Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108030515/ln3114sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108030515/ln3114Isup2.hkl |
CCDC reference: 707224
Sodium methoxide (1.44 mmol) was added to a mixture of malononitrile (1.44 mmol) and 1,3-diphenyl-2-propen-1-one (chalcone, 1.44 mmol) dissolved in methanol (20 ml), and the reaction mixture was then stirred at ambient temperature for 6 h. The mixture was neutralized with 10% aqueous acetic acid solution and then evaporated to dryness under reduced pressure. The resulting solid product was recrystallized from aqueous methanol to give the title compound, (I), in 38% yield as colourless crystals suitable for single-crystal X-ray diffraction.
Crystals of (I) are triclinic; the space group P1 was selected and confirmed by the structure analysis. All H atoms were located in difference maps and then treated as riding atoms with C—H distances of 0.95 (aromatic), 0.99 (CH2) or 1.00 Å (aliphatic C—H) and O—H distances of 0.84 Å, and with Uiso(H) equal to 1.2Ueq(C) or 1.5Ueq(O).
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: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).
C33H26N2O2 | Z = 2 |
Mr = 482.56 | F(000) = 508 |
Triclinic, P1 | Dx = 1.246 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.9251 (18) Å | Cell parameters from 5800 reflections |
b = 11.777 (3) Å | θ = 6.5–27.5° |
c = 11.9438 (12) Å | µ = 0.08 mm−1 |
α = 90.417 (13)° | T = 120 K |
β = 112.616 (9)° | Block, colourless |
γ = 112.750 (14)° | 0.59 × 0.47 × 0.35 mm |
V = 1286.1 (5) Å3 |
Bruker–Nonius KappaCCD diffractometer | 5800 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 3387 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.086 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 6.5° |
ϕ and ω scans | h = −14→14 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −15→15 |
Tmin = 0.946, Tmax = 0.973 | l = −15→14 |
33243 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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0362P)2 + 0.7168P] where P = (Fo2 + 2Fc2)/3 |
5800 reflections | (Δ/σ)max = 0.001 |
334 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C33H26N2O2 | γ = 112.750 (14)° |
Mr = 482.56 | V = 1286.1 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.9251 (18) Å | Mo Kα radiation |
b = 11.777 (3) Å | µ = 0.08 mm−1 |
c = 11.9438 (12) Å | T = 120 K |
α = 90.417 (13)° | 0.59 × 0.47 × 0.35 mm |
β = 112.616 (9)° |
Bruker–Nonius KappaCCD diffractometer | 5800 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3387 reflections with I > 2σ(I) |
Tmin = 0.946, Tmax = 0.973 | Rint = 0.086 |
33243 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.25 e Å−3 |
5800 reflections | Δρmin = −0.21 e Å−3 |
334 parameters |
x | y | z | Uiso*/Ueq | ||
O1 | 0.53960 (15) | 0.58734 (12) | 0.35717 (12) | 0.0251 (3) | |
O2 | 0.25019 (15) | 0.48131 (13) | 0.30028 (13) | 0.0309 (4) | |
N41 | 0.6343 (2) | 0.69770 (19) | 0.81250 (18) | 0.0376 (5) | |
N42 | 0.5983 (2) | 0.99903 (17) | 0.63209 (17) | 0.0322 (4) | |
C1 | 0.5207 (2) | 0.69971 (17) | 0.34195 (17) | 0.0210 (4) | |
C2 | 0.3978 (2) | 0.69596 (17) | 0.37755 (17) | 0.0201 (4) | |
C3 | 0.4313 (2) | 0.67677 (17) | 0.51117 (17) | 0.0206 (4) | |
C4 | 0.5857 (2) | 0.77537 (17) | 0.60374 (17) | 0.0199 (4) | |
C5 | 0.7070 (2) | 0.78034 (18) | 0.56326 (17) | 0.0217 (4) | |
C6 | 0.6651 (2) | 0.80289 (18) | 0.43170 (17) | 0.0232 (4) | |
C11 | 0.4932 (2) | 0.72289 (18) | 0.21140 (18) | 0.0237 (4) | |
C12 | 0.4560 (2) | 0.8192 (2) | 0.17013 (19) | 0.0290 (5) | |
C13 | 0.4355 (2) | 0.8418 (2) | 0.0523 (2) | 0.0339 (5) | |
C14 | 0.4551 (2) | 0.7698 (2) | −0.0248 (2) | 0.0364 (6) | |
C15 | 0.4956 (2) | 0.6761 (2) | 0.0163 (2) | 0.0348 (5) | |
C16 | 0.5140 (2) | 0.65207 (19) | 0.13308 (19) | 0.0280 (5) | |
C21 | 0.1251 (2) | 0.60207 (19) | 0.21120 (18) | 0.0247 (4) | |
C22 | −0.0006 (2) | 0.4945 (2) | 0.14290 (18) | 0.0299 (5) | |
C23 | −0.1243 (2) | 0.5023 (2) | 0.0614 (2) | 0.0365 (5) | |
C24 | −0.1258 (2) | 0.6167 (2) | 0.0457 (2) | 0.0395 (6) | |
C25 | −0.0020 (3) | 0.7243 (2) | 0.1116 (2) | 0.0394 (6) | |
C26 | 0.1225 (2) | 0.7172 (2) | 0.19504 (19) | 0.0318 (5) | |
C27 | 0.2542 (2) | 0.58626 (18) | 0.29525 (17) | 0.0228 (4) | |
C31 | 0.3125 (2) | 0.67000 (18) | 0.55012 (17) | 0.0218 (4) | |
C32 | 0.2588 (2) | 0.57233 (19) | 0.60622 (18) | 0.0260 (5) | |
C33 | 0.1529 (2) | 0.5644 (2) | 0.6448 (2) | 0.0333 (5) | |
C34 | 0.0992 (2) | 0.6538 (2) | 0.6283 (2) | 0.0341 (5) | |
C35 | 0.1514 (2) | 0.7506 (2) | 0.5723 (2) | 0.0335 (5) | |
C36 | 0.2571 (2) | 0.75928 (19) | 0.53292 (19) | 0.0282 (5) | |
C41 | 0.6150 (2) | 0.73616 (19) | 0.72437 (19) | 0.0249 (4) | |
C42 | 0.5907 (2) | 0.90076 (19) | 0.61915 (17) | 0.0228 (4) | |
C51 | 0.8587 (2) | 0.87208 (18) | 0.65243 (18) | 0.0240 (4) | |
C52 | 0.9193 (2) | 0.9951 (2) | 0.6380 (2) | 0.0308 (5) | |
C53 | 1.0587 (2) | 1.0758 (2) | 0.7199 (2) | 0.0389 (6) | |
C54 | 1.1391 (3) | 1.0350 (2) | 0.8156 (2) | 0.0447 (6) | |
C55 | 1.0802 (3) | 0.9137 (2) | 0.8309 (2) | 0.0460 (6) | |
C56 | 0.9408 (2) | 0.8325 (2) | 0.7494 (2) | 0.0339 (5) | |
H1 | 0.4543 | 0.5300 | 0.3257 | 0.038* | |
H2 | 0.3865 | 0.7761 | 0.3675 | 0.024* | |
H3 | 0.4349 | 0.5933 | 0.5149 | 0.025* | |
H5 | 0.7066 | 0.6953 | 0.5624 | 0.026* | |
H6A | 0.7431 | 0.8084 | 0.4062 | 0.028* | |
H6B | 0.6576 | 0.8840 | 0.4280 | 0.028* | |
H12 | 0.4442 | 0.8705 | 0.2233 | 0.035* | |
H13 | 0.4079 | 0.9072 | 0.0245 | 0.041* | |
H14 | 0.4405 | 0.7851 | −0.1059 | 0.044* | |
H15 | 0.5112 | 0.6274 | −0.0361 | 0.042* | |
H16 | 0.5411 | 0.5862 | 0.1602 | 0.034* | |
H22 | −0.0004 | 0.4146 | 0.1530 | 0.036* | |
H23 | −0.2095 | 0.4280 | 0.0156 | 0.044* | |
H24 | −0.2120 | 0.6220 | −0.0106 | 0.047* | |
H25 | −0.0025 | 0.8038 | 0.0994 | 0.047* | |
H26 | 0.2068 | 0.7918 | 0.2416 | 0.038* | |
H32 | 0.2955 | 0.5101 | 0.6183 | 0.031* | |
H33 | 0.1166 | 0.4967 | 0.6830 | 0.040* | |
H34 | 0.0265 | 0.6485 | 0.6555 | 0.041* | |
H35 | 0.1142 | 0.8125 | 0.5604 | 0.040* | |
H36 | 0.2922 | 0.8267 | 0.4939 | 0.034* | |
H52 | 0.8647 | 1.0240 | 0.5714 | 0.037* | |
H53 | 1.0992 | 1.1603 | 0.7098 | 0.047* | |
H54 | 1.2355 | 1.0907 | 0.8713 | 0.054* | |
H55 | 1.1355 | 0.8854 | 0.8977 | 0.055* | |
H56 | 0.9009 | 0.7483 | 0.7603 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0256 (7) | 0.0213 (7) | 0.0276 (7) | 0.0112 (6) | 0.0091 (6) | 0.0020 (6) |
O2 | 0.0267 (8) | 0.0207 (8) | 0.0360 (8) | 0.0065 (6) | 0.0076 (7) | 0.0013 (6) |
N41 | 0.0372 (11) | 0.0511 (13) | 0.0336 (11) | 0.0247 (10) | 0.0175 (9) | 0.0174 (10) |
N42 | 0.0334 (11) | 0.0255 (10) | 0.0350 (10) | 0.0120 (8) | 0.0124 (8) | 0.0010 (8) |
C1 | 0.0231 (10) | 0.0204 (10) | 0.0208 (10) | 0.0100 (8) | 0.0097 (8) | 0.0019 (8) |
C2 | 0.0205 (10) | 0.0188 (10) | 0.0201 (10) | 0.0081 (8) | 0.0079 (8) | 0.0026 (8) |
C3 | 0.0207 (10) | 0.0172 (10) | 0.0222 (10) | 0.0069 (8) | 0.0084 (8) | 0.0033 (8) |
C4 | 0.0204 (10) | 0.0200 (10) | 0.0183 (10) | 0.0084 (8) | 0.0071 (8) | 0.0043 (8) |
C5 | 0.0193 (10) | 0.0204 (10) | 0.0230 (10) | 0.0073 (8) | 0.0076 (8) | 0.0023 (8) |
C6 | 0.0216 (10) | 0.0218 (10) | 0.0249 (10) | 0.0069 (8) | 0.0108 (9) | 0.0027 (8) |
C11 | 0.0183 (10) | 0.0249 (11) | 0.0225 (10) | 0.0045 (8) | 0.0080 (8) | 0.0015 (8) |
C12 | 0.0286 (12) | 0.0313 (12) | 0.0275 (11) | 0.0116 (10) | 0.0132 (9) | 0.0068 (9) |
C13 | 0.0274 (12) | 0.0395 (13) | 0.0315 (12) | 0.0107 (10) | 0.0124 (10) | 0.0148 (10) |
C14 | 0.0300 (12) | 0.0447 (14) | 0.0226 (11) | 0.0042 (11) | 0.0109 (10) | 0.0054 (10) |
C15 | 0.0316 (12) | 0.0358 (13) | 0.0275 (12) | 0.0021 (10) | 0.0155 (10) | −0.0055 (10) |
C16 | 0.0249 (11) | 0.0250 (11) | 0.0289 (11) | 0.0047 (9) | 0.0121 (9) | −0.0004 (9) |
C21 | 0.0218 (10) | 0.0291 (11) | 0.0228 (10) | 0.0087 (9) | 0.0108 (9) | 0.0034 (9) |
C22 | 0.0255 (11) | 0.0360 (12) | 0.0221 (11) | 0.0075 (10) | 0.0097 (9) | 0.0055 (9) |
C23 | 0.0245 (12) | 0.0489 (15) | 0.0272 (12) | 0.0099 (11) | 0.0076 (10) | 0.0050 (10) |
C24 | 0.0257 (12) | 0.0654 (17) | 0.0259 (12) | 0.0227 (12) | 0.0062 (10) | 0.0075 (11) |
C25 | 0.0404 (14) | 0.0478 (15) | 0.0362 (13) | 0.0281 (12) | 0.0127 (11) | 0.0119 (11) |
C26 | 0.0301 (12) | 0.0324 (12) | 0.0288 (12) | 0.0139 (10) | 0.0076 (10) | 0.0015 (9) |
C27 | 0.0250 (11) | 0.0220 (11) | 0.0224 (10) | 0.0083 (9) | 0.0124 (9) | 0.0044 (8) |
C31 | 0.0197 (10) | 0.0229 (10) | 0.0204 (10) | 0.0080 (8) | 0.0070 (8) | 0.0017 (8) |
C32 | 0.0251 (11) | 0.0261 (11) | 0.0274 (11) | 0.0114 (9) | 0.0111 (9) | 0.0043 (9) |
C33 | 0.0353 (13) | 0.0339 (13) | 0.0362 (13) | 0.0131 (10) | 0.0220 (11) | 0.0112 (10) |
C34 | 0.0319 (12) | 0.0432 (14) | 0.0389 (13) | 0.0183 (11) | 0.0238 (11) | 0.0098 (11) |
C35 | 0.0338 (12) | 0.0383 (13) | 0.0398 (13) | 0.0221 (11) | 0.0198 (11) | 0.0111 (10) |
C36 | 0.0299 (12) | 0.0278 (11) | 0.0312 (11) | 0.0134 (9) | 0.0157 (10) | 0.0087 (9) |
C41 | 0.0210 (10) | 0.0268 (11) | 0.0279 (12) | 0.0108 (9) | 0.0106 (9) | 0.0035 (9) |
C42 | 0.0188 (10) | 0.0258 (11) | 0.0204 (10) | 0.0079 (9) | 0.0066 (8) | 0.0006 (8) |
C51 | 0.0199 (10) | 0.0235 (11) | 0.0271 (11) | 0.0078 (8) | 0.0099 (9) | −0.0008 (8) |
C52 | 0.0257 (11) | 0.0294 (12) | 0.0327 (12) | 0.0067 (9) | 0.0128 (10) | 0.0028 (9) |
C53 | 0.0295 (12) | 0.0316 (13) | 0.0462 (14) | 0.0014 (10) | 0.0186 (11) | −0.0021 (11) |
C54 | 0.0227 (12) | 0.0382 (14) | 0.0518 (16) | 0.0015 (11) | 0.0063 (11) | −0.0111 (12) |
C55 | 0.0270 (13) | 0.0466 (15) | 0.0470 (15) | 0.0141 (11) | −0.0001 (11) | −0.0013 (12) |
C56 | 0.0239 (11) | 0.0289 (12) | 0.0380 (13) | 0.0096 (10) | 0.0041 (10) | −0.0013 (10) |
O1—C1 | 1.419 (2) | C21—C22 | 1.390 (3) |
O1—H1 | 0.8402 | C21—C27 | 1.466 (3) |
O2—C27 | 1.222 (2) | C22—C23 | 1.367 (3) |
N41—C41 | 1.126 (3) | C22—H22 | 0.95 |
N42—C42 | 1.132 (2) | C23—C24 | 1.367 (3) |
C1—C11 | 1.518 (3) | C23—H23 | 0.95 |
C1—C6 | 1.521 (3) | C24—C25 | 1.376 (3) |
C1—C2 | 1.542 (3) | C24—H24 | 0.95 |
C2—C27 | 1.525 (3) | C25—C26 | 1.378 (3) |
C2—C3 | 1.534 (3) | C25—H25 | 0.95 |
C2—H2 | 1.00 | C26—H26 | 0.95 |
C3—C31 | 1.514 (3) | C31—C32 | 1.381 (3) |
C3—C4 | 1.565 (3) | C31—C36 | 1.383 (3) |
C3—H3 | 1.00 | C32—C33 | 1.374 (3) |
C4—C42 | 1.464 (3) | C32—H32 | 0.95 |
C4—C41 | 1.470 (3) | C33—C34 | 1.371 (3) |
C4—C5 | 1.558 (3) | C33—H33 | 0.95 |
C5—C51 | 1.513 (3) | C34—C35 | 1.370 (3) |
C5—C6 | 1.515 (3) | C34—H34 | 0.95 |
C5—H5 | 1.00 | C35—C36 | 1.376 (3) |
C6—H6A | 0.99 | C35—H35 | 0.95 |
C6—H6B | 0.99 | C36—H36 | 0.95 |
C11—C12 | 1.380 (3) | C51—C56 | 1.377 (3) |
C11—C16 | 1.385 (3) | C51—C52 | 1.384 (3) |
C12—C13 | 1.382 (3) | C52—C53 | 1.379 (3) |
C12—H12 | 0.95 | C52—H52 | 0.95 |
C13—C14 | 1.375 (3) | C53—C54 | 1.368 (3) |
C13—H13 | 0.95 | C53—H53 | 0.95 |
C14—C15 | 1.369 (3) | C54—C55 | 1.368 (4) |
C14—H14 | 0.95 | C54—H54 | 0.95 |
C15—C16 | 1.379 (3) | C55—C56 | 1.379 (3) |
C15—H15 | 0.95 | C55—H55 | 0.95 |
C16—H16 | 0.95 | C56—H56 | 0.95 |
C21—C26 | 1.380 (3) | ||
C1—O1—H1 | 104.7 | C22—C21—C27 | 117.67 (19) |
O1—C1—C11 | 110.44 (15) | C23—C22—C21 | 120.8 (2) |
O1—C1—C6 | 105.13 (15) | C23—C22—H22 | 119.6 |
C11—C1—C6 | 109.13 (16) | C21—C22—H22 | 119.6 |
O1—C1—C2 | 110.36 (15) | C24—C23—C22 | 120.1 (2) |
C11—C1—C2 | 112.43 (16) | C24—C23—H23 | 119.9 |
C6—C1—C2 | 109.08 (15) | C22—C23—H23 | 119.9 |
C27—C2—C3 | 107.17 (15) | C23—C24—C25 | 119.9 (2) |
C27—C2—C1 | 109.90 (15) | C23—C24—H24 | 120.0 |
C3—C2—C1 | 111.12 (15) | C25—C24—H24 | 120.0 |
C27—C2—H2 | 109.5 | C24—C25—C26 | 120.3 (2) |
C3—C2—H2 | 109.5 | C24—C25—H25 | 119.9 |
C1—C2—H2 | 109.5 | C26—C25—H25 | 119.9 |
C31—C3—C2 | 113.25 (16) | C25—C26—C21 | 120.2 (2) |
C31—C3—C4 | 111.96 (15) | C25—C26—H26 | 119.9 |
C2—C3—C4 | 112.02 (15) | C21—C26—H26 | 119.9 |
C31—C3—H3 | 106.3 | O2—C27—C21 | 119.88 (18) |
C2—C3—H3 | 106.3 | O2—C27—C2 | 117.02 (17) |
C4—C3—H3 | 106.3 | C21—C27—C2 | 123.09 (17) |
C42—C4—C41 | 107.31 (16) | C32—C31—C36 | 118.81 (18) |
C42—C4—C5 | 109.65 (16) | C32—C31—C3 | 118.96 (17) |
C41—C4—C5 | 109.01 (15) | C36—C31—C3 | 122.23 (18) |
C42—C4—C3 | 112.23 (15) | C33—C32—C31 | 120.5 (2) |
C41—C4—C3 | 107.08 (16) | C33—C32—H32 | 119.7 |
C5—C4—C3 | 111.40 (15) | C31—C32—H32 | 119.7 |
C51—C5—C6 | 113.80 (16) | C34—C33—C32 | 120.4 (2) |
C51—C5—C4 | 113.03 (16) | C34—C33—H33 | 119.8 |
C6—C5—C4 | 108.78 (15) | C32—C33—H33 | 119.8 |
C51—C5—H5 | 106.9 | C35—C34—C33 | 119.4 (2) |
C6—C5—H5 | 106.9 | C35—C34—H34 | 120.3 |
C4—C5—H5 | 106.9 | C33—C34—H34 | 120.3 |
C5—C6—C1 | 112.37 (16) | C34—C35—C36 | 120.7 (2) |
C5—C6—H6A | 109.1 | C34—C35—H35 | 119.7 |
C1—C6—H6A | 109.1 | C36—C35—H35 | 119.7 |
C5—C6—H6B | 109.1 | C35—C36—C31 | 120.1 (2) |
C1—C6—H6B | 109.1 | C35—C36—H36 | 119.9 |
H6A—C6—H6B | 107.9 | C31—C36—H36 | 119.9 |
C12—C11—C16 | 118.28 (19) | N41—C41—C4 | 175.0 (2) |
C12—C11—C1 | 121.26 (18) | N42—C42—C4 | 178.2 (2) |
C16—C11—C1 | 120.34 (18) | C56—C51—C52 | 118.57 (19) |
C11—C12—C13 | 120.8 (2) | C56—C51—C5 | 119.62 (18) |
C11—C12—H12 | 119.6 | C52—C51—C5 | 121.80 (18) |
C13—C12—H12 | 119.6 | C53—C52—C51 | 120.3 (2) |
C14—C13—C12 | 120.2 (2) | C53—C52—H52 | 119.8 |
C14—C13—H13 | 119.9 | C51—C52—H52 | 119.8 |
C12—C13—H13 | 119.9 | C54—C53—C52 | 120.4 (2) |
C15—C14—C13 | 119.5 (2) | C54—C53—H53 | 119.8 |
C15—C14—H14 | 120.3 | C52—C53—H53 | 119.8 |
C13—C14—H14 | 120.3 | C53—C54—C55 | 119.8 (2) |
C14—C15—C16 | 120.5 (2) | C53—C54—H54 | 120.1 |
C14—C15—H15 | 119.8 | C55—C54—H54 | 120.1 |
C16—C15—H15 | 119.8 | C54—C55—C56 | 120.1 (2) |
C15—C16—C11 | 120.7 (2) | C54—C55—H55 | 119.9 |
C15—C16—H16 | 119.6 | C56—C55—H55 | 119.9 |
C11—C16—H16 | 119.6 | C51—C56—C55 | 120.8 (2) |
C26—C21—C22 | 118.63 (19) | C51—C56—H56 | 119.6 |
C26—C21—C27 | 123.69 (18) | C55—C56—H56 | 119.6 |
O1—C1—C2—C27 | −60.36 (19) | C26—C21—C22—C23 | 0.0 (3) |
C11—C1—C2—C27 | 63.4 (2) | C27—C21—C22—C23 | −179.02 (19) |
C6—C1—C2—C27 | −175.38 (15) | C21—C22—C23—C24 | 0.3 (3) |
O1—C1—C2—C3 | 58.09 (19) | C22—C23—C24—C25 | 0.4 (3) |
C11—C1—C2—C3 | −178.12 (15) | C23—C24—C25—C26 | −1.2 (3) |
C6—C1—C2—C3 | −56.9 (2) | C24—C25—C26—C21 | 1.5 (3) |
C27—C2—C3—C31 | −58.9 (2) | C22—C21—C26—C25 | −0.8 (3) |
C1—C2—C3—C31 | −178.94 (15) | C27—C21—C26—C25 | 178.1 (2) |
C27—C2—C3—C4 | 173.34 (15) | C26—C21—C27—O2 | −176.55 (19) |
C1—C2—C3—C4 | 53.3 (2) | C22—C21—C27—O2 | 2.4 (3) |
C31—C3—C4—C42 | −57.2 (2) | C26—C21—C27—C2 | 2.5 (3) |
C2—C3—C4—C42 | 71.3 (2) | C22—C21—C27—C2 | −178.59 (18) |
C31—C3—C4—C41 | 60.3 (2) | C3—C2—C27—O2 | −59.3 (2) |
C2—C3—C4—C41 | −171.22 (16) | C1—C2—C27—O2 | 61.5 (2) |
C31—C3—C4—C5 | 179.41 (15) | C3—C2—C27—C21 | 121.62 (19) |
C2—C3—C4—C5 | −52.1 (2) | C1—C2—C27—C21 | −117.52 (19) |
C42—C4—C5—C51 | 56.8 (2) | C2—C3—C31—C32 | 130.31 (19) |
C41—C4—C5—C51 | −60.4 (2) | C4—C3—C31—C32 | −101.9 (2) |
C3—C4—C5—C51 | −178.38 (16) | C2—C3—C31—C36 | −50.6 (2) |
C42—C4—C5—C6 | −70.64 (19) | C4—C3—C31—C36 | 77.3 (2) |
C41—C4—C5—C6 | 172.16 (16) | C36—C31—C32—C33 | −0.3 (3) |
C3—C4—C5—C6 | 54.2 (2) | C3—C31—C32—C33 | 178.84 (18) |
C51—C5—C6—C1 | 172.70 (16) | C31—C32—C33—C34 | −0.2 (3) |
C4—C5—C6—C1 | −60.3 (2) | C32—C33—C34—C35 | 0.5 (3) |
O1—C1—C6—C5 | −56.50 (19) | C33—C34—C35—C36 | −0.2 (3) |
C11—C1—C6—C5 | −174.97 (16) | C34—C35—C36—C31 | −0.3 (3) |
C2—C1—C6—C5 | 61.9 (2) | C32—C31—C36—C35 | 0.5 (3) |
O1—C1—C11—C12 | 172.97 (17) | C3—C31—C36—C35 | −178.59 (19) |
C6—C1—C11—C12 | −71.9 (2) | C6—C5—C51—C56 | −145.95 (19) |
C2—C1—C11—C12 | 49.2 (2) | C4—C5—C51—C56 | 89.3 (2) |
O1—C1—C11—C16 | −11.0 (2) | C6—C5—C51—C52 | 32.7 (3) |
C6—C1—C11—C16 | 104.1 (2) | C4—C5—C51—C52 | −92.1 (2) |
C2—C1—C11—C16 | −134.75 (18) | C56—C51—C52—C53 | −0.4 (3) |
C16—C11—C12—C13 | 1.9 (3) | C5—C51—C52—C53 | −179.03 (19) |
C1—C11—C12—C13 | 178.05 (19) | C51—C52—C53—C54 | 0.6 (3) |
C11—C12—C13—C14 | −1.3 (3) | C52—C53—C54—C55 | −0.7 (4) |
C12—C13—C14—C15 | −0.3 (3) | C53—C54—C55—C56 | 0.6 (4) |
C13—C14—C15—C16 | 1.3 (3) | C52—C51—C56—C55 | 0.3 (3) |
C14—C15—C16—C11 | −0.7 (3) | C5—C51—C56—C55 | 179.0 (2) |
C12—C11—C16—C15 | −1.0 (3) | C54—C55—C56—C51 | −0.4 (4) |
C1—C11—C16—C15 | −177.10 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2 | 0.84 | 1.97 | 2.702 (2) | 145 |
C12—H12···N42i | 0.95 | 2.59 | 3.536 (3) | 177 |
C24—H24···N41ii | 0.95 | 2.56 | 3.449 (3) | 157 |
C26—H26···N42i | 0.95 | 2.51 | 3.451 (3) | 171 |
C32—H32···O1iii | 0.95 | 2.42 | 3.325 (3) | 159 |
C56—H56···O2iii | 0.95 | 2.48 | 3.379 (3) | 157 |
C54—H54···Cgiv | 0.95 | 2.85 | 3.690 (3) | 148 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1, y, z−1; (iii) −x+1, −y+1, −z+1; (iv) −x+2, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C33H26N2O2 |
Mr | 482.56 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 10.9251 (18), 11.777 (3), 11.9438 (12) |
α, β, γ (°) | 90.417 (13), 112.616 (9), 112.750 (14) |
V (Å3) | 1286.1 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.59 × 0.47 × 0.35 |
Data collection | |
Diffractometer | Bruker–Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.946, 0.973 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 33243, 5800, 3387 |
Rint | 0.086 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.128, 1.04 |
No. of reflections | 5800 |
No. of parameters | 334 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.21 |
Computer programs: COLLECT (Hooft, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2 | 0.84 | 1.97 | 2.702 (2) | 145 |
C12—H12···N42i | 0.95 | 2.59 | 3.536 (3) | 177 |
C24—H24···N41ii | 0.95 | 2.56 | 3.449 (3) | 157 |
C26—H26···N42i | 0.95 | 2.51 | 3.451 (3) | 171 |
C32—H32···O1iii | 0.95 | 2.42 | 3.325 (3) | 159 |
C56—H56···O2iii | 0.95 | 2.48 | 3.379 (3) | 157 |
C54—H54···Cgiv | 0.95 | 2.85 | 3.690 (3) | 148 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1, y, z−1; (iii) −x+1, −y+1, −z+1; (iv) −x+2, −y+2, −z+1. |
As part of a programme for the synthesis of highly-substituted hydropyridone derivatives as potential bioactive compounds, we have considered the use, as a synthetic intermediate, of the Michael adduct obtained from malononitrile and 1,3-diphenyl-2-propen-1-one (chalcone). However, we have now found that under basic conditions this reaction provides not the expected simple adduct (López et al., 2001) but instead a mixture of compounds (Victory et al., 1991), from which the title compound, (I), was obtained in crystalline form. We report here the molecular and crystal structures of (I) (Fig. 1) at 120 K.
The structure of (I) has been reported using diffraction data collected at 294 K (Rong et al., 2006), but the unit cell reported by these authors [a = 10.996 (2) Å, b = 12.017 (2) Å, c = 12.109 (2) Å, α = 89.950 (4)°, β = 67.150 (3)° and γ = 67.821 (3)°] appears to differ significantly from that found here. While the repeat vectors are very similar, the reduced unit-cell angles at 294 K are all close to the supplementary values of the reduced angles at 120 K, i.e. each reduced angle θ (θ = α, β or γ) at 294 K corresponds closely to (180° - θ) at 120 K, with a maximum difference of ca 0.57° occurring in the angles γ; the corresponding atomic coordinates at the two temperatures are very precisely related by the transformation (1 - x, y, z). Furthermore, the crystal structure was described as a three-dimensional array of C—H···O and C—H···N hydrogen bonds (Rong et al., 2006), whereas at 120 K we find that the hydrogen-bonded structure is two-dimensional. We first describe the structure at 120 K, and we shall return below to both these points concerning the structure reported at 294 K.
The cyclohexane ring in (I) adopts the usual chair conformation, and the benzoyl and the three phenyl substituents all occupy equatorial sites, so that the hydroxy substituent necessarily occupies an axial site. There are four stereogenic centres and the configuration in the selected asymmetric unit is (1R,2S,3R,5S); since the compound crystallizes in a centrosymmetric space group, the overall configuration for the racemic mixture can be described as (1RS,2SR,3RS,5SR). The bond lengths and angles present no unusual features.
There is an intramolecular O—H···O hydrogen bond (Table 1), and the molecules are linked into complex sheets by a combination of three C—H···N hydrogen bonds and two C—H···O hydrogen bonds. The sheet formation is readily analysed in terms of two one-dimensional substructures, one of which utilizes just one hydrogen bond while the other utilizes four hydrogen bonds. In the simpler of the two substructures, atom C24 in the benzoyl group of the molecule at (x, y, z) acts as a hydrogen-bond donor to atom N41 in the equatorial cyano substituent of the molecule at (-1 + x, y, -1 + z); in this way a C(11) (Bernstein et al., 1995) chain is generated by translation along the [101] direction (Fig. 2).
The second and more complex of the one-dimensional substructures is built from two C—H···O and two C—H···N hydrogen bonds. The aryl atoms C32 and C56 in the molecule at (x, y, z) act as donors, respectively, to atoms O1 and O2 both in the molecule at (1 - x, 1 - y, 1 - z). Within the resulting dimeric unit the two hydrogen bonds acting independently generate centrosymmetric R22(14) and R22(18) rings, respectively, while their combination generates a noncentrosymmetric R22(14) motif. In addition, the aryl atoms C12 and C26 in the molecule at (x, y, z) both act as hydrogen-bond donors to the axial cyano atom N42 in the molecule at (1 - x, 2 - y, 1 - z); in combination, these interactions generate an R12(10) motif, while individually, each independently generates a centrosymmetric R22(18) ring. The combination of these four hydrogen bonds then generates a complex chain of rings running parallel to the [010] direction, with the centrosymmetric rings built from C—H···O hydrogen bonds and centred at (1/2, 1/2 + n, 1/2) (where n represents zero or an integer) alternating with the corresponding rings built from C—H···N hydrogen bonds and centred at (1/2, n, 1/2) (where n represents zero or an integer) (Fig. 3). The combination of the chains along [010] and [101] generates a complex sheet lying parallel to (101) (Fig. 4). The only direction-specific interaction linking the adjacent sheets is a single C—H···π(arene) interaction (Table 1).
As expected the repeat vectors reported at 294 K (Rong et al., 2006) are greater than those found here at 120 K, with the maximum difference of 0.240 (3) Å (ca 2%) occurring in the vector b. Similarly, for the unit-cell angles the magnitudes of the differences between θ at 294 K and (180° - θ) at 120 K range from 0.234 (9)° in β to 0.57 (2)° in γ. However, at both temperatures the cell angle α is very close to 90°, and the angle reported at 294 K is 89.950 (4)°. If this value is artificially set to be 90.050 (4)°, then the resulting reduced cell has values of β and γ corresponding almost exactly to those found at 120 K. Hence the apparently substantial differences between the unit-cell dimensions at 120 and 294 K are most plausibly explained as a consequence of a small change in the angle α from one side of 90° to the other, resulting in a change in the reduced cell angles and a concomitant change in the atom coordinates. It has been suggested, although without formal proof (Andrews et al., 1980), that the combination of reduced cell lengths in real and reciprocal spaces together with the reduced cell volume provides a unique description of a crystal lattice. Accordingly, the use of this set of parameters enables comparison of lattices or of unit cells without reference to the cell angles. This proposal was developed specifically in response to the large and discontinuous jumps in the unit-cell angles which can occur when there are only very small changes in the overall lattice, exactly as in the example described here.
The overall hydrogen-bonded structures are the same at the two temperatures. Although Rong et al. (2006) described their hydrogen-bonded structure as three-dimensional, an analysis based on the hydrogen bonds found at 294 K shows clearly that the structure is two-dimensional, exactly as at 120 K (Fig. 5). The packing diagram presented in the earlier report (Rong et al., 2006) in fact shows a centrosymmetric aggregate of four molecules, those at (x, y, z), (-1 + x, y, 1 + z), (1 - x, 1 - y, 1 - z) and (2 - x, 1 - y, -z), which does not illustrate a repeating unit even in one dimension, far less the three-dimensional network postulated.
An interesting comparison can be made with the 3,5-bis(4-methylphenyl) analogue (II) [Cambridge Structural Database (CSD; Allen, 2002) refcode JEVYEO (Al-Arab, 1990)], which also crystallizes in space group P1. The unit-cell angles for (II) are rather similar to those reported for (I) at 294 K, except that now it is the cell angle γ = 89.46 (2)° which is very close to 90°, while the atomic coordinates can be related to those reported here for corresponding atoms by the transformation (1/2 - z, y, x). The a and b unit-cell vectors reported for (II) at 130 K are almost identical to the values of b and c, respectively, found here for (I) at 120 K, but there has been a reordering of the repeat vectors, thus (cab). This, and the interchange of the x and z coordinates, results from the slight `stretching' of the crystal structure, predominantly in one direction, which is a consequence of the introduction of methyl groups into two of the aryl rings. As a result of this stretching of the structure of (II) as compared with that of (I), only two of the intermolecular contacts found in (I) are still within effective hydrogen-bonding distances in (II), one each of the C—H···O and C—H···N types. These form, respectively, a centrosymmetric R22(14) ring and a C(11) chain generated by translation, exactly analogous to the corresponding motifs in (I). In combination, these two hydrogen bonds link the molecules of (II) into a chain of alternating centrosymmetric R22(14) and R44(36) rings (Fig. 6).
In the more heavily-substituted analogue (III) [CSD refcode PEHYUW (Al-Arab et al., 1992)], which crystallizes in P1 as a stoichiometric acetic acid solvate, with the cyano group occupying an axial site, the molecules of the cyclohexanol component are linked by paired C—H···N hydrogen bonds into a centrosymmetric R22(14) dimer (Fig. 7), while the acetic acid component independently forms the usual R22(8) dimer. The structure of the trifluoromethyl derivative (IV) has been reported [CSD code NAVZAL (Sanin et al., 1997)], but no H-atom coordinates are deposited in the CSD, so that useful discussion of the intermolecular aggregation is not possible.