PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. Jun 1, 2012; 68(Pt 6): o1697.
Published online May 12, 2012. doi:  10.1107/S1600536812020120
PMCID: PMC3379292
2-tert-Butyl 4-methyl 3,5-dimethyl-1H-pyrrole-2,4-dicarboxyl­ate
Hong-Xin Caia* and Zhao-Po Zhanga
aDepartment of Physics and Chemistry, Henan Polytechnic University, Jiaozuo 454000, People’s Republic of China
Correspondence e-mail: me2001/at/hpu.edu.cn
Received April 8, 2012; Accepted May 4, 2012.
Abstract
In the title mol­ecule, C13H19NO4, except for two C atoms of the tert-butyl group, the non-H atoms are almost coplanar (r.m.s. deviation = 0.2542 Å). In the crystal, mol­ecules are linked into centrosymmetric dimers by two inter­molecular N—H(...)O hydrogen bonds, forming an R 2 2(10) ring motif.
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-o1697-scheme1.jpg Object name is e-68-o1697-scheme1.jpg
Crystal data  
  • C13H19NO4
  • M r = 253.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-o1697-efi3.jpg
  • a = 11.788 (4) Å
  • b = 17.045 (6) Å
  • c = 7.229 (2) Å
  • β = 106.420 (7)°
  • V = 1393.2 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 296 K
  • 0.19 × 0.18 × 0.16 mm
Data collection  
  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2007 [triangle]) T min = 0.983, T max = 0.986
  • 7149 measured reflections
  • 2458 independent reflections
  • 1334 reflections with I > 2σ(I)
  • R int = 0.050
Refinement  
  • R[F 2 > 2σ(F 2)] = 0.071
  • wR(F 2) = 0.250
  • S = 1.02
  • 2458 reflections
  • 163 parameters
  • H-atom parameters constrained
  • Δρmax = 0.28 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/S1600536812020120/vm2170sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812020120/vm2170Isup2.hkl
Supplementary material file. DOI: 10.1107/S1600536812020120/vm2170Isup3.cml
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors are grateful for financial support from the Doctoral Foundation of Henan Polytechnic University (grant No. 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). 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 C12 and C13 atoms of the tert-butyl, the non-hydrogen atoms are almost coplanar (r.m.s. deviation of the non-hydrogen atoms being 0.2542 Å). In the crystal, the molecules are linked into centrosymmetric dimers by two intermolecular N—H···O hydrogen bonds (Table 1), forming a R22(10) ring motif (Fig. 2).
Experimental
The 2-tert-butyl 4-methyl 3,5-dimethyl-1H-pyrrole-2,4-dicarboxylate was prepared by a Knorr-type reaction from the condensation of methyl acetoacetate and tert-butyl oximinoacetoacetate according to a literature method (Sun et al., 2003).
Refinement
The H atoms were positioned geometrically (N—H = 0.86 Å, C—H = 0.96 Å) and refined as riding with Uiso(H) =1.2Ueq(N) or 1.5Ueq(methyl C).
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 the dashed lines. Unlabelled atoms are related with the labelled ones by symmetry operation (-x, 1/2 - y, 1/2 + z).
Crystal data
C13H19NO4F(000) = 544
Mr = 253.29Dx = 1.208 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1135 reflections
a = 11.788 (4) Åθ = 3.0–21.5°
b = 17.045 (6) ŵ = 0.09 mm1
c = 7.229 (2) ÅT = 296 K
β = 106.420 (7)°Plate, colorless
V = 1393.2 (8) Å30.19 × 0.18 × 0.16 mm
Z = 4
Data collection
Bruker SMART CCD diffractometer2458 independent reflections
Radiation source: fine-focus sealed tube1334 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.050
[var phi] and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2007)h = −13→14
Tmin = 0.983, Tmax = 0.986k = −19→20
7149 measured reflectionsl = −8→7
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)] = 0.071Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.250H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.1445P)2] where P = (Fo2 + 2Fc2)/3
2458 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.28 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
C11.1539 (4)0.4652 (3)1.0373 (8)0.1274 (19)
H1B1.09610.50631.01930.191*
H1C1.19530.46960.94090.191*
H1D1.20910.46991.16300.191*
C21.1615 (3)0.3246 (2)1.0408 (5)0.0768 (11)
C31.0936 (3)0.25230 (19)1.0199 (4)0.0587 (9)
C40.9687 (3)0.24090 (18)0.9753 (4)0.0554 (8)
C50.9521 (2)0.16057 (19)0.9724 (4)0.0586 (9)
C61.1478 (3)0.1795 (2)1.0403 (5)0.0657 (9)
C70.8755 (3)0.30226 (19)0.9401 (5)0.0692 (10)
H7A0.79920.27780.91380.104*
H7B0.87880.33370.83150.104*
H7C0.88810.33501.05210.104*
C81.2746 (3)0.1548 (3)1.0879 (7)0.0978 (14)
H8A1.27920.09861.08970.147*
H8B1.31670.17501.21230.147*
H8C1.30920.17500.99230.147*
C90.8486 (3)0.1108 (2)0.9370 (5)0.0632 (9)
C100.6297 (3)0.1201 (2)0.8529 (6)0.0735 (11)
C110.6041 (4)0.0676 (3)0.6820 (8)0.131 (2)
H11A0.65400.02220.71160.197*
H11B0.61890.09520.57530.197*
H11C0.52270.05170.64880.197*
C120.6181 (4)0.0814 (3)1.0336 (7)0.1063 (15)
H12A0.66570.03481.05840.159*
H12B0.53680.06771.01750.159*
H12C0.64430.11691.14030.159*
C130.5522 (3)0.1940 (3)0.8125 (8)0.1084 (16)
H13A0.56970.22610.92610.163*
H13B0.47030.17900.77760.163*
H13C0.56800.22290.70860.163*
O11.0949 (2)0.38906 (15)1.0199 (4)0.0925 (9)
O21.2657 (3)0.32986 (18)1.0728 (6)0.1295 (13)
O30.74888 (17)0.15373 (14)0.8891 (3)0.0713 (8)
O40.85058 (19)0.03974 (15)0.9488 (4)0.0876 (9)
N11.0615 (2)0.12471 (17)1.0127 (4)0.0674 (8)
H1A1.07300.07481.01920.081*
Atomic displacement parameters (Å2)
U11U22U33U12U13U23
C10.101 (3)0.078 (3)0.197 (6)−0.040 (3)0.032 (3)−0.010 (3)
C20.053 (2)0.083 (3)0.088 (3)−0.0142 (19)0.0105 (18)0.0009 (19)
C30.0448 (18)0.064 (2)0.066 (2)−0.0079 (15)0.0136 (14)0.0011 (15)
C40.0457 (17)0.063 (2)0.0539 (18)−0.0049 (14)0.0090 (13)−0.0018 (14)
C50.0379 (16)0.070 (2)0.064 (2)−0.0014 (14)0.0084 (13)−0.0017 (16)
C60.0442 (18)0.078 (2)0.074 (2)−0.0119 (16)0.0149 (15)−0.0050 (16)
C70.0512 (19)0.060 (2)0.091 (2)0.0005 (16)0.0119 (17)0.0041 (17)
C80.043 (2)0.099 (3)0.146 (4)0.005 (2)0.019 (2)−0.001 (3)
C90.0475 (19)0.058 (2)0.083 (2)−0.0048 (15)0.0169 (16)−0.0033 (17)
C100.0416 (18)0.074 (2)0.102 (3)−0.0111 (16)0.0146 (17)−0.009 (2)
C110.067 (3)0.164 (5)0.141 (4)−0.010 (3)−0.005 (3)−0.062 (4)
C120.075 (3)0.098 (3)0.152 (4)−0.020 (2)0.041 (3)0.009 (3)
C130.050 (2)0.110 (4)0.159 (4)0.008 (2)0.018 (2)0.002 (3)
O10.0673 (17)0.0635 (16)0.145 (3)−0.0193 (14)0.0268 (16)−0.0068 (15)
O20.0530 (18)0.103 (2)0.215 (4)−0.0239 (15)0.0100 (19)0.007 (2)
O30.0359 (12)0.0687 (15)0.1046 (19)−0.0050 (10)0.0120 (11)0.0016 (12)
O40.0523 (14)0.0607 (17)0.144 (2)−0.0030 (11)0.0180 (14)−0.0099 (14)
N10.0442 (15)0.0624 (16)0.093 (2)−0.0020 (13)0.0149 (13)−0.0030 (14)
Geometric parameters (Å, º)
C1—O11.461 (5)C8—H8B0.9600
C1—H1B0.9600C8—H8C0.9600
C1—H1C0.9600C9—O41.215 (4)
C1—H1D0.9600C9—O31.344 (4)
C2—O21.188 (4)C10—O31.470 (4)
C2—O11.334 (4)C10—C111.486 (6)
C2—C31.454 (5)C10—C121.504 (6)
C3—C61.385 (5)C10—C131.534 (5)
C3—C41.429 (4)C11—H11A0.9600
C4—C51.383 (4)C11—H11B0.9600
C4—C71.486 (4)C11—H11C0.9600
C5—N11.382 (4)C12—H12A0.9600
C5—C91.448 (4)C12—H12B0.9600
C6—N11.354 (4)C12—H12C0.9600
C6—C81.496 (5)C13—H13A0.9600
C7—H7A0.9600C13—H13B0.9600
C7—H7B0.9600C13—H13C0.9600
C7—H7C0.9600N1—H1A0.8600
C8—H8A0.9600
O1—C1—H1B109.5O4—C9—O3124.0 (3)
O1—C1—H1C109.5O4—C9—C5125.0 (3)
H1B—C1—H1C109.5O3—C9—C5111.0 (3)
O1—C1—H1D109.5O3—C10—C11110.0 (3)
H1B—C1—H1D109.5O3—C10—C12109.5 (3)
H1C—C1—H1D109.5C11—C10—C12114.2 (4)
O2—C2—O1120.2 (4)O3—C10—C13101.7 (3)
O2—C2—C3126.4 (4)C11—C10—C13111.4 (4)
O1—C2—C3113.4 (3)C12—C10—C13109.3 (3)
C6—C3—C4108.5 (3)C10—C11—H11A109.5
C6—C3—C2121.7 (3)C10—C11—H11B109.5
C4—C3—C2129.8 (3)H11A—C11—H11B109.5
C5—C4—C3105.7 (3)C10—C11—H11C109.5
C5—C4—C7126.9 (3)H11A—C11—H11C109.5
C3—C4—C7127.4 (3)H11B—C11—H11C109.5
N1—C5—C4108.4 (3)C10—C12—H12A109.5
N1—C5—C9117.9 (3)C10—C12—H12B109.5
C4—C5—C9133.7 (3)H12A—C12—H12B109.5
N1—C6—C3107.3 (3)C10—C12—H12C109.5
N1—C6—C8120.0 (3)H12A—C12—H12C109.5
C3—C6—C8132.6 (3)H12B—C12—H12C109.5
C4—C7—H7A109.5C10—C13—H13A109.5
C4—C7—H7B109.5C10—C13—H13B109.5
H7A—C7—H7B109.5H13A—C13—H13B109.5
C4—C7—H7C109.5C10—C13—H13C109.5
H7A—C7—H7C109.5H13A—C13—H13C109.5
H7B—C7—H7C109.5H13B—C13—H13C109.5
C6—C8—H8A109.5C2—O1—C1118.1 (3)
C6—C8—H8B109.5C9—O3—C10123.8 (3)
H8A—C8—H8B109.5C6—N1—C5110.1 (3)
C6—C8—H8C109.5C6—N1—H1A124.9
H8A—C8—H8C109.5C5—N1—H1A124.9
H8B—C8—H8C109.5
O2—C2—C3—C61.3 (6)N1—C5—C9—O43.7 (5)
O1—C2—C3—C6−178.8 (3)C4—C5—C9—O4−176.5 (4)
O2—C2—C3—C4−177.7 (4)N1—C5—C9—O3−176.4 (3)
O1—C2—C3—C42.2 (5)C4—C5—C9—O33.4 (5)
C6—C3—C4—C50.6 (4)O2—C2—O1—C10.1 (6)
C2—C3—C4—C5179.7 (3)C3—C2—O1—C1−179.8 (3)
C6—C3—C4—C7−179.6 (3)O4—C9—O3—C102.7 (5)
C2—C3—C4—C7−0.6 (6)C5—C9—O3—C10−177.2 (3)
C3—C4—C5—N1−0.2 (3)C11—C10—O3—C9−63.7 (5)
C7—C4—C5—N1−179.9 (3)C12—C10—O3—C962.6 (4)
C3—C4—C5—C9180.0 (3)C13—C10—O3—C9178.1 (3)
C7—C4—C5—C90.2 (6)C3—C6—N1—C50.7 (4)
C4—C3—C6—N1−0.8 (4)C8—C6—N1—C5179.4 (3)
C2—C3—C6—N1−180.0 (3)C4—C5—N1—C6−0.4 (4)
C4—C3—C6—C8−179.3 (4)C9—C5—N1—C6179.5 (3)
C2—C3—C6—C81.5 (6)
Hydrogen-bond geometry (Å, º)
D—H···AD—HH···AD···AD—H···A
N1—H1A···O4i0.862.142.974 (4)165
Symmetry code: (i) −x+2, −y, −z+2.
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: VM2170).
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., et al. (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]
Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of
International Union of Crystallography