organic compounds 2-Amino derivatives of 5-nitrophenylacetamide

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1 organic compounds Acta Crystallographica Section C Crystal Structure Communications ISSN these publications and from the Cambridge Structural Database. Thus, to compare the structural peculiarities of (I), (II) and (III) we had to redetermine the crystal structure of (III). 2-Amino derivatives of 5-nitrophenylacetamide Ronald D. Clark, a Angela Romero, a Oleg Ya. Borbulevych, a * Mikhail Yu. Antipin, a,b Vladimir N. Nesterov a and Tatiana V. Timofeeva a a Department of Physical Sciences, New Mexico Highlands University, Las Vegas, NM 87701, USA, and b Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov St., B-334, Moscow, Russian Federation Correspondence oleg@xrlab.ineos.ac.ru Received 4 November 1999 Accepted 22 November 1999 The structures of the potential non-linear optical (NLO) materials N-[2-(isopropylamino)-5-nitrophenyl]acetamide, (I) C 11 H 15 N 3 O 3,andN-[2-(butylamino)-5-nitrophenyl]acetamide, (II) C 12 H 17 N 3 O 3, have been investigated by X-ray analysis. To compare them with the structure of N-[2-(dimethylamino)-5- nitrophenyl]acetamide, (III) C 10 H 13 N 3 O 3, a known NLO compound, we had to redetermine the structure of (III), since it was described only brie y 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. 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 C7ÐN1ÐC1ÐC6 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 C9Ð N2ÐC2ÐC3 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 C7ÐN1ÐC1ÐC6 torsion angles of 57.1 (4) and 46.4 (3), and C9ÐN2ÐC2ÐC3 torsion angles of 4.2 (4) and 11.7 (3). Comment In recent years organic non-linear 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 non-centrosymmetric 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 brie y in each case (Baumert et al., 1987; Norman et al., 1987) and atomic coordinates are absent from Figure 1 A view of the two independent molecules of (I) showing the atomnumbering 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. 336 # 2000 International Union of Crystallography Printed in Great Britain ± all rights reserved Acta Cryst. (2000). C56, 336±338

2 organic compounds 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. 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. Compound (I) Crystal data Figure 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. The nitro groups in molecule A of (I) and in (II) and (III) are nearly coplanar with the benzene ring, with the O2ÐN3Ð C5ÐC4 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 NÐHO bonds (Tables 2 and 3) forming in nite 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), in nite zigzag chains due to intermolecular NÐHO bonds (Table 1) are observed, and molecules A and B alternate within them. C 11 H 15 N 3 O 3 M r = Monoclinic, P2 1 =n a = (7) A Ê b = (4) A Ê c = (6) A Ê = (4) V = (18) A Ê 3 Z =8 Data collection Syntex P2 1 /PC diffractometer /2 scans 4351 measured re ections 4164 independent re ections 2976 re ections with I > 2(I) R int = max = Re nement Re nement on F 2 R[F 2 >2(F 2 )] = wr(f 2 ) = S = re ections 427 parameters All H-atom parameters re ned D x = Mg m 3 Mo K radiation Cell parameters from 24 re ections = 10±11 = mm 1 T = 293 (2) K Prism, yellow mm h = 12! 15 k = 7! 15 l = 16! 15 2 standard re ections every 98 re ections intensity decay: 4.7% w = 1/[ 2 (F o 2 ) + (0.0622P) P] where P =(F o 2 +2F c 2 )/3 (/) max = max = 0.20 e A Ê 3 min = 0.27 e A Ê 3 Table 1 Hydrogen-bonding geometry (A Ê, ) for (I). DÐHA DÐH HA DA DÐHA N1ÐH1O1 0i 0.86 (2) 1.99 (3) (3) 159 (2) N2ÐH2O1 0i 0.92 (3) 2.25 (3) (3) 147 (2) N1 0 ÐH1 0 O (2) 2.00 (2) (3) 168 (2) N2 0 ÐH2 0 O (3) 2.19 (3) (3) 162 (2) Symmetry code: (i) 1 2 x; 1 2 y; 1 2 z. Compound (II) Figure 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. Crystal data C 12 H 17 N 3 O 3 M r = Triclinic, P1 a = (2) A Ê b = (5) A Ê c = (7) A Ê = = = V = (5) A Ê 3 Z =2 D x = Mg m 3 Mo K radiation Cell parameters from 24 re ections = 10±11 = mm 1 T = 193 (2) K Prism, yellow mm Acta Cryst. (2000). C56, 336±338 Ronald D. Clark et al. C 10 H 13 N 3 O 3,C 11 H 15 N 3 O 3 and C 12 H 17 N 3 O 3 337

3 organic compounds Data collection Syntex P2 1 /PC diffractometer /2 scans 2900 measured re ections 2569 independent re ections 1391 re ections with I > 2(I) R int = max = Re nement Re nement on F 2 R[F 2 >2(F 2 )] = wr(f 2 ) = S = re ections 173 parameters Table 2 Hydrogen-bonding geometry (A Ê, ) for (II). Compound (III) h = 5! 5 k = 14! 14 l = 15! 15 2 standard re ections every 98 re ections intensity decay: 4.1% H atoms: see below w = 1/[ 2 (F o 2 ) + (0.0901P) 2 ] where P =(F o 2 +2F c 2 )/3 (/) max < max = 0.25 e A Ê 3 min = 0.30 e A Ê 3 DÐHA DÐH HA DA DÐHA N1ÐH1O1 i 0.86 (4) 2.21 (4) (4) 142 (3) N1ÐH1O3 ii 0.86 (4) 2.55 (4) (4) 139 (3) N2ÐH2O1 i 0.87 (3) 2.21 (4) (4) 146 (3) Symmetry codes: (i) x 1; y; z; (ii) x; 1 y; 1 z. Table 3 Hydrogen-bonding geometry (A Ê, ) for (III). DÐHA DÐH HA DA DÐHA N1ÐH1O1 i (2) 163 Symmetry code: (i) 1 x; y; z. For (II), H atoms on N were located in difference Fourier syntheses and then re ned freely, those in methyl groups were located similarly and re ned as part of rigid rotating groups, and all others were placed geometrically. In (III), the Hl(ÐNl) atom was treated as a riding atom; all other H atom positions were re ned isotropically. For all compounds, data collection: P3 (Siemens, 1989); cell re nement: P3; data reduction: XDISK (Siemens, 1991); program(s) used to solve structure: SHELXTL/PC (Sheldrick, 1994); program(s) used to re ne structure: SHELXTL/PC; molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXTL/PC. We thank the NASA Alliance for Nonlinear Optics (NAG5-6532) for support of this project, NASA for funding via cooperative agreement NCC8-144, and AFOSR (Grant F ). Supplementary data for this paper are available from the IUCr electronic archives (Reference: BM1387). Services for accessing these data are described at the back of the journal. Crystal data C 10 H 13 N 3 O 3 M r = Monoclinic, P 2 1 a = (10) A Ê b = (3) A Ê c = (2) A Ê = (3) V = (2) A Ê 3 Z =2 Data collection Siemens P3 diffractometer /2 scans 2053 measured re ections 1817 independent re ections 1486 re ections with I > 2(I) R int = max = Re nement Re nement on F 2 R[F 2 >2(F 2 )] = wr(f 2 ) = S = re ections 193 parameters H-atoms: see below D x = Mg m 3 Mo K radiation Cell parameters from 24 re ections = 10±11 = mm 1 T = 293 (2) K Needle, yellow mm h =0! 5 k = 15! 15 l = 10! 10 2 standard re ections every 98 re ections intensity decay: 4.8% w = 1/[ 2 (F o 2 ) + (0.0645P) P] where P =(F o 2 +2F c 2 )/3 (/) max = max = 0.11 e A Ê 3 min = 0.12 e A Ê 3 References Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1Ð19. Antipin, M. Yu., Barr, T. A., Cardelino, B. H., Clark, R. D., Moor, C. E., Myers, T., Penn, B., Sanghadasa, M. & Timofeeva, T. V. (1997). J. Phys. Chem. B. 101, 2770±2781. Antipin, M. Yu., Timofeeva, T. V., Clark, R. D., Nesterov, V. N., Sanghadasa, M., Barr, T. A., Penn, B., Romero, L. & Romero, L. (1998). J. Phys. Chem. A, 102, 7222±7232. Baumert, J.-C., Twieg, R. J., Bjorklund, G. C., Logan, J. A. & Dirk, C. W. (1987). Appl. Phys. Lett. 51, 1484±1486. Flack, H. D. (1983). Acta Cryst. A39, 876±881. Martinez, A., Ballard, J., Mascarenas, M., Penn, B. & Clark, R. D. (1993). Science and Technology Alliance Materials Conference '93, edited by J. Sankas, pp. 226±231. Lancaster and Basel: Technomic Publishing Company, Inc. Norman, P. A., Bloor, D., Obhi, J. S., Karaulov, S. A., Hursthouse, M. B., Kolinsky, P. V., Jones, R. J. & Hall, S. R. (1987). J. Opt. Soc. Am. 4, 1013± Siemens (1989). P3. Version 4.20PC. Siemens Analytical X-ray Instruments Inc., Karlsruhe, Germany. Siemens (1991). XDISK. Version 4.20PC. Siemens Analytical X-ray Instruments Inc., Karlsruhe, Germany. Sheldrick, G. M. (1994). SHELXTL/PC. Version Siemens Analytical X-ray Instruments Inc., Karlsruhe, Germany. Zyss, J., Ledoux, I. & Nicoud, J. F. (1994). Molecular Nonlinear Optics: Materials, Physics, and Devices, edited by J. Zyss, pp. 129±200. London: Academic Press. 338 Ronald D. Clark et al. C 10 H 13 N 3 O 3,C 11 H 15 N 3 O 3 and C 12 H 17 N 3 O 3 Acta Cryst. (2000). C56, 336±338

4 [doi: /s ] 2-Amino derivatives of 5-nitrophenylacetamide Ronald D. Clark, Angela Romero, Oleg Ya. Borbulevych, Mikhail Yu. Antipin, Vladimir N. Nesterov and Tatiana V. Timofeeva 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. (I) N-[2-(isopropylamino)-5-nitrophenyl]acetamide Crystal data C 11 H 15 N 3 O 3 M r = Monoclinic, P2 1 /n a = (7) Å b = (4) Å c = (6) Å β = (4) V = (18) Å 3 Z = 8 Data collection Syntex P2 1 /PC diffractometer Radiation source: fine-focus sealed tube Graphite monochromator θ/2θ scans 4351 measured reflections 4164 independent reflections 2976 reflections with I > 2σ(I) Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 427 parameters 0 restraints Primary atom site location: structure-invariant direct methods F(000) = 1008 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 24 reflections θ = µ = 0.10 mm 1 T = 293 K Prism, yellow mm R int = θ max = 25.1, θ min = 1.9 h = k = 7 15 l = standard reflections every 98 reflections intensity decay: 4.7% Secondary atom site location: difference Fourier map Hydrogen site location: difference Fourier map All H-atom parameters refined Calculated w = 1/[σ 2 (F o2 ) + (0.0622P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.20 e Å 3 Δρ min = 0.27 e Å 3 sup-1

5 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 F 2 for ALL reflections except for 58 with very negative F 2 or flagged by the user for potential systematic errors. Weighted R-factors wr and all goodnesses of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The observed criterion of F 2 > σ(f 2 ) is used only for calculating R factor obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 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 (Å 2 ) x y z U iso */U eq N (14) (14) (14) (4) H (19) (17) (18) (6)* N (2) (14) (15) (5) H (2) (2) (2) (8)* N (2) (2) (15) (5) O (11) (11) (11) (4) O (14) (2) (2) (5) O (13) (14) (14) (5) C (2) (2) (2) (5) C (2) (2) (2) (5) C (2) (2) (2) (6) H (19) (2) (19) (7)* C (2) (2) (2) (6) H (2) (19) (19) (7)* C (2) (2) (2) (5) C (2) (2) (2) (5) H (17) (19) (17) (6)* C (2) (2) (2) (5) C (2) (2) (2) (5) H8A (2) (2) (2) (8)* H8B (2) (2) (2) (8)* H8C (2) (2) (2) (9)* C (2) (2) (2) (6) H (18) (18) (19) (7)* C (3) (2) (2) (7) H10A (2) (2) (2) (8)* H10B (3) (3) (3) (12)* H10C (3) (4) (3) (10)* C (2) (2) (2) (7) H11A (3) (3) (2) (10)* H11B (2) (2) (2) (7)* H11C (2) (2) (3) (9)* N (14) (13) (14) (4) H (18) (17) (17) (6)* sup-2

6 N (15) (14) (15) (4) H (2) (2) (19) (8)* N (15) (15) (2) (5) O (12) (12) (13) (4) O (13) (14) (2) (5) O (13) (13) (2) (5) C (2) (2) (15) (5) C (2) (2) (15) (5) C (2) (2) (2) (5) H (18) (19) (17) (6)* C (2) (2) (2) (5) H (18) (18) (17) (6)* C (2) (2) (2) (5) C (2) (2) (2) (5) H (17) (19) (17) (6)* C (2) (2) (2) (5) C (2) (2) (2) (6) H8D (3) (3) (3) (13)* H8E (3) (3) (3) (10)* H8F (3) (3) (3) (12)* C (2) (2) (2) (5) H (16) (16) (16) (6)* C (2) (2) (2) (6) H10D (2) (2) (2) (8)* H10E (2) (2) (2) (8)* H10F (3) (2) (2) (10)* C (2) (2) (2) (6) H11D (2) (2) (2) (7)* H11E (2) (2) (2) (9)* H11F (2) (2) (2) (8)* Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 N (10) (10) (10) (8) (8) (8) N (12) (10) (11) (9) (9) (8) N (12) (13) (11) (10) (9) (9) O (8) (8) (8) (7) (7) (7) O (11) (13) (14) (9) (9) (11) O (11) (11) (12) (8) (9) (9) C (13) (11) (11) (9) (9) (8) C (13) (12) (11) (10) (9) (9) C (15) (13) (14) (11) (11) (10) C (15) (14) (14) (12) (11) (11) C (13) (13) (12) (10) (9) (10) C (13) (12) (11) (10) (9) (9) C (12) (11) (12) (9) (9) (9) C (13) (13) (14) (10) (11) (11) sup-3

7 C (2) (12) (13) (11) (12) (10) C (2) (2) (2) (15) (2) (14) C (2) (2) (2) (14) (14) (13) N (10) (9) (10) (8) (8) (8) N (11) (10) (12) (9) (9) (8) N (11) (11) (12) (9) (9) (9) O (9) (9) (10) (7) (7) (8) O (10) (11) (15) (9) (10) (10) O (10) (10) (2) (8) (10) (10) C (11) (10) (10) (9) (8) (9) C (12) (11) (11) (9) (9) (9) C (13) (12) (13) (10) (10) (10) C (13) (12) (13) (10) (10) (10) C (12) (12) (12) (9) (9) (9) C (12) (11) (12) (9) (9) (9) C (12) (11) (11) (9) (9) (9) C (14) (14) (2) (11) (12) (12) C (13) (12) (13) (10) (10) (10) C (2) (14) (2) (12) (13) (12) C (14) (14) (2) (11) (12) (12) Geometric parameters (Å, º) N1 C (3) N1 C (3) N1 C (3) N1 C (3) N2 C (3) N2 C (3) N2 C (3) N2 C (3) N3 O (3) N3 O (3) N3 O (3) N3 O (3) N3 C (3) N3 C (3) O1 C (3) O1 C (3) C1 C (3) C1 C (3) C1 C (3) C1 C (3) C2 C (3) C2 C (3) C3 C (4) C3 C (3) C4 C (3) C4 C (3) C5 C (3) C5 C (3) C7 C (3) C7 C (3) C9 C (4) C9 C (3) C9 C (4) C9 C (4) C7 N1 C (2) C7 N1 C (2) C2 N2 C (2) C2 N2 C (2) O3 N3 O (2) O3 N3 O (2) O3 N3 C (2) O3 N3 C (2) O2 N3 C (2) O2 N3 C (2) C6 C1 C (2) C6 C1 N (2) C6 C1 N (2) C6 C1 C (2) sup-4

8 C2 C1 N (2) N1 C1 C (2) N2 C2 C (2) N2 C2 C (2) N2 C2 C (2) N2 C2 C (2) C3 C2 C (2) C3 C2 C (2) C4 C3 C (2) C4 C3 C (2) C3 C4 C (2) C3 C4 C (2) C6 C5 C (2) C4 C5 C (2) C6 C5 N (2) C4 C5 N (2) C4 C5 N (2) C6 C5 N (2) C1 C6 C (2) C1 C6 C (2) O1 C7 N (2) O1 C7 N (2) O1 C7 C (2) O1 C7 C (2) N1 C7 C (2) N1 C7 C (2) N2 C9 C (2) N2 C9 C (2) N2 C9 C (2) N2 C9 C (2) C10 C9 C (2) C11 C9 C (2) C7 N1 C1 C (3) C7 N1 C1 C (3) C7 N1 C1 C (2) C7 N1 C1 C (2) C9 N2 C2 C (3) C9 N2 C2 C3 3.9 (3) C9 N2 C2 C (2) C9 N2 C2 C (2) C6 C1 C2 N (2) C6 C1 C2 N (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 C (2) N1 C1 C2 C (2) N2 C2 C3 C (2) N2 C2 C3 C (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 N (2) C3 C4 C5 N (2) O3 N3 C5 C6 4.3 (3) O3 N3 C5 C (2) O2 N3 C5 C (2) O2 N3 C5 C (3) O3 N3 C5 C (2) O3 N3 C5 C (3) O2 N3 C5 C4 3.8 (3) O2 N3 C5 C (2) C2 C1 C6 C5 2.2 (3) N1 C1 C6 C (2) N1 C1 C6 C (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 C (2) N3 C5 C6 C (2) C1 N1 C7 O1 6.6 (3) C1 N1 C7 O1 0.9 (3) C1 N1 C7 C (2) C1 N1 C7 C (2) C2 N2 C9 C (3) C2 N2 C9 C (2) C2 N2 C9 C (2) C2 N2 C9 C (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) (3) 159 (2) N2 H2 O1 i 0.92 (3) 2.25 (3) (3) 147 (2) sup-5

9 N1 H1 O (2) 2.00 (2) (3) 168 (2) N2 H2 O (3) 2.19 (3) (3) 162 (2) Symmetry code: (i) x+1/2, y+1/2, z+1/2. (II) N-[2-(butylamino)-5-nitrophenyl]acetamide Crystal data C 12 H 17 N 3 O 3 M r = Triclinic, P1 a = (2) Å b = (5) Å c = (7) Å α = β = γ = V = (5) Å 3 Data collection Syntex P2 1 /PC diffractometer Radiation source: fine-focus sealed tube Graphite monochromator θ/2θ scans 2900 measured reflections 2569 independent reflections 1391 reflections with I > 2σ(I) Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 173 parameters 0 restraints Primary atom site location: structure-invariant direct methods Z = 2 F(000) = 268 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 24 reflections θ = µ = 0.10 mm 1 T = 193 K Prism, yellow mm R int = θ max = 27.1, θ min = 1.7 h = 5 5 k = l = standard reflections every 98 reflections intensity decay: 4.1% Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H atoms treated by a mixture of independent and constrained refinement Calculated w = 1/[σ 2 (F o2 ) + (0.0901P) 2 ] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.25 e Å 3 Δρ min = 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 F 2 for ALL reflections except for 66 with very negative F 2 or flagged by the user for potential systematic errors. Weighted R-factors wr and all goodnesses of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The observed criterion of F 2 > σ(f 2 ) is used only for calculating R factor obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. sup-6

10 Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq N (6) (2) (2) (6) H (8) (3) (3) (10)* N (5) (2) (2) (7) H (7) (3) (3) (9)* N (5) (2) (2) (6) O (4) (2) (2) (6) O (5) (2) (2) (7) O (5) (2) (2) (6) C (6) (3) (2) (7) C (6) (3) (2) (7) C (6) (3) (2) (7) H (6) (3) (2) 0.033* C (6) (3) (3) (7) H (6) (3) (3) 0.032* C (6) (3) (2) (7) C (6) (3) (2) (7) H (6) (3) (2) 0.031* C (6) (3) (2) (7) C (7) (3) (3) (8) H8A (8) (17) (16) 0.056* H8B (4) (6) (12) 0.056* H8C (4) (12) (6) 0.056* C (6) (3) (3) (7) H9A (6) (3) (3) 0.034* H9B (6) (3) (3) 0.034* C (7) (3) (3) (8) H10A (7) (3) (3) 0.040* H10B (7) (3) (3) 0.040* C (8) (3) (3) (9) H11A (8) (3) (3) 0.049* H11C (8) (3) (3) 0.049* C (9) (4) (3) (11) H12A (5) (8) (10) 0.084* H12B (14) (2) (6) 0.084* H12C (5) (18) (6) 0.084* Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 N (14) (14) (2) (12) (12) (12) N (15) (15) (2) (12) (13) (13) N (15) (14) (15) (12) (12) (12) O (12) (13) (13) (10) (10) (10) O (2) (2) (14) (12) (11) (12) O (15) (13) (15) (12) (12) (11) sup-7

11 C (2) (15) (2) (13) (14) (13) C (2) (2) (2) (13) (13) (13) C (2) (15) (2) (13) (14) (13) C (2) (2) (2) (14) (14) (13) C (2) (2) (2) (13) (13) (13) C (2) (14) (2) (12) (14) (13) C (2) (2) (2) (13) (13) (13) C (2) (2) (2) (2) (2) (2) C (2) (2) (2) (14) (14) (13) C (2) (2) (2) (2) (15) (15) C (2) (2) (2) (2) (2) (2) C (3) (2) (2) (2) (2) (2) Geometric parameters (Å, º) N1 C (4) C1 C (4) N1 C (4) C2 C (4) N2 C (4) C3 C (4) N2 C (4) C4 C (4) N3 O (3) C5 C (4) N3 O (3) C7 C (4) N3 C (4) C9 C (4) O1 C (4) C10 C (5) C1 C (4) C11 C (5) C7 N1 C (3) C3 C4 C (3) C2 N2 C (3) C4 C5 C (3) O3 N3 O (3) C4 C5 N (3) O3 N3 C (3) C6 C5 N (3) O2 N3 C (3) C1 C6 C (3) C6 C1 C (3) O1 C7 N (3) C6 C1 N (3) O1 C7 C (3) C2 C1 N (3) N1 C7 C (3) N2 C2 C (3) N2 C9 C (2) N2 C2 C (3) C9 C10 C (3) C3 C2 C (3) C12 C11 C (3) C4 C3 C (3) C7 N1 C1 C (4) O3 N3 C5 C (3) C7 N1 C1 C (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 C (3) O2 N3 C5 C (3) C6 C1 C2 N (3) C2 C1 C6 C5 0.7 (4) N1 C1 C2 N2 6.9 (4) N1 C1 C6 C (3) C6 C1 C2 C3 3.1 (4) C4 C5 C6 C1 2.6 (4) N1 C1 C2 C (3) N3 C5 C6 C (3) N2 C2 C3 C (3) C1 N1 C7 O1 8.4 (5) C1 C2 C3 C4 2.2 (4) C1 N1 C7 C (3) sup-8

12 C2 C3 C4 C5 1.0 (4) C2 N2 C9 C (3) C3 C4 C5 C6 3.5 (4) N2 C9 C10 C (3) C3 C4 C5 N (3) C9 C10 C11 C (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) (4) 142 (3) N1 H1 O3 ii 0.86 (4) 2.55 (4) (4) 139 (3) N2 H2 O1 i 0.87 (3) 2.21 (4) (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 C 10 H 13 N 3 O 3 M r = Monoclinic, P2 1 a = (1) Å b = (3) Å c = (2) Å β = (3) V = (2) Å 3 Z = 2 Data collection Siemens P3 diffractometer Radiation source: fine-focus sealed tube Graphite monochromator θ/2θ scans 2053 measured reflections 1817 independent reflections 1486 reflections with I > 2σ(I) Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 193 parameters 1 restraint Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map F(000) = 236 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 24 reflections θ = µ = 0.10 mm 1 T = 293 K Needles, yellow mm R int = θ max = 25.1, θ min = 2.3 h = 0 5 k = l = standard reflections every 98 reflections intensity decay: 4.8% Hydrogen site location: difference Fourier map All H-atom parameters refined Calculated w = 1/[σ 2 (F o2 ) + (0.0645P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.11 e Å 3 Δρ min = 0.12 e Å 3 Absolute structure: Flack (1983) Absolute structure parameter: not reliably determined sup-9

13 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 F 2 for ALL reflections except for 63 with very negative F 2 or flagged by the user for potential systematic errors. Weighted R-factors wr and all goodnesses of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The observed criterion of F 2 > σ(f 2 ) is used only for calculating R factor obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 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 (Å 2 ) x y z U iso */U eq N (4) (12) (2) (4) H * N (3) (13) (2) (4) N (4) (2) (2) (5) O (3) (14) (2) (5) O (5) (2) (2) (6) O (5) (2) (2) (6) C (4) (14) (2) (4) C (4) (14) (2) (5) C (5) (2) (2) (5) H (5) (2) (3) (6)* C (5) (2) (2) (5) H (5) (19) (3) (7)* C (4) (15) (2) (5) C (4) (2) (2) (5) H (5) (2) (2) (6)* C (4) (15) (2) (4) C (5) (2) (3) (6) H8A (8) (4) (4) (13)* H8B (6) (2) (3) (7)* H8C (7) (3) (3) (10)* C (6) (2) (4) (6) H9A (7) (3) (3) (8)* H9B (7) (2) (4) (8)* H9C (6) (2) (3) (7)* C (7) (3) (3) (6) H10A (6) (2) (3) (8)* H10B (8) (3) (4) (11)* H10C (9) (3) (5) (12)* Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 N (8) (9) (9) (7) (6) (8) N (10) (9) (10) (7) (7) (8) sup-10

14 N (12) (13) (10) (10) (8) (10) O (9) (10) (10) (7) (6) (9) O (15) (14) (10) (12) (9) (10) O (14) (14) (11) (11) (9) (9) C (9) (9) (10) (8) (7) (8) C (10) (10) (11) (7) (8) (8) C (12) (11) (12) (9) (9) (9) C (13) (13) (11) (10) (9) (10) C (11) (12) (11) (8) (8) (8) C (11) (10) (11) (8) (8) (8) C (12) (9) (10) (8) (7) (8) C (14) (15) (13) (11) (11) (11) C (15) (14) (2) (11) (13) (12) C (2) (2) (14) (2) (11) (13) Geometric parameters (Å, º) N1 C (3) O1 C (3) N1 C (2) C1 C (3) N2 C (3) C1 C (3) N2 C (3) C2 C (3) N2 C (3) C3 C (3) N3 O (3) C4 C (3) N3 O (3) C5 C (3) N3 C (3) C7 C (3) C7 N1 C (2) N2 C2 C (2) C2 N2 C (2) C3 C2 C (2) C2 N2 C (2) C4 C3 C (2) C9 N2 C (2) C3 C4 C (2) O2 N3 O (2) C4 C5 C (2) O2 N3 C (2) C4 C5 N (2) O3 N3 C (2) C6 C5 N (2) C6 C1 N (2) C1 C6 C (2) C6 C1 C (2) O1 C7 N (2) N1 C1 C (2) O1 C7 C (2) N2 C2 C (2) N1 C7 C (2) C7 N1 C1 C (3) C3 C4 C5 C6 4.5 (3) C7 N1 C1 C (2) C3 C4 C5 N (2) C9 N2 C2 C (3) O2 N3 C5 C4 0.4 (3) C10 N2 C2 C (2) O3 N3 C5 C (2) C9 N2 C2 C (2) O2 N3 C5 C (2) C10 N2 C2 C (3) O3 N3 C5 C6 1.9 (3) C6 C1 C2 N (2) N1 C1 C6 C (2) N1 C1 C2 N (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 C (2) N3 C5 C6 C (2) sup-11

15 N2 C2 C3 C (2) C1 N1 C7 O1 3.2 (3) C1 C2 C3 C4 4.9 (3) C1 N1 C7 C (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 (2) 163 Symmetry code: (i) x+1, y, z. sup-12