Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049811/lh2521sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049811/lh2521Isup2.hkl |
CCDC reference: 656252
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.008 Å
- R factor = 0.046
- wR factor = 0.154
- Data-to-parameter ratio = 13.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for S1 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 8 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C7 PLAT414_ALERT_2_C Short Intra D-H..H-X H1 .. H7A .. 1.90 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H1 .. O1 .. 2.69 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For the crystal structures of metal complexes with related aroylhydrazone derivatives, see: Matthews et al. (1999); Bernhardt et al. (2006). For bond lengths in molecules related to the title compound, see: Allen et al. (1987); Pan & Yang (2005).
Pyridine-2-carboxylic acid hydrazide (1.37 g, 10 mmol) was dissolved in anhydrous ethanol (30 ml), and 2-acetylthiophene (1.26 g, 10 mmol) was added. The reaction mixture was refluxed for 6 h to give a clear yellow solution. Light-yellow crystals suitable for X-ray diffraction were obtained at the bottom of the vessel after standing at room temperature in air for 8 d (yield 83%, m.p. 443–444 K). Analysis calculated for C12H11N3OS: C 58.76, H 4.52, N 17.13%; found: C 58.74, H 4.58, N 17.10%.
All H atoms were placed geometrically and treated as riding on their parent atoms with C—H 0.96 Å (methyl) [Uiso(H) = 1.5Ueq(C)] and N—H 0.86 C—H 0.93 Å [Uiso(H) = 1.2Ueq(C, N)].
In recent years, much attention has been devoted to multinuclear complex systems with aroylhydrazone ligands due to their interesting structural and magnetic properties (Matthews et al., 1999; Bernhardt et al. 2006). Investigation of the crystal structures of aroylhydrazone ligands may provide useful information concerning their coordination potential. In the present study, we report the synthesis and structure of the title compound.
The molecular structure of the title compound is shown in Fig. 1. The X-ray single-crystal analysis reveals that the compound is non-planar and the dihedral angle between the two aromatic rings is 24.4 (3)°. The molecule displays a trans configuration with respect to the C—N double bond. All bond lengths show normal values (Allen et al., 1987; Pan et al., 2005). The C8—N2 bond length of 1.285 (7) Å conforms to the value for a double bond. Bond lengths C1—O1 and C1—N2 are 1.215 (6) Å and 1.335 (7) Å, respectively, indicating that the molecule exists in the keto form.
Atoms C11 of the thiophene group in one molecule and atoms N2 of the hydrazide group in adjacent molecule act as acceptor and donor to form the C—H···N weak interactions (Table 2). The occurrence of C—H···N weak interactions results in the formation of infinite zigzag chains along [010]. The chains are further assembled into a two-dimensional supramolecular structure through intermolecular C—H···O weak interactions and N—H···O hydrogen bonds (Fig. 2).
For the crystal structures of metal complexes with related aroylhydrazone derivatives, see: Matthews et al. (1999); Bernhardt et al. (2006). For bond lengths in molecules related to the title compound, see: Allen et al. (1987); Pan & Yang (2005).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).
C12H11N3OS | F(000) = 512 |
Mr = 245.30 | Dx = 1.377 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2156 reflections |
a = 12.162 (2) Å | θ = 2.7–26.2° |
b = 9.8259 (16) Å | µ = 0.26 mm−1 |
c = 10.2461 (17) Å | T = 298 K |
β = 104.857 (2)° | Block, light-yellow |
V = 1183.5 (4) Å3 | 0.56 × 0.50 × 0.22 mm |
Z = 4 |
Siemens SMART CCD area-detector diffractometer | 2088 independent reflections |
Radiation source: fine-focus sealed tube | 1531 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
φ and ω scans | θmax = 25.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→14 |
Tmin = 0.868, Tmax = 0.945 | k = −11→6 |
5755 measured reflections | l = −12→12 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0845P)2 + 0.601P] where P = (Fo2 + 2Fc2)/3 |
2088 reflections | (Δ/σ)max < 0.001 |
154 parameters | Δρmax = 0.32 e Å−3 |
1 restraint | Δρmin = −0.26 e Å−3 |
C12H11N3OS | V = 1183.5 (4) Å3 |
Mr = 245.30 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.162 (2) Å | µ = 0.26 mm−1 |
b = 9.8259 (16) Å | T = 298 K |
c = 10.2461 (17) Å | 0.56 × 0.50 × 0.22 mm |
β = 104.857 (2)° |
Siemens SMART CCD area-detector diffractometer | 2088 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1531 reflections with I > 2σ(I) |
Tmin = 0.868, Tmax = 0.945 | Rint = 0.025 |
5755 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 1 restraint |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.32 e Å−3 |
2088 reflections | Δρmin = −0.26 e Å−3 |
154 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.1445 (4) | 0.8579 (5) | 0.0924 (5) | 0.0484 (12) | |
H1 | 0.1133 | 0.8729 | 0.0084 | 0.058* | |
N2 | 0.2426 (4) | 0.9265 (4) | 0.1575 (4) | 0.0447 (11) | |
N3 | −0.0534 (4) | 0.7579 (5) | −0.0438 (4) | 0.0482 (12) | |
O1 | 0.1393 (3) | 0.7400 (4) | 0.2790 (4) | 0.0579 (12) | |
S1 | 0.43434 (14) | 1.0654 (2) | 0.33637 (15) | 0.0677 (7) | |
C1 | 0.0987 (4) | 0.7684 (6) | 0.1611 (5) | 0.0431 (13) | |
C2 | −0.0087 (4) | 0.7049 (5) | 0.0788 (5) | 0.0416 (12) | |
C3 | −0.0575 (5) | 0.5980 (6) | 0.1313 (6) | 0.0512 (15) | |
H3 | −0.0241 | 0.5642 | 0.2171 | 0.061* | |
C4 | −0.1572 (5) | 0.5424 (7) | 0.0530 (6) | 0.0585 (16) | |
H4 | −0.1922 | 0.4701 | 0.0850 | 0.070* | |
C5 | −0.2034 (5) | 0.5957 (7) | −0.0723 (6) | 0.0595 (17) | |
H5 | −0.2705 | 0.5604 | −0.1269 | 0.071* | |
C6 | −0.1494 (5) | 0.7020 (7) | −0.1162 (6) | 0.0568 (16) | |
H6 | −0.1817 | 0.7372 | −0.2017 | 0.068* | |
C7 | 0.2513 (5) | 1.0330 (7) | −0.0622 (6) | 0.0583 (16) | |
H7A | 0.1828 | 0.9830 | −0.1004 | 0.087* | |
H7B | 0.3093 | 1.0058 | −0.1051 | 0.087* | |
H7C | 0.2368 | 1.1286 | −0.0761 | 0.087* | |
C8 | 0.2906 (4) | 1.0040 (5) | 0.0875 (5) | 0.0414 (12) | |
C9 | 0.3943 (4) | 1.0717 (5) | 0.1632 (5) | 0.0426 (13) | |
C10 | 0.4717 (5) | 1.1431 (7) | 0.1159 (6) | 0.0607 (17) | |
H10 | 0.4650 | 1.1585 | 0.0247 | 0.073* | |
C11 | 0.5637 (5) | 1.1916 (7) | 0.2204 (7) | 0.0663 (18) | |
H11 | 0.6242 | 1.2413 | 0.2049 | 0.080* | |
C12 | 0.5543 (5) | 1.1585 (7) | 0.3430 (7) | 0.0596 (17) | |
H12 | 0.6068 | 1.1831 | 0.4227 | 0.071* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.040 (2) | 0.055 (3) | 0.044 (2) | −0.009 (2) | −0.0010 (19) | 0.006 (2) |
N2 | 0.035 (2) | 0.048 (3) | 0.046 (3) | −0.004 (2) | 0.0006 (19) | 0.003 (2) |
N3 | 0.041 (3) | 0.054 (3) | 0.047 (3) | −0.004 (2) | 0.007 (2) | 0.000 (2) |
O1 | 0.052 (2) | 0.070 (3) | 0.046 (2) | −0.008 (2) | 0.0029 (18) | 0.010 (2) |
S1 | 0.0572 (11) | 0.0936 (14) | 0.0457 (10) | −0.0204 (9) | 0.0013 (7) | −0.0024 (8) |
C1 | 0.037 (3) | 0.045 (3) | 0.046 (3) | 0.003 (2) | 0.008 (2) | 0.001 (2) |
C2 | 0.039 (3) | 0.042 (3) | 0.045 (3) | 0.002 (2) | 0.012 (2) | −0.002 (2) |
C3 | 0.048 (3) | 0.057 (4) | 0.049 (3) | −0.003 (3) | 0.013 (3) | 0.003 (3) |
C4 | 0.054 (4) | 0.062 (4) | 0.062 (4) | −0.016 (3) | 0.021 (3) | −0.002 (3) |
C5 | 0.048 (3) | 0.073 (4) | 0.056 (4) | −0.018 (3) | 0.011 (3) | −0.013 (3) |
C6 | 0.050 (3) | 0.068 (4) | 0.048 (3) | −0.004 (3) | 0.004 (3) | −0.002 (3) |
C7 | 0.061 (4) | 0.064 (4) | 0.044 (3) | −0.010 (3) | 0.003 (3) | −0.001 (3) |
C8 | 0.040 (3) | 0.040 (3) | 0.041 (3) | 0.002 (2) | 0.005 (2) | 0.001 (2) |
C9 | 0.041 (3) | 0.038 (3) | 0.046 (3) | 0.001 (2) | 0.006 (2) | 0.001 (2) |
C10 | 0.060 (4) | 0.063 (4) | 0.057 (4) | −0.018 (3) | 0.012 (3) | 0.002 (3) |
C11 | 0.054 (4) | 0.062 (4) | 0.081 (5) | −0.019 (3) | 0.014 (3) | −0.010 (4) |
C12 | 0.043 (3) | 0.066 (4) | 0.062 (4) | −0.007 (3) | −0.001 (3) | −0.015 (3) |
N1—C1 | 1.335 (7) | C5—C6 | 1.370 (9) |
N1—N2 | 1.384 (6) | C5—H5 | 0.9300 |
N1—H1 | 0.8600 | C6—H6 | 0.9300 |
N2—C8 | 1.285 (7) | C7—C8 | 1.512 (7) |
N3—C6 | 1.331 (7) | C7—H7A | 0.9600 |
N3—C2 | 1.339 (7) | C7—H7B | 0.9600 |
O1—C1 | 1.215 (6) | C7—H7C | 0.9600 |
S1—C12 | 1.709 (6) | C8—C9 | 1.460 (7) |
S1—C9 | 1.716 (6) | C9—C10 | 1.359 (8) |
C1—C2 | 1.497 (7) | C10—C11 | 1.419 (9) |
C2—C3 | 1.382 (8) | C10—H10 | 0.9300 |
C3—C4 | 1.384 (8) | C11—C12 | 1.330 (9) |
C3—H3 | 0.9300 | C11—H11 | 0.9300 |
C4—C5 | 1.367 (9) | C12—H12 | 0.9300 |
C4—H4 | 0.9300 | ||
C1—N1—N2 | 119.5 (4) | C5—C6—H6 | 118.1 |
C1—N1—H1 | 120.2 | C8—C7—H7A | 109.5 |
N2—N1—H1 | 120.2 | C8—C7—H7B | 109.5 |
C8—N2—N1 | 118.6 (4) | H7A—C7—H7B | 109.5 |
C6—N3—C2 | 116.7 (5) | C8—C7—H7C | 109.5 |
C12—S1—C9 | 92.0 (3) | H7A—C7—H7C | 109.5 |
O1—C1—N1 | 123.9 (5) | H7B—C7—H7C | 109.5 |
O1—C1—C2 | 122.6 (5) | N2—C8—C9 | 115.3 (5) |
N1—C1—C2 | 113.6 (5) | N2—C8—C7 | 127.4 (5) |
N3—C2—C3 | 123.3 (5) | C9—C8—C7 | 117.4 (5) |
N3—C2—C1 | 116.9 (5) | C10—C9—C8 | 128.9 (5) |
C3—C2—C1 | 119.8 (5) | C10—C9—S1 | 110.4 (4) |
C2—C3—C4 | 118.3 (6) | C8—C9—S1 | 120.7 (4) |
C2—C3—H3 | 120.8 | C9—C10—C11 | 112.9 (6) |
C4—C3—H3 | 120.8 | C9—C10—H10 | 123.5 |
C5—C4—C3 | 118.8 (6) | C11—C10—H10 | 123.5 |
C5—C4—H4 | 120.6 | C12—C11—C10 | 112.8 (6) |
C3—C4—H4 | 120.6 | C12—C11—H11 | 123.6 |
C4—C5—C6 | 119.0 (6) | C10—C11—H11 | 123.6 |
C4—C5—H5 | 120.5 | C11—C12—S1 | 111.9 (5) |
C6—C5—H5 | 120.5 | C11—C12—H12 | 124.1 |
N3—C6—C5 | 123.9 (6) | S1—C12—H12 | 124.1 |
N3—C6—H6 | 118.1 |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···O1i | 0.96 | 2.50 | 3.250 (7) | 135 |
N1—H1···O1i | 0.86 | 2.69 | 3.337 (6) | 133 |
C11—H11···N2ii | 0.93 | 2.60 | 3.306 (8) | 133 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H11N3OS |
Mr | 245.30 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 12.162 (2), 9.8259 (16), 10.2461 (17) |
β (°) | 104.857 (2) |
V (Å3) | 1183.5 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.56 × 0.50 × 0.22 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.868, 0.945 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5755, 2088, 1531 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.154, 1.01 |
No. of reflections | 2088 |
No. of parameters | 154 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.26 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···O1i | 0.96 | 2.50 | 3.250 (7) | 134.5 |
N1—H1···O1i | 0.86 | 2.69 | 3.337 (6) | 133.1 |
C11—H11···N2ii | 0.93 | 2.60 | 3.306 (8) | 133.2 |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, y+1/2, −z+1/2. |
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In recent years, much attention has been devoted to multinuclear complex systems with aroylhydrazone ligands due to their interesting structural and magnetic properties (Matthews et al., 1999; Bernhardt et al. 2006). Investigation of the crystal structures of aroylhydrazone ligands may provide useful information concerning their coordination potential. In the present study, we report the synthesis and structure of the title compound.
The molecular structure of the title compound is shown in Fig. 1. The X-ray single-crystal analysis reveals that the compound is non-planar and the dihedral angle between the two aromatic rings is 24.4 (3)°. The molecule displays a trans configuration with respect to the C—N double bond. All bond lengths show normal values (Allen et al., 1987; Pan et al., 2005). The C8—N2 bond length of 1.285 (7) Å conforms to the value for a double bond. Bond lengths C1—O1 and C1—N2 are 1.215 (6) Å and 1.335 (7) Å, respectively, indicating that the molecule exists in the keto form.
Atoms C11 of the thiophene group in one molecule and atoms N2 of the hydrazide group in adjacent molecule act as acceptor and donor to form the C—H···N weak interactions (Table 2). The occurrence of C—H···N weak interactions results in the formation of infinite zigzag chains along [010]. The chains are further assembled into a two-dimensional supramolecular structure through intermolecular C—H···O weak interactions and N—H···O hydrogen bonds (Fig. 2).