A novel stilbene-based salicylhydrazone compound {systematic name: (E)-4,4′-(ethene-1,2-diyl)bis[(N′E)-N′-(2-hydroxybenzylidene)benzohydrazide] dimethyl sulfoxide disolvate, C30H24N4O4·2C2H6OS or L·2DMSO} was synthesized and characterized by single-crystal X-ray diffraction, powder X-ray diffraction and luminescence spectroscopy. The title compound crystallizes in the monoclinic space group P21/c, with half a symmetry-independent L molecule and one dimethyl sulfoxide (DMSO) solvent molecule in the asymmetric unit. The L molecule adopts an almost planar structure, with a small dihedral angle between the planes of the stilbene and salicylhydrazone groups. There are multiple π–π stacking interactions between adjacent L molecules. The DMSO solvent molecules act as proton donors and acceptors, forming hydrogen bonds of various strengths with the L molecules. In addition, the geometry optimization of a single molecule of L and its luminescence properties either in solution, as a solvated solid or as a desolvated solid were studied. The compound shows an aggregation-induced emission (AIE) effect and exhibits switchable luminescence colouration in the solid state by the simple removal or re-addition of the DMSO solvent.
Supporting information
CCDC reference: 1977499
Data collection: SAINT (Bruker, 2012); cell refinement: APEX2 (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: olex2.solve (Bourhis et al., 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
(
E)-4,4'-(Ethene-1,2-diyl)bis[(
N'
E)-
N'-(2-hydroxybenzylidene)benzohydrazide] dimethyl sulfoxide disolvate
top
Crystal data top
C30H24N4O4·2C2H6OS | F(000) = 696 |
Mr = 660.79 | Dx = 1.359 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 4.7581 (6) Å | Cell parameters from 2855 reflections |
b = 18.599 (2) Å | θ = 2.2–24.8° |
c = 18.266 (2) Å | µ = 0.22 mm−1 |
β = 92.409 (5)° | T = 150 K |
V = 1615.0 (3) Å3 | Long plate, yellow |
Z = 2 | 1.00 × 0.80 × 0.01 mm |
Data collection top
Bruker D8 VENTURE PHOTON II diffractometer | 1714 reflections with I > 2σ(I) |
Radiation source: Ius 3.0 | Rint = 0.083 |
ω and phi scans | θmax = 25.1°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −5→5 |
Tmin = 0.589, Tmax = 0.745 | k = −22→21 |
17483 measured reflections | l = −21→21 |
2816 independent reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.051 | H-atom parameters constrained |
wR(F2) = 0.151 | w = 1/[σ2(Fo2) + (0.0581P)2 + 1.0113P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
2816 reflections | Δρmax = 0.26 e Å−3 |
208 parameters | Δρmin = −0.34 e Å−3 |
0 restraints | |
Special details top
Experimental. SADABS (Bruker, 2012) was used for absorption correction.
wR2(int) was 0.1447 before and 0.0772 after correction.
The Ratio of minimum to maximum transmission is 0.7904.
The λ/2 correction factor is Not present. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | −0.9364 (5) | 0.75111 (11) | 1.34452 (12) | 0.0461 (7) | |
H1A | −0.8278 | 0.7723 | 1.3165 | 0.055* | |
O2 | −0.4093 (5) | 0.78393 (11) | 1.19027 (12) | 0.0414 (6) | |
N1 | −0.6492 (5) | 0.85910 (13) | 1.29516 (13) | 0.0324 (7) | |
N2 | −0.4542 (5) | 0.88889 (13) | 1.25063 (13) | 0.0319 (7) | |
H2A | −0.4016 | 0.9340 | 1.2563 | 0.038* | |
C1 | −1.0492 (7) | 0.79944 (17) | 1.39020 (17) | 0.0355 (8) | |
C2 | −0.9720 (7) | 0.87243 (17) | 1.38986 (16) | 0.0319 (8) | |
C3 | −1.0979 (7) | 0.91854 (18) | 1.43910 (18) | 0.0393 (9) | |
H3A | −1.0481 | 0.9680 | 1.4396 | 0.047* | |
C4 | −1.2923 (8) | 0.8942 (2) | 1.48696 (18) | 0.0445 (9) | |
H4A | −1.3759 | 0.9264 | 1.5200 | 0.053* | |
C5 | −1.3645 (7) | 0.8220 (2) | 1.48630 (18) | 0.0450 (9) | |
H5A | −1.4978 | 0.8048 | 1.5194 | 0.054* | |
C6 | −1.2460 (7) | 0.77524 (19) | 1.43849 (18) | 0.0418 (9) | |
H6A | −1.2989 | 0.7260 | 1.4384 | 0.050* | |
C7 | −0.7644 (7) | 0.90022 (17) | 1.34077 (17) | 0.0331 (8) | |
H7A | −0.7145 | 0.9497 | 1.3428 | 0.040* | |
C8 | −0.3444 (7) | 0.84730 (17) | 1.19759 (16) | 0.0311 (8) | |
C9 | −0.1424 (7) | 0.88249 (15) | 1.14859 (16) | 0.0291 (7) | |
C10 | −0.0511 (7) | 0.84209 (17) | 1.09033 (17) | 0.0345 (8) | |
H10A | −0.1177 | 0.7943 | 1.0836 | 0.041* | |
C11 | 0.1340 (7) | 0.87015 (17) | 1.04216 (18) | 0.0368 (8) | |
H11A | 0.1927 | 0.8414 | 1.0026 | 0.044* | |
C12 | 0.2373 (7) | 0.94003 (17) | 1.05023 (17) | 0.0330 (8) | |
C13 | 0.1402 (7) | 0.98025 (17) | 1.10800 (18) | 0.0372 (8) | |
H13A | 0.2028 | 1.0285 | 1.1140 | 0.045* | |
C14 | −0.0444 (7) | 0.95246 (16) | 1.15692 (17) | 0.0335 (8) | |
H14A | −0.1045 | 0.9812 | 1.1963 | 0.040* | |
C15 | 0.4376 (7) | 0.96784 (16) | 0.99881 (18) | 0.0356 (8) | |
H15A | 0.4839 | 0.9370 | 0.9596 | 0.043* | |
S1S | 0.4159 (2) | 0.89954 (5) | 0.68655 (5) | 0.0424 (3) | |
O1S | 0.2730 (6) | 0.97004 (11) | 0.69869 (14) | 0.0601 (8) | |
C1S | 0.1520 (8) | 0.83818 (19) | 0.6599 (3) | 0.0644 (12) | |
H1SA | 0.2365 | 0.7910 | 0.6513 | 0.097* | |
H1SB | 0.0549 | 0.8550 | 0.6147 | 0.097* | |
H1SC | 0.0169 | 0.8342 | 0.6988 | 0.097* | |
C2S | 0.5060 (10) | 0.86450 (19) | 0.7747 (2) | 0.0629 (12) | |
H2SA | 0.6007 | 0.8181 | 0.7697 | 0.094* | |
H2SB | 0.3349 | 0.8580 | 0.8020 | 0.094* | |
H2SC | 0.6322 | 0.8981 | 0.8012 | 0.094* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0506 (17) | 0.0377 (13) | 0.0511 (15) | −0.0097 (12) | 0.0157 (12) | 0.0001 (11) |
O2 | 0.0503 (16) | 0.0269 (12) | 0.0479 (14) | −0.0120 (11) | 0.0122 (12) | 0.0016 (10) |
N1 | 0.0316 (17) | 0.0354 (15) | 0.0304 (15) | −0.0016 (13) | 0.0030 (12) | 0.0060 (12) |
N2 | 0.0330 (16) | 0.0280 (14) | 0.0351 (15) | −0.0060 (12) | 0.0071 (12) | 0.0065 (12) |
C1 | 0.035 (2) | 0.0375 (19) | 0.0337 (19) | 0.0007 (17) | −0.0003 (16) | 0.0044 (15) |
C2 | 0.0253 (19) | 0.0382 (19) | 0.0320 (18) | −0.0021 (16) | 0.0005 (14) | 0.0049 (15) |
C3 | 0.040 (2) | 0.040 (2) | 0.038 (2) | 0.0034 (17) | 0.0042 (17) | 0.0038 (16) |
C4 | 0.044 (2) | 0.055 (2) | 0.034 (2) | 0.0067 (19) | 0.0075 (17) | 0.0056 (17) |
C5 | 0.035 (2) | 0.063 (3) | 0.037 (2) | −0.0031 (19) | 0.0072 (16) | 0.0136 (18) |
C6 | 0.041 (2) | 0.044 (2) | 0.041 (2) | −0.0081 (18) | 0.0032 (18) | 0.0110 (17) |
C7 | 0.034 (2) | 0.0305 (17) | 0.0342 (18) | −0.0021 (16) | −0.0004 (15) | 0.0063 (15) |
C8 | 0.031 (2) | 0.0306 (18) | 0.0311 (18) | −0.0022 (15) | −0.0008 (15) | 0.0062 (14) |
C9 | 0.0272 (19) | 0.0265 (17) | 0.0332 (18) | 0.0003 (14) | −0.0023 (14) | 0.0066 (14) |
C10 | 0.034 (2) | 0.0269 (17) | 0.043 (2) | −0.0015 (15) | 0.0061 (16) | 0.0042 (15) |
C11 | 0.040 (2) | 0.0313 (18) | 0.040 (2) | 0.0010 (16) | 0.0088 (16) | 0.0009 (15) |
C12 | 0.0273 (19) | 0.039 (2) | 0.0329 (18) | −0.0003 (16) | 0.0020 (15) | 0.0073 (15) |
C13 | 0.039 (2) | 0.0323 (18) | 0.040 (2) | −0.0131 (16) | 0.0024 (16) | 0.0050 (15) |
C14 | 0.038 (2) | 0.0293 (17) | 0.0336 (18) | −0.0030 (16) | 0.0036 (15) | −0.0016 (14) |
C15 | 0.031 (2) | 0.0400 (19) | 0.0354 (19) | −0.0002 (16) | 0.0004 (15) | 0.0037 (16) |
S1S | 0.0467 (6) | 0.0376 (5) | 0.0437 (6) | −0.0029 (4) | 0.0110 (4) | −0.0022 (4) |
O1S | 0.095 (2) | 0.0223 (12) | 0.0630 (17) | 0.0027 (13) | 0.0075 (15) | −0.0006 (11) |
C1S | 0.050 (3) | 0.036 (2) | 0.105 (3) | 0.005 (2) | −0.024 (2) | −0.010 (2) |
C2S | 0.095 (4) | 0.040 (2) | 0.054 (3) | 0.008 (2) | −0.001 (2) | −0.0064 (18) |
Geometric parameters (Å, º) top
O1—C1 | 1.353 (4) | C9—C14 | 1.389 (4) |
O1—H1A | 0.8400 | C10—C11 | 1.374 (4) |
O2—C8 | 1.224 (4) | C10—H10A | 0.9500 |
N1—C7 | 1.272 (4) | C11—C12 | 1.395 (4) |
N1—N2 | 1.376 (3) | C11—H11A | 0.9500 |
N2—C8 | 1.361 (4) | C12—C13 | 1.389 (4) |
N2—H2A | 0.8800 | C12—C15 | 1.461 (4) |
C1—C6 | 1.388 (4) | C13—C14 | 1.379 (4) |
C1—C2 | 1.407 (4) | C13—H13A | 0.9500 |
C2—C3 | 1.396 (4) | C14—H14A | 0.9500 |
C2—C7 | 1.456 (4) | C15—C15i | 1.336 (6) |
C3—C4 | 1.376 (5) | C15—H15A | 0.9500 |
C3—H3A | 0.9500 | S1S—O1S | 1.498 (2) |
C4—C5 | 1.385 (5) | S1S—C1S | 1.750 (4) |
C4—H4A | 0.9500 | S1S—C2S | 1.773 (4) |
C5—C6 | 1.371 (5) | C1S—H1SA | 0.9800 |
C5—H5A | 0.9500 | C1S—H1SB | 0.9800 |
C6—H6A | 0.9500 | C1S—H1SC | 0.9800 |
C7—H7A | 0.9500 | C2S—H2SA | 0.9800 |
C8—C9 | 1.492 (4) | C2S—H2SB | 0.9800 |
C9—C10 | 1.387 (4) | C2S—H2SC | 0.9800 |
| | | |
C1—O1—H1A | 109.5 | C11—C10—H10A | 119.5 |
C7—N1—N2 | 117.7 (3) | C9—C10—H10A | 119.5 |
C8—N2—N1 | 118.7 (2) | C10—C11—C12 | 121.3 (3) |
C8—N2—H2A | 120.6 | C10—C11—H11A | 119.4 |
N1—N2—H2A | 120.6 | C12—C11—H11A | 119.4 |
O1—C1—C6 | 118.2 (3) | C13—C12—C11 | 117.1 (3) |
O1—C1—C2 | 121.9 (3) | C13—C12—C15 | 123.0 (3) |
C6—C1—C2 | 119.9 (3) | C11—C12—C15 | 119.9 (3) |
C3—C2—C1 | 118.1 (3) | C14—C13—C12 | 122.1 (3) |
C3—C2—C7 | 120.0 (3) | C14—C13—H13A | 118.9 |
C1—C2—C7 | 121.9 (3) | C12—C13—H13A | 118.9 |
C4—C3—C2 | 121.7 (3) | C13—C14—C9 | 120.0 (3) |
C4—C3—H3A | 119.2 | C13—C14—H14A | 120.0 |
C2—C3—H3A | 119.2 | C9—C14—H14A | 120.0 |
C3—C4—C5 | 119.1 (3) | C15i—C15—C12 | 126.7 (4) |
C3—C4—H4A | 120.4 | C15i—C15—H15A | 116.7 |
C5—C4—H4A | 120.4 | C12—C15—H15A | 116.7 |
C6—C5—C4 | 120.8 (3) | O1S—S1S—C1S | 106.69 (18) |
C6—C5—H5A | 119.6 | O1S—S1S—C2S | 106.33 (16) |
C4—C5—H5A | 119.6 | C1S—S1S—C2S | 99.0 (2) |
C5—C6—C1 | 120.4 (3) | S1S—C1S—H1SA | 109.5 |
C5—C6—H6A | 119.8 | S1S—C1S—H1SB | 109.5 |
C1—C6—H6A | 119.8 | H1SA—C1S—H1SB | 109.5 |
N1—C7—C2 | 120.8 (3) | S1S—C1S—H1SC | 109.5 |
N1—C7—H7A | 119.6 | H1SA—C1S—H1SC | 109.5 |
C2—C7—H7A | 119.6 | H1SB—C1S—H1SC | 109.5 |
O2—C8—N2 | 121.5 (3) | S1S—C2S—H2SA | 109.5 |
O2—C8—C9 | 121.5 (3) | S1S—C2S—H2SB | 109.5 |
N2—C8—C9 | 117.0 (3) | H2SA—C2S—H2SB | 109.5 |
C10—C9—C14 | 118.5 (3) | S1S—C2S—H2SC | 109.5 |
C10—C9—C8 | 116.9 (3) | H2SA—C2S—H2SC | 109.5 |
C14—C9—C8 | 124.6 (3) | H2SB—C2S—H2SC | 109.5 |
C11—C10—C9 | 121.0 (3) | | |
Symmetry code: (i) −x+1, −y+2, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N1 | 0.84 | 1.87 | 2.611 (3) | 146 |
N2—H2A···O1Sii | 0.88 | 2.05 | 2.901 (3) | 163 |
C14—H14A···O1Sii | 0.95 | 2.30 | 3.234 (4) | 169 |
C7—H7A···O1Sii | 0.95 | 2.71 | 3.457 (4) | 136 |
C1S—H1SA···O2iii | 0.98 | 2.28 | 3.118 (4) | 143 |
C2S—H2SA···O2iii | 0.98 | 2.39 | 3.196 (4) | 139 |
C1S—H1SC···S1Siv | 0.98 | 3.11 | 3.735 (4) | 123 |
Symmetry codes: (ii) −x, −y+2, −z+2; (iii) x+1, −y+3/2, z−1/2; (iv) x−1, y, z. |