3-Indolyl­form­aldehyde isonicotinoyl­hydrazone methanol solvate

The title compound, C₁₅H₁₂N₄O·CH₄O, an aroyl­hydrazone, has been synthesized. The C=O bond length is 1.2302 (18) Å, which suggests that the title compound is in the keto form. The C=N double bond has a length of 1.2789 (19) Å. In the crystal structure, the mol­ecules are stabilized by N—H...N, N—H...O and O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.040
• wR factor = 0.107
• Data-to-parameter ratio = 13.0

checkCIF results

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S1. Comment

The chemical and pharmacological properties of aroylhydrazones have been investigated extensively, owing to their chelating ability with metal ions and to their potentially benefical chemistry and biological activities, such as magnetic (Bu et al., 2001; Zhang et al., 1996), antitumor, antineoplastic, antibacterial and antimalarial activities (Liao et al., 2000; Fun et al., 1996; Lu et al., 1996). As part of our studies on the synthesis and characterization of these compounds, in this paper, we report the synthesis and crystal structure of 3-indolylformaldehyde isonicotinoylhydrazone monomethanol solvate, (I).

It can be seen that the molecule is in the keto form and that the configuration of the N3—C7 bond is E. The bonds and angles observed in this structure are normal and the molecule is practically planar. As the distances for C7═N3 and C6═O1 are 1.2789 (19) and 1.2302 (18) Å, respectively, typical for double bonds, this is a novel kind of aroylhydrazone. In the crystal, the molecules are stabilized by N—H···N, N—H···O and O—H···O hydrogen bonds (Table 1 and Fig. 2).

S2. Experimental

The solution of 3-indolylformaldehyde (10 mmol) in 50 ml e thanol was added to a solution of isonicotinoyl hydrazine (10 mmol) in 10 ml e thanol. The reaction mixture was refluxed for 4 h with stirring, then the resulting pale yellow precipitate was obtained by filtration, washed several times with ethanol and dried in vacuo (yield 90%). Analysis calculated for the title compound (C₁₆H₁₆N₄O₂): C 64.86, H 5.41, N 18.92%; found: C 64.66, H 5.40, N 18.88%. IR (KBr, cm⁻¹): 3340 (–OH), 1657 (C═O), 1641 (C═N), 1599. The methanol solution of the title compound was slowly evaporated and pale-yellow crystals were obtained after three weeks and used for X-ray diffraction study.

S3. Refinement

The positions of all H atoms were fixed geometrically.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecule with labelling of the non-H atoms and 30% probabiility ellipsoids.
	Fig. 2. A view of the packing.

3-Indolylformaldehyde isonicotinoylhydrazone monomethanol

Crystal data

C15H12N4O·CH4O	F(000) = 624
Mr = 296.33	Dx = 1.321 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.520 (2) Å	Cell parameters from 694 reflections
b = 14.020 (3) Å	θ = 2.5–23.6°
c = 11.146 (3) Å	µ = 0.09 mm^−1
β = 115.02 (1)°	T = 293 K
V = 1489.7 (6) Å^3	Plate, pale yellow
Z = 4	0.3 × 0.2 × 0.2 mm

Data collection

Bruker SMART Apex CCD diffractometer	1836 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.048
Graphite monochromator	θmax = 25.0°, θmin = 2.1°
ϕ and ω scans	h = −12→12
7186 measured reflections	k = −16→12
2621 independent reflections	l = −13→11

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.107	w = 1/[σ^2(Fo^2) + (0.0567P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.96	(Δ/σ)max = 0.001
2621 reflections	Δρmax = 0.14 e Å^−3
202 parameters	Δρmin = −0.15 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.017 (2)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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 (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.19559 (18)	0.28135 (13)	0.37420 (18)	0.0559 (5)
H1	−0.1691	0.3284	0.3304	0.067*
C2	−0.2996 (2)	0.29898 (14)	0.41623 (19)	0.0659 (6)
H2	−0.3416	0.3588	0.3994	0.079*
C3	−0.27956 (19)	0.15215 (15)	0.50263 (19)	0.0609 (5)
H3	−0.3071	0.1069	0.5478	0.073*
C4	−0.17561 (17)	0.12745 (13)	0.46488 (17)	0.0519 (5)
H4	−0.1351	0.0672	0.4840	0.062*
C5	−0.13182 (15)	0.19349 (11)	0.39792 (15)	0.0407 (4)
C6	−0.01976 (16)	0.16207 (12)	0.35757 (16)	0.0431 (4)
C7	0.17092 (16)	0.25209 (12)	0.19377 (15)	0.0463 (4)
H7	0.1292	0.3118	0.1698	0.056*
C8	0.28288 (16)	0.22478 (12)	0.15949 (15)	0.0439 (4)
C9	0.32855 (16)	0.27403 (13)	0.07909 (16)	0.0502 (4)
H9	0.2927	0.3322	0.0391	0.060*
C10	0.45941 (16)	0.14278 (13)	0.13866 (16)	0.0472 (4)
C11	0.55589 (18)	0.07111 (14)	0.15407 (18)	0.0591 (5)
H11	0.6157	0.0743	0.1122	0.071*
C12	0.5598 (2)	−0.00428 (14)	0.2330 (2)	0.0674 (6)
H12	0.6237	−0.0533	0.2455	0.081*
C13	0.4692 (2)	−0.00895 (14)	0.2954 (2)	0.0665 (5)
H13	0.4748	−0.0609	0.3493	0.080*
C14	0.37244 (18)	0.06107 (13)	0.27885 (17)	0.0547 (5)
H14	0.3119	0.0566	0.3199	0.066*
C15	0.36653 (16)	0.13929 (12)	0.19903 (15)	0.0440 (4)
O2	−0.00306 (15)	0.43229 (9)	0.28725 (14)	0.0774 (4)
H2E	−0.0198	0.4716	0.2280	0.116*
C16	0.1067 (3)	0.4640 (2)	0.4007 (3)	0.1208 (10)
H2A	0.0862	0.5269	0.4218	0.145*
H2B	0.1908	0.4657	0.3870	0.145*
H2C	0.1197	0.4215	0.4725	0.145*
N1	−0.34306 (15)	0.23570 (12)	0.47919 (14)	0.0610 (4)
N2	0.02328 (13)	0.22389 (10)	0.29073 (12)	0.0460 (4)
H2D	−0.0133	0.2797	0.2696	0.055*
N3	0.12908 (13)	0.19360 (10)	0.25752 (13)	0.0479 (4)
N4	0.43341 (14)	0.22574 (11)	0.06633 (13)	0.0533 (4)
H4A	0.4770	0.2440	0.0202	0.064*
O1	0.02967 (13)	0.08129 (8)	0.38568 (13)	0.0624 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0630 (11)	0.0490 (11)	0.0725 (12)	0.0071 (9)	0.0451 (10)	0.0089 (9)
C2	0.0694 (12)	0.0616 (13)	0.0850 (14)	0.0181 (10)	0.0505 (12)	0.0089 (11)
C3	0.0648 (12)	0.0679 (13)	0.0683 (12)	−0.0044 (11)	0.0459 (10)	0.0053 (10)
C4	0.0575 (10)	0.0495 (11)	0.0612 (11)	0.0011 (9)	0.0373 (9)	0.0049 (9)
C5	0.0416 (9)	0.0422 (10)	0.0440 (9)	−0.0034 (8)	0.0235 (8)	−0.0046 (7)
C6	0.0502 (10)	0.0372 (10)	0.0512 (10)	−0.0013 (8)	0.0305 (8)	−0.0027 (8)
C7	0.0476 (10)	0.0498 (10)	0.0474 (9)	0.0012 (8)	0.0258 (8)	0.0020 (8)
C8	0.0431 (9)	0.0501 (10)	0.0443 (9)	−0.0057 (8)	0.0242 (8)	−0.0025 (8)
C9	0.0478 (10)	0.0569 (11)	0.0532 (10)	−0.0031 (9)	0.0284 (8)	0.0033 (9)
C10	0.0458 (9)	0.0540 (11)	0.0477 (10)	−0.0090 (9)	0.0256 (8)	−0.0063 (9)
C11	0.0526 (11)	0.0683 (13)	0.0706 (12)	−0.0022 (10)	0.0399 (10)	−0.0079 (10)
C12	0.0655 (12)	0.0576 (12)	0.0927 (15)	0.0090 (10)	0.0464 (12)	0.0043 (11)
C13	0.0712 (12)	0.0554 (12)	0.0871 (14)	0.0026 (11)	0.0472 (12)	0.0097 (11)
C14	0.0553 (11)	0.0565 (11)	0.0649 (12)	−0.0028 (9)	0.0377 (9)	0.0014 (9)
C15	0.0418 (9)	0.0525 (11)	0.0440 (9)	−0.0082 (8)	0.0241 (8)	−0.0054 (8)
O2	0.0863 (10)	0.0555 (9)	0.0812 (10)	−0.0098 (8)	0.0266 (8)	0.0135 (7)
C16	0.123 (2)	0.098 (2)	0.103 (2)	−0.0201 (18)	0.0109 (18)	0.0075 (17)
N1	0.0577 (9)	0.0746 (11)	0.0661 (10)	0.0038 (9)	0.0411 (8)	−0.0007 (9)
N2	0.0489 (8)	0.0443 (8)	0.0585 (9)	0.0069 (7)	0.0359 (7)	0.0064 (7)
N3	0.0498 (8)	0.0515 (9)	0.0559 (9)	0.0037 (7)	0.0355 (7)	0.0010 (7)
N4	0.0523 (8)	0.0667 (10)	0.0560 (9)	−0.0036 (8)	0.0374 (7)	0.0036 (8)
O1	0.0833 (9)	0.0416 (7)	0.0882 (10)	0.0115 (7)	0.0613 (8)	0.0088 (6)

Geometric parameters (Å, º)

C1—C5	1.374 (2)	C10—N4	1.375 (2)
C1—C2	1.382 (2)	C10—C11	1.386 (2)
C1—H1	0.9300	C10—C15	1.402 (2)
C2—N1	1.327 (2)	C11—C12	1.365 (3)
C2—H2	0.9300	C11—H11	0.9300
C3—N1	1.319 (2)	C12—C13	1.399 (2)
C3—C4	1.372 (2)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.369 (2)
C4—C5	1.385 (2)	C13—H13	0.9300
C4—H4	0.9300	C14—C15	1.397 (2)
C5—C6	1.495 (2)	C14—H14	0.9300
C6—O1	1.2302 (18)	O2—C16	1.377 (3)
C6—N2	1.3403 (19)	O2—H2E	0.8200
C7—N3	1.2789 (19)	C16—H2A	0.9600
C7—C8	1.435 (2)	C16—H2B	0.9600
C7—H7	0.9300	C16—H2C	0.9600
C8—C9	1.369 (2)	N2—N3	1.3801 (16)
C8—C15	1.441 (2)	N2—H2D	0.8600
C9—N4	1.352 (2)	N4—H4A	0.8600
C9—H9	0.9300
C5—C1—C2	119.15 (16)	C12—C11—C10	117.53 (16)
C5—C1—H1	120.4	C12—C11—H11	121.2
C2—C1—H1	120.4	C10—C11—H11	121.2
N1—C2—C1	123.99 (18)	C11—C12—C13	121.03 (17)
N1—C2—H2	118.0	C11—C12—H12	119.5
C1—C2—H2	118.0	C13—C12—H12	119.5
N1—C3—C4	124.49 (17)	C14—C13—C12	121.58 (17)
N1—C3—H3	117.8	C14—C13—H13	119.2
C4—C3—H3	117.8	C12—C13—H13	119.2
C3—C4—C5	119.11 (17)	C13—C14—C15	118.60 (16)
C3—C4—H4	120.4	C13—C14—H14	120.7
C5—C4—H4	120.4	C15—C14—H14	120.7
C1—C5—C4	117.17 (15)	C14—C15—C10	118.73 (16)
C1—C5—C6	126.12 (14)	C14—C15—C8	134.80 (14)
C4—C5—C6	116.72 (15)	C10—C15—C8	106.47 (14)
O1—C6—N2	122.08 (14)	C16—O2—H2E	109.5
O1—C6—C5	119.79 (14)	O2—C16—H2A	109.5
N2—C6—C5	118.13 (15)	O2—C16—H2B	109.5
N3—C7—C8	119.39 (15)	H2A—C16—H2B	109.5
N3—C7—H7	120.3	O2—C16—H2C	109.5
C8—C7—H7	120.3	H2A—C16—H2C	109.5
C9—C8—C7	126.46 (16)	H2B—C16—H2C	109.5
C9—C8—C15	106.35 (14)	C3—N1—C2	116.08 (15)
C7—C8—C15	127.16 (14)	C6—N2—N3	116.77 (13)
N4—C9—C8	110.13 (16)	C6—N2—H2D	121.6
N4—C9—H9	124.9	N3—N2—H2D	121.6
C8—C9—H9	124.9	C7—N3—N2	117.25 (14)
N4—C10—C11	129.75 (15)	C9—N4—C10	109.31 (13)
N4—C10—C15	107.74 (15)	C9—N4—H4A	125.3
C11—C10—C15	122.51 (16)	C10—N4—H4A	125.3

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N1^i	0.86	2.15	2.9491 (19)	155
N2—H2D···O2	0.86	2.15	2.934 (2)	152
O2—H2E···O1^ii	0.82	1.97	2.7751 (18)	168

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