3-(6-Methyl-2-pyridylamino)isobenzofuran-1(3H)-one

The crystal structure of the title compound, C₁₄H₁₂N₂O₂, is stabilized by inter­molecular N—H...O and C—H...N hydrogen bonds and also by C—H...π and π–π [centroid–centroid distance 3.822 (1) Å and a plane-to-plane separation 3.697 Å] inter­actions. The N—H...O and C—H...N hydrogen bonds generate edge-fused R₂¹(6)R₄⁴(24)R₂¹(6) ring motifs. The phthalide group is planar and oriented with respect to the pyridine ring at a dihedral angle of 83.21 (9)°.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.037
• wR factor = 0.095
• Data-to-parameter ratio = 11.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.64 mm
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C1     -   C2      ..       6.23 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C2     -   C3      ..       6.59 su
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4     ..  N2      ..       2.78 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H11    ..  N2      ..       2.70 Ang.

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C8     = ...          R

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Phthalides (isobenzofuranones) possess several important properties, such as fungicidal (Aoki et al., 1973; Lacova, 1973), bactericidal and herbicidal (Lacova, 1973), analgesic (Elderfield, 1951), hypertensive and vasorelaxant activities (Tsi & Tan, 1997). In addition, phthalide derivatives are useful in the treatment of circulatory and heart-related diseases (Bellasio, 1974). They are also found to be associated with pesticidal activities (Roy & Sarkar, 2005). Considering the potential interest of such phthalide-3-phosphonates in synthetic organic chemistry, and as agrochemical and pharmaceutical agents, we decided to investigate the solid-state structures of 3-substituted phthalides by X-ray diffraction methods. As part of a continuing study of the interplay between molecular conformation and supramolecular aggregation in 3-substituted phthalides, we report herein the structure of the title compound, (I).

The geometry of the title molecule, (I), (Fig. 1) does not show any significant difference from the average geometry found for 3-anilinoisobenzofuran-1(3H) -ones (Büyükgüngör & Odabaşoğlu, 2006a,b, 2007; Odabaşoğlu & Büyükgüngör, 2006a,b, 2007a,b,c). The phthalide group (C1—C8/O2) is planar, the largest deviation from the mean plane being -0.017 (2) Å (for C2). The dihedral angle between the planar phthalide group and phenyl ring is 83.21 (9)°.

In (I), the crystal packing is stabilized by intermolecular N—H···O and C—H···N hydrogen bonds (Table 1, Fig. 2), which generate edge-fused R₂¹(6)R₄⁴(24)R₂¹(6) ring motifs (Etter, 1990). These motifs also generate a three dimensional network by C—H···π and π···π interactions (Table 1, Fig. 3), where the π···π interactions occur between (C2—C7) and (C9—C14) rings and their symmetry-related counterparts [symmetry code: x, 1/2 - y, 1/2 + z], with a centroid-to-centroid distance of 3.822 (1) Å and a plane to plane separation of 3.697 Å.

Related literature

For related structures, see: Büyükgüngör & Odabaşoğlu (2006a,b, 2007); Odabaşoğlu & Büyükgüngör (2006a,b,c,d,e,f,g,h,i,j,k,l,m,n,o,p,q,r, 2007a,b,c,d). For related literature, see: Aoki et al. (1973); Lacova (1973); Elderfield (1951); Tsi & Tan (1997); Bellasio (1974); Roy & Sarkar (2005). For general background, see: Etter (1990).

S2. Experimental

The title compound was prepared according to the method described by Odabaşoğlu & Büyükgüngör (2006a), using phthalaldehydic acid and 2-hydroxy-5-chloroaniline as starting materials (yield; 80%; m.p. 420–422 K). Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution (95%) at room temperature.

S3. Refinement

H atoms were located in a difference syntheses and refined isotropically [N—H = 0.88 (2) Å, U_iso(H) = 0.101 (7) Ų and C—H = 0.93 (3)–1.02 (2) Å, U_iso(H) = 0.075 (5)–0.149 (10) Ų].

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level
	Fig. 2. A partial packing diagram of (I), showing the formation of R4^4(24) motif [symmetry codes: (i) x - 1, y, z; (ii) x - 1/2, y, 1/2 - z; (iii) x - 1/2, 1/2 - y, 1 - z].
	Fig. 3. A partial packing diagram of (I), showing the C—H···N and N—H···O hydrogen bonds along y-axis [symmetry codes: (i) x - 1/2, y, 1/2 - z; (ii) x - 1/2, y - 1/2, 1 - z; (iii) x + 1/2, y, 1/2 - z; (iv) x - 1/2, y - 1/2, 1 - z].

3-(6-Methyl-2-pyridylamino)isobenzofuran-1(3H)-one

Crystal data

C14H12N2O2	F(000) = 1008
Mr = 240.26	Dx = 1.292 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 11933 reflections
a = 10.1367 (7) Å	θ = 1.8–27.2°
b = 22.519 (2) Å	µ = 0.09 mm^−1
c = 10.8253 (8) Å	T = 296 K
V = 2471.0 (3) Å^3	Prism, colorless
Z = 8	0.64 × 0.36 × 0.14 mm

Data collection

Stoe IPDSII diffractometer	2437 independent reflections
Radiation source: fine-focus sealed tube	1265 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 1.8°
ω scans	h = −12→12
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −27→27
Tmin = 0.970, Tmax = 0.990	l = −13→13
17021 measured reflections

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)] = 0.037	All H-atom parameters refined
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0472P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.89	(Δ/σ)max < 0.001
2437 reflections	Δρmax = 0.09 e Å^−3
212 parameters	Δρmin = −0.09 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: 0.0065 (8)

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	1.04032 (18)	0.07038 (8)	0.25289 (16)	0.1286 (6)
O2	0.90927 (13)	0.10288 (5)	0.40304 (13)	0.0841 (4)
N1	0.68545 (16)	0.10890 (7)	0.46993 (17)	0.0761 (4)
N2	0.75182 (13)	0.18310 (6)	0.60452 (13)	0.0676 (4)
C1	0.9574 (2)	0.06011 (9)	0.3292 (2)	0.0861 (6)
C2	0.89111 (19)	0.00431 (7)	0.35851 (16)	0.0757 (5)
C3	0.9070 (3)	−0.05216 (11)	0.3075 (2)	0.0988 (7)
C4	0.8291 (4)	−0.09672 (11)	0.3527 (3)	0.1144 (9)
C5	0.7376 (3)	−0.08594 (11)	0.4421 (3)	0.1152 (9)
C6	0.7198 (3)	−0.03037 (10)	0.4921 (2)	0.0935 (7)
C7	0.79959 (19)	0.01458 (7)	0.44879 (16)	0.0699 (5)
C8	0.80476 (19)	0.07843 (7)	0.48549 (19)	0.0697 (5)
C9	0.66928 (16)	0.16633 (7)	0.51600 (16)	0.0662 (5)
C10	0.56963 (19)	0.20219 (10)	0.4707 (2)	0.0774 (5)
C11	0.5581 (2)	0.25831 (10)	0.5175 (2)	0.0854 (6)
C12	0.6424 (2)	0.27651 (10)	0.6096 (2)	0.0822 (6)
C13	0.73612 (17)	0.23811 (8)	0.65240 (16)	0.0698 (5)
C14	0.8268 (3)	0.25249 (12)	0.7571 (2)	0.0890 (6)
H1	0.642 (2)	0.0998 (9)	0.402 (2)	0.101 (7)*
H3	0.975 (2)	−0.0544 (9)	0.2473 (19)	0.097 (7)*
H4	0.846 (2)	−0.1345 (13)	0.322 (3)	0.149 (10)*
H5	0.681 (2)	−0.1199 (13)	0.470 (2)	0.145 (9)*
H6	0.652 (2)	−0.0223 (10)	0.555 (2)	0.127 (9)*
H8	0.8356 (16)	0.0860 (7)	0.5700 (17)	0.075 (5)*
H10	0.5152 (18)	0.1888 (8)	0.4067 (18)	0.092 (6)*
H11	0.489 (2)	0.2842 (10)	0.4852 (17)	0.104 (7)*
H12	0.6383 (19)	0.3151 (9)	0.6451 (19)	0.104 (7)*
H14A	0.796 (2)	0.2350 (10)	0.839 (2)	0.125 (8)*
H14B	0.838 (2)	0.2951 (12)	0.767 (2)	0.133 (8)*
H14C	0.914 (3)	0.2369 (10)	0.741 (2)	0.131 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.1376 (13)	0.1322 (14)	0.1159 (12)	−0.0053 (11)	0.0510 (11)	0.0183 (10)
O2	0.0910 (9)	0.0629 (7)	0.0984 (9)	−0.0112 (7)	0.0080 (8)	0.0032 (7)
N1	0.0799 (11)	0.0667 (9)	0.0816 (11)	0.0010 (8)	−0.0150 (9)	−0.0069 (8)
N2	0.0709 (9)	0.0630 (9)	0.0688 (9)	−0.0049 (7)	−0.0005 (7)	−0.0018 (7)
C1	0.0979 (15)	0.0846 (14)	0.0760 (13)	0.0008 (12)	0.0063 (12)	0.0061 (11)
C2	0.0993 (14)	0.0608 (11)	0.0671 (11)	0.0033 (10)	−0.0075 (10)	0.0013 (9)
C3	0.132 (2)	0.0886 (17)	0.0760 (14)	0.0162 (15)	−0.0067 (15)	−0.0102 (12)
C4	0.173 (3)	0.0621 (15)	0.108 (2)	0.0023 (17)	−0.029 (2)	−0.0098 (14)
C5	0.156 (3)	0.0672 (16)	0.123 (2)	−0.0222 (16)	−0.0116 (19)	0.0085 (15)
C6	0.1133 (18)	0.0702 (14)	0.0970 (16)	−0.0151 (12)	0.0007 (14)	0.0097 (12)
C7	0.0862 (12)	0.0593 (10)	0.0641 (10)	−0.0044 (9)	−0.0073 (10)	0.0030 (9)
C8	0.0821 (12)	0.0608 (10)	0.0662 (12)	−0.0044 (9)	−0.0026 (10)	−0.0005 (9)
C9	0.0693 (11)	0.0625 (11)	0.0669 (11)	−0.0044 (9)	0.0053 (9)	0.0021 (8)
C10	0.0692 (12)	0.0848 (14)	0.0781 (12)	0.0037 (10)	−0.0038 (11)	0.0058 (11)
C11	0.0792 (14)	0.0812 (14)	0.0958 (16)	0.0155 (11)	0.0072 (12)	0.0070 (12)
C12	0.0846 (14)	0.0691 (13)	0.0930 (15)	0.0054 (11)	0.0195 (12)	−0.0039 (11)
C13	0.0717 (11)	0.0647 (11)	0.0730 (11)	−0.0081 (9)	0.0128 (9)	−0.0058 (9)
C14	0.0944 (17)	0.0871 (15)	0.0855 (16)	−0.0145 (14)	0.0044 (13)	−0.0210 (12)

Geometric parameters (Å, º)

C1—O1	1.201 (2)	C8—H8	0.982 (18)
C1—O2	1.343 (2)	C9—N2	1.327 (2)
C1—C2	1.460 (3)	C9—C10	1.383 (2)
C2—C7	1.367 (2)	C9—N1	1.396 (2)
C2—C3	1.396 (3)	C10—C11	1.367 (3)
C3—C4	1.367 (4)	C10—H10	0.94 (2)
C3—H3	0.95 (2)	C11—C12	1.376 (3)
C4—C5	1.363 (4)	C11—H11	0.97 (2)
C4—H4	0.93 (3)	C12—C13	1.365 (3)
C5—C6	1.375 (4)	C12—H12	0.95 (2)
C5—H5	1.00 (3)	C13—N2	1.352 (2)
C6—C7	1.378 (3)	C13—C14	1.495 (3)
C6—H6	0.99 (2)	C14—H14A	1.02 (2)
C7—C8	1.493 (2)	C14—H14B	0.97 (3)
C8—N1	1.401 (2)	C14—H14C	0.97 (2)
C8—O2	1.491 (2)	N1—H1	0.88 (2)
O1—C1—O2	121.7 (2)	N2—C9—C10	123.38 (17)
O1—C1—C2	129.6 (2)	N2—C9—N1	116.60 (16)
O2—C1—C2	108.70 (18)	C10—C9—N1	120.01 (18)
C7—C2—C3	121.0 (2)	C11—C10—C9	118.1 (2)
C7—C2—C1	108.79 (16)	C11—C10—H10	121.5 (12)
C3—C2—C1	130.2 (2)	C9—C10—H10	120.3 (12)
C4—C3—C2	117.4 (3)	C10—C11—C12	119.4 (2)
C4—C3—H3	128.7 (13)	C10—C11—H11	118.7 (12)
C2—C3—H3	113.8 (13)	C12—C11—H11	121.9 (12)
C5—C4—C3	121.1 (3)	C13—C12—C11	119.3 (2)
C5—C4—H4	122.9 (17)	C13—C12—H12	118.2 (12)
C3—C4—H4	115.9 (17)	C11—C12—H12	122.5 (12)
C4—C5—C6	122.1 (3)	N2—C13—C12	122.15 (18)
C4—C5—H5	118.0 (15)	N2—C13—C14	114.63 (18)
C6—C5—H5	120.0 (15)	C12—C13—C14	123.20 (19)
C5—C6—C7	117.2 (3)	C13—C14—H14A	112.6 (13)
C5—C6—H6	122.1 (14)	C13—C14—H14B	111.6 (14)
C7—C6—H6	120.7 (14)	H14A—C14—H14B	108.8 (19)
C2—C7—C6	121.15 (19)	C13—C14—H14C	110.4 (14)
C2—C7—C8	109.23 (16)	H14A—C14—H14C	107 (2)
C6—C7—C8	129.63 (19)	H14B—C14—H14C	106 (2)
N1—C8—O2	111.15 (15)	C9—N1—C8	120.81 (16)
N1—C8—C7	114.17 (16)	C9—N1—H1	117.0 (13)
O2—C8—C7	102.79 (14)	C8—N1—H1	114.8 (13)
N1—C8—H8	107.6 (10)	C9—N2—C13	117.60 (15)
O2—C8—H8	105.5 (10)	C1—O2—C8	110.47 (14)
C7—C8—H8	115.2 (9)
O1—C1—C2—C7	−177.3 (2)	N2—C9—C10—C11	1.8 (3)
O2—C1—C2—C7	1.7 (2)	N1—C9—C10—C11	−179.36 (17)
O1—C1—C2—C3	1.0 (4)	C9—C10—C11—C12	−1.9 (3)
O2—C1—C2—C3	−179.99 (19)	C10—C11—C12—C13	0.1 (3)
C7—C2—C3—C4	−1.0 (3)	C11—C12—C13—N2	2.1 (3)
C1—C2—C3—C4	−179.2 (2)	C11—C12—C13—C14	−176.25 (19)
C2—C3—C4—C5	1.5 (4)	N2—C9—N1—C8	−20.1 (2)
C3—C4—C5—C6	−0.7 (4)	C10—C9—N1—C8	160.99 (17)
C4—C5—C6—C7	−0.6 (4)	O2—C8—N1—C9	−73.3 (2)
C3—C2—C7—C6	−0.2 (3)	C7—C8—N1—C9	170.95 (16)
C1—C2—C7—C6	178.32 (18)	C10—C9—N2—C13	0.3 (2)
C3—C2—C7—C8	179.97 (18)	N1—C9—N2—C13	−178.60 (15)
C1—C2—C7—C8	−1.5 (2)	C12—C13—N2—C9	−2.3 (2)
C5—C6—C7—C2	1.0 (3)	C14—C13—N2—C9	176.23 (16)
C5—C6—C7—C8	−179.2 (2)	O1—C1—O2—C8	177.9 (2)
C2—C7—C8—N1	121.33 (18)	C2—C1—O2—C8	−1.1 (2)
C6—C7—C8—N1	−58.5 (3)	N1—C8—O2—C1	−122.34 (17)
C2—C7—C8—O2	0.84 (19)	C7—C8—O2—C1	0.2 (2)
C6—C7—C8—O2	−178.99 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.88 (2)	2.08 (2)	2.955 (2)	174.9 (19)
C4—H4···N2^ii	0.93 (3)	2.78 (3)	3.417 (3)	126.99 (18)
C11—H11···N2^iii	0.97 (2)	2.70 (2)	3.623 (2)	158.83 (19)
C14—H14A···Cg1^iv	1.02 (2)	2.98 (2)	3.780 (3)	136.3 (2)

Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) −x+3/2, −y, z−1/2; (iii) x−1/2, −y+1/2, −z+1; (iv) x, −y+1/2, z+1/2.