N-(4-Nitro­phen­yl)-N′-phenyl­succinamide

In the title compound, C₁₆H₁₅N₃O₄, the dihedral angle between the two benzene ring is 16.66 (6)°. The mol­ecule crystallizes in a centrosymmetric space group and hence does not exhibit nonlinear optical second harmonic generation properties. The angle between the mean plane of the 4-nitro­phenyl group and the adjacent NCO group is 26.2 (8)°, while the angle between the mean plane of the phenyl ring and its adjacent NCO group is 40.8 (5)°. The dihedral angle between the two NCO groups is 5.2 (3)°. The crystal packing is stabilized by intra­molecular C—H...O and inter­molecular N—H...O inter­actions, which link the mol­ecules into chains along the b axis in the bc plane, with the phenyl rings arranged oblique to this plane.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.054
• wR factor = 0.149
• Data-to-parameter ratio = 20.5

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.802     1.000
            Tmin(prime) and Tmax expected:      0.936     0.958
            RR(prime) =      0.821
            Please check that your absorption correction is appropriate.
DIFMX01_ALERT_2_C  The maximum difference density is > 0.1*ZMAX*0.75
            _refine_diff_density_max given =      0.719
            Test value =      0.600
DIFMX02_ALERT_1_C  The maximum difference density is > 0.1*ZMAX*0.75
            The relevant atom site should be identified.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.82
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.96
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.28
PLAT097_ALERT_2_C Maximum (Positive) Residual Density ............       0.72 e/A   
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.958
            Tmax scaled      0.958 Tmin scaled      0.768

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

   2 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
   4 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

Organic nonlinear optical (NLO) materials are of increasing interest due to their large second harmonic conversion efficiency, ultra fast response, high laser damage resistance, and flexibility they offer to tune the nonlinear optical properties through structure modification [Munn & Ironside (1993)]. Due to the presence of inversion symmetry in (I), the second harmonic response is zero. However, it exhibits third order nonlinear optical properties (nonlinear absorption and nonlinear refraction). The detailed measurement on the third order nonlinear properties of (I) has not yet performed. In order to further understand the structure-property relationship of these compounds, the title compound (I) has been synthesized and its crystal structure is reported.

The geometric parameters for (I) are normal. The C8—C9 bond length of 1.5246 (15) Å is in good agreement with the three isomeric N-(p-chlorophenyl)succinimides [Glidewell et al. (2005); C8—C9 = 1.5276 (19), 1.518 (3) and 1.524 (5) Å] (Fig. 1). The dihedral angle between the two benzene rings [C1—C6 and C11—C16] is 16.66 (6)°. The molecule crystallizes in a cetrosymmetric space group and hence does not exhibit second order nonlinear optical properties. The angle between the mean plane of the 4-nitrophenyl group and the adjacent N1–C7–O1 group is 26.2 (8)° while the angle between the mean plane of the benzene ring and its adjacent N2–C10–O2 group is 40.8 (5)°. The dihedral angle between the two N–C–O groups is 5.2 (3)°. The mean plane through the succinic acid fragment (C7—C10) makes the dihedral angle of 3.26 (9)° and 14.60 (9)° with the C1—C6 and C11—C16 benzene rings, respectively. Crystal packing is stabilized by intermolecular N—H—O interactions which link the molecules into chains along the b axis in the bc plane with the phenyl rings arranged oblique to this plane (Fig. 2).

Related literature

For related structures, see: Crass et al. (1996); Anjum et al. (2005). For related literature, see: Ravindra et al. (2006); Glidewell et al. (2005); Munn & Ironside (1993).

S2. Experimental

Aniline [1.395 (9) g, 0.015 mole] and p-nitrophenylsuccinamic acid [2.381 (1) g, 0.01 mole] were mixed in a test tube and the mixture was heated to 140° for 3 h. After cooling the solid residue was washed with dilute HCl to remove excess aniline and dried. Purification was carried out by successive recrystallization from a dimethylformamide (DMF) solution. Crystal growth was achieved by the slow evaporation of a DMF solution of (I). Analysis found: C 61.29, H 4.52, N 13.38; C₁₆H₁₅N₃O₄ requires: C 61.33, H 4.78, N 13.41.

S3. Refinement

The amide hydrogen atoms (H1A & H2B) were located in a difference Fourier map and along with all other H atoms were placed in their calculated positions and then refined using the riding model with N—H = 0.88 Å and C—H = 0.95 to 0.99 Å, and with U_iso(H) = 1.17–1.22U_eq(C,N). The maximum residual electron density peaks of 0.72 and -0.32 e ų, were located at 0.68 from C13 and 0.50 Å from N3. Owing to the poor diffraction quality of the crystal, the range of Tmax to Tmin is large (0.82).

Computing details

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker 2000); software used to prepare material for publication: SHELXTL (Bruker 2000).

Figures

	Fig. 1. Molecular structure of the title compound, showing atom labeling and 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of C16H15N3O4, viewed down the a axis. Dashed lines indicate intermolecular hydrogen bonding.

N-(4-nitrophenyl)-N'-phenylsuccinamide

Crystal data

C16H15N3O4	Z = 2
Mr = 313.31	F(000) = 328
Triclinic, P1	Dx = 1.469 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7585 (4) Å	Cell parameters from 6328 reflections
b = 9.8447 (8) Å	θ = 2.4–30.5°
c = 12.9961 (10) Å	µ = 0.11 mm^−1
α = 79.216 (1)°	T = 100 K
β = 79.014 (1)°	Block, colorless
γ = 83.779 (1)°	0.60 × 0.53 × 0.40 mm
V = 708.46 (9) Å^3

Data collection

Bruker SMART CCD area detector diffractometer	4260 independent reflections
Radiation source: fine-focus sealed tube	3904 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
φ and ω scans	θmax = 30.5°, θmin = 1.6°
Absorption correction: multi-scan SADABS (Sheldrick, 2004)	h = −8→8
Tmin = 0.802, Tmax = 1.000	k = −14→14
8553 measured reflections	l = −17→18

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0918P)^2 + 0.2598P] where P = (Fo^2 + 2Fc^2)/3
4260 reflections	(Δ/σ)max = 0.003
208 parameters	Δρmax = 0.72 e Å^−3
0 restraints	Δρmin = −0.32 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 > 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	0.20220 (15)	0.59779 (8)	0.11503 (7)	0.0216 (2)
O2	0.85535 (16)	0.89058 (8)	−0.09865 (8)	0.0238 (2)
O31	−0.94624 (17)	0.83821 (11)	0.42542 (8)	0.0303 (2)
O32	−0.83201 (19)	0.62538 (11)	0.48486 (9)	0.0339 (2)
N1	0.06558 (16)	0.81592 (9)	0.14504 (8)	0.01558 (19)
H1A	0.1019	0.9028	0.1300	0.019*
N2	0.97801 (16)	0.67817 (9)	−0.14277 (7)	0.01529 (19)
H2B	0.9512	0.5897	−0.1272	0.018*
N3	−0.79896 (19)	0.73754 (12)	0.42692 (9)	0.0237 (2)
C1	−0.14639 (18)	0.78803 (10)	0.21684 (8)	0.0142 (2)
C2	−0.3242 (2)	0.89650 (11)	0.21885 (9)	0.0192 (2)
H2A	−0.2980	0.9824	0.1725	0.023*
C3	−0.5377 (2)	0.87974 (13)	0.28773 (10)	0.0215 (2)
H3A	−0.6589	0.9533	0.2893	0.026*
C4	−0.5715 (2)	0.75360 (12)	0.35439 (9)	0.0184 (2)
C5	−0.3970 (2)	0.64476 (12)	0.35496 (9)	0.0193 (2)
H5A	−0.4238	0.5596	0.4021	0.023*
C6	−0.1823 (2)	0.66201 (11)	0.28562 (9)	0.0175 (2)
H6A	−0.0608	0.5886	0.2850	0.021*
C7	0.22059 (18)	0.72342 (11)	0.09634 (8)	0.0147 (2)
C8	0.41412 (19)	0.79024 (11)	0.01248 (9)	0.0165 (2)
H8A	0.4492	0.8769	0.0327	0.020*
H8B	0.3566	0.8150	−0.0562	0.020*
C9	0.64177 (19)	0.69581 (10)	−0.00172 (8)	0.0152 (2)
H9A	0.7002	0.6710	0.0668	0.018*
H9B	0.6077	0.6092	−0.0224	0.018*
C10	0.83239 (19)	0.76554 (11)	−0.08602 (8)	0.0151 (2)
C11	1.17126 (19)	0.71785 (11)	−0.22565 (8)	0.0145 (2)
C12	1.1442 (2)	0.83097 (12)	−0.30570 (9)	0.0190 (2)
H12A	0.9966	0.8846	−0.3048	0.023*
C13	1.3342 (2)	0.86508 (13)	−0.38702 (10)	0.0230 (2)
H13A	1.3166	0.9433	−0.4409	0.028*
C14	1.5494 (2)	0.78587 (13)	−0.39017 (10)	0.0236 (3)
H14A	1.6781	0.8092	−0.4463	0.028*
C15	1.5752 (2)	0.67233 (13)	−0.31067 (10)	0.0233 (2)
H15A	1.7217	0.6175	−0.3127	0.028*
C16	1.3867 (2)	0.63844 (12)	−0.22772 (9)	0.0188 (2)
H16A	1.4054	0.5615	−0.1729	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0215 (4)	0.0110 (4)	0.0287 (4)	−0.0031 (3)	0.0062 (3)	−0.0044 (3)
O2	0.0255 (4)	0.0119 (4)	0.0305 (5)	−0.0060 (3)	0.0085 (3)	−0.0058 (3)
O31	0.0197 (4)	0.0355 (5)	0.0326 (5)	0.0023 (4)	0.0018 (4)	−0.0065 (4)
O32	0.0299 (5)	0.0304 (5)	0.0359 (6)	−0.0092 (4)	0.0064 (4)	−0.0003 (4)
N1	0.0159 (4)	0.0096 (4)	0.0194 (4)	−0.0019 (3)	0.0021 (3)	−0.0026 (3)
N2	0.0158 (4)	0.0104 (4)	0.0176 (4)	−0.0025 (3)	0.0025 (3)	−0.0018 (3)
N3	0.0194 (5)	0.0279 (5)	0.0232 (5)	−0.0049 (4)	0.0006 (4)	−0.0053 (4)
C1	0.0143 (4)	0.0130 (4)	0.0153 (5)	−0.0020 (3)	−0.0005 (3)	−0.0037 (3)
C2	0.0192 (5)	0.0141 (5)	0.0215 (5)	0.0014 (4)	−0.0006 (4)	−0.0005 (4)
C3	0.0172 (5)	0.0211 (5)	0.0241 (5)	0.0038 (4)	−0.0012 (4)	−0.0042 (4)
C4	0.0156 (5)	0.0223 (5)	0.0174 (5)	−0.0036 (4)	0.0001 (4)	−0.0056 (4)
C5	0.0209 (5)	0.0176 (5)	0.0175 (5)	−0.0034 (4)	0.0014 (4)	−0.0019 (4)
C6	0.0186 (5)	0.0141 (4)	0.0176 (5)	0.0002 (4)	0.0002 (4)	−0.0014 (4)
C7	0.0142 (4)	0.0122 (4)	0.0168 (5)	−0.0019 (3)	0.0002 (3)	−0.0029 (3)
C8	0.0166 (5)	0.0118 (4)	0.0187 (5)	−0.0021 (3)	0.0023 (4)	−0.0012 (3)
C9	0.0153 (4)	0.0118 (4)	0.0165 (5)	−0.0028 (3)	0.0019 (4)	−0.0013 (3)
C10	0.0149 (4)	0.0130 (4)	0.0165 (5)	−0.0025 (3)	0.0004 (4)	−0.0029 (3)
C11	0.0143 (4)	0.0132 (4)	0.0157 (5)	−0.0029 (3)	0.0002 (3)	−0.0036 (3)
C12	0.0185 (5)	0.0174 (5)	0.0186 (5)	−0.0013 (4)	0.0000 (4)	−0.0001 (4)
C13	0.0251 (6)	0.0229 (5)	0.0182 (5)	−0.0055 (4)	0.0016 (4)	0.0003 (4)
C14	0.0193 (5)	0.0297 (6)	0.0211 (5)	−0.0073 (4)	0.0044 (4)	−0.0073 (4)
C15	0.0150 (5)	0.0280 (6)	0.0268 (6)	0.0004 (4)	−0.0003 (4)	−0.0091 (5)
C16	0.0171 (5)	0.0184 (5)	0.0201 (5)	0.0013 (4)	−0.0027 (4)	−0.0037 (4)

Geometric parameters (Å, º)

O1—C7	1.2273 (13)	C6—H6A	0.9500
O2—C10	1.2293 (13)	C7—C8	1.5133 (14)
O31—N3	1.2324 (14)	C8—C9	1.5246 (15)
O32—N3	1.2256 (15)	C8—H8A	0.9900
N1—C7	1.3605 (13)	C8—H8B	0.9900
N1—C1	1.4067 (13)	C9—C10	1.5166 (14)
N1—H1A	0.8800	C9—H9A	0.9900
N2—C10	1.3536 (13)	C9—H9B	0.9900
N2—C11	1.4252 (13)	C11—C16	1.3913 (15)
N2—H2B	0.8800	C11—C12	1.3918 (15)
N3—C4	1.4655 (15)	C12—C13	1.3901 (15)
C1—C6	1.3968 (15)	C12—H12A	0.9500
C1—C2	1.3973 (14)	C13—C14	1.3889 (18)
C2—C3	1.3820 (16)	C13—H13A	0.9500
C2—H2A	0.9500	C14—C15	1.3890 (18)
C3—C4	1.3842 (17)	C14—H14A	0.9500
C3—H3A	0.9500	C15—C16	1.3963 (16)
C4—C5	1.3873 (16)	C15—H15A	0.9500
C5—C6	1.3903 (15)	C16—H16A	0.9500
C5—H5A	0.9500
C7—N1—C1	127.19 (9)	C9—C8—H8A	109.1
C7—N1—H1A	116.4	C7—C8—H8B	109.1
C1—N1—H1A	116.4	C9—C8—H8B	109.1
C10—N2—C11	125.28 (9)	H8A—C8—H8B	107.8
C10—N2—H2B	117.4	C10—C9—C8	111.42 (9)
C11—N2—H2B	117.4	C10—C9—H9A	109.3
O32—N3—O31	123.96 (11)	C8—C9—H9A	109.3
O32—N3—C4	118.41 (10)	C10—C9—H9B	109.3
O31—N3—C4	117.63 (10)	C8—C9—H9B	109.3
C6—C1—C2	120.11 (10)	H9A—C9—H9B	108.0
C6—C1—N1	123.70 (9)	O2—C10—N2	123.39 (10)
C2—C1—N1	116.17 (9)	O2—C10—C9	122.10 (9)
C3—C2—C1	120.47 (10)	N2—C10—C9	114.47 (9)
C3—C2—H2A	119.8	C16—C11—C12	120.11 (10)
C1—C2—H2A	119.8	C16—C11—N2	118.88 (10)
C2—C3—C4	118.67 (10)	C12—C11—N2	120.97 (10)
C2—C3—H3A	120.7	C13—C12—C11	119.69 (11)
C4—C3—H3A	120.7	C13—C12—H12A	120.2
C3—C4—C5	122.05 (10)	C11—C12—H12A	120.2
C3—C4—N3	117.98 (10)	C14—C13—C12	120.62 (11)
C5—C4—N3	119.97 (10)	C14—C13—H13A	119.7
C4—C5—C6	119.13 (10)	C12—C13—H13A	119.7
C4—C5—H5A	120.4	C15—C14—C13	119.55 (11)
C6—C5—H5A	120.4	C15—C14—H14A	120.2
C5—C6—C1	119.56 (10)	C13—C14—H14A	120.2
C5—C6—H6A	120.2	C14—C15—C16	120.30 (11)
C1—C6—H6A	120.2	C14—C15—H15A	119.9
O1—C7—N1	123.76 (10)	C16—C15—H15A	119.9
O1—C7—C8	122.49 (9)	C11—C16—C15	119.73 (11)
N1—C7—C8	113.69 (9)	C11—C16—H16A	120.1
C7—C8—C9	112.61 (9)	C15—C16—H16A	120.1
C7—C8—H8A	109.1
C7—N1—C1—C6	30.18 (17)	O1—C7—C8—C9	−30.73 (15)
C7—N1—C1—C2	−151.52 (11)	N1—C7—C8—C9	151.83 (10)
C6—C1—C2—C3	−0.80 (17)	C7—C8—C9—C10	−179.91 (9)
N1—C1—C2—C3	−179.16 (10)	C11—N2—C10—O2	−1.76 (18)
C1—C2—C3—C4	−0.03 (18)	C11—N2—C10—C9	−179.55 (10)
C2—C3—C4—C5	0.83 (18)	C8—C9—C10—O2	35.54 (15)
C2—C3—C4—N3	−179.99 (10)	C8—C9—C10—N2	−146.63 (10)
O32—N3—C4—C3	178.70 (12)	C10—N2—C11—C16	135.14 (12)
O31—N3—C4—C3	−0.99 (17)	C10—N2—C11—C12	−47.19 (16)
O32—N3—C4—C5	−2.09 (17)	C16—C11—C12—C13	−0.71 (17)
O31—N3—C4—C5	178.21 (11)	N2—C11—C12—C13	−178.36 (10)
C3—C4—C5—C6	−0.79 (18)	C11—C12—C13—C14	1.16 (18)
N3—C4—C5—C6	−179.96 (10)	C12—C13—C14—C15	−0.60 (19)
C4—C5—C6—C1	−0.06 (17)	C13—C14—C15—C16	−0.41 (19)
C2—C1—C6—C5	0.83 (17)	C12—C11—C16—C15	−0.28 (17)
N1—C1—C6—C5	179.07 (10)	N2—C11—C16—C15	177.41 (10)
C1—N1—C7—O1	−5.20 (18)	C14—C15—C16—C11	0.85 (18)
C1—N1—C7—C8	172.20 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2^i	0.88	2.03	2.9066 (12)	173
N2—H2B···O1^ii	0.88	2.10	2.9478 (12)	162
C6—H6A···O1	0.95	2.42	2.9271 (15)	113

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