N-Phenyl­anthranilic anhydride

Liu, G.-F.; Luo, Y.-W.; Qin, D.-B.

doi:10.1107/S1600536809013002

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1043

doi:10.1107/S1600536809013002

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N-Phenylanthranilic anhydride

Guan-Feng Liu,^a Yong-Wen Luo ^a and Da-Bin Qin ^a ^*

^aSchool of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002, People's Republic of China
^*Correspondence e-mail: qindabincwnu@yahoo.com.cn

(Received 16 March 2009; accepted 6 April 2009; online 18 April 2009)

The complete molecule of the title compound, C₂₆H₂₀N₂O₃, is generated by crystallographic twofold symmetry, with the central O atom lying on the rotation axis. The conformation is stabilized by an intramolecular N—H⋯O hydrogen bond. The dihedral angle between the inner and outer aromatic ring planes is 61.12 (5)°.

Related literature

For the synthesis, see: Martín et al. (2006 ); Wiklund et al. (2004 ). For related structures, see: Duesler et al. (1981 ); Huelgas et al. (2006 ).

Experimental

Crystal data

C₂₆H₂₀N₂O₃
M_r = 408.44
Monoclinic, C 2/c
a = 9.090 (3) Å
b = 21.056 (6) Å
c = 10.623 (3) Å
β = 100.594 (3)°
V = 1998.5 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 93 K
0.33 × 0.30 × 0.18 mm

Data collection

Rigaku Spider diffractometer
Absorption correction: none
8102 measured reflections
2275 independent reflections
2000 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.111
S = 1.00
2275 reflections
145 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1	0.903 (16)	1.966 (15)	2.6629 (14)	132.7 (13)

Data collection: RAPID-AUTO (Rigaku/MSC, 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809013002/hb2927sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809013002/hb2927Isup2.hkl

checkCIF report

Comment top

N-Phenylanthranilic acid derivatives display a antipyretic acitivity, its RhI complex is known as a remarkably active hydrogenation catalyst. N-phenyl anthranilic acid anhydride, which is considered as an important reaction intermediate, We here report the crystal structure of the title compound, (I).

Bond lengths and angles in (I) (Fig. 1) are within their normal ranges. In each independent molecule, the arrangement of N—H···O hydrogen bond and the planar (O=C—O) group is almost coplanar with respect to its carrier benzene ring, with dihedral angle of 6.63 (1)°, but the two benzene rings in the diphenylamine units are twisted with a dihedral angle of 61.12 (4)°. The structure is stabilized by an intramolecular hydrogen bond from an H atom of a amido N atom to a carbonyl O atom on the six-membered ring.

Related literature top

For the synthesis, see: Martín et al. (2006); Wiklund et al. (2004). For related structures, see: Duesler et al. (1981); Huelgas et al.(2006).

Experimental top

The title compound was prepared according to the reported procedure of Martín et al. (2006) and Wiklund et al. (2004). Colourless chunks of (I) were obtained by recrystallization from ethyl acetate.

Computing details top

Data collection: RAPID-AUTO (Rigaku/MSC, 2004); cell refinement: RAPID-AUTO (Rigaku/MSC, 2004); data reduction: RAPID-AUTO (Rigaku/MSC, 2004); 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids for the non-hydrogen atoms. Symmetry code: (i) –x, y, 1/2–y.

N-Phenylanthranilic anhydride top

Crystal data top

C₂₆H₂₀N₂O₃	F(000) = 856
M_r = 408.44	D_x = 1.358 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3250 reflections
a = 9.090 (3) Å	θ = 3.4–27.5°
b = 21.056 (6) Å	µ = 0.09 mm⁻¹
c = 10.623 (3) Å	T = 93 K
β = 100.594 (3)°	Chunk, colourless
V = 1998.5 (10) Å³	0.33 × 0.30 × 0.18 mm
Z = 4

Data collection top

Rigaku Spider diffractometer	2000 reflections with I > 2σ(I)
Radiation source: Rotating Anode	R_int = 0.023
Graphite monochromator	θ_max = 27.5°, θ_min = 3.4°
ω scans	h = −11→11
8102 measured reflections	k = −27→27
2275 independent reflections	l = −10→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0706P)² + 0.28P] where P = (F_o² + 2F_c²)/3
2275 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₂₆H₂₀N₂O₃	V = 1998.5 (10) Å³
M_r = 408.44	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 9.090 (3) Å	µ = 0.09 mm⁻¹
b = 21.056 (6) Å	T = 93 K
c = 10.623 (3) Å	0.33 × 0.30 × 0.18 mm
β = 100.594 (3)°

Data collection top

Rigaku Spider diffractometer	2000 reflections with I > 2σ(I)
8102 measured reflections	R_int = 0.023
2275 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.25 e Å⁻³
2275 reflections	Δρ_min = −0.20 e Å⁻³
145 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
O1	0.11910 (9)	0.38137 (4)	0.34545 (8)	0.0229 (2)
O2	0.0000	0.29421 (5)	0.2500	0.0225 (3)
N1	0.41159 (11)	0.37188 (5)	0.43582 (9)	0.0204 (2)
C1	0.56426 (13)	0.43835 (6)	0.59357 (11)	0.0236 (3)
H1	0.4845	0.4399	0.6401	0.028*
C2	0.69505 (14)	0.47174 (6)	0.63703 (12)	0.0275 (3)
H2	0.7045	0.4964	0.7130	0.033*
C3	0.81191 (14)	0.46930 (6)	0.57006 (13)	0.0274 (3)
H3	0.9020	0.4918	0.6006	0.033*
C4	0.79712 (13)	0.43398 (5)	0.45834 (12)	0.0246 (3)
H4	0.8771	0.4324	0.4121	0.030*
C5	0.66575 (13)	0.40089 (5)	0.41392 (11)	0.0215 (3)
H5	0.6555	0.3771	0.3369	0.026*
C6	0.54946 (12)	0.40262 (5)	0.48214 (11)	0.0185 (3)
C7	0.39399 (12)	0.30870 (5)	0.40566 (10)	0.0176 (2)
C8	0.51448 (12)	0.26579 (6)	0.43627 (11)	0.0207 (3)
H8	0.6099	0.2811	0.4764	0.025*
C9	0.49596 (13)	0.20234 (6)	0.40898 (11)	0.0233 (3)
H9	0.5787	0.1744	0.4313	0.028*
C10	0.35825 (13)	0.17796 (6)	0.34912 (11)	0.0234 (3)
H10	0.3469	0.1339	0.3305	0.028*
C11	0.23933 (13)	0.21874 (5)	0.31759 (11)	0.0206 (3)
H11	0.1453	0.2025	0.2763	0.025*
C12	0.25345 (12)	0.28396 (5)	0.34495 (10)	0.0179 (3)
C13	0.12427 (12)	0.32625 (5)	0.31547 (10)	0.0183 (2)
H1N	0.3269 (17)	0.3947 (7)	0.4330 (15)	0.039 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0191 (4)	0.0209 (4)	0.0273 (5)	0.0013 (3)	0.0006 (3)	−0.0033 (3)
O2	0.0175 (6)	0.0198 (6)	0.0272 (6)	0.000	−0.0037 (5)	0.000
N1	0.0157 (5)	0.0197 (5)	0.0248 (5)	0.0012 (4)	0.0014 (4)	−0.0022 (4)
C1	0.0231 (6)	0.0258 (6)	0.0215 (6)	0.0022 (5)	0.0033 (5)	−0.0004 (5)
C2	0.0299 (7)	0.0248 (6)	0.0244 (6)	0.0003 (5)	−0.0037 (5)	−0.0046 (5)
C3	0.0219 (6)	0.0198 (6)	0.0367 (7)	−0.0020 (4)	−0.0045 (5)	0.0005 (5)
C4	0.0199 (6)	0.0200 (6)	0.0340 (7)	0.0010 (4)	0.0051 (5)	0.0036 (5)
C5	0.0225 (6)	0.0199 (6)	0.0215 (6)	0.0012 (4)	0.0027 (5)	−0.0015 (4)
C6	0.0171 (6)	0.0170 (5)	0.0197 (5)	0.0008 (4)	−0.0009 (4)	0.0014 (4)
C7	0.0181 (6)	0.0189 (5)	0.0158 (5)	−0.0003 (4)	0.0033 (4)	0.0015 (4)
C8	0.0170 (6)	0.0234 (6)	0.0212 (6)	0.0002 (4)	0.0019 (4)	0.0035 (4)
C9	0.0218 (6)	0.0230 (6)	0.0256 (6)	0.0058 (4)	0.0059 (5)	0.0055 (5)
C10	0.0260 (6)	0.0179 (5)	0.0268 (6)	0.0004 (5)	0.0064 (5)	0.0007 (5)
C11	0.0206 (6)	0.0210 (6)	0.0203 (6)	−0.0019 (4)	0.0039 (4)	0.0002 (4)
C12	0.0181 (6)	0.0202 (6)	0.0157 (5)	0.0005 (4)	0.0037 (4)	0.0014 (4)
C13	0.0173 (6)	0.0197 (5)	0.0175 (5)	−0.0021 (4)	0.0023 (4)	0.0002 (4)

Geometric parameters (Å, º) top

O1—C13	1.2067 (14)	C4—H4	0.9500
O2—C13ⁱ	1.3877 (12)	C5—C6	1.3876 (17)
O2—C13	1.3877 (12)	C5—H5	0.9500
N1—C7	1.3708 (15)	C7—C8	1.4109 (15)
N1—C6	1.4159 (14)	C7—C12	1.4199 (15)
N1—H1N	0.903 (16)	C8—C9	1.3708 (17)
C1—C2	1.3853 (18)	C8—H8	0.9500
C1—C6	1.3880 (16)	C9—C10	1.3936 (17)
C1—H1	0.9500	C9—H9	0.9500
C2—C3	1.3838 (19)	C10—C11	1.3728 (16)
C2—H2	0.9500	C10—H10	0.9500
C3—C4	1.3860 (18)	C11—C12	1.4047 (15)
C3—H3	0.9500	C11—H11	0.9500
C4—C5	1.3881 (16)	C12—C13	1.4610 (15)

C13ⁱ—O2—C13	121.84 (12)	N1—C7—C8	121.02 (10)
C7—N1—C6	125.64 (9)	N1—C7—C12	121.25 (10)
C7—N1—H1N	116.5 (10)	C8—C7—C12	117.72 (10)
C6—N1—H1N	117.6 (10)	C9—C8—C7	121.02 (10)
C2—C1—C6	120.13 (11)	C9—C8—H8	119.5
C2—C1—H1	119.9	C7—C8—H8	119.5
C6—C1—H1	119.9	C8—C9—C10	121.37 (11)
C3—C2—C1	120.18 (11)	C8—C9—H9	119.3
C3—C2—H2	119.9	C10—C9—H9	119.3
C1—C2—H2	119.9	C11—C10—C9	118.80 (11)
C2—C3—C4	119.82 (11)	C11—C10—H10	120.6
C2—C3—H3	120.1	C9—C10—H10	120.6
C4—C3—H3	120.1	C10—C11—C12	121.54 (11)
C3—C4—C5	120.16 (12)	C10—C11—H11	119.2
C3—C4—H4	119.9	C12—C11—H11	119.2
C5—C4—H4	119.9	C11—C12—C7	119.53 (10)
C6—C5—C4	119.98 (11)	C11—C12—C13	120.82 (10)
C6—C5—H5	120.0	C7—C12—C13	119.62 (10)
C4—C5—H5	120.0	O1—C13—O2	122.15 (10)
C5—C6—C1	119.73 (10)	O1—C13—C12	126.76 (10)
C5—C6—N1	121.13 (10)	O2—C13—C12	111.05 (10)
C1—C6—N1	119.01 (10)

C6—C1—C2—C3	−0.43 (18)	C8—C9—C10—C11	−0.18 (18)
C1—C2—C3—C4	0.82 (18)	C9—C10—C11—C12	−0.38 (17)
C2—C3—C4—C5	−0.28 (18)	C10—C11—C12—C7	0.54 (17)
C3—C4—C5—C6	−0.66 (17)	C10—C11—C12—C13	−177.48 (11)
C4—C5—C6—C1	1.05 (16)	N1—C7—C12—C11	−178.92 (10)
C4—C5—C6—N1	176.88 (10)	C8—C7—C12—C11	−0.14 (16)
C2—C1—C6—C5	−0.51 (17)	N1—C7—C12—C13	−0.87 (16)
C2—C1—C6—N1	−176.42 (10)	C8—C7—C12—C13	177.90 (10)
C7—N1—C6—C5	56.75 (16)	C13ⁱ—O2—C13—O1	18.14 (8)
C7—N1—C6—C1	−127.39 (12)	C13ⁱ—O2—C13—C12	−164.03 (10)
C6—N1—C7—C8	9.20 (17)	C11—C12—C13—O1	172.29 (11)
C6—N1—C7—C12	−172.07 (10)	C7—C12—C13—O1	−5.73 (18)
N1—C7—C8—C9	178.37 (10)	C11—C12—C13—O2	−5.43 (14)
C12—C7—C8—C9	−0.41 (17)	C7—C12—C13—O2	176.56 (9)
C7—C8—C9—C10	0.58 (18)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.903 (16)	1.966 (15)	2.6629 (14)	132.7 (13)

Experimental details

Crystal data
Chemical formula	C₂₆H₂₀N₂O₃
M_r	408.44
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	93
a, b, c (Å)	9.090 (3), 21.056 (6), 10.623 (3)
β (°)	100.594 (3)
V (Å³)	1998.5 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.33 × 0.30 × 0.18

Data collection
Diffractometer	Rigaku Spider diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8102, 2275, 2000
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.111, 1.00
No. of reflections	2275
No. of parameters	145
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.20

Computer programs: RAPID-AUTO (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.903 (16)	1.966 (15)	2.6629 (14)	132.7 (13)

Acknowledgements

The authors thank the Scientific Researching Fund Projects of China West Normal University (grant No. 06B003) and the Youth Fund Projects of Sichuan Educational Department (grant No. 2006B039).

References

Duesler, E. N., Kress, R. B., Lin, C. T., Shiau, W. I., Paul, I. C. & Curtin, D. Y. (1981). J. Am. Chem. Soc. 103, 875–879. CSD CrossRef CAS Web of Science Google Scholar
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