Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803001569/fl6016sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803001569/fl60164sup2.hkl |
CCDC reference: 204714
Single crystals were obtained from methanol–methylene chloride solutions. Due to the weakly diffracting nature of the sample and the small crystal size, it was necessary to collect data using synchrotron radiation rather than a laboratory source. A suitable crystal was mounted on the tip of a glass fiber with paratone-N and immediately transferred to the goniostat bathed in a cold stream. Intensity data were collected at 173 K using a Proteum300 detector at Beamline 11.3.1 at the Advanced Light Source (Lawrence Berkeley National Laboratory). The detector was set at a distance of 6.6 cm from the crystal. A series of 1 s data frames measured at 0.2° increments of ω were collected to calculate a unit cell and to measure a hemisphere of intensity data. Data were corrected for absorption using SADABS (6, 1 harmonics) and a high resolution limit of 0.85 Å applied, based on examination of the final merged listing from SAINT. A high |I-<I>| error was also applied (10 s.u.) to remove outliers from the data set.
All H atoms were included in calculated geometries (C—H = 0.95 Å) riding on the atoms to which they are bonded. The isotropic displacement parameters for the H atoms were set as 1.2Ueq of the adjacent atom.
Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Crystal Impact, 1997); software used to prepare material for publication: SHELXTL.
C32H21NO2 | F(000) = 944 |
Mr = 451.50 | Dx = 1.253 Mg m−3 |
Monoclinic, P21/c | Synchrotron radiation, λ = 0.88500 Å |
a = 13.583 (3) Å | Cell parameters from 4292 reflections |
b = 7.6515 (14) Å | θ = 6.9–29.0° |
c = 23.399 (5) Å | µ = 0.08 mm−1 |
β = 100.093 (11)° | T = 173 K |
V = 2394.2 (9) Å3 | Needle, orange |
Z = 4 | 0.07 × 0.06 × 0.05 mm |
Proteum 300 detector diffractometer | 3438 independent reflections |
Radiation source: Beamline 11.3.1 ALS at LBL | 2579 reflections with I > 2σ(I) |
Channel cut SiIII monochromator | Rint = 0.095 |
ω scans | θmax = 29.5°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −15→15 |
Tmin = 0.995, Tmax = 0.996 | k = −7→8 |
19213 measured reflections | l = −25→25 |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + 0.5111P] where P = (Fo2 + 2Fc2)/3 |
3438 reflections | (Δ/σ)max < 0.001 |
316 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C32H21NO2 | V = 2394.2 (9) Å3 |
Mr = 451.50 | Z = 4 |
Monoclinic, P21/c | Synchrotron radiation, λ = 0.88500 Å |
a = 13.583 (3) Å | µ = 0.08 mm−1 |
b = 7.6515 (14) Å | T = 173 K |
c = 23.399 (5) Å | 0.07 × 0.06 × 0.05 mm |
β = 100.093 (11)° |
Proteum 300 detector diffractometer | 3438 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 2579 reflections with I > 2σ(I) |
Tmin = 0.995, Tmax = 0.996 | Rint = 0.095 |
19213 measured reflections | θmax = 29.5° |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.19 e Å−3 |
3438 reflections | Δρmin = −0.24 e Å−3 |
316 parameters |
Experimental. Single crystals were obtained from methanol-methylene chloride solutions. Due to the weakly diffracting nature of the sample and the small crystal size, it was necessary to collect data using synchrotron radiation rather than a lab source. A suitable crystal was mounted on the tip of a glass fiber with paratone-N and immediately transferred to the goniostat bathed in a cold stream. Intensity data was collected at 173 K using a Proteum300 detector at Beamline 11.3.1 at the Advanced Light Source (Lawrence Berkeley National Laboratory). The detector was set at a distance of 6.6-cm from the crystal. A series of 1 − s data frames measured at 0.2° increments of ω were collected to calculate a unit cell and to measure a hemisphere of intensity data. Data was corrected for absorption using SADABS (6, 1 harmonics) and a high resolution limit of 0.85 Å applied, based on examination of the final merged listing from SAINT. A high |I-<I>| error was also applied (10 su) to remove outliers from the dataset. No formal measure of the extent of decay is printed out by this program. The final unit cell is obtained from the refinement of the XYZ weighted centroids of reflections above 20 σ(I). Note that the absorption correction parameters Tmin and Tmax also reflect beam corrections, etc. As a result, the numerical values for Tmin and Tmax may differ from expected values based solely absorption effects and crystal size. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections out to 0.85 Å. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.02775 (16) | 0.9713 (3) | 0.13521 (12) | 0.0680 (8) | |
O2 | −0.05727 (15) | 0.8194 (3) | 0.18773 (11) | 0.0639 (7) | |
N1 | 0.02171 (19) | 0.8735 (3) | 0.17582 (13) | 0.0453 (7) | |
C1 | 0.38061 (18) | 0.6603 (3) | 0.32111 (12) | 0.0304 (6) | |
H1 | 0.3725 | 0.6362 | 0.3598 | 0.037* | |
C2 | 0.47420 (17) | 0.6394 (3) | 0.30964 (11) | 0.0253 (6) | |
C3 | 0.49742 (17) | 0.6450 (3) | 0.25153 (11) | 0.0253 (6) | |
H3 | 0.4447 | 0.6119 | 0.2212 | 0.030* | |
C4 | 0.58388 (17) | 0.6910 (3) | 0.23476 (11) | 0.0232 (6) | |
C5 | 0.55104 (19) | 0.5937 (3) | 0.35773 (12) | 0.0322 (7) | |
C6 | 0.6116 (2) | 0.5504 (3) | 0.39859 (12) | 0.0342 (7) | |
C7 | 0.66254 (18) | 0.7693 (3) | 0.27574 (11) | 0.0254 (6) | |
C8 | 0.72854 (18) | 0.8400 (3) | 0.30769 (11) | 0.0262 (6) | |
C11 | 0.29091 (18) | 0.7152 (3) | 0.28175 (11) | 0.0262 (6) | |
C12 | 0.29205 (18) | 0.8179 (3) | 0.23300 (12) | 0.0289 (6) | |
H12 | 0.3544 | 0.8525 | 0.2235 | 0.035* | |
C13 | 0.20470 (19) | 0.8709 (3) | 0.19798 (12) | 0.0316 (7) | |
H13 | 0.2062 | 0.9412 | 0.1647 | 0.038* | |
C14 | 0.11478 (18) | 0.8188 (3) | 0.21268 (12) | 0.0322 (7) | |
C15 | 0.11026 (19) | 0.7179 (3) | 0.26037 (13) | 0.0370 (7) | |
H15 | 0.0476 | 0.6833 | 0.2694 | 0.044* | |
C16 | 0.19769 (19) | 0.6675 (3) | 0.29493 (12) | 0.0348 (7) | |
H16 | 0.1952 | 0.5989 | 0.3285 | 0.042* | |
C21 | 0.68427 (18) | 0.4998 (3) | 0.44801 (11) | 0.0291 (6) | |
C22 | 0.6596 (2) | 0.3797 (3) | 0.48760 (13) | 0.0403 (7) | |
H22 | 0.5942 | 0.3315 | 0.4824 | 0.048* | |
C23 | 0.7305 (2) | 0.3304 (3) | 0.53474 (12) | 0.0428 (8) | |
H23 | 0.7137 | 0.2473 | 0.5616 | 0.051* | |
C24 | 0.8246 (2) | 0.4003 (3) | 0.54289 (12) | 0.0389 (7) | |
H24 | 0.8727 | 0.3662 | 0.5755 | 0.047* | |
C25 | 0.8495 (2) | 0.5194 (3) | 0.50418 (12) | 0.0364 (7) | |
H25 | 0.9148 | 0.5683 | 0.5101 | 0.044* | |
C26 | 0.78007 (19) | 0.5686 (3) | 0.45645 (12) | 0.0335 (7) | |
H26 | 0.7981 | 0.6499 | 0.4294 | 0.040* | |
C31 | 0.81010 (18) | 0.9151 (3) | 0.34704 (11) | 0.0247 (6) | |
C32 | 0.7951 (2) | 1.0115 (3) | 0.39437 (12) | 0.0396 (7) | |
H32 | 0.7291 | 1.0308 | 0.4013 | 0.048* | |
C33 | 0.8757 (3) | 1.0803 (4) | 0.43174 (14) | 0.0557 (9) | |
H33 | 0.8652 | 1.1466 | 0.4645 | 0.067* | |
C34 | 0.9715 (3) | 1.0527 (4) | 0.42150 (15) | 0.0556 (10) | |
H34 | 1.0268 | 1.1006 | 0.4472 | 0.067* | |
C35 | 0.9872 (2) | 0.9574 (4) | 0.37489 (14) | 0.0456 (8) | |
H35 | 1.0533 | 0.9382 | 0.3683 | 0.055* | |
C36 | 0.90747 (19) | 0.8890 (3) | 0.33745 (12) | 0.0328 (7) | |
H36 | 0.9187 | 0.8234 | 0.3047 | 0.039* | |
C41 | 0.60290 (18) | 0.6674 (3) | 0.17517 (11) | 0.0262 (6) | |
C42 | 0.6912 (2) | 0.7229 (3) | 0.15912 (14) | 0.0442 (8) | |
H42 | 0.7403 | 0.7774 | 0.1874 | 0.053* | |
C43 | 0.7102 (3) | 0.7023 (4) | 0.10406 (16) | 0.0577 (9) | |
H43 | 0.7713 | 0.7435 | 0.0946 | 0.069* | |
C44 | 0.6417 (3) | 0.6226 (4) | 0.06259 (14) | 0.0528 (9) | |
H44 | 0.6538 | 0.6104 | 0.0240 | 0.063* | |
C45 | 0.5545 (2) | 0.5600 (4) | 0.07773 (14) | 0.0584 (9) | |
H45 | 0.5070 | 0.5019 | 0.0494 | 0.070* | |
C46 | 0.5354 (2) | 0.5805 (4) | 0.13287 (13) | 0.0456 (8) | |
H46 | 0.4753 | 0.5348 | 0.1425 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0564 (15) | 0.0513 (12) | 0.083 (2) | 0.0100 (11) | −0.0259 (13) | 0.0134 (13) |
O2 | 0.0229 (12) | 0.0813 (15) | 0.0836 (19) | 0.0082 (11) | −0.0016 (11) | −0.0222 (13) |
N1 | 0.0337 (16) | 0.0364 (13) | 0.0584 (19) | 0.0103 (12) | −0.0120 (13) | −0.0161 (13) |
C1 | 0.0300 (16) | 0.0351 (13) | 0.0251 (16) | −0.0014 (12) | 0.0019 (12) | −0.0020 (12) |
C2 | 0.0222 (14) | 0.0266 (12) | 0.0248 (16) | −0.0013 (10) | −0.0026 (11) | −0.0020 (11) |
C3 | 0.0211 (14) | 0.0261 (12) | 0.0260 (15) | 0.0003 (10) | −0.0036 (11) | 0.0015 (11) |
C4 | 0.0232 (15) | 0.0169 (11) | 0.0275 (16) | 0.0009 (10) | −0.0011 (11) | 0.0025 (10) |
C5 | 0.0277 (15) | 0.0374 (14) | 0.0311 (17) | −0.0013 (12) | 0.0036 (13) | −0.0008 (13) |
C6 | 0.0313 (16) | 0.0412 (15) | 0.0293 (17) | 0.0024 (12) | 0.0028 (14) | 0.0022 (13) |
C7 | 0.0223 (14) | 0.0178 (11) | 0.0364 (17) | 0.0010 (11) | 0.0059 (12) | 0.0030 (11) |
C8 | 0.0252 (15) | 0.0210 (11) | 0.0324 (17) | −0.0025 (11) | 0.0055 (12) | 0.0023 (11) |
C11 | 0.0227 (14) | 0.0252 (12) | 0.0304 (16) | −0.0007 (10) | 0.0035 (11) | −0.0055 (12) |
C12 | 0.0202 (14) | 0.0238 (12) | 0.0418 (18) | −0.0043 (10) | 0.0034 (12) | −0.0023 (12) |
C13 | 0.0324 (16) | 0.0222 (12) | 0.0376 (18) | −0.0001 (11) | −0.0010 (13) | −0.0011 (11) |
C14 | 0.0213 (15) | 0.0257 (12) | 0.0460 (19) | 0.0049 (11) | −0.0041 (12) | −0.0125 (13) |
C15 | 0.0209 (15) | 0.0399 (15) | 0.052 (2) | 0.0010 (12) | 0.0104 (13) | −0.0086 (14) |
C16 | 0.0311 (16) | 0.0399 (14) | 0.0354 (17) | 0.0003 (12) | 0.0115 (13) | −0.0008 (13) |
C21 | 0.0309 (15) | 0.0329 (13) | 0.0217 (15) | 0.0017 (12) | −0.0003 (11) | −0.0025 (12) |
C22 | 0.0381 (17) | 0.0481 (16) | 0.0335 (18) | −0.0099 (13) | 0.0030 (13) | 0.0020 (14) |
C23 | 0.060 (2) | 0.0428 (15) | 0.0252 (17) | −0.0025 (15) | 0.0053 (14) | 0.0072 (13) |
C24 | 0.0455 (19) | 0.0398 (15) | 0.0260 (17) | 0.0042 (14) | −0.0084 (13) | −0.0035 (13) |
C25 | 0.0315 (16) | 0.0377 (14) | 0.0368 (18) | −0.0009 (12) | −0.0024 (13) | −0.0059 (13) |
C26 | 0.0363 (16) | 0.0320 (13) | 0.0311 (17) | −0.0027 (12) | 0.0026 (12) | 0.0050 (12) |
C31 | 0.0301 (15) | 0.0159 (10) | 0.0260 (16) | −0.0014 (10) | −0.0006 (11) | 0.0040 (11) |
C32 | 0.0485 (18) | 0.0324 (13) | 0.0373 (19) | −0.0004 (13) | 0.0058 (14) | −0.0035 (13) |
C33 | 0.087 (3) | 0.0383 (15) | 0.037 (2) | −0.0080 (17) | −0.0037 (18) | −0.0118 (14) |
C34 | 0.064 (2) | 0.0416 (17) | 0.048 (2) | −0.0186 (16) | −0.0258 (18) | 0.0075 (16) |
C35 | 0.0334 (17) | 0.0461 (16) | 0.051 (2) | −0.0066 (13) | −0.0113 (15) | 0.0056 (16) |
C36 | 0.0294 (16) | 0.0311 (13) | 0.0359 (17) | −0.0020 (11) | 0.0001 (12) | 0.0003 (12) |
C41 | 0.0262 (14) | 0.0207 (11) | 0.0312 (17) | 0.0010 (11) | 0.0036 (11) | 0.0047 (11) |
C42 | 0.0440 (18) | 0.0455 (16) | 0.046 (2) | −0.0193 (14) | 0.0157 (15) | −0.0096 (14) |
C43 | 0.069 (2) | 0.0522 (18) | 0.061 (3) | −0.0232 (17) | 0.0359 (19) | −0.0114 (17) |
C44 | 0.076 (2) | 0.0515 (18) | 0.036 (2) | 0.0057 (17) | 0.0239 (18) | 0.0065 (15) |
C45 | 0.055 (2) | 0.087 (2) | 0.032 (2) | −0.0006 (18) | 0.0016 (16) | −0.0109 (17) |
C46 | 0.0319 (17) | 0.0696 (19) | 0.0344 (19) | −0.0056 (14) | 0.0031 (14) | −0.0047 (15) |
O1—N1 | 1.224 (3) | C23—C24 | 1.368 (4) |
O2—N1 | 1.227 (3) | C23—H23 | 0.9500 |
N1—C14 | 1.461 (3) | C24—C25 | 1.368 (4) |
C1—C2 | 1.354 (3) | C24—H24 | 0.9500 |
C1—C11 | 1.454 (3) | C25—C26 | 1.382 (4) |
C1—H1 | 0.9500 | C25—H25 | 0.9500 |
C2—C5 | 1.437 (4) | C26—H26 | 0.9500 |
C2—C3 | 1.449 (4) | C31—C32 | 1.376 (4) |
C3—C4 | 1.348 (3) | C31—C36 | 1.394 (4) |
C3—H3 | 0.9500 | C32—C33 | 1.380 (4) |
C4—C7 | 1.436 (3) | C32—H32 | 0.9500 |
C4—C41 | 1.473 (4) | C33—C34 | 1.380 (5) |
C5—C6 | 1.193 (3) | C33—H33 | 0.9500 |
C6—C21 | 1.436 (4) | C34—C35 | 1.360 (5) |
C7—C8 | 1.192 (3) | C34—H34 | 0.9500 |
C8—C31 | 1.431 (3) | C35—C36 | 1.371 (4) |
C11—C12 | 1.388 (4) | C35—H35 | 0.9500 |
C11—C16 | 1.403 (4) | C36—H36 | 0.9500 |
C12—C13 | 1.379 (3) | C41—C42 | 1.385 (4) |
C12—H12 | 0.9500 | C41—C46 | 1.394 (4) |
C13—C14 | 1.384 (4) | C42—C43 | 1.367 (4) |
C13—H13 | 0.9500 | C42—H42 | 0.9500 |
C14—C15 | 1.367 (4) | C43—C44 | 1.364 (4) |
C15—C16 | 1.370 (4) | C43—H43 | 0.9500 |
C15—H15 | 0.9500 | C44—C45 | 1.380 (4) |
C16—H16 | 0.9500 | C44—H44 | 0.9500 |
C21—C26 | 1.386 (4) | C45—C46 | 1.369 (4) |
C21—C22 | 1.387 (4) | C45—H45 | 0.9500 |
C22—C23 | 1.384 (4) | C46—H46 | 0.9500 |
C22—H22 | 0.9500 | ||
O1—N1—O2 | 124.3 (3) | C23—C24—C25 | 120.1 (3) |
O1—N1—C14 | 117.7 (3) | C23—C24—H24 | 119.9 |
O2—N1—C14 | 118.0 (3) | C25—C24—H24 | 119.9 |
C2—C1—C11 | 128.3 (3) | C24—C25—C26 | 120.2 (3) |
C2—C1—H1 | 115.8 | C24—C25—H25 | 119.9 |
C11—C1—H1 | 115.8 | C26—C25—H25 | 119.9 |
C1—C2—C5 | 116.8 (2) | C25—C26—C21 | 120.2 (2) |
C1—C2—C3 | 123.3 (2) | C25—C26—H26 | 119.9 |
C5—C2—C3 | 119.6 (2) | C21—C26—H26 | 119.9 |
C4—C3—C2 | 128.6 (2) | C32—C31—C36 | 119.0 (2) |
C4—C3—H3 | 115.7 | C32—C31—C8 | 121.8 (2) |
C2—C3—H3 | 115.7 | C36—C31—C8 | 119.2 (2) |
C3—C4—C7 | 119.9 (2) | C31—C32—C33 | 120.1 (3) |
C3—C4—C41 | 123.3 (2) | C31—C32—H32 | 119.9 |
C7—C4—C41 | 116.7 (2) | C33—C32—H32 | 119.9 |
C6—C5—C2 | 176.8 (3) | C34—C33—C32 | 119.9 (3) |
C5—C6—C21 | 179.5 (3) | C34—C33—H33 | 120.0 |
C8—C7—C4 | 176.8 (3) | C32—C33—H33 | 120.0 |
C7—C8—C31 | 176.7 (2) | C35—C34—C33 | 120.4 (3) |
C12—C11—C16 | 117.9 (2) | C35—C34—H34 | 119.8 |
C12—C11—C1 | 123.7 (2) | C33—C34—H34 | 119.8 |
C16—C11—C1 | 118.3 (2) | C34—C35—C36 | 120.0 (3) |
C13—C12—C11 | 121.5 (2) | C34—C35—H35 | 120.0 |
C13—C12—H12 | 119.3 | C36—C35—H35 | 120.0 |
C11—C12—H12 | 119.3 | C35—C36—C31 | 120.5 (3) |
C12—C13—C14 | 118.2 (3) | C35—C36—H36 | 119.7 |
C12—C13—H13 | 120.9 | C31—C36—H36 | 119.7 |
C14—C13—H13 | 120.9 | C42—C41—C46 | 116.6 (3) |
C15—C14—C13 | 122.2 (2) | C42—C41—C4 | 121.5 (2) |
C15—C14—N1 | 119.0 (3) | C46—C41—C4 | 121.8 (2) |
C13—C14—N1 | 118.7 (3) | C43—C42—C41 | 122.4 (3) |
C14—C15—C16 | 118.8 (3) | C43—C42—H42 | 118.8 |
C14—C15—H15 | 120.6 | C41—C42—H42 | 118.8 |
C16—C15—H15 | 120.6 | C44—C43—C42 | 120.3 (3) |
C15—C16—C11 | 121.3 (3) | C44—C43—H43 | 119.9 |
C15—C16—H16 | 119.4 | C42—C43—H43 | 119.9 |
C11—C16—H16 | 119.4 | C43—C44—C45 | 118.8 (3) |
C26—C21—C22 | 119.2 (2) | C43—C44—H44 | 120.6 |
C26—C21—C6 | 120.6 (2) | C45—C44—H44 | 120.6 |
C22—C21—C6 | 120.3 (2) | C46—C45—C44 | 121.0 (3) |
C23—C22—C21 | 119.8 (3) | C46—C45—H45 | 119.5 |
C23—C22—H22 | 120.1 | C44—C45—H45 | 119.5 |
C21—C22—H22 | 120.1 | C45—C46—C41 | 120.9 (3) |
C24—C23—C22 | 120.5 (3) | C45—C46—H46 | 119.5 |
C24—C23—H23 | 119.8 | C41—C46—H46 | 119.5 |
C22—C23—H23 | 119.8 |
Experimental details
Crystal data | |
Chemical formula | C32H21NO2 |
Mr | 451.50 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 13.583 (3), 7.6515 (14), 23.399 (5) |
β (°) | 100.093 (11) |
V (Å3) | 2394.2 (9) |
Z | 4 |
Radiation type | Synchrotron, λ = 0.88500 Å |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.07 × 0.06 × 0.05 |
Data collection | |
Diffractometer | Proteum 300 detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.995, 0.996 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19213, 3438, 2579 |
Rint | 0.095 |
θmax (°) | 29.5 |
(sin θ/λ)max (Å−1) | 0.556 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.156, 1.07 |
No. of reflections | 3438 |
No. of parameters | 316 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.24 |
Computer programs: SMART (Bruker, 2001), SMART, SAINT (Bruker, 2001), SHELXTL (Bruker, 2001), SHELXTL and DIAMOND (Crystal Impact, 1997).
O1—N1 | 1.224 (3) | C3—C4 | 1.348 (3) |
O2—N1 | 1.227 (3) | C4—C7 | 1.436 (3) |
N1—C14 | 1.461 (3) | C4—C41 | 1.473 (4) |
C1—C2 | 1.354 (3) | C5—C6 | 1.193 (3) |
C1—C11 | 1.454 (3) | C6—C21 | 1.436 (4) |
C2—C5 | 1.437 (4) | C7—C8 | 1.192 (3) |
C2—C3 | 1.449 (4) | C8—C31 | 1.431 (3) |
O1—N1—O2 | 124.3 (3) | C4—C3—C2 | 128.6 (2) |
O1—N1—C14 | 117.7 (3) | C3—C4—C7 | 119.9 (2) |
O2—N1—C14 | 118.0 (3) | C6—C5—C2 | 176.8 (3) |
C2—C1—C11 | 128.3 (3) | C5—C6—C21 | 179.5 (3) |
C1—C2—C5 | 116.8 (2) | C8—C7—C4 | 176.8 (3) |
C1—C2—C3 | 123.3 (2) | C7—C8—C31 | 176.7 (2) |
C5—C2—C3 | 119.6 (2) |
In this paper, we report the X-ray structure and stacking of 1-(4-nitrophenyl)-4-phenyl-2,4-bis(phenylethynyl)butadiene, (IV). This compound was isolated as a side product during the Sonogashira (Shonogashira et al., 1975) coupling reaction of β,β-dibromo-p-nitrostyrene, (I), and phenylacetylene to afford Y-enyne (II) (Kaafarani & Neckers, 2001; Kaafarani et al., 2001; Kaafarani, Wex, Krause Bauer & Neckers, 2002; Kaafarani, Wex, Strehmel & Neckers, 2002). Diyne, formed by reductive elimination, is a classical side product in the course of the Sonogahsira coupling reaction [in this case, 1,4-diphenylbutadiyne (III)] (Nicholaou & Sorensen, 1996). It appears to us that compound (IV) is formed after the addition of another phenylacetylene to Y-enyne (II). To the best of our knowledge, this is the first report of such a side product in the Sonogashira coupling reaction.
The molecular structure of (IV) is shown in Fig. 1. Nitro substitution was reported to induce π–π-stacking interactions (Garden et al., 2002). The nitro-substitution-induced π–π-stacking and nitro–π-stacking interactions in (IV) are shown in Fig. 2. The distance between the centroids of the phenyl rings alternates between 4.96 and 5.35 Å. The distance between the centers of the acetylene triple bonds is 3.28 Å. The strong electron-withdrawing NO2 group interacts with the π-system of the phenyl ring of a neighboring molecule. The distance between the N atom and the center of the phenyl rings varies between 3.58 and 5.08 Å for the alternating layers (Fig. 2). The molecular packing of (IV) is shown in Fig. 3.
The scanning electron micrograph (SEM) of (IV) shows its crystal habit in the form of complex, cactus-like needles with a diameter of several micrometers (Fig. 4). Interestingly, these tubes seem hollow; however, a shadow effect induced by the restricted lateral placement of the detector in the SEM can not be excluded and further analysis will be required to confirm this observation.