Crystal structures and hydrogen bonding in the co-crystalline adducts of 3,5-di­nitro­benzoic acid with 4-amino­salicylic acid and 2-hy­droxy-3-(1H-indol-3-yl)propenoic acid

Smith, G.; Lynch, D.E.

doi:10.1107/S1600536814019898

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ISSN: 2056-9890

Volume 70| Part 10| October 2014| Pages 183-187

doi:10.1107/S1600536814019898

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Crystal structures and hydrogen bonding in the co-crystalline adducts of 3,5-dinitrobenzoic acid with 4-aminosalicylic acid and 2-hydroxy-3-(1H-indol-3-yl)propenoic acid

Graham Smith ^a ^* and Daniel E. Lynch ^b

^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 30 August 2014; accepted 3 September 2014; online 10 September 2014)

The structures of the co-crystalline adducts of 3,5-dinitrobenzoic acid (3,5-DNBA) with 4-aminosalicylic acid (PASA), the 1:1 partial hydrate, C₇H₄N₂O₆·C₇H₇NO₃·0.2H₂O, (I), and with 2-hydroxy-3-(1H-indol-3-yl)propenoic acid (HIPA), the 1:1:1 d⁶-dimethyl sulfoxide solvate, C₇H₄N₂O₆·C₁₁H₉NO₃·C₂D₆OS, (II), are reported. The crystal substructure of (I) comprises two centrosymmetric hydrogen-bonded R₂²(8) homodimers, one with 3,5-DNBA, the other with PASA, and an R₂²(8) 3,5-DNBA–PASA heterodimer. In the crystal, inter-unit amine N—H⋯O and water O—H⋯O hydrogen bonds generate a three-dimensional supramolecular structure. In (II), the asymmetric unit consists of the three constituent molecules, which form an essentially planar cyclic hydrogen-bonded heterotrimer unit [graph set R₃²(17)] through carboxyl, hydroxy and amino groups. These units associate across a crystallographic inversion centre through the HIPA carboxylic acid group in an R₂²(8) hydrogen-bonding association, giving a zero-dimensional structure lying parallel to (100). In both structures, π–π interactions are present [minimum ring-centroid separations = 3.6471 (18) Å in (I) and 3.5819 (10) Å in (II)].

Keywords: co-crystal structures; carboxylic acid molecular adducts; 3,5-dinitrobenzoic acid; 4-aminosalicylic acid; 2-hydroxy-3-(1H-indol-3-yl)propenoic acid; hydrogen bonding; homodimers; heterodimers; π–π interactions..

CCDC references: 1022646; 1022647

1. Chemical context

3,5-Dinitrobenzoic acid (3,5-DNBA) has been an important acid for the formation of crystalline materials, which have allowed structural characterization using single crystal X-ray methods. Most commonly proton-transfer salts are formed with organic Lewis bases, e.g. with 1-H-pyrazole (Aakeröy et al., 2012 ) but salt–adducts are also known, e.g. 2-pyridyl-4′-pyridinium⁺–3,5-DNBA⁻–3,5-DNBA (1/1/1) (Chantrapromma et al., 2002 ). Although co-crystalline non-transfer molecular adducts with 3,5-DNBA are now relatively common, interest was stimulated with the original reporting of non-transfer adduct formation with 4-aminobenzoic acid to form a chiral 1:1 co-crystalline material (Etter & Frankenbach, 1989 ), which represented one of the earliest examples of designed crystal engineering, in that case with a view to producing non-linear optical materials. In the crystalline state, carboxylic acids usually form cyclic hydrogen-bonded dimers through head-to-head carboxyl O—H⋯O hydrogen bonds (Leiserowitz, 1976 ) [graph set R₂²(8)]. This is the case with 3,5-DNBA (A), which when co-crystallized with certain aromatic acids, e.g. 4-(N,N-dimethylamino)benzoic acid (B), gives separate mixed AA and BB homodimer pairs (Sharma et al., 1993 ). Although uncommon with 3,5-DNBA, with other aromatic acid analogues, AB heterodimer formation appears more prevalent, e.g. the 1:1 adducts of 3,5-dinitrocinnamic acid with 4-(N,N-dimethylamino)benzoic acid and 2,4-dinitrocinnamic acid with 2,5-dimethoxycinnamic acid (Sharma et al., 1993). In both AA and BB structure types, π–π interactions are commonly involved in stabilization, usually accompanied by enhanced colour generation. Absence of dimer pairs in 3,5-DNBA adducts is usually the result of preferential hydrogen bonding with solvent molecules, such as is found in the structure of 3,5-DNBA–phenoxyacetic acid–water (2/1/1) (Lynch et al., 1991 ), in which a cyclic R₃³(10) interaction is found, involving two 3,5-DNBA molecules and the water molecule. The title adducts C₇H₄N₂O₆·C₇H₇NO₃·0.2H₂O (I) and C₇H₄N₂O₆·C₁₁H₉NO₃·C₂D₆OS (II) were prepared from the interaction of 3,5-DNBA with 4-aminosalicylic acid (PASA) and 2-hydroxy-3-(1H-indol-3-yl)propenoic acid (HIPA), respectively, and the structures are reported herein. With (II), the incorporation of C₂D₆OS resulted from recrystallization from d⁶-dimethylsulfoxide.

2. Structural commentary

In the co-crystal of 3,5-DNBA with 4-aminosalicylic acid, (I) (Fig. 1), the asymmetric unit consists of two PASA molecules (A and B), two 3,5-DNBA molecules (C and D) and a partially occupied water molecule of solvation (O1W), with site occupancy = 0.4. However, what is most unusual in this structure is the presence of not four homodimers in the unit cell, but two homodimers (centrosymmetric PASA A–Aⁱ and 3,5-DNBA C–Cⁱⁱ pairs), as well as two heterodimer B–D pairs (for symmetry codes, see Table 1). All dimers are formed through the common cyclic R₂²(8) ring motif. Present in the PASA molecules are the expected intramolecular salicylic acid phenolic O—H⋯O_carboxyl hydrogen bonds, also present in the parent acid (Montis & Hursthouse, 2012 ).

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O11A—H11A⋯O12Aⁱ	0.91 (3)	1.78 (3)	2.678 (3)	175 (3)
O11B—H11B⋯O11D	0.94 (3)	1.74 (3)	2.673 (3)	175 (3)
O11C—H11C⋯O12Cⁱⁱ	0.91 (3)	1.73 (3)	2.640 (3)	177 (2)
O12D—H12D⋯O12B	0.90 (3)	1.71 (3)	2.610 (3)	176 (2)
N4B—H41B⋯O31C	0.86 (3)	2.58 (3)	3.350 (4)	150 (3)
N4B—H42B⋯O52Dⁱⁱⁱ	0.85 (2)	2.44 (3)	3.210 (4)	151 (3)
O2A—H2A⋯O12A	0.84	1.89	2.625 (3)	145
O2B—H2B⋯O12B	0.84	1.85	2.587 (3)	145
O1W—H11W⋯O2B	0.90	2.05	2.952 (6)	179
O1W—H12W⋯O32C^iv	0.93	2.08	3.005 (5)	179
C3B—H3B⋯O31C	0.95	2.58	3.382 (3)	142
C4D—H4D⋯O32C^v	0.95	2.49	3.425 (3)	170
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x, -y+2, -z+1; (iii) -x, -y+1, -z; (iv) x+1, y, z; (v) -x+1, -y+2, -z.

Figure 1
Molecular conformation and atom-naming scheme for the two PABA molecules (A and B), the two 3,5-DNBA molecules (C and D) and the disordered water molecule (O1W) in the asymmetric unit of adduct (I)

, with displacement ellipsoids drawn at the 40% probability level. Inter-species hydrogen bonds are shown as dashed lines.

In the ternary co-crystal of 3,5-DNBA (B) with 2-hydroxy-3-(1H-indol-3-yl)propenoic acid (A) and d⁶-dimethylsulfoxide (C), (II) the three molecules inter-associate through carboxylic acid O—H⋯O and N—H⋯O hydrogen bonds, forming a cyclic R₃²(17) heterotrimeric asymmetric unit (Fig. 2). This unit is essentially planar with a dihedral angle of 4.97 (7)° between the indole ring of A and the benzene ring of B. With the HIPA molecule there is a maximum deviation from the least-squares plane of the 15-atom molecule of 0.120 (2) Å (C6A). The planar conformation of the acid side chain in this molecule is maintained by the presence of delocalization extending from C2A of the ring to O14A of the carboxylic acid group [torsion angle C11A—C12A—C13A—O14A = −177.43 (16)°]. This is also found in the parent acid, which has the similar enol configuration as in (II) [corresponding torsion angle 170.0 (3)°] with an E orientation and in the crystal forms a centrosymmetric homodimer with an R₂²(8) hydrogen-bond motif (Okabe & Adachi, 1998 ).

Figure 2
Molecular conformation and atom-naming scheme for adduct (II)

, with displacement ellipsoids drawn at the 40% probability level. Inter-species hydrogen bonds are shown as dashed lines.

In the adducts (I) and (II), the 3,5-DNBA molecules are essentially planar with the exception of the C3-nitro groups of the C molecule in (I), and the B molecule in (II), where the defining C2—C3—N3—O32 torsion angles are 158.2 (3) and 168.39 (17)°, respectively. The overall torsion angle range for the remaining groups in both (I) and (II) is 170.8 (3)–179.2 (2)°. These minor deviations from planarity are consistent with conformational features of both polymorphs of the parent acid 3,5-DNBA (Prince et al., 1991 ) and in examples both of its salts (Aakeröy et al., 2012) and its adducts (Aakeröy et al., 2001 ; Jones et al., 2010 ; Chadwick et al., 2009 ).

3. Supramolecular features

In the supramolecular structure of (I), the carboxylic acid dimers are extended through inter-dimer or inter-heterodimer amine N—H⋯O and water O—H⋯O hydrogen bonds (Table 1), giving a three-dimensional framework structure (Fig. 3). Within the structure there are a number of inter-ring π–π associations [ring-centroid separations: A⋯C^vi, 3.7542 (16); A⋯C^vii, 3.6471 (16); B⋯D^viii, 3.6785 (14) Å] [symmetry codes: (vi) x + 1, y − 1, z; (vii) x, y − 1, z; (viii) −x + 1, −y + 1, −z]. The B⋯D heterodimers in the π–π association are not only related by inversion but are cyclically linked by the amine N4B—H⋯O52Dⁱⁱⁱ hydrogen bond, forming an enlarged R₂²(32) ring motif. This cyclic relationship with associated π–π bonding is also found in some aromatic homodimer carboxylic acid structures (Sharma et al., 1993). In (I), the disordered water molecule also provides a link between the B molecule [the phenolic O2B acceptor] and the C molecule [the nitro O32C^iv acceptor]. Also present in the structure are two very weak C—H⋯O_nitro interactions [C3B—H⋯O31C 3.382 (3) and C4D—H⋯O32C^v 3.425 (3) Å; Table 1]. The H atoms of the N4A amine group have no acceptors with the PASA A homodimer unassociated in the overall structure except for the previously mentioned π–π ring interactions.

Figure 3
A partial expansion in the three-dimensional hydrogen-bonded structure of the adduct (I)

in the unit cell, viewed down a. Non-associative H atoms have been omitted. For symmetry codes, see Table 1

In (II) the hydrogen-bonded heterotrimer units associate across a crystallographic inversion centre through the HIPA carboxylic acid group [O13A—H⋯O14A]ⁱ in a cyclic R₂²(8) hydrogen-bonding association, giving a zero-dimensional heterohexamer structure which is essentially planar and lies parallel to (100) (Fig. 4). Only two very weak intermolecular d⁶-DMSO methyl C—H⋯O interactions are present between these units interactions [C1C—D⋯O14Aⁱⁱ 3.472 (3) and C1C—D⋯O12Bⁱⁱⁱ 3.372 (3) Å; Table 2]. In the structure, π–π interactions are also present between the benzene rings of the A and B^viii molecules] [minimum ring-centroid separation 3.5819 (10) Å; symmetry code: (viii) −x, −y + 2, −z + 1].

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1A⋯O2C	0.87 (2)	2.02 (2)	2.856 (2)	161 (2)
O11B—H11B⋯O2C	0.88 (2)	1.72 (2)	2.591 (2)	174 (2)
O12A—H12A⋯O14A	0.88 (2)	2.15 (2)	2.672 (2)	118 (2)
O12A—H12A⋯O52B	0.88 (2)	2.20 (2)	2.951 (2)	144 (2)
O13A—H13A⋯O14Aⁱ	0.90 (2)	1.75 (2)	2.644 (2)	178 (2)
C1C—D12C⋯O14Aⁱⁱ	0.98	2.56	3.472 (3)	155
C1C—D13C⋯O12Bⁱⁱⁱ	0.98	2.52	3.372 (3)	145
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x, -y+1, -z+1; (iii) -x, -y, -z+1.

Figure 4
The centrosymmetric hydrogen-bonded heterohexameric structure of the adduct (II)

in the unit cell, viewed down a. For symmetry code (i), see Table 2

4. Synthesis and crystallization

The title co-crystalline adducts (I) and (II) were prepared by dissolving equimolar quantities of 3,5-dinitrobenzoic acid and the respective acids 4-aminosalicylic acid [for (I)] or (1H-indol-3-yl)propenoic acid [for (II)] in ethanol and heating under reflux for 5 min after which room-temperature evaporation of the solutions gave for (I), yellow prisms and for (II), a red powder. This latter compound was dissolved in d⁶-deuterated DMSO and solvent diffusion of water into this solution gave red prisms of (II). Specimens were cleaved from both prismatic crystals for the X-ray analyses.

5. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3. Hydrogen atoms on all potentially interactive O—H and N—H groups in all molecular species were located by difference-Fourier methods and positional and displacement parameters were refined for all but those of the phenolic O2A and O2B groups and on the disordered water molecule O1W, with riding restraints [O—H bond length = 0.90 (2) Å and U_iso(H) = 1.5U_eq(O) or N—H = 0.88 (2) Å, with U_iso(H) = 1.2U_eq(N)]. The phenolic and water H atoms were set invariant with U_iso(H) = 1.2U_eq(O). Other H atoms were included in the refinement at calculated positions [C—H (aromatic) = 0.95 or (methylene) 0.99 Å] , with U_iso(H) = 1.2U_eq(C), using a riding-model approximation. The site-occupancy factor for the disordered water molecule of solvation was determined as 0.403 (4) [for the (2:2) 3,5-DNBA:PASA pair in the asymmetric unit] and was subsequently fixed as 0.40. In the structure of (I), the relatively large maximum residual electron density (0.835 e Å⁻³) was located 0.80 Å from H6B.

Table 3
Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₇H₄N₂O₆·C₇H₇NO₃·0.2H₂O	C₇H₄N₂O₆·C₁₁H₉NO₃·C₂D₆OS
M_r	368.86	499.49
Crystal system, space group	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$
Temperature (K)	200	200
a, b, c (Å)	7.0717 (5), 7.5974 (4), 28.7175 (19)	7.6488 (6), 12.3552 (10), 13.3768 (10)
α, β, γ (°)	87.926 (5), 86.498 (6), 87.584 (5)	116.833 (8), 96.274 (6), 97.626 (7)
V (Å³)	1537.77 (17)	1097.40 (18)
Z	4	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.14	0.21
Crystal size (mm)	0.35 × 0.35 × 0.30	0.45 × 0.40 × 0.32

Data collection
Diffractometer	Oxford Diffraction Gemini-S CCD detector	Oxford Diffraction Gemini-S CCD detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013 )	Multi-scan (CrysAlis PRO; Agilent, 2013)
T_min, T_max	0.966, 0.990	0.94, 0.98
No. of measured, independent and observed [I > 2σ(I)] reflections	10302, 6044, 4158	7457, 4310, 3490
R_int	0.027	0.023
(sin θ/λ)_max (Å⁻¹)	0.617	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.149, 1.01	0.040, 0.097, 1.02
No. of reflections	6044	4310
No. of parameters	502	319
No. of restraints	8	4
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
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.28	0.26, −0.25
Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) within WinGX (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC references: 1022646; 1022647

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S1600536814019898/sj5421sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814019898/sj5421Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S1600536814019898/sj5421IIsup3.hkl

Supporting information file. DOI: 10.1107/S1600536814019898/sj5421Isup4.cml

Supporting information file. DOI: 10.1107/S1600536814019898/sj5421IIsup5.cml

checkCIF report

Chemical context top

3,5-Dinitrobenzoic acid (3,5-DNBA) has been an important acid for the formation of crystalline materials, which have allowed structural characterization using single crystal X-ray methods. Most commonly proton-transfer salts are formed with organic Lewis bases, e.g. with 1-H-pyrazole (Aakeröy et al., 2012) but salt–adducts are also known, e.g. 2-pyridyl-4'-pyridinium⁺–3,5-DNBA^-–3,5-DNBA (1/1/1) (Chantrapromma et al., 2002). Although co-crystalline non-transfer molecular adducts with 3,5-DNBA are now relatively common, interest was stimulated with the original reporting of non-transfer adduct formation with 4-aminobenzoic acid to form a chiral 1:1 co-crystalline material (Etter & Frankenbach, 1989), which represented one of the earliest examples of designed crystal engineering, in that case with a view to producing non-linear optical materials. In the crystalline state, carboxylic acids usually form cyclic hydrogen-bonded dimers through head-to-head carboxyl O—H···O hydrogen bonds (Leiserowitz, 1976) [graph set R₂²(8)]. This is the case with 3,5-DNBA (A), which when co-crystallized with certain aromatic acids, e.g. 4-(N,N-dimethylamino)benzoic acid (B), gives separate mixed AA and BB homodimer pairs (Sharma et al., 1993). Although uncommon with 3,5-DNBA, with other aromatic acid analogues, AB heterodimer formation appears more prevalent, e.g. the 1:1 adducts of 3,5-dinitrocinnamic acid with 4-(N,N-dimethylamino)benzoic acid and 2,4-dinitrocinnamic acid with 2,5-dimethoxycinnamic acid (Sharma et al., 1993). In both AA and BB structure types, π–π interactions are commonly involved in stabilization, usually accompanied by enhanced colour generation. Absence of dimer pairs in 3,5-DNBA adducts is usually the result of preferential hydrogen bonding with solvent molecules, such as is found in the structure of 3,5-DNBA–phenoxyacetic acid–water (2/1/1) (Lynch et al., 1991), in which a cyclic R³₃(10) interaction is found, involving two 3,5-DNBA molecules and the water molecule. The title adducts C₇H₄N₂O6.C₇H₇NO₃.0.2H₂O (I) and C₇H₄N₂O6.C₁₁H₉NO₃.C₂D₆OS (II) were prepared from the interaction of 3,5-DNBA with 4-aminosalicylic acid (PASA) and 2-hydroxy-3-(1H-indol-3-yl)propenoic acid (HIPA), respectively, and the structures are reported herein. With (II), the incorporation of C₂D₆OS resulted from recrystallization from d⁶-dimethylsulfoxide.

Structural commentary top

In the co-crystal of 3,5-DNBA with 4-aminosalicylic acid, (I) (Fig. 1), the asymmetric unit consists of two PASA molecules (A and B), two 3,5-DNBA molecules (C and D) and a partial water molecule of solvation (O1W), with site occupancy = 0.4. However, what is most unusual in this structure is the presence of not four homodimers in the unit cell, but two homodimers (centrosymmetric PASA A–Aⁱ and 3,5-DNBA C–Cⁱⁱ pairs), as well as two heterodimer B–D pairs (for symmetry codes, see Table 1). All dimers are formed through the common cyclic R₂²(8) ring motif. Present in the PASA molecules are the expected intramolecular salicylic acid phenolic O—H···O_carboxyl hydrogen bonds, also present in the parent acid (Montis & Hursthouse, 2012).

In the ternary co-crystal of 3,5-DNBA (B) with 2-hydroxy-3-(1H-indol-3-yl)propenoic acid (A) and d⁶-dimethylsulfoxide (C), (II) the three molecules inter-associate through carboxylic acid O—H···O and N—H···O hydrogen bonds, forming a cyclic R₃²(17) heterotrimeric asymmetric unit (Fig. 2). This unit is essentially planar with a dihedral angle of 4.97 (7)° between the indole ring of A and the benzene ring of B. With the HIPA molecule there is a maximum deviation from the least squares plane of the 15-atom molecule of 0.120 (2) Å (C6A). The planar conformation of the acid side chain in this molecule is maintained by the presence of delocalization extending from C2A of the ring to O14A of the carboxylic acid group [torsion angle C11A—C12A—C13A—O14A = -177.43 (16)°]. This is also found in the parent acid, which has the similar enol configuration as in (II) [corresponding torsion angle 170.0 (3)°] with an E orientation and in the crystal forms a centrosymmetric homodimer with an R₂²(8) hydrogen-bond motif (Okabe & Adachi, 1998).

In the adducts (I) and (II), the 3,5-DNBA molecules are essentially planar with the exception of the C3-nitro groups of the C molecule in (I), and the B molecule in (II), where the defining C2—C3—N3—O32 torsion angles are 158.2 (3) and 168.39 (17)°, respectively. The overall torsion angle range for the remaining groups in both (I) and (II) is 170.8 (3)–179.2 (2)°. These minor deviations from planarity are consistent with conformational features of both polymorphs of the parent acid 3,5-DNBA (Prince et al., 1991) and in examples both of its salts (Aakeröy et al., 2012) and its adducts (Aakeröy et al., 2001; Jones et al., 2010; Chadwick et al., 2009).

Supramolecular features top

In the supramolecular structure of (I), the carboxylic acid dimers are extended through inter-dimer or inter-heterodimer amine N—H···O and water O—H···O hydrogen bonds (Table 1), giving a three-dimensional framework structure (Fig. 3). Within the structure there are a number of inter-ring π–π associations [ring-centroid separations: A···C^vi, 3.7542 (16); A···C^vii, 3.6471 (16); B···D^viii, 3.6785 (14) Å] [symmetry codes: (vi) x + 1, y - 1, z; (vii) x, y - 1, z; (viii) -x + 1, -y + 1, -z]. The B···D heterodimers in the π–π association are not only related by inversion but are cyclically linked by the amine N4B—H···O52Dⁱⁱⁱ hydrogen bond, forming an enlarged R₂²(32) ring motif. This cyclic relationship with associated π–π-bonding is also found in some aromatic homodimer carboxylic acid structures (Sharma et al., 1993). In (I), the partial water molecule also provides a link between the B molecule [the phenolic O2B acceptor] and the C molecule [the nitro O32C^iv acceptor]. Also present in the structure are two very weak C—H···O_nitro interactions [C3B—H···O31C 3.382 (3) and C4D—H···O32C^v 3.425 (3) Å; Table 1]. The H atoms of the N4A amine group have no acceptors with the PASA A homodimer unassociated in the overall structure except for the previously mentioned π–π ring interactions.

In (II) the hydrogen-bonded heterotrimer units associate across a crystallographic inversion centre through the HIPA carboxylic acid group [O13A—H···O14A]ⁱ in a cyclic R₂²(8) hydrogen-bonding association, giving a zero-dimensional heterohexamer structure which is essentially planar and lies parallel to (100) (Fig. 4). Only two very weak intermolecular d⁶-DMSO methyl C—H···O interactions are present between these units interactions [C1C—D···O14Aⁱⁱ 3.472 (3) and C1C—D···O12Bⁱⁱⁱ 3.372 (3) Å; Table 2].In the structure, π–π interactions are also present between the benzene rings of the A and B^viii molecules] [minimum ring-centroid separation 3.5819 (10) Å] [symmetry code (viii): -x, -y + 2, -z + 1].

Synthesis and crystallization top

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 3. Hydrogen atoms on all potentially interactive O—H and N—H groups in all molecular species were located by difference-Fourier methods and positional and thermal parameters were refined for all but those of the phenolic O2A and O2B groups and on the partial water O1W, with riding restraints [O—H bond length = 0.90 (2) Å and U_iso(H) = 1.5U_eq(O) or N—H = 0.88 (2) Å, with U_iso(H) = 1.2U_eq(N). The phenolic and water H atoms, were set invariant with U_iso(H) = 1.2U_eq(O). Other H atoms were included in the refinement at calculated positions [C—H (aromatic) = 0.95 or (methylene) 0.99 Å ], with U_iso(H) = 1.2U_eq(C), using a riding-model approximation. The site-occupancy factor for the partial water molecule of solvation was determined as 0.403 (4) [for the (2:2) 3,5-DNBA:PASA pair in the asymmetric unit] and was subsequently fixed as 0.40. In structure of (I), the relatively large maximum residual electron density (0.835 e Å^-3) was located 0.80 Å from H6B.

Related literature top

For related literature, see: Aakeröy et al. (2001, 2012); Chadwick et al. (2009); Chantrapromma et al. (2002); Etter & Frankenbach (1989); Leiserowitz (1976); Lynch et al. (1991); Montis & Hursthouse (2012); Okabe & Adachi (1998); Prince et al. (1991); Sharma et al. (1993).

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: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular conformation and atom-naming scheme for the two PABA molecules (A and B), the two 3,5-DNBA molecules (C and D) and the partial water molecule (O1W) in the asymmetric unit of adduct (I), with displacement ellipsoids drawn at the 40% probability level. Inter-species hydrogen bonds are shown as dashed lines. For symmetry codes, see Table 1.
	Fig. 2. Molecular conformation and atom-naming scheme for adduct (II), with displacement ellipsoids drawn at the 40% probability level. Inter-species hydrogen bonds are shown as dashed lines.
	Fig. 3. A partial expansion in the three-dimensional hydrogen-bonded structure of the adduct (I) in the unit cell, viewed down a. Non-associative H atoms have been omitted. For symmetry codes, see Table 1.
	Fig. 4. The centrosymmetric hydrogen-bonded heterohexameric structure of the adduct (II) in the unit cell, viewed down a. For symmetry code (i), see Table 2.

(I) 4-Amino-2-hydroxybenzoic acid–3,5-dinitrobenzoic acid–water (2/2/0.4) top

Crystal data top

C₇H₄N₂O₆·C₇H₇NO₃·0.2H₂O	Z = 4
M_r = 368.86	F(000) = 760
Triclinic, P1	D_x = 1.593 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0717 (5) Å	Cell parameters from 2357 reflections
b = 7.5974 (4) Å	θ = 3.3–27.2°
c = 28.7175 (19) Å	µ = 0.14 mm⁻¹
α = 87.926 (5)°	T = 200 K
β = 86.498 (6)°	Block, yellow
γ = 87.584 (5)°	0.35 × 0.35 × 0.30 mm
V = 1537.77 (17) Å³

Data collection top

Oxford Diffraction Gemini-S CCD detector diffractometer	6044 independent reflections
Radiation source: Enhance (Mo) X-ray source	4158 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 16.077 pixels mm^-1	θ_max = 26.0°, θ_min = 3.1°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −9→8
T_min = 0.966, T_max = 0.990	l = −35→31
10302 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.149	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0599P)² + 0.6456P] where P = (F_o² + 2F_c²)/3
6044 reflections	(Δ/σ)_max < 0.001
502 parameters	Δρ_max = 0.86 e Å⁻³
8 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₇H₄N₂O₆·C₇H₇NO₃·0.2H₂O	γ = 87.584 (5)°
M_r = 368.86	V = 1537.77 (17) Å³
Triclinic, P1	Z = 4
a = 7.0717 (5) Å	Mo Kα radiation
b = 7.5974 (4) Å	µ = 0.14 mm⁻¹
c = 28.7175 (19) Å	T = 200 K
α = 87.926 (5)°	0.35 × 0.35 × 0.30 mm
β = 86.498 (6)°

Data collection top

Oxford Diffraction Gemini-S CCD detector diffractometer	6044 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	4158 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.990	R_int = 0.027
10302 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	8 restraints
wR(F²) = 0.149	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.86 e Å⁻³
6044 reflections	Δρ_min = −0.28 e Å⁻³
502 parameters

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 e.s.d.'s 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 > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O11C	−0.1050 (3)	1.2197 (3)	0.48465 (7)	0.0453 (7)
O12C	−0.0102 (3)	0.9810 (2)	0.44480 (6)	0.0412 (7)
O31C	−0.1244 (4)	0.9769 (3)	0.27862 (8)	0.0629 (9)
O32C	−0.3286 (3)	1.1671 (3)	0.25221 (7)	0.0562 (8)
O51C	−0.3819 (3)	1.7339 (3)	0.32553 (8)	0.0560 (9)
O52C	−0.2958 (4)	1.7528 (3)	0.39588 (8)	0.0573 (9)
N3C	−0.2215 (4)	1.1123 (3)	0.28179 (8)	0.0409 (9)
N5C	−0.3155 (4)	1.6703 (3)	0.36123 (9)	0.0396 (8)
C1C	−0.1424 (4)	1.2259 (3)	0.40352 (9)	0.0284 (8)
C2C	−0.1454 (4)	1.1313 (3)	0.36322 (9)	0.0299 (8)
C3C	−0.2105 (4)	1.2152 (3)	0.32363 (9)	0.0302 (8)
C4C	−0.2689 (4)	1.3908 (3)	0.32177 (9)	0.0310 (8)
C5C	−0.2592 (4)	1.4815 (3)	0.36191 (9)	0.0299 (8)
C6C	−0.1988 (4)	1.4038 (3)	0.40322 (9)	0.0307 (8)
C11C	−0.0797 (4)	1.1307 (3)	0.44630 (9)	0.0305 (8)
O11D	0.4620 (3)	0.6430 (2)	−0.04675 (6)	0.0354 (6)
O12D	0.6448 (3)	0.8050 (3)	−0.00552 (7)	0.0467 (8)
O31D	1.2556 (3)	0.9762 (2)	−0.06601 (7)	0.0462 (8)
O32D	1.3586 (3)	0.9146 (3)	−0.13627 (8)	0.0477 (8)
O51D	0.9545 (3)	0.6273 (3)	−0.23683 (7)	0.0493 (8)
O52D	0.6769 (3)	0.5502 (3)	−0.21049 (7)	0.0479 (8)
N3D	1.2378 (3)	0.9137 (3)	−0.10404 (9)	0.0352 (8)
N5D	0.8272 (3)	0.6196 (3)	−0.20596 (8)	0.0337 (8)
C1D	0.7529 (4)	0.7425 (3)	−0.08154 (9)	0.0279 (8)
C2D	0.9234 (4)	0.8206 (3)	−0.07471 (9)	0.0291 (8)
C3D	1.0568 (4)	0.8320 (3)	−0.11161 (9)	0.0282 (8)
C4D	1.0307 (4)	0.7687 (3)	−0.15504 (9)	0.0292 (8)
C5D	0.8599 (4)	0.6923 (3)	−0.16043 (8)	0.0273 (8)
C6D	0.7212 (4)	0.6777 (3)	−0.12500 (9)	0.0284 (8)
C11D	0.6060 (4)	0.7264 (3)	−0.04270 (9)	0.0306 (8)
O2A	0.3595 (3)	0.0813 (2)	0.35993 (7)	0.0414 (7)
O11A	0.4058 (3)	0.2349 (3)	0.49746 (7)	0.0460 (8)
O12A	0.4496 (3)	0.0192 (2)	0.44648 (7)	0.0413 (7)
N4A	0.1581 (4)	0.6629 (4)	0.31680 (10)	0.0531 (10)
C1A	0.3356 (4)	0.3003 (3)	0.41957 (9)	0.0293 (8)
C2A	0.3186 (4)	0.2488 (3)	0.37348 (9)	0.0299 (8)
C3A	0.2632 (4)	0.3695 (4)	0.33956 (9)	0.0339 (9)
C4A	0.2202 (4)	0.5441 (4)	0.35021 (10)	0.0360 (9)
C5A	0.2345 (4)	0.5972 (4)	0.39630 (10)	0.0390 (10)
C6A	0.2913 (4)	0.4775 (3)	0.42978 (10)	0.0347 (9)
C11A	0.4010 (4)	0.1748 (3)	0.45526 (9)	0.0321 (9)
O2B	0.2909 (3)	0.8426 (3)	0.14868 (7)	0.0481 (8)
O11B	0.1793 (3)	0.6474 (3)	0.01942 (7)	0.0421 (7)
O12B	0.3803 (3)	0.7848 (2)	0.06171 (7)	0.0412 (7)
N4B	−0.3161 (4)	0.6924 (4)	0.21044 (10)	0.0465 (9)
C1B	0.0835 (4)	0.7114 (3)	0.09718 (9)	0.0280 (8)
C2B	0.1231 (4)	0.7741 (3)	0.14100 (9)	0.0282 (8)
C3B	−0.0089 (4)	0.7679 (3)	0.17821 (9)	0.0314 (8)
C4B	−0.1867 (4)	0.6999 (3)	0.17321 (10)	0.0333 (9)
C5B	−0.2278 (4)	0.6362 (3)	0.12966 (10)	0.0348 (9)
C6B	−0.0968 (4)	0.6421 (3)	0.09281 (10)	0.0324 (9)
C11B	0.2232 (4)	0.7176 (3)	0.05843 (9)	0.0307 (8)
O1W	0.3006 (7)	0.9987 (7)	0.24093 (19)	0.0511 (19)	0.400
H2C	−0.10340	1.01090	0.36290	0.0360*
H4C	−0.31350	1.44600	0.29410	0.0370*
H6C	−0.19590	1.47020	0.43050	0.0370*
H11C	−0.067 (5)	1.148 (4)	0.5085 (9)	0.0680*
H2D	0.94710	0.86520	−0.04520	0.0350*
H4D	1.12510	0.77710	−0.17990	0.0350*
H6D	0.60550	0.62430	−0.13010	0.0340*
H12D	0.552 (4)	0.793 (4)	0.0173 (10)	0.0700*
H2A	0.39860	0.02000	0.38260	0.0620*
H3A	0.25440	0.33300	0.30850	0.0410*
H5A	0.20480	0.71610	0.40410	0.0470*
H6A	0.30110	0.51490	0.46070	0.0420*
H11A	0.460 (5)	0.148 (4)	0.5152 (11)	0.0690*
H41A	0.167 (5)	0.636 (4)	0.2874 (7)	0.0640*
H42A	0.173 (5)	0.773 (3)	0.3223 (12)	0.0640*
H2B	0.36360	0.83470	0.12460	0.0720*
H3B	0.02110	0.81010	0.20750	0.0380*
H5B	−0.34780	0.58860	0.12590	0.0420*
H6B	−0.12730	0.59900	0.06370	0.0390*
H11B	0.279 (4)	0.653 (4)	−0.0035 (10)	0.0630*
H41B	−0.304 (5)	0.751 (4)	0.2349 (8)	0.0560*
H42B	−0.424 (3)	0.659 (4)	0.2034 (12)	0.0560*
H11W	0.29970	0.95200	0.21260	0.0760*	0.400
H12W	0.41470	1.05100	0.24460	0.0760*	0.400

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O11C	0.0629 (15)	0.0449 (12)	0.0267 (11)	0.0126 (10)	−0.0028 (10)	0.0005 (8)
O12C	0.0515 (14)	0.0378 (11)	0.0336 (11)	0.0079 (9)	−0.0057 (10)	0.0021 (8)
O31C	0.097 (2)	0.0468 (13)	0.0441 (14)	0.0108 (13)	0.0001 (13)	−0.0157 (10)
O32C	0.0653 (16)	0.0726 (15)	0.0330 (12)	−0.0158 (12)	−0.0147 (12)	−0.0005 (11)
O51C	0.0687 (17)	0.0423 (12)	0.0548 (15)	0.0133 (11)	−0.0044 (12)	0.0108 (10)
O52C	0.0886 (19)	0.0330 (11)	0.0500 (14)	−0.0017 (11)	0.0021 (13)	−0.0088 (10)
N3C	0.0536 (17)	0.0410 (14)	0.0282 (13)	−0.0132 (12)	0.0038 (12)	−0.0015 (10)
N5C	0.0421 (15)	0.0323 (13)	0.0427 (15)	0.0006 (11)	0.0065 (12)	0.0045 (11)
C1C	0.0236 (14)	0.0330 (14)	0.0281 (14)	−0.0024 (11)	0.0015 (11)	0.0021 (10)
C2C	0.0303 (15)	0.0279 (13)	0.0309 (15)	−0.0028 (11)	0.0021 (12)	0.0014 (11)
C3C	0.0312 (15)	0.0318 (14)	0.0273 (14)	−0.0069 (11)	0.0044 (11)	−0.0024 (11)
C4C	0.0248 (14)	0.0394 (15)	0.0283 (14)	−0.0050 (11)	−0.0001 (11)	0.0062 (11)
C5C	0.0259 (14)	0.0290 (13)	0.0340 (15)	−0.0019 (11)	0.0034 (12)	0.0005 (11)
C6C	0.0288 (15)	0.0358 (14)	0.0273 (14)	−0.0065 (11)	0.0036 (11)	−0.0013 (11)
C11C	0.0269 (14)	0.0350 (15)	0.0295 (15)	−0.0011 (11)	−0.0014 (11)	0.0001 (11)
O11D	0.0368 (12)	0.0388 (10)	0.0309 (11)	−0.0069 (9)	0.0016 (9)	−0.0034 (8)
O12D	0.0429 (13)	0.0667 (14)	0.0316 (12)	−0.0123 (11)	0.0053 (9)	−0.0173 (10)
O31D	0.0454 (13)	0.0455 (12)	0.0505 (14)	−0.0058 (10)	−0.0148 (10)	−0.0141 (10)
O32D	0.0302 (12)	0.0610 (13)	0.0517 (14)	−0.0065 (10)	−0.0005 (10)	0.0018 (10)
O51D	0.0509 (14)	0.0709 (14)	0.0262 (11)	−0.0136 (11)	0.0059 (10)	−0.0057 (9)
O52D	0.0460 (14)	0.0623 (13)	0.0379 (12)	−0.0188 (11)	−0.0070 (10)	−0.0087 (10)
N3D	0.0331 (14)	0.0318 (12)	0.0410 (15)	0.0006 (10)	−0.0077 (12)	0.0012 (10)
N5D	0.0409 (15)	0.0354 (12)	0.0254 (13)	−0.0039 (10)	−0.0059 (11)	0.0015 (9)
C1D	0.0338 (15)	0.0234 (12)	0.0264 (14)	0.0014 (11)	−0.0041 (11)	−0.0008 (10)
C2D	0.0383 (16)	0.0243 (13)	0.0251 (14)	0.0048 (11)	−0.0074 (12)	−0.0040 (10)
C3D	0.0284 (14)	0.0204 (12)	0.0360 (15)	0.0015 (10)	−0.0068 (12)	−0.0001 (10)
C4D	0.0337 (15)	0.0261 (13)	0.0271 (14)	0.0022 (11)	0.0001 (12)	0.0023 (10)
C5D	0.0341 (15)	0.0252 (12)	0.0228 (13)	0.0005 (11)	−0.0051 (11)	0.0008 (10)
C6D	0.0303 (15)	0.0255 (13)	0.0296 (14)	−0.0005 (11)	−0.0041 (12)	0.0000 (10)
C11D	0.0344 (16)	0.0300 (14)	0.0273 (14)	0.0032 (12)	−0.0043 (12)	−0.0024 (11)
O2A	0.0521 (14)	0.0347 (11)	0.0376 (12)	0.0061 (9)	−0.0087 (10)	−0.0013 (8)
O11A	0.0634 (16)	0.0445 (12)	0.0300 (12)	0.0093 (10)	−0.0124 (10)	0.0038 (9)
O12A	0.0514 (13)	0.0353 (11)	0.0367 (11)	0.0072 (9)	−0.0081 (10)	0.0050 (8)
N4A	0.065 (2)	0.0487 (16)	0.0446 (16)	0.0085 (15)	−0.0121 (15)	0.0137 (14)
C1A	0.0250 (14)	0.0340 (14)	0.0285 (14)	−0.0005 (11)	−0.0007 (11)	0.0037 (10)
C2A	0.0236 (14)	0.0331 (14)	0.0322 (15)	0.0007 (11)	0.0016 (11)	0.0008 (11)
C3A	0.0293 (15)	0.0427 (16)	0.0293 (15)	0.0000 (12)	−0.0017 (12)	0.0025 (11)
C4A	0.0292 (16)	0.0401 (16)	0.0377 (16)	0.0006 (12)	−0.0008 (13)	0.0090 (12)
C5A	0.0395 (17)	0.0323 (15)	0.0446 (18)	0.0018 (12)	−0.0019 (14)	0.0009 (12)
C6A	0.0354 (16)	0.0346 (15)	0.0339 (16)	0.0004 (12)	−0.0021 (13)	−0.0011 (11)
C11A	0.0278 (15)	0.0372 (15)	0.0309 (15)	−0.0016 (11)	−0.0019 (12)	0.0053 (11)
O2B	0.0414 (13)	0.0614 (13)	0.0422 (13)	−0.0122 (10)	0.0013 (10)	−0.0081 (10)
O11B	0.0445 (13)	0.0539 (12)	0.0281 (11)	−0.0045 (10)	0.0005 (9)	−0.0058 (9)
O12B	0.0357 (12)	0.0495 (12)	0.0383 (12)	−0.0072 (9)	0.0045 (9)	−0.0053 (9)
N4B	0.0396 (16)	0.0567 (17)	0.0433 (16)	−0.0129 (13)	0.0087 (13)	−0.0106 (12)
C1B	0.0322 (15)	0.0235 (12)	0.0279 (14)	0.0025 (10)	−0.0021 (11)	−0.0010 (10)
C2B	0.0257 (14)	0.0225 (12)	0.0366 (15)	−0.0017 (10)	−0.0033 (12)	−0.0018 (10)
C3B	0.0355 (16)	0.0282 (13)	0.0305 (15)	−0.0003 (11)	−0.0019 (12)	−0.0024 (11)
C4B	0.0324 (16)	0.0276 (13)	0.0390 (16)	0.0003 (11)	0.0028 (13)	−0.0006 (11)
C5B	0.0285 (15)	0.0323 (14)	0.0438 (17)	−0.0029 (11)	−0.0022 (13)	−0.0016 (12)
C6B	0.0335 (16)	0.0282 (13)	0.0362 (16)	−0.0010 (11)	−0.0081 (13)	−0.0021 (11)
C11B	0.0333 (16)	0.0265 (13)	0.0320 (15)	0.0023 (11)	−0.0036 (12)	0.0014 (11)
O1W	0.034 (3)	0.057 (3)	0.066 (4)	−0.010 (2)	−0.017 (3)	−0.022 (3)

Geometric parameters (Å, º) top

O11C—C11C	1.312 (3)	C1C—C11C	1.485 (4)
O12C—C11C	1.221 (3)	C2C—C3C	1.378 (4)
O31C—N3C	1.216 (3)	C3C—C4C	1.380 (3)
O32C—N3C	1.223 (3)	C4C—C5C	1.371 (4)
O51C—N5C	1.228 (3)	C5C—C6C	1.389 (4)
O52C—N5C	1.213 (3)	C2C—H2C	0.9500
O11C—H11C	0.91 (3)	C4C—H4C	0.9500
O11D—C11D	1.235 (3)	C6C—H6C	0.9500
O12D—C11D	1.291 (3)	C1D—C6D	1.392 (4)
O31D—N3D	1.222 (3)	C1D—C11D	1.482 (4)
O32D—N3D	1.221 (3)	C1D—C2D	1.394 (4)
O51D—N5D	1.226 (3)	C2D—C3D	1.378 (4)
O52D—N5D	1.222 (3)	C3D—C4D	1.378 (4)
O12D—H12D	0.90 (3)	C4D—C5D	1.381 (4)
O2A—C2A	1.359 (3)	C5D—C6D	1.374 (4)
O11A—C11A	1.313 (3)	C2D—H2D	0.9500
O12A—C11A	1.247 (3)	C4D—H4D	0.9500
O2A—H2A	0.8400	C6D—H6D	0.9500
O11A—H11A	0.91 (3)	C1A—C2A	1.407 (4)
O2B—C2B	1.349 (3)	C1A—C6A	1.407 (3)
O11B—C11B	1.317 (3)	C1A—C11A	1.457 (4)
O12B—C11B	1.252 (3)	C2A—C3A	1.377 (4)
O2B—H2B	0.8400	C3A—C4A	1.389 (4)
O11B—H11B	0.94 (3)	C4A—C5A	1.408 (4)
O1W—H12W	0.9300	C5A—C6A	1.366 (4)
O1W—H11W	0.9000	C3A—H3A	0.9500
N3C—C3C	1.465 (3)	C5A—H5A	0.9500
N5C—C5C	1.472 (3)	C6A—H6A	0.9500
N3D—C3D	1.477 (3)	C1B—C11B	1.443 (4)
N5D—C5D	1.472 (3)	C1B—C6B	1.414 (4)
N4A—C4A	1.372 (4)	C1B—C2B	1.410 (4)
N4A—H41A	0.87 (2)	C2B—C3B	1.376 (4)
N4A—H42A	0.87 (2)	C3B—C4B	1.397 (4)
N4B—C4B	1.365 (4)	C4B—C5B	1.408 (4)
N4B—H41B	0.86 (3)	C5B—C6B	1.364 (4)
N4B—H42B	0.85 (2)	C3B—H3B	0.9500
C1C—C2C	1.386 (4)	C5B—H5B	0.9500
C1C—C6C	1.393 (3)	C6B—H6B	0.9500

C11C—O11C—H11C	107.4 (18)	C4D—C5D—C6D	123.0 (2)
C11D—O12D—H12D	111.4 (19)	N5D—C5D—C6D	118.6 (2)
C2A—O2A—H2A	109.00	C1D—C6D—C5D	119.0 (2)
C11A—O11A—H11A	107 (2)	O11D—C11D—C1D	121.3 (2)
C2B—O2B—H2B	110.00	O12D—C11D—C1D	113.9 (2)
C11B—O11B—H11B	111.6 (18)	O11D—C11D—O12D	124.8 (2)
H11W—O1W—H12W	111.00	C1D—C2D—H2D	121.00
O31C—N3C—O32C	123.8 (2)	C3D—C2D—H2D	121.00
O31C—N3C—C3C	118.1 (2)	C5D—C4D—H4D	122.00
O32C—N3C—C3C	118.1 (2)	C3D—C4D—H4D	122.00
O51C—N5C—C5C	117.5 (2)	C5D—C6D—H6D	121.00
O52C—N5C—C5C	118.4 (2)	C1D—C6D—H6D	121.00
O51C—N5C—O52C	124.1 (2)	C2A—C1A—C11A	121.0 (2)
O31D—N3D—C3D	117.7 (2)	C2A—C1A—C6A	117.8 (2)
O31D—N3D—O32D	124.7 (2)	C6A—C1A—C11A	121.2 (2)
O32D—N3D—C3D	117.7 (2)	C1A—C2A—C3A	120.7 (2)
O51D—N5D—C5D	118.2 (2)	O2A—C2A—C1A	122.5 (2)
O51D—N5D—O52D	123.5 (2)	O2A—C2A—C3A	116.9 (2)
O52D—N5D—C5D	118.2 (2)	C2A—C3A—C4A	120.8 (2)
C4A—N4A—H41A	120 (2)	N4A—C4A—C5A	120.0 (3)
C4A—N4A—H42A	115 (2)	C3A—C4A—C5A	119.2 (3)
H41A—N4A—H42A	116 (3)	N4A—C4A—C3A	120.8 (3)
C4B—N4B—H42B	113 (2)	C4A—C5A—C6A	119.9 (3)
H41B—N4B—H42B	121 (3)	C1A—C6A—C5A	121.6 (3)
C4B—N4B—H41B	122 (2)	O11A—C11A—C1A	116.1 (2)
C2C—C1C—C6C	120.2 (2)	O11A—C11A—O12A	121.7 (2)
C6C—C1C—C11C	122.1 (2)	O12A—C11A—C1A	122.3 (2)
C2C—C1C—C11C	117.8 (2)	C2A—C3A—H3A	120.00
C1C—C2C—C3C	118.7 (2)	C4A—C3A—H3A	120.00
C2C—C3C—C4C	123.1 (2)	C6A—C5A—H5A	120.00
N3C—C3C—C2C	118.4 (2)	C4A—C5A—H5A	120.00
N3C—C3C—C4C	118.5 (2)	C1A—C6A—H6A	119.00
C3C—C4C—C5C	116.6 (2)	C5A—C6A—H6A	119.00
N5C—C5C—C4C	118.5 (2)	C2B—C1B—C11B	120.8 (2)
C4C—C5C—C6C	123.1 (2)	C6B—C1B—C11B	121.6 (2)
N5C—C5C—C6C	118.4 (2)	C2B—C1B—C6B	117.6 (2)
C1C—C6C—C5C	118.2 (2)	O2B—C2B—C3B	116.7 (2)
O12C—C11C—C1C	121.2 (2)	C1B—C2B—C3B	121.2 (3)
O11C—C11C—O12C	124.0 (2)	O2B—C2B—C1B	122.1 (2)
O11C—C11C—C1C	114.9 (2)	C2B—C3B—C4B	120.4 (2)
C3C—C2C—H2C	121.00	N4B—C4B—C3B	120.1 (3)
C1C—C2C—H2C	121.00	C3B—C4B—C5B	118.9 (3)
C3C—C4C—H4C	122.00	N4B—C4B—C5B	121.0 (3)
C5C—C4C—H4C	122.00	C4B—C5B—C6B	120.6 (3)
C1C—C6C—H6C	121.00	C1B—C6B—C5B	121.2 (3)
C5C—C6C—H6C	121.00	O12B—C11B—C1B	121.7 (2)
C6D—C1D—C11D	119.8 (2)	O11B—C11B—C1B	117.1 (2)
C2D—C1D—C6D	119.8 (2)	O11B—C11B—O12B	121.2 (2)
C2D—C1D—C11D	120.4 (2)	C4B—C3B—H3B	120.00
C1D—C2D—C3D	118.6 (2)	C2B—C3B—H3B	120.00
N3D—C3D—C4D	118.4 (2)	C4B—C5B—H5B	120.00
C2D—C3D—C4D	123.2 (3)	C6B—C5B—H5B	120.00
N3D—C3D—C2D	118.4 (2)	C1B—C6B—H6B	119.00
C3D—C4D—C5D	116.4 (2)	C5B—C6B—H6B	119.00
N5D—C5D—C4D	118.3 (2)

O31C—N3C—C3C—C2C	−21.4 (4)	C1D—C2D—C3D—N3D	−179.5 (2)
O32C—N3C—C3C—C2C	158.2 (3)	C2D—C3D—C4D—C5D	0.5 (4)
O31C—N3C—C3C—C4C	159.7 (3)	N3D—C3D—C4D—C5D	179.6 (2)
O32C—N3C—C3C—C4C	−20.7 (4)	C3D—C4D—C5D—N5D	−178.8 (2)
O51C—N5C—C5C—C4C	5.3 (4)	C3D—C4D—C5D—C6D	−0.3 (4)
O52C—N5C—C5C—C4C	−175.5 (3)	N5D—C5D—C6D—C1D	178.5 (2)
O51C—N5C—C5C—C6C	−174.7 (3)	C4D—C5D—C6D—C1D	0.0 (4)
O52C—N5C—C5C—C6C	4.5 (4)	C6A—C1A—C2A—O2A	179.4 (3)
O31D—N3D—C3D—C4D	176.8 (2)	C6A—C1A—C2A—C3A	1.0 (4)
O32D—N3D—C3D—C4D	−2.9 (3)	C11A—C1A—C2A—O2A	0.7 (4)
O32D—N3D—C3D—C2D	176.2 (2)	C11A—C1A—C2A—C3A	−177.7 (3)
O31D—N3D—C3D—C2D	−4.1 (3)	C2A—C1A—C6A—C5A	−0.4 (4)
O52D—N5D—C5D—C4D	179.2 (2)	C11A—C1A—C6A—C5A	178.3 (3)
O51D—N5D—C5D—C6D	−177.3 (2)	C2A—C1A—C11A—O11A	−177.8 (3)
O51D—N5D—C5D—C4D	1.3 (3)	C2A—C1A—C11A—O12A	2.1 (4)
O52D—N5D—C5D—C6D	0.6 (3)	C6A—C1A—C11A—O11A	3.5 (4)
C2C—C1C—C6C—C5C	0.7 (4)	C6A—C1A—C11A—O12A	−176.5 (3)
C11C—C1C—C2C—C3C	177.4 (3)	O2A—C2A—C3A—C4A	−179.5 (3)
C6C—C1C—C11C—O11C	8.5 (4)	C1A—C2A—C3A—C4A	−1.0 (4)
C2C—C1C—C11C—O12C	9.2 (4)	C2A—C3A—C4A—N4A	−177.5 (3)
C2C—C1C—C11C—O11C	−170.8 (3)	C2A—C3A—C4A—C5A	0.2 (4)
C6C—C1C—C2C—C3C	−2.0 (4)	N4A—C4A—C5A—C6A	178.2 (3)
C6C—C1C—C11C—O12C	−171.4 (3)	C3A—C4A—C5A—C6A	0.4 (4)
C11C—C1C—C6C—C5C	−178.7 (3)	C4A—C5A—C6A—C1A	−0.3 (4)
C1C—C2C—C3C—N3C	−177.2 (3)	C6B—C1B—C2B—O2B	−180.0 (2)
C1C—C2C—C3C—C4C	1.6 (4)	C6B—C1B—C2B—C3B	0.1 (4)
C2C—C3C—C4C—C5C	0.1 (4)	C11B—C1B—C2B—O2B	0.3 (4)
N3C—C3C—C4C—C5C	179.0 (3)	C11B—C1B—C2B—C3B	−179.7 (2)
C3C—C4C—C5C—C6C	−1.5 (4)	C2B—C1B—C6B—C5B	0.0 (4)
C3C—C4C—C5C—N5C	178.5 (3)	C11B—C1B—C6B—C5B	179.8 (2)
C4C—C5C—C6C—C1C	1.1 (4)	C2B—C1B—C11B—O11B	176.3 (2)
N5C—C5C—C6C—C1C	−178.9 (3)	C2B—C1B—C11B—O12B	−3.0 (4)
C2D—C1D—C6D—C5D	0.0 (4)	C6B—C1B—C11B—O11B	−3.5 (4)
C6D—C1D—C2D—C3D	0.2 (4)	C6B—C1B—C11B—O12B	177.3 (2)
C11D—C1D—C2D—C3D	179.6 (2)	O2B—C2B—C3B—C4B	179.6 (2)
C6D—C1D—C11D—O11D	6.3 (4)	C1B—C2B—C3B—C4B	−0.4 (4)
C11D—C1D—C6D—C5D	−179.4 (2)	C2B—C3B—C4B—N4B	179.3 (2)
C6D—C1D—C11D—O12D	−174.2 (2)	C2B—C3B—C4B—C5B	0.7 (4)
C2D—C1D—C11D—O12D	6.4 (3)	N4B—C4B—C5B—C6B	−179.1 (3)
C2D—C1D—C11D—O11D	−173.1 (2)	C3B—C4B—C5B—C6B	−0.6 (4)
C1D—C2D—C3D—C4D	−0.5 (4)	C4B—C5B—C6B—C1B	0.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11A—H11A···O12Aⁱ	0.91 (3)	1.78 (3)	2.678 (3)	175 (3)
O11B—H11B···O11D	0.94 (3)	1.74 (3)	2.673 (3)	175 (3)
O11C—H11C···O12Cⁱⁱ	0.91 (3)	1.73 (3)	2.640 (3)	177 (2)
O12D—H12D···O12B	0.90 (3)	1.71 (3)	2.610 (3)	176 (2)
N4B—H41B···O31C	0.86 (3)	2.58 (3)	3.350 (4)	150 (3)
N4B—H42B···O52Dⁱⁱⁱ	0.85 (2)	2.44 (3)	3.210 (4)	151 (3)
O2A—H2A···O12A	0.84	1.89	2.625 (3)	145
O2B—H2B···O12B	0.84	1.85	2.587 (3)	145
O1W—H11W···O2B	0.90	2.05	2.952 (6)	179
O1W—H12W···O32C^iv	0.93	2.08	3.005 (5)	179
C3B—H3B···O31C	0.95	2.58	3.382 (3)	142
C4D—H4D···O32C^v	0.95	2.49	3.425 (3)	170

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

(II) 3,5-Dinitrobenzoic acid–2-hydroxy-3-(1H-indol-3-yl)propenoic acid–d⁶-dimethyl sulfoxide (1/1/1) top

Crystal data top

C₇H₄N₂O₆·C₁₁H₉NO₃·C₂D₆OS	Z = 2
M_r = 499.49	F(000) = 512
Triclinic, P1	D_x = 1.511 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6488 (6) Å	Cell parameters from 2343 reflections
b = 12.3552 (10) Å	θ = 3.3–28.4°
c = 13.3768 (10) Å	µ = 0.21 mm⁻¹
α = 116.833 (8)°	T = 200 K
β = 96.274 (6)°	Block, red
γ = 97.626 (7)°	0.45 × 0.40 × 0.32 mm
V = 1097.40 (18) Å³

Data collection top

Oxford Diffraction Gemini-S CCD detector diffractometer	4310 independent reflections
Radiation source: Enhance (Mo) X-ray source	3490 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 16.077 pixels mm^-1	θ_max = 26.0°, θ_min = 3.3°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −15→15
T_min = 0.94, T_max = 0.98	l = −16→16
7457 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0394P)² + 0.3315P] where P = (F_o² + 2F_c²)/3
4310 reflections	(Δ/σ)_max < 0.001
319 parameters	Δρ_max = 0.26 e Å⁻³
4 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₇H₄N₂O₆·C₁₁H₉NO₃·C₂D₆OS	γ = 97.626 (7)°
M_r = 499.49	V = 1097.40 (18) Å³
Triclinic, P1	Z = 2
a = 7.6488 (6) Å	Mo Kα radiation
b = 12.3552 (10) Å	µ = 0.21 mm⁻¹
c = 13.3768 (10) Å	T = 200 K
α = 116.833 (8)°	0.45 × 0.40 × 0.32 mm
β = 96.274 (6)°

Data collection top

Oxford Diffraction Gemini-S CCD detector diffractometer	4310 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	3490 reflections with I > 2σ(I)
T_min = 0.94, T_max = 0.98	R_int = 0.023
7457 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	4 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.26 e Å⁻³
4310 reflections	Δρ_min = −0.25 e Å⁻³
319 parameters

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

	x	y	z	U_iso*/U_eq
O11B	0.11950 (19)	0.35376 (12)	0.50949 (11)	0.0386 (5)
O12B	0.0099 (2)	0.24989 (12)	0.59702 (12)	0.0458 (5)
O31B	−0.19578 (19)	0.48461 (14)	0.95269 (12)	0.0438 (5)
O32B	−0.0994 (2)	0.68345 (14)	1.05107 (12)	0.0483 (5)
O51B	0.1446 (2)	0.90405 (13)	0.86272 (12)	0.0504 (5)
O52B	0.2503 (2)	0.80830 (13)	0.71029 (12)	0.0443 (5)
N3B	−0.1163 (2)	0.58414 (16)	0.96484 (14)	0.0353 (6)
N5B	0.1697 (2)	0.80906 (14)	0.78469 (13)	0.0331 (5)
C1B	0.0493 (2)	0.46984 (16)	0.69011 (14)	0.0272 (5)
C2B	−0.0251 (2)	0.47096 (17)	0.78086 (15)	0.0291 (6)
C3B	−0.0359 (2)	0.58338 (17)	0.86952 (14)	0.0282 (5)
C4B	0.0267 (2)	0.69546 (17)	0.87299 (15)	0.0289 (5)
C5B	0.1009 (2)	0.69054 (16)	0.78195 (14)	0.0268 (5)
C6B	0.1133 (2)	0.58021 (16)	0.68980 (15)	0.0273 (5)
C11B	0.0569 (2)	0.34589 (17)	0.59463 (16)	0.0312 (6)
O12A	0.36207 (19)	0.66095 (12)	0.49243 (11)	0.0372 (4)
O13A	0.5239 (2)	0.85805 (12)	0.37886 (12)	0.0423 (5)
O14A	0.42998 (17)	0.89974 (12)	0.54337 (11)	0.0365 (4)
N1A	0.3546 (2)	0.28647 (14)	0.26491 (13)	0.0311 (5)
C2A	0.3735 (2)	0.41030 (16)	0.33443 (15)	0.0293 (6)
C3A	0.4425 (2)	0.47577 (16)	0.28182 (14)	0.0259 (5)
C4A	0.5334 (2)	0.39011 (17)	0.08035 (15)	0.0298 (6)
C5A	0.5337 (3)	0.28088 (18)	−0.01547 (16)	0.0369 (7)
C6A	0.4707 (3)	0.16552 (18)	−0.02214 (17)	0.0397 (7)
C7A	0.4090 (3)	0.15632 (17)	0.06754 (16)	0.0351 (6)
C8A	0.4094 (2)	0.26675 (16)	0.16438 (15)	0.0280 (6)
C9A	0.4681 (2)	0.38401 (15)	0.17227 (14)	0.0247 (5)
C11A	0.4720 (2)	0.60721 (16)	0.32128 (15)	0.0273 (5)
C12A	0.4337 (2)	0.69302 (16)	0.41764 (15)	0.0281 (5)
C13A	0.4624 (2)	0.82503 (17)	0.45126 (15)	0.0309 (6)
S2C	0.13671 (7)	0.02349 (4)	0.35794 (4)	0.0359 (2)
O2C	0.16071 (19)	0.14384 (12)	0.35128 (11)	0.0422 (5)
C1C	−0.0974 (3)	−0.0384 (2)	0.3210 (2)	0.0547 (9)
C3C	0.2017 (4)	−0.0805 (2)	0.2321 (2)	0.0615 (9)
H2B	−0.06770	0.39570	0.78180	0.0350*
H4B	0.01890	0.77200	0.93490	0.0350*
H6B	0.16420	0.58030	0.62820	0.0330*
H11B	0.130 (3)	0.2799 (17)	0.4585 (17)	0.0580*
H1A	0.308 (3)	0.2298 (16)	0.2818 (16)	0.0370*
H2A	0.34380	0.44630	0.40820	0.0350*
H4A	0.57650	0.46790	0.08410	0.0360*
H5A	0.57740	0.28390	−0.07810	0.0440*
H6A	0.47050	0.09200	−0.08990	0.0480*
H7A	0.36810	0.07810	0.06340	0.0420*
H11A	0.52400	0.63630	0.27430	0.0330*
H12A	0.353 (3)	0.7300 (17)	0.5506 (16)	0.0560*
H13A	0.540 (3)	0.9407 (15)	0.4071 (19)	0.0630*
D11C	−0.14460	−0.04780	0.24570	0.0820*
D12C	−0.15770	0.01790	0.37790	0.0820*
D13C	−0.11950	−0.11940	0.31880	0.0820*
D31C	0.13170	−0.08140	0.16570	0.0920*
D32C	0.17950	−0.16400	0.22480	0.0920*
D33C	0.32990	−0.05370	0.23610	0.0920*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O11B	0.0554 (9)	0.0241 (7)	0.0344 (8)	0.0102 (6)	0.0154 (6)	0.0102 (6)
O12B	0.0661 (10)	0.0244 (8)	0.0504 (9)	0.0104 (7)	0.0179 (7)	0.0190 (7)
O31B	0.0418 (8)	0.0501 (9)	0.0519 (9)	0.0064 (7)	0.0145 (6)	0.0342 (7)
O32B	0.0582 (10)	0.0481 (10)	0.0336 (8)	0.0091 (7)	0.0151 (7)	0.0143 (7)
O51B	0.0814 (11)	0.0227 (8)	0.0397 (8)	0.0078 (7)	0.0175 (7)	0.0080 (6)
O52B	0.0587 (9)	0.0350 (8)	0.0480 (9)	0.0107 (7)	0.0234 (7)	0.0240 (7)
N3B	0.0309 (9)	0.0450 (11)	0.0361 (9)	0.0098 (7)	0.0075 (7)	0.0235 (8)
N5B	0.0404 (9)	0.0248 (9)	0.0323 (9)	0.0047 (7)	0.0051 (7)	0.0128 (7)
C1B	0.0256 (9)	0.0259 (10)	0.0301 (9)	0.0068 (7)	0.0024 (7)	0.0135 (8)
C2B	0.0256 (9)	0.0266 (10)	0.0362 (10)	0.0019 (7)	0.0006 (7)	0.0179 (8)
C3B	0.0240 (9)	0.0338 (10)	0.0274 (9)	0.0039 (7)	0.0024 (7)	0.0161 (8)
C4B	0.0288 (9)	0.0285 (10)	0.0254 (9)	0.0068 (7)	0.0013 (7)	0.0099 (7)
C5B	0.0279 (9)	0.0227 (9)	0.0292 (9)	0.0039 (7)	0.0012 (7)	0.0131 (7)
C6B	0.0266 (9)	0.0278 (10)	0.0280 (9)	0.0066 (7)	0.0036 (7)	0.0137 (7)
C11B	0.0314 (10)	0.0263 (10)	0.0352 (10)	0.0071 (7)	0.0032 (8)	0.0144 (8)
O12A	0.0537 (9)	0.0254 (7)	0.0322 (7)	0.0090 (6)	0.0146 (6)	0.0118 (6)
O13A	0.0594 (9)	0.0207 (7)	0.0456 (8)	0.0053 (6)	0.0244 (7)	0.0124 (6)
O14A	0.0424 (8)	0.0231 (7)	0.0390 (8)	0.0053 (6)	0.0160 (6)	0.0091 (6)
N1A	0.0373 (9)	0.0255 (9)	0.0350 (9)	0.0069 (7)	0.0112 (7)	0.0170 (7)
C2A	0.0317 (10)	0.0265 (10)	0.0295 (10)	0.0083 (7)	0.0075 (7)	0.0121 (8)
C3A	0.0245 (9)	0.0241 (9)	0.0271 (9)	0.0057 (7)	0.0036 (7)	0.0106 (7)
C4A	0.0287 (9)	0.0263 (10)	0.0353 (10)	0.0052 (7)	0.0091 (7)	0.0149 (8)
C5A	0.0392 (11)	0.0383 (12)	0.0359 (11)	0.0114 (9)	0.0176 (8)	0.0166 (9)
C6A	0.0452 (12)	0.0289 (11)	0.0378 (11)	0.0109 (9)	0.0148 (9)	0.0074 (8)
C7A	0.0388 (11)	0.0218 (10)	0.0410 (11)	0.0051 (8)	0.0094 (8)	0.0116 (8)
C8A	0.0263 (9)	0.0275 (10)	0.0315 (10)	0.0074 (7)	0.0062 (7)	0.0145 (8)
C9A	0.0206 (8)	0.0221 (9)	0.0302 (9)	0.0053 (7)	0.0036 (7)	0.0115 (7)
C11A	0.0249 (9)	0.0242 (9)	0.0316 (9)	0.0032 (7)	0.0051 (7)	0.0128 (7)
C12A	0.0272 (9)	0.0241 (9)	0.0312 (9)	0.0031 (7)	0.0041 (7)	0.0125 (8)
C13A	0.0265 (9)	0.0260 (10)	0.0353 (10)	0.0021 (7)	0.0064 (7)	0.0111 (8)
S2C	0.0396 (3)	0.0279 (3)	0.0398 (3)	0.0052 (2)	0.0107 (2)	0.0155 (2)
O2C	0.0567 (9)	0.0236 (7)	0.0450 (8)	0.0049 (6)	0.0255 (7)	0.0127 (6)
C1C	0.0390 (12)	0.0443 (14)	0.0970 (19)	0.0062 (10)	0.0194 (12)	0.0464 (14)
C3C	0.0669 (16)	0.0361 (14)	0.0623 (15)	0.0159 (11)	0.0213 (12)	0.0036 (11)

Geometric parameters (Å, º) top

S2C—C3C	1.770 (3)	C2B—H2B	0.9500
S2C—C1C	1.771 (2)	C4B—H4B	0.9500
S2C—O2C	1.5177 (17)	C6B—H6B	0.9500
O11B—C11B	1.320 (2)	C2A—C3A	1.382 (3)
O12B—C11B	1.209 (3)	C3A—C11A	1.439 (3)
O31B—N3B	1.228 (3)	C3A—C9A	1.447 (2)
O32B—N3B	1.225 (2)	C4A—C9A	1.405 (3)
O51B—N5B	1.225 (2)	C4A—C5A	1.380 (3)
O52B—N5B	1.224 (2)	C5A—C6A	1.402 (3)
O11B—H11B	0.88 (2)	C6A—C7A	1.381 (3)
O12A—C12A	1.371 (2)	C7A—C8A	1.394 (3)
O13A—C13A	1.316 (3)	C8A—C9A	1.411 (3)
O14A—C13A	1.238 (2)	C11A—C12A	1.343 (3)
O12A—H12A	0.88 (2)	C12A—C13A	1.460 (3)
O13A—H13A	0.90 (2)	C2A—H2A	0.9500
N3B—C3B	1.472 (2)	C4A—H4A	0.9500
N5B—C5B	1.472 (3)	C5A—H5A	0.9500
N1A—C8A	1.378 (2)	C6A—H6A	0.9500
N1A—C2A	1.362 (3)	C7A—H7A	0.9500
N1A—H1A	0.87 (2)	C11A—H11A	0.9500
C1B—C6B	1.388 (3)	C1C—D11C	0.9800
C1B—C2B	1.391 (2)	C1C—D12C	0.9800
C1B—C11B	1.501 (3)	C1C—D13C	0.9800
C2B—C3B	1.381 (3)	C3C—D31C	0.9800
C3B—C4B	1.382 (3)	C3C—D32C	0.9800
C4B—C5B	1.379 (2)	C3C—D33C	0.9800
C5B—C6B	1.389 (3)

O2C—S2C—C1C	106.34 (11)	C4A—C5A—C6A	121.28 (19)
O2C—S2C—C3C	103.33 (11)	C5A—C6A—C7A	121.5 (2)
C1C—S2C—C3C	99.20 (13)	C6A—C7A—C8A	117.1 (2)
C11B—O11B—H11B	109.6 (15)	N1A—C8A—C9A	107.34 (16)
C12A—O12A—H12A	106.7 (15)	N1A—C8A—C7A	130.1 (2)
C13A—O13A—H13A	110.2 (14)	C7A—C8A—C9A	122.53 (17)
O32B—N3B—C3B	118.17 (19)	C4A—C9A—C8A	118.90 (17)
O31B—N3B—C3B	117.62 (17)	C3A—C9A—C8A	107.02 (16)
O31B—N3B—O32B	124.21 (18)	C3A—C9A—C4A	134.08 (19)
O51B—N5B—C5B	117.86 (16)	C3A—C11A—C12A	126.73 (18)
O52B—N5B—C5B	118.81 (16)	O12A—C12A—C11A	121.18 (19)
O51B—N5B—O52B	123.33 (19)	C11A—C12A—C13A	124.01 (18)
C2A—N1A—C8A	109.74 (17)	O12A—C12A—C13A	114.81 (15)
C2A—N1A—H1A	123.5 (13)	O14A—C13A—C12A	120.60 (18)
C8A—N1A—H1A	126.7 (13)	O13A—C13A—C12A	116.25 (16)
C2B—C1B—C6B	120.32 (17)	O13A—C13A—O14A	123.2 (2)
C6B—C1B—C11B	122.31 (16)	C3A—C2A—H2A	125.00
C2B—C1B—C11B	117.38 (19)	N1A—C2A—H2A	125.00
C1B—C2B—C3B	118.9 (2)	C5A—C4A—H4A	121.00
N3B—C3B—C4B	118.50 (17)	C9A—C4A—H4A	121.00
N3B—C3B—C2B	118.71 (19)	C4A—C5A—H5A	119.00
C2B—C3B—C4B	122.79 (17)	C6A—C5A—H5A	119.00
C3B—C4B—C5B	116.62 (18)	C7A—C6A—H6A	119.00
C4B—C5B—C6B	123.1 (2)	C5A—C6A—H6A	119.00
N5B—C5B—C6B	119.51 (16)	C6A—C7A—H7A	121.00
N5B—C5B—C4B	117.36 (17)	C8A—C7A—H7A	121.00
C1B—C6B—C5B	118.28 (17)	C3A—C11A—H11A	117.00
O11B—C11B—O12B	124.40 (19)	C12A—C11A—H11A	117.00
O12B—C11B—C1B	122.64 (17)	S2C—C1C—D11C	109.00
O11B—C11B—C1B	112.96 (19)	S2C—C1C—D12C	109.00
C1B—C2B—H2B	121.00	S2C—C1C—D13C	110.00
C3B—C2B—H2B	121.00	D11C—C1C—D12C	109.00
C3B—C4B—H4B	122.00	D11C—C1C—D13C	109.00
C5B—C4B—H4B	122.00	D12C—C1C—D13C	110.00
C5B—C6B—H6B	121.00	S2C—C3C—D31C	109.00
C1B—C6B—H6B	121.00	S2C—C3C—D32C	109.00
N1A—C2A—C3A	109.91 (16)	S2C—C3C—D33C	109.00
C2A—C3A—C11A	128.34 (16)	D31C—C3C—D32C	109.00
C9A—C3A—C11A	125.53 (17)	D31C—C3C—D33C	109.00
C2A—C3A—C9A	105.98 (17)	D32C—C3C—D33C	109.00
C5A—C4A—C9A	118.7 (2)

O31B—N3B—C3B—C2B	−11.4 (2)	C4B—C5B—C6B—C1B	−0.6 (2)
O31B—N3B—C3B—C4B	169.03 (16)	N1A—C2A—C3A—C9A	−0.36 (19)
O32B—N3B—C3B—C2B	168.39 (17)	N1A—C2A—C3A—C11A	175.38 (16)
O32B—N3B—C3B—C4B	−11.2 (2)	C2A—C3A—C9A—C4A	−179.69 (18)
O51B—N5B—C5B—C4B	−5.6 (2)	C2A—C3A—C9A—C8A	0.95 (18)
O51B—N5B—C5B—C6B	174.61 (16)	C11A—C3A—C9A—C4A	4.4 (3)
O52B—N5B—C5B—C4B	173.68 (16)	C11A—C3A—C9A—C8A	−174.95 (15)
O52B—N5B—C5B—C6B	−6.2 (2)	C2A—C3A—C11A—C12A	−1.6 (3)
C2A—N1A—C8A—C9A	0.98 (19)	C9A—C3A—C11A—C12A	173.37 (17)
C8A—N1A—C2A—C3A	−0.4 (2)	C9A—C4A—C5A—C6A	−0.1 (3)
C2A—N1A—C8A—C7A	−177.76 (19)	C5A—C4A—C9A—C3A	−177.79 (19)
C6B—C1B—C2B—C3B	0.8 (2)	C5A—C4A—C9A—C8A	1.5 (2)
C2B—C1B—C11B—O11B	176.16 (15)	C4A—C5A—C6A—C7A	−1.3 (3)
C2B—C1B—C11B—O12B	−3.8 (2)	C5A—C6A—C7A—C8A	1.0 (3)
C6B—C1B—C11B—O11B	−3.9 (2)	C6A—C7A—C8A—N1A	179.11 (19)
C6B—C1B—C11B—O12B	176.13 (17)	C6A—C7A—C8A—C9A	0.5 (3)
C11B—C1B—C6B—C5B	−179.91 (15)	N1A—C8A—C9A—C3A	−1.18 (18)
C11B—C1B—C2B—C3B	−179.31 (15)	N1A—C8A—C9A—C4A	179.34 (15)
C2B—C1B—C6B—C5B	0.0 (2)	C7A—C8A—C9A—C3A	177.68 (17)
C1B—C2B—C3B—N3B	179.41 (15)	C7A—C8A—C9A—C4A	−1.8 (3)
C1B—C2B—C3B—C4B	−1.0 (3)	C3A—C11A—C12A—O12A	1.4 (3)
C2B—C3B—C4B—C5B	0.5 (2)	C3A—C11A—C12A—C13A	−178.19 (16)
N3B—C3B—C4B—C5B	−179.96 (15)	O12A—C12A—C13A—O13A	−177.22 (15)
C3B—C4B—C5B—N5B	−179.48 (15)	O12A—C12A—C13A—O14A	3.0 (2)
C3B—C4B—C5B—C6B	0.4 (2)	C11A—C12A—C13A—O13A	2.4 (2)
N5B—C5B—C6B—C1B	179.23 (15)	C11A—C12A—C13A—O14A	−177.43 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O2C	0.87 (2)	2.02 (2)	2.856 (2)	161 (2)
O11B—H11B···S2C	0.88 (2)	2.84 (2)	3.6757 (17)	160 (2)
O11B—H11B···O2C	0.88 (2)	1.72 (2)	2.591 (2)	174 (2)
O12A—H12A···O14A	0.88 (2)	2.15 (2)	2.672 (2)	118 (2)
O12A—H12A···O52B	0.88 (2)	2.20 (2)	2.951 (2)	144 (2)
O13A—H13A···O14Aⁱ	0.90 (2)	1.75 (2)	2.644 (2)	178 (2)
C2A—H2A···O12A	0.95	2.34	2.876 (2)	115
C11A—H11A···O13A	0.95	2.45	2.794 (3)	101
C1C—D12C···O14Aⁱⁱ	0.98	2.56	3.472 (3)	155
C1C—D13C···O12Bⁱⁱⁱ	0.98	2.52	3.372 (3)	145

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

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
O11A—H11A···O12Aⁱ	0.91 (3)	1.78 (3)	2.678 (3)	175 (3)
O11B—H11B···O11D	0.94 (3)	1.74 (3)	2.673 (3)	175 (3)
O11C—H11C···O12Cⁱⁱ	0.91 (3)	1.73 (3)	2.640 (3)	177 (2)
O12D—H12D···O12B	0.90 (3)	1.71 (3)	2.610 (3)	176 (2)
N4B—H41B···O31C	0.86 (3)	2.58 (3)	3.350 (4)	150 (3)
N4B—H42B···O52Dⁱⁱⁱ	0.85 (2)	2.44 (3)	3.210 (4)	151 (3)
O2A—H2A···O12A	0.84	1.89	2.625 (3)	145
O2B—H2B···O12B	0.84	1.85	2.587 (3)	145
O1W—H11W···O2B	0.90	2.05	2.952 (6)	179
O1W—H12W···O32C^iv	0.93	2.08	3.005 (5)	179
C3B—H3B···O31C	0.95	2.58	3.382 (3)	142
C4D—H4D···O32C^v	0.95	2.49	3.425 (3)	170

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

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O2C	0.87 (2)	2.02 (2)	2.856 (2)	161 (2)
O11B—H11B···S2C	0.88 (2)	2.84 (2)	3.6757 (17)	159.5 (19)
O11B—H11B···O2C	0.88 (2)	1.72 (2)	2.591 (2)	174 (2)
O12A—H12A···O14A	0.88 (2)	2.15 (2)	2.672 (2)	117.7 (17)
O12A—H12A···O52B	0.88 (2)	2.20 (2)	2.951 (2)	144 (2)
O13A—H13A···O14Aⁱ	0.90 (2)	1.75 (2)	2.644 (2)	178 (2)
C1C—D12C···O14Aⁱⁱ	0.98	2.56	3.472 (3)	155
C1C—D13C···O12Bⁱⁱⁱ	0.98	2.52	3.372 (3)	145

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

Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₇H₄N₂O₆·C₇H₇NO₃·0.2H₂O	C₇H₄N₂O₆·C₁₁H₉NO₃·C₂D₆OS
M_r	368.86	499.49
Crystal system, space group	Triclinic, P1	Triclinic, P1
Temperature (K)	200	200
a, b, c (Å)	7.0717 (5), 7.5974 (4), 28.7175 (19)	7.6488 (6), 12.3552 (10), 13.3768 (10)
α, β, γ (°)	87.926 (5), 86.498 (6), 87.584 (5)	116.833 (8), 96.274 (6), 97.626 (7)
V (Å³)	1537.77 (17)	1097.40 (18)
Z	4	2
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.14	0.21
Crystal size (mm)	0.35 × 0.35 × 0.30	0.45 × 0.40 × 0.32

Data collection
Diffractometer	Oxford Diffraction Gemini-S CCD detector diffractometer	Oxford Diffraction Gemini-S CCD detector diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013)	Multi-scan (CrysAlis PRO; Agilent, 2013)
T_min, T_max	0.966, 0.990	0.94, 0.98
No. of measured, independent and observed [I > 2σ(I)] reflections	10302, 6044, 4158	7457, 4310, 3490
R_int	0.027	0.023
(sin θ/λ)_max (Å⁻¹)	0.617	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.149, 1.01	0.040, 0.097, 1.02
No. of reflections	6044	4310
No. of parameters	502	319
No. of restraints	8	4
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
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.28	0.26, −0.25

Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012), PLATON (Spek, 2009).

Acknowledgements

The authors thank the Faculty of Science and Engineering, Queensland University of Technology for financial support.

References

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Volume 70| Part 10| October 2014| Pages 183-187

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures and hydrogen bonding in the co-crystalline adducts of 3,5-di­nitro­benzoic acid with 4-amino­salicylic acid and 2-hy­dr­oxy-3-(1H-indol-3-yl)propenoic acid

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Synthesis and crystallization

5. Refinement details

Supporting information

Acknowledgements

References

research communications

Crystal structures and hydrogen bonding in the co-crystalline adducts of 3,5-dinitrobenzoic acid with 4-aminosalicylic acid and 2-hydroxy-3-(1H-indol-3-yl)propenoic acid

3. Supramolecular features