The supramolecular structural features of organic molecules are very important with regard to their widespread properties in both solids and solutions. Herein, we describe the synthesis of a novel multifunctional 2-pyridone derivative, namely 6-(4-chlorophenyl)-5-formyl-4-methylsulfanyl-2-oxo-1,2-dihydropyridine-3-carbonitrile, C14H9ClN2O2S, denoted P1, and its structural features were established through X-ray crystallography. A Hirshfeld surface analysis followed by a two-dimensional fingerprint plot analysis was carried out. A frontier molecular orbital investigation and natural bond orbital (NBO) calculations explored the charge-transfer interactions associated with the molecular system. The optical properties of the 2-pyridone derivative were elucidated through UV–Vis absorption and emission spectroscopy, indicating a strong blue emissive nature with a colour purity of 82.5%, a short-lived lifetime and a large Stokes shift. Time-dependent density functional theory (TD-DFT) was used to gain some insight into the absorption behaviour and emissive characteristics of P1.
Supporting information
CCDC reference: 1843857
Data collection: APEX2 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and
Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015b).
6-(4-Chlorophenyl)-5-formyl-4-methylsulfanyl-2-oxo-1,2-dihydropyridine-3-carbonitrile
top
Crystal data top
C14H9ClN2O2S | F(000) = 624 |
Mr = 304.74 | Dx = 1.519 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 15.5215 (13) Å | Cell parameters from 2624 reflections |
b = 4.1954 (4) Å | θ = 3.2–24.6° |
c = 20.4883 (16) Å | µ = 0.45 mm−1 |
β = 93.139 (6)° | T = 293 K |
V = 1332.2 (2) Å3 | Needle, gold |
Z = 4 | 0.45 × 0.15 × 0.08 mm |
Data collection top
Bruker Kappa APEX2 CMOS diffractometer | 1376 reflections with I > 2σ(I) |
Radiation source: Sealed tube | Rint = 0.141 |
ω and φ scan | θmax = 25.0°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | h = −18→18 |
Tmin = 0.80, Tmax = 0.91 | k = −4→4 |
14529 measured reflections | l = −24→24 |
2320 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.070 | w = 1/[σ2(Fo2) + (0.0237P)2 + 3.3933P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.135 | (Δ/σ)max < 0.001 |
S = 1.06 | Δρmax = 0.24 e Å−3 |
2320 reflections | Δρmin = −0.24 e Å−3 |
190 parameters | Extinction correction: SHELXL2016; Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0027 (10) |
Special details top
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 | |
C1 | 0.8300 (3) | −0.1560 (13) | 0.4948 (2) | 0.0457 (14) | |
C2 | 0.8417 (3) | 0.0000 (14) | 0.4371 (2) | 0.0490 (15) | |
H2 | 0.896828 | 0.028303 | 0.422493 | 0.059* | |
C3 | 0.7711 (3) | 0.1138 (13) | 0.4014 (2) | 0.0425 (14) | |
H3 | 0.778745 | 0.223295 | 0.362621 | 0.041 (13)* | |
C4 | 0.6882 (3) | 0.0678 (11) | 0.4222 (2) | 0.0307 (11) | |
C5 | 0.6791 (3) | −0.0884 (12) | 0.4810 (2) | 0.0367 (13) | |
H5 | 0.624213 | −0.116069 | 0.496249 | 0.035 (13)* | |
C6 | 0.7497 (3) | −0.2036 (13) | 0.5173 (2) | 0.0431 (13) | |
H6 | 0.742896 | −0.311414 | 0.556344 | 0.052* | |
C7 | 0.6109 (3) | 0.1959 (12) | 0.3857 (2) | 0.0323 (12) | |
C8 | 0.5946 (3) | 0.1942 (12) | 0.3188 (2) | 0.0363 (12) | |
C9 | 0.6550 (3) | 0.0179 (14) | 0.2793 (2) | 0.0465 (15) | |
H9 | 0.688893 | −0.139215 | 0.299920 | 0.063 (19)* | |
C10 | 0.5166 (3) | 0.3366 (12) | 0.2907 (2) | 0.0347 (12) | |
C11 | 0.4618 (3) | 0.4881 (12) | 0.3322 (2) | 0.0322 (12) | |
C12 | 0.3868 (3) | 0.6676 (15) | 0.3143 (2) | 0.0447 (14) | |
C13 | 0.4791 (3) | 0.4863 (12) | 0.4018 (2) | 0.0347 (12) | |
C14 | 0.3841 (3) | 0.3689 (19) | 0.1895 (3) | 0.069 (2) | |
H14A | 0.351515 | 0.259603 | 0.221109 | 0.062 (17)* | |
H14B | 0.367331 | 0.292365 | 0.146489 | 0.09 (2)* | |
H14C | 0.373015 | 0.593602 | 0.191794 | 0.12 (3)* | |
Cl1 | 0.91892 (9) | −0.3044 (4) | 0.54005 (8) | 0.0732 (6) | |
N1 | 0.5531 (2) | 0.3368 (9) | 0.42389 (17) | 0.0334 (10) | |
H1 | 0.564059 | 0.331245 | 0.465478 | 0.043 (14)* | |
N2 | 0.3280 (3) | 0.8321 (14) | 0.3067 (2) | 0.0735 (16) | |
O1 | 0.6633 (2) | 0.0644 (11) | 0.22181 (16) | 0.0685 (13) | |
O2 | 0.4329 (2) | 0.6206 (9) | 0.44044 (14) | 0.0476 (10) | |
S1 | 0.49724 (9) | 0.2960 (4) | 0.20645 (6) | 0.0573 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.041 (3) | 0.044 (4) | 0.052 (3) | 0.009 (3) | 0.009 (2) | −0.003 (3) |
C2 | 0.035 (3) | 0.064 (4) | 0.050 (3) | −0.005 (3) | 0.016 (3) | −0.003 (3) |
C3 | 0.045 (3) | 0.051 (4) | 0.034 (3) | −0.007 (3) | 0.016 (2) | −0.004 (3) |
C4 | 0.035 (3) | 0.026 (3) | 0.032 (2) | −0.005 (2) | 0.011 (2) | −0.005 (2) |
C5 | 0.036 (3) | 0.035 (3) | 0.041 (3) | −0.008 (2) | 0.018 (2) | −0.003 (3) |
C6 | 0.048 (3) | 0.041 (3) | 0.041 (3) | 0.000 (3) | 0.012 (2) | 0.004 (3) |
C7 | 0.036 (3) | 0.030 (3) | 0.032 (2) | −0.008 (2) | 0.015 (2) | −0.001 (2) |
C8 | 0.044 (3) | 0.037 (3) | 0.031 (2) | −0.014 (3) | 0.019 (2) | −0.010 (2) |
C9 | 0.051 (3) | 0.056 (4) | 0.034 (3) | −0.006 (3) | 0.011 (3) | −0.017 (3) |
C10 | 0.041 (3) | 0.033 (3) | 0.031 (2) | −0.009 (2) | 0.010 (2) | −0.004 (2) |
C11 | 0.034 (3) | 0.035 (3) | 0.028 (3) | −0.010 (2) | 0.008 (2) | −0.002 (2) |
C12 | 0.042 (3) | 0.058 (4) | 0.034 (3) | −0.001 (3) | 0.004 (2) | −0.005 (3) |
C13 | 0.033 (3) | 0.042 (3) | 0.030 (3) | −0.005 (3) | 0.007 (2) | −0.002 (3) |
C14 | 0.072 (4) | 0.098 (7) | 0.036 (3) | 0.005 (4) | −0.009 (3) | −0.008 (4) |
Cl1 | 0.0528 (9) | 0.0872 (13) | 0.0792 (11) | 0.0193 (9) | −0.0008 (8) | 0.0046 (10) |
N1 | 0.040 (2) | 0.039 (3) | 0.022 (2) | 0.000 (2) | 0.0101 (17) | −0.0056 (19) |
N2 | 0.060 (3) | 0.094 (5) | 0.066 (3) | 0.020 (3) | 0.000 (3) | −0.008 (3) |
O1 | 0.068 (3) | 0.105 (4) | 0.034 (2) | 0.007 (2) | 0.0202 (18) | −0.018 (2) |
O2 | 0.052 (2) | 0.063 (3) | 0.0293 (17) | 0.019 (2) | 0.0145 (16) | −0.0045 (18) |
S1 | 0.0633 (9) | 0.0820 (13) | 0.0274 (6) | −0.0030 (9) | 0.0088 (6) | −0.0111 (8) |
Geometric parameters (Å, º) top
C1—C6 | 1.367 (6) | C8—C9 | 1.471 (6) |
C1—C2 | 1.371 (7) | C9—O1 | 1.208 (6) |
C1—Cl1 | 1.736 (5) | C9—H9 | 0.9300 |
C2—C3 | 1.370 (6) | C10—C11 | 1.388 (6) |
C2—H2 | 0.9300 | C10—S1 | 1.744 (4) |
C3—C4 | 1.391 (6) | C11—C12 | 1.417 (7) |
C3—H3 | 0.9300 | C11—C13 | 1.438 (6) |
C4—C5 | 1.385 (6) | C12—N2 | 1.149 (6) |
C4—C7 | 1.479 (6) | C13—O2 | 1.233 (5) |
C5—C6 | 1.378 (6) | C13—N1 | 1.364 (6) |
C5—H5 | 0.9300 | C14—S1 | 1.798 (5) |
C6—H6 | 0.9300 | C14—H14A | 0.9600 |
C7—N1 | 1.357 (5) | C14—H14B | 0.9600 |
C7—C8 | 1.381 (6) | C14—H14C | 0.9600 |
C8—C10 | 1.441 (6) | N1—H1 | 0.8600 |
| | | |
C6—C1—C2 | 121.8 (5) | O1—C9—C8 | 124.1 (6) |
C6—C1—Cl1 | 118.7 (4) | O1—C9—H9 | 118.0 |
C2—C1—Cl1 | 119.5 (4) | C8—C9—H9 | 118.0 |
C3—C2—C1 | 119.2 (5) | C11—C10—C8 | 118.3 (4) |
C3—C2—H2 | 120.4 | C11—C10—S1 | 124.9 (4) |
C1—C2—H2 | 120.4 | C8—C10—S1 | 116.8 (3) |
C2—C3—C4 | 120.9 (5) | C10—C11—C12 | 127.4 (4) |
C2—C3—H3 | 119.6 | C10—C11—C13 | 121.2 (4) |
C4—C3—H3 | 119.6 | C12—C11—C13 | 111.4 (4) |
C5—C4—C3 | 118.3 (4) | N2—C12—C11 | 171.9 (6) |
C5—C4—C7 | 119.5 (4) | O2—C13—N1 | 120.4 (4) |
C3—C4—C7 | 122.2 (4) | O2—C13—C11 | 123.4 (4) |
C6—C5—C4 | 121.2 (4) | N1—C13—C11 | 116.1 (4) |
C6—C5—H5 | 119.4 | S1—C14—H14A | 109.5 |
C4—C5—H5 | 119.4 | S1—C14—H14B | 109.5 |
C1—C6—C5 | 118.7 (5) | H14A—C14—H14B | 109.5 |
C1—C6—H6 | 120.7 | S1—C14—H14C | 109.5 |
C5—C6—H6 | 120.7 | H14A—C14—H14C | 109.5 |
N1—C7—C8 | 118.8 (4) | H14B—C14—H14C | 109.5 |
N1—C7—C4 | 114.3 (4) | C7—N1—C13 | 125.5 (4) |
C8—C7—C4 | 126.9 (4) | C7—N1—H1 | 117.3 |
C7—C8—C10 | 120.0 (4) | C13—N1—H1 | 117.3 |
C7—C8—C9 | 117.4 (5) | C10—S1—C14 | 106.8 (2) |
C10—C8—C9 | 122.4 (4) | | |
| | | |
C6—C1—C2—C3 | 0.5 (8) | C10—C8—C9—O1 | 26.8 (8) |
Cl1—C1—C2—C3 | 179.4 (4) | C7—C8—C10—C11 | 3.4 (7) |
C1—C2—C3—C4 | −1.2 (8) | C9—C8—C10—C11 | 177.6 (5) |
C2—C3—C4—C5 | 1.8 (7) | C7—C8—C10—S1 | −175.1 (4) |
C2—C3—C4—C7 | 178.1 (5) | C9—C8—C10—S1 | −0.9 (7) |
C3—C4—C5—C6 | −1.7 (7) | C8—C10—C11—C12 | 173.6 (5) |
C7—C4—C5—C6 | −178.2 (5) | S1—C10—C11—C12 | −8.0 (8) |
C2—C1—C6—C5 | −0.5 (8) | C8—C10—C11—C13 | −4.0 (7) |
Cl1—C1—C6—C5 | −179.4 (4) | S1—C10—C11—C13 | 174.5 (4) |
C4—C5—C6—C1 | 1.1 (7) | C10—C11—C13—O2 | 179.1 (5) |
C5—C4—C7—N1 | 41.0 (6) | C12—C11—C13—O2 | 1.2 (7) |
C3—C4—C7—N1 | −135.4 (5) | C10—C11—C13—N1 | 1.9 (7) |
C5—C4—C7—C8 | −141.3 (5) | C12—C11—C13—N1 | −176.0 (4) |
C3—C4—C7—C8 | 42.3 (7) | C8—C7—N1—C13 | −1.4 (7) |
N1—C7—C8—C10 | −0.8 (7) | C4—C7—N1—C13 | 176.6 (4) |
C4—C7—C8—C10 | −178.5 (4) | O2—C13—N1—C7 | −176.5 (5) |
N1—C7—C8—C9 | −175.3 (4) | C11—C13—N1—C7 | 0.8 (7) |
C4—C7—C8—C9 | 7.1 (8) | C11—C10—S1—C14 | −17.5 (5) |
C7—C8—C9—O1 | −158.9 (5) | C8—C10—S1—C14 | 160.9 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.86 | 1.94 | 2.782 (4) | 168 |
C14—H14C···N2 | 0.96 | 2.69 | 3.245 (8) | 118 |
C14—H14A···N2ii | 0.96 | 2.55 | 3.439 (9) | 154 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z. |
Calculated TD-DFT singlet excitation energy (EE), wavelength (λ), oscillator
strengths (f) and orbital composition of transitions for the most intense
transitions of P1 topExcited State 5: Singlet-A; EE = 34130.95 cm-1; λ = 34130.86 cm-1;
f = 0.2757 | |
Nature of the transition | Contribution in % |
HOMO-3 to LUMO | 4.55 |
HOMO-2 to LUMO | 34.33 |
HOMO-2 to LUMO+1 | 19.03 |
HOMO-1 to LUMO | 6.97 |
HOMO to LUMO+1 | 29.17 |