3-(3-Methoxy­anilino)isobenzofuran-1(3H)-one

The crystal structure of the title compound, C₁₅H₁₃NO₃, is stabilized by inversion-related N—H...O and C—H...O inter­molecular hydrogen bonds and C—H...π inter­actions. The N—H...O hydrogen bonds generate two C(6) chains, one within the other, and these chains are linked by C—H...O inter­molecular hydrogen bonds forming R₄⁴(21) ring motifs. The phthalide part of the mol­ecule is planar, and the dihedral angle between the phthalide group and the other benzene ring is 62.81 (8)°.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.025
• wR factor = 0.063
• Data-to-parameter ratio = 6.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.72 mm
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       6.93

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.00
           From the CIF: _reflns_number_total               1227
           Count of symmetry unique reflns         1250
           Completeness (_total/calc)             98.16%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT792_ALERT_1_G Check the Absolute Configuration of C8     = ...          S
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

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

   1 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
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Phthalides (isobenzofuranones) have important biological activities (Aoki et al., 1973; Lacova, 1973; Elderfield, 1951; Tsi & Tan, 1997; Bellasio, 1974; Roy & Sarkar, 2005). As part of a continuing study of the interplay between molecular conformation and supramolecular aggregation in 3-substituted phthalides, we now report the structure of the title compound, 3-(3-methoxyphenylamino)isobenzofuran-1(3H)-one, (I) (Fig. 1).

The geometry of the molecule of (I) does not show any significant differences from the average geometry found for 2- and 3-metoxy isomers (Odabaşoğlu & Büyükgüngör, 2006b,c) and other isobenzofuran-1(3H)-ones (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; Odabaşoğlu & Büyükgüngör, 2007a,b,c). The phthalide group (C1—C8/O2) is planar, the largest deviation from the mean plane being -0.021 (2) Å for atom C8. The dihedral angle between the mean planes of the phthalide group and the phenyl ring is 62.81 (8) °.

In (I), the crystal packing is stabilized by, N—H···O, C—H···O intermolecular hydrogen bonds and C—H···π interactions (Fig. 2, Table 1). The N—H···O hydrogen bonds generate two C(6) chains one within the other and these chains are linked by C—H···O intermolecular hydrogen bonds forming R₄⁴(21) ring motifs (Fig.3) (Etter, 1990). The C12—H12···Cg1 (Cg1 is the centroid of the C9—C14 ring) interaction parameters are given in Table 1.

Related literature

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

For related literature, see: Büyükgüngör & Odabaşoğlu (2007); Etter (1990).

S2. Experimental

The title compound was prepared according to the method described by Odabaşoğlu & Büyükgüngör (2006a), using phthalaldehydic acid and 3-methoxylaniline as starting materials (yield 90%; m.p. 428–429 K). Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an ethanol (95%) solution at room temperature.

S3. Refinement

All C-bound H atoms were refined using the riding model approximation with d(C—H) = 0.93 for aromatic, d(C—H) = 0.98 for methine and d(C—H) = 0.96 for methyl [U_iso(H) = 1.2 or 1.5U_eq(parent atom)]. N-bound H atom was located in Fourier difference map and refined freely due to its taking part in H-bond. The absolute structure could not be determined, and 1110 Friedel pairs were averaged before the last refinement.

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. A view of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of (I), showing the formation of one within the other two c6 chains [Symmetry codes: (i) x - 1, -y + 1, 1/2 - z; (ii) x, 1 - y, z - 1/2; (iii) 1 - x, y, z - 1/2; (iv) 1 - x, y, -z; (v) x - 1/2, 3/2 - y, z - 1/2].
	Fig. 3. Part of the crystal structure of (I), showing the holes along the x axis·[Symmetry codes: (i) x - 1, 1 - y, z - 1/2; (ii) x, 1 - y, z + 1/2; (iii) x - 1, y, z].

3-(3-Methoxyanilino)isobenzofuran-1(3H)-one

Crystal data

C15H13NO3	F(000) = 536
Mr = 255.26	Dx = 1.335 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 6073 reflections
a = 9.8103 (13) Å	θ = 2.9–27.3°
b = 23.541 (3) Å	µ = 0.09 mm^−1
c = 7.259 (1) Å	T = 296 K
β = 130.756 (9)°	Prismatic plate, colourless
V = 1269.9 (3) Å^3	0.72 × 0.47 × 0.15 mm
Z = 4

Data collection

Stoe IPDS-2 diffractometer	1227 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	1154 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.029
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 2.9°
ω scans	h = −12→11
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −28→28
Tmin = 0.954, Tmax = 0.987	l = −8→8
6073 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.025	w = 1/[σ^2(Fo^2) + (0.0375P)^2 + 0.1156P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.063	(Δ/σ)max < 0.001
S = 1.07	Δρmax = 0.16 e Å^−3
1227 reflections	Δρmin = −0.09 e Å^−3
177 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0125 (17)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1110 Friedel pairs
Secondary atom site location: difference Fourier map

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
C1	0.5126 (3)	0.47569 (8)	0.2907 (3)	0.0423 (4)
C2	0.3358 (2)	0.49461 (7)	0.1978 (3)	0.0389 (4)
C3	0.1898 (3)	0.46323 (8)	0.1291 (3)	0.0477 (4)
H3	0.1935	0.4238	0.1354	0.057*
C4	0.0393 (3)	0.49238 (10)	0.0514 (4)	0.0558 (5)
H4	−0.0609	0.4724	0.0040	0.067*
C5	0.0344 (3)	0.55134 (10)	0.0424 (4)	0.0569 (5)
H5	−0.0683	0.5702	−0.0077	0.068*
C6	0.1793 (3)	0.58260 (9)	0.1066 (4)	0.0508 (5)
H6	0.1748	0.6220	0.0970	0.061*
C7	0.3302 (2)	0.55322 (7)	0.1852 (3)	0.0394 (4)
C8	0.5047 (2)	0.57507 (8)	0.2636 (3)	0.0420 (4)
H8	0.4831	0.5933	0.1253	0.050*
C9	0.7376 (3)	0.64688 (7)	0.5373 (3)	0.0399 (4)
C10	0.8079 (3)	0.68262 (8)	0.7342 (3)	0.0478 (4)
H10	0.7604	0.6823	0.8108	0.057*
C11	0.9473 (3)	0.71831 (8)	0.8144 (4)	0.0553 (5)
H11	0.9915	0.7428	0.9432	0.066*
C12	1.0243 (3)	0.71886 (8)	0.7084 (4)	0.0559 (5)
H12	1.1196	0.7431	0.7655	0.067*
C13	0.9560 (3)	0.68262 (7)	0.5161 (4)	0.0478 (4)
C14	0.8121 (3)	0.64691 (7)	0.4281 (3)	0.0436 (4)
H14	0.7661	0.6232	0.2966	0.052*
C15	1.1826 (5)	0.70784 (16)	0.4999 (7)	0.0928 (10)
H15A	1.1666	0.7477	0.5090	0.111*
H15B	1.2134	0.7022	0.4001	0.111*
H15C	1.2774	0.6935	0.6603	0.111*
N1	0.5904 (2)	0.61331 (7)	0.4565 (3)	0.0483 (4)
O1	0.5718 (2)	0.42796 (6)	0.3314 (3)	0.0554 (4)
O2	0.61074 (18)	0.52137 (5)	0.3283 (2)	0.0479 (3)
O3	1.0211 (2)	0.67872 (7)	0.3974 (3)	0.0660 (4)
H1	0.577 (3)	0.6073 (9)	0.563 (5)	0.053 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0418 (11)	0.0481 (10)	0.0414 (9)	0.0018 (8)	0.0291 (9)	−0.0004 (7)
C2	0.0375 (10)	0.0433 (9)	0.0354 (8)	0.0002 (7)	0.0236 (8)	−0.0010 (7)
C3	0.0446 (12)	0.0512 (10)	0.0453 (9)	−0.0092 (9)	0.0285 (9)	−0.0048 (8)
C4	0.0360 (12)	0.0766 (13)	0.0497 (10)	−0.0106 (10)	0.0257 (10)	−0.0027 (11)
C5	0.0348 (12)	0.0795 (14)	0.0515 (11)	0.0112 (11)	0.0260 (10)	0.0085 (11)
C6	0.0448 (12)	0.0515 (10)	0.0524 (10)	0.0112 (9)	0.0301 (10)	0.0074 (9)
C7	0.0360 (10)	0.0439 (9)	0.0365 (8)	−0.0002 (7)	0.0229 (8)	0.0012 (7)
C8	0.0399 (11)	0.0434 (9)	0.0448 (10)	−0.0015 (8)	0.0286 (9)	0.0008 (7)
C9	0.0390 (10)	0.0337 (8)	0.0423 (9)	0.0010 (7)	0.0244 (8)	0.0034 (6)
C10	0.0485 (12)	0.0457 (10)	0.0497 (10)	0.0024 (8)	0.0323 (10)	−0.0014 (8)
C11	0.0564 (14)	0.0456 (10)	0.0541 (11)	−0.0076 (9)	0.0318 (11)	−0.0124 (8)
C12	0.0514 (13)	0.0453 (10)	0.0655 (13)	−0.0125 (9)	0.0357 (11)	−0.0077 (9)
C13	0.0505 (13)	0.0389 (9)	0.0565 (10)	−0.0031 (8)	0.0360 (10)	0.0017 (8)
C14	0.0461 (11)	0.0365 (8)	0.0463 (9)	−0.0043 (8)	0.0294 (9)	−0.0016 (7)
C15	0.092 (2)	0.110 (2)	0.110 (2)	−0.0432 (18)	0.081 (2)	−0.0240 (18)
N1	0.0511 (11)	0.0514 (9)	0.0492 (9)	−0.0107 (7)	0.0357 (9)	−0.0053 (7)
O1	0.0625 (10)	0.0496 (8)	0.0628 (8)	0.0147 (7)	0.0446 (8)	0.0058 (6)
O2	0.0371 (8)	0.0516 (8)	0.0577 (8)	0.0003 (6)	0.0321 (7)	−0.0014 (6)
O3	0.0706 (11)	0.0706 (10)	0.0785 (10)	−0.0232 (8)	0.0582 (10)	−0.0140 (8)

Geometric parameters (Å, º)

C1—O1	1.209 (2)	C9—C14	1.386 (3)
C1—O2	1.347 (2)	C9—C10	1.393 (3)
C1—C2	1.461 (3)	C9—N1	1.395 (2)
C2—C7	1.382 (2)	C10—C11	1.370 (3)
C2—C3	1.383 (3)	C10—H10	0.9300
C3—C4	1.371 (3)	C11—C12	1.386 (3)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.389 (3)	C12—C13	1.380 (3)
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.383 (3)	C13—O3	1.370 (2)
C5—H5	0.9300	C13—C14	1.389 (3)
C6—C7	1.376 (3)	C14—H14	0.9300
C6—H6	0.9300	C15—O3	1.412 (3)
C7—C8	1.499 (3)	C15—H15A	0.9600
C8—N1	1.393 (2)	C15—H15B	0.9600
C8—O2	1.504 (2)	C15—H15C	0.9600
C8—H8	0.9800	N1—H1	0.87 (2)
O1—C1—O2	121.77 (19)	C14—C9—N1	123.20 (16)
O1—C1—C2	129.19 (19)	C10—C9—N1	117.19 (16)
O2—C1—C2	109.04 (15)	C11—C10—C9	119.68 (18)
C7—C2—C3	121.50 (18)	C11—C10—H10	120.2
C7—C2—C1	108.59 (16)	C9—C10—H10	120.2
C3—C2—C1	129.91 (17)	C10—C11—C12	121.65 (19)
C4—C3—C2	117.66 (18)	C10—C11—H11	119.2
C4—C3—H3	121.2	C12—C11—H11	119.2
C2—C3—H3	121.2	C13—C12—C11	118.34 (19)
C3—C4—C5	120.98 (19)	C13—C12—H12	120.8
C3—C4—H4	119.5	C11—C12—H12	120.8
C5—C4—H4	119.5	O3—C13—C12	124.01 (18)
C6—C5—C4	121.27 (19)	O3—C13—C14	114.89 (17)
C6—C5—H5	119.4	C12—C13—C14	121.10 (18)
C4—C5—H5	119.4	C9—C14—C13	119.62 (16)
C7—C6—C5	117.58 (19)	C9—C14—H14	120.2
C7—C6—H6	121.2	C13—C14—H14	120.2
C5—C6—H6	121.2	O3—C15—H15A	109.5
C6—C7—C2	120.99 (18)	O3—C15—H15B	109.5
C6—C7—C8	129.64 (18)	H15A—C15—H15B	109.5
C2—C7—C8	109.37 (16)	O3—C15—H15C	109.5
N1—C8—C7	113.20 (16)	H15A—C15—H15C	109.5
N1—C8—O2	112.88 (15)	H15B—C15—H15C	109.5
C7—C8—O2	102.45 (14)	C8—N1—C9	124.63 (16)
N1—C8—H8	109.4	C8—N1—H1	116.3 (15)
C7—C8—H8	109.4	C9—N1—H1	115.4 (15)
O2—C8—H8	109.4	C1—O2—C8	110.52 (14)
C14—C9—C10	119.60 (17)	C13—O3—C15	117.35 (19)
O1—C1—C2—C7	178.91 (18)	N1—C9—C10—C11	−177.19 (18)
O2—C1—C2—C7	−1.37 (19)	C9—C10—C11—C12	−1.7 (3)
O1—C1—C2—C3	−1.1 (3)	C10—C11—C12—C13	0.6 (3)
O2—C1—C2—C3	178.65 (17)	C11—C12—C13—O3	−179.4 (2)
C7—C2—C3—C4	−1.1 (3)	C11—C12—C13—C14	0.8 (3)
C1—C2—C3—C4	178.88 (18)	C10—C9—C14—C13	0.0 (3)
C2—C3—C4—C5	0.0 (3)	N1—C9—C14—C13	178.47 (18)
C3—C4—C5—C6	1.4 (3)	O3—C13—C14—C9	179.10 (18)
C4—C5—C6—C7	−1.5 (3)	C12—C13—C14—C9	−1.1 (3)
C5—C6—C7—C2	0.4 (3)	C7—C8—N1—C9	−168.78 (16)
C5—C6—C7—C8	179.40 (18)	O2—C8—N1—C9	75.4 (2)
C3—C2—C7—C6	0.9 (3)	C14—C9—N1—C8	1.9 (3)
C1—C2—C7—C6	−179.03 (16)	C10—C9—N1—C8	−179.54 (18)
C3—C2—C7—C8	−178.27 (15)	O1—C1—O2—C8	−179.84 (17)
C1—C2—C7—C8	1.8 (2)	C2—C1—O2—C8	0.41 (17)
C6—C7—C8—N1	57.6 (3)	N1—C8—O2—C1	122.68 (16)
C2—C7—C8—N1	−123.30 (16)	C7—C8—O2—C1	0.60 (17)
C6—C7—C8—O2	179.43 (18)	C12—C13—O3—C15	9.0 (4)
C2—C7—C8—O2	−1.45 (18)	C14—C13—O3—C15	−171.2 (2)
C14—C9—C10—C11	1.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.87 (2)	2.15 (3)	3.005 (2)	165.7 (19)
C4—H4···O2^ii	0.93	2.58	3.394 (3)	146
C12—H12···Cg1^iii	0.93	2.77	3.594 (3)	148

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