Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030163/ci6657sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030163/ci6657Isup2.hkl |
CCDC reference: 287532
A mixture of o-methoxyaniline (10 mmol), water (50 ml) and concentrated hydrochloric acid (30 mmol) was heated with stirring until a clear solution was obtained. This solution was cooled to 273–278 K and a solution of sodium nitrite (14 mmol) in water was added dropwise while the temperature was maintained below 278 K. The resulting mixture was stirred for 30 min in an ice bath. The pH was raised to 8–9 by adding dilute NaOH solution. Ethyl 4-chloroacetoacetate (10 mmol) solution in ethanol was gradually added to a cooled solution of the o-methoxybenzenediazonium chloride, prepared as described above. The resulting mixture was stirred at 273–278 K for 60 min in an ice bath and the pH was lowered to 5 with dilute HCl. The product was recrystallized from glacial acetic acid to obtain well shaped crystals of (I) (yield 86%, m.p. 423–424 K).
The H atom bonded to N1 was refined freely. All other H atoms were placed in calculated positions and constrained to ride on their parent atoms, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2 Ueq(C) [1.5Ueq(methyl C)].
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C13H15ClN2O4 | Z = 2 |
Mr = 298.72 | F(000) = 312 |
Triclinic, P1 | Dx = 1.409 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71069 Å |
a = 8.605 (5) Å | Cell parameters from 8830 reflections |
b = 8.981 (5) Å | θ = 2.4–27.2° |
c = 9.974 (5) Å | µ = 0.29 mm−1 |
α = 107.615 (5)° | T = 296 K |
β = 103.543 (5)° | Prism, yellow |
γ = 94.952 (5)° | 0.49 × 0.36 × 0.14 mm |
V = 703.9 (7) Å3 |
STOE IPDS-II diffractometer | 2741 independent reflections |
Radiation source: fine-focus sealed tube | 1906 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 2.4° |
w scans | h = −10→10 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −11→11 |
Tmin = 0.885, Tmax = 0.964 | l = −12→12 |
10993 measured reflections |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0645P)2 + 0.0281P] where P = (Fo2 + 2Fc2)/3 |
2741 reflections | (Δ/σ)max = 0.001 |
187 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C13H15ClN2O4 | γ = 94.952 (5)° |
Mr = 298.72 | V = 703.9 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.605 (5) Å | Mo Kα radiation |
b = 8.981 (5) Å | µ = 0.29 mm−1 |
c = 9.974 (5) Å | T = 296 K |
α = 107.615 (5)° | 0.49 × 0.36 × 0.14 mm |
β = 103.543 (5)° |
STOE IPDS-II diffractometer | 2741 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 1906 reflections with I > 2σ(I) |
Tmin = 0.885, Tmax = 0.964 | Rint = 0.027 |
10993 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.15 e Å−3 |
2741 reflections | Δρmin = −0.18 e Å−3 |
187 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 | ||
C1 | 0.1950 (2) | 0.5853 (2) | 0.4889 (2) | 0.0594 (5) | |
C2 | 0.1743 (3) | 0.7305 (3) | 0.5723 (2) | 0.0744 (6) | |
H2 | 0.2404 | 0.7782 | 0.6673 | 0.089* | |
C3 | 0.0556 (3) | 0.8064 (3) | 0.5156 (3) | 0.0921 (7) | |
H3 | 0.0405 | 0.9043 | 0.5725 | 0.110* | |
C4 | −0.0399 (3) | 0.7356 (4) | 0.3742 (4) | 0.0964 (9) | |
H4 | −0.1204 | 0.7861 | 0.3361 | 0.116* | |
C5 | −0.0184 (3) | 0.5927 (4) | 0.2894 (3) | 0.0833 (7) | |
H5 | −0.0828 | 0.5474 | 0.1935 | 0.100* | |
C6 | 0.0993 (2) | 0.5143 (3) | 0.3454 (2) | 0.0655 (5) | |
C7 | 0.0222 (3) | 0.2850 (4) | 0.1324 (2) | 0.0999 (8) | |
H7A | −0.0867 | 0.2728 | 0.1408 | 0.120* | |
H7B | 0.0507 | 0.1824 | 0.0953 | 0.120* | |
H7C | 0.0293 | 0.3426 | 0.0665 | 0.120* | |
C8 | 0.4985 (2) | 0.4883 (2) | 0.74401 (18) | 0.0521 (4) | |
C9 | 0.5891 (2) | 0.5861 (2) | 0.89488 (19) | 0.0554 (4) | |
C10 | 0.5456 (3) | 0.7501 (2) | 0.9452 (2) | 0.0768 (6) | |
H10A | 0.4391 | 0.7408 | 0.9618 | 0.092* | |
H10B | 0.5400 | 0.7961 | 0.8682 | 0.092* | |
C11 | 0.5138 (2) | 0.3230 (2) | 0.67202 (19) | 0.0568 (4) | |
C12 | 0.6319 (3) | 0.1000 (2) | 0.6823 (2) | 0.0728 (6) | |
H12A | 0.6634 | 0.0902 | 0.5931 | 0.087* | |
H12B | 0.5289 | 0.0308 | 0.6572 | 0.087* | |
C13 | 0.7580 (3) | 0.0549 (3) | 0.7864 (3) | 0.0876 (7) | |
H13A | 0.8588 | 0.1253 | 0.8119 | 0.105* | |
H13B | 0.7719 | −0.0519 | 0.7413 | 0.105* | |
H13C | 0.7243 | 0.0623 | 0.8731 | 0.105* | |
N1 | 0.30838 (19) | 0.5002 (2) | 0.54512 (17) | 0.0570 (4) | |
N2 | 0.39947 (17) | 0.56386 (17) | 0.67872 (15) | 0.0536 (4) | |
O1 | 0.43650 (18) | 0.24860 (17) | 0.54691 (14) | 0.0750 (4) | |
O2 | 0.61716 (17) | 0.26297 (15) | 0.75319 (13) | 0.0645 (4) | |
O3 | 0.68687 (18) | 0.54210 (16) | 0.97574 (14) | 0.0745 (4) | |
O4 | 0.13042 (18) | 0.3696 (2) | 0.27202 (15) | 0.0792 (4) | |
Cl1 | 0.68642 (8) | 0.87846 (7) | 1.10700 (6) | 0.0881 (2) | |
H1 | 0.307 (3) | 0.412 (3) | 0.499 (3) | 0.074 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0548 (10) | 0.0677 (12) | 0.0561 (10) | 0.0082 (9) | 0.0013 (8) | 0.0322 (9) |
C2 | 0.0797 (14) | 0.0692 (13) | 0.0743 (13) | 0.0188 (11) | 0.0049 (11) | 0.0345 (11) |
C3 | 0.0944 (17) | 0.0855 (17) | 0.1098 (19) | 0.0348 (14) | 0.0165 (15) | 0.0550 (16) |
C4 | 0.0746 (15) | 0.113 (2) | 0.120 (2) | 0.0290 (15) | 0.0056 (15) | 0.077 (2) |
C5 | 0.0612 (12) | 0.117 (2) | 0.0773 (14) | 0.0083 (13) | −0.0049 (11) | 0.0605 (16) |
C6 | 0.0543 (11) | 0.0858 (15) | 0.0559 (11) | 0.0069 (10) | 0.0002 (9) | 0.0357 (11) |
C7 | 0.0833 (16) | 0.132 (2) | 0.0541 (12) | 0.0032 (15) | −0.0121 (11) | 0.0154 (13) |
C8 | 0.0550 (10) | 0.0515 (10) | 0.0448 (8) | 0.0088 (8) | 0.0018 (7) | 0.0180 (7) |
C9 | 0.0594 (10) | 0.0522 (10) | 0.0473 (9) | 0.0079 (8) | 0.0005 (8) | 0.0176 (8) |
C10 | 0.0890 (15) | 0.0580 (11) | 0.0575 (11) | 0.0137 (10) | −0.0155 (10) | 0.0089 (9) |
C11 | 0.0562 (10) | 0.0590 (11) | 0.0493 (9) | 0.0110 (9) | 0.0043 (8) | 0.0172 (8) |
C12 | 0.0932 (15) | 0.0572 (11) | 0.0577 (11) | 0.0294 (11) | 0.0055 (10) | 0.0116 (9) |
C13 | 0.1139 (19) | 0.0707 (14) | 0.0689 (14) | 0.0370 (14) | 0.0027 (13) | 0.0210 (11) |
N1 | 0.0586 (9) | 0.0589 (10) | 0.0445 (8) | 0.0112 (8) | −0.0041 (7) | 0.0178 (7) |
N2 | 0.0542 (8) | 0.0565 (8) | 0.0437 (7) | 0.0071 (7) | −0.0008 (6) | 0.0190 (6) |
O1 | 0.0829 (9) | 0.0651 (8) | 0.0530 (8) | 0.0236 (7) | −0.0093 (7) | 0.0038 (6) |
O2 | 0.0781 (9) | 0.0546 (7) | 0.0503 (7) | 0.0203 (6) | −0.0010 (6) | 0.0140 (6) |
O3 | 0.0829 (9) | 0.0653 (8) | 0.0560 (7) | 0.0185 (7) | −0.0161 (7) | 0.0177 (6) |
O4 | 0.0683 (9) | 0.1021 (12) | 0.0498 (7) | 0.0104 (8) | −0.0073 (6) | 0.0196 (8) |
Cl1 | 0.1087 (5) | 0.0644 (3) | 0.0593 (3) | 0.0090 (3) | −0.0121 (3) | 0.0034 (2) |
C1—C2 | 1.370 (3) | C8—C9 | 1.475 (2) |
C1—C6 | 1.392 (3) | C9—O3 | 1.203 (2) |
C1—N1 | 1.408 (2) | C9—C10 | 1.516 (3) |
C2—C3 | 1.382 (3) | C10—Cl1 | 1.766 (2) |
C2—H2 | 0.93 | C10—H10A | 0.97 |
C3—C4 | 1.376 (4) | C10—H10B | 0.97 |
C3—H3 | 0.93 | C11—O1 | 1.215 (2) |
C4—C5 | 1.362 (4) | C11—O2 | 1.321 (2) |
C4—H4 | 0.93 | C12—O2 | 1.451 (2) |
C5—C6 | 1.389 (3) | C12—C13 | 1.491 (3) |
C5—H5 | 0.93 | C12—H12A | 0.97 |
C6—O4 | 1.368 (3) | C12—H12B | 0.97 |
C7—O4 | 1.419 (3) | C13—H13A | 0.96 |
C7—H7A | 0.96 | C13—H13B | 0.96 |
C7—H7B | 0.96 | C13—H13C | 0.96 |
C7—H7C | 0.96 | N1—N2 | 1.300 (2) |
C8—N2 | 1.311 (2) | N1—H1 | 0.79 (2) |
C8—C11 | 1.473 (3) | ||
C2—C1—C6 | 120.45 (19) | C8—C9—C10 | 114.38 (15) |
C2—C1—N1 | 121.94 (18) | C9—C10—Cl1 | 112.93 (14) |
C6—C1—N1 | 117.6 (2) | C9—C10—H10A | 109.0 |
C1—C2—C3 | 120.2 (2) | Cl1—C10—H10A | 109.0 |
C1—C2—H2 | 119.9 | C9—C10—H10B | 109.0 |
C3—C2—H2 | 119.9 | Cl1—C10—H10B | 109.0 |
C4—C3—C2 | 119.4 (3) | H10A—C10—H10B | 107.8 |
C4—C3—H3 | 120.3 | O1—C11—O2 | 123.04 (18) |
C2—C3—H3 | 120.3 | O1—C11—C8 | 121.8 (2) |
C5—C4—C3 | 120.9 (2) | O2—C11—C8 | 115.15 (15) |
C5—C4—H4 | 119.5 | O2—C12—C13 | 107.74 (17) |
C3—C4—H4 | 119.5 | O2—C12—H12A | 110.2 |
C4—C5—C6 | 120.3 (2) | C13—C12—H12A | 110.2 |
C4—C5—H5 | 119.8 | O2—C12—H12B | 110.2 |
C6—C5—H5 | 119.8 | C13—C12—H12B | 110.2 |
O4—C6—C5 | 125.7 (2) | H12A—C12—H12B | 108.5 |
O4—C6—C1 | 115.59 (18) | C12—C13—H13A | 109.5 |
C5—C6—C1 | 118.7 (2) | C12—C13—H13B | 109.5 |
O4—C7—H7A | 109.5 | H13A—C13—H13B | 109.5 |
O4—C7—H7B | 109.5 | C12—C13—H13C | 109.5 |
H7A—C7—H7B | 109.5 | H13A—C13—H13C | 109.5 |
O4—C7—H7C | 109.5 | H13B—C13—H13C | 109.5 |
H7A—C7—H7C | 109.5 | N2—N1—C1 | 118.9 (2) |
H7B—C7—H7C | 109.5 | N2—N1—H1 | 121.6 (18) |
N2—C8—C11 | 122.51 (15) | C1—N1—H1 | 119.1 (18) |
N2—C8—C9 | 112.68 (16) | N1—N2—C8 | 122.97 (16) |
C11—C8—C9 | 124.8 (2) | C11—O2—C12 | 115.11 (15) |
O3—C9—C8 | 124.6 (2) | C6—O4—C7 | 117.03 (19) |
O3—C9—C10 | 121.01 (16) | ||
C6—C1—C2—C3 | 1.4 (3) | C8—C9—C10—Cl1 | −166.16 (14) |
N1—C1—C2—C3 | −176.44 (19) | N2—C8—C11—O1 | 1.0 (3) |
C1—C2—C3—C4 | −0.8 (4) | C9—C8—C11—O1 | −179.55 (18) |
C2—C3—C4—C5 | −0.5 (4) | N2—C8—C11—O2 | −179.07 (16) |
C3—C4—C5—C6 | 1.1 (4) | C9—C8—C11—O2 | 0.4 (3) |
C4—C5—C6—O4 | 178.8 (2) | C2—C1—N1—N2 | −2.2 (3) |
C4—C5—C6—C1 | −0.5 (3) | C6—C1—N1—N2 | 179.89 (16) |
C2—C1—C6—O4 | 179.86 (18) | C1—N1—N2—C8 | 174.2 (2) |
N1—C1—C6—O4 | −2.2 (2) | C11—C8—N2—N1 | −0.8 (3) |
C2—C1—C6—C5 | −0.8 (3) | C9—C8—N2—N1 | 179.69 (16) |
N1—C1—C6—C5 | 177.21 (18) | O1—C11—O2—C12 | −0.2 (3) |
N2—C8—C9—O3 | −179.88 (17) | C8—C11—O2—C12 | 179.9 (2) |
C11—C8—C9—O3 | 0.6 (3) | C13—C12—O2—C11 | 177.42 (18) |
N2—C8—C9—C10 | 2.1 (2) | C5—C6—O4—C7 | −7.0 (3) |
C11—C8—C9—C10 | −177.41 (18) | C1—C6—O4—C7 | 172.30 (19) |
O3—C9—C10—Cl1 | 15.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O3i | 0.93 | 2.56 | 3.413 (3) | 153 |
N1—H1···O1 | 0.79 (2) | 2.02 (2) | 2.602 (2) | 131 (2) |
N1—H1···O4 | 0.79 (2) | 2.31 (2) | 2.635 (2) | 106 (2) |
Symmetry code: (i) x−1, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C13H15ClN2O4 |
Mr | 298.72 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 8.605 (5), 8.981 (5), 9.974 (5) |
α, β, γ (°) | 107.615 (5), 103.543 (5), 94.952 (5) |
V (Å3) | 703.9 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.29 |
Crystal size (mm) | 0.49 × 0.36 × 0.14 |
Data collection | |
Diffractometer | STOE IPDS-II diffractometer |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.885, 0.964 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10993, 2741, 1906 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.117, 1.03 |
No. of reflections | 2741 |
No. of parameters | 187 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.15, −0.18 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
C6—O4 | 1.368 (3) | C11—O1 | 1.215 (2) |
C7—O4 | 1.419 (3) | C11—O2 | 1.321 (2) |
C9—O3 | 1.203 (2) | C12—O2 | 1.451 (2) |
N2—C8—C9 | 112.68 (16) | O1—C11—O2 | 123.04 (18) |
C11—C8—C9 | 124.8 (2) | O2—C11—C8 | 115.15 (15) |
O3—C9—C8 | 124.6 (2) | N2—N1—C1 | 118.9 (2) |
C8—C9—C10 | 114.38 (15) | N1—N2—C8 | 122.97 (16) |
N1—C1—C6—O4 | −2.2 (2) | C1—N1—N2—C8 | 174.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O3i | 0.93 | 2.56 | 3.413 (3) | 153 |
N1—H1···O1 | 0.79 (2) | 2.02 (2) | 2.602 (2) | 131 (2) |
N1—H1···O4 | 0.79 (2) | 2.31 (2) | 2.635 (2) | 106 (2) |
Symmetry code: (i) x−1, y, z−1. |
Various hydrazone compounds possess strong bactericidal, herbicidal, insecticidal and fungicidal properties (Sahni et al., 1977). Some phenylhydrazone derivatives have been shown to be potentially DNA-damaging and are mutagenic agents (Okabe et al., 1993). In addition, hydrazones have analytical applications (Heit & Ryan, 1966; Jensen & Pflaum, 1967; Dey et al., 1985). Hydrazones have interesting ligational properties as a result of the presence of several potential coordination sites (Dutta & Hossain, 1985), and both transition and non-transition metal complexes of these ligands have been synthesized previously (Dey et al., 1992).
As part of our ongoing research on phenylhydrazonodiones, the title compound, (I), has been synthesized and its crystal structure is reported here. Previously we reported the structure of ethyl 4-chloro- 3-oxo-2-(phenylhydrazono)butyrate (Alpaslan et al., 2005a), (E)-ethyl 4-chloro-3-[2-(2-fluorophenyl)hydrazono]butanoate (Alpaslan et al., 2005b), ethyl 4-chloro-2-[(2-nitrophenyl) hydrazono]-3-oxobutyrate (Odabaşoǧlu et al., 2005a) and ethyl 4-chloro-2-[(4-nitrophenyl)hydrazono]-3-oxobutyrate (Odabaşoǧlu et al., 2005b).
Our investigations show that, in the solid state, the molecular structure of (I) adopts the keto–hydrazo tautomeric form with intramolecular hydrogen bonds (Fig. 1). The phenylhydrazone fragment is planar within ±0.028 (2) Å, and atoms O4 and C7 deviate from that plane by 0.014 (3) and −0.165 (4) Å, respectively. The oxobutanoate fragment (O1–O3/C8–C13) is planar (r.m.s deviation 0.020 Å). The dihedral angle between the phenylhydrazone and O1–O3/C8–C13 planes is 8.15 (9)°.
It is remarkable that the Z isomer of the methoxyphenylhydrazone derivative was formed preferentially over the E isomer since the latter would almost certainly feature an N—H···O═C intramolecular hydrogen bond. In (I), the imine group adopts a Z configuration, with bond lengths C1—N1 = 1.408 (2) Å, C8—N2 = 1.311 (2) Å and N1—N2 = 1.300 (2) Å. These data show that there is significant elongation of the N1—N2 bond and contraction of the C1—C2 bond in comparsion with azo compounds. For example, the N═N and C—N bonds in azobenzene are 1.255 (2) Å and 1.432 (2) Å, respectively (Patai, 1975), while the C═N double bonds in imine compounds are in the range 1.270 (5)–1.303 (3) Å (Ersanlı, Odabaşoǧlu, et al., 2004; Baughman et al., 2004; Ersanlı, Albayrak et al., 2004; Odabaşoǧlu et al., 2005; Şahin et al., 2005; Butcher et al., 2005). There is a moderately strong intramolecular N1—H1···O1 hydrogen bond, which is a common feature of similar systems {N—H···O = 1.99 (2) Å in ethyl 4-chloro-3-oxo-2-(phenlyhydrazono)butyrate (Alpaslan et al., 2005a); N—H···O = 1.96 (2) Å in (E)-ethyl 4-chloro-3-[2-(2-fluorophenly) hydrazono]butanoate (Alpaslan et al., 2005b)}. The carbonyl groups point in opposite sides of the C9—C11 chain and their bond distances of 1.203 (2) and 1.215 (2) Å are shorter than those observed in similar compounds (Chen et al., 2004; Odabaşoǧlu et al., 2003) but within the normal range for carbonyl compounds (Loudon, 2002).
In the crystal structure, C5—H5···O3i intermolecular hydrogen bonds link the molecules into a chain along [101] (Fig. 2); symmetry code (i) is given in Table 2.