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In recent years, a series of non-linear optically active bis(benzylidene) ketones have been synthesized and investigated by electron crystallography. In most cases, structure refinement was possible by combining electron diffraction analysis and quantum-mechanical calculations with maximum-entropy methods. However, when the torsional angles between the phenyl rings and the C=C double bonds are strongly affected by the crystal field, this method fails because packing-energy calculations are not sufficiently sensitive. This problem can be solved by refining the approximate model with SHELXL, if the data set is sufficiently accurate and the model close to the correct structure. Here it is shown that a considerably superior data set can be obtained at 300 kV with on-line data acquisition.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108767300006668/au0194sup1.cif
Contains datablocks global, sim, Xray, em

CCDC reference: 153322

Computing details top

Figures top
[Figure 1]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
[Figure 7]
[Figure 8]
[Figure 9]
[Figure 10]
[Figure 11]
[Figure 12]
(sim) top
Crystal data top
C22H22O5β = 91.710 (7)°
Mr = 366.40V = 1861.9 (3) Å3
Monoclinic, P21/cZ = 4
a = 15.95 (2) ÅDx = 1.307 Mg m3
b = 13.87 (5) ÅCu radiation, λ = 1.54178 Å
c = 8.42 (1) Å × × mm
Data collection top
h = ??l = ??
k = ??
Refinement top
Crystal data top
C22H22O5β = 91.710 (7)°
Mr = 366.40V = 1861.9 (3) Å3
Monoclinic, P21/cZ = 4
a = 15.95 (2) ÅCu radiation, λ = 1.54178 Å
b = 13.87 (5) Å × × mm
c = 8.42 (1) Å
Data collection top
Refinement top
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzBiso*/Beq
C10.55610.45780.2412
C20.48660.50280.3135
C30.40580.48260.2604
C40.39110.41590.1360
C50.46250.37150.0620
C60.54320.39230.1136
C70.30440.39950.0912
C80.26120.31770.0515
C90.17130.33350.0057
C100.12160.24830.0521
C110.16060.14880.0490
C120.22730.14010.0790
C130.29620.21610.0546
C140.04190.26880.1005
C150.02330.20810.1671
C160.09180.25570.2407
C170.15830.20510.3082
C180.15700.10220.3063
C190.08890.05460.2377
C200.02300.10600.1686
O210.63530.47640.2892
O220.61690.35540.0519
C230.61320.29000.0771
O240.13950.41500.0116
O250.22250.05580.3739
O260.22590.24560.3785
C270.23080.34740.3854
Geometric parameters (Å, º) top
C1—C21.402C10—C141.371
C1—C61.425C11—C121.534
C1—O211.357C12—C131.534
C2—C31.400C14—C151.460
C3—C41.421C15—C161.428
C4—C51.428C15—C201.417
C4—C71.458C16—C171.400
C5—C61.397C17—C181.428
C6—O221.375C17—O261.361
C7—C81.373C18—C191.404
C8—C91.508C18—O251.361
C8—C131.516C19—C201.404
C9—C101.509O22—C231.418
C9—O241.240O26—C271.416
C10—C111.515
C6—C1—C2119.2C14—C10—C9115.4
O21—C1—C2121.3C14—C10—C11125.2
O21—C1—C6119.6C12—C11—C10111.9
C3—C2—C1119.9C13—C12—C11110.9
C4—C3—C2122.0C12—C13—C8112.2
C5—C4—C3117.5C15—C14—C10131.8
C7—C4—C3117.5C16—C15—C14117.2
C7—C4—C5125.0C20—C15—C14125.3
C6—C5—C4120.5C20—C15—C16117.5
C5—C6—C1120.9C17—C16—C15122.3
O22—C6—C1112.9C18—C17—C16119.0
O22—C6—C5126.3O26—C17—C16125.6
C8—C7—C4132.4O26—C17—C18115.5
C9—C8—C7115.2C19—C18—C17119.1
C13—C8—C7125.3O25—C18—C17117.2
C13—C8—C9119.5O25—C18—C19123.7
C10—C9—C8118.4C20—C19—C18121.5
O24—C9—C8120.8C19—C20—C15120.5
O24—C9—C10120.7C23—O22—C6118.8
C11—C10—C9119.4C27—O26—C17118.3
(Xray) top
Crystal data top
C22H22O5β = 91.710 (7)°
Mr = 366.40V = 1824.5 (3) Å3
Monoclinic, P21/cZ = 4
a = 15.937 (2) ÅDx = 1.334 Mg m3
b = 13.819 (1) ÅCu radiation, λ = 1.54178 Å
c = 8.288 (1) Å × × mm
Data collection top
h = ??l = ??
k = ??
Refinement top
Crystal data top
C22H22O5β = 91.710 (7)°
Mr = 366.40V = 1824.5 (3) Å3
Monoclinic, P21/cZ = 4
a = 15.937 (2) ÅCu radiation, λ = 1.54178 Å
b = 13.819 (1) Å × × mm
c = 8.288 (1) Å
Data collection top
Refinement top
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzBiso*/Beq
C10.5674 (2)0.4447 (2)0.1976 (3)
C20.5049 (2)0.4922 (2)0.2844 (3)
C30.4216 (2)0.4723 (2)0.2558 (3)
C40.3995 (2)0.4015 (2)0.1435 (3)
C50.4637 (2)0.3537 (2)0.0563 (3)
C60.5462 (2)0.3759 (2)0.0830 (3)
C70.3102 (6)0.3873 (2)0.1140 (3)
C80.2686 (2)0.3089 (2)0.0627 (3)
C90.1778 (2)0.3216 (2)0.0315 (3)
C100.1274 (2)0.2384 (2)0.0226 (3)
C110.1636 (2)0.1377 (2)0.0108 (3)
C120.2412 (2)0.1324 (2)0.0924 (4)
C130.3054 (2)0.2093 (2)0.0408 (4)
C140.0526 (2)0.2613 (2)0.0849 (3)
C150.0107 (2)0.2047 (2)0.1661 (3)
C160.0795 (2)0.2572 (2)0.2228 (3)
C170.1409 (2)0.2131 (2)0.3114 (3)
C180.1352 (2)0.1142 (2)0.3450 (3)
C190.0687 (2)0.0617 (2)0.2876 (4)
C200.0064 (2)0.1057 (2)0.2000 (4)
O210.6488 (1)0.4654 (2)0.2271 (3)
O220.6149 (1)0.3368 (2)0.0032 (3)
C230.6018 (2)0.2641 (3)0.1120 (5)
O240.1454 (1)0.4035 (1)0.0438 (3)
O250.1958 (1)0.0742 (2)0.4360 (3)
O260.2087 (1)0.2594 (2)0.3738 (8)
C270.2087 (2)0.3620 (3)0.3710 (5)
Geometric parameters (Å, º) top
C1—C21.378 (4)C10—C141.351 (4)
C1—C61.391 (4)C11—C121.526 (4)
C1—O211.357 (3)C12—C131.529 (4)
C2—C31.384 (4)C14—C151.457 (4)
C3—C41.402 (4)C15—C161.407 (4)
C4—C51.401 (4)C15—C201.398 (4)
C4—C71.465 (4)C16—C171.382 (4)
C5—C61.379 (4)C17—C181.397 (4)
C6—O221.370 (3)C17—O261.370 (3)
C7—C81.346 (4)C18—C191.380 (4)
C8—C91.487 (4)C18—O251.361 (3)
C8—C131.505 (4)C19—C201.388 (4)
C9—C101.480 (4)O22—C231.406 (5)
C9—O241.247 (3)O26—C271.418 (4)
C10—C111.511 (4)
C6—C1—C2119.9 (2)C14—C10—C9115.3 (2)
O21—C1—C2119.0 (2)C14—C10—C11125.7 (2)
O21—C1—C6121.1 (2)C12—C11—C10113.4 (2)
C3—C2—C1119.8 (2)C13—C12—C11110.9 (2)
C4—C3—C2121.0 (2)C12—C13—C8110.3 (2)
C5—C4—C3118.5 (2)C15—C14—C10133.0 (2)
C7—C4—C3118.0 (2)C16—C15—C14115.8 (2)
C7—C4—C5123.3 (2)C20—C15—C14125.9 (2)
C6—C5—C4119.9 (2)C20—C15—C16118.1 (2)
C5—C6—C1120.8 (2)C17—C16—C15121.4 (2)
O22—C6—C1113.3 (2)C18—C17—C16119.6 (2)
O22—C6—C5125.9 (2)O26—C17—C16125.0 (2)
C8—C7—C4130.7 (2)O26—C17—C18115.4 (2)
C9—C8—C7116.8 (2)C19—C18—C17119.4 (2)
C13—C8—C7125.4 (2)O25—C18—C17117.7 (2)
C13—C8—C9117.7 (2)O25—C18—C19122.9 (2)
C10—C9—C8120.1 (2)C20—C19—C18121.3 (2)
O24—C9—C8119.7 (2)C19—C20—C15120.1 (2)
O24—C9—C10120.2 (2)C23—O22—C6118.5 (2)
C11—C10—C9119.0 (2)C27—O26—C17117.5 (2)
(em) top
Crystal data top
C22H22O5β = 91.710 (7)°
Mr = 366.40V = 1824.5 (3) Å3
Monoclinic, P21/cZ = 4
a = 15.937 (2) ÅDx = 1.334 Mg m3
b = 13.819 (1) ÅCu radiation, λ = 1.54178 Å
c = 8.288 (1) Å × × mm
Data collection top
h = ??l = ??
k = ??
Refinement top
Crystal data top
C22H22O5β = 91.710 (7)°
Mr = 366.40V = 1824.5 (3) Å3
Monoclinic, P21/cZ = 4
a = 15.937 (2) ÅCu radiation, λ = 1.54178 Å
b = 13.819 (1) Å × × mm
c = 8.288 (1) Å
Data collection top
Refinement top
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzBiso*/Beq
C10.570 (1)0.440 (2)0.198 (2)
C20.508 (2)0.491 (1)0.282 (1)
C30.424 (2)0.473 (1)0.252 (2)
C40.402 (1)0.405 (2)0.138 (2)
C50.465 (2)0.354 (1)0.053 (2)
C60.549 (2)0.372 (1)0.083 (2)
C70.312 (3)0.380 (2)0.120 (3)
C80.270 (3)0.316 (2)0.066 (3)
C90.182 (3)0.325 (2)0.031 (3)
C100.120 (3)0.238 (2)0.022 (3)
C110.164 (2)0.140 (1)0.023 (3)
C120.233 (2)0.129 (2)0.091 (3)
C130.304 (2)0.210 (1)0.040 (3)
C140.055 (3)0.262 (2)0.091 (3)
C150.019 (1)0.205 (1)0.163 (2)
C160.084 (1)0.260 (1)0.225 (2)
C170.143 (1)0.215 (1)0.321 (2)
C180.137 (1)0.117 (2)0.355 (2)
C190.072 (2)0.063 (1)0.292 (2)
C200.013 (1)0.107 (1)0.196 (2)
O210.637 (2)0.469 (1)0.234 (2)
O220.614 (2)0.342 (1)0.011 (3)
C230.602 (2)0.269 (2)0.110 (2)
O240.142 (2)0.413 (2)0.042 (3)
O250.194 (2)0.068 (2)0.428 (2)
O260.212 (3)0.259 (2)0.367 (3)
C270.208 (2)0.358 (1)0.372 (3)
Geometric parameters (Å, º) top
C1—C21.39 (3)C10—C141.25 (6)
C1—C61.39 (3)C11—C121.48 (5)
C1—O211.19 (4)C12—C131.64 (4)
C2—C31.39 (4)C14—C151.55 (4)
C3—C41.39 (3)C15—C161.39 (3)
C4—C51.39 (3)C15—C201.39 (3)
C4—C71.50 (5)C16—C171.39 (3)
C5—C61.39 (4)C17—C181.39 (3)
C6—O221.26 (4)C17—O261.32 (4)
C7—C81.20 (5)C18—C191.39 (3)
C8—C91.45 (7)C18—O251.30 (3)
C8—C131.57 (4)C19—C201.39 (3)
C9—C101.62 (5)O22—C231.44 (3)
C9—O241.37 (5)O26—C271.36 (3)
C10—C111.53 (4)
C6—C1—C2120 (2)C14—C10—C9116 (3)
O21—C1—C2110 (2)C14—C10—C11129 (3)
O21—C1—C6130 (2)C12—C11—C10115 (2)
C3—C2—C1120 (2)C13—C12—C11107 (2)
C4—C3—C2120 (2)C12—C13—C8111 (2)
C5—C4—C3120 (2)C15—C14—C10134 (3)
C7—C4—C3119 (2)C16—C15—C14117 (2)
C7—C4—C5121 (2)C20—C15—C14122 (2)
C6—C5—C4120 (2)C20—C15—C16120 (1)
C5—C6—C1120 (2)C17—C16—C15120 (1)
O22—C6—C1110 (2)C18—C17—C16120 (2)
O22—C6—C5130 (2)O26—C17—C16123 (2)
C8—C7—C4139 (3)O26—C17—C18116 (2)
C9—C8—C7124 (3)C19—C18—C17120 (2)
C13—C8—C7123 (3)O25—C18—C17124 (2)
C13—C8—C9113 (3)O25—C18—C19116 (2)
C10—C9—C8126 (3)C20—C19—C18120 (2)
O24—C9—C8121 (3)C19—C20—C15120 (1)
O24—C9—C10113 (3)C23—O22—C6116 (2)
C11—C10—C9113 (3)C27—O26—C17115 (3)

Experimental details

(sim)(Xray)(em)
Crystal data
Chemical formulaC22H22O5C22H22O5C22H22O5
Mr366.40366.40366.40
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)???
a, b, c (Å)15.95 (2), 13.87 (5), 8.42 (1)15.937 (2), 13.819 (1), 8.288 (1)15.937 (2), 13.819 (1), 8.288 (1)
β (°)?, 91.710 (7), ??, 91.710 (7), ??, 91.710 (7), ?
V3)1861.9 (3)1824.5 (3)1824.5 (3)
Z444
Radiation typeCu, λ = 1.54178 ÅCu, λ = 1.54178 ÅCu, λ = 1.54178 Å
µ (mm1)???
Crystal size (mm) × × × × × ×
Data collection
Diffractometer???
Absorption correction???
No. of measured, independent and
observed (?) reflections
?, ?, ? ?, ?, ? ?, ?, ?
Rint???
Refinement
R[F2 > 2σ(F2)], wR(F2), S ?, ?, ? ?, ?, ? ?, ?, ?
No. of reflections???
No. of parameters???
No. of restraints???
Δρmax, Δρmin (e Å3)?, ??, ??, ?

Selected geometric parameters (Å, º) for (sim) top
C1—C21.402C10—C141.371
C1—C61.425C11—C121.534
C1—O211.357C12—C131.534
C2—C31.400C14—C151.460
C3—C41.421C15—C161.428
C4—C51.428C15—C201.417
C4—C71.458C16—C171.400
C5—C61.397C17—C181.428
C6—O221.375C17—O261.361
C7—C81.373C18—C191.404
C8—C91.508C18—O251.361
C8—C131.516C19—C201.404
C9—C101.509O22—C231.418
C9—O241.240O26—C271.416
C10—C111.515
C6—C1—C2119.2C14—C10—C9115.4
O21—C1—C2121.3C14—C10—C11125.2
O21—C1—C6119.6C12—C11—C10111.9
C3—C2—C1119.9C13—C12—C11110.9
C4—C3—C2122.0C12—C13—C8112.2
C5—C4—C3117.5C15—C14—C10131.8
C7—C4—C3117.5C16—C15—C14117.2
C7—C4—C5125.0C20—C15—C14125.3
C6—C5—C4120.5C20—C15—C16117.5
C5—C6—C1120.9C17—C16—C15122.3
O22—C6—C1112.9C18—C17—C16119.0
O22—C6—C5126.3O26—C17—C16125.6
C8—C7—C4132.4O26—C17—C18115.5
C9—C8—C7115.2C19—C18—C17119.1
C13—C8—C7125.3O25—C18—C17117.2
C13—C8—C9119.5O25—C18—C19123.7
C10—C9—C8118.4C20—C19—C18121.5
O24—C9—C8120.8C19—C20—C15120.5
O24—C9—C10120.7C23—O22—C6118.8
C11—C10—C9119.4C27—O26—C17118.3
Selected geometric parameters (Å, º) for (Xray) top
C1—C21.378 (4)C10—C141.351 (4)
C1—C61.391 (4)C11—C121.526 (4)
C1—O211.357 (3)C12—C131.529 (4)
C2—C31.384 (4)C14—C151.457 (4)
C3—C41.402 (4)C15—C161.407 (4)
C4—C51.401 (4)C15—C201.398 (4)
C4—C71.465 (4)C16—C171.382 (4)
C5—C61.379 (4)C17—C181.397 (4)
C6—O221.370 (3)C17—O261.370 (3)
C7—C81.346 (4)C18—C191.380 (4)
C8—C91.487 (4)C18—O251.361 (3)
C8—C131.505 (4)C19—C201.388 (4)
C9—C101.480 (4)O22—C231.406 (5)
C9—O241.247 (3)O26—C271.418 (4)
C10—C111.511 (4)
C6—C1—C2119.9 (2)C14—C10—C9115.3 (2)
O21—C1—C2119.0 (2)C14—C10—C11125.7 (2)
O21—C1—C6121.1 (2)C12—C11—C10113.4 (2)
C3—C2—C1119.8 (2)C13—C12—C11110.9 (2)
C4—C3—C2121.0 (2)C12—C13—C8110.3 (2)
C5—C4—C3118.5 (2)C15—C14—C10133.0 (2)
C7—C4—C3118.0 (2)C16—C15—C14115.8 (2)
C7—C4—C5123.3 (2)C20—C15—C14125.9 (2)
C6—C5—C4119.9 (2)C20—C15—C16118.1 (2)
C5—C6—C1120.8 (2)C17—C16—C15121.4 (2)
O22—C6—C1113.3 (2)C18—C17—C16119.6 (2)
O22—C6—C5125.9 (2)O26—C17—C16125.0 (2)
C8—C7—C4130.7 (2)O26—C17—C18115.4 (2)
C9—C8—C7116.8 (2)C19—C18—C17119.4 (2)
C13—C8—C7125.4 (2)O25—C18—C17117.7 (2)
C13—C8—C9117.7 (2)O25—C18—C19122.9 (2)
C10—C9—C8120.1 (2)C20—C19—C18121.3 (2)
O24—C9—C8119.7 (2)C19—C20—C15120.1 (2)
O24—C9—C10120.2 (2)C23—O22—C6118.5 (2)
C11—C10—C9119.0 (2)C27—O26—C17117.5 (2)
Selected geometric parameters (Å, º) for (em) top
C1—C21.39 (3)C10—C141.25 (6)
C1—C61.39 (3)C11—C121.48 (5)
C1—O211.19 (4)C12—C131.64 (4)
C2—C31.39 (4)C14—C151.55 (4)
C3—C41.39 (3)C15—C161.39 (3)
C4—C51.39 (3)C15—C201.39 (3)
C4—C71.50 (5)C16—C171.39 (3)
C5—C61.39 (4)C17—C181.39 (3)
C6—O221.26 (4)C17—O261.32 (4)
C7—C81.20 (5)C18—C191.39 (3)
C8—C91.45 (7)C18—O251.30 (3)
C8—C131.57 (4)C19—C201.39 (3)
C9—C101.62 (5)O22—C231.44 (3)
C9—O241.37 (5)O26—C271.36 (3)
C10—C111.53 (4)
C6—C1—C2120 (2)C14—C10—C9116 (3)
O21—C1—C2110 (2)C14—C10—C11129 (3)
O21—C1—C6130 (2)C12—C11—C10115 (2)
C3—C2—C1120 (2)C13—C12—C11107 (2)
C4—C3—C2120 (2)C12—C13—C8111 (2)
C5—C4—C3120 (2)C15—C14—C10134 (3)
C7—C4—C3119 (2)C16—C15—C14117 (2)
C7—C4—C5121 (2)C20—C15—C14122 (2)
C6—C5—C4120 (2)C20—C15—C16120 (1)
C5—C6—C1120 (2)C17—C16—C15120 (1)
O22—C6—C1110 (2)C18—C17—C16120 (2)
O22—C6—C5130 (2)O26—C17—C16123 (2)
C8—C7—C4139 (3)O26—C17—C18116 (2)
C9—C8—C7124 (3)C19—C18—C17120 (2)
C13—C8—C7123 (3)O25—C18—C17124 (2)
C13—C8—C9113 (3)O25—C18—C19116 (2)
C10—C9—C8126 (3)C20—C19—C18120 (2)
O24—C9—C8121 (3)C19—C20—C15120 (1)
O24—C9—C10113 (3)C23—O22—C6116 (2)
C11—C10—C9113 (3)C27—O26—C17115 (3)
 

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