Crystal structure, Hirshfeld surface analysis and HOMO–LUMO analysis of (E)-N′-(3-hy­droxy-4-meth­oxy­benzyl­idene)nicotinohydrazide monohydrate

Sivajeyanthi, P.; Edison, B.; Balasubramani, K.; Premkumar, G.; Swu, T.

doi:10.1107/S2056989019006492

Crystal structure, Hirshfeld surface analysis and HOMO–LUMO analysis of (E)-N′-(3-hydroxy-4-methoxybenzylidene)nicotinohydrazide monohydrate

P. Sivajeyanthi, B. Edison, K. Balasubramani, G. Premkumar and T. Swu

The title Schiff base compound displays an E configuration with respect to the C=N double bond. The pyridine and benzene rings subtend a dihedral angle of 29.63 (7)°. In the crystal, the molecules are linked by N—H

O, C—H

O, O—H

O and O—H

N hydrogen-bonding interactions.

Keywords: crystal structure; Schiff base; intermolecular interactions; Hirshfeld surface analysis.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989019006492/rz5252sup1.cif Contains datablocks global, I, 1
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989019006492/rz5252Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989019006492/rz5252Isup3.cml Supplementary material

CCDC reference: 1587259

checkCIF report

Key indicators

Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.002 Å
R factor = 0.036
wR factor = 0.101
Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT910_ALERT_3_B Missing # of FCF Reflection(s) Below Theta(Min).         11 Note

Alert level C
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          5 Report

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          4 Report
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT128_ALERT_4_G Alternate Setting for Input Space Group  P21/c        P21/n Note
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          2 Note
PLAT960_ALERT_3_G Number of Intensities with I  <   - 2*sig(I) ...          1 Check
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          5 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2017 (Sheldrick, 2015).

(E)-N'-(3-Hydroxy-4-methoxybenzylidene)nicotinohydrazide monohydrate top

Crystal data top

C₁₄H₁₃N₃O₃·H₂O	F(000) = 608
M_r = 289.29	D_x = 1.395 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.1153 (4) Å	Cell parameters from 3729 reflections
b = 11.0075 (6) Å	θ = 3.9–29.2°
c = 18.2771 (10) Å	µ = 0.10 mm⁻¹
β = 105.766 (5)°	T = 295 K
V = 1377.64 (14) Å³	Block, colourless
Z = 4	0.30 × 0.25 × 0.18 mm

Data collection top

Agilent Xcalibur Eos diffractometer	2549 independent reflections
Radiation source: fine-focus sealed tube	2027 reflections with I > 2σ(I)
Detector resolution: 15.9821 pixels mm^-1	R_int = 0.027
ω scans	θ_max = 25.5°, θ_min = 3.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −8→8
T_min = 0.969, T_max = 0.981	k = −13→12
8396 measured reflections	l = −22→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.101	w = 1/[σ²(F_o²) + (0.0462P)² + 0.2987P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2549 reflections	Δρ_max = 0.16 e Å⁻³
192 parameters	Δρ_min = −0.13 e Å⁻³
0 restraints	Extinction correction: SHELXL2017 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.030 (3)

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O3	−0.03769 (14)	0.40424 (10)	0.06695 (6)	0.0455 (3)
O2	0.20750 (15)	0.23383 (10)	0.06507 (7)	0.0537 (3)
H10	0.287088	0.178188	0.073527	0.081*
O1	1.15498 (17)	0.21431 (11)	0.30304 (8)	0.0604 (4)
N3	0.85559 (17)	0.37007 (12)	0.26300 (7)	0.0418 (3)
N2	1.03456 (17)	0.40123 (12)	0.31206 (7)	0.0410 (3)
H2N	1.053128	0.472235	0.332397	0.049*
N1	1.61018 (19)	0.51282 (12)	0.42610 (8)	0.0452 (4)
C8	0.5291 (2)	0.43898 (15)	0.20366 (8)	0.0371 (4)
C9	0.4682 (2)	0.33704 (14)	0.15750 (8)	0.0384 (4)
H9	0.555924	0.274429	0.157443	0.046*
C10	0.2791 (2)	0.32888 (14)	0.11216 (8)	0.0372 (4)
C11	0.1465 (2)	0.42290 (14)	0.11294 (8)	0.0355 (4)
C12	0.2059 (2)	0.52410 (15)	0.15746 (9)	0.0409 (4)
H12	0.118419	0.586791	0.157676	0.049*
C13	0.3972 (2)	0.53171 (15)	0.20196 (9)	0.0423 (4)
H13	0.437730	0.600772	0.231319	0.051*
C14	−0.1795 (2)	0.49637 (17)	0.06553 (10)	0.0492 (4)
H14A	−0.192906	0.508196	0.115902	0.074*
H14B	−0.302791	0.472017	0.032256	0.074*
H14C	−0.138193	0.570937	0.047468	0.074*
C7	0.7260 (2)	0.45278 (15)	0.25379 (8)	0.0411 (4)
H7	0.758441	0.525352	0.280265	0.049*
C6	1.1785 (2)	0.31829 (14)	0.32729 (9)	0.0390 (4)
C2	1.4323 (2)	0.47808 (14)	0.38578 (8)	0.0387 (4)
H2	1.343594	0.537888	0.362746	0.046*
C1	1.3728 (2)	0.35815 (13)	0.37638 (8)	0.0354 (4)
C5	1.5059 (2)	0.27035 (15)	0.41019 (10)	0.0502 (4)
H5	1.472088	0.188603	0.404400	0.060*
C4	1.6891 (2)	0.30435 (17)	0.45260 (11)	0.0599 (5)
H4	1.780614	0.246398	0.476287	0.072*
C3	1.7334 (2)	0.42511 (17)	0.45907 (10)	0.0533 (5)
H3	1.857046	0.447633	0.488254	0.064*
O4	1.07802 (17)	0.65762 (11)	0.34578 (7)	0.0594 (4)
H4WA	1.034030	0.696974	0.377588	0.089*
H4WB	1.043530	0.692674	0.302788	0.089*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0286 (5)	0.0448 (7)	0.0558 (7)	0.0044 (5)	−0.0009 (5)	−0.0023 (5)
O2	0.0385 (6)	0.0378 (6)	0.0712 (8)	0.0062 (5)	−0.0085 (5)	−0.0115 (6)
O1	0.0513 (7)	0.0382 (7)	0.0744 (9)	−0.0022 (5)	−0.0127 (6)	−0.0079 (6)
N3	0.0309 (6)	0.0455 (8)	0.0416 (7)	−0.0061 (6)	−0.0029 (5)	0.0026 (6)
N2	0.0311 (6)	0.0390 (7)	0.0448 (7)	−0.0032 (6)	−0.0037 (5)	−0.0026 (6)
N1	0.0361 (7)	0.0419 (8)	0.0509 (8)	−0.0062 (6)	0.0006 (6)	0.0030 (6)
C8	0.0317 (7)	0.0424 (9)	0.0351 (8)	−0.0033 (7)	0.0054 (6)	0.0051 (7)
C9	0.0306 (7)	0.0373 (8)	0.0437 (8)	0.0036 (6)	0.0039 (6)	0.0062 (7)
C10	0.0343 (8)	0.0327 (8)	0.0408 (8)	−0.0019 (6)	0.0038 (6)	0.0024 (7)
C11	0.0281 (7)	0.0388 (9)	0.0369 (8)	−0.0003 (6)	0.0039 (6)	0.0052 (7)
C12	0.0369 (8)	0.0403 (9)	0.0435 (8)	0.0051 (7)	0.0073 (6)	−0.0004 (7)
C13	0.0399 (8)	0.0422 (9)	0.0412 (8)	−0.0020 (7)	0.0049 (7)	−0.0052 (7)
C14	0.0325 (8)	0.0598 (11)	0.0520 (10)	0.0118 (8)	0.0056 (7)	0.0013 (8)
C7	0.0348 (8)	0.0446 (9)	0.0397 (8)	−0.0055 (7)	0.0030 (6)	0.0012 (7)
C6	0.0370 (8)	0.0345 (9)	0.0398 (8)	−0.0047 (7)	0.0007 (6)	0.0025 (7)
C2	0.0320 (8)	0.0364 (8)	0.0432 (8)	−0.0003 (6)	0.0023 (6)	0.0041 (7)
C1	0.0321 (7)	0.0359 (8)	0.0345 (7)	−0.0008 (6)	0.0026 (6)	0.0024 (6)
C5	0.0457 (9)	0.0361 (9)	0.0580 (10)	−0.0003 (7)	−0.0041 (8)	0.0050 (8)
C4	0.0432 (10)	0.0477 (11)	0.0728 (13)	0.0060 (8)	−0.0114 (9)	0.0120 (9)
C3	0.0328 (8)	0.0540 (11)	0.0611 (11)	−0.0043 (8)	−0.0075 (7)	0.0063 (9)
O4	0.0627 (8)	0.0475 (7)	0.0583 (7)	0.0186 (6)	−0.0002 (6)	−0.0017 (6)

Geometric parameters (Å, º) top

O3—C11	1.3664 (17)	C12—C13	1.386 (2)
O3—C14	1.4257 (19)	C12—H12	0.9300
O2—C10	1.3627 (18)	C13—H13	0.9300
O2—H10	0.8198	C14—H14A	0.9600
O1—C6	1.2223 (19)	C14—H14B	0.9600
N3—C7	1.274 (2)	C14—H14C	0.9600
N3—N2	1.3866 (16)	C7—H7	0.9300
N2—C6	1.343 (2)	C6—C1	1.4950 (19)
N2—H2N	0.8602	C2—C1	1.383 (2)
N1—C3	1.333 (2)	C2—H2	0.9300
N1—C2	1.3355 (19)	C1—C5	1.376 (2)
C8—C13	1.381 (2)	C5—C4	1.376 (2)
C8—C9	1.400 (2)	C5—H5	0.9300
C8—C7	1.459 (2)	C4—C3	1.364 (3)
C9—C10	1.378 (2)	C4—H4	0.9300
C9—H9	0.9300	C3—H3	0.9300
C10—C11	1.404 (2)	O4—H4WA	0.8500
C11—C12	1.377 (2)	O4—H4WB	0.8495

C11—O3—C14	117.37 (12)	H14A—C14—H14B	109.5
C10—O2—H10	109.5	O3—C14—H14C	109.5
C7—N3—N2	114.41 (13)	H14A—C14—H14C	109.5
C6—N2—N3	118.71 (13)	H14B—C14—H14C	109.5
C6—N2—H2N	120.6	N3—C7—C8	123.07 (15)
N3—N2—H2N	120.7	N3—C7—H7	118.5
C3—N1—C2	116.76 (14)	C8—C7—H7	118.5
C13—C8—C9	118.80 (13)	O1—C6—N2	122.66 (13)
C13—C8—C7	117.90 (14)	O1—C6—C1	120.37 (14)
C9—C8—C7	123.31 (14)	N2—C6—C1	116.97 (13)
C10—C9—C8	120.43 (14)	N1—C2—C1	123.65 (14)
C10—C9—H9	119.8	N1—C2—H2	118.2
C8—C9—H9	119.8	C1—C2—H2	118.2
O2—C10—C9	124.50 (13)	C5—C1—C2	117.67 (13)
O2—C10—C11	115.81 (12)	C5—C1—C6	118.33 (14)
C9—C10—C11	119.69 (14)	C2—C1—C6	123.84 (13)
O3—C11—C12	125.07 (13)	C4—C5—C1	119.55 (15)
O3—C11—C10	114.71 (13)	C4—C5—H5	120.2
C12—C11—C10	120.22 (13)	C1—C5—H5	120.2
C11—C12—C13	119.40 (14)	C3—C4—C5	118.38 (15)
C11—C12—H12	120.3	C3—C4—H4	120.8
C13—C12—H12	120.3	C5—C4—H4	120.8
C8—C13—C12	121.44 (15)	N1—C3—C4	123.96 (15)
C8—C13—H13	119.3	N1—C3—H3	118.0
C12—C13—H13	119.3	C4—C3—H3	118.0
O3—C14—H14A	109.5	H4WA—O4—H4WB	109.5
O3—C14—H14B	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4WA···O2ⁱ	0.85	2.28	3.0483 (17)	150
O4—H4WA···O3ⁱ	0.85	2.49	3.2011 (16)	141
O4—H4WB···O1ⁱⁱ	0.85	2.08	2.8429 (19)	150
O4—H4WB···N3ⁱⁱ	0.85	2.50	3.1875 (18)	139
N2—H2N···O4	0.86	2.06	2.8889 (18)	162
O2—H10···N1ⁱⁱⁱ	0.82	1.96	2.7411 (17)	159
C2—H2···O4	0.93	2.25	3.129 (2)	156
C4—H4···O3^iv	0.93	2.45	3.347 (2)	163

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+2, y+1/2, −z+1/2; (iii) −x+2, y−1/2, −z+1/2; (iv) x+2, −y+1/2, z+1/2.

Calculated frontier molecular orbital energies (eV) top

FMO	Energy
E_HOMO	-5.7171
E_LUMO	-1.8174
E_HOMO-1	-6.5750
E_LUMO+1	-1.2770
(E_HOMO - E_LUMO) gap	3.8997
(E_HOMO-1 - E_LUMO+1) gap	5.2980
Chemical hardness	1.9498
Chemical potential	3.7672
Electronegativity	-3.7672
Electrophilicity index	3.6393

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Crystal structure, Hirshfeld surface analysis and HOMO–LUMO analysis of (E)-N′-(3-hy­droxy-4-meth­oxy­benzyl­idene)nicotinohydrazide monohydrate

Supporting information

Key indicators

checkCIF/PLATON results

Crystal structure, Hirshfeld surface analysis and HOMO–LUMO analysis of (E)-N′-(3-hydroxy-4-methoxybenzylidene)nicotinohydrazide monohydrate