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In the title compound, C14H21NO4, all the non-H atoms, except for one methyl C atom, lie on a crystallographic mirror plane. An N—H...O hydrogen bond helps to consolidate the crystal packing. A short intra­molecular C—H...O contact also occurs.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047186/hb2539sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047186/hb2539Isup2.hkl
Contains datablock I

CCDC reference: 664217

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](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

Comment top

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.

Related literature top

For background, see: Sun et al. (2002).

Experimental top

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.

Refinement top

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).

Structure description top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level (arbitrary spheres for the H atoms). The intramolecular C9—H9A···O2 contact is indicated by a dashed line. C12A is generated by the symmetry operation (x, -y, z).
2-tert-Butyl 4-ethyl 3,5-dimethyl-1H-pyrrole-2,4-dicarboxylate top
Crystal data top
C14H21NO4F(000) = 576
Mr = 267.32Dx = 1.203 Mg m3
Monoclinic, C2/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yCell parameters from 25 reflections
a = 18.570 (4) Åθ = 9–13°
b = 7.1420 (14) ŵ = 0.09 mm1
c = 12.431 (3) ÅT = 293 K
β = 116.46 (3)°Block, white
V = 1476.0 (5) Å30.40 × 0.10 × 0.10 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer
920 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.000
Graphite monochromatorθmax = 26.0°, θmin = 1.8°
ω/2θ scansh = 2220
Absorption correction: ψ scan
(North et al., 1968)
k = 08
Tmin = 0.966, Tmax = 0.991l = 015
1578 measured reflections3 standard reflections every 200 reflections
1578 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.075Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.177H-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 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C14H21NO4V = 1476.0 (5) Å3
Mr = 267.32Z = 4
Monoclinic, C2/mMo Kα radiation
a = 18.570 (4) ŵ = 0.09 mm1
b = 7.1420 (14) ÅT = 293 K
c = 12.431 (3) Å0.40 × 0.10 × 0.10 mm
β = 116.46 (3)°
Data collection top
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 = 0.9913 standard reflections every 200 reflections
1578 measured reflections intensity decay: none
1578 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0750 restraints
wR(F2) = 0.177H-atom parameters constrained
S = 1.11Δρmax = 0.30 e Å3
1578 reflectionsΔρmin = 0.26 e Å3
113 parameters
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
xyzUiso*/Ueq
N10.1275 (2)0.00000.0227 (3)0.0429 (9)
H10.07630.00000.02140.051*
O10.32742 (17)0.00000.0354 (3)0.0565 (9)
O20.39992 (18)0.00000.1619 (3)0.0745 (12)
O30.04155 (18)0.00000.1558 (3)0.0615 (10)
O40.15571 (17)0.00000.3287 (2)0.0527 (9)
C10.3784 (3)0.00000.1789 (4)0.0621 (14)
H1A0.42600.00000.19110.093*
H1B0.34710.10980.21520.093*
C20.4002 (2)0.00000.0504 (4)0.0473 (11)
H2A0.43230.10870.01420.057*
C30.3360 (3)0.00000.0753 (4)0.0480 (11)
C40.2571 (2)0.00000.0810 (4)0.0449 (11)
C50.2468 (2)0.00000.1835 (4)0.0487 (11)
C60.1645 (2)0.00000.1481 (4)0.0430 (10)
C70.1821 (2)0.00000.0197 (4)0.0420 (10)
C80.1544 (3)0.00000.1516 (4)0.0532 (12)
H8A0.09690.00000.19660.080*
H8B0.17600.10980.17120.080*
C90.3123 (3)0.00000.3113 (4)0.0628 (14)
H9A0.36450.00000.31300.094*
H9B0.30660.10980.35140.094*
C100.1142 (3)0.00000.2074 (4)0.0475 (12)
C120.0679 (2)0.1808 (6)0.3897 (3)0.0838 (13)
H12A0.10180.28650.39760.126*
H12B0.04830.18820.44920.126*
H12C0.02320.18090.31100.126*
C130.1879 (3)0.00000.5340 (4)0.0783 (18)
H13A0.22110.10660.54080.117*
H13C0.16980.00000.59520.117*
C110.1162 (3)0.00000.4075 (4)0.0581 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0415 (18)0.042 (2)0.0424 (19)0.0000.0165 (16)0.000
O10.0466 (17)0.060 (2)0.065 (2)0.0000.0271 (16)0.000
O20.0435 (18)0.110 (3)0.058 (2)0.0000.0110 (16)0.000
O30.0490 (18)0.079 (3)0.0529 (18)0.0000.0199 (15)0.000
O40.0554 (18)0.062 (2)0.0473 (17)0.0000.0288 (15)0.000
C10.075 (3)0.044 (3)0.075 (3)0.0000.041 (3)0.000
C20.052 (2)0.034 (3)0.063 (3)0.0000.032 (2)0.000
C30.049 (3)0.038 (3)0.057 (3)0.0000.023 (2)0.000
C40.047 (2)0.037 (3)0.052 (3)0.0000.023 (2)0.000
C50.044 (2)0.046 (3)0.053 (3)0.0000.018 (2)0.000
C60.045 (2)0.028 (3)0.049 (2)0.0000.015 (2)0.000
C70.046 (2)0.032 (3)0.044 (2)0.0000.017 (2)0.000
C80.056 (3)0.050 (3)0.055 (3)0.0000.025 (2)0.000
C90.062 (3)0.064 (4)0.051 (3)0.0000.016 (2)0.000
C100.045 (2)0.054 (3)0.039 (2)0.0000.014 (2)0.000
C120.085 (3)0.087 (3)0.083 (3)0.008 (3)0.041 (2)0.006 (3)
C130.085 (4)0.098 (5)0.050 (3)0.0000.028 (3)0.000
C110.059 (3)0.057 (4)0.056 (3)0.0000.024 (2)0.000
Geometric parameters (Å, º) top
N1—C71.335 (5)C5—C61.389 (6)
N1—C61.395 (5)C5—C91.511 (6)
N1—H10.8600C6—C101.425 (6)
O1—C31.312 (5)C7—C81.483 (5)
O1—C21.444 (5)C8—H8A0.9601
O2—C31.195 (5)C8—H8B0.9600
O3—C101.208 (5)C9—H9A0.9600
O4—C101.353 (5)C9—H9B0.9600
O4—C111.463 (5)C12—C111.531 (5)
C1—C21.464 (6)C12—H12A0.9600
C1—H1A0.9600C12—H12B0.9600
C1—H1B0.9601C12—H12C0.9600
C2—H2A0.9600C13—C111.542 (6)
C3—C41.500 (6)C13—H13A0.9601
C4—C51.370 (6)C13—H13C0.9589
C4—C71.397 (5)C11—C12i1.531 (5)
C7—N1—C6111.0 (3)C4—C7—C8135.0 (4)
C7—N1—H1124.5C7—C8—H8A113.1
C6—N1—H1124.5C7—C8—H8B107.7
C3—O1—C2116.8 (3)H8A—C8—H8B109.5
C10—O4—C11122.7 (3)C5—C9—H9A110.8
C2—C1—H1A110.2C5—C9—H9B108.8
C2—C1—H1B109.1H9A—C9—H9B109.5
H1A—C1—H1B109.5O3—C10—O4122.6 (4)
O1—C2—C1108.8 (4)O3—C10—C6124.0 (4)
O1—C2—H2A111.2O4—C10—C6113.4 (4)
C1—C2—H2A108.8C11—C12—H12A109.5
O2—C3—O1123.5 (4)C11—C12—H12B109.5
O2—C3—C4123.8 (4)H12A—C12—H12B109.5
O1—C3—C4112.6 (4)C11—C12—H12C109.5
C5—C4—C7109.7 (4)H12A—C12—H12C109.5
C5—C4—C3126.0 (4)H12B—C12—H12C109.5
C7—C4—C3124.2 (4)C11—C13—H13A108.6
C4—C5—C6107.1 (4)C11—C13—H13C111.1
C4—C5—C9126.7 (4)H13A—C13—H13C111.7
C6—C5—C9126.2 (4)O4—C11—C12i109.8 (3)
N1—C6—C5106.2 (4)O4—C11—C12109.8 (3)
N1—C6—C10117.9 (4)C12i—C11—C12115.0 (4)
C5—C6—C10135.9 (4)O4—C11—C13102.7 (4)
N1—C7—C4105.9 (3)C12i—C11—C13109.4 (3)
N1—C7—C8119.1 (4)C12—C11—C13109.4 (3)
C3—O1—C2—C1180.0C9—C5—C6—C100.0
C2—O1—C3—O20.0C6—N1—C7—C40.0
C2—O1—C3—C4180.0C6—N1—C7—C8180.0
O2—C3—C4—C50.0C5—C4—C7—N10.0
O1—C3—C4—C5180.0C3—C4—C7—N1180.0
O2—C3—C4—C7180.0C5—C4—C7—C8180.0
O1—C3—C4—C70.0C3—C4—C7—C80.0
C7—C4—C5—C60.0C11—O4—C10—O30.0
C3—C4—C5—C6180.0C11—O4—C10—C6180.0
C7—C4—C5—C9180.0N1—C6—C10—O30.0
C3—C4—C5—C90.0C5—C6—C10—O3180.0
C7—N1—C6—C50.0N1—C6—C10—O4180.0
C7—N1—C6—C10180.0C5—C6—C10—O40.0
C4—C5—C6—N10.0C10—O4—C11—C12i63.7 (3)
C9—C5—C6—N1180.0C10—O4—C11—C1263.7 (3)
C4—C5—C6—C10180.0C10—O4—C11—C13180.0
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O3ii0.862.082.928 (5)169
C9—H9A···O20.962.252.965 (7)131
Symmetry code: (ii) x, y, z.

Experimental details

Crystal data
Chemical formulaC14H21NO4
Mr267.32
Crystal system, space groupMonoclinic, C2/m
Temperature (K)293
a, b, c (Å)18.570 (4), 7.1420 (14), 12.431 (3)
β (°) 116.46 (3)
V3)1476.0 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.40 × 0.10 × 0.10
Data collection
DiffractometerEnraf–Nonius CAD-4
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.966, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
1578, 1578, 920
Rint0.000
(sin θ/λ)max1)0.616
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.075, 0.177, 1.11
No. of reflections1578
No. of parameters113
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O3i0.862.082.928 (5)169
C9—H9A···O20.962.252.965 (7)131
Symmetry code: (i) x, y, z.
 

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