The title compound, C
12H
12N
3O
5, adopts a keto-hydrazo tautomeric form stabilized by intramolecular hydrogen bonds. The aromatic ring and aliphatic chain, which adopt a
trans configuration about the C=N double bond, are nearly coplanar, with a dihedral angle of 7.56 (1)° between them. The molecules pack
via weak intermolecular C—H
O hydrogen bonds which, together with intramolecular N—H
O bonds, form an
S(6)
S(6)[
R22(13)]
S(6)
S(6) motif.
Supporting information
CCDC reference: 277783
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.005 Å
- R factor = 0.061
- wR factor = 0.190
- Data-to-parameter ratio = 15.7
checkCIF/PLATON results
No syntax errors found
Datablock: I
Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5
PLAT360_ALERT_2_C Short C(sp3)-C(sp3) Bond C11 - C12 ... 1.38 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H12B .. O5 .. 2.69 Ang.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
4 ALERT level C = Check and explain
0 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
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, 1997); 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).
4-Chloro-2-[(2-nitro-phenyl)-hydrazono]-3-oxo-butyric acid ethyl ester
top
Crystal data top
C12H12ClN3O5 | Z = 2 |
Mr = 313.70 | F(000) = 324 |
Triclinic, P1 | Dx = 1.506 Mg m−3 |
Hall symbol: -P 1 | Melting point = 421–423 K |
a = 5.1656 (10) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.9102 (16) Å | Cell parameters from 11207 reflections |
c = 17.669 (3) Å | θ = 2.3–27.2° |
α = 83.721 (15)° | µ = 0.30 mm−1 |
β = 82.709 (15)° | T = 296 K |
γ = 75.683 (15)° | Plate, red |
V = 691.6 (2) Å3 | 0.24 × 0.20 × 0.14 mm |
Data collection top
Stoe IPDS 2 diffractometer | 3089 independent reflections |
Radiation source: fine-focus sealed tube | 1700 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.099 |
Detector resolution: 6.67 pixels mm-1 | θmax = 27.2°, θmin = 2.3° |
rotation ω scans | h = −6→6 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −10→10 |
Tmin = 0.930, Tmax = 0.959 | l = −22→22 |
11207 measured reflections | |
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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.190 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0974P)2 + 0.024P] where P = (Fo2 + 2Fc2)/3 |
3065 reflections | (Δ/σ)max < 0.001 |
195 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.40 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 >
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 (Å2) top | x | y | z | Uiso*/Ueq | |
C6 | 0.9056 (5) | 0.1468 (4) | 0.23578 (18) | 0.0574 (7) | |
C5 | 1.1210 (6) | 0.0470 (4) | 0.2732 (2) | 0.0679 (9) | |
H5 | 1.2647 | −0.0239 | 0.2456 | 0.081* | |
C4 | 1.1228 (6) | 0.0522 (4) | 0.3493 (2) | 0.0722 (10) | |
H4 | 1.2687 | −0.0132 | 0.3739 | 0.087* | |
C3 | 0.9065 (6) | 0.1553 (5) | 0.3906 (2) | 0.0712 (9) | |
H3 | 0.9063 | 0.1571 | 0.4432 | 0.085* | |
C2 | 0.6911 (6) | 0.2555 (4) | 0.35458 (18) | 0.0623 (8) | |
H2 | 0.5483 | 0.3252 | 0.3829 | 0.075* | |
C1 | 0.6858 (5) | 0.2533 (4) | 0.27644 (17) | 0.0510 (7) | |
C7 | −0.0462 (6) | 0.6344 (4) | 0.39134 (17) | 0.0624 (8) | |
H7B | 0.1048 | 0.6876 | 0.3900 | 0.075* | |
H7A | 0.0137 | 0.5112 | 0.4076 | 0.075* | |
C8 | −0.1340 (5) | 0.6527 (4) | 0.31167 (16) | 0.0548 (7) | |
C9 | 0.0666 (5) | 0.5607 (4) | 0.25421 (16) | 0.0503 (6) | |
C10 | 0.0304 (6) | 0.5750 (4) | 0.17117 (18) | 0.0585 (8) | |
C11 | −0.1614 (8) | 0.7578 (7) | 0.0655 (2) | 0.0968 (13) | |
H11B | −0.1852 | 0.8816 | 0.0499 | 0.116* | |
H11A | −0.0028 | 0.6946 | 0.0359 | 0.116* | |
C12 | −0.3825 (9) | 0.7029 (8) | 0.0518 (3) | 0.1211 (18) | |
H12A | −0.3446 | 0.5774 | 0.0579 | 0.182* | |
H12C | −0.4248 | 0.7426 | 0.0005 | 0.182* | |
H12B | −0.5326 | 0.7504 | 0.0874 | 0.182* | |
N3 | 0.9206 (6) | 0.1349 (4) | 0.15381 (17) | 0.0701 (7) | |
N2 | 0.4699 (4) | 0.3595 (3) | 0.24064 (15) | 0.0536 (6) | |
N1 | 0.2752 (4) | 0.4583 (3) | 0.28307 (13) | 0.0498 (6) | |
O5 | 1.1314 (6) | 0.0569 (4) | 0.12090 (18) | 0.1025 (9) | |
O4 | 0.7260 (5) | 0.2048 (4) | 0.12024 (15) | 0.0888 (8) | |
O3 | −0.3571 (4) | 0.7320 (3) | 0.29810 (13) | 0.0823 (8) | |
O1 | 0.1486 (5) | 0.4653 (3) | 0.13005 (13) | 0.0791 (7) | |
O2 | −0.1255 (5) | 0.7259 (4) | 0.14793 (13) | 0.0882 (8) | |
Cl1 | −0.3070 (2) | 0.73385 (16) | 0.45843 (5) | 0.0952 (4) | |
H1 | 0.457 (7) | 0.346 (5) | 0.196 (2) | 0.073 (11)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C6 | 0.0504 (15) | 0.0528 (17) | 0.0684 (19) | −0.0110 (13) | −0.0076 (13) | −0.0033 (14) |
C5 | 0.0483 (16) | 0.060 (2) | 0.090 (3) | −0.0031 (13) | −0.0123 (16) | 0.0000 (17) |
C4 | 0.0524 (17) | 0.066 (2) | 0.094 (3) | −0.0058 (15) | −0.0224 (17) | 0.0089 (19) |
C3 | 0.0655 (19) | 0.083 (2) | 0.063 (2) | −0.0142 (17) | −0.0229 (16) | 0.0133 (17) |
C2 | 0.0511 (15) | 0.072 (2) | 0.0577 (17) | −0.0049 (14) | −0.0094 (13) | 0.0046 (15) |
C1 | 0.0429 (13) | 0.0510 (16) | 0.0579 (16) | −0.0090 (11) | −0.0103 (12) | 0.0022 (13) |
C7 | 0.0616 (17) | 0.068 (2) | 0.0514 (16) | −0.0005 (14) | −0.0137 (13) | −0.0048 (14) |
C8 | 0.0508 (15) | 0.0568 (17) | 0.0518 (16) | −0.0022 (13) | −0.0126 (12) | 0.0016 (13) |
C9 | 0.0479 (14) | 0.0532 (16) | 0.0482 (15) | −0.0091 (12) | −0.0122 (12) | 0.0045 (12) |
C10 | 0.0513 (15) | 0.071 (2) | 0.0517 (16) | −0.0110 (14) | −0.0132 (13) | 0.0013 (15) |
C11 | 0.092 (3) | 0.129 (4) | 0.064 (2) | −0.012 (2) | −0.030 (2) | 0.012 (2) |
C12 | 0.096 (3) | 0.200 (6) | 0.078 (3) | −0.045 (3) | −0.014 (2) | −0.031 (3) |
N3 | 0.0643 (16) | 0.0687 (18) | 0.0728 (18) | −0.0039 (13) | −0.0021 (14) | −0.0203 (14) |
N2 | 0.0464 (12) | 0.0628 (16) | 0.0477 (14) | −0.0051 (10) | −0.0087 (11) | −0.0024 (12) |
N1 | 0.0457 (11) | 0.0517 (13) | 0.0510 (13) | −0.0090 (10) | −0.0094 (10) | 0.0000 (11) |
O5 | 0.0853 (18) | 0.113 (2) | 0.096 (2) | 0.0051 (15) | 0.0041 (15) | −0.0364 (17) |
O4 | 0.0800 (16) | 0.109 (2) | 0.0694 (15) | 0.0071 (14) | −0.0187 (13) | −0.0271 (14) |
O3 | 0.0601 (12) | 0.1026 (19) | 0.0658 (14) | 0.0216 (12) | −0.0177 (11) | −0.0086 (13) |
O1 | 0.0876 (16) | 0.0891 (17) | 0.0535 (13) | 0.0017 (13) | −0.0202 (11) | −0.0119 (12) |
O2 | 0.0919 (17) | 0.1012 (19) | 0.0535 (13) | 0.0151 (14) | −0.0238 (12) | 0.0039 (13) |
Cl1 | 0.0881 (7) | 0.1216 (9) | 0.0542 (5) | 0.0166 (5) | −0.0042 (4) | −0.0114 (5) |
Geometric parameters (Å, º) top
C6—C5 | 1.391 (4) | C8—C9 | 1.468 (4) |
C6—C1 | 1.403 (4) | C9—N1 | 1.302 (3) |
C6—N3 | 1.453 (4) | C9—C10 | 1.491 (4) |
C5—C4 | 1.353 (5) | C10—O1 | 1.191 (4) |
C5—H5 | 0.9300 | C10—O2 | 1.320 (4) |
C4—C3 | 1.385 (5) | C11—C12 | 1.375 (6) |
C4—H4 | 0.9300 | C11—O2 | 1.478 (4) |
C3—C2 | 1.380 (4) | C11—H11B | 0.9700 |
C3—H3 | 0.9300 | C11—H11A | 0.9700 |
C2—C1 | 1.386 (4) | C12—H12A | 0.9600 |
C2—H2 | 0.9300 | C12—H12C | 0.9600 |
C1—N2 | 1.396 (3) | C12—H12B | 0.9600 |
C7—C8 | 1.514 (4) | N3—O4 | 1.214 (3) |
C7—Cl1 | 1.764 (3) | N3—O5 | 1.221 (4) |
C7—H7B | 0.9700 | N2—N1 | 1.316 (3) |
C7—H7A | 0.9700 | N2—H1 | 0.83 (4) |
C8—O3 | 1.208 (3) | | |
| | | |
C5—C6—C1 | 120.7 (3) | N1—C9—C8 | 113.6 (2) |
C5—C6—N3 | 117.0 (3) | N1—C9—C10 | 122.7 (3) |
C1—C6—N3 | 122.3 (3) | C8—C9—C10 | 123.6 (2) |
C4—C5—C6 | 120.5 (3) | O1—C10—O2 | 124.5 (3) |
C4—C5—H5 | 119.8 | O1—C10—C9 | 122.2 (3) |
C6—C5—H5 | 119.8 | O2—C10—C9 | 113.1 (3) |
C5—C4—C3 | 119.7 (3) | C12—C11—O2 | 109.6 (4) |
C5—C4—H4 | 120.1 | C12—C11—H11B | 109.7 |
C3—C4—H4 | 120.1 | O2—C11—H11B | 109.7 |
C2—C3—C4 | 120.7 (3) | C12—C11—H11A | 109.7 |
C2—C3—H3 | 119.7 | O2—C11—H11A | 109.7 |
C4—C3—H3 | 119.7 | H11B—C11—H11A | 108.2 |
C3—C2—C1 | 120.6 (3) | C11—C12—H12A | 109.5 |
C3—C2—H2 | 119.7 | C11—C12—H12C | 109.5 |
C1—C2—H2 | 119.7 | H12A—C12—H12C | 109.5 |
C2—C1—N2 | 119.7 (3) | C11—C12—H12B | 109.5 |
C2—C1—C6 | 117.9 (3) | H12A—C12—H12B | 109.5 |
N2—C1—C6 | 122.4 (3) | H12C—C12—H12B | 109.5 |
C8—C7—Cl1 | 112.2 (2) | O4—N3—O5 | 122.3 (3) |
C8—C7—H7B | 109.2 | O4—N3—C6 | 119.2 (3) |
Cl1—C7—H7B | 109.2 | O5—N3—C6 | 118.5 (3) |
C8—C7—H7A | 109.2 | N1—N2—C1 | 118.2 (2) |
Cl1—C7—H7A | 109.2 | N1—N2—H1 | 122 (2) |
H7B—C7—H7A | 107.9 | C1—N2—H1 | 119 (2) |
O3—C8—C9 | 123.3 (3) | C9—N1—N2 | 122.1 (2) |
O3—C8—C7 | 121.6 (3) | C10—O2—C11 | 117.5 (3) |
C9—C8—C7 | 115.1 (2) | | |
| | | |
C1—C6—C5—C4 | −0.6 (5) | N1—C9—C10—O1 | 19.7 (5) |
N3—C6—C5—C4 | 179.4 (3) | C8—C9—C10—O1 | −157.0 (3) |
C6—C5—C4—C3 | 1.2 (5) | N1—C9—C10—O2 | −155.0 (3) |
C5—C4—C3—C2 | −1.3 (5) | C8—C9—C10—O2 | 28.3 (4) |
C4—C3—C2—C1 | 0.8 (5) | C5—C6—N3—O4 | 172.3 (3) |
C3—C2—C1—N2 | −178.1 (3) | C1—C6—N3—O4 | −7.7 (5) |
C3—C2—C1—C6 | −0.2 (5) | C5—C6—N3—O5 | −8.9 (5) |
C5—C6—C1—C2 | 0.1 (4) | C1—C6—N3—O5 | 171.1 (3) |
N3—C6—C1—C2 | −179.9 (3) | C2—C1—N2—N1 | −0.5 (4) |
C5—C6—C1—N2 | 178.0 (3) | C6—C1—N2—N1 | −178.4 (3) |
N3—C6—C1—N2 | −2.1 (4) | C8—C9—N1—N2 | 176.9 (3) |
Cl1—C7—C8—O3 | 2.0 (4) | C10—C9—N1—N2 | −0.1 (4) |
Cl1—C7—C8—C9 | −175.3 (2) | C1—N2—N1—C9 | −179.8 (2) |
O3—C8—C9—N1 | −168.4 (3) | O1—C10—O2—C11 | 1.9 (5) |
C7—C8—C9—N1 | 8.8 (4) | C9—C10—O2—C11 | 176.4 (3) |
O3—C8—C9—C10 | 8.5 (5) | C12—C11—O2—C10 | 91.5 (5) |
C7—C8—C9—C10 | −174.2 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1···O4 | 0.83 (4) | 2.01 (4) | 2.613 (4) | 129 (3) |
N2—H1···O1 | 0.83 (4) | 2.06 (4) | 2.655 (3) | 128 (3) |
C5—H5···O3i | 0.93 | 2.57 | 3.227 (4) | 128 |
C12—H12B···O5ii | 0.96 | 2.69 | 3.482 (6) | 141 |
Symmetry codes: (i) x+2, y−1, z; (ii) x−2, y+1, z. |