(E)-N′-[(5-Methyl­thio­phen-2-yl)methyl­ene]isonicotinohydrazide

In the title compound, C₁₂H₁₁N₃OS, the dihedral angle between the thio­phene and pyridine planes is 12.30 (2)°. The mol­ecules are linked via weak inter­molecular N—H...O hydrogen bonding, forming a chain supra­molecular arrangement along the c axis.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.043
• wR factor = 0.115
• Data-to-parameter ratio = 13.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

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

---

S1. Comment

In order to establish control over the preparation of crystalline solid materials so that their architecture and properties are predictable (Belloni et al., 2005; Tynan et al., 2005; Parashar et al., 1988), the synthesis of new and designed crystal structures has become a major strand of modern chemistry. Metal complexes based on Schiff bases have attracted much attention because they can be utilized as model compounds of the active centres in various proteins and enzymes (Kahwa et al., 1986; Santos et al.,2001). As part of an investigation of the coordination properties of Shiff bases functioning as ligands, we report the synthesis and crystal structure of the title compound, (I).

In the molecular structure of the compound (I) (Fig. 1), the geometric parameters are normal. One molecules of the unit, the thiophen ring (C2–C5/S1) is approximately planar, with a maximum deviation from the mean plane of 0.0048 (2) Å for atom S1,as are the pyridine group (C8—C11/N3) is approximately planar, with a maximum deviation from the mean plane of 0.0068 (2) Å for atom N3.The dihedral angle between these two planes is 12.30 (2)°·The molecules are linked via weak intermolecular N—H···O hydrogen bond(Table 1), Forming a chain supramolecular arrangement along the c axis.,as illustraed in Fig.2.

Related literature

For general background, see: Belloni et al. (2005); Kahwa et al. (1986); Parashar et al. (1988); Santos et al. (2001); Tynan et al. (2005).

S2. Experimental

An anhydrous ethanol solution (50 ml) of 5-methylthiophene-2-carbaldehyde (1.26 g, 10 mmol) was added to an anhydrous ethanol solution (50 ml) of isonicotinohydrazide (1.37 g, 10 mmol), and the mixture was stirred at 350 K for 6 h under N₂, whereupon a yelllow precipitate appeared. The product was isolated, recrystallized from anhydrous ethanol and then dried in vacuo to give pure compound (I) in 81% yield. Yellow single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an anhydrous ethanol solution.

S3. Refinement

All H atoms were included in calculated positions, with N—H = 0.86 (amine), C—H = 0.93 (aromatic) or 0.96 Å (methyl), and refined using a riding model, with U_iso(H) = 1.2U_eq(C,N) for aromatic and amine H atoms and 1.5U_eq(C) for methyl H atoms.

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of (I), viwed down the a axis. Hydrogen bonds are indicated by dashed lines.

(E)-N'-[(5-Methylthiophen-2-yl)methylene]isonicotinohydrazide

Crystal data

C12H11N3OS	F(000) = 512
Mr = 245.30	Dx = 1.418 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1387 reflections
a = 19.172 (7) Å	θ = 3.6–24.6°
b = 5.884 (2) Å	µ = 0.27 mm^−1
c = 10.273 (4) Å	T = 294 K
β = 97.309 (7)°	Block, yellow
V = 1149.4 (8) Å^3	0.24 × 0.22 × 0.16 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2018 independent reflections
Radiation source: fine-focus sealed tube	1361 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
ϕ and ω scans	θmax = 25.0°, θmin = 1.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→22
Tmin = 0.939, Tmax = 0.959	k = −7→6
5666 measured reflections	l = −11→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0602P)^2 + 0.0201P] where P = (Fo^2 + 2Fc^2)/3
2018 reflections	(Δ/σ)max = 0.004
155 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

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
S1	0.38071 (4)	1.38538 (11)	0.10139 (6)	0.0449 (2)
O1	0.20976 (10)	0.7241 (3)	0.18993 (17)	0.0563 (5)
N1	0.26629 (10)	1.0178 (3)	0.02564 (19)	0.0406 (5)
N2	0.21957 (11)	0.8469 (3)	−0.01604 (19)	0.0426 (6)
H2	0.2071	0.8268	−0.0987	0.051*
N3	0.03831 (13)	0.2277 (4)	−0.0882 (2)	0.0545 (6)
C1	0.47021 (16)	1.7636 (5)	0.1251 (3)	0.0602 (8)
H1A	0.5095	1.7888	0.0776	0.090*
H1B	0.4856	1.6820	0.2045	0.090*
H1C	0.4507	1.9072	0.1464	0.090*
C2	0.41553 (13)	1.6283 (4)	0.0427 (3)	0.0414 (6)
C3	0.38671 (15)	1.6675 (5)	−0.0821 (3)	0.0498 (7)
H3	0.3982	1.7932	−0.1299	0.060*
C4	0.33807 (15)	1.5035 (5)	−0.1333 (3)	0.0493 (7)
H4	0.3147	1.5076	−0.2183	0.059*
C5	0.32862 (13)	1.3368 (4)	−0.0450 (2)	0.0395 (6)
C6	0.28111 (13)	1.1477 (4)	−0.0664 (3)	0.0430 (7)
H6	0.2601	1.1187	−0.1514	0.052*
C7	0.19310 (13)	0.7107 (4)	0.0714 (2)	0.0401 (6)
C8	0.13952 (13)	0.5436 (4)	0.0116 (2)	0.0369 (6)
C9	0.09620 (14)	0.5838 (5)	−0.1038 (2)	0.0457 (7)
H9	0.1004	0.7173	−0.1507	0.055*
C10	0.04682 (15)	0.4237 (5)	−0.1483 (3)	0.0553 (8)
H10	0.0175	0.4544	−0.2255	0.066*
C11	0.08050 (15)	0.1924 (5)	0.0227 (3)	0.0531 (8)
H11	0.0759	0.0560	0.0666	0.064*
C12	0.13018 (14)	0.3430 (5)	0.0768 (3)	0.0478 (7)
H12	0.1573	0.3108	0.1563	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0546 (5)	0.0465 (4)	0.0323 (4)	−0.0060 (3)	0.0004 (3)	0.0045 (3)
O1	0.0644 (13)	0.0732 (13)	0.0284 (11)	−0.0133 (11)	−0.0055 (9)	−0.0013 (9)
N1	0.0410 (13)	0.0488 (13)	0.0311 (12)	−0.0031 (11)	0.0010 (10)	−0.0061 (10)
N2	0.0462 (14)	0.0548 (14)	0.0254 (11)	−0.0072 (11)	−0.0014 (9)	−0.0073 (10)
N3	0.0580 (16)	0.0593 (16)	0.0455 (15)	−0.0120 (13)	0.0040 (12)	−0.0078 (12)
C1	0.071 (2)	0.0535 (18)	0.059 (2)	−0.0150 (16)	0.0179 (17)	−0.0079 (15)
C2	0.0477 (16)	0.0377 (14)	0.0411 (16)	0.0024 (13)	0.0146 (13)	−0.0001 (12)
C3	0.064 (2)	0.0433 (16)	0.0447 (17)	0.0023 (15)	0.0180 (14)	0.0085 (13)
C4	0.0543 (18)	0.0615 (18)	0.0316 (15)	0.0122 (15)	0.0041 (13)	0.0087 (14)
C5	0.0394 (15)	0.0480 (16)	0.0302 (14)	0.0054 (13)	0.0013 (11)	−0.0005 (12)
C6	0.0415 (16)	0.0551 (17)	0.0311 (15)	0.0039 (13)	−0.0002 (12)	−0.0060 (13)
C7	0.0398 (16)	0.0491 (15)	0.0304 (15)	0.0055 (13)	0.0008 (12)	−0.0043 (12)
C8	0.0371 (15)	0.0435 (15)	0.0304 (14)	0.0016 (12)	0.0048 (11)	−0.0029 (11)
C9	0.0511 (17)	0.0485 (17)	0.0358 (16)	−0.0054 (13)	−0.0020 (13)	0.0021 (12)
C10	0.0577 (19)	0.067 (2)	0.0387 (17)	−0.0083 (16)	−0.0043 (14)	−0.0012 (14)
C11	0.060 (2)	0.0494 (17)	0.0508 (19)	−0.0045 (15)	0.0089 (15)	0.0009 (14)
C12	0.0501 (18)	0.0549 (18)	0.0369 (16)	0.0038 (14)	0.0001 (13)	0.0015 (13)

Geometric parameters (Å, º)

S1—C2	1.719 (2)	C3—H3	0.9300
S1—C5	1.720 (3)	C4—C5	1.363 (3)
O1—C7	1.222 (3)	C4—H4	0.9300
N1—C6	1.275 (3)	C5—C6	1.437 (3)
N1—N2	1.378 (3)	C6—H6	0.9300
N2—C7	1.350 (3)	C7—C8	1.496 (3)
N2—H2	0.8600	C8—C9	1.379 (3)
N3—C11	1.327 (4)	C8—C12	1.380 (3)
N3—C10	1.328 (4)	C9—C10	1.372 (4)
C1—C2	1.492 (4)	C9—H9	0.9300
C1—H1A	0.9600	C10—H10	0.9300
C1—H1B	0.9600	C11—C12	1.366 (4)
C1—H1C	0.9600	C11—H11	0.9300
C2—C3	1.349 (4)	C12—H12	0.9300
C3—C4	1.398 (4)
C2—S1—C5	92.26 (13)	C6—C5—S1	123.27 (19)
C6—N1—N2	113.8 (2)	N1—C6—C5	123.2 (2)
C7—N2—N1	120.7 (2)	N1—C6—H6	118.4
C7—N2—H2	119.6	C5—C6—H6	118.4
N1—N2—H2	119.6	O1—C7—N2	123.5 (2)
C11—N3—C10	116.0 (3)	O1—C7—C8	122.0 (2)
C2—C1—H1A	109.5	N2—C7—C8	114.4 (2)
C2—C1—H1B	109.5	C9—C8—C12	117.6 (2)
H1A—C1—H1B	109.5	C9—C8—C7	123.2 (2)
C2—C1—H1C	109.5	C12—C8—C7	119.2 (2)
H1A—C1—H1C	109.5	C10—C9—C8	118.9 (3)
H1B—C1—H1C	109.5	C10—C9—H9	120.5
C3—C2—C1	128.4 (2)	C8—C9—H9	120.5
C3—C2—S1	110.2 (2)	N3—C10—C9	124.1 (3)
C1—C2—S1	121.4 (2)	N3—C10—H10	117.9
C2—C3—C4	114.3 (2)	C9—C10—H10	117.9
C2—C3—H3	122.8	N3—C11—C12	124.4 (3)
C4—C3—H3	122.8	N3—C11—H11	117.8
C5—C4—C3	112.6 (3)	C12—C11—H11	117.8
C5—C4—H4	123.7	C11—C12—C8	119.0 (3)
C3—C4—H4	123.7	C11—C12—H12	120.5
C4—C5—C6	126.2 (2)	C8—C12—H12	120.5
C4—C5—S1	110.5 (2)
C6—N1—N2—C7	−173.0 (2)	N1—N2—C7—C8	176.13 (19)
C5—S1—C2—C3	1.1 (2)	O1—C7—C8—C9	149.0 (3)
C5—S1—C2—C1	−178.4 (2)	N2—C7—C8—C9	−29.4 (3)
C1—C2—C3—C4	178.0 (2)	O1—C7—C8—C12	−28.0 (4)
S1—C2—C3—C4	−1.4 (3)	N2—C7—C8—C12	153.6 (2)
C2—C3—C4—C5	1.0 (3)	C12—C8—C9—C10	−0.5 (4)
C3—C4—C5—C6	178.4 (2)	C7—C8—C9—C10	−177.5 (2)
C3—C4—C5—S1	−0.2 (3)	C11—N3—C10—C9	1.1 (4)
C2—S1—C5—C4	−0.51 (19)	C8—C9—C10—N3	−1.1 (4)
C2—S1—C5—C6	−179.1 (2)	C10—N3—C11—C12	0.5 (4)
N2—N1—C6—C5	180.0 (2)	N3—C11—C12—C8	−2.0 (4)
C4—C5—C6—N1	−168.5 (2)	C9—C8—C12—C11	1.9 (4)
S1—C5—C6—N1	9.9 (4)	C7—C8—C12—C11	179.1 (2)
N1—N2—C7—O1	−2.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^i	0.86	2.20	3.031 (3)	163

Symmetry code: (i) x, −y+3/2, z−1/2.