Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807050325/kj2061sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807050325/kj2061Isup2.hkl |
CCDC reference: 667431
The title compound (I) was prepared by the method reported by Brunton & Jones (2000). The compound was purified by recrystallization from ethanol. The crystals used for single-crystal X-ray studies were grown by slow evaporation of an acetone solution of the purified compound.
H-atom positions were located from difference Fourier maps and all associated parameters were refined freely. Refined C—H distances were in the range 0.949 (14)–0.995 (14) Å, where as N—H and O—H distances are 0.852 (15) Å and 0.863 (19) Å respectively.
Crystallization in a noncentrosymmetric space group is required for organic nonlinear optical (NLO) materials to exhibit efficient second harmonic generation (SHG) (Munn et al., 1993). Our interest in organic nonlinear optical materials, particularly in acid anhydride derivatives (Ravindra et al., 2006) of nitroaniline, has led us to synthesize the title compound. This compound crystallizes in a centrosymmetric structure and hence exhibits no second harmonic generation. However, the molecule shows third order nonlinear response (nonlinear absorption), which can be observed in molecules with both centrosymmetic and noncentrosymmetric structures.
A projection view of the molecule with 50% probability displacement ellipsoids is shown in Fig 1. The C2—C3 bond length is in good agreement with the three isomeric N-(p-chlorophenyl)succinimides (Glidewell et al., 2005) which display C—C bond lengths of 1.5276 (19), 1.518 (3) and 1.524 (5) Å. The nitro and amine groups attached to C8 and C5 are almost coplanar with the C5—C10 benzene ring, with O5—N2—C8—C9 and C4—N1—C5—C10 torsion angles of 5.65 (14)° and 6.43 (15)°,respectively.
The hydrogen bonding parameters are listed in Table 2. As expected, the carboxyl groups of two molecules form strong intermolecular hydrogen bonding resulting in the head to tail dimers. The N—H hydrogen atom forms bifurcated intermolecular hydrogen bonds to the NO2 group of a second molecule. Thus the crystal structure is stabilized by the formation of two-dimensional networks involving bifurcated and dimeric hydrogen bonds involving N1—H1A···O4, N1—H1A···O5 and O1—H1···O1. The extended hydrogen bonding network results in a step like arrangement between the layers in the crystal lattice with the carboxyl dimers as the steps.
For related literature, see: Glidewell et al. (2005); Munn & Ironside (1993); Ravindra et al. (2006); Brunton & Jones (2000).
Data collection: APEXII (Bruker, 2005); cell refinement: APEXII (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2005); program(s) used to refine structure: SHELXTL (Sheldrick, 2005); molecular graphics: SHELXTL (Sheldrick, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2005).
C10H10N2O5 | F(000) = 496 |
Mr = 238.20 | Dx = 1.578 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6073 reflections |
a = 5.0179 (4) Å | θ = 2.4–30.6° |
b = 17.3056 (15) Å | µ = 0.13 mm−1 |
c = 11.5804 (9) Å | T = 100 K |
β = 94.487 (4)° | Irregular, colourless |
V = 1002.53 (14) Å3 | 0.33 × 0.27 × 0.22 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 3066 independent reflections |
Radiation source: fine-focus sealed tube | 2686 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
φ and ω scans | θmax = 30.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −6→7 |
Tmin = 0.959, Tmax = 0.972 | k = −24→24 |
30488 measured reflections | l = −16→16 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | All H-atom parameters refined |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0495P)2 + 0.3297P] where P = (Fo2 + 2Fc2)/3 |
3066 reflections | (Δ/σ)max = 0.001 |
194 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C10H10N2O5 | V = 1002.53 (14) Å3 |
Mr = 238.20 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.0179 (4) Å | µ = 0.13 mm−1 |
b = 17.3056 (15) Å | T = 100 K |
c = 11.5804 (9) Å | 0.33 × 0.27 × 0.22 mm |
β = 94.487 (4)° |
Bruker APEXII CCD area-detector diffractometer | 3066 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 2686 reflections with I > 2σ(I) |
Tmin = 0.959, Tmax = 0.972 | Rint = 0.031 |
30488 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.097 | All H-atom parameters refined |
S = 1.06 | Δρmax = 0.39 e Å−3 |
3066 reflections | Δρmin = −0.26 e Å−3 |
194 parameters |
Experimental. All H atoms were located and refined freely. |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.31721 (15) | 0.59418 (4) | 0.95848 (7) | 0.01813 (16) | |
O2 | 0.25598 (14) | 0.46856 (4) | 0.91943 (6) | 0.01693 (16) | |
O3 | 0.20764 (14) | 0.50534 (4) | 0.63580 (6) | 0.01685 (16) | |
O4 | 0.47768 (17) | 0.15785 (4) | 0.28173 (7) | 0.02248 (18) | |
O5 | 0.68389 (18) | 0.26212 (5) | 0.23997 (8) | 0.0289 (2) | |
N1 | −0.02051 (16) | 0.39108 (5) | 0.62342 (7) | 0.01322 (16) | |
N2 | 0.52247 (17) | 0.22718 (5) | 0.29519 (7) | 0.01579 (17) | |
C1 | 0.19088 (18) | 0.53594 (5) | 0.90384 (8) | 0.01307 (18) | |
C2 | −0.04231 (18) | 0.55979 (6) | 0.82212 (8) | 0.01367 (18) | |
C3 | −0.15950 (19) | 0.49103 (6) | 0.75392 (8) | 0.01358 (18) | |
C4 | 0.02909 (18) | 0.46387 (5) | 0.66623 (8) | 0.01233 (17) | |
C5 | 0.12121 (18) | 0.35175 (5) | 0.54208 (8) | 0.01224 (17) | |
C6 | 0.05349 (19) | 0.27432 (5) | 0.51835 (8) | 0.01431 (18) | |
C7 | 0.18377 (19) | 0.23258 (6) | 0.43764 (8) | 0.01480 (18) | |
C8 | 0.38209 (19) | 0.26926 (5) | 0.38056 (8) | 0.01336 (18) | |
C9 | 0.45402 (19) | 0.34517 (6) | 0.40309 (8) | 0.01467 (18) | |
C10 | 0.32460 (19) | 0.38663 (6) | 0.48410 (8) | 0.01455 (18) | |
H1 | 0.446 (4) | 0.5748 (11) | 1.0030 (16) | 0.045 (5)* | |
H1A | −0.147 (3) | 0.3663 (8) | 0.6518 (12) | 0.022 (3)* | |
H2A | −0.175 (3) | 0.5839 (8) | 0.8700 (12) | 0.021 (3)* | |
H2B | 0.022 (3) | 0.5992 (8) | 0.7723 (12) | 0.022 (3)* | |
H3A | −0.327 (3) | 0.5060 (8) | 0.7124 (12) | 0.020 (3)* | |
H3B | −0.198 (3) | 0.4475 (8) | 0.8060 (12) | 0.020 (3)* | |
H6 | −0.084 (3) | 0.2505 (8) | 0.5578 (12) | 0.022 (3)* | |
H7 | 0.135 (3) | 0.1795 (9) | 0.4192 (12) | 0.023 (3)* | |
H9 | 0.593 (3) | 0.3686 (8) | 0.3641 (13) | 0.025 (4)* | |
H10 | 0.375 (3) | 0.4392 (8) | 0.5002 (12) | 0.020 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0185 (3) | 0.0143 (3) | 0.0208 (3) | −0.0005 (3) | −0.0030 (3) | −0.0024 (3) |
O2 | 0.0178 (3) | 0.0139 (3) | 0.0186 (3) | 0.0014 (3) | −0.0016 (3) | −0.0013 (3) |
O3 | 0.0156 (3) | 0.0158 (3) | 0.0200 (3) | −0.0042 (3) | 0.0065 (3) | −0.0034 (3) |
O4 | 0.0297 (4) | 0.0142 (3) | 0.0242 (4) | 0.0033 (3) | 0.0061 (3) | −0.0035 (3) |
O5 | 0.0329 (5) | 0.0281 (4) | 0.0285 (4) | −0.0060 (3) | 0.0208 (4) | −0.0062 (3) |
N1 | 0.0126 (4) | 0.0135 (4) | 0.0142 (4) | −0.0030 (3) | 0.0053 (3) | −0.0010 (3) |
N2 | 0.0164 (4) | 0.0169 (4) | 0.0144 (4) | 0.0024 (3) | 0.0029 (3) | −0.0016 (3) |
C1 | 0.0127 (4) | 0.0152 (4) | 0.0119 (4) | −0.0005 (3) | 0.0042 (3) | −0.0013 (3) |
C2 | 0.0137 (4) | 0.0139 (4) | 0.0135 (4) | 0.0015 (3) | 0.0021 (3) | −0.0015 (3) |
C3 | 0.0118 (4) | 0.0155 (4) | 0.0137 (4) | −0.0003 (3) | 0.0029 (3) | −0.0010 (3) |
C4 | 0.0118 (4) | 0.0135 (4) | 0.0117 (4) | 0.0004 (3) | 0.0005 (3) | −0.0002 (3) |
C5 | 0.0124 (4) | 0.0129 (4) | 0.0115 (4) | 0.0005 (3) | 0.0018 (3) | −0.0001 (3) |
C6 | 0.0144 (4) | 0.0132 (4) | 0.0158 (4) | −0.0023 (3) | 0.0044 (3) | 0.0007 (3) |
C7 | 0.0165 (4) | 0.0123 (4) | 0.0159 (4) | −0.0006 (3) | 0.0026 (3) | 0.0001 (3) |
C8 | 0.0143 (4) | 0.0139 (4) | 0.0122 (4) | 0.0024 (3) | 0.0031 (3) | −0.0010 (3) |
C9 | 0.0145 (4) | 0.0151 (4) | 0.0150 (4) | −0.0018 (3) | 0.0047 (3) | −0.0003 (3) |
C10 | 0.0157 (4) | 0.0132 (4) | 0.0153 (4) | −0.0028 (3) | 0.0043 (3) | −0.0013 (3) |
O1—C1 | 1.3248 (12) | C3—C4 | 1.5159 (13) |
O1—H1 | 0.863 (19) | C3—H3A | 0.970 (14) |
O2—C1 | 1.2206 (12) | C3—H3B | 0.995 (14) |
O3—C4 | 1.2212 (11) | C5—C10 | 1.4013 (12) |
O4—N2 | 1.2283 (11) | C5—C6 | 1.4043 (13) |
O5—N2 | 1.2295 (12) | C6—C7 | 1.3851 (13) |
N1—C4 | 1.3695 (12) | C6—H6 | 0.949 (14) |
N1—C5 | 1.4004 (11) | C7—C8 | 1.3904 (13) |
N1—H1A | 0.852 (15) | C7—H7 | 0.971 (15) |
N2—C8 | 1.4536 (12) | C8—C9 | 1.3818 (13) |
C1—C2 | 1.5039 (13) | C9—C10 | 1.3826 (13) |
C2—C3 | 1.5208 (13) | C9—H9 | 0.952 (14) |
C2—H2A | 0.991 (14) | C10—H10 | 0.959 (14) |
C2—H2B | 0.964 (14) | ||
C1—O1—H1 | 107.4 (12) | O3—C4—N1 | 123.55 (9) |
C4—N1—C5 | 127.09 (8) | O3—C4—C3 | 121.45 (8) |
C4—N1—H1A | 116.3 (9) | N1—C4—C3 | 114.99 (8) |
C5—N1—H1A | 116.6 (10) | N1—C5—C10 | 122.70 (8) |
O4—N2—O5 | 122.40 (9) | N1—C5—C6 | 117.87 (8) |
O4—N2—C8 | 118.82 (8) | C10—C5—C6 | 119.43 (8) |
O5—N2—C8 | 118.78 (8) | C7—C6—C5 | 120.66 (8) |
O2—C1—O1 | 122.93 (9) | C7—C6—H6 | 119.7 (9) |
O2—C1—C2 | 122.77 (9) | C5—C6—H6 | 119.6 (9) |
O1—C1—C2 | 114.30 (8) | C6—C7—C8 | 118.41 (9) |
C1—C2—C3 | 111.24 (8) | C6—C7—H7 | 121.3 (8) |
C1—C2—H2A | 106.7 (8) | C8—C7—H7 | 120.3 (8) |
C3—C2—H2A | 111.8 (8) | C9—C8—C7 | 122.03 (8) |
C1—C2—H2B | 106.9 (9) | C9—C8—N2 | 118.13 (8) |
C3—C2—H2B | 112.1 (8) | C7—C8—N2 | 119.84 (8) |
H2A—C2—H2B | 107.9 (12) | C8—C9—C10 | 119.45 (8) |
C4—C3—C2 | 110.74 (8) | C8—C9—H9 | 120.4 (9) |
C4—C3—H3A | 108.2 (8) | C10—C9—H9 | 120.2 (9) |
C2—C3—H3A | 109.5 (8) | C9—C10—C5 | 120.00 (9) |
C4—C3—H3B | 109.5 (8) | C9—C10—H10 | 119.6 (8) |
C2—C3—H3B | 111.4 (8) | C5—C10—H10 | 120.4 (8) |
H3A—C3—H3B | 107.4 (11) | ||
O2—C1—C2—C3 | −6.53 (12) | C6—C7—C8—C9 | 0.80 (15) |
O1—C1—C2—C3 | 174.30 (8) | C6—C7—C8—N2 | −179.90 (8) |
C1—C2—C3—C4 | −70.73 (10) | O4—N2—C8—C9 | 173.57 (9) |
C5—N1—C4—O3 | 1.31 (15) | O5—N2—C8—C9 | −5.65 (14) |
C5—N1—C4—C3 | −179.94 (8) | O4—N2—C8—C7 | −5.76 (14) |
C2—C3—C4—O3 | −18.34 (12) | O5—N2—C8—C7 | 175.02 (9) |
C2—C3—C4—N1 | 162.88 (8) | C7—C8—C9—C10 | −0.51 (15) |
C4—N1—C5—C10 | −6.43 (15) | N2—C8—C9—C10 | −179.82 (9) |
C4—N1—C5—C6 | 173.81 (9) | C8—C9—C10—C5 | −0.38 (15) |
N1—C5—C6—C7 | 179.13 (9) | N1—C5—C10—C9 | −178.81 (9) |
C10—C5—C6—C7 | −0.64 (14) | C6—C5—C10—C9 | 0.94 (14) |
C5—C6—C7—C8 | −0.22 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.863 (19) | 1.843 (19) | 2.7002 (10) | 172.5 (17) |
N1—H1A···O4ii | 0.852 (15) | 2.536 (14) | 3.3378 (11) | 157.1 (12) |
N1—H1A···O5ii | 0.852 (15) | 2.616 (15) | 3.3711 (12) | 148.4 (12) |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x−1, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C10H10N2O5 |
Mr | 238.20 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 5.0179 (4), 17.3056 (15), 11.5804 (9) |
β (°) | 94.487 (4) |
V (Å3) | 1002.53 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.33 × 0.27 × 0.22 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.959, 0.972 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 30488, 3066, 2686 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.714 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.097, 1.06 |
No. of reflections | 3066 |
No. of parameters | 194 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.39, −0.26 |
Computer programs: APEXII (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2005).
N1—C4 | 1.3695 (12) | N1—C5 | 1.4004 (11) |
C4—N1—C5 | 127.09 (8) | O2—C1—O1 | 122.93 (9) |
C2—C3—C4—O3 | −18.34 (12) | O4—N2—C8—C7 | −5.76 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.863 (19) | 1.843 (19) | 2.7002 (10) | 172.5 (17) |
N1—H1A···O4ii | 0.852 (15) | 2.536 (14) | 3.3378 (11) | 157.1 (12) |
N1—H1A···O5ii | 0.852 (15) | 2.616 (15) | 3.3711 (12) | 148.4 (12) |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x−1, −y+1/2, z+1/2. |
Crystallization in a noncentrosymmetric space group is required for organic nonlinear optical (NLO) materials to exhibit efficient second harmonic generation (SHG) (Munn et al., 1993). Our interest in organic nonlinear optical materials, particularly in acid anhydride derivatives (Ravindra et al., 2006) of nitroaniline, has led us to synthesize the title compound. This compound crystallizes in a centrosymmetric structure and hence exhibits no second harmonic generation. However, the molecule shows third order nonlinear response (nonlinear absorption), which can be observed in molecules with both centrosymmetic and noncentrosymmetric structures.
A projection view of the molecule with 50% probability displacement ellipsoids is shown in Fig 1. The C2—C3 bond length is in good agreement with the three isomeric N-(p-chlorophenyl)succinimides (Glidewell et al., 2005) which display C—C bond lengths of 1.5276 (19), 1.518 (3) and 1.524 (5) Å. The nitro and amine groups attached to C8 and C5 are almost coplanar with the C5—C10 benzene ring, with O5—N2—C8—C9 and C4—N1—C5—C10 torsion angles of 5.65 (14)° and 6.43 (15)°,respectively.
The hydrogen bonding parameters are listed in Table 2. As expected, the carboxyl groups of two molecules form strong intermolecular hydrogen bonding resulting in the head to tail dimers. The N—H hydrogen atom forms bifurcated intermolecular hydrogen bonds to the NO2 group of a second molecule. Thus the crystal structure is stabilized by the formation of two-dimensional networks involving bifurcated and dimeric hydrogen bonds involving N1—H1A···O4, N1—H1A···O5 and O1—H1···O1. The extended hydrogen bonding network results in a step like arrangement between the layers in the crystal lattice with the carboxyl dimers as the steps.