2-Amino derivatives of 5-nitro­phenyl­acet­amide

The structures of the potential non-linear optical (NLO) materials N-[2-(iso­propyl­amino)-5-nitro­phenyl]­acet­amide, (I) C₁₁H₁₅N₃O₃, and N-[2-(butyl­amino)-5-nitro­phenyl]­acet­amide, (II) C₁₂H₁₇N₃O₃, have been investigated by X-ray analysis. To compare them with the structure of N-[2-(di­methyl­amino)-5-nitro­phenyl]­acet­amide, (III) C₁₀H₁₃N₃O₃, a known NLO compound, we had to redetermine the structure of (III), since it was described only briefly in the literature. There are two mol­ecules in the asymmetric unit of compound (I), which have different orientations of the substituents with respect to the benzene ring. The packing of mol­ecules in (II) and (III) contains stacks but both (I) and (II) crystallize in a centrosymmetric space group, which renders them inappropriate for NLO applications.

S1. Comment

In recent years organic nonlinear optical (NLO) materials have been the subject of intensive study because of their crucial advantages in comparison with currently used inorganics (Zyss et al., 1994). To possess NLO properties organic molecules should contain a polar and highly conjugated p-electron system terminated with electron donor and acceptor groups. One such compound is the donor-acceptor substituted benzene derivative N-[2-(dimethylamino)-5-nitrophenyl]acetamide, (III), which crystallizes in a noncentrosymmetric space group and which therefore allows second-harmonic generation (Baumert et al., 1987; Norman et al., 1987). As a part of a search for new NLO materials (Antipin et al., 1997, 1998), we synthesized two new compounds, N-[2-(isopropylamino)-5-nitrophenyl]acetamide, (I), and N-[2-(butylamino)-5-nitrophenyl]acetamide, (II), which are analogous to (III). In this work we present the results of structural investigations of the compounds (I), (II) and (III). Despite the fact that the structure of (III) has been published at least twice, it was discussed only very briefly in each case (Baumert et al., 1987; Norman et al., 1987) and atomic coordinates are absent from these publications and from the Cambridge Structural Database (Allen et al., 1987?). Thus, to compare the structural peculiarities of (I), (II) and (III) we had to redetermine the crystal structure of (III). \scheme

There are two molecules, A and B, in the asymmetric unit of compound (I) (Fig. 1) which differ primarily by the degree of rotation of the acetamido group with respect to the benzene ring: the C7—N1—C1—C6 torsion angle is -63.7 (3)° in molecule A and 38.3 (3)° in molecule B. In addition, the aminoisopropyl group of molecule A is twisted with respect to the ring somewhat more than that of molecule B [the C9—N2—C2—C3 torsion angles are -11.9 (3) and -3.9 (3)°, respectively]. Molecules of (II) (Fig. 2) and (III) (Fig. 3) are also non-planar, with respective C7—N1—C1—C6 torsion angles of -57.1 (4) and -46.4 (3)°, and C9—N2—C2—C3 torsion angles of -4.2 (4) and -11.7 (3)°.

The nitro groups in molecule A of (I) and in (II) and (III) are nearly coplanar with the benzene ring, with the O2—N3—C5—C4 torsion angle adopting values of -3.8 (3), -0.2 (4) and -0.5 (3)°, but in molecule B of (I) this group is rotated out of the ring plane by -15.7 (3)°. All bond lengths in the molecules studied are close to standard values (Allen et al., 1987).

In the crystal phase molecules (II) and (III) are stacked along the [100] direction, linked by intermolecular N—H···O bonds (Tables 2 and 3) forming infinite chains. In addition, in (II) neighbouring stacks (symmetry code: -x, -y, -z) are connected by bifurcated intermolecular hydrogen bonds involving O3 (Table 2). In the case of (I), infinite zigzag chains due to intermolecular N—H···O bonds (Table 1) are observed, and molecules A and B alternate within them. Stacking is absent here. Finally, X-ray investigation has shown that (I) and (II) crystallize in centrosymmetric space groups, where the second-order NLO effect is necessarily absent, rendering these compounds inappropriate as possible NLO materials.

S2. Experimental

Compounds (I), (II) and (III) were prepared according to a known procedure (Martinez et al., 1993). Suitable single crystals were obtained by isothermal evaporation of solvent from solutions of (I), (II) and (III) in ethanol at ambient temperature.

S3. Refinement

The dataset for (II) is complete to 2θ_max = 50°, although some data were collected to 54°. For (II), H atoms on N were located in difference Fourier syntheses and then refined freely, those in methyl groups were located similarly and refined as part of rigid rotating groups, and all others were placed geometrically. In (III), the H1(–N1) atom was treated as a riding atom; all other H atom positions were refined isotropically.

Computing details

For all compounds, data collection: P3 (Siemens, 1989); cell refinement: P3; data reduction: XDISK (Siemens, 1991); program(s) used to solve structure: SHELXTL/PC (Sheldrick, 1994); program(s) used to refine structure: SHELXTL/PC; molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXTL/PC.

Figures

	Fig. 1. A view of the two independent molecules of (I) showing the atom-numbering scheme. Non-H atoms are shown with displacement ellipsoids drawn at the 50% probability level and H atoms are drawn as spheres of arbitrary small radius for clarity.
	Fig. 2. A view of a molecule of (II) showing the atom-numbering scheme. Non-H atoms are shown with displacement ellipsoids drawn at the 50% probability level and H atoms are drawn as spheres of arbitrary small radius for clarity.
	Fig. 3. A view of a molecule of (III) showing the atom-numbering scheme. Non-H atoms are shown with displacement ellipsoids drawn at the 50% probability level and H atoms are drawn as spheres of arbitrary small radius for clarity.

(I) N-[2-(isopropylamino)-5-nitrophenyl]acetamide

Crystal data

C11H15N3O3	F(000) = 1008
Mr = 237.26	Dx = 1.339 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.408 (7) Å	Cell parameters from 24 reflections
b = 13.277 (4) Å	θ = 10–11°
c = 13.577 (6) Å	µ = 0.10 mm^−1
β = 103.07 (4)°	T = 293 K
V = 2354.3 (18) Å^3	Prism, yellow
Z = 8	0.4 × 0.3 × 0.3 mm

Data collection

Syntex P21/PC diffractometer	Rint = 0.039
Radiation source: fine-focus sealed tube	θmax = 25.1°, θmin = 1.9°
Graphite monochromator	h = −12→15
θ/2θ scans	k = −7→15
4351 measured reflections	l = −16→15
4164 independent reflections	2 standard reflections every 98 reflections
2976 reflections with I > 2σ(I)	intensity decay: 4.7%

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)] = 0.049	Hydrogen site location: difference Fourier map
wR(F^2) = 0.110	All H-atom parameters refined
S = 1.03	Calculated w = 1/[σ^2(Fo^2) + (0.0622P)^2 + 1.0315P] where P = (Fo^2 + 2Fc^2)/3
4106 reflections	(Δ/σ)max = 0.001
427 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.27 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 on F² for ALL reflections except for 58 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R factor obs 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
N1	0.73029 (14)	0.33587 (14)	0.98352 (14)	0.0256 (4)
H1	0.7799 (19)	0.3186 (17)	1.0331 (18)	0.027 (6)*
N2	0.7233 (2)	0.12639 (14)	0.95543 (15)	0.0303 (5)
H2	0.782 (2)	0.161 (2)	0.982 (2)	0.045 (8)*
N3	0.3650 (2)	0.3359 (2)	0.97602 (15)	0.0354 (5)
O1	0.68140 (11)	0.42438 (11)	0.83819 (11)	0.0282 (4)
O2	0.28318 (14)	0.2890 (2)	0.9614 (2)	0.0541 (5)
O3	0.37067 (13)	0.42607 (14)	0.99527 (14)	0.0448 (5)
C1	0.6366 (2)	0.2821 (2)	0.9748 (2)	0.0252 (5)
C2	0.6352 (2)	0.1755 (2)	0.9612 (2)	0.0269 (5)
C3	0.5409 (2)	0.1259 (2)	0.9523 (2)	0.0341 (6)
H3	0.5369 (19)	0.054 (2)	0.9429 (19)	0.041 (7)*
C4	0.4531 (2)	0.1779 (2)	0.9559 (2)	0.0353 (6)
H4	0.391 (2)	0.1428 (19)	0.9484 (19)	0.040 (7)*
C5	0.4574 (2)	0.2815 (2)	0.9709 (2)	0.0291 (5)
C6	0.5489 (2)	0.3334 (2)	0.9811 (2)	0.0261 (5)
H6	0.5518 (17)	0.4019 (19)	0.9906 (17)	0.028 (6)*
C7	0.7452 (2)	0.4067 (2)	0.9172 (2)	0.0237 (5)
C8	0.8444 (2)	0.4633 (2)	0.9453 (2)	0.0313 (5)
H8A	0.873 (2)	0.472 (2)	0.886 (2)	0.047 (8)*
H8B	0.830 (2)	0.528 (2)	0.972 (2)	0.054 (8)*
H8C	0.895 (2)	0.431 (2)	1.000 (2)	0.058 (9)*
C9	0.7348 (2)	0.0162 (2)	0.9585 (2)	0.0348 (6)
H9	0.7076 (18)	−0.0111 (18)	1.0137 (19)	0.035 (7)*
C10	0.6813 (3)	−0.0331 (2)	0.8596 (2)	0.0483 (7)
H10A	0.720 (2)	−0.022 (2)	0.809 (2)	0.047 (8)*
H10B	0.611 (3)	−0.008 (3)	0.831 (3)	0.083 (12)*
H10C	0.685 (3)	−0.105 (4)	0.875 (3)	0.075 (10)*
C11	0.8483 (2)	−0.0093 (2)	0.9827 (2)	0.0446 (7)
H11A	0.859 (3)	−0.081 (3)	0.992 (2)	0.076 (10)*
H11B	0.875 (2)	0.011 (2)	0.925 (2)	0.044 (7)*
H11C	0.887 (2)	0.024 (2)	1.046 (3)	0.062 (9)*
N1'	0.47907 (14)	0.37470 (13)	0.73534 (14)	0.0226 (4)
H1'	0.5374 (18)	0.3849 (17)	0.7738 (17)	0.021 (6)*
N2'	0.52413 (15)	0.58013 (14)	0.74652 (15)	0.0279 (4)
H2'	0.572 (2)	0.536 (2)	0.7591 (19)	0.041 (8)*
N3'	0.12761 (15)	0.45403 (15)	0.7528 (2)	0.0334 (5)
O1'	0.38257 (12)	0.26966 (12)	0.62057 (13)	0.0365 (4)
O2'	0.07007 (13)	0.51303 (14)	0.7835 (2)	0.0506 (5)
O3'	0.10023 (13)	0.36966 (13)	0.7200 (2)	0.0506 (5)
C1'	0.4019 (2)	0.4456 (2)	0.74413 (15)	0.0215 (5)
C2'	0.4282 (2)	0.5496 (2)	0.75166 (15)	0.0230 (5)
C3'	0.3515 (2)	0.6192 (2)	0.7607 (2)	0.0278 (5)
H3'	0.3675 (18)	0.6866 (19)	0.7655 (17)	0.030 (6)*
C4'	0.2543 (2)	0.5879 (2)	0.7630 (2)	0.0290 (5)
H4'	0.2030 (18)	0.6366 (18)	0.7678 (17)	0.029 (6)*
C5'	0.2305 (2)	0.4870 (2)	0.7531 (2)	0.0255 (5)
C6'	0.3035 (2)	0.4151 (2)	0.7436 (2)	0.0244 (5)
H6'	0.2856 (17)	0.3452 (19)	0.7363 (17)	0.030 (6)*
C7'	0.4660 (2)	0.2923 (2)	0.6762 (2)	0.0247 (5)
C8'	0.5595 (2)	0.2291 (2)	0.6804 (2)	0.0350 (6)
H8D	0.574 (3)	0.222 (3)	0.616 (3)	0.092 (13)*
H8E	0.619 (3)	0.256 (3)	0.727 (3)	0.076 (10)*
H8F	0.549 (3)	0.163 (3)	0.697 (3)	0.086 (12)*
C9'	0.5553 (2)	0.6855 (2)	0.7435 (2)	0.0281 (5)
H9'	0.5303 (16)	0.7212 (16)	0.7959 (16)	0.021 (6)*
C10'	0.5101 (2)	0.7328 (2)	0.6407 (2)	0.0391 (6)
H10D	0.531 (2)	0.806 (2)	0.644 (2)	0.048 (8)*
H10E	0.542 (2)	0.700 (2)	0.589 (2)	0.053 (8)*
H10F	0.436 (3)	0.729 (2)	0.623 (2)	0.067 (10)*
C11'	0.6717 (2)	0.6896 (2)	0.7682 (2)	0.0351 (6)
H11D	0.696 (2)	0.649 (2)	0.719 (2)	0.042 (7)*
H11E	0.702 (2)	0.664 (2)	0.837 (2)	0.061 (9)*
H11F	0.696 (2)	0.760 (2)	0.764 (2)	0.052 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0225 (10)	0.0237 (10)	0.0269 (10)	−0.0012 (8)	−0.0023 (8)	0.0038 (8)
N2	0.0336 (12)	0.0231 (10)	0.0340 (11)	−0.0015 (9)	0.0073 (9)	−0.0021 (8)
N3	0.0328 (12)	0.0414 (13)	0.0331 (11)	−0.0030 (10)	0.0102 (9)	−0.0026 (9)
O1	0.0251 (8)	0.0290 (8)	0.0271 (8)	−0.0017 (7)	−0.0009 (7)	0.0052 (7)
O2	0.0308 (11)	0.0630 (13)	0.0716 (14)	−0.0104 (9)	0.0178 (9)	−0.0103 (11)
O3	0.0398 (11)	0.0403 (11)	0.0561 (12)	0.0047 (8)	0.0148 (9)	−0.0079 (9)
C1	0.0318 (13)	0.0215 (11)	0.0208 (11)	−0.0027 (9)	0.0028 (9)	0.0022 (8)
C2	0.0351 (13)	0.0243 (12)	0.0225 (11)	−0.0023 (10)	0.0089 (9)	0.0003 (9)
C3	0.0419 (15)	0.0244 (13)	0.0390 (14)	−0.0098 (11)	0.0158 (11)	−0.0035 (10)
C4	0.0351 (15)	0.0368 (14)	0.0377 (14)	−0.0120 (12)	0.0161 (11)	−0.0040 (11)
C5	0.0286 (13)	0.0341 (13)	0.0261 (12)	−0.0030 (10)	0.0097 (9)	−0.0020 (10)
C6	0.0320 (13)	0.0223 (12)	0.0234 (11)	−0.0005 (10)	0.0049 (9)	0.0020 (9)
C7	0.0234 (12)	0.0200 (11)	0.0271 (12)	0.0023 (9)	0.0047 (9)	−0.0018 (9)
C8	0.0259 (13)	0.0288 (13)	0.0365 (14)	−0.0033 (10)	0.0013 (11)	0.0008 (11)
C9	0.051 (2)	0.0224 (12)	0.0349 (13)	0.0014 (11)	0.0182 (12)	0.0031 (10)
C10	0.057 (2)	0.039 (2)	0.053 (2)	−0.0073 (15)	0.021 (2)	−0.0167 (14)
C11	0.058 (2)	0.038 (2)	0.036 (2)	0.0202 (14)	0.0077 (14)	0.0054 (13)
N1'	0.0176 (10)	0.0218 (9)	0.0246 (10)	−0.0008 (8)	−0.0034 (8)	−0.0016 (8)
N2'	0.0237 (11)	0.0200 (10)	0.0403 (12)	−0.0019 (9)	0.0080 (9)	−0.0013 (8)
N3'	0.0242 (11)	0.0303 (11)	0.0454 (12)	0.0003 (9)	0.0076 (9)	0.0047 (9)
O1'	0.0280 (9)	0.0307 (9)	0.0440 (10)	0.0002 (7)	−0.0062 (7)	−0.0142 (8)
O2'	0.0291 (10)	0.0453 (11)	0.0820 (15)	0.0043 (9)	0.0221 (10)	−0.0081 (10)
O3'	0.0318 (10)	0.0307 (10)	0.090 (2)	−0.0086 (8)	0.0152 (10)	−0.0036 (10)
C1'	0.0226 (11)	0.0209 (10)	0.0195 (10)	0.0012 (9)	0.0017 (8)	0.0006 (9)
C2'	0.0221 (12)	0.0234 (11)	0.0225 (11)	−0.0032 (9)	0.0030 (9)	−0.0004 (9)
C3'	0.0284 (13)	0.0186 (12)	0.0360 (13)	−0.0015 (10)	0.0064 (10)	−0.0028 (10)
C4'	0.0258 (13)	0.0266 (12)	0.0341 (13)	0.0050 (10)	0.0059 (10)	−0.0012 (10)
C5'	0.0186 (12)	0.0271 (12)	0.0303 (12)	−0.0018 (9)	0.0047 (9)	0.0005 (9)
C6'	0.0252 (12)	0.0192 (11)	0.0271 (12)	−0.0032 (9)	0.0027 (9)	0.0009 (9)
C7'	0.0246 (12)	0.0207 (11)	0.0264 (11)	−0.0033 (9)	0.0010 (9)	−0.0003 (9)
C8'	0.0282 (14)	0.0289 (14)	0.046 (2)	0.0041 (11)	0.0038 (12)	−0.0058 (12)
C9'	0.0292 (13)	0.0226 (12)	0.0344 (13)	−0.0057 (10)	0.0110 (10)	−0.0054 (10)
C10'	0.043 (2)	0.0310 (14)	0.045 (2)	−0.0017 (12)	0.0136 (13)	0.0051 (12)
C11'	0.0297 (14)	0.0307 (14)	0.048 (2)	−0.0090 (11)	0.0151 (12)	−0.0109 (12)

Geometric parameters (Å, º)

N1—C7	1.348 (3)	N1'—C7'	1.345 (3)
N1—C1	1.427 (3)	N1'—C1'	1.424 (3)
N2—C2	1.367 (3)	N2'—C2'	1.365 (3)
N2—C9	1.471 (3)	N2'—C9'	1.463 (3)
N3—O3	1.224 (3)	N3'—O3'	1.231 (3)
N3—O2	1.238 (3)	N3'—O2'	1.236 (3)
N3—C5	1.449 (3)	N3'—C5'	1.447 (3)
O1—C7	1.233 (3)	O1'—C7'	1.237 (3)
C1—C6	1.378 (3)	C1'—C6'	1.378 (3)
C1—C2	1.427 (3)	C1'—C2'	1.424 (3)
C2—C3	1.406 (3)	C2'—C3'	1.409 (3)
C3—C4	1.375 (4)	C3'—C4'	1.374 (3)
C4—C5	1.390 (3)	C4'—C5'	1.377 (3)
C5—C6	1.386 (3)	C5'—C6'	1.394 (3)
C7—C8	1.501 (3)	C7'—C8'	1.499 (3)
C9—C10	1.520 (4)	C9'—C11'	1.520 (3)
C9—C11	1.520 (4)	C9'—C10'	1.526 (4)
C7—N1—C1	123.7 (2)	C7'—N1'—C1'	126.1 (2)
C2—N2—C9	124.0 (2)	C2'—N2'—C9'	124.3 (2)
O3—N3—O2	122.4 (2)	O3'—N3'—O2'	122.8 (2)
O3—N3—C5	119.0 (2)	O3'—N3'—C5'	118.9 (2)
O2—N3—C5	118.5 (2)	O2'—N3'—C5'	118.4 (2)
C6—C1—C2	120.8 (2)	C6'—C1'—N1'	121.2 (2)
C6—C1—N1	119.7 (2)	C6'—C1'—C2'	120.5 (2)
C2—C1—N1	119.5 (2)	N1'—C1'—C2'	118.3 (2)
N2—C2—C3	122.9 (2)	N2'—C2'—C3'	121.7 (2)
N2—C2—C1	119.6 (2)	N2'—C2'—C1'	120.4 (2)
C3—C2—C1	117.4 (2)	C3'—C2'—C1'	117.9 (2)
C4—C3—C2	121.5 (2)	C4'—C3'—C2'	121.2 (2)
C3—C4—C5	119.6 (2)	C3'—C4'—C5'	119.5 (2)
C6—C5—C4	120.9 (2)	C4'—C5'—C6'	121.6 (2)
C6—C5—N3	119.6 (2)	C4'—C5'—N3'	119.6 (2)
C4—C5—N3	119.5 (2)	C6'—C5'—N3'	118.7 (2)
C1—C6—C5	119.7 (2)	C1'—C6'—C5'	119.3 (2)
O1—C7—N1	122.4 (2)	O1'—C7'—N1'	122.7 (2)
O1—C7—C8	121.8 (2)	O1'—C7'—C8'	121.4 (2)
N1—C7—C8	115.9 (2)	N1'—C7'—C8'	116.0 (2)
N2—C9—C10	112.2 (2)	N2'—C9'—C11'	108.3 (2)
N2—C9—C11	108.7 (2)	N2'—C9'—C10'	111.2 (2)
C10—C9—C11	110.2 (2)	C11'—C9'—C10'	111.3 (2)
C7—N1—C1—C6	−63.7 (3)	C7'—N1'—C1'—C6'	38.3 (3)
C7—N1—C1—C2	117.3 (2)	C7'—N1'—C1'—C2'	−140.6 (2)
C9—N2—C2—C3	−11.9 (3)	C9'—N2'—C2'—C3'	−3.9 (3)
C9—N2—C2—C1	169.5 (2)	C9'—N2'—C2'—C1'	173.7 (2)
C6—C1—C2—N2	−179.8 (2)	C6'—C1'—C2'—N2'	−176.4 (2)
N1—C1—C2—N2	−0.9 (3)	N1'—C1'—C2'—N2'	2.5 (3)
C6—C1—C2—C3	1.5 (3)	C6'—C1'—C2'—C3'	1.4 (3)
N1—C1—C2—C3	−179.6 (2)	N1'—C1'—C2'—C3'	−179.7 (2)
N2—C2—C3—C4	−178.3 (2)	N2'—C2'—C3'—C4'	178.2 (2)
C1—C2—C3—C4	0.4 (3)	C1'—C2'—C3'—C4'	0.5 (3)
C2—C3—C4—C5	−1.5 (4)	C2'—C3'—C4'—C5'	−2.1 (3)
C3—C4—C5—C6	0.8 (4)	C3'—C4'—C5'—C6'	1.9 (3)
C3—C4—C5—N3	−179.2 (2)	C3'—C4'—C5'—N3'	−178.4 (2)
O3—N3—C5—C6	−4.3 (3)	O3'—N3'—C5'—C4'	162.6 (2)
O2—N3—C5—C6	176.2 (2)	O2'—N3'—C5'—C4'	−15.7 (3)
O3—N3—C5—C4	175.7 (2)	O3'—N3'—C5'—C6'	−17.8 (3)
O2—N3—C5—C4	−3.8 (3)	O2'—N3'—C5'—C6'	163.9 (2)
C2—C1—C6—C5	−2.2 (3)	N1'—C1'—C6'—C5'	179.6 (2)
N1—C1—C6—C5	178.9 (2)	C2'—C1'—C6'—C5'	−1.5 (3)
C4—C5—C6—C1	1.0 (3)	C4'—C5'—C6'—C1'	−0.1 (3)
N3—C5—C6—C1	−179.0 (2)	N3'—C5'—C6'—C1'	−179.8 (2)
C1—N1—C7—O1	−6.6 (3)	C1'—N1'—C7'—O1'	0.9 (3)
C1—N1—C7—C8	173.2 (2)	C1'—N1'—C7'—C8'	−179.9 (2)
C2—N2—C9—C10	75.2 (3)	C2'—N2'—C9'—C11'	164.0 (2)
C2—N2—C9—C11	−162.7 (2)	C2'—N2'—C9'—C10'	−73.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1′^i	0.86 (2)	1.99 (3)	2.806 (3)	159 (2)
N2—H2···O1′^i	0.92 (3)	2.25 (3)	3.054 (3)	147 (2)
N1′—H1′···O1	0.85 (2)	2.00 (2)	2.834 (3)	168 (2)
N2′—H2′···O1	0.85 (3)	2.19 (3)	3.014 (3)	162 (2)

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

(II) N-[2-(butylamino)-5-nitrophenyl]acetamide

Crystal data

C12H17N3O3	Z = 2
Mr = 251.29	F(000) = 268
Triclinic, P1	Dx = 1.312 Mg m^−3
a = 4.874 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.002 (5) Å	Cell parameters from 24 reflections
c = 12.335 (7) Å	θ = 10–11°
α = 76.14°	µ = 0.10 mm^−1
β = 82.27°	T = 193 K
γ = 86.99°	Prism, yellow
V = 636.2 (5) Å^3	0.5 × 0.4 × 0.3 mm

Data collection

Syntex P21/PC diffractometer	Rint = 0.060
Radiation source: fine-focus sealed tube	θmax = 27.1°, θmin = 1.7°
Graphite monochromator	h = −5→5
θ/2θ scans	k = −14→14
2900 measured reflections	l = −15→15
2569 independent reflections	2 standard reflections every 98 reflections
1391 reflections with I > 2σ(I)	intensity decay: 4.1%

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Calculated w = 1/[σ^2(Fo^2) + (0.0901P)^2] where P = (Fo^2 + 2Fc^2)/3
2503 reflections	(Δ/σ)max < 0.001
173 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.30 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 on F² for ALL reflections except for 66 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R factor obs 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
N1	−0.0347 (6)	0.6295 (2)	0.2835 (2)	0.0274 (6)
H1	−0.195 (8)	0.600 (3)	0.284 (3)	0.042 (10)*
N2	−0.3423 (5)	0.8540 (2)	0.2790 (2)	0.0295 (7)
H2	−0.360 (7)	0.805 (3)	0.234 (3)	0.034 (9)*
N3	0.3315 (5)	0.6793 (2)	0.6190 (2)	0.0290 (6)
O1	0.4166 (4)	0.6469 (2)	0.2084 (2)	0.0315 (6)
O2	0.3298 (5)	0.7367 (2)	0.6937 (2)	0.0423 (7)
O3	0.4865 (5)	0.5883 (2)	0.6140 (2)	0.0394 (6)
C1	−0.0243 (6)	0.6980 (3)	0.3682 (2)	0.0250 (7)
C2	−0.1940 (6)	0.8071 (3)	0.3661 (2)	0.0253 (7)
C3	−0.1912 (6)	0.8669 (3)	0.4549 (2)	0.0275 (7)
H3	−0.3051 (6)	0.9369 (3)	0.4574 (2)	0.033*
C4	−0.0241 (6)	0.8242 (3)	0.5380 (3)	0.0269 (7)
H4	−0.0270 (6)	0.8641 (3)	0.5966 (3)	0.032*
C5	0.1480 (6)	0.7215 (3)	0.5336 (2)	0.0265 (7)
C6	0.1445 (6)	0.6567 (3)	0.4503 (2)	0.0254 (7)
H6	0.2562 (6)	0.5856 (3)	0.4502 (2)	0.031*
C7	0.1883 (6)	0.6034 (3)	0.2145 (2)	0.0255 (7)
C8	0.1358 (7)	0.5140 (3)	0.1444 (3)	0.0371 (8)
H8A	−0.0598 (8)	0.5098 (17)	0.1429 (16)	0.056*
H8B	0.208 (4)	0.4323 (6)	0.1767 (12)	0.056*
H8C	0.226 (4)	0.5430 (12)	0.0691 (6)	0.056*
C9	−0.5226 (6)	0.9636 (3)	0.2737 (3)	0.0281 (7)
H9A	−0.4242 (6)	1.0302 (3)	0.2900 (3)	0.034*
H9B	−0.6820 (6)	0.9438 (3)	0.3306 (3)	0.034*
C10	−0.6200 (7)	1.0082 (3)	0.1590 (3)	0.0336 (8)
H10A	−0.7209 (7)	0.9419 (3)	0.1435 (3)	0.040*
H10B	−0.4601 (7)	1.0262 (3)	0.1022 (3)	0.040*
C11	−0.8049 (8)	1.1246 (3)	0.1510 (3)	0.0406 (9)
H11A	−0.9711 (8)	1.1041 (3)	0.2041 (3)	0.049*
H11C	−0.7090 (8)	1.1880 (3)	0.1733 (3)	0.049*
C12	−0.8886 (9)	1.1791 (4)	0.0353 (3)	0.0557 (11)
H12A	−0.969 (5)	1.1150 (8)	0.0093 (10)	0.084*
H12B	−0.7284 (14)	1.211 (2)	−0.0159 (6)	0.084*
H12C	−1.022 (5)	1.2458 (18)	0.0388 (6)	0.084*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0175 (14)	0.0285 (14)	0.040 (2)	−0.0037 (12)	−0.0037 (12)	−0.0152 (12)
N2	0.0260 (15)	0.0284 (15)	0.037 (2)	−0.0009 (12)	−0.0038 (13)	−0.0136 (13)
N3	0.0235 (15)	0.0307 (14)	0.0325 (15)	−0.0070 (12)	−0.0010 (12)	−0.0071 (12)
O1	0.0202 (12)	0.0377 (13)	0.0396 (13)	−0.0078 (10)	−0.0014 (10)	−0.0143 (10)
O2	0.041 (2)	0.054 (2)	0.0396 (14)	0.0026 (12)	−0.0116 (11)	−0.0239 (12)
O3	0.0376 (15)	0.0344 (13)	0.0486 (15)	0.0066 (12)	−0.0131 (12)	−0.0120 (11)
C1	0.022 (2)	0.0235 (15)	0.031 (2)	−0.0059 (13)	0.0000 (14)	−0.0108 (13)
C2	0.019 (2)	0.026 (2)	0.030 (2)	−0.0064 (13)	0.0023 (13)	−0.0071 (13)
C3	0.023 (2)	0.0234 (15)	0.035 (2)	0.0000 (13)	0.0031 (14)	−0.0094 (13)
C4	0.025 (2)	0.027 (2)	0.030 (2)	−0.0087 (14)	0.0000 (14)	−0.0101 (13)
C5	0.022 (2)	0.028 (2)	0.027 (2)	−0.0062 (13)	−0.0007 (13)	−0.0019 (13)
C6	0.019 (2)	0.0205 (14)	0.036 (2)	−0.0046 (12)	0.0029 (14)	−0.0086 (13)
C7	0.023 (2)	0.024 (2)	0.030 (2)	0.0012 (13)	−0.0053 (13)	−0.0068 (13)
C8	0.037 (2)	0.040 (2)	0.040 (2)	−0.001 (2)	−0.007 (2)	−0.020 (2)
C9	0.024 (2)	0.025 (2)	0.034 (2)	−0.0032 (14)	0.0003 (14)	−0.0072 (13)
C10	0.029 (2)	0.039 (2)	0.032 (2)	−0.001 (2)	−0.0023 (15)	−0.0085 (15)
C11	0.040 (2)	0.041 (2)	0.040 (2)	0.007 (2)	−0.008 (2)	−0.008 (2)
C12	0.059 (3)	0.056 (2)	0.047 (2)	0.014 (2)	−0.012 (2)	−0.004 (2)

Geometric parameters (Å, º)

N1—C7	1.351 (4)	C1—C2	1.418 (4)
N1—C1	1.434 (4)	C2—C3	1.408 (4)
N2—C2	1.359 (4)	C3—C4	1.374 (4)
N2—C9	1.448 (4)	C4—C5	1.379 (4)
N3—O3	1.231 (3)	C5—C6	1.386 (4)
N3—O2	1.234 (3)	C7—C8	1.507 (4)
N3—C5	1.449 (4)	C9—C10	1.514 (4)
O1—C7	1.221 (4)	C10—C11	1.518 (5)
C1—C6	1.369 (4)	C11—C12	1.512 (5)
C7—N1—C1	124.2 (3)	C3—C4—C5	119.3 (3)
C2—N2—C9	123.1 (3)	C4—C5—C6	121.1 (3)
O3—N3—O2	122.1 (3)	C4—C5—N3	119.3 (3)
O3—N3—C5	118.9 (3)	C6—C5—N3	119.6 (3)
O2—N3—C5	119.0 (3)	C1—C6—C5	119.7 (3)
C6—C1—C2	121.0 (3)	O1—C7—N1	123.7 (3)
C6—C1—N1	120.0 (3)	O1—C7—C8	121.6 (3)
C2—C1—N1	119.0 (3)	N1—C7—C8	114.7 (3)
N2—C2—C3	122.0 (3)	N2—C9—C10	111.5 (2)
N2—C2—C1	120.8 (3)	C9—C10—C11	112.3 (3)
C3—C2—C1	117.2 (3)	C12—C11—C10	114.4 (3)
C4—C3—C2	121.6 (3)
C7—N1—C1—C6	−57.1 (4)	O3—N3—C5—C4	−179.3 (3)
C7—N1—C1—C2	123.8 (3)	O2—N3—C5—C4	−0.2 (4)
C9—N2—C2—C3	−4.2 (4)	O3—N3—C5—C6	1.9 (4)
C9—N2—C2—C1	178.8 (3)	O2—N3—C5—C6	−178.9 (3)
C6—C1—C2—N2	174.1 (3)	C2—C1—C6—C5	0.7 (4)
N1—C1—C2—N2	−6.9 (4)	N1—C1—C6—C5	−178.3 (3)
C6—C1—C2—C3	−3.1 (4)	C4—C5—C6—C1	2.6 (4)
N1—C1—C2—C3	176.0 (3)	N3—C5—C6—C1	−178.6 (3)
N2—C2—C3—C4	−174.9 (3)	C1—N1—C7—O1	−8.4 (5)
C1—C2—C3—C4	2.2 (4)	C1—N1—C7—C8	171.1 (3)
C2—C3—C4—C5	1.0 (4)	C2—N2—C9—C10	169.7 (3)
C3—C4—C5—C6	−3.5 (4)	N2—C9—C10—C11	−178.9 (3)
C3—C4—C5—N3	177.8 (3)	C9—C10—C11—C12	175.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.86 (4)	2.21 (4)	2.928 (4)	142 (3)
N1—H1···O3^ii	0.86 (4)	2.55 (4)	3.247 (4)	139 (3)
N2—H2···O1^i	0.87 (3)	2.21 (4)	2.973 (4)	146 (3)

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

(III) N-[2-(dimethylamino)-5-nitrophenyl]acetamide

Crystal data

C10H13N3O3	F(000) = 236
Mr = 223.23	Dx = 1.366 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 4.786 (1) Å	Cell parameters from 24 reflections
b = 13.030 (3) Å	θ = 10–11°
c = 8.727 (2) Å	µ = 0.10 mm^−1
β = 94.38 (3)°	T = 293 K
V = 542.6 (2) Å^3	Needles, yellow
Z = 2	0.4 × 0.1 × 0.1 mm

Data collection

Siemens P3 diffractometer	Rint = 0.033
Radiation source: fine-focus sealed tube	θmax = 25.1°, θmin = 2.3°
Graphite monochromator	h = 0→5
θ/2θ scans	k = −15→15
2053 measured reflections	l = −10→10
1817 independent reflections	2 standard reflections every 98 reflections
1486 reflections with I > 2σ(I)	intensity decay: 4.8%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	All H-atom parameters refined
wR(F^2) = 0.085	Calculated w = 1/[σ^2(Fo^2) + (0.0645P)^2 + 0.0191P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = −0.012
1754 reflections	Δρmax = 0.11 e Å^−3
193 parameters	Δρmin = −0.12 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: not reliably determined

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 on F² for ALL reflections except for 63 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R factor obs 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
N1	0.2912 (4)	0.54479 (12)	0.3017 (2)	0.0407 (4)
H1	0.4621	0.54938	0.2783	0.049*
N2	0.5269 (3)	0.34733 (13)	0.3217 (2)	0.0454 (4)
N3	−0.1198 (4)	0.4893 (2)	0.7870 (2)	0.0555 (5)
O1	−0.1482 (3)	0.60305 (14)	0.2415 (2)	0.0596 (5)
O2	−0.1281 (5)	0.4387 (2)	0.9037 (2)	0.0823 (6)
O3	−0.2532 (5)	0.5688 (2)	0.7653 (2)	0.0778 (6)
C1	0.2389 (4)	0.48048 (14)	0.4263 (2)	0.0358 (4)
C2	0.3801 (4)	0.38400 (14)	0.4391 (2)	0.0383 (5)
C3	0.3663 (5)	0.3309 (2)	0.5785 (2)	0.0466 (5)
H3	0.466 (5)	0.270 (2)	0.587 (3)	0.047 (6)*
C4	0.2093 (5)	0.3650 (2)	0.6919 (2)	0.0487 (5)
H4	0.202 (5)	0.3304 (19)	0.786 (3)	0.057 (7)*
C5	0.0549 (4)	0.45426 (15)	0.6696 (2)	0.0426 (5)
C6	0.0735 (4)	0.5128 (2)	0.5380 (2)	0.0401 (5)
H6	−0.013 (5)	0.580 (2)	0.533 (2)	0.047 (6)*
C7	0.0984 (4)	0.59990 (15)	0.2154 (2)	0.0392 (4)
C8	0.2085 (5)	0.6595 (2)	0.0866 (3)	0.0515 (6)
H8A	0.242 (8)	0.723 (4)	0.121 (4)	0.107 (13)*
H8B	0.075 (6)	0.659 (2)	−0.003 (3)	0.068 (7)*
H8C	0.328 (7)	0.626 (3)	0.049 (3)	0.078 (10)*
C9	0.7156 (6)	0.2615 (2)	0.3529 (4)	0.0611 (6)
H9A	0.634 (7)	0.202 (3)	0.361 (3)	0.074 (8)*
H9B	0.834 (7)	0.254 (2)	0.270 (4)	0.074 (8)*
H9C	0.824 (6)	0.272 (2)	0.448 (3)	0.063 (7)*
C10	0.4021 (7)	0.3476 (3)	0.1648 (3)	0.0623 (6)
H10A	0.253 (6)	0.384 (2)	0.149 (3)	0.062 (8)*
H10B	0.378 (8)	0.281 (3)	0.132 (4)	0.099 (11)*
H10C	0.486 (9)	0.387 (3)	0.105 (5)	0.100 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0228 (8)	0.0462 (9)	0.0544 (9)	−0.0014 (7)	0.0099 (6)	0.0119 (8)
N2	0.0346 (10)	0.0441 (9)	0.0579 (10)	0.0028 (7)	0.0055 (7)	−0.0006 (8)
N3	0.0509 (12)	0.0704 (13)	0.0462 (10)	−0.0069 (10)	0.0097 (8)	−0.0036 (10)
O1	0.0222 (9)	0.0820 (10)	0.0750 (10)	0.0048 (7)	0.0074 (6)	0.0234 (9)
O2	0.0970 (15)	0.1035 (14)	0.0497 (10)	−0.0010 (12)	0.0266 (9)	0.0111 (10)
O3	0.0786 (14)	0.0907 (14)	0.0671 (11)	0.0254 (11)	0.0237 (9)	−0.0013 (9)
C1	0.0269 (9)	0.0383 (9)	0.0421 (10)	−0.0052 (8)	0.0009 (7)	0.0045 (8)
C2	0.0251 (10)	0.0390 (10)	0.0500 (11)	−0.0060 (7)	−0.0020 (8)	0.0025 (8)
C3	0.0387 (12)	0.0453 (11)	0.0544 (12)	−0.0012 (9)	−0.0052 (9)	0.0087 (9)
C4	0.0454 (13)	0.0573 (13)	0.0427 (11)	−0.0056 (10)	−0.0017 (9)	0.0100 (10)
C5	0.0347 (11)	0.0528 (12)	0.0398 (11)	−0.0091 (8)	0.0000 (8)	0.0007 (8)
C6	0.0308 (11)	0.0411 (10)	0.0483 (11)	−0.0038 (8)	0.0015 (8)	−0.0008 (8)
C7	0.0291 (12)	0.0393 (9)	0.0489 (10)	−0.0012 (8)	0.0022 (7)	0.0035 (8)
C8	0.0423 (14)	0.0601 (15)	0.0529 (13)	0.0035 (11)	0.0083 (11)	0.0146 (11)
C9	0.0433 (15)	0.0532 (14)	0.086 (2)	0.0066 (11)	0.0003 (13)	−0.0095 (12)
C10	0.060 (2)	0.073 (2)	0.0544 (14)	0.003 (2)	0.0082 (11)	−0.0004 (13)

Geometric parameters (Å, º)

N1—C7	1.352 (3)	O1—C7	1.219 (3)
N1—C1	1.410 (2)	C1—C6	1.368 (3)
N2—C2	1.372 (3)	C1—C2	1.428 (3)
N2—C9	1.450 (3)	C2—C3	1.405 (3)
N2—C10	1.451 (3)	C3—C4	1.362 (3)
N3—O2	1.217 (3)	C4—C5	1.383 (3)
N3—O3	1.224 (3)	C5—C6	1.387 (3)
N3—C5	1.445 (3)	C7—C8	1.495 (3)
C7—N1—C1	126.2 (2)	N2—C2—C1	120.9 (2)
C2—N2—C9	118.4 (2)	C3—C2—C1	116.6 (2)
C2—N2—C10	120.5 (2)	C4—C3—C2	122.2 (2)
C9—N2—C10	112.6 (2)	C3—C4—C5	119.4 (2)
O2—N3—O3	122.6 (2)	C4—C5—C6	120.7 (2)
O2—N3—C5	118.7 (2)	C4—C5—N3	119.9 (2)
O3—N3—C5	118.8 (2)	C6—C5—N3	119.4 (2)
C6—C1—N1	120.9 (2)	C1—C6—C5	119.9 (2)
C6—C1—C2	120.7 (2)	O1—C7—N1	122.9 (2)
N1—C1—C2	118.2 (2)	O1—C7—C8	121.6 (2)
N2—C2—C3	122.4 (2)	N1—C7—C8	115.5 (2)
C7—N1—C1—C6	−46.4 (3)	C3—C4—C5—C6	−4.5 (3)
C7—N1—C1—C2	138.3 (2)	C3—C4—C5—N3	177.9 (2)
C9—N2—C2—C3	−11.8 (3)	O2—N3—C5—C4	−0.4 (3)
C10—N2—C2—C3	133.7 (2)	O3—N3—C5—C4	179.5 (2)
C9—N2—C2—C1	166.5 (2)	O2—N3—C5—C6	−178.0 (2)
C10—N2—C2—C1	−48.0 (3)	O3—N3—C5—C6	1.9 (3)
C6—C1—C2—N2	174.5 (2)	N1—C1—C6—C5	−171.4 (2)
N1—C1—C2—N2	−10.2 (3)	C2—C1—C6—C5	3.8 (3)
C6—C1—C2—C3	−7.2 (3)	C4—C5—C6—C1	2.2 (3)
N1—C1—C2—C3	168.1 (2)	N3—C5—C6—C1	179.8 (2)
N2—C2—C3—C4	−176.7 (2)	C1—N1—C7—O1	3.2 (3)
C1—C2—C3—C4	4.9 (3)	C1—N1—C7—C8	−178.1 (2)
C2—C3—C4—C5	0.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.86	2.04	2.875 (2)	163

Symmetry code: (i) x+1, y, z.