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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.
Supporting information
CCDC reference: 1404102
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.
Crystal data top
C16H19N3O2 | Dx = 1.200 Mg m−3 |
Mr = 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 | Rint = 0.019 |
Absorption correction: multi-scan SADABS V2014/5(Bruker AXS.Inc) | θmax = 25.0°, θmin = 2.1° |
Tmin = 0.980, Tmax = 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(Fo2) + (0.0534P)2 + 0.3884P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.045 | (Δ/σ)max < 0.001 |
wR(F2) = 0.122 | Δρmax = 0.27 e Å−3 |
S = 1.05 | Δρmin = −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 | Uiso*/Ueq | |
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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