Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047186/hb2539sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047186/hb2539Isup2.hkl |
CCDC reference: 664217
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.006 Å
- R factor = 0.075
- wR factor = 0.177
- Data-to-parameter ratio = 14.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT230_ALERT_2_C Hirshfeld Test Diff for O4 - C11 .. 5.29 su PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 6 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C9 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C8
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 4 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 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
tert-Butyl-3-oxobutyrate (20 mmol) in acetic acid (4 ml) was cooled in an ice bath to about 278 K. Sodium nitrite (20 mmol) was added over 45 minutes keeping the temperature under 288 K. The mixture was stirred for 30 minutes and then left standing for 3 h, yielding tert-buty-2-hydroximino-3-oxobutyarate. Ethyl-3-oxobutyrate (20 mmol), zinc dust (50 g) and the crude tert-buty-2-hydroximino-3-oxobutyarate in acetic acid (6 ml) were stirred at 343 K for 1 hr·The reaction mixture was poured into 200 ml water and the filtrate was collected to obtain the title compound. Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of a methanol solution.
The H atoms were geometrically placed (C—H = 0.96 Å N—H = 0.86 Å) and refined as riding with Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(methyl C).
As part of our owning studies of pyrrole derivatives (Sun et al., 2002), we report here the crystal structure of the title compound, (I). All the non-hydrogen atoms except C12 lie on a crystallographic mirror plane (Fig. 1).
An N—H···O hydrogen bond (Table 1) helps to establish the crystal packing in (I). A short intramolecular C—H···O contact also occurs, based on the geometrically positioned H9A atom, which lies on the mirror plane.
For background, see: Sun et al. (2002).
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C14H21NO4 | F(000) = 576 |
Mr = 267.32 | Dx = 1.203 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2y | Cell parameters from 25 reflections |
a = 18.570 (4) Å | θ = 9–13° |
b = 7.1420 (14) Å | µ = 0.09 mm−1 |
c = 12.431 (3) Å | T = 293 K |
β = 116.46 (3)° | Block, white |
V = 1476.0 (5) Å3 | 0.40 × 0.10 × 0.10 mm |
Z = 4 |
Enraf–Nonius CAD-4 diffractometer | 920 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 26.0°, θmin = 1.8° |
ω/2θ scans | h = −22→20 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→8 |
Tmin = 0.966, Tmax = 0.991 | l = 0→15 |
1578 measured reflections | 3 standard reflections every 200 reflections |
1578 independent reflections | intensity decay: none |
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)] = 0.075 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.177 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.05P)2 + 2P] where P = (Fo2 + 2Fc2)/3 |
1578 reflections | (Δ/σ)max = 0.029 |
113 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C14H21NO4 | V = 1476.0 (5) Å3 |
Mr = 267.32 | Z = 4 |
Monoclinic, C2/m | Mo Kα radiation |
a = 18.570 (4) Å | µ = 0.09 mm−1 |
b = 7.1420 (14) Å | T = 293 K |
c = 12.431 (3) Å | 0.40 × 0.10 × 0.10 mm |
β = 116.46 (3)° |
Enraf–Nonius CAD-4 diffractometer | 920 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.000 |
Tmin = 0.966, Tmax = 0.991 | 3 standard reflections every 200 reflections |
1578 measured reflections | intensity decay: none |
1578 independent reflections |
R[F2 > 2σ(F2)] = 0.075 | 0 restraints |
wR(F2) = 0.177 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.30 e Å−3 |
1578 reflections | Δρmin = −0.26 e Å−3 |
113 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 | 0.1275 (2) | 0.0000 | 0.0227 (3) | 0.0429 (9) | |
H1 | 0.0763 | 0.0000 | −0.0214 | 0.051* | |
O1 | 0.32742 (17) | 0.0000 | −0.0354 (3) | 0.0565 (9) | |
O2 | 0.39992 (18) | 0.0000 | 0.1619 (3) | 0.0745 (12) | |
O3 | 0.04155 (18) | 0.0000 | 0.1558 (3) | 0.0615 (10) | |
O4 | 0.15571 (17) | 0.0000 | 0.3287 (2) | 0.0527 (9) | |
C1 | 0.3784 (3) | 0.0000 | −0.1789 (4) | 0.0621 (14) | |
H1A | 0.4260 | 0.0000 | −0.1911 | 0.093* | |
H1B | 0.3471 | −0.1098 | −0.2152 | 0.093* | |
C2 | 0.4002 (2) | 0.0000 | −0.0504 (4) | 0.0473 (11) | |
H2A | 0.4323 | −0.1087 | −0.0142 | 0.057* | |
C3 | 0.3360 (3) | 0.0000 | 0.0753 (4) | 0.0480 (11) | |
C4 | 0.2571 (2) | 0.0000 | 0.0810 (4) | 0.0449 (11) | |
C5 | 0.2468 (2) | 0.0000 | 0.1835 (4) | 0.0487 (11) | |
C6 | 0.1645 (2) | 0.0000 | 0.1481 (4) | 0.0430 (10) | |
C7 | 0.1821 (2) | 0.0000 | −0.0197 (4) | 0.0420 (10) | |
C8 | 0.1544 (3) | 0.0000 | −0.1516 (4) | 0.0532 (12) | |
H8A | 0.0969 | 0.0000 | −0.1966 | 0.080* | |
H8B | 0.1760 | 0.1098 | −0.1712 | 0.080* | |
C9 | 0.3123 (3) | 0.0000 | 0.3113 (4) | 0.0628 (14) | |
H9A | 0.3645 | 0.0000 | 0.3130 | 0.094* | |
H9B | 0.3066 | 0.1098 | 0.3514 | 0.094* | |
C10 | 0.1142 (3) | 0.0000 | 0.2074 (4) | 0.0475 (12) | |
C12 | 0.0679 (2) | 0.1808 (6) | 0.3897 (3) | 0.0838 (13) | |
H12A | 0.1018 | 0.2865 | 0.3976 | 0.126* | |
H12B | 0.0483 | 0.1882 | 0.4492 | 0.126* | |
H12C | 0.0232 | 0.1809 | 0.3110 | 0.126* | |
C13 | 0.1879 (3) | 0.0000 | 0.5340 (4) | 0.0783 (18) | |
H13A | 0.2211 | −0.1066 | 0.5408 | 0.117* | |
H13C | 0.1698 | 0.0000 | 0.5952 | 0.117* | |
C11 | 0.1162 (3) | 0.0000 | 0.4075 (4) | 0.0581 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0415 (18) | 0.042 (2) | 0.0424 (19) | 0.000 | 0.0165 (16) | 0.000 |
O1 | 0.0466 (17) | 0.060 (2) | 0.065 (2) | 0.000 | 0.0271 (16) | 0.000 |
O2 | 0.0435 (18) | 0.110 (3) | 0.058 (2) | 0.000 | 0.0110 (16) | 0.000 |
O3 | 0.0490 (18) | 0.079 (3) | 0.0529 (18) | 0.000 | 0.0199 (15) | 0.000 |
O4 | 0.0554 (18) | 0.062 (2) | 0.0473 (17) | 0.000 | 0.0288 (15) | 0.000 |
C1 | 0.075 (3) | 0.044 (3) | 0.075 (3) | 0.000 | 0.041 (3) | 0.000 |
C2 | 0.052 (2) | 0.034 (3) | 0.063 (3) | 0.000 | 0.032 (2) | 0.000 |
C3 | 0.049 (3) | 0.038 (3) | 0.057 (3) | 0.000 | 0.023 (2) | 0.000 |
C4 | 0.047 (2) | 0.037 (3) | 0.052 (3) | 0.000 | 0.023 (2) | 0.000 |
C5 | 0.044 (2) | 0.046 (3) | 0.053 (3) | 0.000 | 0.018 (2) | 0.000 |
C6 | 0.045 (2) | 0.028 (3) | 0.049 (2) | 0.000 | 0.015 (2) | 0.000 |
C7 | 0.046 (2) | 0.032 (3) | 0.044 (2) | 0.000 | 0.017 (2) | 0.000 |
C8 | 0.056 (3) | 0.050 (3) | 0.055 (3) | 0.000 | 0.025 (2) | 0.000 |
C9 | 0.062 (3) | 0.064 (4) | 0.051 (3) | 0.000 | 0.016 (2) | 0.000 |
C10 | 0.045 (2) | 0.054 (3) | 0.039 (2) | 0.000 | 0.014 (2) | 0.000 |
C12 | 0.085 (3) | 0.087 (3) | 0.083 (3) | 0.008 (3) | 0.041 (2) | −0.006 (3) |
C13 | 0.085 (4) | 0.098 (5) | 0.050 (3) | 0.000 | 0.028 (3) | 0.000 |
C11 | 0.059 (3) | 0.057 (4) | 0.056 (3) | 0.000 | 0.024 (2) | 0.000 |
N1—C7 | 1.335 (5) | C5—C6 | 1.389 (6) |
N1—C6 | 1.395 (5) | C5—C9 | 1.511 (6) |
N1—H1 | 0.8600 | C6—C10 | 1.425 (6) |
O1—C3 | 1.312 (5) | C7—C8 | 1.483 (5) |
O1—C2 | 1.444 (5) | C8—H8A | 0.9601 |
O2—C3 | 1.195 (5) | C8—H8B | 0.9600 |
O3—C10 | 1.208 (5) | C9—H9A | 0.9600 |
O4—C10 | 1.353 (5) | C9—H9B | 0.9600 |
O4—C11 | 1.463 (5) | C12—C11 | 1.531 (5) |
C1—C2 | 1.464 (6) | C12—H12A | 0.9600 |
C1—H1A | 0.9600 | C12—H12B | 0.9600 |
C1—H1B | 0.9601 | C12—H12C | 0.9600 |
C2—H2A | 0.9600 | C13—C11 | 1.542 (6) |
C3—C4 | 1.500 (6) | C13—H13A | 0.9601 |
C4—C5 | 1.370 (6) | C13—H13C | 0.9589 |
C4—C7 | 1.397 (5) | C11—C12i | 1.531 (5) |
C7—N1—C6 | 111.0 (3) | C4—C7—C8 | 135.0 (4) |
C7—N1—H1 | 124.5 | C7—C8—H8A | 113.1 |
C6—N1—H1 | 124.5 | C7—C8—H8B | 107.7 |
C3—O1—C2 | 116.8 (3) | H8A—C8—H8B | 109.5 |
C10—O4—C11 | 122.7 (3) | C5—C9—H9A | 110.8 |
C2—C1—H1A | 110.2 | C5—C9—H9B | 108.8 |
C2—C1—H1B | 109.1 | H9A—C9—H9B | 109.5 |
H1A—C1—H1B | 109.5 | O3—C10—O4 | 122.6 (4) |
O1—C2—C1 | 108.8 (4) | O3—C10—C6 | 124.0 (4) |
O1—C2—H2A | 111.2 | O4—C10—C6 | 113.4 (4) |
C1—C2—H2A | 108.8 | C11—C12—H12A | 109.5 |
O2—C3—O1 | 123.5 (4) | C11—C12—H12B | 109.5 |
O2—C3—C4 | 123.8 (4) | H12A—C12—H12B | 109.5 |
O1—C3—C4 | 112.6 (4) | C11—C12—H12C | 109.5 |
C5—C4—C7 | 109.7 (4) | H12A—C12—H12C | 109.5 |
C5—C4—C3 | 126.0 (4) | H12B—C12—H12C | 109.5 |
C7—C4—C3 | 124.2 (4) | C11—C13—H13A | 108.6 |
C4—C5—C6 | 107.1 (4) | C11—C13—H13C | 111.1 |
C4—C5—C9 | 126.7 (4) | H13A—C13—H13C | 111.7 |
C6—C5—C9 | 126.2 (4) | O4—C11—C12i | 109.8 (3) |
N1—C6—C5 | 106.2 (4) | O4—C11—C12 | 109.8 (3) |
N1—C6—C10 | 117.9 (4) | C12i—C11—C12 | 115.0 (4) |
C5—C6—C10 | 135.9 (4) | O4—C11—C13 | 102.7 (4) |
N1—C7—C4 | 105.9 (3) | C12i—C11—C13 | 109.4 (3) |
N1—C7—C8 | 119.1 (4) | C12—C11—C13 | 109.4 (3) |
C3—O1—C2—C1 | 180.0 | C9—C5—C6—C10 | 0.0 |
C2—O1—C3—O2 | 0.0 | C6—N1—C7—C4 | 0.0 |
C2—O1—C3—C4 | 180.0 | C6—N1—C7—C8 | 180.0 |
O2—C3—C4—C5 | 0.0 | C5—C4—C7—N1 | 0.0 |
O1—C3—C4—C5 | 180.0 | C3—C4—C7—N1 | 180.0 |
O2—C3—C4—C7 | 180.0 | C5—C4—C7—C8 | 180.0 |
O1—C3—C4—C7 | 0.0 | C3—C4—C7—C8 | 0.0 |
C7—C4—C5—C6 | 0.0 | C11—O4—C10—O3 | 0.0 |
C3—C4—C5—C6 | 180.0 | C11—O4—C10—C6 | 180.0 |
C7—C4—C5—C9 | 180.0 | N1—C6—C10—O3 | 0.0 |
C3—C4—C5—C9 | 0.0 | C5—C6—C10—O3 | 180.0 |
C7—N1—C6—C5 | 0.0 | N1—C6—C10—O4 | 180.0 |
C7—N1—C6—C10 | 180.0 | C5—C6—C10—O4 | 0.0 |
C4—C5—C6—N1 | 0.0 | C10—O4—C11—C12i | 63.7 (3) |
C9—C5—C6—N1 | 180.0 | C10—O4—C11—C12 | −63.7 (3) |
C4—C5—C6—C10 | 180.0 | C10—O4—C11—C13 | 180.0 |
Symmetry code: (i) x, −y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3ii | 0.86 | 2.08 | 2.928 (5) | 169 |
C9—H9A···O2 | 0.96 | 2.25 | 2.965 (7) | 131 |
Symmetry code: (ii) −x, y, −z. |
Experimental details
Crystal data | |
Chemical formula | C14H21NO4 |
Mr | 267.32 |
Crystal system, space group | Monoclinic, C2/m |
Temperature (K) | 293 |
a, b, c (Å) | 18.570 (4), 7.1420 (14), 12.431 (3) |
β (°) | 116.46 (3) |
V (Å3) | 1476.0 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.40 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.966, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1578, 1578, 920 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.075, 0.177, 1.11 |
No. of reflections | 1578 |
No. of parameters | 113 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.26 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3i | 0.86 | 2.08 | 2.928 (5) | 169 |
C9—H9A···O2 | 0.96 | 2.25 | 2.965 (7) | 131 |
Symmetry code: (i) −x, y, −z. |
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As part of our owning studies of pyrrole derivatives (Sun et al., 2002), we report here the crystal structure of the title compound, (I). All the non-hydrogen atoms except C12 lie on a crystallographic mirror plane (Fig. 1).
An N—H···O hydrogen bond (Table 1) helps to establish the crystal packing in (I). A short intramolecular C—H···O contact also occurs, based on the geometrically positioned H9A atom, which lies on the mirror plane.