Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113017435/fg3298sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017435/fg3298Isup2.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113017435/fg3298Isup3.cml |
CCDC reference: 963266
Compounds with spiro skeletons not only constitute subunits in numerous alkaloids, but are also templates for drug discovery that have been used as scaffolds for combinatorial libraries (Maier & Wuensch, 2002; Shaabani & Bazgir, 2004; Krasnov & Kartsev, 2005; Lang et al., 2005; Kadutskii & Kozlov, 2006; Kuster et al., 2006; Macleod et al., 2006; Nazarenko et al., 2007). The synthesis of spiro compounds can be achieved using conventional methods and procedures based on three-component one-pot reactions (Marti & Carrei, 2003; Rolandsgard et al., 2005; Arya & Dandia, 2007; Rahimizadeh et al., 2007). However, focused microwave irradiation is now emerging as a powerful tool to simplify and improve classic organic reactions, because it often leads to higher yields and cleaner and shorter reactions, with precise control of the reaction parameters (Kappe, 2004; Martins et al., 2009). We have recently developed a route to spiro compounds through the microwave-assisted reactions between pyrazolo[3,4-b]pyridines, paraformaldehyde and cyclic β-diketones (Quiroga et al., 2010), and we report here the molecular and supramolecular structure of the title compound, (I) (Fig. 1), as a representative product from this procedure, which was obtained using indan-1,3-dione as the cyclic β-diketone component.
A mixture of N-benzyl-3-tert-butyl-1-phenyl-1H-pyrazol-5-amine (2 mmol), indan-1,3-dione (2 mmol) and an excess of paraformaldehyde (30 mol%) was subjected to microwave radiation for 25 min at 473 K and a maximum power of 300 W. The mixture was then dissolved in hot ethanol and subsequently allowed to cool to ambient temperature. The resulting solid product was collected by filtration and washed successively with ethanol (5 ml) and hexane (2 × 5 ml) to give pale-yellow crystals of (I) suitable for single-crystal X-ray diffraction (yield 52%, m.p. 458–160 K). MS (EI 70 eV) m/z (% relative abundance): 475 (M+, 89), 384 (25), 328 (100); HR–MS, found: 475, 2259; C31H29N3O2 requires 475, 2260. Analysis, found: C 77.3, H 6.2, N 9.3%; C31H29N3O2 requires: C 78.3, H 6.1, N 8.8%.
All H atoms were located in difference maps but were subsequently treated as riding in geometrically idealized positions, with C—H = 0.95 (aromatic), 0.98 (CH3) or 0.99 Å (CH2), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, or 1.2 for all other H atoms.
The reduced pyridine ring in (I) is markedly nonplanar, with a ring-puckering amplitude of 0.467 (2) Å; the ring-puckering angles (Cremer & Pople, 1975) calculated for the atom sequence N–C6–C52–C4–C3A–C7A are θ = 128.9 (2)° and ϕ = 283.8 (3)°. These values indicate that this ring adopts a conformation intermediate between the half-chair and envelope forms, for which the idealized values (Boeyens, 1978) are θ = 129.2 and 125.3°, respectively, and ϕ = (60k + 30)° and (60k)°, respectively, where k represents an integer.
As expected, the mean planes of the two rings which are linked via atom C52 are almost orthogonal, with a dihedral angle between the mean planes of 88.1 (3)°. The orientation of the tert-butyl group is of some interest as one of the methyl C atoms, atom C34, is close to the plane of the adjacent pyrazole ring but displaced from it by 0.081 (2) Å, as indicated by the value of the N2—C3—C31—C34 torsion angle (Table 1). Both of the other hydrocarbyl substituents, at atoms N1 and N7, are twisted well out of the mean plane of the pyrazolo[3,4-b]pyridine unit, as indicated by the relevant torsion angles (Table 1), but with the result that the two aryl rings (C11–C16 and C71–C76) are themselves very nearly parallel, with a dihedral angle between them of only 9.7 (2)°. The corresponding ring-centroid separation is 3.787 (2) Å and the shortest perpendicular distance from the centroid of one ring to the plane of the other is ca 3.41 Å, with a ring-centroid offset of ca 1.65 Å. This is indicative of an intramolecular π–π stacking interaction (Fig. 2) and is probably significant in determining the overall orientation of these two substituents. The bond lengths (Table 1) indicate some bond fixation in the pyrazole ring and confirm the reduced nature of the pyridine ring, but otherwise the bond lengths present no features of note.
The supramolecular assembly of (I) is determined by three hydrogen bonds, two of the C—H···O type and one of the C—H···N type (Table 2), but C—H···π(arene) hydrogen bonds and intermolecular π–π stacking interactions are absent. The overall assembly takes the form of a fairly complex bilayer, but the formation of this bilayer is readily analysed in terms of simple substructures (Ferguson et al., 1998a,b; Gregson et al., 2000). Acting alone, the hydrogen bond having atom O51 as the acceptor (Table 2) links molecules related by translation into a C(5) chain (Bernstein et al., 1995) running parallel to the [010] direction, while the hydrogen bond having atom N2 as the acceptor, when acting alone, links molecules related by the c-glide plane at y = 0.25 into a C(10) chain running parallel to the [001] direction. The combination of these two substructural motifs generates a sheet in the form of a (4,4) net lying parallel to (100) and built from R44(28) rings (Fig. 3). This sheet lies in the domain 0 < x < 0.5 and a second sheet, related to the first by inversion, lies in the domain 0.5 < x < 1.0. The final hydrogen bond, having atom O53 as the acceptor, links inversion-related pairs of molecules in a centrosymmetric R22(20) motif (Table 2 and Fig. 4). The two molecules involved in this ring motif lie in different (100) sheets, so that the effect of this final interaction is to link the sheets in pairs to form a bilayer. The interior of the bilayer contains C—H···O hydrogen bonds, while the tert-butyl groups are all on the outer faces. This probably accounts for the absence of any direction-specific interactions between adjacent bilayers.
Data collection: COLLECT (Nonius, 1998); 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).
C31H29N3O2 | F(000) = 1008 |
Mr = 475.57 | Dx = 1.276 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5680 reflections |
a = 16.6917 (18) Å | θ = 3.0–27.5° |
b = 5.9748 (4) Å | µ = 0.08 mm−1 |
c = 24.840 (3) Å | T = 120 K |
β = 91.841 (10)° | Block, pale yellow |
V = 2476.0 (4) Å3 | 0.34 × 0.27 × 0.22 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 5679 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 3889 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ and ω scans | h = −21→21 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −7→7 |
Tmin = 0.973, Tmax = 0.983 | l = −32→32 |
38299 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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0452P)2 + 1.1191P] where P = (Fo2 + 2Fc2)/3 |
5679 reflections | (Δ/σ)max = 0.001 |
322 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C31H29N3O2 | V = 2476.0 (4) Å3 |
Mr = 475.57 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.6917 (18) Å | µ = 0.08 mm−1 |
b = 5.9748 (4) Å | T = 120 K |
c = 24.840 (3) Å | 0.34 × 0.27 × 0.22 mm |
β = 91.841 (10)° |
Bruker Nonius KappaCCD area-detector diffractometer | 5679 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3889 reflections with I > 2σ(I) |
Tmin = 0.973, Tmax = 0.983 | Rint = 0.049 |
38299 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.23 e Å−3 |
5679 reflections | Δρmin = −0.21 e Å−3 |
322 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.24247 (8) | 0.3603 (2) | 0.63330 (5) | 0.0228 (3) | |
N2 | 0.16935 (8) | 0.2808 (2) | 0.64967 (5) | 0.0250 (3) | |
C3 | 0.14271 (9) | 0.1498 (3) | 0.60944 (6) | 0.0224 (3) | |
C3A | 0.19774 (9) | 0.1426 (3) | 0.56725 (6) | 0.0213 (3) | |
C4 | 0.19455 (10) | 0.0355 (3) | 0.51271 (6) | 0.0224 (3) | |
H4A | 0.1388 | 0.0376 | 0.4978 | 0.027* | |
H4B | 0.2122 | −0.1223 | 0.5156 | 0.027* | |
C52 | 0.25005 (9) | 0.1651 (3) | 0.47469 (6) | 0.0216 (3) | |
C6 | 0.33166 (9) | 0.2112 (3) | 0.50430 (6) | 0.0234 (3) | |
H6A | 0.3579 | 0.0662 | 0.5126 | 0.028* | |
H6B | 0.3665 | 0.2940 | 0.4796 | 0.028* | |
N7 | 0.32604 (8) | 0.3391 (2) | 0.55438 (5) | 0.0211 (3) | |
C7A | 0.25948 (9) | 0.2808 (3) | 0.58353 (6) | 0.0208 (3) | |
C51 | 0.20610 (9) | 0.3730 (3) | 0.45367 (6) | 0.0225 (3) | |
O51 | 0.18240 (7) | 0.52709 (19) | 0.48063 (4) | 0.0293 (3) | |
C53 | 0.26266 (10) | 0.0272 (3) | 0.42381 (6) | 0.0236 (4) | |
O53 | 0.29945 (7) | −0.1477 (2) | 0.42245 (5) | 0.0308 (3) | |
C54 | 0.22283 (9) | 0.1434 (3) | 0.37753 (6) | 0.0231 (3) | |
C55 | 0.21537 (10) | 0.0773 (3) | 0.32371 (6) | 0.0274 (4) | |
H55 | 0.2367 | −0.0611 | 0.3120 | 0.033* | |
C56 | 0.17571 (10) | 0.2205 (3) | 0.28785 (7) | 0.0317 (4) | |
H56 | 0.1691 | 0.1791 | 0.2510 | 0.038* | |
C57 | 0.14545 (11) | 0.4244 (3) | 0.30528 (7) | 0.0336 (4) | |
H57 | 0.1189 | 0.5204 | 0.2799 | 0.040* | |
C58 | 0.15310 (10) | 0.4909 (3) | 0.35875 (7) | 0.0279 (4) | |
H58 | 0.1325 | 0.6305 | 0.3703 | 0.033* | |
C59 | 0.19181 (9) | 0.3464 (3) | 0.39461 (6) | 0.0226 (3) | |
C11 | 0.29000 (9) | 0.4909 (3) | 0.67070 (6) | 0.0214 (3) | |
C12 | 0.26215 (10) | 0.6979 (3) | 0.68680 (6) | 0.0265 (4) | |
H12 | 0.2132 | 0.7554 | 0.6720 | 0.032* | |
C13 | 0.30642 (11) | 0.8207 (3) | 0.72471 (7) | 0.0309 (4) | |
H13 | 0.2877 | 0.9630 | 0.7359 | 0.037* | |
C14 | 0.37777 (10) | 0.7363 (3) | 0.74627 (6) | 0.0307 (4) | |
H14 | 0.4076 | 0.8197 | 0.7726 | 0.037* | |
C15 | 0.40544 (10) | 0.5308 (3) | 0.72946 (6) | 0.0293 (4) | |
H15 | 0.4548 | 0.4741 | 0.7439 | 0.035* | |
C16 | 0.36168 (10) | 0.4066 (3) | 0.69159 (6) | 0.0249 (4) | |
H16 | 0.3807 | 0.2652 | 0.6801 | 0.030* | |
C31 | 0.05951 (10) | 0.0486 (3) | 0.61060 (6) | 0.0263 (4) | |
C32 | 0.05998 (11) | −0.1994 (3) | 0.59411 (8) | 0.0341 (4) | |
H32A | 0.0821 | −0.2139 | 0.5582 | 0.051* | |
H32B | 0.0051 | −0.2576 | 0.5935 | 0.051* | |
H32C | 0.0931 | −0.2847 | 0.6201 | 0.051* | |
C33 | 0.00517 (10) | 0.1790 (3) | 0.57030 (7) | 0.0305 (4) | |
H33A | 0.0039 | 0.3372 | 0.5807 | 0.046* | |
H33B | −0.0492 | 0.1174 | 0.5705 | 0.046* | |
H33C | 0.0262 | 0.1653 | 0.5341 | 0.046* | |
C34 | 0.02508 (11) | 0.0698 (4) | 0.66680 (7) | 0.0421 (5) | |
H34A | 0.0573 | −0.0200 | 0.6925 | 0.063* | |
H34B | −0.0304 | 0.0159 | 0.6659 | 0.063* | |
H34C | 0.0263 | 0.2271 | 0.6780 | 0.063* | |
C77 | 0.34898 (10) | 0.5767 (3) | 0.55292 (6) | 0.0230 (3) | |
H77A | 0.3066 | 0.6665 | 0.5697 | 0.028* | |
H77B | 0.3520 | 0.6244 | 0.5149 | 0.028* | |
C71 | 0.42857 (9) | 0.6264 (3) | 0.58165 (6) | 0.0215 (3) | |
C72 | 0.44048 (10) | 0.8345 (3) | 0.60595 (6) | 0.0251 (4) | |
H72 | 0.3995 | 0.9447 | 0.6034 | 0.030* | |
C73 | 0.51192 (10) | 0.8816 (3) | 0.63387 (7) | 0.0293 (4) | |
H73 | 0.5196 | 1.0241 | 0.6502 | 0.035* | |
C74 | 0.57188 (10) | 0.7225 (3) | 0.63803 (7) | 0.0302 (4) | |
H74 | 0.6201 | 0.7541 | 0.6580 | 0.036* | |
C75 | 0.56146 (10) | 0.5170 (3) | 0.61303 (7) | 0.0295 (4) | |
H75 | 0.6030 | 0.4082 | 0.6152 | 0.035* | |
C76 | 0.49021 (10) | 0.4696 (3) | 0.58466 (6) | 0.0251 (4) | |
H76 | 0.4836 | 0.3290 | 0.5672 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0218 (7) | 0.0290 (8) | 0.0176 (6) | −0.0061 (6) | 0.0002 (5) | −0.0029 (6) |
N2 | 0.0224 (7) | 0.0319 (8) | 0.0206 (7) | −0.0057 (6) | −0.0001 (5) | −0.0005 (6) |
C3 | 0.0230 (8) | 0.0242 (8) | 0.0197 (8) | −0.0012 (7) | −0.0033 (6) | 0.0013 (7) |
C3A | 0.0240 (8) | 0.0207 (8) | 0.0192 (7) | 0.0004 (7) | −0.0023 (6) | 0.0002 (6) |
C4 | 0.0250 (8) | 0.0215 (8) | 0.0204 (8) | −0.0007 (7) | −0.0028 (6) | −0.0013 (6) |
C52 | 0.0251 (8) | 0.0206 (8) | 0.0191 (7) | 0.0006 (7) | 0.0000 (6) | −0.0017 (6) |
C6 | 0.0240 (8) | 0.0262 (9) | 0.0200 (8) | −0.0012 (7) | 0.0000 (6) | −0.0017 (7) |
N7 | 0.0224 (7) | 0.0217 (7) | 0.0192 (6) | −0.0030 (6) | 0.0004 (5) | −0.0013 (5) |
C7A | 0.0223 (8) | 0.0218 (8) | 0.0181 (7) | −0.0003 (7) | −0.0011 (6) | 0.0004 (6) |
C51 | 0.0234 (8) | 0.0230 (9) | 0.0210 (8) | −0.0029 (7) | −0.0001 (6) | −0.0014 (7) |
O51 | 0.0394 (7) | 0.0232 (6) | 0.0252 (6) | 0.0039 (5) | −0.0011 (5) | −0.0052 (5) |
C53 | 0.0247 (8) | 0.0227 (9) | 0.0233 (8) | −0.0015 (7) | 0.0025 (6) | −0.0034 (7) |
O53 | 0.0361 (7) | 0.0264 (7) | 0.0301 (6) | 0.0052 (6) | 0.0036 (5) | −0.0042 (5) |
C54 | 0.0204 (8) | 0.0285 (9) | 0.0204 (8) | −0.0038 (7) | 0.0021 (6) | −0.0025 (7) |
C55 | 0.0255 (9) | 0.0347 (10) | 0.0222 (8) | −0.0043 (8) | 0.0034 (7) | −0.0065 (7) |
C56 | 0.0280 (9) | 0.0483 (12) | 0.0189 (8) | −0.0058 (8) | 0.0009 (7) | −0.0025 (8) |
C57 | 0.0325 (10) | 0.0453 (12) | 0.0226 (8) | −0.0004 (9) | −0.0027 (7) | 0.0086 (8) |
C58 | 0.0282 (9) | 0.0300 (9) | 0.0254 (8) | 0.0007 (8) | 0.0002 (7) | 0.0016 (7) |
C59 | 0.0206 (8) | 0.0277 (9) | 0.0194 (7) | −0.0026 (7) | 0.0007 (6) | −0.0013 (7) |
C11 | 0.0228 (8) | 0.0256 (9) | 0.0159 (7) | −0.0059 (7) | 0.0003 (6) | −0.0015 (6) |
C12 | 0.0248 (8) | 0.0288 (9) | 0.0259 (8) | 0.0000 (7) | 0.0005 (7) | −0.0005 (7) |
C13 | 0.0370 (10) | 0.0274 (9) | 0.0288 (9) | −0.0055 (8) | 0.0081 (7) | −0.0074 (7) |
C14 | 0.0306 (9) | 0.0392 (11) | 0.0222 (8) | −0.0132 (8) | 0.0003 (7) | −0.0075 (8) |
C15 | 0.0232 (8) | 0.0414 (11) | 0.0230 (8) | −0.0019 (8) | −0.0036 (7) | 0.0011 (8) |
C16 | 0.0251 (8) | 0.0277 (9) | 0.0219 (8) | 0.0002 (7) | 0.0010 (6) | −0.0011 (7) |
C31 | 0.0234 (8) | 0.0324 (10) | 0.0231 (8) | −0.0045 (7) | −0.0013 (6) | −0.0015 (7) |
C32 | 0.0277 (9) | 0.0314 (10) | 0.0429 (11) | −0.0055 (8) | −0.0042 (8) | 0.0045 (8) |
C33 | 0.0246 (9) | 0.0322 (10) | 0.0342 (9) | 0.0006 (8) | −0.0054 (7) | −0.0068 (8) |
C34 | 0.0289 (10) | 0.0693 (15) | 0.0283 (9) | −0.0172 (10) | 0.0029 (7) | −0.0027 (9) |
C77 | 0.0253 (8) | 0.0222 (8) | 0.0213 (8) | −0.0014 (7) | −0.0022 (6) | 0.0023 (7) |
C71 | 0.0239 (8) | 0.0238 (8) | 0.0167 (7) | −0.0035 (7) | 0.0012 (6) | 0.0032 (6) |
C72 | 0.0289 (9) | 0.0226 (9) | 0.0235 (8) | −0.0020 (7) | −0.0020 (7) | 0.0027 (7) |
C73 | 0.0338 (10) | 0.0271 (9) | 0.0267 (9) | −0.0093 (8) | −0.0029 (7) | −0.0001 (7) |
C74 | 0.0235 (9) | 0.0405 (11) | 0.0266 (9) | −0.0082 (8) | −0.0020 (7) | 0.0025 (8) |
C75 | 0.0234 (9) | 0.0369 (10) | 0.0284 (9) | 0.0017 (8) | 0.0025 (7) | 0.0034 (8) |
C76 | 0.0248 (8) | 0.0256 (9) | 0.0250 (8) | −0.0015 (7) | 0.0033 (7) | −0.0012 (7) |
N1—N2 | 1.3830 (18) | C12—C13 | 1.388 (2) |
N1—C11 | 1.433 (2) | C12—H12 | 0.9500 |
N2—C3 | 1.334 (2) | C13—C14 | 1.385 (2) |
C3—C3A | 1.416 (2) | C13—H13 | 0.9500 |
C3—C31 | 1.516 (2) | C14—C15 | 1.381 (3) |
C3A—C7A | 1.371 (2) | C14—H14 | 0.9500 |
C7A—N1 | 1.3628 (19) | C15—C16 | 1.387 (2) |
C3A—C4 | 1.498 (2) | C15—H15 | 0.9500 |
C4—C52 | 1.551 (2) | C16—H16 | 0.9500 |
C4—H4A | 0.9900 | C31—C34 | 1.532 (2) |
C4—H4B | 0.9900 | C31—C32 | 1.537 (2) |
C52—C51 | 1.526 (2) | C31—C33 | 1.541 (2) |
C52—C53 | 1.529 (2) | C32—H32A | 0.9800 |
C52—C6 | 1.552 (2) | C32—H32B | 0.9800 |
C6—N7 | 1.4656 (19) | C32—H32C | 0.9800 |
C6—H6A | 0.9900 | C33—H33A | 0.9800 |
C6—H6B | 0.9900 | C33—H33B | 0.9800 |
N7—C7A | 1.3900 (19) | C33—H33C | 0.9800 |
N7—C77 | 1.471 (2) | C34—H34A | 0.9800 |
C51—O51 | 1.2124 (19) | C34—H34B | 0.9800 |
C51—C59 | 1.487 (2) | C34—H34C | 0.9800 |
C53—O53 | 1.2135 (19) | C77—C71 | 1.517 (2) |
C53—C54 | 1.482 (2) | C77—H77A | 0.9900 |
C54—C59 | 1.391 (2) | C77—H77B | 0.9900 |
C54—C55 | 1.396 (2) | C71—C76 | 1.392 (2) |
C55—C56 | 1.388 (2) | C71—C72 | 1.393 (2) |
C55—H55 | 0.9500 | C72—C73 | 1.389 (2) |
C56—C57 | 1.393 (3) | C72—H72 | 0.9500 |
C56—H56 | 0.9500 | C73—C74 | 1.382 (3) |
C57—C58 | 1.388 (2) | C73—H73 | 0.9500 |
C57—H57 | 0.9500 | C74—C75 | 1.385 (3) |
C58—C59 | 1.386 (2) | C74—H74 | 0.9500 |
C58—H58 | 0.9500 | C75—C76 | 1.392 (2) |
C11—C16 | 1.384 (2) | C75—H75 | 0.9500 |
C11—C12 | 1.385 (2) | C76—H76 | 0.9500 |
C7A—N1—N2 | 111.00 (12) | C11—C12—H12 | 120.3 |
C7A—N1—C11 | 130.59 (13) | C13—C12—H12 | 120.3 |
N2—N1—C11 | 118.16 (12) | C14—C13—C12 | 120.15 (16) |
C3—N2—N1 | 104.91 (12) | C14—C13—H13 | 119.9 |
N2—C3—C3A | 111.32 (14) | C12—C13—H13 | 119.9 |
N2—C3—C31 | 120.21 (14) | C15—C14—C13 | 119.90 (16) |
C3A—C3—C31 | 128.20 (14) | C15—C14—H14 | 120.0 |
C7A—C3A—C3 | 105.22 (13) | C13—C14—H14 | 120.0 |
C7A—C3A—C4 | 121.91 (14) | C14—C15—C16 | 120.43 (16) |
C3—C3A—C4 | 132.64 (14) | C14—C15—H15 | 119.8 |
C3A—C4—C52 | 109.45 (13) | C16—C15—H15 | 119.8 |
C3A—C4—H4A | 109.8 | C11—C16—C15 | 119.33 (16) |
C52—C4—H4A | 109.8 | C11—C16—H16 | 120.3 |
C3A—C4—H4B | 109.8 | C15—C16—H16 | 120.3 |
C52—C4—H4B | 109.8 | C3—C31—C34 | 110.80 (13) |
H4A—C4—H4B | 108.2 | C3—C31—C32 | 111.51 (14) |
C51—C52—C53 | 103.48 (12) | C34—C31—C32 | 109.14 (15) |
C51—C52—C4 | 108.94 (13) | C3—C31—C33 | 107.86 (14) |
C53—C52—C4 | 109.59 (13) | C34—C31—C33 | 108.67 (15) |
C51—C52—C6 | 115.01 (13) | C32—C31—C33 | 108.80 (14) |
C53—C52—C6 | 110.21 (13) | C31—C32—H32A | 109.5 |
C4—C52—C6 | 109.42 (12) | C31—C32—H32B | 109.5 |
N7—C6—C52 | 114.57 (13) | H32A—C32—H32B | 109.5 |
N7—C6—H6A | 108.6 | C31—C32—H32C | 109.5 |
C52—C6—H6A | 108.6 | H32A—C32—H32C | 109.5 |
N7—C6—H6B | 108.6 | H32B—C32—H32C | 109.5 |
C52—C6—H6B | 108.6 | C31—C33—H33A | 109.5 |
H6A—C6—H6B | 107.6 | C31—C33—H33B | 109.5 |
C7A—N7—C6 | 112.68 (12) | H33A—C33—H33B | 109.5 |
C7A—N7—C77 | 117.90 (13) | C31—C33—H33C | 109.5 |
C6—N7—C77 | 117.28 (12) | H33A—C33—H33C | 109.5 |
N1—C7A—C3A | 107.52 (13) | H33B—C33—H33C | 109.5 |
N1—C7A—N7 | 125.35 (14) | C31—C34—H34A | 109.5 |
C3A—C7A—N7 | 127.08 (14) | C31—C34—H34B | 109.5 |
O51—C51—C59 | 125.52 (15) | H34A—C34—H34B | 109.5 |
O51—C51—C52 | 126.22 (14) | C31—C34—H34C | 109.5 |
C59—C51—C52 | 108.12 (13) | H34A—C34—H34C | 109.5 |
O53—C53—C54 | 126.63 (15) | H34B—C34—H34C | 109.5 |
O53—C53—C52 | 124.78 (15) | N7—C77—C71 | 113.70 (13) |
C54—C53—C52 | 108.58 (13) | N7—C77—H77A | 108.8 |
C59—C54—C55 | 121.08 (15) | C71—C77—H77A | 108.8 |
C59—C54—C53 | 109.52 (13) | N7—C77—H77B | 108.8 |
C55—C54—C53 | 129.39 (16) | C71—C77—H77B | 108.8 |
C56—C55—C54 | 117.81 (16) | H77A—C77—H77B | 107.7 |
C56—C55—H55 | 121.1 | C76—C71—C72 | 118.84 (15) |
C54—C55—H55 | 121.1 | C76—C71—C77 | 121.88 (15) |
C55—C56—C57 | 120.65 (16) | C72—C71—C77 | 119.28 (14) |
C55—C56—H56 | 119.7 | C73—C72—C71 | 120.36 (16) |
C57—C56—H56 | 119.7 | C73—C72—H72 | 119.8 |
C58—C57—C56 | 121.63 (16) | C71—C72—H72 | 119.8 |
C58—C57—H57 | 119.2 | C74—C73—C72 | 120.39 (16) |
C56—C57—H57 | 119.2 | C74—C73—H73 | 119.8 |
C59—C58—C57 | 117.61 (17) | C72—C73—H73 | 119.8 |
C59—C58—H58 | 121.2 | C73—C74—C75 | 119.77 (16) |
C57—C58—H58 | 121.2 | C73—C74—H74 | 120.1 |
C58—C59—C54 | 121.20 (15) | C75—C74—H74 | 120.1 |
C58—C59—C51 | 128.65 (15) | C74—C75—C76 | 120.03 (16) |
C54—C59—C51 | 110.15 (14) | C74—C75—H75 | 120.0 |
C16—C11—C12 | 120.72 (15) | C76—C75—H75 | 120.0 |
C16—C11—N1 | 119.94 (15) | C71—C76—C75 | 120.56 (16) |
C12—C11—N1 | 119.30 (14) | C71—C76—H76 | 119.7 |
C11—C12—C13 | 119.45 (16) | C75—C76—H76 | 119.7 |
C7A—N1—N2—C3 | 0.73 (17) | C59—C54—C55—C56 | −0.3 (2) |
C11—N1—N2—C3 | −174.20 (14) | C53—C54—C55—C56 | −179.00 (16) |
N1—N2—C3—C3A | 0.22 (18) | C54—C55—C56—C57 | 0.8 (2) |
N1—N2—C3—C31 | −174.25 (14) | C55—C56—C57—C58 | −0.5 (3) |
N2—C3—C3A—C7A | −1.06 (18) | C56—C57—C58—C59 | −0.3 (3) |
C31—C3—C3A—C7A | 172.86 (16) | C57—C58—C59—C54 | 0.8 (2) |
N2—C3—C3A—C4 | −175.40 (16) | C57—C58—C59—C51 | −178.19 (16) |
C31—C3—C3A—C4 | −1.5 (3) | C55—C54—C59—C58 | −0.6 (2) |
C7A—C3A—C4—C52 | −19.4 (2) | C53—C54—C59—C58 | 178.40 (15) |
C3—C3A—C4—C52 | 154.13 (17) | C55—C54—C59—C51 | 178.61 (14) |
C3A—C4—C52—C51 | −80.74 (15) | C53—C54—C59—C51 | −2.42 (18) |
C3A—C4—C52—C53 | 166.70 (13) | O51—C51—C59—C58 | 3.1 (3) |
C3A—C4—C52—C6 | 45.76 (17) | C52—C51—C59—C58 | 178.98 (16) |
C51—C52—C6—N7 | 64.66 (17) | O51—C51—C59—C54 | −176.01 (16) |
C53—C52—C6—N7 | −178.87 (13) | C52—C51—C59—C54 | −0.13 (17) |
C4—C52—C6—N7 | −58.31 (17) | C7A—N1—C11—C16 | −61.5 (2) |
C52—C6—N7—C7A | 37.90 (18) | N2—N1—C11—C16 | 112.29 (17) |
C52—C6—N7—C77 | −103.91 (16) | C7A—N1—C11—C12 | 120.54 (19) |
N2—N1—C7A—C3A | −1.41 (18) | C16—C11—C12—C13 | −0.6 (2) |
C11—N1—C7A—C3A | 172.71 (15) | N1—C11—C12—C13 | 177.32 (14) |
N2—N1—C7A—N7 | 176.11 (14) | C11—C12—C13—C14 | −0.1 (2) |
C11—N1—C7A—N7 | −9.8 (3) | C12—C13—C14—C15 | 0.9 (3) |
C3—C3A—C7A—N1 | 1.45 (17) | C13—C14—C15—C16 | −0.9 (3) |
C4—C3A—C7A—N1 | 176.55 (14) | C12—C11—C16—C15 | 0.6 (2) |
C3—C3A—C7A—N7 | −176.01 (15) | N1—C11—C16—C15 | −177.31 (14) |
C4—C3A—C7A—N7 | −0.9 (3) | C14—C15—C16—C11 | 0.1 (2) |
C6—N7—C7A—N1 | 174.92 (15) | N2—C3—C31—C32 | −135.75 (16) |
C77—N7—C7A—N1 | −43.5 (2) | C3A—C3—C31—C32 | 50.8 (2) |
C6—N7—C7A—C3A | −8.1 (2) | N2—C3—C31—C33 | 104.85 (17) |
C77—N7—C7A—C3A | 133.50 (17) | N2—C3—C31—C34 | −14.0 (2) |
C53—C52—C51—O51 | 178.31 (15) | C3A—C3—C31—C34 | 172.58 (17) |
C4—C52—C51—O51 | 61.8 (2) | C3A—C3—C31—C33 | −68.6 (2) |
C6—C52—C51—O51 | −61.4 (2) | N2—N1—C11—C12 | −65.69 (19) |
C53—C52—C51—C59 | 2.47 (16) | C7A—N7—C77—C71 | 113.17 (15) |
C4—C52—C51—C59 | −114.06 (14) | C6—N7—C77—C71 | −107.03 (15) |
C6—C52—C51—C59 | 122.71 (14) | N7—C77—C71—C76 | 30.4 (2) |
C51—C52—C53—O53 | 176.06 (15) | N7—C77—C71—C72 | −149.38 (14) |
C4—C52—C53—O53 | −67.9 (2) | C76—C71—C72—C73 | −1.7 (2) |
C6—C52—C53—O53 | 52.6 (2) | C77—C71—C72—C73 | 178.07 (15) |
C51—C52—C53—C54 | −3.88 (16) | C71—C72—C73—C74 | −0.2 (2) |
C4—C52—C53—C54 | 112.20 (14) | C72—C73—C74—C75 | 1.7 (3) |
C6—C52—C53—C54 | −127.34 (14) | C73—C74—C75—C76 | −1.2 (2) |
O53—C53—C54—C59 | −175.90 (16) | C72—C71—C76—C75 | 2.2 (2) |
C52—C53—C54—C59 | 4.04 (18) | C77—C71—C76—C75 | −177.57 (15) |
O53—C53—C54—C55 | 3.0 (3) | C74—C75—C76—C71 | −0.8 (2) |
C52—C53—C54—C55 | −177.10 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4B···O51i | 0.99 | 2.32 | 3.145 (2) | 141 |
C56—H56···N2ii | 0.95 | 2.53 | 3.431 (2) | 158 |
C75—H75···O53iii | 0.95 | 2.46 | 3.342 (2) | 154 |
Symmetry codes: (i) x, y−1, z; (ii) x, −y+1/2, z−1/2; (iii) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C31H29N3O2 |
Mr | 475.57 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 16.6917 (18), 5.9748 (4), 24.840 (3) |
β (°) | 91.841 (10) |
V (Å3) | 2476.0 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.34 × 0.27 × 0.22 |
Data collection | |
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.973, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 38299, 5679, 3889 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.115, 1.04 |
No. of reflections | 5679 |
No. of parameters | 322 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.21 |
Computer programs: COLLECT (Nonius, 1998), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
N1—N2 | 1.3830 (18) | C3A—C4 | 1.498 (2) |
N2—C3 | 1.334 (2) | C4—C52 | 1.551 (2) |
C3—C3A | 1.416 (2) | C52—C6 | 1.552 (2) |
C3A—C7A | 1.371 (2) | C6—N7 | 1.4656 (19) |
C7A—N1 | 1.3628 (19) | N7—C7A | 1.3900 (19) |
N2—C3—C31—C32 | −135.75 (16) | N2—N1—C11—C12 | −65.69 (19) |
N2—C3—C31—C33 | 104.85 (17) | C7A—N7—C77—C71 | 113.17 (15) |
N2—C3—C31—C34 | −14.0 (2) | N7—C77—C71—C72 | −149.38 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4B···O51i | 0.99 | 2.32 | 3.145 (2) | 141 |
C56—H56···N2ii | 0.95 | 2.53 | 3.431 (2) | 158 |
C75—H75···O53iii | 0.95 | 2.46 | 3.342 (2) | 154 |
Symmetry codes: (i) x, y−1, z; (ii) x, −y+1/2, z−1/2; (iii) −x+1, −y, −z+1. |