2-(1-Methyl-2-oxoindolin-3-yl­idene)malono­nitrile

Wang, D.-C.; Tang, W.; Su, P.; Ou-Yang, P.-K.

doi:10.1107/S1600536813016012

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 7| July 2013| Page o1095

https://doi.org/10.1107/S1600536813016012

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2-(1-Methyl-2-oxoindolin-3-ylidene)malononitrile

De-Cai Wang,^a ^* Wei Tang,^a Peng Su ^a and Ping-Kai Ou-Yang ^a

^aState Key Laboratory of Materials-Oriented Chemical Engineering, School of Pharmaceutical Sciences, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: dcwang@njut.edu.cn

(Received 20 May 2013; accepted 8 June 2013; online 15 June 2013)

The title molecule, C₁₂H₇N₃O, is almost planar, with an r.m.s. deviation of 0.026 Å. No directional interactions could be detected in the crystal.

Related literature

For background literature, see: Demchuk et al. (2011 ). For the crystal structure of a related compound, see: Spencer et al. (2010).

Experimental

Crystal data

C₁₂H₇N₃O
M_r = 209.21
Monoclinic, P 2₁ /n
a = 6.9720 (14) Å
b = 9.929 (2) Å
c = 15.084 (3) Å
β = 100.25 (3)°
V = 1027.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.973, T_max = 0.991
2056 measured reflections
1896 independent reflections
1278 reflections with I > 2σ(I)
R_int = 0.081
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.176
S = 1.00
1896 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.19 e Å⁻³

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, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813016012/pv2634sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813016012/pv2634Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813016012/pv2634Isup3.cml

checkCIF report

Comment top

The title compound is an important intermediate in the synthesis of 2-(1-methyl-2-oxoindolin-3-yl)malononitrile, which in turn is a useful pharmaceutical intermediate (Demchuk et al., 2011). We report herein the crystal structure of the title compound.

The bond distances and angles in the title compound (Fig. 1) agree very well with the corresponding bond distances and angles reported in a closely related compound (Spencer et al., 2010). The crystal structure is devoid of any classic hydrogen bonds (Fig. 2).

Related literature top

For background literature, see: Demchuk et al. (2011). For the crystal structure of a related compound, see: Spencer et al. (2010). ).

Experimental top

A solution of 1-methylindoline-2,3-dione (8.1 g, 0.05 mol) in acetonitrile (20 ml) was added dropwise, while stirring, to malononitrile (6.6 g, 0.1 mol) dissolved in acetonitrile (10 ml), at room temperature. After stirring for 40 minutes, the precipitated 2-(1-methyl-2-oxoindolin-3-ylidene)malononitrile was filtered off and washed with 40 ml portions of acetonitrile, and the combined filtrates were concentrated under reduced pressure; yellow crytalline 2-(1-methyl-2-oxoindolin-3-ylidene)malononitrile, the title compound, was thus obtained (8.2 g; yield = 60%). The crystals suitable for X-ray diffraction were obtained by slow evaporation of EtOH solution.

Structure description top

For background literature, see: Demchuk et al. (2011). For the crystal structure of a related compound, see: Spencer et al. (2010). ).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo,1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A unit cell packing diagram of the title compound.

2-(1-Methyl-2-oxoindolin-3-ylidene)malononitrile top

Crystal data top

C₁₂H₇N₃O	F(000) = 432
M_r = 209.21	D_x = 1.352 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 6.9720 (14) Å	θ = 9–13°
b = 9.929 (2) Å	µ = 0.09 mm⁻¹
c = 15.084 (3) Å	T = 293 K
β = 100.25 (3)°	Block, yellow
V = 1027.5 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1278 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.081
Graphite monochromator	θ_max = 25.4°, θ_min = 2.5°
ω/2θ scans	h = 0→8
Absorption correction: ψ scan (North et al., 1968)	k = 0→11
T_min = 0.973, T_max = 0.991	l = −18→17
2056 measured reflections	3 standard reflections every 200 reflections
1896 independent reflections	intensity decay: 1%

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)] = 0.057	H-atom parameters constrained
wR(F²) = 0.176	w = 1/[σ²(F_o²) + (0.1P)² + 0.150P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1896 reflections	Δρ_max = 0.18 e Å⁻³
146 parameters	Δρ_min = −0.19 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: 0.082 (11)

Crystal data top

C₁₂H₇N₃O	V = 1027.5 (4) Å³
M_r = 209.21	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.9720 (14) Å	µ = 0.09 mm⁻¹
b = 9.929 (2) Å	T = 293 K
c = 15.084 (3) Å	0.30 × 0.20 × 0.10 mm
β = 100.25 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1278 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.081
T_min = 0.973, T_max = 0.991	3 standard reflections every 200 reflections
2056 measured reflections	intensity decay: 1%
1896 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.176	H-atom parameters constrained
S = 1.00	Δρ_max = 0.18 e Å⁻³
1896 reflections	Δρ_min = −0.19 e Å⁻³
146 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

	x	y	z	U_iso*/U_eq
O	0.0898 (3)	0.2173 (2)	0.80717 (13)	0.0706 (7)
C1	0.0975 (4)	−0.0799 (3)	0.83219 (16)	0.0473 (7)
N1	0.1159 (4)	−0.3343 (3)	0.86555 (18)	0.0819 (9)
C2	0.1095 (4)	−0.2216 (3)	0.85071 (18)	0.0553 (7)
N2	−0.0627 (5)	−0.0331 (3)	0.66758 (18)	0.0853 (9)
C3	0.0117 (4)	−0.0467 (3)	0.74109 (18)	0.0583 (8)
N3	0.2174 (3)	0.2233 (2)	0.95933 (14)	0.0526 (6)
C4	0.1582 (3)	0.0124 (2)	0.89713 (16)	0.0439 (6)
C5	0.1483 (4)	0.1621 (3)	0.87912 (17)	0.0505 (7)
C6	0.2761 (3)	0.1273 (2)	1.02696 (16)	0.0452 (6)
C7	0.3584 (4)	0.1494 (3)	1.11602 (17)	0.0535 (7)
H7A	0.3832	0.2361	1.1385	0.064*
C8	0.4027 (4)	0.0373 (3)	1.17050 (18)	0.0560 (7)
H8A	0.4573	0.0493	1.2309	0.067*
C9	0.3678 (4)	−0.0923 (3)	1.13745 (17)	0.0572 (7)
H9A	0.3983	−0.1654	1.1759	0.069*
C10	0.2876 (4)	−0.1141 (3)	1.04742 (16)	0.0492 (7)
H10A	0.2649	−0.2010	1.0250	0.059*
C11	0.2423 (3)	−0.0029 (2)	0.99178 (15)	0.0427 (6)
C12	0.2311 (5)	0.3684 (3)	0.9719 (2)	0.0769 (10)
H12A	0.1816	0.4126	0.9159	0.115*
H12B	0.3649	0.3933	0.9917	0.115*
H12C	0.1558	0.3951	1.0164	0.115*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O	0.1073 (17)	0.0532 (12)	0.0506 (12)	0.0063 (10)	0.0123 (11)	0.0123 (9)
C1	0.0525 (15)	0.0477 (16)	0.0421 (14)	0.0037 (11)	0.0098 (11)	0.0010 (11)
N1	0.119 (2)	0.0507 (17)	0.0754 (19)	0.0038 (15)	0.0144 (16)	−0.0016 (14)
C2	0.0689 (18)	0.0507 (17)	0.0453 (15)	0.0021 (13)	0.0077 (12)	−0.0035 (13)
N2	0.116 (2)	0.089 (2)	0.0472 (15)	0.0060 (17)	0.0046 (14)	0.0044 (14)
C3	0.077 (2)	0.0517 (16)	0.0466 (17)	0.0008 (14)	0.0122 (14)	−0.0018 (13)
N3	0.0735 (15)	0.0372 (12)	0.0488 (13)	0.0004 (10)	0.0155 (11)	0.0023 (10)
C4	0.0474 (13)	0.0426 (14)	0.0429 (13)	0.0025 (10)	0.0112 (10)	0.0025 (11)
C5	0.0622 (16)	0.0464 (15)	0.0452 (15)	0.0013 (12)	0.0155 (12)	0.0052 (12)
C6	0.0472 (14)	0.0453 (15)	0.0451 (14)	0.0006 (11)	0.0135 (10)	0.0006 (11)
C7	0.0581 (16)	0.0550 (16)	0.0482 (15)	−0.0048 (12)	0.0118 (12)	−0.0078 (13)
C8	0.0581 (16)	0.0666 (19)	0.0415 (14)	0.0021 (13)	0.0042 (11)	−0.0007 (13)
C9	0.0619 (17)	0.0606 (18)	0.0477 (16)	0.0066 (13)	0.0060 (12)	0.0107 (13)
C10	0.0545 (15)	0.0454 (15)	0.0475 (14)	0.0045 (11)	0.0089 (11)	0.0044 (11)
C11	0.0436 (13)	0.0444 (14)	0.0408 (13)	0.0025 (10)	0.0095 (10)	0.0011 (11)
C12	0.122 (3)	0.0415 (17)	0.072 (2)	−0.0048 (16)	0.0294 (18)	−0.0016 (14)

Geometric parameters (Å, º) top

O—C5	1.220 (3)	C6—C11	1.402 (3)
C1—C4	1.353 (4)	C7—C8	1.386 (4)
C1—C2	1.434 (4)	C7—H7A	0.9300
C1—C3	1.436 (4)	C8—C9	1.386 (4)
N1—C2	1.140 (4)	C8—H8A	0.9300
N2—C3	1.146 (3)	C9—C10	1.390 (4)
N3—C5	1.363 (3)	C9—H9A	0.9300
N3—C6	1.403 (3)	C10—C11	1.388 (3)
N3—C12	1.455 (4)	C10—H10A	0.9300
C4—C11	1.452 (3)	C12—H12A	0.9600
C4—C5	1.510 (4)	C12—H12B	0.9600
C6—C7	1.381 (3)	C12—H12C	0.9600

C4—C1—C2	121.6 (2)	C8—C7—H7A	121.3
C4—C1—C3	124.1 (2)	C9—C8—C7	121.8 (3)
C2—C1—C3	114.3 (2)	C9—C8—H8A	119.1
N1—C2—C1	178.9 (3)	C7—C8—H8A	119.1
N2—C3—C1	173.3 (3)	C8—C9—C10	120.7 (3)
C5—N3—C6	110.7 (2)	C8—C9—H9A	119.7
C5—N3—C12	124.2 (2)	C10—C9—H9A	119.7
C6—N3—C12	125.1 (2)	C11—C10—C9	118.4 (3)
C1—C4—C11	131.3 (2)	C11—C10—H10A	120.8
C1—C4—C5	122.5 (2)	C9—C10—H10A	120.8
C11—C4—C5	106.1 (2)	C10—C11—C6	120.0 (2)
O—C5—N3	126.8 (3)	C10—C11—C4	133.4 (2)
O—C5—C4	126.9 (2)	C6—C11—C4	106.7 (2)
N3—C5—C4	106.3 (2)	N3—C12—H12A	109.5
C7—C6—C11	121.9 (2)	N3—C12—H12B	109.5
C7—C6—N3	128.0 (2)	H12A—C12—H12B	109.5
C11—C6—N3	110.1 (2)	N3—C12—H12C	109.5
C6—C7—C8	117.3 (3)	H12A—C12—H12C	109.5
C6—C7—H7A	121.3	H12B—C12—H12C	109.5

C2—C1—C4—C11	0.1 (4)	C11—C6—C7—C8	−1.5 (4)
C3—C1—C4—C11	178.2 (2)	N3—C6—C7—C8	179.4 (2)
C2—C1—C4—C5	179.6 (2)	C6—C7—C8—C9	0.5 (4)
C3—C1—C4—C5	−2.3 (4)	C7—C8—C9—C10	0.4 (4)
C6—N3—C5—O	−178.5 (3)	C8—C9—C10—C11	−0.4 (4)
C12—N3—C5—O	0.5 (4)	C9—C10—C11—C6	−0.5 (4)
C6—N3—C5—C4	1.6 (3)	C9—C10—C11—C4	−179.6 (2)
C12—N3—C5—C4	−179.4 (2)	C7—C6—C11—C10	1.6 (4)
C1—C4—C5—O	−1.0 (4)	N3—C6—C11—C10	−179.3 (2)
C11—C4—C5—O	178.6 (2)	C7—C6—C11—C4	−179.1 (2)
C1—C4—C5—N3	178.9 (2)	N3—C6—C11—C4	0.0 (3)
C11—C4—C5—N3	−1.5 (3)	C1—C4—C11—C10	−0.4 (5)
C5—N3—C6—C7	178.0 (2)	C5—C4—C11—C10	−179.9 (3)
C12—N3—C6—C7	−0.9 (4)	C1—C4—C11—C6	−179.6 (2)
C5—N3—C6—C11	−1.1 (3)	C5—C4—C11—C6	0.9 (3)
C12—N3—C6—C11	179.9 (2)

Experimental details

Crystal data
Chemical formula	C₁₂H₇N₃O
M_r	209.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.9720 (14), 9.929 (2), 15.084 (3)
β (°)	100.25 (3)
V (Å³)	1027.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.973, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	2056, 1896, 1278
R_int	0.081
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.176, 1.00
No. of reflections	1896
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo,1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

References

Demchuk, D. V., Elinson, M. N. & Nikishin, G. I. (2011). Mendeleev Commun. 51, 224–225. Web of Science CrossRef Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spencer, J., Chowdhry, B. Z., Hamid, S., Mendham, A. P., Male, L., Coles, S. J. & Hursthouse, M. B. (2010). Acta Cryst. C66, o71–o78. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar