3-(2,4-Dichloro­anilino)iso­benzo­furan-1(3H)-one

In the mol­ecule of the title compound, C₁₄H₉Cl₂NO₂, the essentially planar phthalide group is oriented at a dihedral angle of 63.23 (5)° with respect to the substituted aromatic ring. In the crystal structure, inter­molecular C—H...O and N—H...O hydrogen bonds link the mol­ecules, generating R₄⁴(21) ring motifs to form a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.048
• wR factor = 0.113
• Data-to-parameter ratio = 14.2

checkCIF/PLATON results

No syntax errors found



Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.114
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.11
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.62 mm
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C12

Alert level G
PLAT793_ALERT_2_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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Phthalides (isobenzofuranones) are five-membered lactones found in plants and they are known to show diverse biological activities, such as fungicidal, bactericidal, herbicidal, analgesic, pesticidal, hypotensive and vasorelaxant activities (Aoki et al., 1973, 1974; Tsi & Tan, 1997; Roy & Sarkar, 2005). In addition, phthalide derivatives are useful in the treatment of circulatory and heart-related diseases (Bellasio, 1974, 1975). As part of our ongoing research on 3-substituted phthalides (Büyükgüngör & Odabaşoğlu, 2006; Odabaşoǧlu & Büyükgüngör, 2006), the title compound, (I), has been synthesized and its crystal structure is reported here.

In the molecule of (I), (Fig. 1), rings A (C2-C7), B (C1/C2/C7/C8/O2) and C (C9-C14) are, of course, planar. The dihedral angles between them are A/B = 2.60 (5)°, A/C = 63.44 (4)° and B/C = 63.11 (5)°. So, rings A and B are also nearly coplanar. Ring C is oriented with respect to the coplanar ring system at a dihedral angle of 63.23 (5)°. The geometry of (I) does not show any significant difference from the average geometry found for 3-(4-chloroanilino)isobenzofuran-1(3H)-one (Büyükgüngör & Odabaşoğlu, 2006).

In the crystal structure, intermolecular C-H···O and N-H···O hydrogen bonds (Table 1) link the molecules, generating R₄⁴(21) (Fig. 2) ring motifs (Bernstein et al., 1995; Etter, 1990), to form a three-dimensional network, in which they may be effective in the stabilization of the structure.

Related literature

For general background, see: Aoki et al. (1973, 1974); Tsi & Tan (1997); Roy & Sarkar (2005); Bellasio (1974, 1975). For related structures, see: Büyükgüngör & Odabaşoğlu (2006); Odabaşoğlu & Büyükgüngör (2006). For ring motif details, see: Bernstein et al. (1995); Etter (1990).

S2. Experimental

The title compound was prepared according to the method described by Odabaşoğlu & Büyükgüngör (2006), using phthalaldehydic acid and 2,4-dichloroaniline as starting materials (yield; 80%). Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an ethanol-DMF (1:1) solution at room temperature.

S3. Refinement

H atom (for NH) was located in difference synthesis and refined freely [N-H = 0.86 (3) Å and U_iso(H) = 0.069 (7) Ų]. The remaining H atoms were positioned geometrically, with C-H = 0.93 and 0.98 Å for aromatic and methine H, respectively, and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C).

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, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); 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(21) ring motif. Hydrogen bonds are shown as dashed lines [symmetry codes: (i) x, 1/2 - y, z + 1/2; (ii) x - 1, y, z; (iii) x - 1, 1/2 - y, 1/2 - z]. H atoms not involved in hydrogen bondings have been omitted for clarity.

3-(2,4-dichloroanilino)isobenzofuran-1(3H)-one

Crystal data

C14H9Cl2NO2	F(000) = 600
Mr = 294.12	Dx = 1.472 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7695 reflections
a = 7.7647 (4) Å	θ = 1.7–26.1°
b = 23.9293 (12) Å	µ = 0.48 mm^−1
c = 7.3261 (4) Å	T = 296 K
β = 102.768 (5)°	Prism, colorless
V = 1327.56 (12) Å^3	0.62 × 0.40 × 0.29 mm
Z = 4

Data collection

Stoe IPDS II diffractometer	2500 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	1860 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.114
Detector resolution: 6.67 pixels mm^-1	θmax = 25.7°, θmin = 1.7°
w–scan rotation method	h = −9→9
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −28→28
Tmin = 0.486, Tmax = 0.854	l = −8→8
7695 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0573P)^2 + 0.1182P] where P = (Fo^2 + 2Fc^2)/3
2500 reflections	(Δ/σ)max < 0.001
176 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.38 e Å^−3

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 > 2sigma(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
Cl1	0.54932 (11)	0.44014 (3)	0.87525 (9)	0.0799 (3)
Cl2	0.05955 (13)	0.48298 (5)	0.25003 (14)	0.1281 (5)
O1	0.7384 (2)	0.18458 (7)	0.5396 (2)	0.0666 (4)
O2	0.69942 (18)	0.27650 (6)	0.4919 (2)	0.0552 (4)
H1	0.719 (3)	0.3623 (11)	0.752 (4)	0.069 (7)*
N1	0.7106 (3)	0.36695 (8)	0.6346 (3)	0.0570 (5)
C1	0.7958 (3)	0.23169 (9)	0.5653 (3)	0.0502 (5)
C2	0.9681 (3)	0.25091 (9)	0.6711 (3)	0.0468 (5)
C3	1.1115 (3)	0.22004 (10)	0.7623 (3)	0.0574 (6)
H3	1.1072	0.1812	0.7669	0.069*
C4	1.2615 (3)	0.24907 (13)	0.8465 (3)	0.0685 (7)
H4	1.3608	0.2296	0.9088	0.082*
C5	1.2657 (3)	0.30675 (14)	0.8391 (3)	0.0722 (7)
H5	1.3685	0.3253	0.8971	0.087*
C6	1.1218 (3)	0.33757 (11)	0.7482 (3)	0.0643 (6)
H6	1.1255	0.3764	0.7449	0.077*
C7	0.9719 (3)	0.30836 (9)	0.6624 (3)	0.0497 (5)
C8	0.8012 (3)	0.32888 (9)	0.5450 (3)	0.0506 (5)
H8	0.8241	0.3464	0.4318	0.061*
C9	0.5585 (3)	0.39413 (9)	0.5407 (3)	0.0518 (5)
C10	0.4694 (3)	0.43014 (9)	0.6373 (3)	0.0583 (6)
C11	0.3179 (3)	0.45773 (11)	0.5500 (4)	0.0716 (7)
H11	0.2602	0.4814	0.6177	0.086*
C12	0.2532 (3)	0.44977 (12)	0.3615 (4)	0.0730 (7)
C13	0.3382 (3)	0.41567 (11)	0.2614 (3)	0.0685 (6)
H13	0.2942	0.4110	0.1336	0.082*
C14	0.4896 (3)	0.38808 (10)	0.3495 (3)	0.0597 (6)
H14	0.5468	0.3649	0.2799	0.072*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1151 (6)	0.0677 (4)	0.0658 (4)	0.0114 (4)	0.0389 (4)	−0.0076 (3)
Cl2	0.0912 (6)	0.1702 (11)	0.1280 (7)	0.0701 (6)	0.0349 (5)	0.0507 (7)
O1	0.0662 (10)	0.0565 (10)	0.0751 (10)	−0.0104 (8)	0.0116 (8)	−0.0096 (8)
O2	0.0437 (8)	0.0569 (9)	0.0613 (8)	0.0026 (7)	0.0036 (6)	−0.0052 (7)
N1	0.0652 (12)	0.0584 (11)	0.0487 (10)	0.0134 (9)	0.0153 (9)	−0.0014 (8)
C1	0.0471 (11)	0.0545 (13)	0.0509 (10)	−0.0004 (10)	0.0147 (9)	−0.0061 (9)
C2	0.0419 (10)	0.0541 (12)	0.0470 (10)	0.0009 (10)	0.0153 (8)	−0.0022 (8)
C3	0.0503 (12)	0.0652 (14)	0.0587 (12)	0.0101 (11)	0.0165 (10)	0.0023 (10)
C4	0.0434 (12)	0.098 (2)	0.0626 (13)	0.0103 (14)	0.0089 (10)	0.0015 (13)
C5	0.0426 (12)	0.103 (2)	0.0696 (14)	−0.0124 (14)	0.0087 (11)	−0.0137 (14)
C6	0.0552 (13)	0.0676 (15)	0.0710 (14)	−0.0150 (12)	0.0160 (11)	−0.0097 (11)
C7	0.0451 (11)	0.0574 (13)	0.0487 (10)	−0.0020 (10)	0.0152 (8)	−0.0032 (9)
C8	0.0511 (12)	0.0495 (12)	0.0527 (11)	0.0022 (10)	0.0147 (9)	−0.0008 (9)
C9	0.0580 (13)	0.0448 (11)	0.0569 (12)	0.0047 (10)	0.0219 (10)	0.0056 (9)
C10	0.0724 (15)	0.0471 (12)	0.0641 (13)	0.0061 (11)	0.0338 (12)	0.0062 (10)
C11	0.0778 (17)	0.0614 (14)	0.0886 (17)	0.0191 (14)	0.0463 (15)	0.0147 (13)
C12	0.0648 (15)	0.0764 (17)	0.0840 (17)	0.0203 (13)	0.0297 (14)	0.0266 (13)
C13	0.0671 (15)	0.0741 (16)	0.0656 (13)	0.0081 (13)	0.0175 (12)	0.0144 (12)
C14	0.0647 (14)	0.0591 (14)	0.0589 (12)	0.0133 (11)	0.0212 (11)	0.0046 (10)

Geometric parameters (Å, º)

C1—O1	1.212 (3)	C8—O2	1.487 (3)
C1—O2	1.349 (3)	C8—H8	0.9800
C1—C2	1.465 (3)	C9—N1	1.390 (3)
C2—C7	1.377 (3)	C9—C14	1.392 (3)
C2—C3	1.379 (3)	C9—C10	1.392 (3)
C3—C4	1.379 (3)	C10—C11	1.376 (3)
C3—H3	0.9300	C10—Cl1	1.733 (2)
C4—C5	1.382 (4)	C11—C12	1.375 (4)
C4—H4	0.9300	C11—H11	0.9300
C5—C6	1.381 (4)	C12—C13	1.362 (4)
C5—H5	0.9300	C12—Cl2	1.737 (3)
C6—C7	1.384 (3)	C13—C14	1.378 (3)
C6—H6	0.9300	C13—H13	0.9300
C7—C8	1.494 (3)	C14—H14	0.9300
C8—N1	1.400 (3)	N1—H1	0.86 (3)
O1—C1—O2	121.7 (2)	O2—C8—H8	108.9
O1—C1—C2	129.5 (2)	C7—C8—H8	108.9
O2—C1—C2	108.85 (18)	N1—C9—C14	123.02 (19)
C7—C2—C3	122.3 (2)	N1—C9—C10	120.1 (2)
C7—C2—C1	108.35 (18)	C14—C9—C10	116.9 (2)
C3—C2—C1	129.3 (2)	C11—C10—C9	122.0 (2)
C4—C3—C2	117.3 (2)	C11—C10—Cl1	118.71 (17)
C4—C3—H3	121.4	C9—C10—Cl1	119.26 (18)
C2—C3—H3	121.4	C12—C11—C10	119.0 (2)
C3—C4—C5	120.7 (2)	C12—C11—H11	120.5
C3—C4—H4	119.6	C10—C11—H11	120.5
C5—C4—H4	119.6	C13—C12—C11	120.7 (2)
C6—C5—C4	121.9 (2)	C13—C12—Cl2	119.6 (2)
C6—C5—H5	119.1	C11—C12—Cl2	119.7 (2)
C4—C5—H5	119.1	C12—C13—C14	120.0 (2)
C5—C6—C7	117.3 (2)	C12—C13—H13	120.0
C5—C6—H6	121.3	C14—C13—H13	120.0
C7—C6—H6	121.3	C13—C14—C9	121.3 (2)
C2—C7—C6	120.5 (2)	C13—C14—H14	119.3
C2—C7—C8	109.26 (18)	C9—C14—H14	119.3
C6—C7—C8	130.2 (2)	C9—N1—C8	122.17 (18)
N1—C8—O2	112.22 (16)	C9—N1—H1	115.0 (17)
N1—C8—C7	114.69 (17)	C8—N1—H1	117.1 (17)
O2—C8—C7	103.07 (16)	C1—O2—C8	110.45 (15)
N1—C8—H8	108.9
O1—C1—C2—C7	−179.3 (2)	C14—C9—C10—C11	1.4 (3)
O2—C1—C2—C7	1.0 (2)	N1—C9—C10—Cl1	−0.5 (3)
O1—C1—C2—C3	2.9 (3)	C14—C9—C10—Cl1	−179.37 (17)
O2—C1—C2—C3	−176.77 (17)	C9—C10—C11—C12	−0.4 (4)
C7—C2—C3—C4	0.2 (3)	Cl1—C10—C11—C12	−179.66 (19)
C1—C2—C3—C4	177.70 (18)	C10—C11—C12—C13	−0.8 (4)
C2—C3—C4—C5	0.2 (3)	C10—C11—C12—Cl2	178.56 (19)
C3—C4—C5—C6	0.0 (4)	C11—C12—C13—C14	0.9 (4)
C4—C5—C6—C7	−0.5 (3)	Cl2—C12—C13—C14	−178.4 (2)
C3—C2—C7—C6	−0.8 (3)	C12—C13—C14—C9	0.1 (4)
C1—C2—C7—C6	−178.75 (17)	N1—C9—C14—C13	179.9 (2)
C3—C2—C7—C8	176.66 (16)	C10—C9—C14—C13	−1.2 (3)
C1—C2—C7—C8	−1.3 (2)	C14—C9—N1—C8	−3.5 (3)
C5—C6—C7—C2	0.9 (3)	C10—C9—N1—C8	177.7 (2)
C5—C6—C7—C8	−175.9 (2)	O2—C8—N1—C9	−69.0 (2)
C2—C7—C8—N1	123.40 (19)	C7—C8—N1—C9	173.83 (19)
C6—C7—C8—N1	−59.5 (3)	O1—C1—O2—C8	179.98 (18)
C2—C7—C8—O2	1.11 (19)	C2—C1—O2—C8	−0.3 (2)
C6—C7—C8—O2	178.20 (19)	N1—C8—O2—C1	−124.39 (18)
N1—C9—C10—C11	−179.7 (2)	C7—C8—O2—C1	−0.46 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.86 (3)	2.36 (3)	3.176 (2)	159 (2)
C4—H4···O2^ii	0.93	2.57	3.387 (3)	147

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