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Acta Crystallogr Sect E Struct Rep Online. Jul 1, 2012; 68(Pt 7): o2133.
Published online Jun 20, 2012. doi:  10.1107/S1600536812026700
PMCID: PMC3393944
Di-tert-butyl 3,5-dimethyl-1H-pyrrole-2,4-dicarboxyl­ate
Zhao-Po Zhanga and Wei-Na Wua*
aDepartment of Physics and Chemistry, Henan Polytechnic University, Jiaozuo 454000, People’s Republic of China
Correspondence e-mail: wuwn08/at/hpu.edu.cn
Received May 15, 2012; Accepted June 13, 2012.
Abstract
In the title mol­ecule, C16H25NO4, the non-H atoms, except for the two tert-butyl groups, are roughly planar (r.m.s. deviation of the non-H atoms = 0.086 Å). In the crystal, mol­ecules are linked into inversion dimers by pairs of N—H(...)O hydrogen bonds, forming R 2 2(10) ring motifs.
Related literature  
For complexes of Schiff bases containing a pyrrole unit, see: Wu et al. (2003 [triangle]); Wang et al. (2008 [triangle]). For the synthesis of the title compound, see: Sun et al. (2003 [triangle]).
An external file that holds a picture, illustration, etc.
Object name is e-68-o2133-scheme1.jpg Object name is e-68-o2133-scheme1.jpg
Crystal data  
  • C16H25NO4
  • M r = 295.37
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-o2133-efi1.jpg
  • a = 5.8976 (10) Å
  • b = 11.511 (2) Å
  • c = 13.460 (2) Å
  • α = 103.956 (4)°
  • β = 90.078 (3)°
  • γ = 104.804 (3)°
  • V = 855.5 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 296 K
  • 0.21 × 0.19 × 0.16 mm
Data collection  
  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2007 [triangle]) T min = 0.983, T max = 0.987
  • 4496 measured reflections
  • 2989 independent reflections
  • 1704 reflections with I > 2σ(I)
  • R int = 0.023
Refinement  
  • R[F 2 > 2σ(F 2)] = 0.058
  • wR(F 2) = 0.150
  • S = 1.04
  • 2989 reflections
  • 191 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.27 e Å−3
  • Δρmin = −0.21 e Å−3
Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.
Table 1
Table 1
Hydrogen-bond geometry (Å, °)
Supplementary Material
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812026700/vm2177sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812026700/vm2177Isup2.hkl
Supplementary material file. DOI: 10.1107/S1600536812026700/vm2177Isup3.cml
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors are grateful for financial support by the Doctoral Foundation of Henan Polytechnic University (B2009–70 648364).
supplementary crystallographic information
Comment
Schiff bases containing pyrrole units have been extensively investigated due to their excellent coordination abilities (Wu et al., 2003; Wang et al., 2008). However, tert-butyl pyrrole-2-carboxylate derivatives are important intermediates to form 2-formyl pyrroles (Sun et al., 2003). As part of our studies on bis(pyrrol-2-yl-methyleneamine) ligands, the crystal structure of the title compound is reported here.
In the title molecule (Fig. 1), except for the two tert-butyl groups, the non-hydrogen atoms are situated in a fair plane (r.m.s. deviation of the non-hydrogen atoms being 0.2542 Å). In the crystal, the molecules are linked into a centrosymmetric dimer by two intermolecular N—H···O hydrogen bonds (Table 1), forming a R22(10) ring motif (Fig. 2).
Experimental
The di-tert-butyl 3,5-dimethyl-1H-pyrrole-2,4-dicarboxylate was prepared by a Knorr-type reaction from the condensation of tert-butyl acetoacetate and tert-butyl oximinoacetoacetate according to literature (Sun et al., 2003).
Refinement
All methyl H atoms were positioned geometrically (C—H = 0.96 Å) and refined as riding with Uiso(H) = 1.5Ueq. Atom H1A was positioned geometrically with the N1—H1A distance free to refine and Uiso(H1A) = 1.2Ueq(N1).
Figures
Fig. 1.
Fig. 1.
The molecular structure shown with 30% probability displacement ellipsoids.
Fig. 2.
Fig. 2.
The dimer of the title compounds formed via N—H···O hydrogen bonds shown as dashed lines. Unlabelled atoms are related with the labelled ones by symmetry operation -1 - x, -y, -z.
Crystal data
C16H25NO4Z = 2
Mr = 295.37F(000) = 320
Triclinic, P1Dx = 1.147 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.8976 (10) ÅCell parameters from 771 reflections
b = 11.511 (2) Åθ = 3.2–20.5°
c = 13.460 (2) ŵ = 0.08 mm1
α = 103.956 (4)°T = 296 K
β = 90.078 (3)°Plate, colorless
γ = 104.804 (3)°0.21 × 0.19 × 0.16 mm
V = 855.5 (3) Å3
Data collection
Bruker SMART CCD diffractometer2989 independent reflections
Radiation source: fine-focus sealed tube1704 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
[var phi] and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2007)h = −6→6
Tmin = 0.983, Tmax = 0.987k = −13→13
4496 measured reflectionsl = −16→13
Refinement
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.150H atoms treated by a mixture of independent and constrained refinement
S = 1.04w = 1/[σ2(Fo2) + (0.0557P)2 + 0.202P] where P = (Fo2 + 2Fc2)/3
2989 reflections(Δ/σ)max < 0.001
191 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = −0.21 e Å3
Special details
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)
xyzUiso*/Ueq
C1−0.2311 (4)0.1845 (2)−0.08222 (19)0.0471 (7)
C2−0.1610 (4)0.2579 (2)−0.14921 (19)0.0476 (7)
C3−0.3401 (5)0.2180 (2)−0.23018 (19)0.0478 (7)
C4−0.5147 (5)0.1215 (2)−0.2090 (2)0.0484 (7)
C50.0637 (5)0.3586 (3)−0.1403 (2)0.0673 (9)
H5A0.15270.3670−0.07810.101*
H5B0.02760.4356−0.13930.101*
H5C0.15400.3375−0.19800.101*
C6−0.7463 (5)0.0472 (3)−0.2626 (2)0.0691 (9)
H6A−0.8212−0.0121−0.22550.104*
H6B−0.72290.0045−0.33080.104*
H6C−0.84400.1015−0.26600.104*
C7−0.1316 (4)0.1787 (2)0.0145 (2)0.0479 (7)
C80.1962 (5)0.2870 (3)0.1451 (2)0.0537 (7)
C90.2769 (5)0.1727 (3)0.1469 (2)0.0726 (9)
H9A0.37210.15530.09030.109*
H9B0.14240.10320.14150.109*
H9C0.36740.18700.21010.109*
C100.0441 (5)0.3201 (3)0.2315 (2)0.0693 (9)
H10A−0.00050.39350.22740.104*
H10B0.13010.33510.29600.104*
H10C−0.09440.25290.22630.104*
C110.4029 (6)0.3960 (3)0.1429 (3)0.0819 (10)
H11A0.34690.46700.14170.123*
H11B0.48610.37540.08270.123*
H11C0.50670.41470.20300.123*
C12−0.3408 (5)0.2728 (3)−0.3174 (2)0.0549 (7)
C13−0.5671 (6)0.2464 (3)−0.4787 (2)0.0673 (9)
C14−0.3574 (7)0.2685 (4)−0.5428 (3)0.1043 (13)
H14A−0.31030.1930−0.56570.156*
H14B−0.22980.3317−0.50220.156*
H14C−0.39900.2948−0.60120.156*
C15−0.6498 (7)0.3616 (4)−0.4426 (3)0.1023 (13)
H15A−0.78270.3448−0.40230.153*
H15B−0.69430.3873−0.50090.153*
H15C−0.52520.4265−0.40170.153*
C16−0.7630 (8)0.1391 (4)−0.5360 (3)0.1329 (19)
H16A−0.89320.1267−0.49350.199*
H16B−0.70850.0654−0.55360.199*
H16C−0.81230.1567−0.59760.199*
N1−0.4459 (4)0.10303 (19)−0.12068 (16)0.0492 (6)
H1A−0.526 (2)0.0471 (17)−0.0913 (9)0.059*
O1−0.2209 (3)0.10146 (17)0.06093 (14)0.0565 (5)
O20.0654 (3)0.26788 (16)0.04613 (13)0.0594 (6)
O3−0.2064 (4)0.3672 (2)−0.32547 (15)0.0789 (7)
O4−0.5120 (4)0.20430 (18)−0.38930 (14)0.0728 (7)
Atomic displacement parameters (Å2)
U11U22U33U12U13U23
C10.0392 (15)0.0471 (16)0.0494 (16)0.0026 (13)−0.0034 (13)0.0109 (13)
C20.0431 (16)0.0459 (16)0.0501 (16)0.0040 (13)0.0011 (13)0.0133 (13)
C30.0487 (17)0.0433 (15)0.0484 (16)0.0059 (13)−0.0017 (13)0.0123 (12)
C40.0481 (17)0.0447 (16)0.0490 (16)0.0062 (13)−0.0060 (13)0.0117 (13)
C50.0580 (19)0.069 (2)0.066 (2)−0.0086 (16)−0.0064 (16)0.0271 (16)
C60.062 (2)0.065 (2)0.068 (2)−0.0084 (16)−0.0152 (16)0.0191 (16)
C70.0364 (15)0.0501 (16)0.0511 (16)0.0022 (13)−0.0015 (13)0.0109 (14)
C80.0435 (16)0.0598 (18)0.0503 (17)0.0019 (14)−0.0090 (13)0.0121 (14)
C90.056 (2)0.088 (2)0.078 (2)0.0266 (18)−0.0060 (16)0.0190 (18)
C100.068 (2)0.070 (2)0.064 (2)0.0160 (17)0.0038 (17)0.0075 (16)
C110.058 (2)0.089 (2)0.079 (2)−0.0151 (18)−0.0104 (17)0.0205 (18)
C120.0551 (18)0.0514 (18)0.0541 (17)0.0048 (15)−0.0033 (15)0.0152 (14)
C130.067 (2)0.075 (2)0.0572 (19)0.0036 (17)−0.0113 (17)0.0290 (16)
C140.103 (3)0.154 (4)0.063 (2)0.040 (3)0.009 (2)0.033 (2)
C150.105 (3)0.133 (4)0.092 (3)0.050 (3)0.004 (2)0.050 (2)
C160.137 (4)0.125 (3)0.107 (3)−0.041 (3)−0.073 (3)0.053 (3)
N10.0457 (14)0.0490 (13)0.0491 (13)0.0005 (11)−0.0029 (11)0.0181 (11)
O10.0495 (12)0.0582 (12)0.0572 (12)−0.0030 (9)−0.0060 (9)0.0240 (10)
O20.0486 (12)0.0636 (13)0.0566 (12)−0.0083 (10)−0.0105 (9)0.0220 (9)
O30.0853 (16)0.0726 (15)0.0676 (14)−0.0133 (13)−0.0132 (12)0.0327 (11)
O40.0795 (15)0.0684 (14)0.0620 (13)−0.0075 (11)−0.0240 (11)0.0292 (11)
Geometric parameters (Å, º)
C1—C21.375 (3)C9—H9C0.9600
C1—N11.381 (3)C10—H10A0.9600
C1—C71.450 (4)C10—H10B0.9600
C2—C31.422 (3)C10—H10C0.9600
C2—C51.504 (3)C11—H11A0.9600
C3—C41.394 (3)C11—H11B0.9600
C3—C121.462 (4)C11—H11C0.9600
C4—N11.337 (3)C12—O31.200 (3)
C4—C61.490 (3)C12—O41.342 (3)
C5—H5A0.9600C13—O41.466 (3)
C5—H5B0.9600C13—C151.502 (5)
C5—H5C0.9600C13—C161.505 (4)
C6—H6A0.9600C13—C141.512 (5)
C6—H6B0.9600C14—H14A0.9600
C6—H6C0.9600C14—H14B0.9600
C7—O11.220 (3)C14—H14C0.9600
C7—O21.328 (3)C15—H15A0.9600
C8—O21.479 (3)C15—H15B0.9600
C8—C101.506 (4)C15—H15C0.9600
C8—C91.514 (4)C16—H16A0.9600
C8—C111.516 (4)C16—H16B0.9600
C9—H9A0.9600C16—H16C0.9600
C9—H9B0.9600N1—H1A0.873 (17)
C2—C1—N1107.7 (2)C8—C10—H10C109.5
C2—C1—C7134.1 (2)H10A—C10—H10C109.5
N1—C1—C7118.2 (2)H10B—C10—H10C109.5
C1—C2—C3106.5 (2)C8—C11—H11A109.5
C1—C2—C5126.9 (2)C8—C11—H11B109.5
C3—C2—C5126.6 (2)H11A—C11—H11B109.5
C4—C3—C2107.8 (2)C8—C11—H11C109.5
C4—C3—C12127.0 (2)H11A—C11—H11C109.5
C2—C3—C12125.2 (2)H11B—C11—H11C109.5
N1—C4—C3107.2 (2)O3—C12—O4123.1 (3)
N1—C4—C6120.3 (2)O3—C12—C3125.1 (3)
C3—C4—C6132.5 (2)O4—C12—C3111.8 (2)
C2—C5—H5A109.5O4—C13—C15108.9 (3)
C2—C5—H5B109.5O4—C13—C16102.4 (2)
H5A—C5—H5B109.5C15—C13—C16111.3 (3)
C2—C5—H5C109.5O4—C13—C14111.3 (3)
H5A—C5—H5C109.5C15—C13—C14111.4 (3)
H5B—C5—H5C109.5C16—C13—C14111.2 (3)
C4—C6—H6A109.5C13—C14—H14A109.5
C4—C6—H6B109.5C13—C14—H14B109.5
H6A—C6—H6B109.5H14A—C14—H14B109.5
C4—C6—H6C109.5C13—C14—H14C109.5
H6A—C6—H6C109.5H14A—C14—H14C109.5
H6B—C6—H6C109.5H14B—C14—H14C109.5
O1—C7—O2124.6 (2)C13—C15—H15A109.5
O1—C7—C1123.5 (2)C13—C15—H15B109.5
O2—C7—C1111.9 (2)H15A—C15—H15B109.5
O2—C8—C10109.2 (2)C13—C15—H15C109.5
O2—C8—C9109.9 (2)H15A—C15—H15C109.5
C10—C8—C9112.8 (2)H15B—C15—H15C109.5
O2—C8—C11101.8 (2)C13—C16—H16A109.5
C10—C8—C11111.4 (2)C13—C16—H16B109.5
C9—C8—C11111.2 (3)H16A—C16—H16B109.5
C8—C9—H9A109.5C13—C16—H16C109.5
C8—C9—H9B109.5H16A—C16—H16C109.5
H9A—C9—H9B109.5H16B—C16—H16C109.5
C8—C9—H9C109.5C4—N1—C1110.9 (2)
H9A—C9—H9C109.5C4—N1—H1A124.5 (8)
H9B—C9—H9C109.5C1—N1—H1A124.6 (8)
C8—C10—H10A109.5C7—O2—C8122.9 (2)
C8—C10—H10B109.5C12—O4—C13122.3 (2)
H10A—C10—H10B109.5
N1—C1—C2—C3−0.3 (3)C2—C3—C12—O3−9.7 (5)
C7—C1—C2—C3−179.0 (3)C4—C3—C12—O4−12.0 (4)
N1—C1—C2—C5−178.9 (2)C2—C3—C12—O4170.3 (2)
C7—C1—C2—C52.5 (5)C3—C4—N1—C10.2 (3)
C1—C2—C3—C40.4 (3)C6—C4—N1—C1−177.7 (2)
C5—C2—C3—C4179.0 (3)C2—C1—N1—C40.1 (3)
C1—C2—C3—C12178.5 (3)C7—C1—N1—C4179.0 (2)
C5—C2—C3—C12−3.0 (4)O1—C7—O2—C8−2.5 (4)
C2—C3—C4—N1−0.3 (3)C1—C7—O2—C8176.8 (2)
C12—C3—C4—N1−178.3 (3)C10—C8—O2—C7−63.0 (3)
C2—C3—C4—C6177.1 (3)C9—C8—O2—C761.2 (3)
C12—C3—C4—C6−0.9 (5)C11—C8—O2—C7179.2 (2)
C2—C1—C7—O1−177.3 (3)O3—C12—O4—C13−7.2 (5)
N1—C1—C7—O14.1 (4)C3—C12—O4—C13172.8 (3)
C2—C1—C7—O23.3 (4)C15—C13—O4—C12−63.2 (4)
N1—C1—C7—O2−175.2 (2)C16—C13—O4—C12178.9 (3)
C4—C3—C12—O3168.0 (3)C14—C13—O4—C1260.0 (4)
Hydrogen-bond geometry (Å, º)
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.873 (17)2.087 (18)2.933 (3)163.2 (12)
Symmetry code: (i) −x−1, −y, −z.
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: VM2177).
References
  • Bruker (2007). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA .
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sun, L., Liang, C., Shirazian, S., Zhou, Y., Miller, T., Cui, J., Fukuda, J. Y., Chu, J.-Y., Nematalla, A., Wang, X., Chen, H., Sistla, A., Luu, T. C., Tang, F., Wei, J. & Tang, C. (2003). J. Med. Chem. 46, 1116–1119. [PubMed]
  • Wang, Y., Yang, Z.-Y. & Chen, Z.-N. (2008). Bioorg. Med. Chem. Lett. 18, 298–303. [PubMed]
  • Wu, Z. K., Chen, Q. Q., Xiong, S. X., Xin, B., Zhao, Z. W., Jiang, L. J. & Ma, J. S. (2003). Angew. Chem. Int. Ed. 42, 3271–3274. [PubMed]
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