N′-[(Thio­phen-3-yl)methyl­ene]­isonicotino­hydrazide

In the title compound, C₁₁H₉N₃OS, the dihedral angle between the thio­phene and pyridine planes is 24.06 (9)°. Inter­molecular N—H...O, C—H...S and C—H...N hydrogen bonds link the mol­ecules into a two-dimensional network parallel to the (100) plane.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C)= 0.002 Å
• R factor = 0.039
• wR factor = 0.098
• Data-to-parameter ratio = 16.4

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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 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. The thiophene ring (C1—C4/S1) is essentially planar, with a maximum deviation from the mean plane of 0.005 (1) Å for atom C4. The pyridine ring (C7—C11/N3) is planar within ±0.009 (1) Å. The dihedral angle between the thiophene and pyridine planes is 24.06 (9)°. The O1/N1/N2/C5/C6 plane makes dihedral angles of 28.87 (9) and 4.89 (12)° with the pyridine and thiophene rings, respectively.

Intermolecular N—H···O hydrogen bonds (Table 1) link the molecules into a chain along the c axis (Fig. 2). The chains are cross-linked by C—H···S and C—H···N hydrogen bonds, forming a two-dimensional network parallel to the (1 0 0) plane.

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 thiophene-3-carbaldehyde (1.12 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 yellow precipitate appeared. The product was isolated, recrystallized from anhydrous ethanol and then dried in vacuo to give pure compound (I) in 91% yield. Yellow single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an anhydrous ethanol solution.

S3. Refinement

The N-bound H atom was located in a difference Fourier map and its positional parameters were refined, with U_iso(H) = 1.2U_eq(N). C-bound H atoms were included in calculated positions [C—H = 0.95 Å] and refined using a riding model, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CrystalStructure (Rigaku/MSC, 2005); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005).

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 b axis, showing N—H···O hydrogen bonded (dashed lines) chains.

N'-[(Thiophen-3-yl)methylene]isonicotinohydrazide

Crystal data

C11H9N3OS	F(000) = 480
Mr = 231.27	Dx = 1.497 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6540 reflections
a = 19.861 (4) Å	θ = 2.3–22.5°
b = 5.1856 (10) Å	µ = 0.29 mm^−1
c = 10.103 (2) Å	T = 113 K
β = 99.55 (3)°	Block, yellow
V = 1026.1 (4) Å^3	0.10 × 0.08 × 0.04 mm
Z = 4

Data collection

Rigaku Saturn diffractometer	2440 independent reflections
Radiation source: rotating anode	2195 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.045
Detector resolution: 7.31 pixels mm^-1	θmax = 27.9°, θmin = 2.1°
ω and φ scans	h = −26→26
Absorption correction: multi-scan CrystalClear (Rigaku/MSC, 2005)	k = −6→6
Tmin = 0.964, Tmax = 0.988	l = −13→13
11875 measured reflections

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0424P)^2 + 0.7091P] where P = (Fo^2 + 2Fc^2)/3
2440 reflections	(Δ/σ)max = 0.001
149 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.40 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	0.43768 (2)	1.25594 (7)	0.87336 (4)	0.01810 (13)
O1	0.22717 (6)	0.2606 (2)	0.45121 (11)	0.0203 (3)
N1	0.28541 (6)	0.5670 (2)	0.66051 (12)	0.0158 (3)
N2	0.23603 (6)	0.3826 (3)	0.67066 (13)	0.0158 (3)
N3	0.03908 (7)	−0.2485 (2)	0.60415 (13)	0.0183 (3)
C1	0.44033 (8)	1.1592 (3)	0.71162 (14)	0.0162 (3)
H1	0.4699	1.2304	0.6563	0.019*
C2	0.39400 (7)	0.9650 (3)	0.67280 (15)	0.0170 (3)
H2	0.3879	0.8854	0.5869	0.020*
C3	0.35604 (7)	0.8963 (3)	0.77658 (14)	0.0150 (3)
C4	0.37454 (7)	1.0421 (3)	0.89057 (15)	0.0165 (3)
H4	0.3546	1.0255	0.9693	0.020*
C5	0.30414 (8)	0.6968 (3)	0.76887 (15)	0.0165 (3)
H5	0.2836	0.6615	0.8454	0.020*
C6	0.20863 (7)	0.2435 (3)	0.56109 (15)	0.0145 (3)
C7	0.15088 (7)	0.0699 (3)	0.58219 (14)	0.0142 (3)
C8	0.13685 (8)	−0.1481 (3)	0.50177 (15)	0.0165 (3)
H8	0.1648	−0.1912	0.4372	0.020*
C9	0.08158 (8)	−0.3008 (3)	0.51736 (16)	0.0187 (3)
H9	0.0732	−0.4513	0.4635	0.022*
C10	0.05238 (8)	−0.0364 (3)	0.67959 (15)	0.0180 (3)
H10	0.0224	0.0056	0.7405	0.022*
C11	0.10758 (8)	0.1260 (3)	0.67384 (14)	0.0163 (3)
H11	0.1156	0.2719	0.7311	0.020*
H2A	0.2262 (11)	0.345 (4)	0.750 (2)	0.031 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0206 (2)	0.0185 (2)	0.0154 (2)	−0.00303 (14)	0.00348 (15)	−0.00190 (13)
O1	0.0216 (6)	0.0261 (6)	0.0145 (5)	−0.0057 (5)	0.0065 (4)	−0.0030 (4)
N1	0.0140 (6)	0.0170 (6)	0.0162 (6)	−0.0020 (5)	0.0018 (4)	0.0011 (5)
N2	0.0159 (6)	0.0197 (7)	0.0123 (6)	−0.0042 (5)	0.0034 (5)	0.0001 (5)
N3	0.0191 (6)	0.0189 (7)	0.0165 (6)	−0.0031 (5)	0.0018 (5)	0.0021 (5)
C1	0.0177 (7)	0.0196 (8)	0.0116 (7)	0.0012 (6)	0.0035 (5)	−0.0001 (6)
C2	0.0181 (7)	0.0197 (8)	0.0134 (7)	−0.0006 (6)	0.0029 (5)	−0.0014 (6)
C3	0.0136 (6)	0.0169 (7)	0.0142 (7)	0.0006 (5)	0.0014 (5)	0.0011 (5)
C4	0.0171 (7)	0.0187 (7)	0.0144 (7)	0.0001 (6)	0.0048 (5)	0.0006 (6)
C5	0.0157 (7)	0.0196 (7)	0.0147 (7)	0.0000 (6)	0.0039 (5)	0.0009 (6)
C6	0.0139 (7)	0.0151 (7)	0.0144 (7)	0.0013 (5)	0.0022 (5)	0.0000 (5)
C7	0.0141 (6)	0.0157 (7)	0.0122 (6)	0.0007 (5)	0.0009 (5)	0.0018 (5)
C8	0.0185 (7)	0.0170 (7)	0.0145 (7)	0.0008 (6)	0.0043 (5)	0.0001 (6)
C9	0.0222 (8)	0.0176 (7)	0.0157 (7)	−0.0014 (6)	0.0013 (6)	−0.0009 (6)
C10	0.0166 (7)	0.0222 (8)	0.0156 (7)	0.0008 (6)	0.0038 (5)	0.0014 (6)
C11	0.0191 (7)	0.0164 (7)	0.0134 (7)	−0.0001 (6)	0.0029 (5)	−0.0011 (6)

Geometric parameters (Å, º)

S1—C4	1.7044 (16)	C3—C4	1.375 (2)
S1—C1	1.7185 (15)	C3—C5	1.453 (2)
O1—C6	1.2295 (19)	C4—H4	0.95
N1—C5	1.287 (2)	C5—H5	0.95
N1—N2	1.3856 (18)	C6—C7	1.501 (2)
N2—C6	1.3572 (19)	C7—C8	1.393 (2)
N2—H2A	0.88 (2)	C7—C11	1.395 (2)
N3—C10	1.339 (2)	C8—C9	1.384 (2)
N3—C9	1.342 (2)	C8—H8	0.95
C1—C2	1.377 (2)	C9—H9	0.95
C1—H1	0.95	C10—C11	1.391 (2)
C2—C3	1.434 (2)	C10—H10	0.95
C2—H2	0.95	C11—H11	0.95
C4—S1—C1	92.64 (8)	C3—C5—H5	119.3
C5—N1—N2	113.98 (13)	O1—C6—N2	123.95 (14)
C6—N2—N1	119.96 (13)	O1—C6—C7	121.46 (13)
C6—N2—H2A	120.4 (14)	N2—C6—C7	114.55 (13)
N1—N2—H2A	119.3 (14)	C8—C7—C11	118.07 (14)
C10—N3—C9	116.86 (13)	C8—C7—C6	119.18 (13)
C2—C1—S1	111.10 (11)	C11—C7—C6	122.62 (13)
C2—C1—H1	124.4	C9—C8—C7	118.93 (14)
S1—C1—H1	124.4	C9—C8—H8	120.5
C1—C2—C3	112.38 (13)	C7—C8—H8	120.5
C1—C2—H2	123.8	N3—C9—C8	123.76 (15)
C3—C2—H2	123.8	N3—C9—H9	118.1
C4—C3—C2	112.09 (13)	C8—C9—H9	118.1
C4—C3—C5	121.64 (14)	N3—C10—C11	123.76 (14)
C2—C3—C5	126.27 (14)	N3—C10—H10	118.1
C3—C4—S1	111.78 (11)	C11—C10—H10	118.1
C3—C4—H4	124.1	C10—C11—C7	118.59 (14)
S1—C4—H4	124.1	C10—C11—H11	120.7
N1—C5—C3	121.37 (14)	C7—C11—H11	120.7
N1—C5—H5	119.3
C5—N1—N2—C6	175.80 (13)	O1—C6—C7—C8	27.3 (2)
C4—S1—C1—C2	−0.55 (12)	N2—C6—C7—C8	−154.84 (13)
S1—C1—C2—C3	0.19 (17)	O1—C6—C7—C11	−148.57 (15)
C1—C2—C3—C4	0.39 (19)	N2—C6—C7—C11	29.3 (2)
C1—C2—C3—C5	−178.99 (14)	C11—C7—C8—C9	−0.9 (2)
C2—C3—C4—S1	−0.80 (17)	C6—C7—C8—C9	−176.99 (13)
C5—C3—C4—S1	178.62 (11)	C10—N3—C9—C8	−0.6 (2)
C1—S1—C4—C3	0.78 (12)	C7—C8—C9—N3	1.6 (2)
N2—N1—C5—C3	179.34 (13)	C9—N3—C10—C11	−1.1 (2)
C4—C3—C5—N1	177.64 (14)	N3—C10—C11—C7	1.7 (2)
C2—C3—C5—N1	−3.0 (2)	C8—C7—C11—C10	−0.6 (2)
N1—N2—C6—O1	3.7 (2)	C6—C7—C11—C10	175.34 (13)
N1—N2—C6—C7	−174.11 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1^i	0.88 (2)	2.10 (2)	2.9634 (17)	167 (2)
C1—H1···S1^ii	0.95	2.82	3.4374 (16)	123
C4—H4···N1^iii	0.95	2.59	3.535 (2)	171
C10—H10···N3^iv	0.95	2.49	3.409 (2)	162

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+5/2, z−1/2; (iii) x, −y+3/2, z+1/2; (iv) −x, y+1/2, −z+3/2.