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ISSN: 2056-9890
Volume 71| Part 6| June 2015| Pages 671-674
doi:10.1107/S205698901500907X

Crystal structures and hydrogen bonding in the anhydrous tryptaminium salts of the isomeric (2,4-di­chloro­phen­­oxy)acetic and (3,5-di­chloro­phen­­oxy)acetic acids

Graham Smitha* and Daniel E. Lynchb

aScience and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia, and bExilica Ltd., The Technocentre, Puma Way, Coventry CV1 2TT, England
*Correspondence e-mail: g.smith@qut.edu.au

Edited by J. Simpson, University of Otago, New Zealand (Received 6 May 2015; accepted 11 May 2015; online 23 May 2015)

The anhydrous salts of 2-(1H-indol-3-yl)ethanamine (tryptamine) with isomeric (2,4-di­chloro­phen­oxy)acetic acid (2,4-D) and (3,5-di­chloro­phen­oxy)acetic (3,5-D), both C10H13N2+·C8H5Cl2O3− [(I) and (II), respectively], have been determined and their one-dimensional hydrogen-bonded polymeric structures are described. In the crystal of (I), the aminium H atoms are involved in three separate inter-species N—H⋯O hydrogen-bonding inter­actions, two with carboxyl­ate O-atom acceptors and the third in an asymmetric three-centre bidentate carboxyl­ate O,O′ chelate [graph set R12(4)]. The indole H atom forms an N—H⋯Ocarboxyl­ate hydrogen bond, extending the chain structure along the b-axis direction. In (II), two of the three aminium H atoms are also involved in N—H⋯Ocarboxyl­ate hydrogen bonds similar to (I) but with the third, a three-centre asymmetric inter­action with carboxyl­ate and phen­oxy O atoms is found [graph set R12(5)]. The chain polymeric extension is also along b. There are no π–π ring inter­actions in either of the structures. The aminium side-chain conformations differ significantly between the two structures, reflecting the conformational ambivalence of the tryptaminium cation, as found also in the benzoate salts.

CCDC references: 1400285; 1400284

1. Chemical context

2-(1H-Indol-3-yl)ethanamine (tryptamine) is an alkaloid found in plants and fungi and is a possible inter­mediate in the biosynthetic pathway to the plant hormone indole-3-acetic acid (Takahashi, 1986[Takahashi, N. (1986). In Chemistry of Plant Hormones. Florida: CRC Press.]). It is also found in trace amounts in the mammalian brain, possibly acting as a neuromodulator or neurotransmitter (Jones, 1982[Jones, R. S. G. (1982). Prog. Neurobiol. 19, 117-139.]). As a relatively strong base (pKa = 10.2), it readily forms salts with a number of organic acids. To investigate the modes of hydrogen-bonding inter­action in crystals of the tryptaminium salts of ring-substituted phen­oxy­acetic acid analogues, the reaction of tryptamine with two isomeric homologues, the herbicidally active (2,4-di­chloro­phen­oxy)acetic acid (2,4-D) (Zumdahl, 2010[Zumdahl, R. L. (2010). In A History of Weed Science in the United States. New York: Elsevier.]) and (3,5-di­chloro­phen­oxy)acetic acid (3,5-D), gave the anhydrous salts, C10H13N2+·C8H5Cl2O3−, (I)[link] and (II)[link], respectively. Their structures and hydrogen-bonding modes are reported herein. The structure of the anhydrous salt with phen­oxy­acetic acid (Koshima et al., 1999[Koshima, H., Honke, S. & Fujita, J. (1999). J. Org. Chem. 64, 3916-3921.]) represents the only reported example of a salt from this acid series. In that crystal, chirality was generated through hydrogen bonding, giving cation–anion units related along a 21 screw axes. A similar phenomenon was also observed in the tryptaminium 4-chloro­benzoate crystal (Koshima et al., 2005[Koshima, H., Nagano, M. & Asahi, T. (2005). J. Am. Chem. Soc. 127, 2455-2463.]).

[Scheme 1]

2. Structural commentary

The asymmetric units of (I)[link] and (II)[link] comprise a tryptaminium cation (A) and either a 2,4-di­chloro­phen­oxy­acetate anion (B) (I)[link] (Fig. 1[link]) or a (3,5-di­chloro­phen­oxy)acetate anion (II)[link] (Fig. 2[link]). Unlike a number of tryptaminium salts of benzoic acids in which the benzene rings in the cation and anion species are essentially parallel, giving π–π inter­actions, these planes in (I)[link] and (II)[link] are not so [dihedral angles = 74.1 (3) and 24.68 (17)°, respectively], giving no π–π inter­active effects.

[Figure 1]
Figure 1
The atom-numbering scheme and the mol­ecular conformation of the TRYP+ cation (A) and the 2,4-D− anion (B) in (I)[link] with displacement ellipsoids drawn at the 40% probability level. The cation–anion hydrogen bonds are shown as dashed lines.
[Figure 2]
Figure 2
The atom-numbering scheme and the mol­ecular conformation of the TRYP+ cation (A) and the 3,5-D− anion (B) in (II)[link] with displacement ellipsoids drawn at the 40% probability level. The cation–anion hydrogen bond is shown as a dashed line.

The alkyl­aminium side chains in the cations of (I)[link] and (II)[link] differ significantly, with the torsion angles C2A—C3A—C31A—C32A and C3A—C31A—C32A—C32A—N32A being −113.1 (5), 58.6 (5)° in (I)[link], 7.3 (5) and in 75.7 (4)° (II)[link], respectively. This variability is a standard feature in the structures of the known tryptaminium benzoate salts, which include the parent benzoate (Terakita et al., 2004[Terakita, A., Matsunaga, H., Ueda, T., Eguchi, T., Echigoya, M., Umemoto, K. & Godo, M. (2004). Chem. Pharm. Bull. 52, 546-551.]), 4-chloro­benzoate (Koshima et al., 2005[Koshima, H., Nagano, M. & Asahi, T. (2005). J. Am. Chem. Soc. 127, 2455-2463.]), 3,4-di­meth­oxy­benzoate (Siripaisarnpipat & Larsen, 1987[Siripaisarnpipat, S. & Larsen, S. (1987). Acta Chem. Scand. Ser. A, 41, 539-547.]), 3,5-di­nitro-2-hy­droxy­benzoate (Lynch et al., 2015[Lynch, D. E., Cox, M. & Smith, G. (2015). Dyes Pigments, doi: 10.1016/j. dyepig. 2015.01.028.]) and the pseudopolymorphic anhydrous, mono- and dihydrate 3,5-di­nitro­benzoates salts (Lynch et al., 2015[Lynch, D. E., Cox, M. & Smith, G. (2015). Dyes Pigments, doi: 10.1016/j. dyepig. 2015.01.028.]). In the structure of tryptamine, determined from powder diffraction data (Nowell et al., 2002[Nowell, H., Attfield, J. P. & Cole, J. C. (2002). Acta Cryst. B58, 835-840.]), the corres­ponding angles are −89.4 (6) and 60.7 (6)°.

In (I)[link] the phen­oxy­acetate side chain of the 2,4-D anion is significantly rotated out of the benzene plane [defining torsion angle C1B—O11B—C12B—C13B = 81.2 (6)°], similar to that of the parent acid which also has the synclinal side chain conformation (torsion angle 90±30°) (comparative torsion angle = 75.2°; Smith et al., 1976[Smith, G., Kennard, C. H. L. & White, A. H. (1976). J. Chem. Soc. Perkin Trans. 2, pp. 791-792.]). However, in the potassium salt (Kennard et al., 1983[Kennard, C. H. L., Smith, G. & O'Reilly, E. J. (1983). Inorg. Chim. Acta, 77, L181-L184.]) and the ammonium salt (Liu et al., 2009[Liu, H.-L., Guo, S.-H., Li, Y.-Y. & Jian, F.-F. (2009). Acta Cryst. E65, o1905.]) (both hemihydrates), the anti­periplanar (180±30°) conformation is found. The 3,5-D anion in (II)[link] adopts the anti­periplanar conformation with the defining C1B—O1B—C12B—C13B torsion angle = −166.5 (3). The structure of the parent acid is not known but the equivalent angle in the ammonium salt is −171.35 (15)° (Smith, 2015[Smith, G. (2015). Unpublished results.]) but in the 2:1 adduct of 3,5-D with 4,4′-bi­pyridine (Lynch et al., 2003[Lynch, D. E., Barfield, J., Frost, J., Antrobus, R. & Simmons, J. (2003). Cryst. Eng. 6, 109-122.]), the angle is −71.6 (3)° (synclinal).

3. Supra­molecular features

In the crystal structures of (I)[link] and (II)[link], one-dimensional hydrogen-bonded structures involving N—H⋯Ocarboxyl­ate inter­actions are found. However, the hydrogen-bonding patterns differ significantly. In the crystal of (I)[link], the three aminium H atoms give different inter-species inter­actions, two with single carboxyl­ate O-atom acceptors (O13Biii, O14Bii) and third giving a three-centre O,O′ chelate with carboxyl­ate O atoms (O13, O14) [graph set R21(4)] (Table 1[link]). The indole H atom gives an N—H⋯Ocarboxyl­ate hydrogen bond, extending the chain structure down the [010] axis (Fig. 3[link]). In the crystal of (II)[link], as with (I)[link], two of the three aminium N—H⋯O inter­actions are with single carboxyl­ate O atoms [(O13B, O14Biii) but the third differs in that it forms a three-centre asymmetric inter­action with carboxyl­ate and phen­oxy O atoms of the anion (O13Bii, O11Bii) [graph set R12(4)] (Table 2[link]). The chain polymeric N1—H⋯ O14B extension is also along [010] (Fig. 4[link]).

Table 1
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1A—H1A⋯O13Bi 0.87 (4) 2.13 (5) 2.879 (6) 144 (6)
N32A—H34A⋯O14Bii 0.89 (4) 1.89 (4) 2.782 (6) 175 (2)
N32A—H35A⋯O13Biii 0.90 (4) 2.10 (5) 2.817 (6) 137 (4)
N32A—H36A⋯O13B 0.89 (3) 2.57 (4) 3.231 (6) 132 (4)
N32A—H36A⋯O14B 0.89 (3) 1.94 (4) 2.816 (6) 171 (5)
Symmetry codes: (i) x, y+1, z; (ii) [-x+1, y-{\script{1\over 2}}, -z+1]; (iii) [-x+1, y+{\script{1\over 2}}, -z+1].

Table 2
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1A—H1A⋯O14Bi 0.87 (4) 2.04 (4) 2.838 (4) 152 (4)
N32A—H34A⋯O13B 0.87 (2) 2.05 (3) 2.875 (4) 160 (4)
N32A—H35A⋯O11Bii 0.89 (3) 2.60 (4) 3.160 (4) 122 (3)
N32A—H35A⋯O13Bii 0.89 (3) 1.87 (3) 2.739 (4) 164 (4)
N32A—H36A⋯O14Biii 0.89 (4) 1.90 (4) 2.775 (4) 170 (4)
C2A—H2A⋯O13Biii 0.95 2.55 3.495 (4) 177
Symmetry codes: (i) x, y+1, z; (ii) [-x+1, y-{\script{1\over 2}}, -z+1]; (iii) [-x+1, y+{\script{1\over 2}}, -z+1].
[Figure 3]
Figure 3
The one-dimensional hydrogen-bonded polymeric structure of (I)[link] extending along [010], with non-associative H atoms omitted. For symmetry codes, see Table 1[link].
[Figure 4]
Figure 4
The one-dimensional hydrogen-bonded polymeric structure of (II)[link] extending along [010], with non-associative H-atoms omitted. For symmetry codes, see Table 2[link].

The present pair of structures of salts of tryptamine with isomeric (2,4-di­chloro­phen­oxy)acetic acid and (3,5-di­chloro­phen­oxy)acetic acid provide examples which further reflect the conformational ambivalence of the cationic alkyl­aminium side chain of the tryptamine cation, shown also in the benzoate salts.

4. Synthesis and crystallization

The title compounds (I)[link] and (II)[link] were prepared by warming together for 2 min, solutions containing equimolar qu­anti­ties of (2,4-di­chloro­phen­oxy)acetic acid (2,4-D) or (3,5-di­chloro­phen­oxy)acetic acid (3,5-D) (138 mg) with 100 mg of tryptamine in ethanol. Room temperature evaporation of the solutions gave in both cases, colourless needles of (I)[link] and (II)[link] from which specimens were cleaved for the X-ray analyses.

5. Refinement details

Crystal data, data collection and structure refinement details are given in Table 3[link]. Hydrogen atoms were placed in calculated positions [C—Haromatic = 0.95 Å or C—Hmethyl­ene = 0.99 Å] and were allowed to ride in the refinements, with Uiso(H) = 1.2Ueq(C). The aminium H atoms were located in difference-Fourier analyses and were allowed to refine with bond length restraints [d(N—H = 0.88 (2) Å], and with Uiso(H) = 1.2Ueq(N). Although possibly not of relevance in these crystals involving achiral mol­ecules, the Flack absolute structure factors (Flack, 1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) were determined as 0.01 (7) for (II)[link] (2232 Friedel pairs) and 0.45 (15) for (I)[link] (1619 Friedel pairs), in the case of (I)[link] suggesting possible racemic twinning. No indication of conventional twinning was found with the crystals of either isomer.

Table 3
Experimental details

  (I) (II)
Crystal data
Chemical formula C10H13N2+·C8H5Cl2O3− C10H13N2+·C8H5Cl2O3−
Mr 381.25 381.24
Crystal system, space group Monoclinic, P21 Monoclinic, P21
Temperature (K) 200 200
a, b, c (Å) 8.9818 (11), 6.8899 (7), 14.6850 (15) 9.5154 (8), 6.1951 (5), 15.3646 (9)
β (°) 93.565 (9) 102.579 (7)
V (Å3) 907.00 (17) 883.99 (12)
Z 2 2
Radiation type Mo Kα Mo Kα
μ (mm−1) 0.38 0.39
Crystal size (mm) 0.50 × 0.15 × 0.05 0.50 × 0.12 × 0.06
 
Data collection
Diffractometer Oxford Diffraction Gemini-S CCD-detector Oxford Diffraction Gemini-S CCD-detector
Absorption correction Multi-scan (CrysAlis PRO; Agilent, 2013[Agilent (2013). CrysAlis PRO. Agilent Technologies Ltd., Yarnton, England.]) Multi-scan (CrysAlis PRO; Agilent, 2013[Agilent (2013). CrysAlis PRO. Agilent Technologies Ltd., Yarnton, England.])
Tmin, Tmax 0.940, 0.990 0.872, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections 3991, 2896, 2299 3845, 2800, 2451
Rint 0.035 0.027
(sin θ/λ)max (Å−1) 0.617 0.617
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.068, 0.187, 1.06 0.042, 0.105, 1.08
No. of reflections 2896 2800
No. of parameters 226 238
No. of restraints 1 5
H-atom treatment H atoms treated by a mixture of independent and constrained refinement H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.37, −0.26 0.22, −0.24
Absolute structure Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.])
Absolute structure parameter 0.45 (15) 0.01 (7)
Computer programs: CrysAlis PRO (Agilent, 2013[Agilent (2013). CrysAlis PRO. Agilent Technologies Ltd., Yarnton, England.]), SIR92 (Altomare et al., 1993[Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.]), SHELX97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) within WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information

CCDC references: 1400285; 1400284

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S205698901500907X/sj5460sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S205698901500907X/sj5460Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S205698901500907X/sj5460IIsup3.hkl

Supporting information file. DOI: 10.1107/S205698901500907X/sj5460Isup4.cml

Supporting information file. DOI: 10.1107/S205698901500907X/sj5460IIsup5.cml

checkCIF report


Chemical context top

2-(1H-Indol-3-yl)ethanamine (tryptamine) is an alkaloid found in plants and fungi and is a possible inter­mediate in the biosynthetic pathway to the plant hormone Indole-3-acetic acid (Takahashi, 1986). It is also found in trace amounts in the mammalian brain, possibly acting as a neuromodulator or neurotransmitter (Jones, 1982). As a relatively strong base (pKa = 10.2), it readily forms salts with a number of organic acids. To investigate the modes of hydrogen-bonding inter­action in crystals of the tryptaminium salts of ring-substituted phen­oxy­acetic acid analogues, the reaction of tryptamine with two isomeric homologues, the herbicidally active (2,4-di­chloro­phen­oxy)­acetic acid (2,4-D) (Zumdahl, 2010) and (3,5-di­chloro­phen­oxy)­acetic acid (3,5-D), gave the anhydrous salts, C10H13N2+.C8H5Cl2O3-, (I) and (II), respectively. Their structures and hydrogen-bonding modes are reported herein. The structure of the anhydrous salt with phen­oxy­acetic acid (Koshima et al., 1999) represents the only reported example of a salt from this acid series. In that crystal, chirality was generated through hydrogen bonding, giving cation–anion units related along a 21 screw axes. A similar phenomenon was also observed in the tryptaminium 4-chloro­benzoate crystal (Koshima et al., 2005).

Structural commentary top

The asymmetric units of (I) and (II) comprise a tryptaminium cation (A and either a 2,4-di­chloro­phen­oxy­acetate anion (B) (I) (Fig. 1) or a (3,5-di­chloro­phen­oxy)­acetate anion (II) (Fig. 2). Unlike a number of tryptaminium salts of benzoic acids in which the benzene rings in the cation and anion species are essentially parallel, giving π–π inter­actions, these planes in (I) and (II) are not so [dihedral angles = 74.1 (3) and 24.68 (17)°, respectively], giving no π–π inter­active effects.

The alkyl­aminium side chains in the cations of (I) and (II) differ significantly, with the torsion angles C2A—C3A—C31A—C32A and C3A—C31A—C32A—C32A—N32A being -113.1 (5), 58.6 (5)° in (I), 7.3 (5) and in 75.7 (4)° (II), respectively. This variability is a standard feature in the structures of the known tryptaminium benzoate salts, which include the parent benzoate (Terakita et al., 2004), 4-chloro­benzoate (Koshima et al., 2005), 3,4-di­meth­oxy­benzoate (Siripaisarnpipat & Larsen, 1987), 3,5-di­nitro-2-hy­droxy­benzoate (Lynch et al., 2015) and the pseudopolymorphic anhydrous mono- and dihydrate 3,4-di­nitro­benzoates salts (Lynch et al., 2015). In the structure of tryptamine, determined from powder diffraction data (Nowell et al., 2002), the corresponding angles are -89.4 (6) and 60.7 (6)°.

In (I) the phen­oxy­acetate side chain of the 2,4-D anion is significantly rotated out of the benzene plane [defining torsion angle C1B—O11B—C12B—C13B = 81.2 (6)°], similar to that of the parent acid which also has the synclinal side chain conformation (torsion angle 90±30°) (comparative torsion angle = 75.2°; Smith et al., 1976). However, in the potassium salt (Kennard et al., 1983) and the ammonium salt (Liu et al., 2009) (both hemihydrates), the anti­periplanar (180±30°) conformation is found. The 3,5-D anion in (II) adopts the anti­periplanar conformation with the defining C1B—O1B—C12B—C13B torsion angle = -166.5 (3). The structure of the parent acid is not known but the equivalent angle in the ammonium salt is -171.35 (15)° (Smith, 2015) but in the 2:1 adduct of 3,5-D with 4,4'-bi­pyridine (Lynch et al., 2003), the angle is -71.6 (3)° (synclinal).

Supra­molecular features top

In the crystal structures of (I) and (II), one-dimensional hydrogen-bonded structures involving N—H···Ocarboxyl­ate inter­actions are found. However, the hydrogen-bonding patterns differ significantly. In the crystal of (I), the three aminium H atoms give different inter-species inter­actions, two with single carboxyl­ate O-atom acceptors (O13Biii, O14Bii) and third giving a three-centre O,O' chelate with carboxyl­ate O atoms (O13, O14) [graph set R2/1(4)] (Table 1). The indole H-atom gives an N—H···Ocarboxyl­ate hydrogen bond, extending the chain structure down the [010] axis (Fig. 3). In the crystal of (II), as with (I), two of the three aminium N—H···O inter­actions are with single carboxyl­ate O atoms [(O13B, O14Biii) but third differs in that it forms a three-centre asymmetric inter­action with carboxyl­ate and phen­oxy O atoms of the anion (O13Bii, O11Bii) [graph set R12(4)] (Table 2). The chain polymeric N1—H··· O14B extension is also along [010] (Fig. 4).

The present pair of structures of salts of tryptamine with isomeric (2,4-di­chloro­phen­oxy)­acetic acid and (3,5-di­chloro­phen­oxy)­acetic acid provide examples which further reflect the conformational ambivalence of the cationic propyl­aminium side chain of the tryptamine cation, shown also in the benzoate salts.

Synthesis and crystallization top

The title compounds (I) and (II) were prepared by warming together for 2 min, solutions containing equimolar qu­anti­ties of (2,4-di­chloro­phen­oxy)­acetic acid (2,4-D) or (3,5-di­chloro­phen­oxy)­acetic acid (3,5-D) (138 mg) with 100 mg of tryptamine in ethanol. Room temperature evaporation of the solutions gave in both cases, colourless needles of (I) and (II) from which specimens were cleaved for the X-ray analyses.

Refinement details top

Crystal data, data collection and structure refinement details are given in Table 1. Hydrogen atoms were placed in calculated positions [C—Haromatic = 0.95 Å or C—Hmethyl­ene = 0.99 Å] and were allowed to ride in the refinements, with Uiso(H) = 1.2Ueq(C). The aminium H-atoms were located in difference-Fourier analyses and were allowed to refine with bond length restraints [d(N—H = 0.88 (2) °], and with Uiso(H) = 1.2Ueq(N). Although possibly not of relevance in these crystals involving achiral molecules, the Flack absolute structure factors (Flack, 1983) were determined as 0.01 (7) for (II) (2232 Friedel pairs) and 0.45 (15) for (I) (1619 Friedel pairs), in the case of (I) suggesting possible racemic twinning. No indication of conventional twinning was found with the crystals of either isomer.

top

Crystal data, data collection and structure refinement details are given in Table 3. Hydrogen atoms were placed in calculated positions [C—Haromatic = 0.95 Å or C—Hmethyl­ene = 0.99 Å] and were allowed to ride in the refinements, with Uiso(H) = 1.2Ueq(C). The aminium H atoms were located in difference-Fourier analyses and were allowed to refine with bond length restraints [d(N—H = 0.88 (2) Å], and with Uiso(H) = 1.2Ueq(N). Although possibly not of relevance in these crystals involving achiral molecules, the Flack absolute structure factors (Flack, 1983) were determined as 0.01 (7) for (II) (2232 Friedel pairs) and 0.45 (15) for (I) (1619 Friedel pairs), in the case of (I) suggesting possible racemic twinning. No indication of conventional twinning was found with the crystals of either isomer.

Related literature top

For related literature, see: Flack (1983); Jones (1982); Kennard et al. (1983); Koshima et al. (1999, 2005); Liu et al. (2009); Lynch et al. (2003, 2015); Nowell et al. (2002); Siripaisarnpipat & Larsen (1987); Smith (2015); Smith et al. (1976); Takahashi (1986); Terakita et al. (2004); Zumdahl (2010).

Computing details top

For both compounds, data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SIR92 (Altomare et al., 1993). Program(s) used to refine structure: SHELX97 (Sheldrick, 2008) within WinGX (Farrugia, 2012) for (I); SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012) for (II). For both compounds, molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The atom-numbering scheme and the molecular conformation of the TRYP+ cation (A) and the 2,4-D- anion (B ) in (I) with displacement ellipsoids drawn at the 40% probability level. The cation–anion hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. The atom-numbering scheme and the molecular conformation of the TRYP+ cation (A) and the 3,5-D- anion (B) in (II) with displacement ellipsoids drawn at the 40% probability level. The cation–anion hydrogen bond is shown as a dashed line.
[Figure 3] Fig. 3. The one-dimensional hydrogen-bonded polymeric structure of (I) extending along [010], with non-associative H atoms omitted. For symmetry codes, see Table 1.
[Figure 4] Fig. 4. The one-dimensional hydrogen-bonded polymeric structure of (II) extending along [010], with non-associative H-atoms omitted. For symmetry codes, see Table 2.
(I) 2-(1H-Indol-3-yl)ethanaminium (2,4-dichlorophenoxy)acetate top
Crystal data top
C10H13N2+·C8H5Cl2O3−F(000) = 396
Mr = 381.25Dx = 1.396 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 940 reflections
a = 8.9818 (11) Åθ = 3.8–24.0°
b = 6.8899 (7) ŵ = 0.38 mm−1
c = 14.6850 (15) ÅT = 200 K
β = 93.565 (9)°Needle, colourless
V = 907.00 (17) Å30.50 × 0.15 × 0.05 mm
Z = 2
Data collection top
Oxford Diffraction Gemini-S CCD-detector
diffractometer		2896 independent reflections
Radiation source: Enhance (Mo) X-ray source2299 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
Detector resolution: 16.077 pixels mm-1θmax = 26.0°, θmin = 3.3°
ω scansh = −10→11
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)		k = −7→8
Tmin = 0.940, Tmax = 0.990l = −17→18
3991 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.068H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.187 w = 1/[σ2(Fo2) + (0.0918P)2 + 0.3461P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2896 reflectionsΔρmax = 0.37 e Å−3
226 parametersΔρmin = −0.26 e Å−3
1 restraintAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.45 (15)
Crystal data top
C10H13N2+·C8H5Cl2O3−V = 907.00 (17) Å3
Mr = 381.25Z = 2
Monoclinic, P21Mo Kα radiation
a = 8.9818 (11) ŵ = 0.38 mm−1
b = 6.8899 (7) ÅT = 200 K
c = 14.6850 (15) Å0.50 × 0.15 × 0.05 mm
β = 93.565 (9)°
Data collection top
Oxford Diffraction Gemini-S CCD-detector
diffractometer		2896 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)		2299 reflections with I > 2σ(I)
Tmin = 0.940, Tmax = 0.990Rint = 0.035
3991 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.068H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.187Δρmax = 0.37 e Å−3
S = 1.06Δρmin = −0.26 e Å−3
2896 reflectionsAbsolute structure: Flack (1983)
226 parametersAbsolute structure parameter: 0.45 (15)
1 restraint
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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
xyzUiso*/Ueq
Cl2B0.28249 (19)0.2639 (3)0.84021 (11)0.0625 (6)
Cl4B0.8117 (2)0.2352 (4)1.03185 (12)0.0817 (8)
O11B0.3858 (5)0.6285 (7)0.7750 (3)0.0565 (16)
O13B0.5619 (4)0.6213 (5)0.6335 (3)0.0378 (12)
O14B0.5207 (4)0.9327 (5)0.6033 (3)0.0346 (11)
C1B0.4889 (7)0.5483 (10)0.8340 (4)0.0444 (19)
C2B0.4569 (7)0.3677 (10)0.8717 (4)0.047 (2)
C3B0.5495 (7)0.2673 (11)0.9322 (3)0.049 (2)
C4B0.6859 (8)0.3564 (12)0.9564 (4)0.057 (3)
C5B0.7253 (7)0.5320 (11)0.9216 (4)0.051 (2)
C6B0.6281 (8)0.6256 (11)0.8585 (4)0.055 (2)
C12B0.4160 (7)0.8064 (9)0.7333 (4)0.045 (2)
C13B0.5129 (5)0.7839 (8)0.6498 (3)0.0290 (17)
N1A0.7673 (5)1.3071 (7)0.6100 (3)0.0397 (16)
N32A0.6027 (5)0.7972 (7)0.4326 (3)0.0317 (14)
C2A0.7670 (5)1.2445 (7)0.5215 (3)0.0262 (14)
C3A0.8329 (5)1.0707 (7)0.5166 (3)0.0274 (16)
C4A0.9521 (6)0.8575 (9)0.6506 (4)0.0410 (17)
C5A0.9790 (7)0.8583 (11)0.7434 (4)0.052 (2)
C6A0.9345 (8)1.0100 (12)0.7973 (5)0.060 (3)
C7A0.8638 (7)1.1725 (11)0.7595 (4)0.055 (2)
C8A0.8359 (6)1.1754 (9)0.6647 (4)0.0388 (19)
C9A0.8793 (5)1.0155 (8)0.6100 (4)0.0296 (16)
C31A0.8527 (6)0.9501 (7)0.4333 (3)0.0304 (17)
C32A0.7656 (5)0.7611 (8)0.4290 (3)0.0296 (16)
H3B0.522900.145000.956200.0580*
H5B0.818400.589500.940300.0620*
H6B0.657600.744200.831900.0660*
H12B0.468400.892500.778800.0550*
H13B0.320400.869400.713200.0550*
H1A0.743 (7)1.423 (5)0.627 (4)0.0480*
H2A0.725501.314900.470400.0310*
H4A0.982600.751300.615000.0490*
H5A1.029800.751300.771800.0620*
H6A0.952801.002500.861600.0720*
H7A0.835401.277700.796500.0660*
H30B0.960100.919700.430500.0360*
H31B0.822301.028300.378800.0360*
H32B0.784600.691900.371800.0360*
H33B0.800100.677200.480900.0360*
H34A0.559 (6)0.684 (5)0.419 (3)0.0380*
H35A0.581 (6)0.883 (6)0.388 (3)0.0380*
H36A0.581 (6)0.828 (8)0.4889 (19)0.0380*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl2B0.0639 (11)0.0664 (11)0.0572 (10)−0.0152 (10)0.0030 (7)−0.0014 (9)
Cl4B0.0779 (13)0.1142 (19)0.0512 (10)0.0072 (13)−0.0110 (8)0.0160 (11)
O11B0.055 (3)0.064 (3)0.051 (2)0.004 (2)0.007 (2)0.017 (2)
O13B0.044 (2)0.024 (2)0.045 (2)0.0037 (17)−0.0007 (17)0.0043 (16)
O14B0.0250 (19)0.029 (2)0.050 (2)−0.0007 (16)0.0030 (15)0.0017 (17)
C1B0.047 (3)0.055 (4)0.032 (3)0.005 (3)0.009 (2)−0.002 (3)
C2B0.063 (4)0.050 (4)0.029 (3)0.004 (3)0.009 (3)−0.005 (3)
C3B0.069 (4)0.049 (4)0.029 (3)−0.005 (3)0.011 (2)0.004 (3)
C4B0.069 (5)0.074 (5)0.028 (3)0.007 (4)0.012 (3)0.005 (3)
C5B0.036 (3)0.064 (5)0.054 (4)−0.010 (3)0.004 (3)−0.008 (4)
C6B0.059 (4)0.059 (4)0.047 (4)0.000 (4)0.008 (3)0.004 (3)
C12B0.048 (4)0.042 (4)0.047 (3)0.016 (3)0.010 (3)0.015 (3)
C13B0.028 (3)0.025 (3)0.033 (3)0.006 (2)−0.0060 (18)−0.002 (2)
N1A0.031 (2)0.028 (3)0.060 (3)0.004 (2)0.003 (2)−0.009 (2)
N32A0.024 (2)0.035 (3)0.036 (2)−0.003 (2)0.0010 (17)0.000 (2)
C2A0.019 (2)0.016 (2)0.043 (3)−0.004 (2)−0.0016 (18)0.001 (2)
C3A0.018 (2)0.023 (3)0.041 (3)0.000 (2)0.0008 (19)−0.004 (2)
C4A0.030 (3)0.043 (3)0.050 (3)0.013 (3)0.003 (2)0.003 (3)
C5A0.042 (3)0.062 (4)0.050 (4)0.013 (3)−0.008 (3)0.000 (3)
C6A0.068 (5)0.072 (5)0.041 (4)−0.016 (4)0.003 (3)−0.002 (4)
C7A0.045 (4)0.075 (5)0.045 (3)0.003 (4)0.009 (3)−0.012 (3)
C8A0.027 (3)0.044 (4)0.046 (3)−0.002 (3)0.008 (2)−0.005 (3)
C9A0.020 (2)0.027 (3)0.042 (3)−0.005 (2)0.0047 (19)−0.003 (2)
C31A0.026 (3)0.030 (3)0.035 (3)−0.002 (2)0.001 (2)−0.004 (2)
C32A0.025 (2)0.023 (3)0.041 (3)−0.001 (2)0.0029 (19)−0.001 (2)
Geometric parameters (Å, º) top
Cl2B—C2B1.758 (7)C6B—H6B0.9500
Cl4B—C4B1.745 (7)C12B—H13B0.9900
O11B—C1B1.347 (8)C12B—H12B0.9900
O11B—C12B1.404 (8)C2A—C3A1.340 (7)
O13B—C13B1.233 (6)C3A—C9A1.459 (7)
O14B—C13B1.236 (6)C3A—C31A1.499 (6)
N1A—C8A1.337 (8)C4A—C5A1.369 (8)
N1A—C2A1.369 (6)C4A—C9A1.386 (8)
N32A—C32A1.488 (6)C5A—C6A1.385 (10)
N1A—H1A0.87 (4)C6A—C7A1.386 (11)
N32A—H34A0.89 (4)C7A—C8A1.399 (8)
N32A—H36A0.89 (3)C8A—C9A1.432 (8)
N32A—H35A0.90 (4)C31A—C32A1.518 (7)
C1B—C2B1.399 (9)C2A—H2A0.9500
C1B—C6B1.386 (10)C4A—H4A0.9500
C2B—C3B1.367 (9)C5A—H5A0.9500
C3B—C4B1.396 (10)C6A—H6A0.9500
C4B—C5B1.369 (11)C7A—H7A0.9500
C5B—C6B1.391 (9)C31A—H30B0.9900
C12B—C13B1.555 (7)C31A—H31B0.9900
C3B—H3B0.9500C32A—H32B0.9900
C5B—H5B0.9500C32A—H33B0.9900
C1B—O11B—C12B119.7 (5)N1A—C2A—C3A111.0 (4)
C2A—N1A—C8A109.3 (5)C2A—C3A—C9A106.5 (4)
C8A—N1A—H1A125 (4)C2A—C3A—C31A127.9 (4)
C2A—N1A—H1A125 (4)C9A—C3A—C31A125.6 (4)
C32A—N32A—H35A105 (3)C5A—C4A—C9A118.3 (6)
H34A—N32A—H36A107 (5)C4A—C5A—C6A122.2 (7)
C32A—N32A—H36A110 (3)C5A—C6A—C7A121.5 (6)
H34A—N32A—H35A110 (4)C6A—C7A—C8A117.3 (6)
C32A—N32A—H34A105 (3)N1A—C8A—C9A108.5 (5)
H35A—N32A—H36A118 (4)C7A—C8A—C9A120.6 (6)
O11B—C1B—C2B118.0 (6)N1A—C8A—C7A130.9 (6)
C2B—C1B—C6B116.3 (6)C3A—C9A—C4A135.2 (5)
O11B—C1B—C6B125.6 (6)C3A—C9A—C8A104.8 (5)
Cl2B—C2B—C1B117.4 (5)C4A—C9A—C8A120.1 (5)
C1B—C2B—C3B125.2 (6)C3A—C31A—C32A115.0 (4)
Cl2B—C2B—C3B117.5 (5)N32A—C32A—C31A111.1 (4)
C2B—C3B—C4B115.6 (6)N1A—C2A—H2A125.00
Cl4B—C4B—C5B119.2 (5)C3A—C2A—H2A125.00
Cl4B—C4B—C3B118.3 (6)C5A—C4A—H4A121.00
C3B—C4B—C5B122.5 (6)C9A—C4A—H4A121.00
C4B—C5B—C6B119.5 (6)C4A—C5A—H5A119.00
C1B—C6B—C5B120.9 (7)C6A—C5A—H5A119.00
O11B—C12B—C13B112.9 (5)C5A—C6A—H6A119.00
O13B—C13B—O14B127.8 (5)C7A—C6A—H6A119.00
O13B—C13B—C12B117.9 (5)C6A—C7A—H7A121.00
O14B—C13B—C12B114.0 (5)C8A—C7A—H7A121.00
C2B—C3B—H3B122.00C3A—C31A—H30B108.00
C4B—C3B—H3B122.00C3A—C31A—H31B109.00
C6B—C5B—H5B120.00C32A—C31A—H30B109.00
C4B—C5B—H5B120.00C32A—C31A—H31B109.00
C1B—C6B—H6B120.00H30B—C31A—H31B108.00
C5B—C6B—H6B120.00N32A—C32A—H32B109.00
O11B—C12B—H13B109.00N32A—C32A—H33B109.00
C13B—C12B—H13B109.00C31A—C32A—H32B109.00
H12B—C12B—H13B108.00C31A—C32A—H33B109.00
C13B—C12B—H12B109.00H32B—C32A—H33B108.00
O11B—C12B—H12B109.00
C12B—O11B—C1B—C2B−177.8 (5)N1A—C2A—C3A—C9A0.3 (5)
C12B—O11B—C1B—C6B−0.5 (9)N1A—C2A—C3A—C31A178.5 (5)
C1B—O11B—C12B—C13B81.2 (6)C2A—C3A—C9A—C4A−179.6 (6)
C8A—N1A—C2A—C3A0.9 (6)C2A—C3A—C9A—C8A−1.3 (5)
C2A—N1A—C8A—C7A−179.8 (6)C31A—C3A—C9A—C4A2.1 (9)
C2A—N1A—C8A—C9A−1.7 (6)C31A—C3A—C9A—C8A−179.6 (5)
C6B—C1B—C2B—C3B2.3 (10)C2A—C3A—C31A—C32A−113.1 (5)
O11B—C1B—C6B—C5B178.8 (6)C9A—C3A—C31A—C32A64.8 (6)
C2B—C1B—C6B—C5B−3.8 (9)C9A—C4A—C5A—C6A0.7 (9)
O11B—C1B—C2B—C3B179.9 (6)C5A—C4A—C9A—C3A179.0 (6)
C6B—C1B—C2B—Cl2B−178.9 (5)C5A—C4A—C9A—C8A0.8 (8)
O11B—C1B—C2B—Cl2B−1.3 (8)C4A—C5A—C6A—C7A−1.9 (11)
Cl2B—C2B—C3B—C4B−179.1 (5)C5A—C6A—C7A—C8A1.5 (10)
C1B—C2B—C3B—C4B−0.2 (9)C6A—C7A—C8A—N1A178.0 (6)
C2B—C3B—C4B—Cl4B−178.9 (5)C6A—C7A—C8A—C9A0.1 (9)
C2B—C3B—C4B—C5B−0.4 (9)N1A—C8A—C9A—C3A1.8 (6)
C3B—C4B—C5B—C6B−1.1 (10)N1A—C8A—C9A—C4A−179.5 (5)
Cl4B—C4B—C5B—C6B177.3 (5)C7A—C8A—C9A—C3A−179.9 (5)
C4B—C5B—C6B—C1B3.4 (10)C7A—C8A—C9A—C4A−1.2 (8)
O11B—C12B—C13B—O13B−5.6 (7)C3A—C31A—C32A—N32A58.6 (5)
O11B—C12B—C13B—O14B168.9 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O13Bi0.87 (4)2.13 (5)2.879 (6)144 (6)
N32A—H34A···O14Bii0.89 (4)1.89 (4)2.782 (6)175 (2)
N32A—H35A···O13Biii0.90 (4)2.10 (5)2.817 (6)137 (4)
N32A—H36A···O13B0.89 (3)2.57 (4)3.231 (6)132 (4)
N32A—H36A···O14B0.89 (3)1.94 (4)2.816 (6)171 (5)
C2A—H2A···O14Biii0.952.533.336 (6)142
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y−1/2, −z+1; (iii) −x+1, y+1/2, −z+1.
(II) 2-(1H-Indol-3-yl)ethanaminium (3,5-dichlorophenoxy)acetate top
Crystal data top
C10H13N2+·C8H5Cl2O3−F(000) = 396
Mr = 381.24Dx = 1.432 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 1140 reflections
a = 9.5154 (8) Åθ = 3.9–28.2°
b = 6.1951 (5) ŵ = 0.39 mm−1
c = 15.3646 (9) ÅT = 200 K
β = 102.579 (7)°Needle, colourless
V = 883.99 (12) Å30.50 × 0.12 × 0.06 mm
Z = 2
Data collection top
Oxford Diffraction Gemini-S CCD-detector
diffractometer		2800 independent reflections
Radiation source: fine-focus sealed tube2451 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
Detector resolution: 16.077 pixels mm-1θmax = 26.0°, θmin = 3.1°
ω scansh = −11→7
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)		k = −7→7
Tmin = 0.872, Tmax = 0.980l = −18→18
3845 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.105 w = 1/[σ2(Fo2) + (0.0513P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
2800 reflectionsΔρmax = 0.22 e Å−3
238 parametersΔρmin = −0.24 e Å−3
5 restraintsAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.01 (7)
Crystal data top
C10H13N2+·C8H5Cl2O3−V = 883.99 (12) Å3
Mr = 381.24Z = 2
Monoclinic, P21Mo Kα radiation
a = 9.5154 (8) ŵ = 0.39 mm−1
b = 6.1951 (5) ÅT = 200 K
c = 15.3646 (9) Å0.50 × 0.12 × 0.06 mm
β = 102.579 (7)°
Data collection top
Oxford Diffraction Gemini-S CCD-detector
diffractometer		2800 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)		2451 reflections with I > 2σ(I)
Tmin = 0.872, Tmax = 0.980Rint = 0.027
3845 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.105Δρmax = 0.22 e Å−3
S = 1.08Δρmin = −0.24 e Å−3
2800 reflectionsAbsolute structure: Flack (1983)
238 parametersAbsolute structure parameter: 0.01 (7)
5 restraints
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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
xyzUiso*/Ueq
Cl3B0.88773 (13)1.0762 (2)0.94414 (6)0.0556 (4)
Cl5B0.61601 (10)0.46571 (17)1.09183 (5)0.0421 (3)
O11B0.6022 (3)0.4935 (4)0.75745 (13)0.0337 (8)
O13B0.5666 (3)0.2827 (4)0.60040 (14)0.0269 (7)
O14B0.4608 (3)0.0059 (4)0.65216 (15)0.0353 (8)
C1B0.6435 (3)0.5773 (6)0.84115 (19)0.0266 (10)
C2B0.7290 (4)0.7600 (6)0.8496 (2)0.0304 (10)
C3B0.7776 (4)0.8496 (6)0.9324 (2)0.0301 (11)
C4B0.7436 (4)0.7632 (6)1.0088 (2)0.0306 (10)
C5B0.6601 (4)0.5807 (7)0.99749 (19)0.0298 (10)
C6B0.6062 (3)0.4868 (6)0.91596 (19)0.0279 (10)
C12B0.5268 (4)0.2927 (6)0.7495 (2)0.0297 (11)
C13B0.5178 (3)0.1909 (5)0.6593 (2)0.0243 (10)
N1A0.2443 (3)0.6837 (5)0.6332 (2)0.0339 (10)
N32A0.3860 (3)0.2111 (5)0.42680 (18)0.0238 (8)
C2A0.2536 (3)0.5745 (7)0.5567 (2)0.0314 (11)
C3A0.1828 (3)0.3819 (6)0.5518 (2)0.0238 (10)
C4A0.0375 (4)0.2219 (7)0.6612 (2)0.0366 (11)
C5A−0.0092 (4)0.2656 (7)0.7385 (2)0.0435 (14)
C6A0.0307 (4)0.4575 (8)0.7856 (2)0.0420 (13)
C7A0.1174 (4)0.6077 (7)0.7582 (2)0.0366 (11)
C8A0.1640 (3)0.5635 (6)0.6792 (2)0.0293 (10)
C9A0.1237 (3)0.3729 (6)0.6306 (2)0.0258 (10)
C31A0.1548 (4)0.2190 (6)0.4786 (2)0.0307 (11)
C32A0.2298 (3)0.2630 (6)0.4028 (2)0.0290 (10)
H2B0.753800.822800.798500.0360*
H4B0.776600.827201.065800.0370*
H6B0.545300.363800.910800.0340*
H12B0.428300.316800.758900.0350*
H13B0.576700.192700.796500.0350*
H1A0.291 (4)0.803 (5)0.649 (3)0.0530*
H2A0.302600.626100.513200.0380*
H4A0.011300.091100.629600.0440*
H5A−0.068900.164600.759800.0530*
H6A−0.003500.484200.838300.0500*
H7A0.144900.736400.791200.0440*
H30A0.049700.211900.454000.0370*
H31A0.185800.075600.504300.0370*
H32A0.183500.175900.350300.0350*
H33A0.217600.417200.385900.0350*
H34A0.420 (4)0.237 (7)0.4830 (14)0.0530*
H35A0.407 (4)0.080 (4)0.409 (3)0.0530*
H36A0.438 (4)0.292 (7)0.398 (3)0.0530*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl3B0.0674 (7)0.0572 (7)0.0408 (5)−0.0354 (6)0.0090 (5)−0.0097 (5)
Cl5B0.0558 (6)0.0482 (6)0.0235 (4)−0.0057 (5)0.0112 (4)0.0014 (4)
O11B0.0576 (15)0.0254 (14)0.0187 (10)−0.0111 (13)0.0099 (10)−0.0035 (10)
O13B0.0352 (13)0.0241 (13)0.0215 (11)−0.0037 (11)0.0061 (10)−0.0029 (10)
O14B0.0435 (14)0.0235 (15)0.0423 (13)−0.0097 (12)0.0168 (11)−0.0078 (11)
C1B0.0358 (18)0.0236 (18)0.0205 (15)−0.0006 (16)0.0066 (14)−0.0050 (15)
C2B0.0355 (18)0.032 (2)0.0243 (16)−0.0005 (17)0.0081 (15)0.0001 (16)
C3B0.0319 (19)0.027 (2)0.0300 (17)−0.0034 (16)0.0038 (16)−0.0043 (16)
C4B0.0289 (17)0.037 (2)0.0240 (16)−0.0029 (16)0.0015 (14)−0.0103 (16)
C5B0.0341 (18)0.034 (2)0.0215 (15)0.0066 (18)0.0066 (13)0.0039 (16)
C6B0.0336 (17)0.0249 (19)0.0251 (15)−0.0020 (16)0.0059 (14)0.0008 (15)
C12B0.042 (2)0.024 (2)0.0236 (16)−0.0046 (17)0.0085 (15)−0.0044 (15)
C13B0.0266 (17)0.0200 (19)0.0257 (15)−0.0023 (16)0.0041 (14)0.0012 (15)
N1A0.0349 (17)0.0248 (17)0.0427 (16)−0.0066 (14)0.0099 (14)−0.0069 (15)
N32A0.0264 (14)0.0230 (17)0.0216 (12)0.0016 (13)0.0044 (12)0.0005 (13)
C2A0.0261 (17)0.033 (2)0.0366 (18)−0.0040 (17)0.0103 (14)−0.0023 (17)
C3A0.0202 (16)0.0249 (19)0.0268 (16)−0.0021 (14)0.0064 (14)0.0008 (15)
C4A0.041 (2)0.034 (2)0.0362 (18)−0.0090 (19)0.0115 (17)0.0043 (17)
C5A0.044 (2)0.052 (3)0.038 (2)−0.008 (2)0.0163 (19)0.007 (2)
C6A0.040 (2)0.061 (3)0.0260 (16)0.009 (2)0.0092 (16)0.004 (2)
C7A0.0336 (19)0.044 (2)0.0280 (17)0.0066 (18)−0.0026 (15)−0.0081 (18)
C8A0.0212 (16)0.035 (2)0.0297 (17)0.0061 (16)0.0010 (14)0.0006 (17)
C9A0.0213 (16)0.028 (2)0.0262 (16)0.0012 (15)0.0012 (14)0.0018 (15)
C31A0.0281 (17)0.029 (2)0.0348 (18)−0.0045 (16)0.0062 (15)−0.0042 (16)
C32A0.0267 (17)0.032 (2)0.0269 (17)0.0044 (16)0.0027 (15)−0.0013 (16)
Geometric parameters (Å, º) top
Cl3B—C3B1.738 (4)C6B—H6B0.9500
Cl5B—C5B1.746 (3)C12B—H13B0.9900
O11B—C1B1.363 (4)C12B—H12B0.9900
O11B—C12B1.428 (5)C2A—C3A1.364 (5)
O13B—C13B1.241 (4)C3A—C9A1.443 (4)
O14B—C13B1.263 (4)C3A—C31A1.491 (5)
N1A—C8A1.369 (4)C4A—C5A1.383 (5)
N1A—C2A1.376 (5)C4A—C9A1.392 (5)
N32A—C32A1.487 (4)C5A—C6A1.401 (6)
N1A—H1A0.87 (4)C6A—C7A1.369 (6)
N32A—H34A0.87 (2)C7A—C8A1.407 (4)
N32A—H36A0.89 (4)C8A—C9A1.405 (5)
N32A—H35A0.89 (3)C31A—C32A1.517 (5)
C1B—C2B1.383 (5)C2A—H2A0.9500
C1B—C6B1.393 (4)C4A—H4A0.9500
C2B—C3B1.373 (4)C5A—H5A0.9500
C3B—C4B1.391 (5)C6A—H6A0.9500
C4B—C5B1.371 (6)C7A—H7A0.9500
C5B—C6B1.375 (4)C31A—H30A0.9900
C12B—C13B1.508 (4)C31A—H31A0.9900
C2B—H2B0.9500C32A—H32A0.9900
C4B—H4B0.9500C32A—H33A0.9900
C1B—O11B—C12B116.7 (2)N1A—C2A—C3A110.8 (3)
C2A—N1A—C8A108.7 (3)C2A—C3A—C9A105.4 (3)
C8A—N1A—H1A129 (3)C2A—C3A—C31A129.7 (3)
C2A—N1A—H1A122 (3)C9A—C3A—C31A124.6 (3)
C32A—N32A—H35A114 (3)C5A—C4A—C9A118.8 (4)
H34A—N32A—H36A105 (4)C4A—C5A—C6A120.6 (4)
C32A—N32A—H36A113 (3)C5A—C6A—C7A122.1 (3)
H34A—N32A—H35A114 (4)C6A—C7A—C8A117.2 (4)
C32A—N32A—H34A110 (3)N1A—C8A—C9A107.5 (3)
H35A—N32A—H36A100 (4)C7A—C8A—C9A121.4 (3)
O11B—C1B—C2B116.3 (3)N1A—C8A—C7A131.0 (3)
C2B—C1B—C6B120.2 (3)C3A—C9A—C4A132.5 (3)
O11B—C1B—C6B123.5 (3)C3A—C9A—C8A107.6 (3)
C1B—C2B—C3B119.4 (3)C4A—C9A—C8A119.9 (3)
C2B—C3B—C4B122.2 (3)C3A—C31A—C32A114.9 (3)
Cl3B—C3B—C4B118.0 (3)N32A—C32A—C31A112.5 (3)
Cl3B—C3B—C2B119.8 (3)N1A—C2A—H2A125.00
C3B—C4B—C5B116.4 (3)C3A—C2A—H2A125.00
Cl5B—C5B—C4B117.9 (2)C5A—C4A—H4A121.00
Cl5B—C5B—C6B118.3 (3)C9A—C4A—H4A121.00
C4B—C5B—C6B123.7 (3)C4A—C5A—H5A120.00
C1B—C6B—C5B118.0 (3)C6A—C5A—H5A120.00
O11B—C12B—C13B111.7 (3)C5A—C6A—H6A119.00
O13B—C13B—O14B125.1 (3)C7A—C6A—H6A119.00
O13B—C13B—C12B121.5 (3)C6A—C7A—H7A121.00
O14B—C13B—C12B113.4 (3)C8A—C7A—H7A121.00
C1B—C2B—H2B120.00C3A—C31A—H30A109.00
C3B—C2B—H2B120.00C3A—C31A—H31A109.00
C5B—C4B—H4B122.00C32A—C31A—H30A109.00
C3B—C4B—H4B122.00C32A—C31A—H31A109.00
C1B—C6B—H6B121.00H30A—C31A—H31A107.00
C5B—C6B—H6B121.00N32A—C32A—H32A109.00
O11B—C12B—H13B109.00N32A—C32A—H33A109.00
C13B—C12B—H13B109.00C31A—C32A—H32A109.00
H12B—C12B—H13B108.00C31A—C32A—H33A109.00
C13B—C12B—H12B109.00H32A—C32A—H33A108.00
O11B—C12B—H12B109.00
C12B—O11B—C1B—C2B173.6 (3)N1A—C2A—C3A—C9A0.8 (4)
C12B—O11B—C1B—C6B−5.2 (5)N1A—C2A—C3A—C31A174.8 (3)
C1B—O11B—C12B—C13B−166.5 (3)C2A—C3A—C9A—C4A177.5 (4)
C2A—N1A—C8A—C7A−176.4 (3)C2A—C3A—C9A—C8A−0.3 (4)
C2A—N1A—C8A—C9A0.8 (4)C31A—C3A—C9A—C4A3.1 (6)
C8A—N1A—C2A—C3A−1.0 (4)C31A—C3A—C9A—C8A−174.8 (3)
O11B—C1B—C6B—C5B177.0 (3)C2A—C3A—C31A—C32A7.3 (5)
C2B—C1B—C6B—C5B−1.8 (5)C9A—C3A—C31A—C32A−179.7 (3)
O11B—C1B—C2B—C3B−178.3 (3)C9A—C4A—C5A—C6A−0.6 (6)
C6B—C1B—C2B—C3B0.6 (5)C5A—C4A—C9A—C3A−176.3 (3)
C1B—C2B—C3B—Cl3B178.8 (3)C5A—C4A—C9A—C8A1.3 (5)
C1B—C2B—C3B—C4B−0.1 (6)C4A—C5A—C6A—C7A−0.5 (6)
Cl3B—C3B—C4B—C5B−178.1 (3)C5A—C6A—C7A—C8A0.9 (6)
C2B—C3B—C4B—C5B0.9 (6)C6A—C7A—C8A—N1A176.6 (4)
C3B—C4B—C5B—C6B−2.3 (6)C6A—C7A—C8A—C9A−0.2 (5)
C3B—C4B—C5B—Cl5B179.5 (3)N1A—C8A—C9A—C3A−0.3 (4)
Cl5B—C5B—C6B—C1B−179.1 (3)N1A—C8A—C9A—C4A−178.4 (3)
C4B—C5B—C6B—C1B2.7 (6)C7A—C8A—C9A—C3A177.2 (3)
O11B—C12B—C13B—O13B−2.9 (5)C7A—C8A—C9A—C4A−0.9 (5)
O11B—C12B—C13B—O14B175.3 (3)C3A—C31A—C32A—N32A75.7 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O14Bi0.87 (4)2.04 (4)2.838 (4)152 (4)
N32A—H34A···O13B0.87 (2)2.05 (3)2.875 (4)160 (4)
N32A—H35A···O11Bii0.89 (3)2.60 (4)3.160 (4)122 (3)
N32A—H35A···O13Bii0.89 (3)1.87 (3)2.739 (4)164 (4)
N32A—H36A···O14Biii0.89 (4)1.90 (4)2.775 (4)170 (4)
C2A—H2A···O13Biii0.952.553.495 (4)177
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y−1/2, −z+1; (iii) −x+1, y+1/2, −z+1.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O13Bi0.87 (4)2.13 (5)2.879 (6)144 (6)
N32A—H34A···O14Bii0.89 (4)1.89 (4)2.782 (6)175 (2)
N32A—H35A···O13Biii0.90 (4)2.10 (5)2.817 (6)137 (4)
N32A—H36A···O13B0.89 (3)2.57 (4)3.231 (6)132 (4)
N32A—H36A···O14B0.89 (3)1.94 (4)2.816 (6)171 (5)
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y−1/2, −z+1; (iii) −x+1, y+1/2, −z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O14Bi0.87 (4)2.04 (4)2.838 (4)152 (4)
N32A—H34A···O13B0.87 (2)2.05 (3)2.875 (4)160 (4)
N32A—H35A···O11Bii0.89 (3)2.60 (4)3.160 (4)122 (3)
N32A—H35A···O13Bii0.89 (3)1.87 (3)2.739 (4)164 (4)
N32A—H36A···O14Biii0.89 (4)1.90 (4)2.775 (4)170 (4)
C2A—H2A···O13Biii0.952.553.495 (4)177
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y−1/2, −z+1; (iii) −x+1, y+1/2, −z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC10H13N2+·C8H5Cl2O3−C10H13N2+·C8H5Cl2O3−
Mr381.25381.24
Crystal system, space groupMonoclinic, P21Monoclinic, P21
Temperature (K)200200
a, b, c (Å)8.9818 (11), 6.8899 (7), 14.6850 (15)9.5154 (8), 6.1951 (5), 15.3646 (9)
β (°) 93.565 (9) 102.579 (7)
V (Å3)907.00 (17)883.99 (12)
Z22
Radiation typeMo KαMo Kα
µ (mm−1)0.380.39
Crystal size (mm)0.50 × 0.15 × 0.050.50 × 0.12 × 0.06
Data collection
DiffractometerOxford Diffraction Gemini-S CCD-detector
diffractometer		Oxford Diffraction Gemini-S CCD-detector
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2013)		Multi-scan
(CrysAlis PRO; Agilent, 2013)
Tmin, Tmax0.940, 0.9900.872, 0.980
No. of measured, independent and
observed [I > 2σ(I)] reflections		3991, 2896, 2299 3845, 2800, 2451
Rint0.0350.027
(sin θ/λ)max (Å−1)0.6170.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.068, 0.187, 1.06 0.042, 0.105, 1.08
No. of reflections28962800
No. of parameters226238
No. of restraints15
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.37, −0.260.22, −0.24
Absolute structureFlack (1983)Flack (1983)
Absolute structure parameter0.45 (15)0.01 (7)

Computer programs: CrysAlis PRO (Agilent, 2013), SIR92 (Altomare et al., 1993), SHELX97 (Sheldrick, 2008) within WinGX (Farrugia, 2012), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012), PLATON (Spek, 2009).

 

Acknowledgements

GS acknowledges financial support from the Science and Engineering Faculty, Queensland University of Technology.

References

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ISSN: 2056-9890
Volume 71| Part 6| June 2015| Pages 671-674
doi:10.1107/S205698901500907X
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