Methyl 4-p-tolyl-1H-pyrrole-2-carboxyl­ate

The molecules of the title compound, C₁₃H₁₃NO₂, are close to planar [maximum deviation of 0.0753 (15) Å from the least-squares plane defined by all non-H atoms in the mol­ecule]. Mol­ecules form centrosymmetric dimers through N—H...O hydrogen bonding. Mol­ecules further associate through edge-to-face π-stacking between each face of the p-tolyl substituent and ortho H atoms of the p-tolyl units of adjacent mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 193 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.044
• wR factor = 0.135
• Data-to-parameter ratio = 13.2

checkCIF/PLATON results

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Alert level B
PLAT027_ALERT_3_B _diffrn_reflns_theta_full (too) Low ............      24.98 Deg.

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   0 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; 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: X-SEED (Barbour, 2001) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Methyl 4-p-tolyl-1H-pyrrole-2-carboxylate

Crystal data

C13H13NO2	F(000) = 456
Mr = 215.24	Dx = 1.292 Mg m^−3
Monoclinic, P21/n	Melting point = 448–450 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 7.7119 (15) Å	Cell parameters from 25 reflections
b = 5.4554 (11) Å	θ = 9.8–14.3°
c = 26.385 (5) Å	µ = 0.09 mm^−1
β = 94.61 (3)°	T = 193 K
V = 1106.5 (4) Å^3	Block, colourless
Z = 4	0.55 × 0.55 × 0.45 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer	Rint = 0.020
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 1.6°
Graphite monochromator	h = −9→9
non–profiled ω/2θ scans	k = 0→6
1975 measured reflections	l = 0→31
1931 independent reflections	3 standard reflections every 60 min
1648 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.135	w = 1/[σ^2(Fo^2) + (0.0637P)^2 + 0.8352P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
1931 reflections	Δρmax = 0.25 e Å^−3
146 parameters	Δρmin = −0.27 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.028 (4)

Special details

Experimental. Spectroscopic analysis: ¹H NMR (300 MHz, CDCl₃, δ, p.p.m.): 2.35 (3H, s), 3.89 (3H, s), 7.19 (3H, m), 7.22 (1H, dd, J 3.0, 1.5 Hz), 7.43 (2H, m), 9.32 (1H, bs); ¹³C NMR (75 MHz, CDCl₃, δ, p.p.m.): 21.3, 51.4, 112.7, 119.6, 125.4, 127.1, 129.6, 131.8, 136.3, 138.4, 162.2; IR (Medium?, \v, cm^-1): 3320, 1682, 1134, 803, 758.

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.

Specified hydrogen bonds (with e.s.d.'s except fixed and riding H)

D—H H···A D···A <(DHA)

0.88 2.12 2.955 (2) 159.3 N1—H1···O1_$2

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

6.5787 (0.0049) x - 2.8266 (0.0042) y - 3.4417 (0.0202) z = 3.6980 (0.0086)

* -0.0064 (0.0013) C7 * 0.0002 (0.0013) C8 * 0.0068 (0.0014) C9 * -0.0076 (0.0014) C10 * 0.0014 (0.0014) C11 * 0.0056 (0.0014) C12 - 0.0599 (0.0029) C3

Rms deviation of fitted atoms = 0.0055

6.7665 (0.0051) x - 2.5462 (0.0050) y - 4.7803 (0.0246) z = 3.8172 (0.0082)

Angle to previous plane (with approximate e.s.d.) = 4.30 (0.12)

* -0.0016 (0.0011) N1 * 0.0022 (0.0011) C1 * -0.0019 (0.0011) C2 * 0.0010 (0.0011) C3 * 0.0004 (0.0012) C4 0.0574 (0.0032) C5 - 0.0275 (0.0032) C7

Rms deviation of fitted atoms = 0.0015

6.6483 (0.0049) x - 2.7544 (0.0042) y - 2.9755 (0.0401) z = 3.6891 (0.0055)

Angle to previous plane (with approximate e.s.d.) = 4.52 (0.12)

* 0.0040 (0.0011) C5 * 0.0017 (0.0005) C6 * -0.0021 (0.0006) O1 * -0.0035 (0.0010) O2 0.0162 (0.0038) C1

Rms deviation of fitted atoms = 0.0030

6.6675 (0.0039) x - 2.7071 (0.0026) y - 3.9176 (0.0050) z = 3.7166 (0.0036)

Angle to previous plane (with approximate e.s.d.) = 2.11 (0.09)

* -0.0753 (0.0015) N1 * 0.0337 (0.0014) O1 * -0.0238 (0.0014) O2 * -0.0339 (0.0017) C1 * 0.0210 (0.0018) C2 * 0.0221 (0.0017) C3 * -0.0394 (0.0017) C4 * -0.0032 (0.0017) C5 * 0.0211 (0.0016) C6 * 0.0462 (0.0017) C7 * 0.0113 (0.0018) C8 * -0.0097 (0.0017) C9 * -0.0119 (0.0018) C10 * 0.0384 (0.0018) C11 * 0.0705 (0.0019) C12 * -0.0672 (0.0019) C13

Rms deviation of fitted atoms = 0.0395

6.8164 (0.0051) x - 2.5339 (0.0052) y - 3.3149 (0.0221) z = 3.9833 (0.0072)

Angle to previous plane (with approximate e.s.d.) = 2.55 (0.10)

* -0.0185 (0.0004) H1 * 0.0178 (0.0006) N1 * 0.0043 (0.0010) C1 * -0.0193 (0.0013) C5 * 0.0158 (0.0007) O1 0.6170 (0.0040) H1_$2 0.5807 (0.0049) N1_$2 0.5942 (0.0041) C1_$2 0.6178 (0.0046) C5_$2 0.5827 (0.0044) O1_$2

Rms deviation of fitted atoms = 0.0161

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. All H atoms were calculated using the riding model of SHELXL. Disorder was apparent in both of the methyl groups, and was modelled using a 50:50% site occupacy model (HFIX 123).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.85678 (19)	0.7428 (3)	−0.01239 (5)	0.0379 (4)
O2	0.74376 (18)	0.4260 (3)	0.02886 (5)	0.0348 (4)
N1	0.9777 (2)	0.9395 (3)	0.08533 (6)	0.0318 (4)
H1	0.9992	1.0434	0.0611	0.038*
C1	0.8911 (2)	0.7211 (4)	0.07833 (7)	0.0270 (4)
C2	0.8835 (2)	0.6136 (4)	0.12571 (7)	0.0276 (5)
H2	0.8302	0.4611	0.1323	0.033*
C3	0.9689 (2)	0.7700 (3)	0.16268 (7)	0.0264 (4)
C4	1.0251 (3)	0.9699 (4)	0.13582 (8)	0.0309 (5)
H4	1.0870	1.1066	0.1504	0.037*
C5	0.8314 (2)	0.6365 (4)	0.02729 (7)	0.0283 (5)
C6	0.6797 (3)	0.3219 (4)	−0.01974 (8)	0.0393 (5)
H6A	0.6178	0.1687	−0.0141	0.059*	0.50
H6B	0.7779	0.2886	−0.0401	0.059*	0.50
H6C	0.6001	0.4382	−0.0379	0.059*	0.50
H6D	0.7128	0.4283	−0.0473	0.059*	0.50
H6E	0.5527	0.3084	−0.0213	0.059*	0.50
H6F	0.7304	0.1588	−0.0235	0.059*	0.50
C7	0.9896 (2)	0.7311 (4)	0.21863 (7)	0.0262 (5)
C8	0.9149 (3)	0.5280 (4)	0.24071 (7)	0.0299 (5)
H8	0.8535	0.4107	0.2196	0.036*
C9	0.9293 (3)	0.4951 (4)	0.29334 (7)	0.0318 (5)
H9	0.8784	0.3543	0.3073	0.038*
C10	1.0164 (3)	0.6631 (4)	0.32602 (7)	0.0317 (5)
C11	1.0924 (3)	0.8637 (4)	0.30385 (8)	0.0365 (5)
H11	1.1542	0.9806	0.3250	0.044*
C12	1.0799 (3)	0.8971 (4)	0.25129 (8)	0.0324 (5)
H12	1.1338	1.0356	0.2374	0.039*
C13	1.0260 (3)	0.6242 (5)	0.38335 (8)	0.0465 (6)
H13A	1.0916	0.7588	0.4004	0.070*	0.50
H13B	1.0846	0.4684	0.3919	0.070*	0.50
H13C	0.9081	0.6204	0.3947	0.070*	0.50
H13D	0.9646	0.4729	0.3909	0.070*	0.50
H13E	0.9716	0.7633	0.3994	0.070*	0.50
H13F	1.1481	0.6114	0.3966	0.070*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0497 (9)	0.0400 (9)	0.0242 (8)	−0.0044 (7)	0.0048 (6)	0.0047 (6)
O2	0.0418 (8)	0.0355 (8)	0.0269 (8)	−0.0059 (6)	0.0018 (6)	0.0000 (6)
N1	0.0400 (9)	0.0306 (9)	0.0256 (9)	−0.0021 (7)	0.0071 (7)	0.0056 (7)
C1	0.0286 (9)	0.0288 (10)	0.0238 (10)	0.0016 (8)	0.0043 (7)	0.0006 (8)
C2	0.0315 (10)	0.0263 (10)	0.0255 (10)	0.0012 (8)	0.0054 (8)	0.0028 (8)
C3	0.0260 (9)	0.0277 (10)	0.0260 (10)	0.0034 (8)	0.0046 (7)	0.0041 (8)
C4	0.0343 (10)	0.0296 (10)	0.0291 (10)	−0.0019 (8)	0.0040 (8)	0.0009 (9)
C5	0.0285 (9)	0.0300 (10)	0.0270 (11)	0.0046 (8)	0.0061 (8)	0.0021 (8)
C6	0.0415 (11)	0.0406 (12)	0.0354 (12)	−0.0022 (10)	0.0007 (9)	−0.0065 (10)
C7	0.0255 (9)	0.0270 (10)	0.0262 (10)	0.0043 (7)	0.0026 (7)	0.0011 (8)
C8	0.0333 (10)	0.0325 (10)	0.0234 (10)	−0.0035 (9)	−0.0006 (8)	0.0023 (8)
C9	0.0337 (10)	0.0354 (11)	0.0265 (10)	−0.0019 (9)	0.0032 (8)	0.0084 (9)
C10	0.0317 (10)	0.0395 (11)	0.0238 (10)	0.0082 (9)	0.0012 (8)	0.0008 (9)
C11	0.0403 (11)	0.0344 (11)	0.0338 (12)	0.0009 (9)	−0.0031 (9)	−0.0047 (9)
C12	0.0378 (11)	0.0288 (10)	0.0302 (11)	−0.0017 (8)	0.0003 (8)	0.0024 (8)
C13	0.0475 (13)	0.0640 (16)	0.0278 (12)	0.0058 (12)	0.0015 (9)	0.0007 (11)

Geometric parameters (Å, º)

O1—C5	1.226 (2)	C6—H6F	0.9800
O2—C5	1.335 (2)	C7—C12	1.397 (3)
O2—C6	1.452 (3)	C7—C8	1.397 (3)
N1—C4	1.363 (3)	C8—C9	1.396 (3)
N1—C1	1.371 (3)	C8—H8	0.9500
N1—H1	0.8800	C9—C10	1.393 (3)
C1—C2	1.387 (3)	C9—H9	0.9500
C1—C5	1.462 (3)	C10—C11	1.393 (3)
C2—C3	1.418 (3)	C10—C13	1.523 (3)
C2—H2	0.9500	C11—C12	1.394 (3)
C3—C4	1.389 (3)	C11—H11	0.9500
C3—C7	1.487 (3)	C12—H12	0.9500
C4—H4	0.9500	C13—H13A	0.9800
C6—H6A	0.9800	C13—H13B	0.9800
C6—H6B	0.9800	C13—H13C	0.9800
C6—H6C	0.9800	C13—H13D	0.9800
C6—H6D	0.9800	C13—H13E	0.9800
C6—H6E	0.9800	C13—H13F	0.9800
C5—O2—C6	116.49 (16)	C12—C7—C8	117.30 (18)
C4—N1—C1	109.06 (16)	C12—C7—C3	121.89 (18)
C4—N1—H1	125.5	C8—C7—C3	120.80 (17)
C1—N1—H1	125.5	C9—C8—C7	120.96 (19)
N1—C1—C2	107.56 (17)	C9—C8—H8	119.5
N1—C1—C5	120.81 (17)	C7—C8—H8	119.5
C2—C1—C5	131.59 (19)	C10—C9—C8	121.79 (19)
C1—C2—C3	108.34 (17)	C10—C9—H9	119.1
C1—C2—H2	125.8	C8—C9—H9	119.1
C3—C2—H2	125.8	C11—C10—C9	117.08 (19)
C4—C3—C2	105.56 (17)	C11—C10—C13	122.5 (2)
C4—C3—C7	127.28 (18)	C9—C10—C13	120.4 (2)
C2—C3—C7	127.14 (17)	C10—C11—C12	121.5 (2)
N1—C4—C3	109.48 (18)	C10—C11—H11	119.2
N1—C4—H4	125.3	C12—C11—H11	119.2
C3—C4—H4	125.3	C11—C12—C7	121.35 (19)
O1—C5—O2	123.31 (19)	C11—C12—H12	119.3
O1—C5—C1	125.24 (19)	C7—C12—H12	119.3
O2—C5—C1	111.45 (16)	C10—C13—H13A	109.5
O2—C6—H6A	109.5	C10—C13—H13B	109.5
O2—C6—H6B	109.5	H13A—C13—H13B	109.5
H6A—C6—H6B	109.5	C10—C13—H13C	109.5
O2—C6—H6C	109.5	H13A—C13—H13C	109.5
H6A—C6—H6C	109.5	H13B—C13—H13C	109.5
H6B—C6—H6C	109.5	C10—C13—H13D	109.5
O2—C6—H6D	109.5	H13A—C13—H13D	141.1
H6A—C6—H6D	141.1	H13B—C13—H13D	56.3
H6B—C6—H6D	56.3	H13C—C13—H13D	56.3
H6C—C6—H6D	56.3	C10—C13—H13E	109.5
O2—C6—H6E	109.5	H13A—C13—H13E	56.3
H6A—C6—H6E	56.3	H13B—C13—H13E	141.1
H6B—C6—H6E	141.1	H13C—C13—H13E	56.3
H6C—C6—H6E	56.3	H13D—C13—H13E	109.5
H6D—C6—H6E	109.5	C10—C13—H13F	109.5
O2—C6—H6F	109.5	H13A—C13—H13F	56.3
H6A—C6—H6F	56.3	H13B—C13—H13F	56.3
H6B—C6—H6F	56.3	H13C—C13—H13F	141.1
H6C—C6—H6F	141.1	H13D—C13—H13F	109.5
H6D—C6—H6F	109.5	H13E—C13—H13F	109.5
H6E—C6—H6F	109.5
C4—N1—C1—C2	0.4 (2)	C4—C3—C7—C12	−3.1 (3)
C4—N1—C1—C5	−177.43 (17)	C2—C3—C7—C12	178.76 (18)
N1—C1—C2—C3	−0.4 (2)	C4—C3—C7—C8	175.30 (18)
C5—C1—C2—C3	177.08 (18)	C2—C3—C7—C8	−2.9 (3)
C1—C2—C3—C4	0.3 (2)	C12—C7—C8—C9	0.5 (3)
C1—C2—C3—C7	178.75 (17)	C3—C7—C8—C9	−177.92 (17)
C1—N1—C4—C3	−0.2 (2)	C7—C8—C9—C10	0.7 (3)
C2—C3—C4—N1	0.0 (2)	C8—C9—C10—C11	−1.4 (3)
C7—C3—C4—N1	−178.53 (17)	C8—C9—C10—C13	178.60 (19)
C6—O2—C5—O1	0.9 (3)	C9—C10—C11—C12	0.9 (3)
C6—O2—C5—C1	−179.22 (16)	C13—C10—C11—C12	−179.13 (19)
N1—C1—C5—O1	2.6 (3)	C10—C11—C12—C7	0.4 (3)
C2—C1—C5—O1	−174.6 (2)	C8—C7—C12—C11	−1.1 (3)
N1—C1—C5—O2	−177.28 (16)	C3—C7—C12—C11	177.37 (18)
C2—C1—C5—O2	5.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.88	2.12	2.955 (2)	159

Symmetry code: (i) −x+2, −y+2, −z.