15 | 119.6 | C51—C52—H52 | 119.8 |
C15—C16—C11 | 119.48 (17) | C53—C52—H52 | 119.8 |
C15—C16—H16 | 120.3 | C54—C53—C52 | 119.07 (17) |
C11—C16—H16 | 120.3 | C54—C53—H53 | 120.5 |
C3—C31—C32 | 109.56 (16) | C52—C53—H53 | 120.5 |
C3—C31—C33 | 110.60 (16) | C53—C54—C55 | 121.83 (18) |
C32—C31—C33 | 109.72 (16) | C53—C54—Cl54 | 118.88 (15) |
C3—C31—C34 | 109.37 (15) | C55—C54—Cl54 | 119.28 (15) |
C32—C31—C34 | 109.00 (17) | C54—C55—C56 | 118.25 (17) |
C33—C31—C34 | 108.57 (16) | C54—C55—H55 | 120.9 |
C31—C32—H32A | 109.5 | C56—C55—H55 | 120.9 |
C31—C32—H32B | 109.5 | C55—C56—C51 | 121.60 (18) |
H32A—C32—H32B | 109.5 | C55—C56—H56 | 119.2 |
C31—C32—H32C | 109.5 | C51—C56—H56 | 119.2 |
C5—N1—N2—C3 | 1.21 (19) | N1—C11—C16—C15 | −179.77 (16) |
C11—N1—N2—C3 | 175.93 (15) | N2—C3—C31—C32 | 153.33 (17) |
N1—N2—C3—C4 | −1.0 (2) | C4—C3—C31—C32 | −29.2 (3) |
N1—N2—C3—C31 | 176.89 (15) | N2—C3—C31—C33 | 32.3 (2) |
N2—C3—C4—C5 | 0.4 (2) | C4—C3—C31—C33 | −150.29 (19) |
C31—C3—C4—C5 | −177.26 (17) | N2—C3—C31—C34 | −87.3 (2) |
N2—N1—C5—C4 | −1.0 (2) | C4—C3—C31—C34 | 90.2 (2) |
C11—N1—C5—C4 | −175.15 (17) | N1—C5—N51—C57 | −163.66 (16) |
N2—N1—C5—N51 | 178.72 (16) | C4—C5—N51—C57 | 16.0 (3) |
C11—N1—C5—N51 | 4.6 (3) | C5—N51—C57—C51 | −89.3 (2) |
C3—C4—C5—N1 | 0.4 (2) | N51—C57—C51—C52 | −0.6 (2) |
C3—C4—C5—N51 | −179.31 (19) | N51—C57—C51—C56 | −179.02 (16) |
C5—N1—C11—C16 | 133.66 (19) | C56—C51—C52—C53 | −1.0 (3) |
N2—N1—C11—C16 | −40.1 (2) | C57—C51—C52—C53 | −179.49 (17) |
C5—N1—C11—C12 | −46.8 (3) | C51—C52—C53—C54 | 0.8 (3) |
N2—N1—C11—C12 | 139.50 (17) | C52—C53—C54—C55 | 0.1 (3) |
C16—C11—C12—C13 | −1.1 (3) | C52—C53—C54—Cl54 | −179.08 (14) |
N1—C11—C12—C13 | 179.38 (16) | C53—C54—C55—C56 | −0.8 (3) |
C11—C12—C13—C14 | 0.6 (3) | Cl54—C54—C55—C56 | 178.40 (14) |
C12—C13—C14—C15 | 0.2 (3) | C54—C55—C56—C51 | 0.6 (3) |
C13—C14—C15—C16 | −0.6 (3) | C52—C51—C56—C55 | 0.3 (3) |
C14—C15—C16—C11 | 0.2 (3) | C57—C51—C56—C55 | 178.86 (17) |
C12—C11—C16—C15 | 0.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N51—H51···Cl54i | 0.88 | 2.83 | 3.486 (2) | 133 |
C55—H55···N2ii | 0.95 | 2.49 | 3.410 (3) | 163 |
C57—H572···Cg3iii | 0.99 | 2.88 | 3.557 (2) | 126 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, y, z+1; (iii) −x+1, −y, −z+1. |
C20H22BrN3 | F(000) = 1584 |
Mr = 384.32 | Dx = 1.430 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 4071 reflections |
a = 20.1981 (6) Å | θ = 2.9–27.5° |
b = 7.3960 (9) Å | µ = 2.31 mm−1 |
c = 24.171 (4) Å | T = 120 K |
β = 98.634 (7)° | Needle, colourless |
V = 3569.9 (7) Å3 | 0.44 × 0.13 × 0.11 mm |
Z = 8 |
Bruker–Nonius KappaCCD diffractometer | 4071 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 2871 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ and ω scans | h = −25→26 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −9→9 |
Tmin = 0.499, Tmax = 0.785 | l = −31→31 |
28981 measured reflections |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0569P)2 + 13.3406P] where P = (Fo2 + 2Fc2)/3 |
4071 reflections | (Δ/σ)max = 0.001 |
220 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.63 e Å−3 |
C20H22BrN3 | V = 3569.9 (7) Å3 |
Mr = 384.32 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.1981 (6) Å | µ = 2.31 mm−1 |
b = 7.3960 (9) Å | T = 120 K |
c = 24.171 (4) Å | 0.44 × 0.13 × 0.11 mm |
β = 98.634 (7)° |
Bruker–Nonius KappaCCD diffractometer | 4071 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2871 reflections with I > 2σ(I) |
Tmin = 0.499, Tmax = 0.785 | Rint = 0.051 |
28981 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0569P)2 + 13.3406P] where P = (Fo2 + 2Fc2)/3 |
4071 reflections | Δρmax = 0.41 e Å−3 |
220 parameters | Δρmin = −0.63 e Å−3 |
x | y | z | Uiso*/Ueq | ||
N1 | 0.80342 (13) | 0.5250 (4) | 0.26616 (11) | 0.0161 (5) | |
N2 | 0.84310 (13) | 0.4995 (4) | 0.31685 (10) | 0.0173 (5) | |
C3 | 0.80086 (16) | 0.4875 (4) | 0.35294 (13) | 0.0177 (6) | |
C4 | 0.73400 (16) | 0.5064 (4) | 0.32722 (13) | 0.0176 (6) | |
H4 | 0.6948 | 0.5015 | 0.3446 | 0.021* | |
C5 | 0.73765 (15) | 0.5331 (4) | 0.27197 (13) | 0.0153 (6) | |
C11 | 0.83441 (16) | 0.5489 (4) | 0.21827 (13) | 0.0169 (6) | |
C12 | 0.80415 (16) | 0.4858 (4) | 0.16672 (13) | 0.0185 (6) | |
H12 | 0.7625 | 0.4241 | 0.1632 | 0.022* | |
C13 | 0.83556 (17) | 0.5141 (5) | 0.12051 (14) | 0.0224 (7) | |
H13 | 0.8148 | 0.4741 | 0.0848 | 0.027* | |
C14 | 0.89664 (18) | 0.5996 (5) | 0.12568 (15) | 0.0261 (8) | |
H14 | 0.9177 | 0.6196 | 0.0936 | 0.031* | |
C15 | 0.92702 (18) | 0.6559 (5) | 0.17759 (16) | 0.0279 (8) | |
H15 | 0.9696 | 0.7127 | 0.1814 | 0.033* | |
C16 | 0.89611 (17) | 0.6304 (5) | 0.22403 (14) | 0.0224 (7) | |
H16 | 0.9173 | 0.6690 | 0.2598 | 0.027* | |
C31 | 0.82519 (17) | 0.4664 (4) | 0.41454 (13) | 0.0196 (7) | |
C32 | 0.90061 (17) | 0.4395 (5) | 0.42545 (15) | 0.0264 (8) | |
H32A | 0.9120 | 0.3255 | 0.4085 | 0.040* | |
H32B | 0.9158 | 0.4356 | 0.4659 | 0.040* | |
H32C | 0.9226 | 0.5400 | 0.4090 | 0.040* | |
C33 | 0.8068 (2) | 0.6369 (5) | 0.44358 (15) | 0.0307 (8) | |
H33A | 0.8271 | 0.7418 | 0.4279 | 0.046* | |
H33B | 0.8235 | 0.6283 | 0.4837 | 0.046* | |
H33C | 0.7580 | 0.6507 | 0.4379 | 0.046* | |
C34 | 0.79148 (19) | 0.3058 (5) | 0.43727 (15) | 0.0293 (8) | |
H34A | 0.7428 | 0.3215 | 0.4297 | 0.044* | |
H34B | 0.8059 | 0.2967 | 0.4777 | 0.044* | |
H34C | 0.8039 | 0.1951 | 0.4190 | 0.044* | |
N51 | 0.68844 (13) | 0.5587 (4) | 0.22681 (11) | 0.0188 (6) | |
H51 | 0.7007 | 0.6478 | 0.2064 | 0.023* | |
C51 | 0.57057 (15) | 0.5712 (5) | 0.18715 (13) | 0.0166 (6) | |
C52 | 0.51577 (17) | 0.6843 (5) | 0.17890 (14) | 0.0235 (7) | |
H52 | 0.5119 | 0.7781 | 0.2051 | 0.028* | |
C53 | 0.46654 (17) | 0.6638 (5) | 0.13350 (15) | 0.0266 (8) | |
H53 | 0.4282 | 0.7397 | 0.1289 | 0.032* | |
C44 | 0.47381 (17) | 0.5321 (5) | 0.09504 (14) | 0.0220 (7) | |
Br54 | 0.40667 (2) | 0.50388 (6) | 0.033022 (16) | 0.03814 (16) | |
C55 | 0.52881 (16) | 0.4213 (5) | 0.10105 (14) | 0.0208 (7) | |
H55 | 0.5337 | 0.3327 | 0.0735 | 0.025* | |
C56 | 0.57672 (16) | 0.4397 (4) | 0.14735 (14) | 0.0182 (7) | |
H56 | 0.6145 | 0.3616 | 0.1522 | 0.022* | |
C57 | 0.62110 (15) | 0.5897 (5) | 0.23852 (13) | 0.0189 (7) | |
H571 | 0.6182 | 0.7127 | 0.2542 | 0.023* | |
H572 | 0.6109 | 0.5018 | 0.2670 | 0.023* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0164 (13) | 0.0165 (14) | 0.0153 (12) | −0.0001 (10) | 0.0019 (10) | 0.0033 (10) |
N2 | 0.0196 (13) | 0.0166 (13) | 0.0148 (12) | −0.0005 (11) | −0.0002 (10) | 0.0003 (11) |
C3 | 0.0219 (15) | 0.0116 (15) | 0.0192 (15) | −0.0036 (13) | 0.0022 (12) | −0.0006 (13) |
C4 | 0.0183 (15) | 0.0173 (15) | 0.0178 (14) | −0.0027 (13) | 0.0046 (11) | −0.0017 (13) |
C5 | 0.0173 (15) | 0.0104 (16) | 0.0184 (15) | −0.0001 (11) | 0.0039 (11) | 0.0004 (11) |
C11 | 0.0218 (16) | 0.0115 (15) | 0.0183 (15) | 0.0056 (12) | 0.0057 (12) | 0.0044 (12) |
C12 | 0.0198 (15) | 0.0156 (16) | 0.0201 (15) | 0.0040 (13) | 0.0032 (12) | 0.0023 (13) |
C13 | 0.0298 (18) | 0.0195 (17) | 0.0183 (15) | 0.0087 (14) | 0.0052 (13) | 0.0021 (14) |
C14 | 0.0298 (19) | 0.0242 (19) | 0.0272 (19) | 0.0075 (15) | 0.0141 (15) | 0.0076 (15) |
C15 | 0.0223 (18) | 0.027 (2) | 0.036 (2) | −0.0004 (15) | 0.0089 (15) | 0.0049 (16) |
C16 | 0.0225 (17) | 0.0195 (17) | 0.0251 (18) | 0.0014 (13) | 0.0032 (13) | 0.0031 (14) |
C31 | 0.0255 (17) | 0.0170 (17) | 0.0156 (15) | −0.0033 (13) | 0.0011 (12) | 0.0014 (12) |
C32 | 0.0254 (18) | 0.033 (2) | 0.0193 (17) | −0.0048 (15) | −0.0006 (13) | 0.0021 (15) |
C33 | 0.042 (2) | 0.031 (2) | 0.0189 (18) | 0.0020 (17) | 0.0040 (15) | −0.0061 (15) |
C34 | 0.033 (2) | 0.032 (2) | 0.0218 (18) | −0.0112 (16) | 0.0007 (14) | 0.0086 (16) |
N51 | 0.0161 (13) | 0.0216 (14) | 0.0193 (14) | 0.0009 (11) | 0.0042 (10) | 0.0032 (11) |
C51 | 0.0141 (15) | 0.0169 (15) | 0.0202 (16) | 0.0012 (12) | 0.0070 (12) | 0.0029 (13) |
C52 | 0.0254 (18) | 0.0202 (18) | 0.0267 (18) | 0.0060 (14) | 0.0093 (14) | −0.0016 (14) |
C53 | 0.0186 (17) | 0.0251 (19) | 0.037 (2) | 0.0087 (14) | 0.0061 (14) | 0.0069 (16) |
C44 | 0.0178 (16) | 0.0241 (19) | 0.0227 (16) | −0.0037 (13) | −0.0009 (12) | 0.0078 (14) |
Br54 | 0.0331 (2) | 0.0449 (3) | 0.0316 (2) | −0.00233 (18) | −0.01112 (15) | 0.00885 (19) |
C55 | 0.0216 (17) | 0.0190 (17) | 0.0217 (17) | 0.0001 (14) | 0.0035 (13) | −0.0005 (14) |
C56 | 0.0164 (15) | 0.0148 (15) | 0.0241 (17) | 0.0033 (12) | 0.0052 (12) | 0.0033 (13) |
C57 | 0.0181 (16) | 0.0190 (17) | 0.0203 (16) | −0.0001 (13) | 0.0053 (12) | −0.0004 (13) |
N1—C5 | 1.358 (4) | C32—H32B | 0.9800 |
N1—N2 | 1.373 (4) | C32—H32C | 0.9800 |
N1—C11 | 1.408 (4) | C33—H33A | 0.9800 |
N2—C3 | 1.312 (4) | C33—H33B | 0.9800 |
C3—C4 | 1.406 (4) | C33—H33C | 0.9800 |
C3—C31 | 1.504 (4) | C34—H34A | 0.9800 |
C4—C5 | 1.363 (4) | C34—H34B | 0.9800 |
C4—H4 | 0.9500 | C34—H34C | 0.9800 |
C5—N51 | 1.375 (4) | N51—C57 | 1.449 (4) |
C11—C16 | 1.372 (5) | N51—H51 | 0.8797 |
C11—C12 | 1.384 (5) | C57—C51 | 1.490 (4) |
C12—C13 | 1.381 (4) | C57—H571 | 0.9900 |
C12—H12 | 0.9500 | C57—H572 | 0.9900 |
C13—C14 | 1.375 (5) | C51—C52 | 1.378 (5) |
C13—H13 | 0.9500 | C51—C56 | 1.386 (5) |
C14—C15 | 1.376 (5) | C52—C53 | 1.374 (5) |
C14—H14 | 0.9500 | C52—H52 | 0.9500 |
C15—C16 | 1.377 (5) | C53—C44 | 1.370 (5) |
C15—H15 | 0.9500 | C53—H53 | 0.9500 |
C16—H16 | 0.9500 | C44—C55 | 1.370 (5) |
C31—C34 | 1.513 (5) | C44—Br54 | 1.876 (3) |
C31—C33 | 1.516 (5) | C55—C56 | 1.372 (5) |
C31—C32 | 1.519 (5) | C55—H55 | 0.9500 |
C32—H32A | 0.9800 | C56—H56 | 0.9500 |
C5—N1—N2 | 111.3 (2) | H32A—C32—H32C | 109.5 |
C5—N1—C11 | 130.0 (3) | H32B—C32—H32C | 109.5 |
N2—N1—C11 | 118.6 (3) | C31—C33—H33A | 109.5 |
C3—N2—N1 | 104.6 (3) | C31—C33—H33B | 109.5 |
N2—C3—C4 | 112.1 (3) | H33A—C33—H33B | 109.5 |
N2—C3—C31 | 121.1 (3) | C31—C33—H33C | 109.5 |
C4—C3—C31 | 126.7 (3) | H33A—C33—H33C | 109.5 |
C5—C4—C3 | 105.0 (3) | H33B—C33—H33C | 109.5 |
C5—C4—H4 | 127.5 | C31—C34—H34A | 109.5 |
C3—C4—H4 | 127.5 | C31—C34—H34B | 109.5 |
N1—C5—C4 | 107.0 (3) | H34A—C34—H34B | 109.5 |
N1—C5—N51 | 121.7 (3) | C31—C34—H34C | 109.5 |
C4—C5—N51 | 131.2 (3) | H34A—C34—H34C | 109.5 |
C16—C11—C12 | 120.7 (3) | H34B—C34—H34C | 109.5 |
C16—C11—N1 | 118.7 (3) | C5—N51—C57 | 117.1 (3) |
C12—C11—N1 | 120.5 (3) | C5—N51—H51 | 108.5 |
C13—C12—C11 | 118.9 (3) | C57—N51—H51 | 110.0 |
C13—C12—H12 | 120.6 | N51—C57—C51 | 111.6 (3) |
C11—C12—H12 | 120.6 | N51—C57—H571 | 109.3 |
C14—C13—C12 | 120.7 (3) | C51—C57—H571 | 109.3 |
C14—C13—H13 | 119.6 | N51—C57—H572 | 109.3 |
C12—C13—H13 | 119.6 | C51—C57—H572 | 109.3 |
C13—C14—C15 | 119.6 (3) | H571—C57—H572 | 108.0 |
C13—C14—H14 | 120.2 | C52—C51—C56 | 118.6 (3) |
C15—C14—H14 | 120.2 | C52—C51—C57 | 120.0 (3) |
C14—C15—C16 | 120.5 (3) | C56—C51—C57 | 121.4 (3) |
C14—C15—H15 | 119.8 | C53—C52—C51 | 121.2 (3) |
C16—C15—H15 | 119.8 | C53—C52—H52 | 119.4 |
C11—C16—C15 | 119.6 (3) | C51—C52—H52 | 119.4 |
C11—C16—H16 | 120.2 | C44—C53—C52 | 118.8 (3) |
C15—C16—H16 | 120.2 | C44—C53—H53 | 120.6 |
C3—C31—C34 | 110.0 (3) | C52—C53—H53 | 120.6 |
C3—C31—C33 | 107.8 (3) | C53—C44—C55 | 121.4 (3) |
C34—C31—C33 | 109.3 (3) | C53—C44—Br54 | 118.9 (3) |
C3—C31—C32 | 110.8 (3) | C55—C44—Br54 | 119.7 (3) |
C34—C31—C32 | 109.2 (3) | C44—C55—C56 | 119.2 (3) |
C33—C31—C32 | 109.7 (3) | C44—C55—H55 | 120.4 |
C31—C32—H32A | 109.5 | C56—C55—H55 | 120.4 |
C31—C32—H32B | 109.5 | C55—C56—C51 | 120.7 (3) |
H32A—C32—H32B | 109.5 | C55—C56—H56 | 119.7 |
C31—C32—H32C | 109.5 | C51—C56—H56 | 119.7 |
C5—N1—N2—C3 | 1.6 (3) | C14—C15—C16—C11 | −0.3 (5) |
C11—N1—N2—C3 | 178.0 (3) | N2—C3—C31—C34 | −127.6 (3) |
N1—N2—C3—C4 | −0.6 (3) | C4—C3—C31—C34 | 56.0 (4) |
N1—N2—C3—C31 | −177.5 (3) | N2—C3—C31—C33 | 113.3 (3) |
N2—C3—C4—C5 | −0.6 (4) | C4—C3—C31—C33 | −63.0 (4) |
C31—C3—C4—C5 | 176.0 (3) | N2—C3—C31—C32 | −6.8 (4) |
N2—N1—C5—C4 | −2.1 (3) | C4—C3—C31—C32 | 176.9 (3) |
C11—N1—C5—C4 | −177.9 (3) | N1—C5—N51—C57 | −171.9 (3) |
N2—N1—C5—N51 | 179.7 (3) | C4—C5—N51—C57 | 10.4 (5) |
C11—N1—C5—N51 | 3.9 (5) | C5—N51—C57—C51 | −166.3 (3) |
C3—C4—C5—N1 | 1.6 (3) | N51—C57—C51—C52 | −142.8 (3) |
C3—C4—C5—N51 | 179.6 (3) | N51—C57—C51—C56 | 38.3 (4) |
C5—N1—C11—C16 | 144.7 (3) | C56—C51—C52—C53 | 2.6 (5) |
N2—N1—C11—C16 | −30.9 (4) | C57—C51—C52—C53 | −176.4 (3) |
C5—N1—C11—C12 | −37.4 (5) | C51—C52—C53—C44 | −2.3 (5) |
N2—N1—C11—C12 | 147.0 (3) | C52—C53—C44—C55 | 0.1 (5) |
C16—C11—C12—C13 | −3.1 (5) | C52—C53—C44—Br54 | 180.0 (3) |
N1—C11—C12—C13 | 179.1 (3) | C53—C44—C55—C56 | 1.7 (5) |
C11—C12—C13—C14 | 1.5 (5) | Br54—C44—C55—C56 | −178.2 (2) |
C12—C13—C14—C15 | 0.6 (5) | C44—C55—C56—C51 | −1.4 (5) |
C13—C14—C15—C16 | −1.3 (5) | C52—C51—C56—C55 | −0.8 (5) |
C12—C11—C16—C15 | 2.5 (5) | C57—C51—C56—C55 | 178.2 (3) |
N1—C11—C16—C15 | −179.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···N51 | 0.95 | 2.51 | 2.980 (4) | 111 |
N51—H51···Cg1i | 0.88 | 2.72 | 3.504 (3) | 148 |
C15—H15···Cg3ii | 0.95 | 2.95 | 3.687 (4) | 135 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x, −y, −z. |
C20H22N4O2 | F(000) = 744 |
Mr = 350.42 | Dx = 1.271 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4192 reflections |
a = 9.6594 (11) Å | θ = 2.9–27.5° |
b = 12.3991 (11) Å | µ = 0.09 mm−1 |
c = 15.4338 (15) Å | T = 120 K |
β = 97.744 (8)° | Block, colourless |
V = 1831.6 (3) Å3 | 0.29 × 0.27 × 0.24 mm |
Z = 4 |
Bruker–Nonius KappaCCD diffractometer | 4192 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 2657 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.078 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ and ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −16→15 |
Tmin = 0.959, Tmax = 0.980 | l = −20→20 |
29100 measured reflections |
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)] = 0.062 | H-atom parameters constrained |
wR(F2) = 0.169 | w = 1/[σ2(Fo2) + (0.0706P)2 + 1.4326P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
4192 reflections | Δρmax = 0.66 e Å−3 |
239 parameters | Δρmin = −0.33 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: 0.017 (2) |
C20H22N4O2 | V = 1831.6 (3) Å3 |
Mr = 350.42 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.6594 (11) Å | µ = 0.09 mm−1 |
b = 12.3991 (11) Å | T = 120 K |
c = 15.4338 (15) Å | 0.29 × 0.27 × 0.24 mm |
β = 97.744 (8)° |
Bruker–Nonius KappaCCD diffractometer | 4192 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2657 reflections with I > 2σ(I) |
Tmin = 0.959, Tmax = 0.980 | Rint = 0.078 |
29100 measured reflections |
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.66 e Å−3 |
4192 reflections | Δρmin = −0.33 e Å−3 |
239 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.54515 (19) | 0.29546 (15) | 0.37184 (12) | 0.0206 (4) | |
N2 | 0.5523 (2) | 0.40273 (15) | 0.34981 (13) | 0.0229 (5) | |
C3 | 0.6634 (2) | 0.43900 (19) | 0.40051 (15) | 0.0232 (5) | |
C4 | 0.7276 (3) | 0.35830 (19) | 0.45548 (16) | 0.0242 (5) | |
H4 | 0.8088 | 0.3650 | 0.4973 | 0.029* | |
C5 | 0.6483 (2) | 0.26791 (19) | 0.43621 (15) | 0.0218 (5) | |
C11 | 0.4367 (2) | 0.23064 (19) | 0.32945 (14) | 0.0216 (5) | |
C12 | 0.4654 (3) | 0.1275 (2) | 0.30360 (16) | 0.0267 (6) | |
H12 | 0.5581 | 0.1003 | 0.3142 | 0.032* | |
C13 | 0.3596 (3) | 0.0642 (2) | 0.26241 (17) | 0.0321 (6) | |
H13 | 0.3790 | −0.0075 | 0.2460 | 0.038* | |
C14 | 0.2261 (3) | 0.1039 (2) | 0.24483 (17) | 0.0316 (6) | |
H14 | 0.1534 | 0.0600 | 0.2161 | 0.038* | |
C15 | 0.1980 (3) | 0.2078 (2) | 0.26904 (16) | 0.0288 (6) | |
H15 | 0.1061 | 0.2360 | 0.2559 | 0.035* | |
C16 | 0.3028 (2) | 0.2712 (2) | 0.31232 (15) | 0.0250 (5) | |
H16 | 0.2829 | 0.3422 | 0.3302 | 0.030* | |
C31 | 0.7023 (3) | 0.55641 (19) | 0.39837 (16) | 0.0273 (6) | |
C32 | 0.8514 (3) | 0.5736 (3) | 0.4381 (3) | 0.0600 (11) | |
H32A | 0.8633 | 0.5501 | 0.4993 | 0.090* | |
H32B | 0.8748 | 0.6503 | 0.4353 | 0.090* | |
H32C | 0.9133 | 0.5316 | 0.4057 | 0.090* | |
C33 | 0.6033 (4) | 0.6183 (2) | 0.4499 (2) | 0.0473 (8) | |
H33A | 0.5070 | 0.6097 | 0.4214 | 0.071* | |
H33B | 0.6282 | 0.6950 | 0.4518 | 0.071* | |
H33C | 0.6113 | 0.5899 | 0.5096 | 0.071* | |
C34 | 0.6827 (3) | 0.5997 (2) | 0.30547 (19) | 0.0416 (7) | |
H34A | 0.7484 | 0.5638 | 0.2718 | 0.062* | |
H34B | 0.7003 | 0.6776 | 0.3065 | 0.062* | |
H34C | 0.5868 | 0.5857 | 0.2782 | 0.062* | |
N51 | 0.6612 (2) | 0.16617 (16) | 0.47086 (13) | 0.0234 (5) | |
H51 | 0.5823 | 0.1299 | 0.4673 | 0.028* | |
C51 | 0.8964 (2) | 0.14249 (17) | 0.55521 (15) | 0.0206 (5) | |
C52 | 0.9570 (2) | 0.14165 (18) | 0.47924 (15) | 0.0216 (5) | |
H52 | 0.9004 | 0.1517 | 0.4245 | 0.026* | |
C53 | 1.0986 (3) | 0.12631 (18) | 0.48192 (16) | 0.0235 (5) | |
H53 | 1.1403 | 0.1241 | 0.4296 | 0.028* | |
C54 | 1.1782 (2) | 0.11428 (18) | 0.56191 (16) | 0.0236 (5) | |
C55 | 1.1214 (3) | 0.11572 (19) | 0.63885 (16) | 0.0247 (5) | |
H55 | 1.1786 | 0.1079 | 0.6936 | 0.030* | |
C56 | 0.9799 (3) | 0.12875 (19) | 0.63437 (15) | 0.0243 (5) | |
H56 | 0.9383 | 0.1283 | 0.6867 | 0.029* | |
C57 | 0.7421 (2) | 0.1560 (2) | 0.55646 (15) | 0.0237 (5) | |
H571 | 0.7071 | 0.0931 | 0.5865 | 0.028* | |
H572 | 0.7266 | 0.2211 | 0.5911 | 0.028* | |
N54 | 1.3281 (2) | 0.09935 (16) | 0.56544 (16) | 0.0304 (5) | |
O41 | 1.37432 (19) | 0.08451 (15) | 0.49616 (14) | 0.0381 (5) | |
O42 | 1.40060 (19) | 0.10297 (16) | 0.63617 (14) | 0.0408 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0202 (10) | 0.0182 (10) | 0.0225 (10) | −0.0006 (8) | −0.0003 (8) | 0.0001 (8) |
N2 | 0.0243 (10) | 0.0201 (10) | 0.0241 (10) | −0.0017 (8) | 0.0019 (8) | 0.0009 (8) |
C3 | 0.0207 (12) | 0.0237 (13) | 0.0255 (12) | −0.0010 (10) | 0.0044 (10) | −0.0032 (10) |
C4 | 0.0198 (12) | 0.0252 (13) | 0.0264 (12) | −0.0006 (9) | −0.0007 (10) | −0.0029 (10) |
C5 | 0.0182 (11) | 0.0229 (12) | 0.0242 (12) | 0.0015 (9) | 0.0025 (9) | 0.0001 (10) |
C11 | 0.0214 (12) | 0.0248 (12) | 0.0181 (11) | −0.0024 (9) | 0.0007 (9) | 0.0021 (9) |
C12 | 0.0259 (13) | 0.0274 (13) | 0.0260 (13) | −0.0004 (10) | 0.0006 (10) | −0.0006 (10) |
C13 | 0.0347 (15) | 0.0262 (14) | 0.0333 (14) | −0.0052 (11) | −0.0027 (12) | −0.0049 (11) |
C14 | 0.0300 (14) | 0.0317 (15) | 0.0305 (14) | −0.0097 (11) | −0.0046 (11) | −0.0018 (11) |
C15 | 0.0216 (12) | 0.0357 (15) | 0.0271 (13) | −0.0032 (11) | −0.0037 (10) | 0.0059 (11) |
C16 | 0.0243 (13) | 0.0248 (13) | 0.0250 (12) | −0.0004 (10) | 0.0006 (10) | 0.0027 (10) |
C31 | 0.0275 (13) | 0.0212 (12) | 0.0326 (13) | −0.0040 (10) | 0.0021 (11) | −0.0029 (10) |
C32 | 0.0401 (18) | 0.0311 (17) | 0.100 (3) | −0.0104 (14) | −0.0210 (19) | 0.0092 (17) |
C33 | 0.064 (2) | 0.0319 (16) | 0.0496 (19) | −0.0035 (14) | 0.0189 (16) | −0.0051 (13) |
C34 | 0.0476 (18) | 0.0308 (15) | 0.0468 (18) | −0.0077 (13) | 0.0078 (14) | 0.0051 (13) |
N51 | 0.0185 (10) | 0.0236 (10) | 0.0266 (10) | −0.0019 (8) | −0.0021 (8) | 0.0028 (8) |
C51 | 0.0225 (12) | 0.0153 (11) | 0.0231 (12) | −0.0004 (9) | 0.0000 (10) | 0.0002 (9) |
C52 | 0.0238 (12) | 0.0198 (12) | 0.0205 (11) | −0.0007 (9) | 0.0004 (9) | 0.0031 (9) |
C53 | 0.0264 (13) | 0.0183 (12) | 0.0270 (12) | −0.0011 (9) | 0.0080 (10) | 0.0021 (9) |
C54 | 0.0197 (12) | 0.0159 (11) | 0.0349 (14) | 0.0005 (9) | 0.0023 (10) | 0.0007 (10) |
C55 | 0.0248 (13) | 0.0236 (12) | 0.0237 (12) | 0.0013 (10) | −0.0038 (10) | 0.0001 (10) |
C56 | 0.0267 (13) | 0.0240 (12) | 0.0220 (12) | 0.0003 (10) | 0.0027 (10) | −0.0011 (10) |
C57 | 0.0215 (12) | 0.0276 (13) | 0.0220 (12) | 0.0002 (10) | 0.0030 (10) | 0.0010 (10) |
N54 | 0.0224 (11) | 0.0207 (11) | 0.0478 (14) | −0.0008 (8) | 0.0040 (11) | 0.0033 (10) |
O41 | 0.0270 (10) | 0.0330 (11) | 0.0575 (13) | −0.0012 (8) | 0.0170 (9) | −0.0008 (9) |
O42 | 0.0248 (10) | 0.0425 (12) | 0.0514 (13) | 0.0026 (8) | −0.0079 (9) | 0.0065 (9) |
N1—C5 | 1.353 (3) | C32—H32C | 0.9800 |
N1—N2 | 1.377 (3) | C33—H33A | 0.9800 |
N1—C11 | 1.409 (3) | C33—H33B | 0.9800 |
N2—C3 | 1.319 (3) | C33—H33C | 0.9800 |
C3—C4 | 1.401 (3) | C34—H34A | 0.9800 |
C3—C31 | 1.505 (3) | C34—H34B | 0.9800 |
C4—C5 | 1.367 (3) | C34—H34C | 0.9800 |
C4—H4 | 0.9500 | N51—C57 | 1.447 (3) |
C5—N51 | 1.369 (3) | N51—H51 | 0.8801 |
C11—C12 | 1.379 (3) | C57—C51 | 1.503 (3) |
C11—C16 | 1.380 (3) | C57—H571 | 0.9900 |
C12—C13 | 1.375 (3) | C57—H572 | 0.9900 |
C12—H12 | 0.9500 | C51—C52 | 1.379 (3) |
C13—C14 | 1.372 (4) | C51—C56 | 1.381 (3) |
C13—H13 | 0.9500 | C52—C53 | 1.376 (3) |
C14—C15 | 1.379 (4) | C52—H52 | 0.9500 |
C14—H14 | 0.9500 | C53—C54 | 1.372 (3) |
C15—C16 | 1.380 (3) | C53—H53 | 0.9500 |
C15—H15 | 0.9500 | C54—C55 | 1.374 (3) |
C16—H16 | 0.9500 | C54—N54 | 1.453 (3) |
C31—C32 | 1.503 (4) | C55—C56 | 1.369 (3) |
C31—C34 | 1.519 (4) | C55—H55 | 0.9500 |
C31—C33 | 1.530 (4) | C56—H56 | 0.9500 |
C32—H32A | 0.9800 | N54—O42 | 1.216 (3) |
C32—H32B | 0.9800 | N54—O41 | 1.227 (3) |
C5—N1—N2 | 111.64 (18) | C31—C33—H33A | 109.5 |
C5—N1—C11 | 128.7 (2) | C31—C33—H33B | 109.5 |
N2—N1—C11 | 119.68 (18) | H33A—C33—H33B | 109.5 |
C3—N2—N1 | 104.28 (18) | C31—C33—H33C | 109.5 |
N2—C3—C4 | 111.9 (2) | H33A—C33—H33C | 109.5 |
N2—C3—C31 | 120.1 (2) | H33B—C33—H33C | 109.5 |
C4—C3—C31 | 127.8 (2) | C31—C34—H34A | 109.5 |
C5—C4—C3 | 105.4 (2) | C31—C34—H34B | 109.5 |
C5—C4—H4 | 127.3 | H34A—C34—H34B | 109.5 |
C3—C4—H4 | 127.3 | C31—C34—H34C | 109.5 |
N1—C5—C4 | 106.7 (2) | H34A—C34—H34C | 109.5 |
N1—C5—N51 | 122.6 (2) | H34B—C34—H34C | 109.5 |
C4—C5—N51 | 130.7 (2) | C5—N51—C57 | 116.49 (19) |
C12—C11—C16 | 120.2 (2) | C5—N51—H51 | 114.5 |
C12—C11—N1 | 119.8 (2) | C57—N51—H51 | 111.6 |
C16—C11—N1 | 120.0 (2) | N51—C57—C51 | 114.4 (2) |
C13—C12—C11 | 119.8 (2) | N51—C57—H571 | 108.7 |
C13—C12—H12 | 120.1 | C51—C57—H571 | 108.7 |
C11—C12—H12 | 120.1 | N51—C57—H572 | 108.7 |
C14—C13—C12 | 120.4 (2) | C51—C57—H572 | 108.7 |
C14—C13—H13 | 119.8 | H571—C57—H572 | 107.6 |
C12—C13—H13 | 119.8 | C52—C51—C56 | 119.2 (2) |
C13—C14—C15 | 119.7 (2) | C52—C51—C57 | 123.1 (2) |
C13—C14—H14 | 120.1 | C56—C51—C57 | 117.7 (2) |
C15—C14—H14 | 120.1 | C53—C52—C51 | 120.6 (2) |
C14—C15—C16 | 120.3 (2) | C53—C52—H52 | 119.7 |
C14—C15—H15 | 119.8 | C51—C52—H52 | 119.7 |
C16—C15—H15 | 119.8 | C54—C53—C52 | 118.5 (2) |
C11—C16—C15 | 119.5 (2) | C54—C53—H53 | 120.8 |
C11—C16—H16 | 120.2 | C52—C53—H53 | 120.8 |
C15—C16—H16 | 120.2 | C53—C54—C55 | 122.4 (2) |
C32—C31—C3 | 110.9 (2) | C53—C54—N54 | 118.8 (2) |
C32—C31—C34 | 109.0 (2) | C55—C54—N54 | 118.8 (2) |
C3—C31—C34 | 111.3 (2) | C56—C55—C54 | 118.1 (2) |
C32—C31—C33 | 110.4 (3) | C56—C55—H55 | 121.0 |
C3—C31—C33 | 107.4 (2) | C54—C55—H55 | 121.0 |
C34—C31—C33 | 107.9 (2) | C55—C56—C51 | 121.3 (2) |
C31—C32—H32A | 109.5 | C55—C56—H56 | 119.4 |
C31—C32—H32B | 109.5 | C51—C56—H56 | 119.4 |
H32A—C32—H32B | 109.5 | O42—N54—O41 | 123.7 (2) |
C31—C32—H32C | 109.5 | O42—N54—C54 | 118.6 (2) |
H32A—C32—H32C | 109.5 | O41—N54—C54 | 117.7 (2) |
H32B—C32—H32C | 109.5 | ||
C5—N1—N2—C3 | 1.4 (2) | C4—C3—C31—C32 | 21.8 (4) |
C11—N1—N2—C3 | −180.0 (2) | N2—C3—C31—C34 | −40.9 (3) |
N1—N2—C3—C4 | −0.7 (3) | C4—C3—C31—C34 | 143.3 (3) |
N1—N2—C3—C31 | −177.1 (2) | N2—C3—C31—C33 | 77.0 (3) |
N2—C3—C4—C5 | −0.3 (3) | C4—C3—C31—C33 | −98.9 (3) |
C31—C3—C4—C5 | 175.8 (2) | N1—C5—N51—C57 | −159.4 (2) |
N2—N1—C5—C4 | −1.6 (3) | C4—C5—N51—C57 | 20.5 (4) |
C11—N1—C5—C4 | 179.9 (2) | C5—N51—C57—C51 | −86.6 (3) |
N2—N1—C5—N51 | 178.4 (2) | N51—C57—C51—C52 | 1.1 (3) |
C11—N1—C5—N51 | −0.1 (4) | N51—C57—C51—C56 | −177.9 (2) |
C3—C4—C5—N1 | 1.1 (3) | C56—C51—C52—C53 | 0.6 (3) |
C3—C4—C5—N51 | −178.8 (2) | C57—C51—C52—C53 | −178.4 (2) |
C5—N1—C11—C12 | −43.7 (3) | C51—C52—C53—C54 | −1.4 (3) |
N2—N1—C11—C12 | 137.9 (2) | C52—C53—C54—C55 | 0.8 (3) |
C5—N1—C11—C16 | 137.6 (2) | C52—C53—C54—N54 | −179.3 (2) |
N2—N1—C11—C16 | −40.8 (3) | C53—C54—C55—C56 | 0.6 (3) |
C16—C11—C12—C13 | −1.5 (4) | N54—C54—C55—C56 | −179.3 (2) |
N1—C11—C12—C13 | 179.9 (2) | C54—C55—C56—C51 | −1.4 (3) |
C11—C12—C13—C14 | 1.7 (4) | C52—C51—C56—C55 | 0.8 (3) |
C12—C13—C14—C15 | −0.3 (4) | C57—C51—C56—C55 | 179.9 (2) |
C13—C14—C15—C16 | −1.3 (4) | C53—C54—N54—O42 | 170.4 (2) |
C12—C11—C16—C15 | −0.1 (3) | C55—C54—N54—O42 | −9.6 (3) |
N1—C11—C16—C15 | 178.6 (2) | C53—C54—N54—O41 | −9.1 (3) |
C14—C15—C16—C11 | 1.5 (4) | C55—C54—N54—O41 | 170.9 (2) |
N2—C3—C31—C32 | −162.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···N51 | 0.95 | 2.62 | 3.026 (3) | 106 |
N51—H51···O41i | 0.88 | 2.19 | 3.025 (3) | 158 |
Symmetry code: (i) x−1, y, z. |
C23H29N3O3 | Z = 4 |
Mr = 395.49 | F(000) = 848 |
Triclinic, P1 | Dx = 1.251 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.1533 (11) Å | Cell parameters from 9621 reflections |
b = 11.1645 (10) Å | θ = 2.8–27.5° |
c = 20.927 (2) Å | µ = 0.08 mm−1 |
α = 84.820 (8)° | T = 120 K |
β = 82.988 (8)° | Block, colourless |
γ = 63.153 (7)° | 0.48 × 0.35 × 0.25 mm |
V = 2099.0 (4) Å3 |
Bruker–Nonius KappaCCD diffractometer | 9621 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 5050 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.094 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ and ω scans | h = −13→13 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −14→14 |
Tmin = 0.961, Tmax = 0.986 | l = −27→27 |
50489 measured reflections |
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)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.174 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0692P)2 + 1.2088P] where P = (Fo2 + 2Fc2)/3 |
9621 reflections | (Δ/σ)max = 0.001 |
535 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
C23H29N3O3 | γ = 63.153 (7)° |
Mr = 395.49 | V = 2099.0 (4) Å3 |
Triclinic, P1 | Z = 4 |
a = 10.1533 (11) Å | Mo Kα radiation |
b = 11.1645 (10) Å | µ = 0.08 mm−1 |
c = 20.927 (2) Å | T = 120 K |
α = 84.820 (8)° | 0.48 × 0.35 × 0.25 mm |
β = 82.988 (8)° |
Bruker–Nonius KappaCCD diffractometer | 9621 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 5050 reflections with I > 2σ(I) |
Tmin = 0.961, Tmax = 0.986 | Rint = 0.094 |
50489 measured reflections |
R[F2 > 2σ(F2)] = 0.064 | 0 restraints |
wR(F2) = 0.174 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.48 e Å−3 |
9621 reflections | Δρmin = −0.35 e Å−3 |
535 parameters |
x | y | z | Uiso*/Ueq | ||
N11 | 0.4845 (2) | 0.5027 (2) | 0.37462 (9) | 0.0215 (5) | |
N12 | 0.4429 (2) | 0.6033 (2) | 0.32691 (10) | 0.0237 (5) | |
C13 | 0.3008 (3) | 0.6418 (3) | 0.32406 (12) | 0.0233 (6) | |
C14 | 0.2485 (3) | 0.5671 (3) | 0.36792 (12) | 0.0247 (6) | |
H14 | 0.1501 | 0.5766 | 0.3748 | 0.030* | |
C15 | 0.3685 (3) | 0.4777 (3) | 0.39877 (12) | 0.0230 (6) | |
C111 | 0.6336 (3) | 0.4403 (2) | 0.38909 (12) | 0.0231 (6) | |
C112 | 0.6730 (3) | 0.3844 (3) | 0.44909 (13) | 0.0263 (6) | |
H112 | 0.5990 | 0.3879 | 0.4824 | 0.032* | |
C113 | 0.8195 (3) | 0.3234 (3) | 0.46074 (14) | 0.0335 (7) | |
H113 | 0.8470 | 0.2841 | 0.5022 | 0.040* | |
C114 | 0.9268 (3) | 0.3189 (3) | 0.41289 (15) | 0.0368 (7) | |
H114 | 1.0282 | 0.2756 | 0.4211 | 0.044* | |
C115 | 0.8871 (3) | 0.3771 (3) | 0.35320 (15) | 0.0349 (7) | |
H115 | 0.9610 | 0.3756 | 0.3203 | 0.042* | |
C116 | 0.7411 (3) | 0.4372 (3) | 0.34092 (13) | 0.0272 (6) | |
H116 | 0.7138 | 0.4766 | 0.2995 | 0.033* | |
C131 | 0.2167 (3) | 0.7451 (3) | 0.27459 (12) | 0.0259 (6) | |
C132 | 0.2825 (3) | 0.8429 (3) | 0.25543 (13) | 0.0332 (7) | |
H12A | 0.2759 | 0.8921 | 0.2931 | 0.050* | |
H12B | 0.2273 | 0.9065 | 0.2218 | 0.050* | |
H12C | 0.3867 | 0.7931 | 0.2390 | 0.050* | |
C133 | 0.2247 (3) | 0.6728 (3) | 0.21475 (13) | 0.0325 (7) | |
H13A | 0.3284 | 0.6231 | 0.1978 | 0.049* | |
H13B | 0.1691 | 0.7388 | 0.1819 | 0.049* | |
H13C | 0.1815 | 0.6101 | 0.2261 | 0.049* | |
C134 | 0.0560 (3) | 0.8233 (3) | 0.30055 (14) | 0.0374 (7) | |
H14A | 0.0105 | 0.7620 | 0.3098 | 0.056* | |
H14B | 0.0024 | 0.8925 | 0.2684 | 0.056* | |
H14C | 0.0513 | 0.8661 | 0.3402 | 0.056* | |
N151 | 0.3801 (2) | 0.3805 (2) | 0.44557 (10) | 0.0249 (5) | |
H151 | 0.4609 | 0.3038 | 0.4421 | 0.030* | |
C157 | 0.2476 (3) | 0.3603 (3) | 0.45965 (13) | 0.0301 (6) | |
H57A | 0.2133 | 0.3512 | 0.4189 | 0.036* | |
H57B | 0.1678 | 0.4395 | 0.4813 | 0.036* | |
C151 | 0.2780 (3) | 0.2370 (3) | 0.50204 (12) | 0.0252 (6) | |
C152 | 0.2948 (3) | 0.1215 (3) | 0.47569 (12) | 0.0245 (6) | |
H152 | 0.2845 | 0.1212 | 0.4312 | 0.029* | |
C153 | 0.3266 (3) | 0.0065 (3) | 0.51401 (12) | 0.0235 (6) | |
C154 | 0.3460 (3) | 0.0051 (2) | 0.57797 (12) | 0.0224 (6) | |
C155 | 0.3286 (3) | 0.1213 (3) | 0.60472 (12) | 0.0236 (6) | |
C156 | 0.2927 (3) | 0.2376 (3) | 0.56680 (12) | 0.0265 (6) | |
H156 | 0.2781 | 0.3179 | 0.5852 | 0.032* | |
O13 | 0.3456 (2) | −0.11283 (18) | 0.49307 (8) | 0.0303 (4) | |
C136 | 0.3171 (3) | −0.1144 (3) | 0.42827 (13) | 0.0360 (7) | |
H16A | 0.2134 | −0.0521 | 0.4226 | 0.054* | |
H16B | 0.3360 | −0.2054 | 0.4187 | 0.054* | |
H16C | 0.3822 | −0.0867 | 0.3989 | 0.054* | |
O14 | 0.38984 (19) | −0.11335 (17) | 0.61413 (8) | 0.0255 (4) | |
C137 | 0.2707 (3) | −0.1236 (3) | 0.65358 (13) | 0.0303 (6) | |
H17A | 0.2278 | −0.0515 | 0.6844 | 0.045* | |
H17B | 0.3077 | −0.2109 | 0.6771 | 0.045* | |
H17C | 0.1947 | −0.1155 | 0.6265 | 0.045* | |
O15 | 0.3523 (2) | 0.10801 (18) | 0.66821 (8) | 0.0294 (4) | |
C138 | 0.3325 (3) | 0.2260 (3) | 0.69753 (13) | 0.0317 (7) | |
H18A | 0.3981 | 0.2611 | 0.6740 | 0.048* | |
H18B | 0.3567 | 0.2041 | 0.7424 | 0.048* | |
H18C | 0.2292 | 0.2940 | 0.6964 | 0.048* | |
N21 | 0.9342 (2) | 0.5185 (2) | 0.87675 (10) | 0.0233 (5) | |
N22 | 0.8767 (2) | 0.6204 (2) | 0.83089 (10) | 0.0248 (5) | |
C23 | 0.7324 (3) | 0.6593 (3) | 0.83826 (12) | 0.0252 (6) | |
C24 | 0.6943 (3) | 0.5851 (3) | 0.88833 (12) | 0.0246 (6) | |
H24 | 0.5975 | 0.5964 | 0.9036 | 0.029* | |
C25 | 0.8253 (3) | 0.4930 (3) | 0.91064 (11) | 0.0226 (6) | |
C211 | 1.0891 (3) | 0.4567 (2) | 0.88130 (12) | 0.0220 (6) | |
C212 | 1.1495 (3) | 0.3944 (3) | 0.93789 (12) | 0.0264 (6) | |
H212 | 1.0872 | 0.3919 | 0.9752 | 0.032* | |
C213 | 1.3012 (3) | 0.3358 (3) | 0.93968 (13) | 0.0292 (6) | |
H213 | 1.3433 | 0.2913 | 0.9783 | 0.035* | |
C214 | 1.3919 (3) | 0.3411 (3) | 0.88638 (13) | 0.0306 (6) | |
H214 | 1.4964 | 0.3003 | 0.8880 | 0.037* | |
C215 | 1.3306 (3) | 0.4057 (3) | 0.83074 (13) | 0.0287 (6) | |
H215 | 1.3928 | 0.4111 | 0.7940 | 0.034* | |
C216 | 1.1799 (3) | 0.4625 (3) | 0.82787 (12) | 0.0252 (6) | |
H216 | 1.1383 | 0.5059 | 0.7890 | 0.030* | |
C231 | 0.6306 (3) | 0.7693 (3) | 0.79524 (13) | 0.0280 (6) | |
C232 | 0.7078 (4) | 0.7734 (4) | 0.72993 (16) | 0.0725 (13) | |
H22A | 0.7425 | 0.6870 | 0.7099 | 0.109* | |
H22B | 0.7928 | 0.7906 | 0.7342 | 0.109* | |
H22C | 0.6388 | 0.8452 | 0.7030 | 0.109* | |
C233 | 0.4964 (4) | 0.7500 (4) | 0.7893 (2) | 0.0805 (15) | |
H23A | 0.4439 | 0.7523 | 0.8321 | 0.121* | |
H23B | 0.5265 | 0.6630 | 0.7707 | 0.121* | |
H23C | 0.4307 | 0.8220 | 0.7614 | 0.121* | |
C234 | 0.5794 (5) | 0.9038 (3) | 0.82534 (19) | 0.0680 (12) | |
H24A | 0.6652 | 0.9205 | 0.8284 | 0.102* | |
H24B | 0.5303 | 0.9024 | 0.8685 | 0.102* | |
H24C | 0.5096 | 0.9754 | 0.7985 | 0.102* | |
N251 | 0.8534 (2) | 0.3909 (2) | 0.95660 (10) | 0.0238 (5) | |
H251 | 0.9324 | 0.3143 | 0.9494 | 0.029* | |
C257 | 0.7249 (3) | 0.3702 (3) | 0.98259 (12) | 0.0258 (6) | |
H271 | 0.6702 | 0.3688 | 0.9468 | 0.031* | |
H272 | 0.6573 | 0.4453 | 1.0103 | 0.031* | |
C251 | 0.7731 (3) | 0.2405 (3) | 1.02110 (12) | 0.0248 (6) | |
C252 | 0.7750 (3) | 0.1311 (3) | 0.99469 (12) | 0.0265 (6) | |
H252 | 0.7399 | 0.1400 | 0.9536 | 0.032* | |
C253 | 0.8280 (3) | 0.0082 (3) | 1.02820 (12) | 0.0241 (6) | |
C254 | 0.8802 (3) | −0.0053 (2) | 1.08764 (12) | 0.0234 (6) | |
C255 | 0.8760 (3) | 0.1064 (3) | 1.11431 (12) | 0.0242 (6) | |
C256 | 0.8224 (3) | 0.2290 (3) | 1.08126 (12) | 0.0260 (6) | |
H256 | 0.8192 | 0.3051 | 1.0996 | 0.031* | |
O23 | 0.8383 (2) | −0.10741 (18) | 1.00659 (9) | 0.0322 (5) | |
C236 | 0.7802 (3) | −0.0986 (3) | 0.94749 (13) | 0.0366 (7) | |
H26A | 0.8308 | −0.0641 | 0.9134 | 0.055* | |
H26B | 0.6739 | −0.0377 | 0.9512 | 0.055* | |
H26C | 0.7957 | −0.1880 | 0.9368 | 0.055* | |
O24 | 0.94095 (19) | −0.12907 (17) | 1.11896 (8) | 0.0253 (4) | |
C237 | 0.8378 (3) | −0.1487 (3) | 1.16599 (12) | 0.0287 (6) | |
H27A | 0.7564 | −0.1475 | 1.1446 | 0.043* | |
H27B | 0.7981 | −0.0767 | 1.1967 | 0.043* | |
H27C | 0.8879 | −0.2356 | 1.1890 | 0.043* | |
O25 | 0.9283 (2) | 0.08157 (18) | 1.17327 (8) | 0.0307 (5) | |
C238 | 0.9182 (3) | 0.1937 (3) | 1.20450 (13) | 0.0333 (7) | |
H28A | 0.8147 | 0.2619 | 1.2091 | 0.050* | |
H28B | 0.9786 | 0.2318 | 1.1788 | 0.050* | |
H28C | 0.9545 | 0.1646 | 1.2472 | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N11 | 0.0227 (11) | 0.0187 (11) | 0.0246 (11) | −0.0102 (9) | −0.0044 (9) | 0.0009 (9) |
N12 | 0.0262 (12) | 0.0191 (11) | 0.0255 (11) | −0.0093 (9) | −0.0056 (9) | 0.0005 (9) |
C13 | 0.0238 (14) | 0.0208 (14) | 0.0252 (13) | −0.0086 (11) | −0.0035 (11) | −0.0062 (11) |
C14 | 0.0220 (13) | 0.0241 (14) | 0.0291 (14) | −0.0110 (11) | −0.0046 (11) | 0.0007 (11) |
C15 | 0.0270 (14) | 0.0216 (14) | 0.0229 (13) | −0.0128 (11) | −0.0032 (11) | −0.0016 (11) |
C111 | 0.0215 (13) | 0.0136 (13) | 0.0333 (15) | −0.0056 (11) | −0.0054 (11) | −0.0050 (11) |
C112 | 0.0272 (14) | 0.0199 (14) | 0.0334 (15) | −0.0109 (11) | −0.0060 (11) | −0.0027 (11) |
C113 | 0.0357 (16) | 0.0262 (15) | 0.0393 (16) | −0.0115 (13) | −0.0176 (13) | 0.0015 (13) |
C114 | 0.0240 (15) | 0.0279 (16) | 0.059 (2) | −0.0102 (12) | −0.0122 (14) | 0.0001 (14) |
C115 | 0.0273 (15) | 0.0284 (16) | 0.0514 (19) | −0.0151 (13) | −0.0020 (13) | 0.0002 (14) |
C116 | 0.0288 (15) | 0.0202 (14) | 0.0338 (15) | −0.0118 (12) | −0.0032 (12) | −0.0017 (12) |
C131 | 0.0264 (14) | 0.0210 (14) | 0.0297 (14) | −0.0093 (11) | −0.0057 (11) | −0.0018 (11) |
C132 | 0.0396 (17) | 0.0260 (15) | 0.0350 (16) | −0.0144 (13) | −0.0110 (13) | 0.0038 (12) |
C133 | 0.0333 (16) | 0.0302 (16) | 0.0339 (15) | −0.0124 (13) | −0.0099 (12) | −0.0017 (12) |
C134 | 0.0322 (16) | 0.0321 (17) | 0.0368 (16) | −0.0041 (13) | −0.0086 (13) | 0.0032 (13) |
N151 | 0.0205 (11) | 0.0208 (12) | 0.0310 (12) | −0.0075 (9) | −0.0033 (9) | 0.0017 (10) |
C157 | 0.0278 (15) | 0.0286 (15) | 0.0360 (16) | −0.0146 (12) | −0.0070 (12) | 0.0062 (12) |
C151 | 0.0183 (13) | 0.0245 (14) | 0.0333 (15) | −0.0103 (11) | −0.0046 (11) | 0.0033 (12) |
C152 | 0.0197 (13) | 0.0277 (15) | 0.0259 (13) | −0.0102 (11) | −0.0044 (10) | −0.0003 (12) |
C153 | 0.0217 (13) | 0.0204 (14) | 0.0309 (14) | −0.0111 (11) | −0.0016 (11) | −0.0045 (11) |
C154 | 0.0196 (13) | 0.0182 (13) | 0.0283 (14) | −0.0079 (11) | −0.0012 (10) | 0.0002 (11) |
C155 | 0.0251 (14) | 0.0250 (15) | 0.0243 (14) | −0.0140 (12) | −0.0042 (11) | 0.0003 (11) |
C156 | 0.0271 (14) | 0.0212 (14) | 0.0326 (15) | −0.0112 (12) | −0.0035 (11) | −0.0037 (12) |
O13 | 0.0399 (11) | 0.0249 (10) | 0.0276 (10) | −0.0144 (9) | −0.0053 (8) | −0.0055 (8) |
C136 | 0.0424 (17) | 0.0371 (17) | 0.0311 (15) | −0.0179 (14) | −0.0065 (13) | −0.0087 (13) |
O14 | 0.0280 (10) | 0.0192 (10) | 0.0281 (10) | −0.0097 (8) | −0.0017 (8) | −0.0002 (8) |
C137 | 0.0380 (16) | 0.0270 (15) | 0.0298 (15) | −0.0190 (13) | 0.0039 (12) | −0.0044 (12) |
O15 | 0.0436 (11) | 0.0232 (10) | 0.0262 (10) | −0.0183 (9) | −0.0058 (8) | −0.0020 (8) |
C138 | 0.0421 (17) | 0.0271 (15) | 0.0334 (15) | −0.0211 (13) | −0.0020 (13) | −0.0081 (12) |
N21 | 0.0245 (11) | 0.0199 (11) | 0.0251 (11) | −0.0092 (9) | −0.0051 (9) | 0.0017 (9) |
N22 | 0.0266 (12) | 0.0198 (11) | 0.0277 (12) | −0.0098 (10) | −0.0052 (9) | 0.0018 (9) |
C23 | 0.0288 (15) | 0.0213 (14) | 0.0255 (14) | −0.0103 (12) | −0.0034 (11) | −0.0044 (11) |
C24 | 0.0236 (14) | 0.0247 (14) | 0.0260 (14) | −0.0111 (11) | −0.0013 (11) | −0.0037 (11) |
C25 | 0.0277 (14) | 0.0202 (14) | 0.0221 (13) | −0.0120 (11) | −0.0023 (11) | −0.0040 (11) |
C211 | 0.0242 (14) | 0.0158 (13) | 0.0274 (14) | −0.0093 (11) | −0.0020 (11) | −0.0057 (11) |
C212 | 0.0283 (15) | 0.0231 (14) | 0.0278 (14) | −0.0110 (12) | −0.0015 (11) | −0.0039 (11) |
C213 | 0.0306 (15) | 0.0245 (15) | 0.0325 (15) | −0.0108 (12) | −0.0074 (12) | −0.0033 (12) |
C214 | 0.0236 (14) | 0.0290 (16) | 0.0394 (16) | −0.0110 (12) | −0.0039 (12) | −0.0045 (13) |
C215 | 0.0290 (15) | 0.0261 (15) | 0.0321 (15) | −0.0136 (12) | −0.0004 (12) | −0.0030 (12) |
C216 | 0.0285 (15) | 0.0215 (14) | 0.0263 (14) | −0.0114 (12) | −0.0039 (11) | −0.0008 (11) |
C231 | 0.0274 (14) | 0.0245 (15) | 0.0312 (15) | −0.0104 (12) | −0.0076 (11) | 0.0035 (12) |
C232 | 0.049 (2) | 0.082 (3) | 0.043 (2) | 0.005 (2) | −0.0047 (17) | 0.023 (2) |
C233 | 0.057 (2) | 0.078 (3) | 0.120 (4) | −0.041 (2) | −0.057 (2) | 0.057 (3) |
C234 | 0.085 (3) | 0.0309 (19) | 0.070 (3) | −0.0029 (19) | −0.039 (2) | 0.0020 (18) |
N251 | 0.0236 (11) | 0.0179 (11) | 0.0281 (12) | −0.0081 (9) | −0.0025 (9) | 0.0009 (9) |
C257 | 0.0251 (14) | 0.0249 (15) | 0.0283 (14) | −0.0126 (12) | −0.0016 (11) | 0.0023 (11) |
C251 | 0.0222 (13) | 0.0214 (14) | 0.0299 (14) | −0.0097 (11) | −0.0007 (11) | 0.0007 (11) |
C252 | 0.0267 (14) | 0.0274 (15) | 0.0278 (14) | −0.0138 (12) | −0.0043 (11) | −0.0001 (12) |
C253 | 0.0239 (14) | 0.0215 (14) | 0.0282 (14) | −0.0115 (11) | 0.0007 (11) | −0.0036 (11) |
C254 | 0.0229 (13) | 0.0191 (14) | 0.0262 (14) | −0.0087 (11) | −0.0007 (11) | 0.0024 (11) |
C255 | 0.0240 (13) | 0.0256 (15) | 0.0235 (13) | −0.0120 (11) | −0.0016 (11) | 0.0000 (11) |
C256 | 0.0286 (14) | 0.0210 (14) | 0.0310 (15) | −0.0131 (12) | −0.0027 (11) | −0.0023 (12) |
O23 | 0.0442 (12) | 0.0241 (10) | 0.0324 (10) | −0.0171 (9) | −0.0083 (9) | −0.0038 (8) |
C236 | 0.0456 (18) | 0.0352 (17) | 0.0330 (16) | −0.0193 (15) | −0.0093 (13) | −0.0061 (13) |
O24 | 0.0291 (10) | 0.0185 (9) | 0.0277 (10) | −0.0108 (8) | −0.0011 (8) | 0.0002 (8) |
C237 | 0.0352 (16) | 0.0246 (15) | 0.0302 (15) | −0.0168 (12) | −0.0022 (12) | −0.0020 (12) |
O25 | 0.0444 (12) | 0.0238 (10) | 0.0293 (10) | −0.0188 (9) | −0.0097 (8) | 0.0006 (8) |
C238 | 0.0452 (18) | 0.0309 (16) | 0.0305 (15) | −0.0218 (14) | −0.0059 (13) | −0.0034 (12) |
N11—C15 | 1.359 (3) | N21—C25 | 1.365 (3) |
N11—N12 | 1.382 (3) | N21—N22 | 1.377 (3) |
N11—C111 | 1.411 (3) | N21—C211 | 1.415 (3) |
N12—C13 | 1.314 (3) | N22—C23 | 1.319 (3) |
C13—C14 | 1.400 (4) | C23—C24 | 1.403 (4) |
C13—C131 | 1.497 (3) | C23—C231 | 1.506 (4) |
C14—C15 | 1.369 (3) | C24—C25 | 1.370 (3) |
C14—H14 | 0.9500 | C24—H24 | 0.9500 |
C15—N151 | 1.368 (3) | C25—N251 | 1.371 (3) |
C111—C112 | 1.372 (4) | C211—C216 | 1.376 (4) |
C111—C116 | 1.382 (4) | C211—C212 | 1.380 (4) |
C112—C113 | 1.371 (4) | C212—C213 | 1.379 (4) |
C112—H112 | 0.9500 | C212—H212 | 0.9500 |
C113—C114 | 1.373 (4) | C213—C214 | 1.372 (4) |
C113—H113 | 0.9500 | C213—H213 | 0.9500 |
C114—C115 | 1.373 (4) | C214—C215 | 1.372 (4) |
C114—H114 | 0.9500 | C214—H214 | 0.9500 |
C115—C116 | 1.370 (4) | C215—C216 | 1.373 (4) |
C115—H115 | 0.9500 | C215—H215 | 0.9500 |
C116—H116 | 0.9500 | C216—H216 | 0.9500 |
C131—C134 | 1.518 (4) | C231—C233 | 1.494 (4) |
C131—C132 | 1.521 (4) | C231—C232 | 1.498 (4) |
C131—C133 | 1.525 (4) | C231—C234 | 1.519 (4) |
C132—H12A | 0.9800 | C232—H22A | 0.9800 |
C132—H12B | 0.9800 | C232—H22B | 0.9800 |
C132—H12C | 0.9800 | C232—H22C | 0.9800 |
C133—H13A | 0.9800 | C233—H23A | 0.9800 |
C133—H13B | 0.9800 | C233—H23B | 0.9800 |
C133—H13C | 0.9800 | C233—H23C | 0.9800 |
C134—H14A | 0.9800 | C234—H24A | 0.9800 |
C134—H14B | 0.9800 | C234—H24B | 0.9800 |
C134—H14C | 0.9800 | C234—H24C | 0.9800 |
N151—C157 | 1.453 (3) | N251—C257 | 1.459 (3) |
N151—H151 | 0.8797 | N251—H251 | 0.8785 |
C157—C151 | 1.496 (4) | C257—C251 | 1.494 (3) |
C157—H57A | 0.9900 | C257—H271 | 0.9900 |
C157—H57B | 0.9900 | C257—H272 | 0.9900 |
C151—C152 | 1.380 (4) | C251—C252 | 1.377 (4) |
C151—C156 | 1.382 (4) | C251—C256 | 1.385 (4) |
C152—C153 | 1.378 (4) | C252—C253 | 1.384 (4) |
C152—H152 | 0.9500 | C252—H252 | 0.9500 |
C153—O13 | 1.362 (3) | C253—O23 | 1.361 (3) |
C153—C154 | 1.374 (4) | C253—C254 | 1.380 (4) |
C154—O14 | 1.375 (3) | C254—O24 | 1.373 (3) |
C154—C155 | 1.388 (4) | C254—C255 | 1.393 (4) |
C155—O15 | 1.362 (3) | C255—O25 | 1.359 (3) |
C155—C156 | 1.380 (4) | C255—C256 | 1.377 (4) |
C156—H156 | 0.9500 | C256—H256 | 0.9500 |
O13—C136 | 1.424 (3) | O23—C236 | 1.411 (3) |
C136—H16A | 0.9800 | C236—H26A | 0.9800 |
C136—H16B | 0.9800 | C236—H26B | 0.9800 |
C136—H16C | 0.9800 | C236—H26C | 0.9800 |
O14—C137 | 1.422 (3) | O24—C237 | 1.425 (3) |
C137—H17A | 0.9800 | C237—H27A | 0.9800 |
C137—H17B | 0.9800 | C237—H27B | 0.9800 |
C137—H17C | 0.9800 | C237—H27C | 0.9800 |
O15—C138 | 1.424 (3) | O25—C238 | 1.421 (3) |
C138—H18A | 0.9800 | C238—H28A | 0.9800 |
C138—H18B | 0.9800 | C238—H28B | 0.9800 |
C138—H18C | 0.9800 | C238—H28C | 0.9800 |
C15—N11—N12 | 110.92 (19) | C25—N21—N22 | 111.1 (2) |
C15—N11—C111 | 130.5 (2) | C25—N21—C211 | 130.6 (2) |
N12—N11—C111 | 118.5 (2) | N22—N21—C211 | 118.4 (2) |
C13—N12—N11 | 105.1 (2) | C23—N22—N21 | 105.1 (2) |
N12—C13—C14 | 111.6 (2) | N22—C23—C24 | 111.4 (2) |
N12—C13—C131 | 121.0 (2) | N22—C23—C231 | 120.7 (2) |
C14—C13—C131 | 127.2 (2) | C24—C23—C231 | 127.8 (2) |
C15—C14—C13 | 105.8 (2) | C25—C24—C23 | 105.8 (2) |
C15—C14—H14 | 127.1 | C25—C24—H24 | 127.1 |
C13—C14—H14 | 127.1 | C23—C24—H24 | 127.1 |
N11—C15—N151 | 123.0 (2) | N21—C25—C24 | 106.5 (2) |
N11—C15—C14 | 106.6 (2) | N21—C25—N251 | 123.1 (2) |
N151—C15—C14 | 130.3 (2) | C24—C25—N251 | 130.4 (2) |
C112—C111—C116 | 120.1 (2) | C216—C211—C212 | 120.0 (2) |
C112—C111—N11 | 121.7 (2) | C216—C211—N21 | 118.3 (2) |
C116—C111—N11 | 118.1 (2) | C212—C211—N21 | 121.7 (2) |
C113—C112—C111 | 119.7 (3) | C213—C212—C211 | 119.3 (2) |
C113—C112—H112 | 120.1 | C213—C212—H212 | 120.3 |
C111—C112—H112 | 120.1 | C211—C212—H212 | 120.3 |
C112—C113—C114 | 120.4 (3) | C214—C213—C212 | 120.8 (3) |
C112—C113—H113 | 119.8 | C214—C213—H213 | 119.6 |
C114—C113—H113 | 119.8 | C212—C213—H213 | 119.6 |
C113—C114—C115 | 119.8 (3) | C215—C214—C213 | 119.4 (3) |
C113—C114—H114 | 120.1 | C215—C214—H214 | 120.3 |
C115—C114—H114 | 120.1 | C213—C214—H214 | 120.3 |
C116—C115—C114 | 120.2 (3) | C214—C215—C216 | 120.5 (3) |
C116—C115—H115 | 119.9 | C214—C215—H215 | 119.8 |
C114—C115—H115 | 119.9 | C216—C215—H215 | 119.8 |
C115—C116—C111 | 119.7 (3) | C215—C216—C211 | 120.0 (2) |
C115—C116—H116 | 120.1 | C215—C216—H216 | 120.0 |
C111—C116—H116 | 120.1 | C211—C216—H216 | 120.0 |
C13—C131—C134 | 110.0 (2) | C233—C231—C232 | 110.2 (3) |
C13—C131—C132 | 111.8 (2) | C233—C231—C23 | 109.9 (2) |
C134—C131—C132 | 108.9 (2) | C232—C231—C23 | 111.3 (2) |
C13—C131—C133 | 108.3 (2) | C233—C231—C234 | 107.7 (3) |
C134—C131—C133 | 109.5 (2) | C232—C231—C234 | 108.3 (3) |
C132—C131—C133 | 108.3 (2) | C23—C231—C234 | 109.2 (2) |
C131—C132—H12A | 109.5 | C231—C232—H22A | 109.5 |
C131—C132—H12B | 109.5 | C231—C232—H22B | 109.5 |
H12A—C132—H12B | 109.5 | H22A—C232—H22B | 109.5 |
C131—C132—H12C | 109.5 | C231—C232—H22C | 109.5 |
H12A—C132—H12C | 109.5 | H22A—C232—H22C | 109.5 |
H12B—C132—H12C | 109.5 | H22B—C232—H22C | 109.5 |
C131—C133—H13A | 109.5 | C231—C233—H23A | 109.5 |
C131—C133—H13B | 109.5 | C231—C233—H23B | 109.5 |
H13A—C133—H13B | 109.5 | H23A—C233—H23B | 109.5 |
C131—C133—H13C | 109.5 | C231—C233—H23C | 109.5 |
H13A—C133—H13C | 109.5 | H23A—C233—H23C | 109.5 |
H13B—C133—H13C | 109.5 | H23B—C233—H23C | 109.5 |
C131—C134—H14A | 109.5 | C231—C234—H24A | 109.5 |
C131—C134—H14B | 109.5 | C231—C234—H24B | 109.5 |
H14A—C134—H14B | 109.5 | H24A—C234—H24B | 109.5 |
C131—C134—H14C | 109.5 | C231—C234—H24C | 109.5 |
H14A—C134—H14C | 109.5 | H24A—C234—H24C | 109.5 |
H14B—C134—H14C | 109.5 | H24B—C234—H24C | 109.5 |
C15—N151—C157 | 114.3 (2) | C25—N251—C257 | 115.0 (2) |
C15—N151—H151 | 116.4 | C25—N251—H251 | 118.0 |
C157—N151—H151 | 111.8 | C257—N251—H251 | 111.6 |
N151—C157—C151 | 110.8 (2) | N251—C257—C251 | 110.2 (2) |
N151—C157—H57A | 109.5 | N251—C257—H271 | 109.6 |
C151—C157—H57A | 109.5 | C251—C257—H271 | 109.6 |
N151—C157—H57B | 109.5 | N251—C257—H272 | 109.6 |
C151—C157—H57B | 109.5 | C251—C257—H272 | 109.6 |
H57A—C157—H57B | 108.1 | H271—C257—H272 | 108.1 |
C152—C151—C156 | 120.1 (2) | C252—C251—C256 | 120.5 (2) |
C152—C151—C157 | 119.5 (2) | C252—C251—C257 | 119.2 (2) |
C156—C151—C157 | 120.4 (3) | C256—C251—C257 | 120.2 (2) |
C153—C152—C151 | 119.9 (2) | C251—C252—C253 | 119.8 (2) |
C153—C152—H152 | 120.0 | C251—C252—H252 | 120.1 |
C151—C152—H152 | 120.0 | C253—C252—H252 | 120.1 |
O13—C153—C154 | 114.9 (2) | O23—C253—C254 | 114.6 (2) |
O13—C153—C152 | 124.8 (2) | O23—C253—C252 | 125.1 (2) |
C154—C153—C152 | 120.3 (2) | C254—C253—C252 | 120.3 (2) |
C153—C154—O14 | 119.5 (2) | O24—C254—C253 | 120.1 (2) |
C153—C154—C155 | 120.0 (2) | O24—C254—C255 | 120.4 (2) |
O14—C154—C155 | 120.5 (2) | C253—C254—C255 | 119.5 (2) |
O15—C155—C156 | 125.2 (2) | O25—C255—C256 | 125.3 (2) |
O15—C155—C154 | 115.0 (2) | O25—C255—C254 | 114.3 (2) |
C156—C155—C154 | 119.8 (2) | C256—C255—C254 | 120.3 (2) |
C155—C156—C151 | 119.9 (2) | C255—C256—C251 | 119.6 (2) |
C155—C156—H156 | 120.0 | C255—C256—H256 | 120.2 |
C151—C156—H156 | 120.0 | C251—C256—H256 | 120.2 |
C153—O13—C136 | 117.0 (2) | C253—O23—C236 | 117.2 (2) |
O13—C136—H16A | 109.5 | O23—C236—H26A | 109.5 |
O13—C136—H16B | 109.5 | O23—C236—H26B | 109.5 |
H16A—C136—H16B | 109.5 | H26A—C236—H26B | 109.5 |
O13—C136—H16C | 109.5 | O23—C236—H26C | 109.5 |
H16A—C136—H16C | 109.5 | H26A—C236—H26C | 109.5 |
H16B—C136—H16C | 109.5 | H26B—C236—H26C | 109.5 |
C154—O14—C137 | 113.01 (19) | C254—O24—C237 | 112.51 (19) |
O14—C137—H17A | 109.5 | O24—C237—H27A | 109.5 |
O14—C137—H17B | 109.5 | O24—C237—H27B | 109.5 |
H17A—C137—H17B | 109.5 | H27A—C237—H27B | 109.5 |
O14—C137—H17C | 109.5 | O24—C237—H27C | 109.5 |
H17A—C137—H17C | 109.5 | H27A—C237—H27C | 109.5 |
H17B—C137—H17C | 109.5 | H27B—C237—H27C | 109.5 |
C155—O15—C138 | 116.4 (2) | C255—O25—C238 | 116.7 (2) |
O15—C138—H18A | 109.5 | O25—C238—H28A | 109.5 |
O15—C138—H18B | 109.5 | O25—C238—H28B | 109.5 |
H18A—C138—H18B | 109.5 | H28A—C238—H28B | 109.5 |
O15—C138—H18C | 109.5 | O25—C238—H28C | 109.5 |
H18A—C138—H18C | 109.5 | H28A—C238—H28C | 109.5 |
H18B—C138—H18C | 109.5 | H28B—C238—H28C | 109.5 |
C15—N11—N12—C13 | 2.1 (3) | C25—N21—N22—C23 | 1.7 (3) |
C111—N11—N12—C13 | 179.9 (2) | C211—N21—N22—C23 | −179.2 (2) |
N11—N12—C13—C14 | −1.1 (3) | N21—N22—C23—C24 | 0.3 (3) |
N11—N12—C13—C131 | −176.3 (2) | N21—N22—C23—C231 | −179.0 (2) |
N12—C13—C14—C15 | −0.3 (3) | N22—C23—C24—C25 | −2.2 (3) |
C131—C13—C14—C15 | 174.5 (2) | C231—C23—C24—C25 | 177.0 (3) |
N12—N11—C15—N151 | 178.4 (2) | N22—N21—C25—C24 | −3.1 (3) |
C111—N11—C15—N151 | 1.0 (4) | C211—N21—C25—C24 | 178.0 (2) |
N12—N11—C15—C14 | −2.3 (3) | N22—N21—C25—N251 | 176.0 (2) |
C111—N11—C15—C14 | −179.8 (2) | C211—N21—C25—N251 | −2.9 (4) |
C13—C14—C15—N11 | 1.5 (3) | C23—C24—C25—N21 | 3.1 (3) |
C13—C14—C15—N151 | −179.3 (3) | C23—C24—C25—N251 | −175.9 (3) |
C15—N11—C111—C112 | −30.3 (4) | C25—N21—C211—C216 | 155.0 (3) |
N12—N11—C111—C112 | 152.5 (2) | N22—N21—C211—C216 | −23.8 (3) |
C15—N11—C111—C116 | 150.1 (3) | C25—N21—C211—C212 | −26.4 (4) |
N12—N11—C111—C116 | −27.2 (3) | N22—N21—C211—C212 | 154.8 (2) |
C116—C111—C112—C113 | −1.1 (4) | C216—C211—C212—C213 | −1.5 (4) |
N11—C111—C112—C113 | 179.3 (2) | N21—C211—C212—C213 | −180.0 (2) |
C111—C112—C113—C114 | 0.4 (4) | C211—C212—C213—C214 | 1.2 (4) |
C112—C113—C114—C115 | 0.8 (4) | C212—C213—C214—C215 | 0.1 (4) |
C113—C114—C115—C116 | −1.3 (4) | C213—C214—C215—C216 | −1.2 (4) |
C114—C115—C116—C111 | 0.7 (4) | C214—C215—C216—C211 | 1.0 (4) |
C112—C111—C116—C115 | 0.5 (4) | C212—C211—C216—C215 | 0.4 (4) |
N11—C111—C116—C115 | −179.8 (2) | N21—C211—C216—C215 | 178.9 (2) |
N12—C13—C131—C134 | −150.1 (2) | N22—C23—C231—C233 | 151.9 (3) |
C14—C13—C131—C134 | 35.5 (4) | C24—C23—C231—C233 | −27.2 (4) |
N12—C13—C131—C132 | −29.0 (3) | N22—C23—C231—C232 | 29.5 (4) |
C14—C13—C131—C132 | 156.6 (3) | C24—C23—C231—C232 | −149.7 (3) |
N12—C13—C131—C133 | 90.2 (3) | N22—C23—C231—C234 | −90.1 (3) |
C14—C13—C131—C133 | −84.1 (3) | C24—C23—C231—C234 | 90.8 (4) |
N11—C15—N151—C157 | −173.7 (2) | N21—C25—N251—C257 | −173.6 (2) |
C14—C15—N151—C157 | 7.3 (4) | C24—C25—N251—C257 | 5.3 (4) |
C15—N151—C157—C151 | 169.7 (2) | C25—N251—C257—C251 | 168.0 (2) |
N151—C157—C151—C152 | −103.8 (3) | N251—C257—C251—C252 | −103.3 (3) |
N151—C157—C151—C156 | 74.7 (3) | N251—C257—C251—C256 | 73.5 (3) |
C156—C151—C152—C153 | −0.1 (4) | C256—C251—C252—C253 | −0.7 (4) |
C157—C151—C152—C153 | 178.3 (2) | C257—C251—C252—C253 | 176.0 (2) |
C151—C152—C153—O13 | −179.9 (2) | C251—C252—C253—O23 | −178.5 (2) |
C151—C152—C153—C154 | −2.0 (4) | C251—C252—C253—C254 | −0.5 (4) |
O13—C153—C154—O14 | 3.6 (3) | O23—C253—C254—O24 | 2.1 (3) |
C152—C153—C154—O14 | −174.6 (2) | C252—C253—C254—O24 | −176.1 (2) |
O13—C153—C154—C155 | −179.6 (2) | O23—C253—C254—C255 | 179.6 (2) |
C152—C153—C154—C155 | 2.2 (4) | C252—C253—C254—C255 | 1.4 (4) |
C153—C154—C155—O15 | −179.2 (2) | O24—C254—C255—O25 | −3.4 (3) |
O14—C154—C155—O15 | −2.5 (3) | C253—C254—C255—O25 | 179.2 (2) |
C153—C154—C155—C156 | −0.4 (4) | O24—C254—C255—C256 | 176.5 (2) |
O14—C154—C155—C156 | 176.4 (2) | C253—C254—C255—C256 | −1.0 (4) |
O15—C155—C156—C151 | 177.0 (2) | O25—C255—C256—C251 | 179.6 (2) |
C154—C155—C156—C151 | −1.7 (4) | C254—C255—C256—C251 | −0.3 (4) |
C152—C151—C156—C155 | 1.9 (4) | C252—C251—C256—C255 | 1.1 (4) |
C157—C151—C156—C155 | −176.5 (2) | C257—C251—C256—C255 | −175.6 (2) |
C154—C153—O13—C136 | 175.9 (2) | C254—C253—O23—C236 | 177.0 (2) |
C152—C153—O13—C136 | −6.0 (4) | C252—C253—O23—C236 | −4.9 (4) |
C153—C154—O14—C137 | −101.0 (3) | C253—C254—O24—C237 | −97.7 (3) |
C155—C154—O14—C137 | 82.3 (3) | C255—C254—O24—C237 | 84.9 (3) |
C156—C155—O15—C138 | 2.4 (4) | C256—C255—O25—C238 | 3.9 (4) |
C154—C155—O15—C138 | −178.8 (2) | C254—C255—O25—C238 | −176.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C112—H112···N151 | 0.95 | 2.48 | 3.004 (4) | 115 |
C212—H212···N251 | 0.95 | 2.46 | 3.002 (4) | 116 |
N151—H151···O13i | 0.88 | 2.57 | 3.316 (3) | 144 |
N151—H151···O14i | 0.88 | 2.30 | 3.095 (3) | 150 |
N251—H251···O24ii | 0.88 | 2.38 | 3.150 (3) | 147 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y, −z+2. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C20H23N3 | C21H25N3 | C21H22F3N3 | C20H22ClN3 |
Mr | 305.41 | 319.44 | 373.42 | 339.86 |
Crystal system, space group | Monoclinic, C2/c | Tetragonal, P43212 | Monoclinic, C2/c | Triclinic, P1 |
Temperature (K) | 120 | 120 | 120 | 120 |
a, b, c (Å) | 20.038 (4), 7.3732 (12), 23.444 (3) | 10.7749 (13), 10.7749 (13), 30.868 (3) | 20.824 (3), 7.3429 (11), 24.225 (4) | 9.385 (3), 9.7584 (19), 10.6014 (17) |
α, β, γ (°) | 90, 106.007 (13), 90 | 90, 90, 90 | 90, 97.275 (11), 90 | 112.459 (13), 95.721 (18), 99.735 (19) |
V (Å3) | 3329.4 (10) | 3583.6 (7) | 3674.3 (10) | 869.8 (4) |
Z | 8 | 8 | 8 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.07 | 0.07 | 0.10 | 0.23 |
Crystal size (mm) | 0.31 × 0.26 × 0.21 | 0.37 × 0.27 × 0.24 | 0.36 × 0.09 × 0.04 | 0.25 × 0.10 × 0.05 |
Data collection | ||||
Diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.967, 0.985 | 0.949, 0.983 | 0.946, 0.996 | 0.958, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 30597, 3813, 2464 | 22266, 2412, 1598 | 21869, 4218, 2014 | 25011, 3991, 2811 |
Rint | 0.075 | 0.075 | 0.151 | 0.059 |
(sin θ/λ)max (Å−1) | 0.650 | 0.649 | 0.650 | 0.650 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.129, 1.06 | 0.052, 0.119, 1.12 | 0.083, 0.196, 1.08 | 0.045, 0.113, 1.08 |
No. of reflections | 3813 | 2412 | 4218 | 3991 |
No. of parameters | 211 | 221 | 247 | 220 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0479P)2 + 3.306P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0473P)2 + 0.8586P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0791P)2] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0483P)2 + 0.3135P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.21, −0.36 | 0.20, −0.30 | 0.29, −0.47 | 0.23, −0.28 |
(V) | (VI) | (VII) | |
Crystal data | |||
Chemical formula | C20H22BrN3 | C20H22N4O2 | C23H29N3O3 |
Mr | 384.32 | 350.42 | 395.49 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 120 | 120 | 120 |
a, b, c (Å) | 20.1981 (6), 7.3960 (9), 24.171 (4) | 9.6594 (11), 12.3991 (11), 15.4338 (15) | 10.1533 (11), 11.1645 (10), 20.927 (2) |
α, β, γ (°) | 90, 98.634 (7), 90 | 90, 97.744 (8), 90 | 84.820 (8), 82.988 (8), 63.153 (7) |
V (Å3) | 3569.9 (7) | 1831.6 (3) | 2099.0 (4) |
Z | 8 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 2.31 | 0.09 | 0.08 |
Crystal size (mm) | 0.44 × 0.13 × 0.11 | 0.29 × 0.27 × 0.24 | 0.48 × 0.35 × 0.25 |
Data collection | |||
Diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.499, 0.785 | 0.959, 0.980 | 0.961, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28981, 4071, 2871 | 29100, 4192, 2657 | 50489, 9621, 5050 |
Rint | 0.051 | 0.078 | 0.094 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 | 0.650 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.137, 1.10 | 0.062, 0.169, 1.06 | 0.064, 0.174, 1.03 |
No. of reflections | 4071 | 4192 | 9621 |
No. of parameters | 220 | 239 | 535 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0569P)2 + 13.3406P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0706P)2 + 1.4326P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0692P)2 + 1.2088P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.41, −0.63 | 0.66, −0.33 | 0.48, −0.35 |
Computer programs: COLLECT (Hooft, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
θ1 | θ2 | θ3 | θ4 | θ5 | |
(I) | 144.41 (16) | 173.57 (18) | -171.61 (16) | -162.80 (15) | -148.74 (17) |
(II) | 151.7 (3) | -26.5 (4) | -175.7 (3) | -177.0 (3) | -130.1 (3) |
(III) | 149.2 (3) | 178.4 (3) | -170.8 (3) | -169.5 (3) | -140.2 (3) |
(IV) | 139.50 (17) | -29.2 (3) | -163.66 (16) | -89.3 (2) | -0.6 (2) |
(V) | 147.0 (3) | 176.9 (3) | -171.9 (3) | -166.3 (3) | -142.8 (3) |
(VI) | 137.9 (3) | 21.8 (4) | -159.4 (2) | -86.6 (3) | 1.1 (3) |
(VII) | |||||
n = 1 | 152.5 (2) | 156.6 (3) | -173.7 (2) | 169.7 (2) | -103.8 (3) |
n = 2 | 154.7 (2) | -149.7 (3) | -173.6 (2) | 168.0 (2) | -103.3 (3) |
Notes: θ1 represents the angle Nx2—Nx1—Cx11—Cx12, θ2 represents the angle Cx4—Cx3—Cx31—Cx32, θ3 represents the angle Nx1—Cx5—Nx51—Cx57, θ4 represents the angle Cx5—Nx51—Cx57—Cx51 and θ5 represents the angle Nx51—Cx57—Cx51—Cx52. For compounds (I)–(VI), x is nul; for compound (VII), where Z' = 2 and x = 1 or 2. |
Compound | D—H···A | D—H | H···A | D···A | D—H···A | |
(I) | C12—H12···N51 | 0.95 | 2.55 | 3.011 (2) | 110 | |
N51—H51···Cg1i | 0.88 | 2.82 | 3.523 (2) | 138 | ||
(II) | C12—H12···N51 | 0.95 | 2.54 | 3.009 (4) | 111 | |
N51—H51···Cg3ii | 0.88 | 2.95 | 3.718 (2) | 147 | ||
C55—H55···Cg2ii | 0.95 | 2.70 | 3.444 (3) | 136 | ||
(III) | C12—H12···N51 | 0.95 | 2.51 | 2.995 (5) | 112 | |
N51—H51···Cg1i | 0.88 | 2.80 | 3.470 (3) | 134 | ||
C53—H53···Cg2iii | 0.95 | 2.91 | 3.809 (4) | 157 | ||
(IV) | N51—H51···Cl54iv | 0.88 | 2.83 | 3.486 (2) | 133 | |
C55—H55···N2v | 0.95 | 2.49 | 3.410 (3) | 163 | ||
C57—H572···Cg1vi | 0.99 | 2.88 | 3.557 (2) | 126 | ||
(V) | C12—H12···N51 | 0.95 | 2.51 | 2.980 (4) | 111 | |
N51—H51···Cg1i | 0.88 | 2.72 | 3.504 (3) | 148 | ||
C15—H15···Cg3vii | 0.95 | 2.95 | 3.687 (4) | 135 | ||
(VI) | C12—H12···N51 | 0.95 | 2.62 | 3.026 (3) | 106 | |
N51—H51···O41viii | 0.88 | 2.19 | 3.025 (3) | 158 | ||
(VII) | C112—H112···N151 | 0.95 | 2.48 | 3.004 (4) | 115 | |
C212—H212···N251 | 0.95 | 2.46 | 3.002 (4) | 116 | ||
N151—H151···O13vi | 0.88 | 2.57 | 3.316 (3) | 144 | ||
N151—H151···O14vi | 0.88 | 2.30 | 3.095 (3) | 150 | ||
N251—H251···O24ix | 0.88 | 2.38 | 3.150 (3) | 147 |
Cg1 represents the centroid of the N1/N2/C3–C5 ring,
Cg2 represents the centroid of the C11–C16 ring and
Cg3 represents the centroid of the C51–C56 ring. Symmetry codes: (i) 1.5-x, 0.5+y, 0.5-z; ii (y, x, 1 - z) iii (-0.5 + x, 0.5 + y, z) iv (1 - x, 1 - y, 2 - z) v (x, y, 1 + z) vi (1 - x, -y, 1 - z) vii (0.5 + x, 0.5 + y, z) viii (-1 + x, y, z) ix (2 - x, -y, 2 - z) |
Pyrazoles are a class of heterocyclic compounds whose members exhibit a wide range of interesting properties, including drug and pesticide activity, as well as forming the basis for new materials (Elguero, 1984, 1996). We have recently determined the structures of a number of new (E)-5-arylidenamino-3-tert-butyl-1-phenyl-1H-pyrazoles, which are the first intermediates isolated in a synthetic pathway developed as a route to new fused heterocyclic compounds containing the pyrazole unit (Castillo et al., 2009). The next step in this pathway requires the reduction of the imine derivatives to give the corresponding 5-arylmethylamino-3-tert-butyl-1-phenyl-1H-pyrazoles, and here we report the molecular and supramolecular structures of seven compounds of this type, namely 5-benzylamino-3-tert-butyl-1-phenyl-1H-pyrazole, (I), and its 4-methylbenzyl, 4-(trifluoromethyl)benzyl, 4-chlorobenzyl, 4-bromobenzyl and 4-nitrobenzyl analogues, compounds (II)–(VI), and the 3,4,5-trimethoxybenzyl analogue, (VII), which we compare with the 4-methoxybenzyl derivative, (VIII), whose structure was reported several years ago (Abonía et al., 2007) (see scheme and Fig. 1).
The crystallization characteristics of the benzylamino series, compounds (I)–(VII), show some unexpected features. It is not infrequently found that the corresponding 4-methylphenyl and 4-chlorophenyl derivatives in a particular series are isomorphous and isostructural; likewise the corresponding 4-chlorophenyl and 4-bromophenyl analogues in other series and not infrequently found to be isomorphous. However, in the present series of compounds, no two of these derivatives, viz. compounds (II), (IV) and (V), are isomorphous. By contrast, and somewhat unexpectedly, the unsubstituted benzyl compound, (I), was found to be isomorphous with both the 4-trifluorobenzyl, (III), and 4-bromobenzyl, (V), compounds. These three compounds all crystallize in the space group C2/c with very similar cell dimensions and very similar values for the coordinates for corresponding atoms. However, the 4-chlorobenzyl analogue, (IV), in the space group P1, is isomorphous neither with 4-methylbenzyl compound (II) nor 4-bromobenzyl compound (V).
4-Methylbenzyl compound (II) and its 4-methoxy analogue, (VIII) (Abonía et al., 2007), are effectively isomorphous, with close correspondence between the two sets of atomic coordinates, although the cell dimensions are slightly larger for (VIII) [a = 10.9665 (14)Å and c = 30.976 (6)Å]. For neither of these compounds was it possible to establish whether the correct space group for the crystal selected for data collection was P41212 or P43212, and hence the correct conformational enantiomorphs present in these crystals could not be determined, although this identification has no chemical significance. For (VIII), the authors concluded that the distribution between the two space groups was probably statistical, as was the distribution of the two conformational enantiomorphs. Since compound (I) and compounds (III)–(VII) all crystallize in centrosymmetric space groups as racemic mixtures of conformational enantiomorphs, this conclusion concerning the space groups seems appropriate for compound (II) also.
All of the compounds studied here crystallize with Z' = 1, with the exception of 3,4,5-trimethoxybenzyl derivative (VII), which crystallizes in P1 with Z' = 2. The various ADDSYM routines in PLATON (Spek, 2009) all showed that no additional symmetry was present. However, the two molecules in the selected asymmetric unit, which were chosen to have the same orientation of the 1-phenyl group relative to the pyrazole ring, are approximately related by a noncrystallographic translation of (1/2, 0, 1/2). As discussed below, the conformations adopted by the tert-butyl groups in the two independent molecules definitively rule out the possibility of any further crystallographic symmetry.
With the exception of the polyatomic substituent groups in the benzyl unit, the overall molecular conformations of compounds (I)–(VII) can be defined in terms of just five torsion angles (Table 1). The orientation of the unsubstituted phenyl ring, as defined by the torsional angles Nx2—Nx1—Cx11—Cx12 and the location of the benzyl methylene unit, as defined by the torsion angles Nx1—Cx5—Nx51—Cx57, show only modest variation across the whole series, In all compounds except (IV) and (VII), there is an intrmolecular C—H···N contact from atom C12 (Table 2): however, the orientation of the unsubstituted phenyl ring does not seem to be significantly influenced by the presence or absence of this contact. The other torsion angles show some interesting variations: in particular, both the position of the substituted aryl ring, as defined by Cx5—Nx51—Cx57—Cx51, and the orientation of this ring, as defined by Nx51—Cx57—Cx51—Cx52, differ markedly in compounds (IV) and (VI) from those in the remainder. In a similar manner, the orientation of the tert-butyl groups in compounds (I), (III) and (V) is such that one methyl group is fairly close to the plane of the pyrazole ring, although by no means coincident with it, while in the other compounds, the projection of one of the C—C bonds in this group is almost normal to the plane of the pyrazole ring. The two independent molecules in compound (VII) have almost identical conformations, apart from their tert-butyl groups, which are rotated in the opposite senses relative to the pyrazole ring. The tert-butyl groups in compounds (I)–(VII) are directly bonded to a planar ring, so that the rotational barriers about the exocyclic C—C bonds will be a close approximation to an idealized sixfold barrier, long known to be extremely low, ca a few tens of J mol-1 (Tannenbaum et al., 1956; Naylor & Wilson, 1957); accordingly, the tert-butyl groups may be acting here essentially as space fillers, adopting whatever orientations are best adapted to the spaces available between the molecules, once the direction-specific intermolecular forces have been accommodated.
A variety of direction-specific intermolecular interactions are present in the structures of compounds (I)–(VII), in particular X—H···π(arene) and X—H···π(pyrazole) hydrogen bonds, both for X = C and N, as well as N—H..O hydrogen bonds in both (VI) and (VII) (Table 2). These interactions link the molecules into supramolecular aggregations ranging from finite (zero-dimensional) dimer units in each of (II) and (VII), via simple chains in (I) and (VI), and chains of rings π-stacked into sheets in (IV), to hydrogen-bonded sheets in each of (III) and (V).
Compounds (I), (III) and (V) are isomorphous, and in each compound molecules related by a 21 screw axis along (3/4, y, 1/4) are linked into chains by an N—H···π(pyrazole) hydrogen bond. While the molecules of the three compounds are arranged almost identically in their unit cells, the weak intermolecular forces show some differences from one compound to another. Thus, in (III), a C—H···π(arene) interaction involving the C11–C16 ring links the initial chains into sheets parallel to (001) (Fig. 2), while in (V), the (001) sheet is generated by a C—H···π(arene) hydrogen bond involving the C51–C56 ring (Fig. 3). In each of (III) and (V), the reference sheet lies in the domain 0 < z < 0.5 with a further sheet, which is related to the first by inversion, lying in the domain 0.5 < z < 1.0: however, there are no direction-specific interactions between adjacent sheets.
Minor changes in the unit-cell dimensions from one compound to another in this group are apparently sufficient to bring different weak interactions into play: this does not, however, detract from the fact that the overall molecular arrangements within this group are effectively the same. Thus, while this group can be regarded as isostructural in terms of the overall molecular arrangement, they are not strictly isostructural in terms of the direction-specific intermolecular interactions which appear to be operative. We have recently reported (Acosta et al., 2009) another series of compounds which similarly are isomorphous in terms of only small changes in their unit-cell dimensions, as well as in their atomic coordinates, but where these changes in cell dimension are sufficient to influence which of the intermolecular interactions are structurally significant, so that those compounds are not strictly isostructural.
In compound (II), the combination of one N—H···π(arene) hydrogen bond and one C—H···π(arene) hydrogen bond, each involving a different arene ring, links pairs of molecules related by the twofold rotation axis along x = y at z = 0.5 into a finite dimeric unit (Fig. 4). The are four of these dimeric units in each unit cell, each lying across a different rotation axis, but there are no direction-specific interactions between the dimers; in particular, aromatic π–π stacking interactions are absent. The supramolecular aggregation in compound (II) is thus significantly different from that in the isomorphous 4-methoxybenzyl analogue (VIII) (Abonía et al., 2007), where a single C—H···N hydrogen bond links molecules related by translation into simple C(9) chains: N—H···π and C—H···π interactions are, however, absent from the structure of (VIII).
The only possible acceptor within hydrogen bonding range of the N—H bond in compound (IV) is the Cl atom of the molecule at (1-x, 1-y, -z). However, it has been concluded that such contacts involving covalently bound Cl are probably no more than van der Waals contacts, and that geometrically they are certainly at the outer limit of what could conceivably be described as a hydrogen bond (Aakeröy et al., 1999; Brammer et al., 2001; Thallapally & Nangia, 2001). Accordingly, we have discounted this contact as it seems unlikely to be of structural significance.
A C—H···N hydrogen bond links molecules of (IV) which are related by translation into a C(9) (Bernstein et al., 1995) chain running parallel to the [001] direction (Fig. 5). Antiparallel pairs of such chains, related by inversion and then linked into a chain of edge-fused rings along (1/2, 0, z) (Fig. 5). The 4-chlorophenyl rings of the molecules at (x, y, z) and (1-x, 1-y, 2-z) are strictly parallel within an interplanar spacing of 3.474 (2)Å; the ring-centroid separation is 3.773 (2)Å, corresponding to a near-ideal ring-centroid offset of 1.472 (2)Å (Fig. 6). The two molecules involved in this π-stacking interaction forms parts of the hydrogen-bonded chains along (1/2, 0, z) and (1/2, 1, z), so that this interactions links hydrogen-bonded chains of rings into a sheet parallel to (100). By contrast, the supramolecular aggregation in compound (VI) depends upon just a single N—H···O hydrogen bond, which links molecules related by translation into a simple chain running parallel to the [100] direction (Fig. 7).
The supramolecular aggregation in 3,4,5-trimethoxybenzyl derivative (VII) depends solely upon N—H···O hydrogen bonds, which generate two independent centrosymmetric dimers. The dimer formed by the type 1 molecules contains an asymmetric three-centre N—H···(O)2 interaction, which generates a centrosymmetric R22(14) ring flanked by two symmetry-related R12(5) rings, while the dimer formed by the type 2 molecules contains a single R22(16) ring (Fig. 8). These two dimers are centred respectively across (1/2, 0, 1/2) and (1, 0, 1), illustrating again the pseudo-translational relationship between the two independent molecules in this structure. As with the conformations of the tert-butyl groups discussed above, so too the different N—H···O interactions within the two independent dimers rules out the possibility of any additional crystallographic symmetry.