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The title compound, C
25H
22P
+·C
5H
5O
2−, crystallizes in space group
P2
1/
c. The phosphonium cations form zigzag chains with P
P distances of 6.475 (1) and 8.287 (2) Å, and are related by inversion centres. Two types of attractive edge-to-face phenyl interactions exist, resulting in a dominant supramolecular motif. The glutaconaldehyde anions occupy the interchain spacing and hold adjacent chains together
via multiple C—H
O hydrogen bonds. The bond-length alternation, a parameter which reveals the non-linear optical efficiency at the molecular level, is optimized in the chromophore anion.
Supporting information
CCDC reference: 150339
Compound (I) was prepared by the cation exchange reaction of potassium glutaconaldehyde with benzyltriphenylphosphonium chloride. Benzyltriphenylphosphonium chloride (0.001 mol) was dissolved in water (25 ml) and the pH was adjusted to 12 by adding 0.01 N aqueous NaOH. This solution was cooled to 263 K and solid potassium glutaconaldehyde (0.001 mol; Becher, 1988) was added with stirring. After 15 min of stirring, the cooling bath was removed. The solution was extracted immediately with CH2Cl2, dried over K2CO3 and evaporated to obtain a brown solid. Recrystallization was carried out by dissolution in ethyl acetate and treatment with activated carbon, followed by filtration and slow evaporation to obtain X-ray quality dark-brown needle crystals of (I).
All H atoms were found by difference Fourier analyses and not refined. Since their refinement introduced an excess of parameters with respect to the number of reflections we preserved their positions, taking into account the remarkable C—H distances between 0.85 and 1.1 Å and the C—C—H angles close to their ideal value. An average displacement factor Uiso = 0.082 Å2 was attributed to each H atom.
Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: KappaCCD Server Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997-1999); program(s) used to solve structure: SIR92 (Altomare et al. 1993); program(s) used to refine structure: TEXSAN for Windows; software used to prepare material for publication: TEXSAN for Windows.
Crystal data top
C25H22P+·C5H5O2− | F(000) = 952.00 |
Mr = 450.52 | Dx = 1.189 Mg m−3 |
Monoclinic, P21/c | Ag Kα radiation, λ = 0.5608 Å |
a = 12.983 (1) Å | Cell parameters from 5616 reflections |
b = 11.435 (1) Å | θ = 2.1–21.0° |
c = 17.028 (2) Å | µ = 0.08 mm−1 |
β = 95.35 (2)° | T = 296 K |
V = 2517.0 (4) Å3 | Needle, dark brown |
Z = 4 | 0.29 × 0.16 × 0.16 mm |
Data collection top
Nonius KappaCCD diffractometer | 3489 reflections with I > 2.6σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.021 |
Graphite monochromator | θmax = 21.0°, θmin = 2.1° |
Data from ϕ = 1°, ϕ scans | h = 0→16 |
10920 measured reflections | k = −14→14 |
5616 independent reflections | l = −21→21 |
Refinement top
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters not refined |
wR(F2) = 0.051 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.00006|Fo|2] |
S = 2.00 | (Δ/σ)max < 0.001 |
3489 reflections | Δρmax = 0.35 e Å−3 |
298 parameters | Δρmin = −0.37 e Å−3 |
Crystal data top
C25H22P+·C5H5O2− | V = 2517.0 (4) Å3 |
Mr = 450.52 | Z = 4 |
Monoclinic, P21/c | Ag Kα radiation, λ = 0.5608 Å |
a = 12.983 (1) Å | µ = 0.08 mm−1 |
b = 11.435 (1) Å | T = 296 K |
c = 17.028 (2) Å | 0.29 × 0.16 × 0.16 mm |
β = 95.35 (2)° | |
Data collection top
Nonius KappaCCD diffractometer | 3489 reflections with I > 2.6σ(I) |
10920 measured reflections | Rint = 0.021 |
5616 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.051 | H-atom parameters not refined |
S = 2.00 | Δρmax = 0.35 e Å−3 |
3489 reflections | Δρmin = −0.37 e Å−3 |
298 parameters | |
Special details top
Experimental. scan mode: 180 exposures, ϕ = 1° |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P | 0.30174 (3) | 0.04186 (3) | 0.59864 (2) | 0.04091 (13) | |
O1 | 0.07113 (9) | 0.46135 (11) | 0.31557 (8) | 0.0913 (5) | |
O2 | 0.49757 (9) | 0.76097 (11) | 0.52492 (7) | 0.0836 (5) | |
C1 | 0.22084 (11) | −0.08083 (12) | 0.61374 (9) | 0.0446 (5) | |
C2 | 0.12640 (13) | −0.0934 (2) | 0.56941 (10) | 0.0619 (6) | |
C3 | 0.0663 (1) | −0.1907 (2) | 0.5808 (1) | 0.0865 (8) | |
C4 | 0.0988 (2) | −0.2737 (2) | 0.6341 (2) | 0.1066 (10) | |
C5 | 0.1924 (2) | −0.2634 (2) | 0.6769 (2) | 0.1028 (9) | |
C6 | 0.25390 (13) | −0.1670 (2) | 0.66799 (11) | 0.0701 (6) | |
C7 | 0.40634 (11) | 0.04830 (13) | 0.67518 (9) | 0.0450 (5) | |
C8 | 0.49173 (13) | −0.0239 (1) | 0.67337 (10) | 0.0623 (6) | |
C9 | 0.56947 (13) | −0.0207 (2) | 0.73501 (12) | 0.0796 (7) | |
C10 | 0.5625 (2) | 0.0533 (2) | 0.79709 (12) | 0.0809 (8) | |
C11 | 0.4786 (2) | 0.1250 (2) | 0.79922 (10) | 0.0771 (7) | |
C12 | 0.40121 (13) | 0.1240 (1) | 0.73853 (10) | 0.0617 (6) | |
C13 | 0.22857 (10) | 0.17393 (12) | 0.60053 (8) | 0.0428 (5) | |
C14 | 0.13318 (12) | 0.17741 (13) | 0.63094 (10) | 0.0555 (5) | |
C15 | 0.07921 (12) | 0.2822 (2) | 0.63044 (11) | 0.0707 (7) | |
C16 | 0.1203 (2) | 0.3812 (2) | 0.60068 (12) | 0.0748 (7) | |
C17 | 0.2156 (2) | 0.3793 (2) | 0.57299 (10) | 0.0675 (6) | |
C18 | 0.27031 (11) | 0.2761 (1) | 0.57284 (9) | 0.0549 (5) | |
C19 | 0.35432 (10) | 0.02719 (12) | 0.50449 (8) | 0.0468 (5) | |
C20 | 0.27452 (11) | 0.0351 (1) | 0.43454 (8) | 0.0445 (5) | |
C21 | 0.24971 (12) | 0.1425 (1) | 0.39924 (10) | 0.0577 (6) | |
C22 | 0.1732 (1) | 0.1512 (2) | 0.33705 (10) | 0.0723 (7) | |
C23 | 0.1207 (1) | 0.0538 (2) | 0.30937 (10) | 0.0773 (7) | |
C24 | 0.1447 (1) | −0.0523 (2) | 0.34194 (11) | 0.0719 (7) | |
C25 | 0.22360 (13) | −0.0629 (1) | 0.40448 (10) | 0.0620 (6) | |
C26 | 0.1587 (1) | 0.4976 (2) | 0.33616 (12) | 0.0718 (7) | |
C27 | 0.19424 (12) | 0.5644 (2) | 0.40103 (11) | 0.0650 (6) | |
C28 | 0.29515 (13) | 0.5969 (2) | 0.41590 (10) | 0.0609 (6) | |
C29 | 0.34425 (13) | 0.6636 (1) | 0.47599 (10) | 0.0638 (6) | |
C30 | 0.4459 (1) | 0.6945 (2) | 0.47825 (11) | 0.0738 (7) | |
H1 | 0.1001 | −0.0341 | 0.5307 | 0.082* | |
H2 | −0.0008 | −0.1923 | 0.5467 | 0.082* | |
H3 | 0.0561 | −0.3355 | 0.6425 | 0.082* | |
H4 | 0.2167 | −0.3166 | 0.7197 | 0.082* | |
H5 | 0.3143 | −0.1546 | 0.6995 | 0.082* | |
H6 | 0.4930 | −0.0759 | 0.6341 | 0.082* | |
H7 | 0.6232 | −0.0729 | 0.7316 | 0.082* | |
H8 | 0.6130 | 0.0537 | 0.8395 | 0.082* | |
H9 | 0.4781 | 0.1804 | 0.8405 | 0.082* | |
H10 | 0.3409 | 0.1764 | 0.7358 | 0.082* | |
H11 | 0.1047 | 0.1077 | 0.6510 | 0.082* | |
H12 | 0.0094 | 0.2809 | 0.6533 | 0.082* | |
H13 | 0.0882 | 0.4457 | 0.6041 | 0.082* | |
H14 | 0.2548 | 0.4434 | 0.5549 | 0.082* | |
H15 | 0.3328 | 0.2737 | 0.5543 | 0.082* | |
H16 | 0.3909 | −0.0471 | 0.5097 | 0.082* | |
H17 | 0.3977 | 0.0878 | 0.5047 | 0.082* | |
H18 | 0.2848 | 0.2123 | 0.4186 | 0.082* | |
H19 | 0.1524 | 0.2300 | 0.3126 | 0.082* | |
H20 | 0.0636 | 0.0595 | 0.2652 | 0.082* | |
H21 | 0.1131 | −0.1195 | 0.3251 | 0.082* | |
H22 | 0.2397 | −0.1346 | 0.4245 | 0.082* | |
H23 | 0.2218 | 0.4675 | 0.3021 | 0.082* | |
H24 | 0.1373 | 0.5903 | 0.4355 | 0.082* | |
H25 | 0.3322 | 0.5704 | 0.3724 | 0.082* | |
H26 | 0.3052 | 0.6934 | 0.5199 | 0.082* | |
H27 | 0.4831 | 0.6551 | 0.4289 | 0.082* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P | 0.0387 (2) | 0.0417 (3) | 0.0425 (3) | −0.0018 (2) | 0.0048 (2) | 0.0025 (2) |
O1 | 0.0594 (8) | 0.0936 (10) | 0.1169 (12) | −0.0150 (7) | −0.0131 (8) | 0.0037 (8) |
O2 | 0.0926 (9) | 0.0786 (9) | 0.0770 (9) | −0.0366 (8) | −0.0059 (7) | 0.0006 (7) |
C1 | 0.0461 (9) | 0.0394 (10) | 0.0500 (10) | −0.0032 (7) | 0.0135 (8) | −0.0016 (8) |
C2 | 0.0589 (11) | 0.0598 (12) | 0.0696 (12) | −0.0173 (9) | 0.0191 (9) | −0.0163 (9) |
C3 | 0.0708 (13) | 0.079 (2) | 0.115 (2) | −0.0348 (12) | 0.0335 (13) | −0.038 (1) |
C4 | 0.100 (2) | 0.051 (1) | 0.181 (3) | −0.031 (1) | 0.080 (2) | −0.023 (2) |
C5 | 0.116 (2) | 0.060 (2) | 0.143 (2) | 0.007 (1) | 0.071 (2) | 0.037 (1) |
C6 | 0.0736 (12) | 0.0591 (12) | 0.081 (1) | −0.0040 (10) | 0.0259 (10) | 0.0169 (10) |
C7 | 0.0449 (9) | 0.0474 (10) | 0.0427 (10) | −0.0012 (8) | 0.0038 (7) | 0.0021 (8) |
C8 | 0.0583 (11) | 0.0733 (12) | 0.0540 (11) | 0.0098 (9) | −0.0013 (9) | −0.0036 (9) |
C9 | 0.0603 (12) | 0.106 (2) | 0.070 (1) | 0.0199 (11) | −0.0078 (11) | 0.0020 (12) |
C10 | 0.0700 (13) | 0.103 (2) | 0.064 (1) | −0.0045 (12) | −0.0219 (11) | 0.0038 (12) |
C11 | 0.090 (1) | 0.078 (1) | 0.0593 (13) | −0.0024 (12) | −0.0166 (11) | −0.0156 (10) |
C12 | 0.0669 (11) | 0.0607 (12) | 0.0555 (12) | −0.0008 (9) | −0.0038 (9) | −0.0059 (10) |
C13 | 0.0442 (9) | 0.0427 (10) | 0.0411 (9) | −0.0026 (7) | 0.0016 (7) | 0.0002 (7) |
C14 | 0.0515 (10) | 0.0498 (11) | 0.0657 (12) | 0.0037 (8) | 0.0079 (9) | −0.0031 (9) |
C15 | 0.0616 (11) | 0.0613 (13) | 0.090 (2) | 0.0065 (10) | 0.0116 (10) | −0.0119 (11) |
C16 | 0.081 (1) | 0.0515 (13) | 0.088 (2) | 0.0207 (11) | −0.0102 (12) | −0.0121 (11) |
C17 | 0.089 (1) | 0.0440 (12) | 0.0691 (13) | −0.0062 (10) | 0.0025 (11) | 0.0035 (9) |
C18 | 0.0581 (10) | 0.0479 (11) | 0.0589 (11) | −0.0025 (9) | 0.0057 (8) | 0.0041 (9) |
C19 | 0.0443 (9) | 0.0502 (10) | 0.0463 (10) | −0.0008 (7) | 0.0064 (7) | 0.0039 (8) |
C20 | 0.0433 (9) | 0.0522 (11) | 0.0392 (10) | −0.0030 (8) | 0.0098 (7) | −0.0017 (8) |
C21 | 0.0650 (11) | 0.0596 (12) | 0.0475 (11) | 0.0018 (9) | 0.0002 (9) | 0.0024 (9) |
C22 | 0.0782 (13) | 0.082 (2) | 0.0545 (12) | 0.0065 (11) | −0.0051 (10) | 0.0062 (11) |
C23 | 0.0602 (12) | 0.119 (2) | 0.0520 (12) | −0.0048 (12) | 0.0011 (9) | −0.0015 (13) |
C24 | 0.0731 (13) | 0.087 (2) | 0.0560 (13) | −0.0281 (11) | 0.0097 (10) | −0.0194 (11) |
C25 | 0.0761 (12) | 0.0589 (12) | 0.0523 (12) | −0.0062 (10) | 0.0140 (10) | −0.0066 (9) |
C26 | 0.0533 (12) | 0.0709 (13) | 0.090 (2) | −0.0102 (10) | 0.0017 (10) | 0.0018 (11) |
C27 | 0.0512 (11) | 0.0699 (13) | 0.0730 (13) | −0.0016 (9) | 0.0020 (9) | 0.0087 (10) |
C28 | 0.0559 (11) | 0.0595 (12) | 0.0678 (12) | −0.0040 (9) | 0.0087 (9) | 0.0024 (10) |
C29 | 0.0641 (12) | 0.0595 (12) | 0.0672 (13) | −0.0057 (9) | 0.0029 (10) | 0.0015 (10) |
C30 | 0.0722 (13) | 0.0738 (13) | 0.076 (1) | −0.0205 (11) | 0.0071 (10) | −0.0057 (11) |
Geometric parameters (Å, º) top
P—C1 | 1.786 (2) | C14—C15 | 1.388 (3) |
P—C13 | 1.786 (2) | C15—H12 | 1.02 |
P—C7 | 1.794 (2) | C15—C16 | 1.368 (3) |
P—C19 | 1.808 (2) | C16—H13 | 0.85 |
O1—C26 | 1.230 (3) | C16—C17 | 1.366 (3) |
O2—C30 | 1.249 (3) | C17—H14 | 0.96 |
C1—C2 | 1.386 (3) | C17—C18 | 1.377 (3) |
C1—C6 | 1.391 (3) | C18—H15 | 0.90 |
C2—H1 | 0.98 | C19—H17 | 0.89 |
C2—C3 | 1.383 (3) | C19—H16 | 0.97 |
C3—H2 | 1.00 | C19—C20 | 1.507 (3) |
C3—C4 | 1.353 (4) | C20—C25 | 1.376 (3) |
C4—H3 | 0.92 | C20—C21 | 1.391 (3) |
C4—C5 | 1.363 (4) | C21—H18 | 0.96 |
C5—H4 | 0.98 | C21—C22 | 1.386 (3) |
C5—C6 | 1.378 (4) | C22—H19 | 1.02 |
C6—H5 | 0.92 | C22—C23 | 1.366 (3) |
C7—C8 | 1.385 (3) | C23—H20 | 1.01 |
C7—C12 | 1.390 (3) | C23—C24 | 1.358 (3) |
C8—H6 | 0.90 | C24—H21 | 0.90 |
C8—C9 | 1.387 (3) | C24—C25 | 1.412 (3) |
C9—H7 | 0.92 | C25—H22 | 0.91 |
C9—C10 | 1.364 (4) | C26—H23 | 1.10 |
C10—H8 | 0.93 | C26—C27 | 1.386 (3) |
C10—C11 | 1.366 (3) | C27—H24 | 1.03 |
C11—H9 | 0.95 | C27—C28 | 1.363 (3) |
C11—C12 | 1.372 (3) | C28—H25 | 0.97 |
C12—H10 | 0.98 | C28—C29 | 1.383 (3) |
C13—C14 | 1.387 (3) | C29—H26 | 1.00 |
C13—C18 | 1.389 (3) | C29—C30 | 1.364 (3) |
C14—H11 | 0.96 | C30—H27 | 1.10 |
| | | |
O1···H3i | 2.3518 | C16···H20xi | 3.0385 |
O1···H20ii | 2.4001 | C16···C23xi | 3.630 (4) |
O1···H13iii | 2.7935 | C17···C27 | 3.603 (3) |
O1···H19 | 2.8504 | C21···H7x | 3.0004 |
O1···H11iv | 2.9823 | C22···H7x | 3.1193 |
O1···C4i | 3.250 (3) | C24···H4xii | 2.7956 |
O1···C23ii | 3.296 (3) | C25···C29ix | 3.655 (3) |
O1···C16iii | 3.480 (3) | C26···H19 | 3.0864 |
O1···C14iv | 3.677 (3) | C27···H14 | 3.0027 |
O1···C15iii | 3.686 (3) | C28···H14 | 3.0319 |
O1···C24ii | 3.697 (3) | C29···H22vii | 2.7770 |
O2···H17v | 2.2850 | C29···H14 | 3.1284 |
O2···H9vi | 2.4632 | C30···H15v | 2.9980 |
O2···H16vii | 2.5948 | C30···H16vii | 3.0981 |
O2···H6vii | 2.6381 | H3···H13ix | 2.6288 |
O2···H15v | 2.7167 | H4···H21viii | 2.4522 |
O2···H18v | 2.9147 | H8···H14xiii | 2.6820 |
O2···C19v | 3.162 (3) | H10···H23xi | 2.5888 |
O2···C11vi | 3.363 (3) | H12···H21i | 2.4864 |
O2···C8vii | 3.533 (3) | H12···H20xi | 2.6843 |
O2···C19vii | 3.568 (3) | H12···H24iii | 2.7472 |
O2···C21v | 3.586 (3) | H15···H27v | 2.5162 |
O2···C18v | 3.601 (3) | H22···H26ix | 2.6404 |
C3···C22i | 3.556 (4) | H3···O1i | 2.3518 |
C3···C23i | 3.563 (4) | H6···O2ix | 2.6381 |
C5···H21viii | 3.1152 | H9···O2xiii | 2.4632 |
C5···C24viii | 3.612 (4) | H15···O2v | 2.7167 |
C6···H26ix | 3.1087 | H16···O2ix | 2.5948 |
C8···C20x | 3.694 (3) | H17···O2v | 2.2850 |
C9···C20x | 3.682 (4) | H20···O1xiv | 2.4001 |
C9···C21x | 3.698 (4) | H23···O1 | 1.9914 |
C12···H23xi | 2.8578 | H24···O1 | 2.5996 |
C15···H20xi | 2.9440 | H26···O2 | 2.6078 |
C15···C23xi | 3.575 (4) | H27···O2 | 2.0293 |
C15···C22xi | 3.694 (4) | | |
| | | |
C1—P—C13 | 109.93 (10) | C16—C15—C14 | 120.2 (2) |
C1—P—C7 | 110.07 (10) | H13—C16—C17 | 120.1 |
C1—P—C19 | 109.31 (9) | H13—C16—C15 | 118.8 |
C13—P—C7 | 108.67 (10) | C17—C16—C15 | 120.8 (2) |
C13—P—C19 | 109.87 (10) | H14—C17—C16 | 128.6 |
C7—P—C19 | 108.98 (9) | H14—C17—C18 | 111.4 |
C2—C1—C6 | 119.4 (2) | C16—C17—C18 | 119.9 (2) |
C2—C1—P | 120.4 (2) | H15—C18—C17 | 120.7 |
C6—C1—P | 120.2 (2) | H15—C18—C13 | 119.1 |
H1—C2—C3 | 118.9 | C17—C18—C13 | 120.2 (2) |
H1—C2—C1 | 121.8 | H17—C19—H16 | 112.0 |
C3—C2—C1 | 119.3 (3) | H17—C19—C20 | 110.1 |
H2—C3—C4 | 125.2 | H17—C19—P | 102.4 |
H2—C3—C2 | 113.9 | H16—C19—C20 | 114.7 |
C4—C3—C2 | 120.9 (3) | H16—C19—P | 102.8 |
H3—C4—C3 | 119.3 | C20—C19—P | 114.00 (13) |
H3—C4—C5 | 120.3 | C25—C20—C21 | 118.3 (2) |
C3—C4—C5 | 120.3 (3) | C25—C20—C19 | 121.1 (2) |
H4—C5—C4 | 123.7 | C21—C20—C19 | 120.6 (2) |
H4—C5—C6 | 115.4 | H18—C21—C22 | 119.0 |
C4—C5—C6 | 120.5 (3) | H18—C21—C20 | 120.1 |
H5—C6—C5 | 122.1 | C22—C21—C20 | 120.9 (2) |
H5—C6—C1 | 118.1 | H19—C22—C23 | 118.4 |
C5—C6—C1 | 119.6 (2) | H19—C22—C21 | 121.3 |
C8—C7—C12 | 119.0 (2) | C23—C22—C21 | 120.2 (2) |
C8—C7—P | 120.8 (2) | H20—C23—C24 | 119.1 |
C12—C7—P | 120.1 (2) | H20—C23—C22 | 120.9 |
H6—C8—C7 | 118.9 | C24—C23—C22 | 120.0 (2) |
H6—C8—C9 | 121.3 | H21—C24—C23 | 123.3 |
C7—C8—C9 | 119.6 (2) | H21—C24—C25 | 116.2 |
H7—C9—C10 | 123.7 | C23—C24—C25 | 120.5 (2) |
H7—C9—C8 | 115.8 | H22—C25—C20 | 120.8 |
C10—C9—C8 | 120.5 (2) | H22—C25—C24 | 119.2 |
H8—C10—C9 | 120.8 | C20—C25—C24 | 120.0 (2) |
H8—C10—C11 | 118.9 | H23—C26—O1 | 117.2 |
C9—C10—C11 | 120.2 (2) | H23—C26—C27 | 112.5 |
H9—C11—C10 | 118.8 | O1—C26—C27 | 130.1 (3) |
H9—C11—C12 | 120.6 | H24—C27—C28 | 123.0 |
C10—C11—C12 | 120.3 (2) | H24—C27—C26 | 114.2 |
H10—C12—C11 | 123.6 | C28—C27—C26 | 122.8 (2) |
H10—C12—C7 | 116.0 | H25—C28—C27 | 108.0 |
C11—C12—C7 | 120.3 (2) | H25—C28—C29 | 120.7 |
C14—C13—C18 | 119.5 (2) | C27—C28—C29 | 131.1 (2) |
C14—C13—P | 121.7 (2) | H26—C29—C30 | 116.5 |
C18—C13—P | 118.7 (2) | H26—C29—C28 | 120.6 |
H11—C14—C13 | 119.9 | C30—C29—C28 | 122.8 (2) |
H11—C14—C15 | 120.7 | H27—C30—O2 | 119.1 |
C13—C14—C15 | 119.4 (2) | H27—C30—C29 | 111.3 |
H12—C15—C16 | 123.0 | O2—C30—C29 | 129.5 (3) |
H12—C15—C14 | 116.8 | | |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x, y+1/2, −z+1/2; (iii) −x, −y+1, −z+1; (iv) x, −y+1/2, z−1/2; (v) −x+1, −y+1, −z+1; (vi) −x+1, y+1/2, −z+3/2; (vii) x, y+1, z; (viii) x, −y−1/2, z+1/2; (ix) x, y−1, z; (x) −x+1, −y, −z+1; (xi) x, −y+1/2, z+1/2; (xii) x, −y−1/2, z−1/2; (xiii) −x+1, y−1/2, −z+3/2; (xiv) −x, y−1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4i—H3i···O1 | 0.92 | 2.35 | 3.250 (3) | 166 |
C8vii—H6vii···O2 | 0.90 | 2.64 | 3.533 (3) | 177 |
C11vi—H9vi···O2 | 0.95 | 2.46 | 3.363 (3) | 159 |
C16iii—H13iii···O1 | 0.85 | 2.79 | 3.480 (3) | 139 |
C18v—H15v···O2 | 0.90 | 2.72 | 3.601 (3) | 168 |
C19vii—H16vii···O2 | 0.97 | 2.60 | 3.568 (3) | 177 |
C19v—H17v···O2 | 0.89 | 2.29 | 3.162 (2) | 167 |
C23ii—H20ii···O1 | 1.01 | 2.40 | 3.296 (3) | 148 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x, y+1/2, −z+1/2; (iii) −x, −y+1, −z+1; (v) −x+1, −y+1, −z+1; (vi) −x+1, y+1/2, −z+3/2; (vii) x, y+1, z. |
Experimental details
Crystal data |
Chemical formula | C25H22P+·C5H5O2− |
Mr | 450.52 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 12.983 (1), 11.435 (1), 17.028 (2) |
β (°) | 95.35 (2) |
V (Å3) | 2517.0 (4) |
Z | 4 |
Radiation type | Ag Kα, λ = 0.5608 Å |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.29 × 0.16 × 0.16 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2.6σ(I)] reflections | 10920, 5616, 3489 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.638 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.051, 2.00 |
No. of reflections | 3489 |
No. of parameters | 298 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.35, −0.37 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4i—H3i···O1 | 0.92 | 2.352 | 3.250 (3) | 166.0 |
C8ii—H6ii···O2 | 0.90 | 2.638 | 3.533 (3) | 176.6 |
C11iii—H9iii···O2 | 0.95 | 2.463 | 3.363 (3) | 158.8 |
C16iv—H13iv···O1 | 0.85 | 2.794 | 3.480 (3) | 138.8 |
C18v—H15v···O2 | 0.90 | 2.717 | 3.601 (3) | 168.4 |
C19ii—H16ii···O2 | 0.97 | 2.595 | 3.568 (3) | 177.0 |
C19v—H17v···O2 | 0.89 | 2.285 | 3.162 (2) | 167.1 |
C23vi—H20vi···O1 | 1.01 | 2.400 | 3.296 (3) | 147.5 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, y+1, z; (iii) −x+1, y+1/2, −z+3/2; (iv) −x, −y+1, −z+1; (v) −x+1, −y+1, −z+1; (vi) −x, y+1/2, −z+1/2. |
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Conjugated polyenes are nonlinear optical chromophores displaying large molecular hyperpolarizabilities. Crystals built up from such chromophores are very rare. We describe here the crystal structure of the title compound, (I), containing a conjugated polyene, the glutaconaldehydate anion, with optimized bond length alternation. This situation is due to the associated cation, the benzyltriphenylphosphonium. Semiempirical calculations performed on push-pull polyenes have shown that the static quadratic hyperpolarizability can be correlated with the ground state polarization and concomitantly with a structural parameter, the bond length alternation (BLA) (Marder et al., 1994; Meyers et al., 1994). The BLA describes the ground state geometry of the molecule and is defined as the average difference in the lengths between adjacent C—C bonds in the polyenic chain. Calculations indicate that the molecular hyperpolarizability (β) is a maximum when the BLA is ± 0.05 (1) Å (Blanchard-Desce et al., 1997). \sch
The glutaconaldehydate anion is not stable in solution at room temperature and at acidic pH and undergoes polymerization. However it is known to be stable in solution at low temperatures and basic pH, and in the solid state only with bulky counterions. In solution, it exists in two similar resonance forms with equal contribution and hence BLA = 0. Computational studies have shown that by modifying the parameters that govern the relative weights of these two resonance forms, it should be possible to optimize the molecular structure so as to maximize the optical nonlinearity in the solid state (Barzoukas et al., 1996). The balance between the two limiting resonance forms of a polyene can be modified by altering the donor-acceptor strengths at the terminals or the nature of the conjugated path with external perturbation. We have attempted to perturb the contribution of the two resonance forms of the glutaconaldehydate anion by external charged centres [metal cations such as sodium (Muthuraman et al., 1999) or bulky organic cations], to optimize the BLA. However, these salts crystallize in centrosymmetric space groups, excluding possible optical nonlinearity at the macroscopic level.
The unit cell of (I) contains four cation-anion entities. In the crystal lattice, the phosphonium cations form a zigzag chain with P···P distances of 8.287 (2) Å (-x, −y, 1 − z) and 6.475 (1) Å (1 − x, −y, 1 − z), running parallel with the a direction. The cations in the chain are held together by two types of edge-to-face (ef) phenyl interactions (Fig. 2). One type involves four phenyl rings (two per phosphonium cation), resulting in two ef interactions leading to a P···P distance of 8.287 (2) Å, related by an inversion centre. The other type involves two phenyl rings and two benzyl groups (one phenyl and one benzyl per phosphonium cation), having two ef interactions leading to a P···P distance of 6.475 (1) Å, also related by inversion centre. The phenylphosphonium cations are known to form supramolecular synthons, the so-called phenyl embraces, through phenyl-phenyl interactions, and Dance et al. (Dance & Sudder, 1996; Sudder & Dance, 1998; Hasselgren et al., 1998) have extensively analysed various kinds of multiple attractive phenyl interactions leading to chains and networks, as shown in Fig. 2.
The anions in (I) occupy the space between the chains and hold the chains together through multiple C—H···O hydrogen bonds (Desiraju, 1996; Steiner & Desiraju, 1998; Table 1). Atom O2(1 − x, 1 − y, 1 − z) of the glutaconaldehydate anion is closer [4.161 (2) Å] to the P than O1(x, 1/2 − y, 1/2 + z) [4.967 (2) Å] and the values of the C—O distances [C26—O1 = 1.230 (3) and C30—O2 = 1.249 (3) Å] suggest that O2 carries more negative charge and C26—O1 has more double bond character than C30—O2. Such an anion dissymetry due to the counterbalance of charges gives an optimal value for the BLA. There are two C—C single bonds and two C=C double bonds in the anion and a BLA of 0.021 (6) Å is calculated [(1.386 + 1.383)/2 - (1.363 + 1.364)/2].
The crystal structure of (I), as well as that of sodium glutaconaldehyde dihydrate (Muthuraman et al., 1999), establishes that the BLA of polyene entities can reach, in the solid state, the ideal values observed at molecular level with polyenes onto which electron donor and acceptor groups are grafted. Thus the hyperpolarizability of anion polyenes can be manipulated by the choice of the associated cations in crystalline materials.