Synthesis, crystal growth, characterization and DFT investigation of a nonlinear optically active cuminaldehyde derivative hydrazone

Meenatchi, V.; Siva, S.; Meenakshisundaram, SP; Cheng, L.

doi:10.1107/S2052520621001517

Synthesis, crystal growth, characterization and DFT investigation of a nonlinear optically active cuminaldehyde derivative hydrazone

V. Meenatchi, S. Subramanian Siva, SP Meenakshisundaram and L. Cheng

Single crystals of (E)-N′-(4-isopropylbenzylidene)isonicotinohydrazide monohydrate (IBIHM) were grown from ethanol by the slow evaporation from solution growth technique at room temperature. The structure was elucidated by single-crystal X-ray diffraction analysis and crystallized in the orthorhombic system with noncentrosymmetric space group P2₁2₁2₁. Optical studies reveal that the absorption was minimum in the visible region and the band-gap energy was estimated using the Kubelka–Munk algorithm. The functional groups were identified by Fourier transform infrared spectral analysis. A scanning electron microscopy study revealed the surface morphology of the grown crystal. Investigation of the intermolecular interactions, crystal packing using Hirshfeld surface analysis and single-crystal X-ray diffraction confirm that the close contacts were associated with molecular interactions. Fingerprint plots of Hirshfeld surfaces are used to locate and analyze the percentage of hydrogen-bonding interactions. The second-harmonic generation efficiency of the grown specimen was superior to that of the reference material, potassium dihydrogen phosphate. The grown crystals were further characterized by mass spectrometry and elemental analysis. Theoretical studies using density functional theory (DFT) greatly substantiated the experimental observations. Large first-order molecular hyperpolarizability (β) of about ∼70× was observed for IBIHM. The efficiency of IBIHM in terms of nonlinear optical response was verified and the molecule displayed greater chemical stability and reactivity.

Keywords: crystal growth; optical properties; hydrogen bonding interactions; hyperpolarizability; SHG efficiency.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520621001517/rm5039sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520621001517/rm5039Isup2.hkl Contains datablock I
	Portable Document Format (PDF) file https://doi.org/10.1107/S2052520621001517/rm5039sup3.pdf Supplementary material

CCDC reference: 1404102

Computing details top

Data collection: Bruker APEX2; cell refinement: Bruker SAINT; data reduction: Bruker SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2014); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.

(I) top

Crystal data top

C₁₆H₁₉N₃O₂	D_x = 1.200 Mg m⁻³
M_r = 285.34	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 2737 reflections
a = 7.7498 (4) Å	θ = 2.6–24.4°
b = 11.7940 (6) Å	µ = 0.08 mm⁻¹
c = 17.2849 (7) Å	T = 296 K
V = 1579.86 (13) Å³	Block, white
Z = 4	0.25 × 0.16 × 0.10 mm
F(000) = 608

Data collection top

Bruker APEX-II CCD diffractometer	2209 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.019
Absorption correction: multi-scan SADABS V2014/5(Bruker AXS.Inc)	θ_max = 25.0°, θ_min = 2.1°
T_min = 0.980, T_max = 0.992	h = −7→9
6423 measured reflections	k = −10→14
2697 independent reflections	l = −20→16

Refinement top

Refinement on F²	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0534P)² + 0.3884P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.045	(Δ/σ)_max < 0.001
wR(F²) = 0.122	Δρ_max = 0.27 e Å⁻³
S = 1.05	Δρ_min = −0.24 e Å⁻³
2697 reflections	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
201 parameters	Extinction coefficient: 0.011 (2)
0 restraints	Absolute structure: Flack x determined using 756 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Hydrogen site location: mixed	Absolute structure parameter: 0.7 (7)

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	U_iso*/U_eq
N2	−0.0128 (4)	0.8828 (2)	0.77823 (14)	0.0540 (7)
H2N	0.0168	0.8152	0.7915	0.065*
N3	−0.0065 (4)	0.9156 (2)	0.70119 (14)	0.0538 (7)
C8	0.0855 (4)	0.8631 (3)	0.57379 (17)	0.0472 (7)
O1	−0.1047 (4)	1.05598 (19)	0.81812 (14)	0.0716 (8)
O2	0.1348 (5)	0.6789 (2)	0.81825 (18)	0.0781 (9)
C7	0.0697 (4)	0.8461 (3)	0.65694 (18)	0.0532 (8)
H7	0.1177	0.7811	0.6786	0.064*
C5	−0.0716 (4)	0.9129 (3)	0.91286 (18)	0.0496 (8)
C6	−0.0655 (5)	0.9575 (3)	0.83189 (18)	0.0519 (8)
C9	0.1684 (5)	0.7823 (3)	0.52965 (19)	0.0577 (9)
H9	0.2195	0.7204	0.5538	0.069*
C11	0.1041 (5)	0.8820 (3)	0.4117 (2)	0.0641 (10)
C4	−0.1388 (5)	0.8078 (3)	0.9307 (2)	0.0624 (9)
H4	−0.1732	0.7581	0.8919	0.075*
C12	0.0217 (5)	0.9635 (3)	0.45628 (19)	0.0656 (10)
H12	−0.0284	1.0256	0.4318	0.079*
C13	0.0119 (5)	0.9553 (3)	0.53535 (19)	0.0567 (9)
H13	−0.0441	1.0115	0.5635	0.068*
N1	−0.1040 (5)	0.8437 (3)	1.06585 (18)	0.0794 (10)
C1	−0.0209 (5)	0.9822 (3)	0.97240 (19)	0.0627 (9)
H1	0.0239	1.0539	0.9624	0.075*
C10	0.1768 (5)	0.7919 (3)	0.4502 (2)	0.0661 (10)
H10	0.2331	0.7360	0.4219	0.079*
C3	−0.1537 (6)	0.7782 (3)	1.0075 (2)	0.0750 (12)
H3	−0.2015	0.7080	1.0193	0.090*
C2	−0.0374 (6)	0.9437 (4)	1.0470 (2)	0.0789 (13)
H2	0.0005	0.9906	1.0868	0.095*
C14	0.1162 (10)	0.8893 (4)	0.3233 (2)	0.125 (2)
H14	0.2414	0.8843	0.3162	0.150*
C16	0.0825 (9)	1.0003 (5)	0.2899 (3)	0.118 (2)
H16A	0.1162	1.0003	0.2364	0.177*
H16B	0.1474	1.0568	0.3173	0.177*
H16C	−0.0384	1.0171	0.2937	0.177*
C15	0.0621 (10)	0.7886 (6)	0.2844 (3)	0.145 (3)
H15A	−0.0617	0.7859	0.2830	0.217*
H15B	0.1052	0.7235	0.3116	0.217*
H15C	0.1064	0.7888	0.2326	0.217*
H1O	0.129 (7)	0.619 (4)	0.782 (3)	0.118 (17)*
H2O	0.210 (8)	0.671 (5)	0.846 (3)	0.13 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0701 (18)	0.0497 (15)	0.0422 (15)	0.0056 (14)	0.0000 (13)	0.0082 (12)
N3	0.0666 (18)	0.0531 (15)	0.0419 (14)	0.0004 (15)	−0.0032 (13)	0.0075 (12)
C8	0.0475 (16)	0.0480 (16)	0.0462 (17)	0.0003 (15)	−0.0047 (14)	−0.0008 (14)
O1	0.104 (2)	0.0555 (14)	0.0558 (14)	0.0210 (14)	0.0090 (14)	0.0101 (12)
O2	0.119 (3)	0.0545 (16)	0.0606 (16)	0.0187 (16)	−0.0293 (18)	−0.0116 (13)
C7	0.0613 (19)	0.0478 (16)	0.0504 (18)	0.0001 (17)	−0.0045 (17)	0.0054 (15)
C5	0.0540 (18)	0.0504 (17)	0.0445 (17)	0.0019 (15)	0.0067 (15)	0.0037 (14)
C6	0.0565 (19)	0.0508 (18)	0.0483 (18)	0.0012 (16)	−0.0001 (16)	0.0037 (15)
C9	0.062 (2)	0.0532 (19)	0.058 (2)	0.0114 (18)	−0.0007 (17)	0.0012 (16)
C11	0.080 (3)	0.067 (2)	0.0449 (18)	0.001 (2)	0.0039 (18)	0.0010 (17)
C4	0.076 (2)	0.058 (2)	0.0528 (19)	−0.0065 (19)	0.0104 (18)	−0.0006 (17)
C12	0.083 (3)	0.063 (2)	0.051 (2)	0.013 (2)	−0.0023 (19)	0.0088 (17)
C13	0.068 (2)	0.0521 (18)	0.0502 (18)	0.0107 (17)	0.0014 (17)	0.0020 (15)
N1	0.107 (3)	0.083 (2)	0.0480 (17)	0.002 (2)	0.0125 (18)	0.0090 (17)
C1	0.075 (2)	0.061 (2)	0.0523 (19)	−0.0054 (19)	0.0034 (18)	0.0004 (17)
C10	0.073 (3)	0.065 (2)	0.061 (2)	0.009 (2)	0.0117 (19)	−0.0071 (19)
C3	0.098 (3)	0.065 (2)	0.062 (2)	−0.004 (2)	0.021 (2)	0.010 (2)
C2	0.102 (3)	0.084 (3)	0.051 (2)	−0.004 (3)	0.002 (2)	−0.006 (2)
C14	0.221 (7)	0.104 (4)	0.051 (2)	0.013 (4)	0.006 (4)	0.002 (3)
C16	0.144 (5)	0.149 (5)	0.061 (3)	−0.025 (4)	0.001 (3)	0.036 (3)
C15	0.203 (7)	0.173 (6)	0.058 (3)	−0.008 (6)	−0.027 (4)	−0.020 (4)

Geometric parameters (Å, º) top

N2—C6	1.343 (4)	C4—H4	0.9300
N2—N3	1.388 (3)	C12—C13	1.372 (4)
N2—H2N	0.8600	C12—H12	0.9300
N3—C7	1.267 (4)	C13—H13	0.9300
C8—C9	1.379 (4)	N1—C3	1.327 (5)
C8—C13	1.396 (4)	N1—C2	1.328 (5)
C8—C7	1.456 (4)	C1—C2	1.373 (5)
O1—C6	1.223 (4)	C1—H1	0.9300
O2—H1O	0.94 (5)	C10—H10	0.9300
O2—H2O	0.76 (6)	C3—H3	0.9300
C7—H7	0.9300	C2—H2	0.9300
C5—C1	1.372 (5)	C14—C15	1.428 (7)
C5—C4	1.379 (5)	C14—C16	1.455 (7)
C5—C6	1.496 (4)	C14—H14	0.9800
C9—C10	1.380 (4)	C16—H16A	0.9600
C9—H9	0.9300	C16—H16B	0.9600
C11—C10	1.374 (5)	C16—H16C	0.9600
C11—C12	1.388 (5)	C15—H15A	0.9600
C11—C14	1.533 (5)	C15—H15B	0.9600
C4—C3	1.378 (5)	C15—H15C	0.9600

C6—N2—N3	119.3 (3)	C3—N1—C2	116.3 (3)
C6—N2—H2N	120.3	C5—C1—C2	118.7 (3)
N3—N2—H2N	120.3	C5—C1—H1	120.6
C7—N3—N2	114.5 (3)	C2—C1—H1	120.6
C9—C8—C13	117.7 (3)	C11—C10—C9	121.7 (3)
C9—C8—C7	119.3 (3)	C11—C10—H10	119.1
C13—C8—C7	122.9 (3)	C9—C10—H10	119.1
H1O—O2—H2O	111 (5)	N1—C3—C4	124.1 (4)
N3—C7—C8	123.1 (3)	N1—C3—H3	118.0
N3—C7—H7	118.5	C4—C3—H3	118.0
C8—C7—H7	118.5	N1—C2—C1	124.0 (4)
C1—C5—C4	118.4 (3)	N1—C2—H2	118.0
C1—C5—C6	118.9 (3)	C1—C2—H2	118.0
C4—C5—C6	122.5 (3)	C15—C14—C16	120.6 (5)
O1—C6—N2	124.3 (3)	C15—C14—C11	113.9 (4)
O1—C6—C5	120.6 (3)	C16—C14—C11	115.9 (4)
N2—C6—C5	115.1 (3)	C15—C14—H14	100.5
C8—C9—C10	121.1 (3)	C16—C14—H14	100.5
C8—C9—H9	119.5	C11—C14—H14	100.5
C10—C9—H9	119.5	C14—C16—H16A	109.5
C10—C11—C12	117.1 (3)	C14—C16—H16B	109.5
C10—C11—C14	120.1 (4)	H16A—C16—H16B	109.5
C12—C11—C14	122.8 (4)	C14—C16—H16C	109.5
C3—C4—C5	118.3 (3)	H16A—C16—H16C	109.5
C3—C4—H4	120.8	H16B—C16—H16C	109.5
C5—C4—H4	120.8	C14—C15—H15A	109.5
C13—C12—C11	122.0 (3)	C14—C15—H15B	109.5
C13—C12—H12	119.0	H15A—C15—H15B	109.5
C11—C12—H12	119.0	C14—C15—H15C	109.5
C12—C13—C8	120.4 (3)	H15A—C15—H15C	109.5
C12—C13—H13	119.8	H15B—C15—H15C	109.5
C8—C13—H13	119.8

C6—N2—N3—C7	169.5 (3)	C11—C12—C13—C8	−0.1 (6)
N2—N3—C7—C8	178.1 (3)	C9—C8—C13—C12	0.5 (5)
C9—C8—C7—N3	−179.1 (3)	C7—C8—C13—C12	−175.9 (3)
C13—C8—C7—N3	−2.7 (5)	C4—C5—C1—C2	0.7 (5)
N3—N2—C6—O1	−2.3 (5)	C6—C5—C1—C2	175.7 (4)
N3—N2—C6—C5	178.6 (3)	C12—C11—C10—C9	0.1 (6)
C1—C5—C6—O1	−38.0 (5)	C14—C11—C10—C9	−179.9 (5)
C4—C5—C6—O1	136.8 (4)	C8—C9—C10—C11	0.3 (6)
C1—C5—C6—N2	141.1 (3)	C2—N1—C3—C4	0.4 (7)
C4—C5—C6—N2	−44.1 (5)	C5—C4—C3—N1	−1.4 (6)
C13—C8—C9—C10	−0.6 (5)	C3—N1—C2—C1	1.2 (7)
C7—C8—C9—C10	176.0 (3)	C5—C1—C2—N1	−1.8 (6)
C1—C5—C4—C3	0.8 (5)	C10—C11—C14—C15	51.1 (8)
C6—C5—C4—C3	−174.0 (4)	C12—C11—C14—C15	−129.0 (6)
C10—C11—C12—C13	−0.2 (6)	C10—C11—C14—C16	−162.6 (5)
C14—C11—C12—C13	179.9 (5)	C12—C11—C14—C16	17.3 (8)

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