(E)-N′-(3-Thienylmethyl­ene)furan-2-carbohydrazide

In the title compound, C₁₀H₈N₂O₂S, the dihedral angle between the thio­phene and furan planes is 12.3 (1)°. The mol­ecules are linked via weak inter­molecular N—H...O, C—H...S and C—H...O hydrogen bonds, forming a two-dimensional network parallel to the ab plane.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.023
• wR factor = 0.065
• Data-to-parameter ratio = 12.1

checkCIF/PLATON results

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Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C9     -   C10     ..       5.36 su

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.01
           From the CIF: _reflns_number_total               1694
           Count of symmetry unique reflns          883
           Completeness (_total/calc)            191.85%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       811
           Fraction of Friedel pairs measured     0.918
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

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

   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
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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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 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 Schiff 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 planar within ±0.002 (1) Å. The furan ring (C7–C10/O2) is essentially planar, with a maximum deviation from the mean plane of 0.004 (1) Å for atom C10. The dihedral angle between these planes is 12.3 (1)°.

The molecules are linked via weak intermolecular N—H···O, C—H···S and C—H···O type hydrogen bonds (Table 1), to form a two-dimensional network parallel to the ab plane, 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 thiophene-3-carbaldehyde (1.12 g, 10 mmol) was added to an anhydrous ethanol solution (50 ml) of furan-2-carbohydrazide (1.26 g, 10 mmol), and the mixture was stirred at 350 K for 6 h under N₂, whereupon a colourless precipitate appeared. The product was isolated, recrystallized from anhydrous ethanol and then dried in vacuo to give pure compound (I) in 79% yield. Colourless 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 refined with a N—H distance restraint of 0.90 (1) Å. C-bound H atoms were included in calculated positions [C—H = 0.93 Å] and refined using a riding model, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; 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.

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'-(3-Thienylmethylene)furan-2-carbohydrazide

Crystal data

C10H8N2O2S	F(000) = 456
Mr = 220.24	Dx = 1.505 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 3232 reflections
a = 10.1150 (15) Å	θ = 4.0–26.2°
b = 4.7969 (7) Å	µ = 0.31 mm^−1
c = 20.033 (3) Å	T = 294 K
V = 972.0 (2) Å^3	Block, colourless
Z = 4	0.24 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1694 independent reflections
Radiation source: fine-focus sealed tube	1616 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→12
Tmin = 0.929, Tmax = 0.946	k = −5→4
4486 measured reflections	l = −23→23

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)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.065	w = 1/[σ^2(Fo^2) + (0.0391P)^2 + 0.0578P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.001
1694 reflections	Δρmax = 0.14 e Å^−3
140 parameters	Δρmin = −0.14 e Å^−3
2 restraints	Absolute structure: Flack (1983), with 811 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (7)

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	0.22029 (5)	1.02129 (9)	0.32352 (3)	0.04200 (14)
O1	−0.15782 (12)	0.0679 (3)	0.10495 (7)	0.0473 (4)
O2	−0.11967 (13)	−0.2927 (3)	0.00357 (7)	0.0547 (4)
N1	0.04650 (14)	0.3353 (3)	0.16534 (7)	0.0352 (3)
N2	0.06307 (14)	0.1461 (3)	0.11429 (8)	0.0352 (3)
C1	0.05895 (18)	0.9185 (4)	0.32440 (11)	0.0412 (4)
H1	−0.0038	0.9854	0.3543	0.049*
C2	0.03343 (17)	0.7284 (4)	0.27648 (10)	0.0398 (4)
H2	−0.0493	0.6488	0.2696	0.048*
C3	0.14683 (17)	0.6629 (4)	0.23753 (9)	0.0324 (4)
C4	0.2551 (2)	0.8089 (4)	0.25789 (10)	0.0383 (4)
H4	0.3382	0.7940	0.2383	0.046*
C5	0.1512 (2)	0.4638 (4)	0.18335 (9)	0.0360 (4)
H5	0.2307	0.4291	0.1615	0.043*
C6	−0.04417 (19)	0.0210 (4)	0.08752 (9)	0.0341 (4)
C7	−0.01324 (16)	−0.1763 (4)	0.03386 (9)	0.0348 (4)
C8	0.0966 (2)	−0.2736 (5)	0.00599 (11)	0.0535 (6)
H8	0.1827	−0.2267	0.0177	0.064*
C9	0.0584 (2)	−0.4613 (5)	−0.04464 (12)	0.0536 (6)
H9	0.1139	−0.5610	−0.0729	0.064*
C10	−0.0714 (3)	−0.4667 (5)	−0.04373 (12)	0.0538 (5)
H10	−0.1232	−0.5756	−0.0718	0.065*
H2A	0.1439 (12)	0.100 (5)	0.1005 (10)	0.043 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0360 (2)	0.0452 (3)	0.0448 (2)	−0.00471 (19)	−0.0011 (2)	−0.0056 (2)
O1	0.0262 (7)	0.0623 (9)	0.0533 (8)	0.0012 (6)	0.0024 (6)	−0.0137 (7)
O2	0.0331 (7)	0.0682 (10)	0.0629 (9)	−0.0067 (6)	−0.0010 (7)	−0.0236 (8)
N1	0.0298 (7)	0.0381 (9)	0.0378 (8)	0.0020 (6)	−0.0006 (6)	−0.0029 (7)
N2	0.0256 (7)	0.0403 (9)	0.0397 (8)	0.0018 (7)	0.0017 (6)	−0.0063 (7)
C1	0.0333 (10)	0.0482 (10)	0.0422 (9)	0.0001 (7)	0.0064 (10)	0.0007 (11)
C2	0.0291 (9)	0.0429 (10)	0.0475 (11)	−0.0016 (8)	0.0014 (8)	−0.0022 (9)
C3	0.0268 (9)	0.0334 (9)	0.0372 (10)	0.0013 (7)	0.0002 (7)	0.0042 (8)
C4	0.0299 (9)	0.0403 (10)	0.0445 (10)	−0.0010 (8)	0.0047 (7)	−0.0001 (8)
C5	0.0293 (9)	0.0382 (10)	0.0407 (10)	0.0023 (7)	0.0016 (8)	0.0021 (8)
C6	0.0294 (12)	0.0367 (10)	0.0362 (10)	0.0005 (7)	0.0005 (7)	0.0035 (7)
C7	0.0309 (9)	0.0367 (9)	0.0367 (9)	−0.0035 (7)	−0.0036 (7)	0.0029 (8)
C8	0.0283 (10)	0.0697 (15)	0.0624 (13)	0.0015 (9)	−0.0026 (9)	−0.0237 (11)
C9	0.0418 (13)	0.0604 (13)	0.0585 (13)	0.0018 (9)	0.0065 (10)	−0.0197 (12)
C10	0.0513 (13)	0.0544 (12)	0.0558 (13)	−0.0036 (10)	−0.0070 (11)	−0.0190 (11)

Geometric parameters (Å, º)

S1—C4	1.7003 (19)	C2—H2	0.93
S1—C1	1.7050 (19)	C3—C4	1.363 (3)
O1—C6	1.222 (2)	C3—C5	1.446 (3)
O2—C10	1.354 (3)	C4—H4	0.93
O2—C7	1.356 (2)	C5—H5	0.93
N1—C5	1.277 (2)	C6—C7	1.466 (3)
N1—N2	1.378 (2)	C7—C8	1.328 (3)
N2—C6	1.351 (2)	C8—C9	1.410 (3)
N2—H2A	0.891 (9)	C8—H8	0.93
C1—C2	1.349 (3)	C9—C10	1.313 (3)
C1—H1	0.93	C9—H9	0.93
C2—C3	1.423 (2)	C10—H10	0.93
C4—S1—C1	91.90 (10)	N1—C5—C3	120.34 (18)
C10—O2—C7	106.30 (16)	N1—C5—H5	119.8
C5—N1—N2	115.26 (15)	C3—C5—H5	119.8
C6—N2—N1	119.32 (15)	O1—C6—N2	124.07 (17)
C6—N2—H2A	120.3 (15)	O1—C6—C7	121.93 (17)
N1—N2—H2A	120.3 (15)	N2—C6—C7	113.98 (16)
C2—C1—S1	111.79 (15)	C8—C7—O2	109.34 (17)
C2—C1—H1	124.1	C8—C7—C6	135.53 (17)
S1—C1—H1	124.1	O2—C7—C6	115.13 (15)
C1—C2—C3	112.67 (17)	C7—C8—C9	107.30 (18)
C1—C2—H2	123.7	C7—C8—H8	126.3
C3—C2—H2	123.7	C9—C8—H8	126.3
C4—C3—C2	111.75 (16)	C10—C9—C8	106.1 (2)
C4—C3—C5	122.64 (18)	C10—C9—H9	127.0
C2—C3—C5	125.60 (17)	C8—C9—H9	127.0
C3—C4—S1	111.89 (15)	C9—C10—O2	111.0 (2)
C3—C4—H4	124.1	C9—C10—H10	124.5
S1—C4—H4	124.1	O2—C10—H10	124.5
C5—N1—N2—C6	−173.46 (17)	N1—N2—C6—C7	−179.80 (14)
C4—S1—C1—C2	0.24 (17)	C10—O2—C7—C8	0.4 (2)
S1—C1—C2—C3	−0.1 (2)	C10—O2—C7—C6	−179.86 (17)
C1—C2—C3—C4	−0.1 (2)	O1—C6—C7—C8	−177.7 (2)
C1—C2—C3—C5	178.91 (18)	N2—C6—C7—C8	3.3 (3)
C2—C3—C4—S1	0.3 (2)	O1—C6—C7—O2	2.6 (3)
C5—C3—C4—S1	−178.77 (15)	N2—C6—C7—O2	−176.41 (15)
C1—S1—C4—C3	−0.29 (15)	O2—C7—C8—C9	0.1 (3)
N2—N1—C5—C3	−178.56 (15)	C6—C7—C8—C9	−179.7 (2)
C4—C3—C5—N1	−178.84 (17)	C7—C8—C9—C10	−0.5 (3)
C2—C3—C5—N1	2.3 (3)	C8—C9—C10—O2	0.7 (3)
N1—N2—C6—O1	1.2 (3)	C7—O2—C10—C9	−0.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1^i	0.89 (1)	2.16 (1)	3.010 (2)	158 (2)
C1—H1···S1^ii	0.93	2.86	3.438 (2)	122
C8—H8···O1^i	0.93	2.50	3.328 (3)	149

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