In the title compound, C
20H
17ClN
2O
3S, the vanillin group makes dihedral angles of 73.65 (11) and 2.16 (16)° with the chloro-substituted benzene ring and the thiophene mean plane, respectively. The crystal packing is stabilized by an intermolecular N—H
O hydrogen bond that forms a centrosymmetric dimer.
Supporting information
CCDC reference: 630023
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.007 Å
- R factor = 0.056
- wR factor = 0.176
- Data-to-parameter ratio = 13.3
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C7
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C3
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C6
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.10
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 7
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
4 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
0 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; 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.
(
E)—
N'-[4-(4-Chlorobenzyloxy)-3-methoxybenzylidene]thiophene-2-carbohydrazide
top
Crystal data top
C20H17ClN2O3S | Z = 2 |
Mr = 400.88 | F(000) = 416 |
Triclinic, P1 | Dx = 1.424 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.275 (3) Å | Cell parameters from 2127 reflections |
b = 9.884 (3) Å | θ = 2.5–24.6° |
c = 11.584 (3) Å | µ = 0.34 mm−1 |
α = 89.503 (5)° | T = 294 K |
β = 81.062 (5)° | Block, colourless |
γ = 86.951 (5)° | 0.14 × 0.12 × 0.08 mm |
V = 934.6 (5) Å3 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 3264 independent reflections |
Radiation source: fine-focus sealed tube | 1803 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
φ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→8 |
Tmin = 0.931, Tmax = 0.973 | k = −11→9 |
4778 measured reflections | l = −13→11 |
Refinement top
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.176 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0663P)2 + 0.5087P] where P = (Fo2 + 2Fc2)/3 |
3264 reflections | (Δ/σ)max < 0.001 |
246 parameters | Δρmax = 0.39 e Å−3 |
6 restraints | Δρmin = −0.39 e Å−3 |
Special details top
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 >
2σ(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 (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 1.32387 (16) | 1.21499 (12) | 0.22251 (12) | 0.0502 (4) | |
Cl1 | 0.6607 (3) | 0.06608 (18) | 0.57963 (17) | 0.1240 (9) | |
O1 | 0.7948 (4) | 0.6408 (3) | 0.2918 (3) | 0.0476 (9) | |
O2 | 0.5900 (4) | 0.7551 (3) | 0.1665 (3) | 0.0477 (9) | |
O3 | 1.1892 (4) | 1.5373 (3) | 0.0465 (3) | 0.0566 (10) | |
N1 | 1.0441 (4) | 1.2169 (3) | 0.1153 (3) | 0.0383 (9) | |
N2 | 1.0575 (4) | 1.3453 (3) | 0.0697 (3) | 0.0432 (10) | |
H2 | 0.9845 | 1.3781 | 0.0304 | 0.052* | |
C1 | 0.7016 (7) | 0.4593 (5) | 0.5230 (5) | 0.0573 (14) | |
H1 | 0.6519 | 0.5399 | 0.5552 | 0.069* | |
C2 | 0.6489 (7) | 0.3381 (6) | 0.5694 (5) | 0.0622 (15) | |
H2A | 0.5632 | 0.3360 | 0.6316 | 0.075* | |
C3 | 0.7246 (8) | 0.2214 (5) | 0.5226 (5) | 0.0592 (15) | |
C4 | 0.8501 (8) | 0.2227 (5) | 0.4313 (5) | 0.0647 (16) | |
H4 | 0.9006 | 0.1419 | 0.4003 | 0.078* | |
C5 | 0.9007 (6) | 0.3439 (5) | 0.3858 (4) | 0.0555 (14) | |
H5 | 0.9871 | 0.3453 | 0.3240 | 0.067* | |
C6 | 0.8261 (6) | 0.4638 (5) | 0.4299 (4) | 0.0457 (12) | |
C7 | 0.8864 (8) | 0.5959 (5) | 0.3807 (5) | 0.0770 (19) | |
H7A | 0.8745 | 0.6632 | 0.4423 | 0.092* | |
H7B | 1.0016 | 0.5846 | 0.3482 | 0.092* | |
C8 | 0.8346 (6) | 0.7647 (4) | 0.2430 (4) | 0.0405 (11) | |
C9 | 0.9754 (6) | 0.8273 (5) | 0.2552 (4) | 0.0523 (13) | |
H9 | 1.0512 | 0.7844 | 0.2966 | 0.063* | |
C10 | 1.0055 (6) | 0.9530 (4) | 0.2064 (4) | 0.0463 (12) | |
H10 | 1.1012 | 0.9941 | 0.2156 | 0.056* | |
C11 | 0.8952 (5) | 1.0187 (4) | 0.1441 (4) | 0.0362 (10) | |
C12 | 0.7538 (5) | 0.9526 (4) | 0.1296 (4) | 0.0386 (11) | |
H12 | 0.6791 | 0.9949 | 0.0870 | 0.046* | |
C13 | 0.7228 (5) | 0.8264 (4) | 0.1771 (4) | 0.0364 (11) | |
C14 | 0.4664 (6) | 0.8191 (5) | 0.1089 (4) | 0.0519 (13) | |
H14A | 0.4309 | 0.9045 | 0.1456 | 0.078* | |
H14B | 0.3750 | 0.7622 | 0.1140 | 0.078* | |
H14C | 0.5099 | 0.8336 | 0.0283 | 0.078* | |
C15 | 0.9201 (5) | 1.1545 (4) | 0.0957 (4) | 0.0373 (11) | |
H15 | 0.8464 | 1.1949 | 0.0512 | 0.045* | |
C16 | 1.1833 (5) | 1.4211 (4) | 0.0855 (4) | 0.0420 (11) | |
C17 | 1.3156 (5) | 1.3663 (4) | 0.1475 (4) | 0.0387 (11) | |
C18 | 1.4525 (6) | 1.4355 (5) | 0.1535 (4) | 0.0465 (12) | |
H18 | 1.4707 | 1.5196 | 0.1185 | 0.056* | |
C19 | 1.5625 (6) | 1.3682 (5) | 0.2171 (4) | 0.0552 (14) | |
H19 | 1.6617 | 1.4018 | 0.2287 | 0.066* | |
C20 | 1.5080 (6) | 1.2482 (5) | 0.2600 (4) | 0.0551 (14) | |
H20 | 1.5651 | 1.1904 | 0.3051 | 0.066* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0477 (8) | 0.0395 (7) | 0.0668 (9) | −0.0068 (5) | −0.0190 (6) | 0.0183 (6) |
Cl1 | 0.198 (2) | 0.0748 (11) | 0.1198 (16) | −0.0761 (13) | −0.0692 (15) | 0.0521 (11) |
O1 | 0.051 (2) | 0.0386 (17) | 0.061 (2) | −0.0157 (15) | −0.0294 (16) | 0.0230 (15) |
O2 | 0.044 (2) | 0.0375 (17) | 0.068 (2) | −0.0165 (14) | −0.0271 (17) | 0.0191 (16) |
O3 | 0.055 (2) | 0.0323 (17) | 0.089 (3) | −0.0152 (15) | −0.0265 (19) | 0.0251 (17) |
N1 | 0.040 (2) | 0.0273 (19) | 0.048 (2) | −0.0081 (16) | −0.0095 (18) | 0.0094 (17) |
N2 | 0.042 (2) | 0.0308 (19) | 0.061 (3) | −0.0109 (17) | −0.0193 (19) | 0.0173 (18) |
C1 | 0.060 (4) | 0.048 (3) | 0.065 (4) | 0.004 (3) | −0.018 (3) | 0.006 (3) |
C2 | 0.054 (4) | 0.079 (4) | 0.053 (4) | −0.015 (3) | −0.003 (3) | 0.014 (3) |
C3 | 0.087 (4) | 0.047 (3) | 0.053 (3) | −0.026 (3) | −0.033 (3) | 0.020 (3) |
C4 | 0.092 (5) | 0.047 (3) | 0.059 (4) | 0.009 (3) | −0.028 (3) | −0.005 (3) |
C5 | 0.055 (3) | 0.070 (4) | 0.041 (3) | −0.002 (3) | −0.004 (2) | 0.007 (3) |
C6 | 0.051 (3) | 0.051 (3) | 0.041 (3) | −0.013 (2) | −0.022 (2) | 0.017 (2) |
C7 | 0.095 (5) | 0.067 (4) | 0.086 (4) | −0.034 (3) | −0.061 (4) | 0.046 (3) |
C8 | 0.046 (3) | 0.032 (2) | 0.048 (3) | −0.011 (2) | −0.018 (2) | 0.011 (2) |
C9 | 0.049 (3) | 0.043 (3) | 0.072 (4) | −0.011 (2) | −0.031 (3) | 0.020 (3) |
C10 | 0.042 (3) | 0.036 (2) | 0.068 (3) | −0.012 (2) | −0.025 (2) | 0.012 (2) |
C11 | 0.041 (3) | 0.029 (2) | 0.038 (3) | −0.0081 (19) | −0.007 (2) | 0.0034 (19) |
C12 | 0.039 (3) | 0.033 (2) | 0.046 (3) | −0.0025 (19) | −0.013 (2) | 0.006 (2) |
C13 | 0.035 (3) | 0.034 (2) | 0.043 (3) | −0.0094 (19) | −0.011 (2) | 0.009 (2) |
C14 | 0.042 (3) | 0.044 (3) | 0.075 (4) | −0.009 (2) | −0.027 (3) | 0.011 (3) |
C15 | 0.041 (3) | 0.032 (2) | 0.041 (3) | −0.006 (2) | −0.010 (2) | 0.005 (2) |
C16 | 0.039 (3) | 0.035 (3) | 0.053 (3) | −0.006 (2) | −0.011 (2) | 0.010 (2) |
C17 | 0.040 (3) | 0.034 (2) | 0.044 (3) | −0.008 (2) | −0.009 (2) | 0.007 (2) |
C18 | 0.047 (3) | 0.040 (3) | 0.054 (3) | −0.011 (2) | −0.011 (2) | 0.003 (2) |
C19 | 0.043 (3) | 0.060 (3) | 0.068 (4) | −0.010 (3) | −0.022 (3) | −0.001 (3) |
C20 | 0.048 (3) | 0.058 (3) | 0.064 (4) | 0.001 (2) | −0.025 (3) | 0.005 (3) |
Geometric parameters (Å, º) top
S1—C20 | 1.697 (5) | C7—H7A | 0.9700 |
S1—C17 | 1.727 (4) | C7—H7B | 0.9700 |
Cl1—C3 | 1.741 (5) | C8—C9 | 1.375 (6) |
O1—C8 | 1.379 (5) | C8—C13 | 1.400 (6) |
O1—C7 | 1.425 (5) | C9—C10 | 1.379 (6) |
O2—C13 | 1.359 (5) | C9—H9 | 0.9300 |
O2—C14 | 1.424 (5) | C10—C11 | 1.382 (6) |
O3—C16 | 1.232 (5) | C10—H10 | 0.9300 |
N1—C15 | 1.275 (5) | C11—C12 | 1.403 (6) |
N1—N2 | 1.374 (4) | C11—C15 | 1.463 (5) |
N2—C16 | 1.350 (5) | C12—C13 | 1.379 (5) |
N2—H2 | 0.8600 | C12—H12 | 0.9300 |
C1—C6 | 1.373 (7) | C14—H14A | 0.9600 |
C1—C2 | 1.373 (7) | C14—H14B | 0.9600 |
C1—H1 | 0.9300 | C14—H14C | 0.9600 |
C2—C3 | 1.359 (8) | C15—H15 | 0.9300 |
C2—H2A | 0.9300 | C16—C17 | 1.476 (6) |
C3—C4 | 1.363 (8) | C17—C18 | 1.365 (6) |
C4—C5 | 1.365 (7) | C18—C19 | 1.397 (6) |
C4—H4 | 0.9300 | C18—H18 | 0.9300 |
C5—C6 | 1.372 (7) | C19—C20 | 1.354 (6) |
C5—H5 | 0.9300 | C19—H19 | 0.9300 |
C6—C7 | 1.499 (6) | C20—H20 | 0.9300 |
| | | |
C20—S1—C17 | 91.5 (2) | C9—C10—C11 | 120.9 (4) |
C8—O1—C7 | 115.2 (3) | C9—C10—H10 | 119.6 |
C13—O2—C14 | 117.7 (3) | C11—C10—H10 | 119.6 |
C15—N1—N2 | 116.0 (4) | C10—C11—C12 | 118.1 (4) |
C16—N2—N1 | 121.2 (4) | C10—C11—C15 | 122.2 (4) |
C16—N2—H2 | 119.4 | C12—C11—C15 | 119.7 (4) |
N1—N2—H2 | 119.4 | C13—C12—C11 | 121.6 (4) |
C6—C1—C2 | 121.3 (5) | C13—C12—H12 | 119.2 |
C6—C1—H1 | 119.4 | C11—C12—H12 | 119.2 |
C2—C1—H1 | 119.4 | O2—C13—C12 | 125.4 (4) |
C3—C2—C1 | 118.6 (5) | O2—C13—C8 | 115.9 (4) |
C3—C2—H2A | 120.7 | C12—C13—C8 | 118.7 (4) |
C1—C2—H2A | 120.7 | O2—C14—H14A | 109.5 |
C2—C3—C4 | 121.4 (5) | O2—C14—H14B | 109.5 |
C2—C3—Cl1 | 119.7 (5) | H14A—C14—H14B | 109.5 |
C4—C3—Cl1 | 118.9 (5) | O2—C14—H14C | 109.5 |
C3—C4—C5 | 119.3 (5) | H14A—C14—H14C | 109.5 |
C3—C4—H4 | 120.4 | H14B—C14—H14C | 109.5 |
C5—C4—H4 | 120.4 | N1—C15—C11 | 119.2 (4) |
C4—C5—C6 | 120.9 (5) | N1—C15—H15 | 120.4 |
C4—C5—H5 | 119.5 | C11—C15—H15 | 120.4 |
C6—C5—H5 | 119.5 | O3—C16—N2 | 119.6 (4) |
C5—C6—C1 | 118.4 (5) | O3—C16—C17 | 119.3 (4) |
C5—C6—C7 | 120.1 (5) | N2—C16—C17 | 121.1 (4) |
C1—C6—C7 | 121.4 (5) | C18—C17—C16 | 122.0 (4) |
O1—C7—C6 | 109.7 (4) | C18—C17—S1 | 110.2 (3) |
O1—C7—H7A | 109.7 | C16—C17—S1 | 127.8 (3) |
C6—C7—H7A | 109.7 | C17—C18—C19 | 113.6 (4) |
O1—C7—H7B | 109.7 | C17—C18—H18 | 123.2 |
C6—C7—H7B | 109.7 | C19—C18—H18 | 123.2 |
H7A—C7—H7B | 108.2 | C20—C19—C18 | 112.1 (4) |
C9—C8—O1 | 123.7 (4) | C20—C19—H19 | 124.0 |
C9—C8—C13 | 120.0 (4) | C18—C19—H19 | 124.0 |
O1—C8—C13 | 116.3 (4) | C19—C20—S1 | 112.5 (4) |
C8—C9—C10 | 120.6 (4) | C19—C20—H20 | 123.7 |
C8—C9—H9 | 119.7 | S1—C20—H20 | 123.7 |
C10—C9—H9 | 119.7 | | |
| | | |
C15—N1—N2—C16 | 179.6 (4) | C14—O2—C13—C8 | 174.7 (4) |
C6—C1—C2—C3 | 1.1 (8) | C11—C12—C13—O2 | −179.5 (4) |
C1—C2—C3—C4 | −0.2 (8) | C11—C12—C13—C8 | 1.2 (7) |
C1—C2—C3—Cl1 | 180.0 (4) | C9—C8—C13—O2 | 177.8 (4) |
C2—C3—C4—C5 | 0.0 (8) | O1—C8—C13—O2 | −1.7 (6) |
Cl1—C3—C4—C5 | 179.8 (4) | C9—C8—C13—C12 | −2.7 (7) |
C3—C4—C5—C6 | −0.7 (8) | O1—C8—C13—C12 | 177.8 (4) |
C4—C5—C6—C1 | 1.6 (7) | N2—N1—C15—C11 | −178.4 (4) |
C4—C5—C6—C7 | 178.4 (4) | C10—C11—C15—N1 | −2.8 (7) |
C2—C1—C6—C5 | −1.8 (7) | C12—C11—C15—N1 | 175.9 (4) |
C2—C1—C6—C7 | −178.6 (5) | N1—N2—C16—O3 | −177.8 (4) |
C8—O1—C7—C6 | 177.4 (4) | N1—N2—C16—C17 | 3.0 (7) |
C5—C6—C7—O1 | 93.8 (6) | O3—C16—C17—C18 | −6.4 (7) |
C1—C6—C7—O1 | −89.4 (6) | N2—C16—C17—C18 | 172.8 (4) |
C7—O1—C8—C9 | 15.4 (7) | O3—C16—C17—S1 | 172.5 (4) |
C7—O1—C8—C13 | −165.1 (5) | N2—C16—C17—S1 | −8.3 (7) |
O1—C8—C9—C10 | −178.3 (4) | C20—S1—C17—C18 | 0.2 (4) |
C13—C8—C9—C10 | 2.3 (7) | C20—S1—C17—C16 | −178.8 (4) |
C8—C9—C10—C11 | −0.2 (7) | C16—C17—C18—C19 | 179.2 (4) |
C9—C10—C11—C12 | −1.4 (7) | S1—C17—C18—C19 | 0.1 (5) |
C9—C10—C11—C15 | 177.3 (4) | C17—C18—C19—C20 | −0.5 (6) |
C10—C11—C12—C13 | 0.9 (7) | C18—C19—C20—S1 | 0.6 (6) |
C15—C11—C12—C13 | −177.8 (4) | C17—S1—C20—C19 | −0.5 (4) |
C14—O2—C13—C12 | −4.7 (6) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O3i | 0.86 | 1.95 | 2.811 (5) | 175 |
Symmetry code: (i) −x+2, −y+3, −z. |