2-(Methoxy­carbonyl)succinanilic acid

The title compound, C₁₂H₁₃NO₅, was synthesized by the condensation of methyl anthranilate and succinic anhydride. The dihedral angle between the phenyl­acetamide and carboxylic acid (–C—COOH) planes is 80.47 (5)°. In the crystal structure, inversion-related mol­ecules form an O—H...O hydrogen-bonded dimer. Adjacent dimers are inter­linked by C—H...O hydrogen bonds to form a chain along [110].

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.042
• wR factor = 0.113
• Data-to-parameter ratio = 14.8

checkCIF/PLATON results

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Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C10
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          1

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

Methyl(2-methoxycarbonyl)succinate, a natural aromatic amide isolated from the methanolic extract of Jolyna laminarioides, has shown potent chymotrypsin inhibitory activity (Atta-ur-Rahman et al., 1997). Therefore, we have synthesized our desired analogue, (I), in 85% yield, by a one-step condensation of methyl anthraanilate and succinic anhydride (see scheme). We report here the structure of (I).

Molecules of the title compound, (I), have normal bond lengths (Allen et al., 1987). The C6—N1—C7 bond angle [130.13 (11)°] is larger compared with the value of 126.69 (10)° observed in N,N'-diphenylsuccinimide (Anjum et al., 2005). The N1—C7 and C8—C9 bonds are trans with respect to the C7—C8 bond for steric reasons, the N1—C7—C8—C9 torsion angle being 175.77 (11)°.

The phenylacetamide moiety is planar to within ±0.018 (1) Å. The C9—C10—O4—O5 and C11—C12—O1—O2 planes form dihedral angles of 80.47 (5) and 9.38 (9)°, respectively, with the phenylacetamide moiety. This orientation is influenced by intramolecular C—H···O and N—H···O interactions, namely N1—H1N···O2, C5—H5···O3 and C2—H2···O1 (Table 1). As seen in Fig. 1, each of these interactions generates rings of graph-set motif S(5) or S(6) (Bernstein et al., 1995).

In the crystal structure, centrosymmetrically related molecules are linked by O5—H1O5···O4ⁱ intermolecular hydrogen bonds to form a dimeric pair (symmetry code as in Table 1). These hydrogen bonds form an R₂²(8) ring motif. The adjacent dimers are interlinked by mutual C9—H9B···O2ⁱⁱ hydrogen bonds to form a chain along [110]. These hydrogen bonds form an R₂²(18) ring motif (Fig. 2). A C—H···π interaction involving atom H8B and the C1–C6 ring is observed, with atom H8B separated from the centroid (Cg1) of the ring by 2.58 Å (Table 1).

S2. Experimental

Succinic anhydride (1.0 g, 0.01 mol) was added to methyl anthraanilate (0.5 g, 0.003 mol) in a round-bottomed flask containing dry toluene (50 ml). The reaction mixture was then refluxed for 15 h using a Dean–Stark trap. The reaction mixture was quickly filtered and left for crystallization at room temperature, to obtain colourless crystals of compound (I) (1.01 g, yield 85%, m.p. 539–540 K).

S3. Refinement

Atom H1O5 was located in a difference Fourier map and refined isotropically. All other H atoms were positioned geometrically and allowed to ride on their parent atoms, with N—H = 0.86 Å and C—H = 0.93–0.97 Å, and with U_iso(H) = 1.2 or 1.5U_eq(C,N). A rotating-group model was used for the methyl group.

Computing details

Data collection: SMART (Siemens, 1997); cell refinement: SAINT (Siemens, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures

	Fig. 1. The structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Part of the crystal structure of (I), showing R2^2(8) and R2^2(18) ring motifs. Dashed lines indicate hydrogen bonds.

2-Methoxycarbonyl succinanilic acid

Crystal data

C12H13NO5	F(000) = 1056
Mr = 251.23	Dx = 1.376 Mg m^−3
Monoclinic, C2/c	Melting point: 397-399K K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 18.301 (2) Å	Cell parameters from 5412 reflections
b = 12.1788 (15) Å	θ = 2.0–26.5°
c = 10.8967 (14) Å	µ = 0.11 mm^−1
β = 93.001 (2)°	T = 293 K
V = 2425.3 (5) Å^3	Block, colourless
Z = 8	0.42 × 0.27 × 0.24 mm

Data collection

Siemens SMART CCD area-detector diffractometer	2498 independent reflections
Radiation source: fine-focus sealed tube	2230 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
Detector resolution: 8.33 pixels mm^-1	θmax = 26.5°, θmin = 2.0°
ω scans	h = −22→22
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −15→14
Tmin = 0.956, Tmax = 0.975	l = −12→13
6736 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)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0551P)^2 + 1.0027P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2498 reflections	Δρmax = 0.20 e Å^−3
169 parameters	Δρmin = −0.17 e Å^−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0070 (10)

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	0.07221 (6)	0.13681 (9)	0.38233 (10)	0.0698 (3)
O2	0.13261 (8)	0.17696 (9)	0.21797 (12)	0.0851 (4)
O3	0.26540 (7)	−0.09981 (9)	−0.00945 (12)	0.0803 (4)
O4	0.42082 (5)	0.04780 (10)	0.03564 (9)	0.0647 (3)
O5	0.44972 (6)	−0.00629 (11)	−0.14972 (10)	0.0679 (3)
N1	0.20032 (7)	0.01423 (9)	0.10851 (10)	0.0514 (3)
H1N	0.1925	0.0830	0.1203	0.062*
C1	0.11698 (7)	−0.01165 (11)	0.27169 (13)	0.0498 (3)
C2	0.08014 (8)	−0.08239 (14)	0.34819 (15)	0.0613 (4)
H2	0.0505	−0.0532	0.4068	0.074*
C3	0.08703 (9)	−0.19425 (14)	0.33833 (17)	0.0681 (4)
H3	0.0621	−0.2404	0.3897	0.082*
C4	0.13086 (9)	−0.23748 (13)	0.25248 (16)	0.0649 (4)
H4	0.1352	−0.3133	0.2461	0.078*
C5	0.16877 (9)	−0.17094 (12)	0.17519 (13)	0.0569 (4)
H5	0.1986	−0.2019	0.1179	0.068*
C6	0.16216 (7)	−0.05669 (11)	0.18342 (12)	0.0474 (3)
C7	0.24768 (7)	−0.00845 (11)	0.02023 (12)	0.0478 (3)
C8	0.27596 (7)	0.09339 (11)	−0.04048 (12)	0.0473 (3)
H8A	0.2972	0.1421	0.0222	0.057*
H8B	0.2353	0.1315	−0.0823	0.057*
C9	0.33291 (7)	0.06764 (12)	−0.13204 (12)	0.0507 (3)
H9A	0.3150	0.0086	−0.1853	0.061*
H9B	0.3398	0.1318	−0.1829	0.061*
C10	0.40495 (7)	0.03491 (10)	−0.07268 (12)	0.0451 (3)
C11	0.10887 (8)	0.10874 (12)	0.28557 (13)	0.0558 (4)
C12	0.06633 (12)	0.25315 (15)	0.40603 (17)	0.0822 (6)
H12A	0.0422	0.2643	0.4812	0.123*
H12B	0.0385	0.2875	0.3395	0.123*
H12C	0.1144	0.2849	0.4131	0.123*
H1O5	0.4900 (13)	−0.0210 (17)	−0.107 (2)	0.094 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0760 (7)	0.0660 (7)	0.0697 (7)	0.0113 (5)	0.0266 (6)	0.0017 (5)
O2	0.1269 (11)	0.0472 (6)	0.0861 (8)	0.0148 (6)	0.0528 (8)	0.0094 (6)
O3	0.0983 (9)	0.0442 (6)	0.1023 (9)	0.0075 (6)	0.0432 (7)	−0.0041 (6)
O4	0.0512 (6)	0.0870 (8)	0.0558 (6)	0.0166 (5)	0.0005 (4)	−0.0161 (5)
O5	0.0473 (6)	0.0996 (9)	0.0575 (6)	0.0100 (5)	0.0081 (5)	−0.0179 (6)
N1	0.0626 (7)	0.0394 (6)	0.0530 (6)	0.0041 (5)	0.0121 (5)	0.0015 (5)
C1	0.0458 (7)	0.0500 (7)	0.0533 (7)	0.0001 (5)	0.0012 (6)	0.0062 (6)
C2	0.0496 (8)	0.0666 (9)	0.0681 (9)	−0.0035 (7)	0.0081 (7)	0.0119 (7)
C3	0.0617 (9)	0.0616 (9)	0.0809 (11)	−0.0166 (7)	0.0034 (8)	0.0177 (8)
C4	0.0759 (10)	0.0441 (7)	0.0732 (10)	−0.0145 (7)	−0.0100 (8)	0.0049 (7)
C5	0.0687 (9)	0.0451 (7)	0.0562 (8)	−0.0036 (6)	−0.0037 (6)	−0.0024 (6)
C6	0.0495 (7)	0.0447 (7)	0.0474 (7)	−0.0024 (5)	−0.0033 (5)	0.0030 (5)
C7	0.0473 (7)	0.0442 (7)	0.0517 (7)	0.0051 (5)	0.0012 (5)	−0.0013 (5)
C8	0.0438 (6)	0.0445 (7)	0.0536 (7)	0.0058 (5)	0.0012 (5)	0.0013 (5)
C9	0.0517 (7)	0.0510 (7)	0.0495 (7)	0.0034 (6)	0.0042 (6)	0.0039 (6)
C10	0.0445 (7)	0.0403 (6)	0.0512 (7)	−0.0029 (5)	0.0085 (5)	−0.0036 (5)
C11	0.0558 (8)	0.0563 (8)	0.0561 (8)	0.0087 (6)	0.0106 (6)	0.0052 (6)
C12	0.1029 (14)	0.0695 (11)	0.0762 (11)	0.0241 (10)	0.0242 (10)	−0.0058 (9)

Geometric parameters (Å, º)

O1—C11	1.3240 (18)	C3—H3	0.93
O1—C12	1.445 (2)	C4—C5	1.381 (2)
O2—C11	1.2063 (18)	C4—H4	0.93
O3—C7	1.2078 (17)	C5—C6	1.3999 (19)
O4—C10	1.2110 (16)	C5—H5	0.93
O5—C10	1.3037 (16)	C7—C8	1.5099 (19)
O5—H1O5	0.87 (2)	C8—C9	1.5129 (18)
N1—C7	1.3566 (17)	C8—H8A	0.97
N1—C6	1.3999 (17)	C8—H8B	0.97
N1—H1N	0.86	C9—C10	1.4921 (19)
C1—C2	1.397 (2)	C9—H9A	0.97
C1—C6	1.4117 (19)	C9—H9B	0.97
C1—C11	1.482 (2)	C12—H12A	0.96
C2—C3	1.373 (2)	C12—H12B	0.96
C2—H2	0.93	C12—H12C	0.96
C3—C4	1.369 (2)
C11—O1—C12	116.17 (13)	N1—C7—C8	112.94 (11)
C10—O5—H1O5	105.8 (14)	C7—C8—C9	112.48 (11)
C7—N1—C6	130.13 (11)	C7—C8—H8A	109.1
C7—N1—H1N	114.9	C9—C8—H8A	109.1
C6—N1—H1N	114.9	C7—C8—H8B	109.1
C2—C1—C6	119.03 (14)	C9—C8—H8B	109.1
C2—C1—C11	119.69 (13)	H8A—C8—H8B	107.8
C6—C1—C11	121.28 (12)	C10—C9—C8	113.15 (11)
C3—C2—C1	121.08 (15)	C10—C9—H9A	108.9
C3—C2—H2	119.5	C8—C9—H9A	108.9
C1—C2—H2	119.5	C10—C9—H9B	108.9
C4—C3—C2	119.64 (15)	C8—C9—H9B	108.9
C4—C3—H3	120.2	H9A—C9—H9B	107.8
C2—C3—H3	120.2	O4—C10—O5	123.42 (13)
C3—C4—C5	121.45 (15)	O4—C10—C9	123.32 (12)
C3—C4—H4	119.3	O5—C10—C9	113.24 (12)
C5—C4—H4	119.3	O2—C11—O1	121.47 (14)
C4—C5—C6	119.75 (15)	O2—C11—C1	125.30 (13)
C4—C5—H5	120.1	O1—C11—C1	113.23 (12)
C6—C5—H5	120.1	O1—C12—H12A	109.5
C5—C6—N1	121.91 (13)	O1—C12—H12B	109.5
C5—C6—C1	119.04 (13)	H12A—C12—H12B	109.5
N1—C6—C1	119.04 (12)	O1—C12—H12C	109.5
O3—C7—N1	124.61 (13)	H12A—C12—H12C	109.5
O3—C7—C8	122.44 (12)	H12B—C12—H12C	109.5
C6—C1—C2—C3	−0.3 (2)	C6—N1—C7—O3	0.1 (2)
C11—C1—C2—C3	−179.44 (14)	C6—N1—C7—C8	179.10 (13)
C1—C2—C3—C4	0.2 (2)	O3—C7—C8—C9	−5.2 (2)
C2—C3—C4—C5	0.2 (2)	N1—C7—C8—C9	175.77 (11)
C3—C4—C5—C6	−0.5 (2)	C7—C8—C9—C10	−73.29 (15)
C4—C5—C6—N1	178.98 (13)	C8—C9—C10—O4	−13.44 (19)
C4—C5—C6—C1	0.4 (2)	C8—C9—C10—O5	168.23 (12)
C7—N1—C6—C5	−0.2 (2)	C12—O1—C11—O2	−3.6 (2)
C7—N1—C6—C1	178.34 (13)	C12—O1—C11—C1	176.13 (14)
C2—C1—C6—C5	0.0 (2)	C2—C1—C11—O2	−172.99 (17)
C11—C1—C6—C5	179.10 (13)	C6—C1—C11—O2	7.9 (2)
C2—C1—C6—N1	−178.64 (13)	C2—C1—C11—O1	7.3 (2)
C11—C1—C6—N1	0.50 (19)	C6—C1—C11—O1	−171.88 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2	0.86	1.94	2.6534 (17)	139
O5—H1O5···O4^i	0.87 (2)	1.80 (2)	2.6657 (15)	173 (2)
C2—H2···O1	0.93	2.36	2.700 (2)	101
C5—H5···O3	0.93	2.27	2.881 (2)	123
C9—H9B···O2^ii	0.97	2.42	3.3184 (19)	154
C8—H8B···Cg1^iii	0.97	2.58	3.4470 (15)	149

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