1,3,6-Trimethyl­pyrano[4,3-b]pyrrol-4(1H)-one

Krishnakumar, V.; Khan, F.N.; Hathwar, V.R.; Nithya, P.; Suresh, S.

doi:10.1107/S1600536809055627

organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o381

https://doi.org/10.1107/S1600536809055627

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1,3,6-Trimethylpyrano[4,3-b]pyrrol-4(1H)-one

V. Krishnakumar,^a F. Nawaz Khan,^a ^* Venkatesha R. Hathwar,^b P. Nithya ^a and S. Suresh ^c

^aSchool of Advanced Sciences, VIT University, Vellore 632 014, Tamil Nadu, India, ^bSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012, Karnataka, India, and ^cDepartment of Chemistry, Aarupadai Veedu Institute of Technology, Vinayaka Missions University, Paiyanoor, Chennai 603 104, Tamil Nadu, India
^*Correspondence e-mail: nawaz_f@yahoo.co.in

(Received 18 December 2009; accepted 28 December 2009; online 16 January 2010)

All the non-H atoms of the title compound, C₁₀H₁₁NO₂, are almost coplanar [maximum deviation = 0.040 (3) Å]. The crystal structure is stabilized by C—H⋯O hydrogen bonds.

Related literature

For general background to isocoumarins, see: Barry (1964 ). For related structures, see: Abid et al. (2006 , 2008 ); Hathwar et al. (2007 ).

Experimental

Crystal data

C₁₀H₁₁NO₂
M_r = 177.20
Monoclinic, P 2₁ /n
a = 7.5556 (7) Å
b = 8.4819 (8) Å
c = 14.3081 (14) Å
β = 93.870 (6)°
V = 914.86 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.33 × 0.28 × 0.15 mm

Data collection

Oxford Xcalibur Eos (Nova) CCD detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO CCD and CrysAlis PRO RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.916, T_max = 0.987
7291 measured reflections
1692 independent reflections
1176 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.179
S = 1.18
1692 reflections
122 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10B⋯O1ⁱ	0.96	2.46	3.404 (3)	170
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO CCD and CrysAlis PRO RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO CCD; data reduction: CrysAlis PRO RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO CCD and CrysAlis PRO RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and CAMERON (Watkin et al., 1993 ); software used to prepare material for publication: WinGX (Farrugia, 1997).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809055627/bt5154sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809055627/bt5154Isup2.hkl

checkCIF report

Comment top

Isocoumarins (Barry, 1964) are also useful intermediates in the synthesis of a variety of important compounds including some carbocyclic and heterocyclic compounds. In view of their natural occurrence, biological activities and utility as synthetic intermediates, we have synthesized the title compound, and reported herein its crystal structure.

Related literature top

For general background to isocoumarins, see: Barry (1964). For related structures, see: Abid et al. (2006, 2008); Hathwar et al. (2007).

Experimental top

A mixture of 2-(carboxymethyl)-1, 4-dimethyl-1H-pyrrole-3-carboxylic acid (2 mmol) and acetic anhydride (8 mmol) in the presence of pyridine was refluxed for 4 h. Completion of the reaction was monitored by Thin Layer Chromatography. After completing of the reaction, the mixture was poured into crushed ice. The solids were separated and purified by silica gel column chromatography. The product was obtained with 90% yield.

Structure description top

For general background to isocoumarins, see: Barry (1964). For related structures, see: Abid et al. (2006, 2008); Hathwar et al. (2007).

Computing details top

Data collection: CrysAlis PRO CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO CCD (Oxford Diffraction, 2009); data reduction: CrysAlis PRO RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: WinGX (Farrugia, 1997).

Figures top

	Fig. 1. A view of the title complex, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The packing diagram depicting C—H···O intermolecular interactions.

1,3,6-Trimethylpyrano[4,3-b]pyrrol-4(1H)-one top

Crystal data top

C₁₀H₁₁NO₂	F(000) = 376
M_r = 177.20	D_x = 1.287 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1235 reflections
a = 7.5556 (7) Å	θ = 2.9–20.4°
b = 8.4819 (8) Å	µ = 0.09 mm⁻¹
c = 14.3081 (14) Å	T = 295 K
β = 93.870 (6)°	Block, colorless
V = 914.86 (15) Å³	0.33 × 0.28 × 0.15 mm
Z = 4

Data collection top

Oxford Xcalibur Eos (Nova) CCD detector diffractometer	1692 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1176 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ω scans	θ_max = 25.5°, θ_min = 2.8°
Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2009)	h = −9→9
T_min = 0.916, T_max = 0.987	k = −9→10
7291 measured reflections	l = −17→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.179	w = 1/[σ²(F_o²) + (0.0888P)² + 0.144P] where P = (F_o² + 2F_c²)/3
S = 1.18	(Δ/σ)_max < 0.001
1692 reflections	Δρ_max = 0.27 e Å⁻³
122 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.004 (1)

Crystal data top

C₁₀H₁₁NO₂	V = 914.86 (15) Å³
M_r = 177.20	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.5556 (7) Å	µ = 0.09 mm⁻¹
b = 8.4819 (8) Å	T = 295 K
c = 14.3081 (14) Å	0.33 × 0.28 × 0.15 mm
β = 93.870 (6)°

Data collection top

Oxford Xcalibur Eos (Nova) CCD detector diffractometer	1692 independent reflections
Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2009)	1176 reflections with I > 2σ(I)
T_min = 0.916, T_max = 0.987	R_int = 0.034
7291 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.179	H-atom parameters constrained
S = 1.18	Δρ_max = 0.27 e Å⁻³
1692 reflections	Δρ_min = −0.18 e Å⁻³
122 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.1293 (2)	0.4172 (2)	0.87406 (12)	0.0412 (5)
O1	0.3720 (3)	0.1280 (3)	1.12304 (13)	0.0818 (7)
O2	0.3792 (2)	0.3881 (2)	1.13262 (10)	0.0586 (6)
C1	0.1778 (3)	0.1674 (3)	0.92158 (16)	0.0466 (6)
C2	0.1079 (3)	0.2591 (3)	0.85100 (16)	0.0466 (6)
H2	0.0534	0.2216	0.7951	0.056*
C3	0.2612 (3)	0.5620 (3)	1.01528 (16)	0.0460 (6)
H3	0.2372	0.6633	0.9929	0.055*
C4	0.3421 (3)	0.5382 (3)	1.09968 (17)	0.0507 (7)
C5	0.3331 (3)	0.2497 (3)	1.08310 (16)	0.0526 (7)
C6	0.2454 (3)	0.2744 (3)	0.99253 (14)	0.0420 (6)
C7	0.2128 (3)	0.4269 (2)	0.96087 (14)	0.0389 (6)
C8	0.4000 (4)	0.6605 (4)	1.1693 (2)	0.0749 (9)
H8A	0.3742	0.7631	1.1435	0.112*
H8B	0.5253	0.6511	1.1842	0.112*
H8C	0.3380	0.6465	1.2251	0.112*
C9	0.1882 (4)	−0.0092 (3)	0.9237 (2)	0.0702 (9)
H9A	0.1145	−0.0518	0.8725	0.105*
H9B	0.1480	−0.0472	0.9818	0.105*
H9C	0.3087	−0.0416	0.9181	0.105*
C10	0.0743 (4)	0.5500 (3)	0.81496 (17)	0.0551 (7)
H10A	0.0008	0.6192	0.8487	0.083*
H10B	0.0085	0.5123	0.7597	0.083*
H10C	0.1771	0.6063	0.7974	0.083*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0466 (11)	0.0379 (11)	0.0382 (10)	0.0025 (8)	−0.0049 (8)	0.0018 (8)
O1	0.1038 (17)	0.0781 (16)	0.0623 (12)	0.0317 (12)	−0.0034 (11)	0.0266 (11)
O2	0.0562 (11)	0.0777 (14)	0.0403 (9)	0.0065 (9)	−0.0082 (7)	−0.0015 (9)
C1	0.0506 (13)	0.0375 (13)	0.0521 (14)	−0.0005 (11)	0.0074 (11)	−0.0007 (11)
C2	0.0488 (13)	0.0463 (14)	0.0442 (12)	−0.0021 (11)	−0.0008 (10)	−0.0089 (12)
C3	0.0474 (13)	0.0415 (14)	0.0489 (13)	−0.0035 (10)	0.0016 (10)	−0.0050 (10)
C4	0.0443 (13)	0.0604 (17)	0.0471 (13)	−0.0021 (12)	0.0015 (10)	−0.0097 (11)
C5	0.0541 (15)	0.0589 (17)	0.0448 (13)	0.0102 (13)	0.0022 (11)	0.0066 (13)
C6	0.0432 (12)	0.0416 (13)	0.0409 (12)	0.0030 (10)	0.0017 (9)	0.0050 (10)
C7	0.0392 (12)	0.0400 (13)	0.0372 (11)	0.0023 (10)	0.0005 (9)	0.0033 (9)
C8	0.0654 (18)	0.096 (2)	0.0630 (17)	−0.0162 (17)	−0.0004 (13)	−0.0329 (16)
C9	0.085 (2)	0.0395 (16)	0.087 (2)	0.0000 (15)	0.0159 (16)	−0.0025 (15)
C10	0.0634 (16)	0.0556 (17)	0.0450 (13)	0.0061 (13)	−0.0055 (11)	0.0116 (11)

Geometric parameters (Å, º) top

N1—C7	1.357 (3)	C4—C8	1.483 (4)
N1—C2	1.388 (3)	C5—C6	1.431 (3)
N1—C10	1.452 (3)	C6—C7	1.387 (3)
O1—C5	1.206 (3)	C8—H8A	0.9600
O2—C4	1.380 (3)	C8—H8B	0.9600
O2—C5	1.403 (3)	C8—H8C	0.9600
C1—C2	1.353 (3)	C9—H9A	0.9600
C1—C6	1.430 (3)	C9—H9B	0.9600
C1—C9	1.500 (4)	C9—H9C	0.9600
C2—H2	0.9300	C10—H10A	0.9600
C3—C4	1.332 (3)	C10—H10B	0.9600
C3—C7	1.419 (3)	C10—H10C	0.9600
C3—H3	0.9300

C7—N1—C2	108.41 (19)	N1—C7—C6	107.66 (19)
C7—N1—C10	125.64 (19)	N1—C7—C3	129.6 (2)
C2—N1—C10	125.94 (19)	C6—C7—C3	122.7 (2)
C4—O2—C5	124.21 (19)	C4—C8—H8A	109.5
C2—C1—C6	105.5 (2)	C4—C8—H8B	109.5
C2—C1—C9	127.3 (2)	H8A—C8—H8B	109.5
C6—C1—C9	127.2 (2)	C4—C8—H8C	109.5
C1—C2—N1	110.2 (2)	H8A—C8—H8C	109.5
C1—C2—H2	124.9	H8B—C8—H8C	109.5
N1—C2—H2	124.9	C1—C9—H9A	109.5
C4—C3—C7	117.4 (2)	C1—C9—H9B	109.5
C4—C3—H3	121.3	H9A—C9—H9B	109.5
C7—C3—H3	121.3	C1—C9—H9C	109.5
C3—C4—O2	121.3 (2)	H9A—C9—H9C	109.5
C3—C4—C8	126.8 (3)	H9B—C9—H9C	109.5
O2—C4—C8	111.9 (2)	N1—C10—H10A	109.5
O1—C5—O2	115.6 (2)	N1—C10—H10B	109.5
O1—C5—C6	129.6 (3)	H10A—C10—H10B	109.5
O2—C5—C6	114.8 (2)	N1—C10—H10C	109.5
C7—C6—C1	108.3 (2)	H10A—C10—H10C	109.5
C7—C6—C5	119.6 (2)	H10B—C10—H10C	109.5
C1—C6—C5	132.2 (2)

C6—C1—C2—N1	0.3 (2)	O1—C5—C6—C7	179.4 (2)
C9—C1—C2—N1	−177.7 (2)	O2—C5—C6—C7	0.0 (3)
C7—N1—C2—C1	−0.5 (2)	O1—C5—C6—C1	−0.4 (4)
C10—N1—C2—C1	178.7 (2)	O2—C5—C6—C1	−179.8 (2)
C7—C3—C4—O2	0.6 (3)	C2—N1—C7—C6	0.4 (2)
C7—C3—C4—C8	−178.2 (2)	C10—N1—C7—C6	−178.74 (19)
C5—O2—C4—C3	−1.5 (3)	C2—N1—C7—C3	−178.8 (2)
C5—O2—C4—C8	177.5 (2)	C10—N1—C7—C3	2.1 (4)
C4—O2—C5—O1	−178.4 (2)	C1—C6—C7—N1	−0.2 (2)
C4—O2—C5—C6	1.1 (3)	C5—C6—C7—N1	179.96 (18)
C2—C1—C6—C7	−0.1 (2)	C1—C6—C7—C3	179.06 (19)
C9—C1—C6—C7	177.9 (2)	C5—C6—C7—C3	−0.8 (3)
C2—C1—C6—C5	179.7 (2)	C4—C3—C7—N1	179.6 (2)
C9—C1—C6—C5	−2.2 (4)	C4—C3—C7—C6	0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10B···O1ⁱ	0.96	2.46	3.404 (3)	170

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁NO₂
M_r	177.20
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	7.5556 (7), 8.4819 (8), 14.3081 (14)
β (°)	93.870 (6)
V (Å³)	914.86 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.33 × 0.28 × 0.15

Data collection
Diffractometer	Oxford Xcalibur Eos (Nova) CCD detector
Absorption correction	Multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2009)
T_min, T_max	0.916, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	7291, 1692, 1176
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.179, 1.18
No. of reflections	1692
No. of parameters	122
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.18

Computer programs: CrysAlis PRO CCD (Oxford Diffraction, 2009), CrysAlis PRO RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and CAMERON (Watkin et al., 1993), WinGX (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10B···O1ⁱ	0.96	2.46	3.404 (3)	170

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.

Acknowledgements

We thank the Department of Science and Technology, India, for use of the CCD facility set up under the IRHPA–DST program at IISc. We thank Professor T. N. Guru Row, IISc, Bangalore, for useful crystallographic discussions. FNK thanks the DST for Fast Track Proposal funding.

References

Abid, O.-U.-R., Qadeer, G., Rama, N. H., Ruzicka, A. & Padelkova, Z. (2008). Acta Cryst. E64, o2018. Web of Science CSD CrossRef IUCr Journals Google Scholar
Abid, O., Rama, N. H., Qadeer, G., Khan, G. S. & Lu, X.-M. (2006). Acta Cryst. E62, o2895–o2896. Web of Science CSD CrossRef IUCr Journals Google Scholar
Barry, R. D. (1964). Chem. Rev. 64, 229–260. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Hathwar, V. R., Manivel, P., Nawaz Khan, F. & Guru Row, T. N. (2007). Acta Cryst. E63, o3707. Web of Science CSD CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2009). CrysAlis PRO CCD and CrysAlis PRO RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Watkin, D. J., Pearce, L. & Prout, C. K. (1993). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England. Google Scholar