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2-Ammonio-5-chloro-4-methyl­benzene­sulfonate, C7H8ClNO3S, (Ia), is an inter­mediate in the synthesis of lake red azo pigments. The present structure determination from single-crystal data confirms the results of a previous powder diffraction determination [Bekö, Thoms, Brüning, Alig, van de Streek, Lakatos, Glaubitz & Schmidt (2010). Z. Kristallogr. 225, 382-387]. The zwitterionic tautomeric form is confirmed. During a polymorph screening, two additional pseudopolymorphs were obtained, viz. 2-ammonio-5-chloro-4-methyl­ben­zene­sulfonate 1-methyl-2-pyrrolidone monosolvate, C7H8ClNO3S·C5H9NO, (Ib), and 2-ammonio-5-chloro-4-methyl­benzene­sulfonate dimethyl sulfoxide monosolvate, C7H8ClNO3S·C2H6OS, (Ic). The mol­ecules of (Ib) have crystallo­graphic m symmetry. The 1-methyl-2-pyrrolidone solvent mol­ecule has an envelope conformation and is disordered around the mirror plane. The structure shows hydrogen-bonded ladders of mol­ecules [graph-set notation C22(6)R22(12)] in the [010] direction. The benzene groups of adjacent ladders are also stacked in this direction. A different type of hydrogen-bonded ladder [graph-set notation C(6)R22(4)R44(12)] occurs in (Ic). In (Ia), (Ib) and (Ic), the mol­ecules correspond to the zwitterionic tautomer. The structure of the cocrystal of 4-amino­benzene­sulfonic acid with 1,4-bis­(4,5-dihydro­imidazol-2-yl)benzene [Shang, Ren, Wang, Lu & Yang (2009). Acta Cryst. E65, o2221-o2222] is corrected; it actually contains 4-amino­benzene­sulfonate anions and 2,2'-(1,4-phenyl­ene)di(dihydroimidazolium) dications, i.e. 2,2'-(1,4-phenyl­ene)di(4,5-dihydro­imidazolium) bis­(4-amino­benzene­sulfonate) dihydrate, C12H16N42+·2C6H6NO3S-·2H2O. Hence, all known structures of amino­benzene­sulfonic acid complexes contain ionic or zwitterionic mol­ecules; there is no known structure with a neutral amino­benzene­sulfonic acid mol­ecule.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111054205/sk3426sup1.cif
Contains datablocks Ia, Ib, Ic, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111054205/sk3426Iasup2.hkl
Contains datablock Ia

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111054205/sk3426Ibsup3.hkl
Contains datablock Ib

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111054205/sk3426Icsup4.hkl
Contains datablock Ic

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111054205/sk3426IIsup5.hkl
Contains datablock II

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111054205/sk3426Iasup6.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111054205/sk3426Ibsup7.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111054205/sk3426Icsup8.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111054205/sk3426IIsup9.cml
Supplementary material

CCDC references: 867012; 867013; 867014; 867015

Comment top

2-Ammonio-5-chloro-4-methylbenzenesulfonate, (Ia), also called CLT acid (from chloro-amino-toluenesulfonic acid), is industrially produced at the scale of several tens of thousands of tonnes per year. It is used as an intermediate in the synthesis of lake red azo pigments (e.g. Pigment Red 52:1, 52:2, 53, 53:1, 53:2, 53:3) for newspapers and journals, such as e.g. Acta Crystallographica Section C. It can exist in two possible tautomers: as a non-zwitterion (2-amino-5-chloro-4-methylbenzenesulfonic acid), having an –NH2 and an –SO3H group, and as a zwitterion (2-ammonio-5-chloro-4-methylbenzenesulfonate) with –NH3+ and –SO3- groups. A crystal structure of the compound was determined by Bekö et al. (2010) from powder diffraction data, as no suitable single crystals were available at that time. The powder data clearly showed that the compound exists as the zwitterionic tautomer.

Polymorph screening of (Ia) was performed by crystallizing the compound from a variety of different solvents and using various methods of crystallization. The polymorph screening resulted in single crystals suitable for X-ray diffraction of the solvent-free compound (Ia), its 1-methyl-2-pyrrolidone (NMP) monosolvate, (Ib), and its dimethyl sulfoxide (DMSO) monosolvate, (Ic). Other polymorphs, pseudopolymorphs or hydrates could not be found.

The molecular structure of (Ia) is shown in Fig. 1. The result of the previous powder diffraction determination (Bekö et al., 2010) and the tautomeric form are confirmed, but the hydrogen-bonding system (Table 1) is more accurately derived from the present single-crystal determination. The molecules are connected by N—H···O hydrogen bonds to form double layers parallel to (010). A weak intermolecular C—H···O contact also adds to the stabilization within the layer. Adjacent double layers are connected by a very weak intermolecular Cmethyl—H···Cl contact with a H···Cl distance of 3.02 Å. For a further description of the structure, see Bekö et al. (2010).

Compound (Ib) crystallizes in the monoclinic space group P21/m with the 2-ammonio-5-chloro-4-methylbenzenesulfonate molecule positioned on a crystallographic mirror plane. The NMP solvent molecule is disordered about the crystallographic mirror plane and has a C10-envelope conformation. The molecular structure and numbering scheme are shown in Fig. 2 and the crystal packing in Fig. 3. The 2-amino-5-chloro-4-methyl-benzenesulfonate molecules are connected by two intermolecular N—H···O hydrogen bonds between the –NH3+ groups and the –SO3- groups (Table 2) to form a ladder structure in the [010] direction (Fig. 4). In graph-set notation (Etter et al., 1990; Bernstein et al., 1995), the hydrogen-bond pattern of the ladder structure is C22(6)R22(12). The third H atom of the –NH3+ group forms an N—H···O hydrogen bond with the NMP molecule. The benzene groups of adjacent ladders form stacks along [010]. The interplanar distance in the stack is b/2 = 3.473 Å, which is a suitable distance for ππ contacts between the benzene groups. Hence, the ladders, running in the b-axis direction, are locked together with neighbouring ladders along the a-axis direction, resulting in a two-dimensional framework parallel to the (001) plane.

The DMSO solvate, (Ic), crystallizes in the triclinic space group P1. The asymmetric unit contains one 2-ammonio-5-chloro-4-methylbenzenesulfonate molecule and one DMSO molecule. The molecular structure and numbering scheme are shown in Fig. 5 and the crystal packing in Fig. 6. The molecules are arranged by hydrogen bonding (Table 3) to form a ladder structure parallel to the a-axis direction. A detailed view of the ladder structure is shown in Fig. 7. Each 2-ammonio-5-chloro-4-methylbenzenesulfonate molecule is connected by four N—H···O hydrogen bonds to three neighbouring molecules. The N1—H1B bond is bifurcated and has longer H···O contact distances than the remaining hydrogen bonds. In terms of graph-set analysis, the hydrogen-bond pattern of the ladder structure is C(6)R44(12). Here, C(6) represents the repetition of the structure along the a-axis direction by the N1—H1C···O1ii hydrogen bond [symmetry code: (ii) x + 1, y, z], while the ring structure results from the combination of N1—H1C···O1ii and N1—H1B···O2 hydrogen bonds and an inversion centre. The bifurcated N1—H1B bond, which is involved in both an intra- and an intermolecular hydrogen bond, results in an additional four-membered ring [graph-set notation R22(4)]. The DMSO solvent molecule is attached to the ladder by an additional N—H···O hydrogen bond and by a very weak intermolecular DMSO–sulfonate C—H···O interaction (Table 3). Adjacent ladders are connected by a weak intermolecular DMSO–DMSO C—H···O interaction. The ladders form a hexagonal rod packing.

In all three structures, the main molecule exists as a 2-ammonio-benzenesulfonate zwitterion rather than as 2-aminobenzenesulfonic acid. A search of the Cambridge Structural Database (Version?; Allen, 2002) for compounds containing 1,2-, 1,3- and 1,4-diaminobenzenesulfonic acid revealed 29 entries with a zwitterionic molecule. Only the structure of Shang et al. (2009) is reported to contain a neutral molecule. Surprisingly, the three S—O bond distances in that determination are almost equal, which is rather suspicious for a sulfonic acid. Therefore, we decided to redetermine that structure from the published reflection data. The results are presented here as structure (II). As expected, the assignment of the sulfonic acid H atom turned out to be incorrect. Also, one of the H-atom positions on the water molecule had to be modified. The correct structure contains 4-aminobenzenesulfonate anions and 1,4-bis(4,5-dihydroimidazol-2-yl)benzene dications, rather than neutral molecules. Thus, all reported crystal structures of aminobenzenesulfonic acids contain zwitterionic molecules or ions. There is no structure with a neutral aminobenzenesulfonic acid molecule. The corrected hydrogen bonds of structure (II) are given in Table 4. A view of the structure is shown in Fig. 8. For a discussion of the structure, see Shang et al. (2009).

In the structures reported here, all H atoms of the ammonio groups are donors of N—H···O hydrogen bonds. In (Ia), which does not contain solvent molecules, all three H atoms are connected to sulfonate O atoms of neighbouring molecules, resulting in a two-dimensional framework. In both (Ib) and (Ic), one N—H bond donates a hydrogen bond to a solvent O atom. Thus, only two H atoms are left for hydrogen-bond formation with sulfonate O atoms. In both cases, this results in ladder-type structures, but they are rather different: in (Ib), each molecule in the ladder is connected to only two neighbouring molecules, resulting in R22(12) rings, while in (Ic), each molecule is connected to three neighbouring molecules, resulting in R22(4) and R44(12) rings.

Related literature top

For related literature, see: Allen (2002); Bekö et al. (2010); Bernstein et al. (1995); Etter et al. (1990); Shang et al. (2009).

Experimental top

The polymorph screening of (Ia) was carried out using commercially available 2-ammonio-5-chloro-4-methylbenzenesulfonate, obtained from abcr GmbH and Co. KG, Germany (purity >98%). For purification, the starting material was recrystallized twice from boiling water. Compound (Ia) was found to be soluble at room temperature in quinoline, morpholine, 2-picoline, N,N'-dimethylformamide, N,N'-dimethylacetamide, 1-methyl-2-pyrrolidone (NMP) and dimethyl sulfoxide (DMSO). Subsequently, different methods of crystallization were employed, including: (i) slurry experiments by suspending (Ia) in different solvents at room temperature; (ii) evaporation crystallization at room temperature and at 353 K; (iii) slow or rapid antisolvent crystallization by overlaying a solution of (Ia) with an antisolvent; (iv) heating under reflux with subsequent slow or fast cooling; (v) treatment of a solution or a suspension of (Ia) in an ultrasonic bath at room temperature; (vi) slow or rapid vapour diffusion experiments by diffusion of an antisolvent into a solution of (Ia) via the gas phase. A multitude of different organic solvents were used as antisolvents, e.g. ketones, ethers, esters, alcohols, benzene and derivatives (e.g. toluene, picolines and chlorobenzenes) and alkanes, and water. All solids thus obtained were analysed using X-ray powder diffraction data recorded under ambient conditions in transmission mode on a Stoe Stadi-P diffractometer with a Ge(111) monochromator and a linear position-sensitive detector using CuKα1 radiation (λ = 1.5406 Å).

IR spectra were measured on an FTIR-8300 device (Shimadzu). The samples were prepared as KBr pellets, with 300 mg KBr to 2 mg sample. 1H NMR spectra were measured on a Bruker Avance 300 device at 300 MHz in tubes filled with d6-DMSO and about 5 mg of substance. Elemental analyses (CHNS) were carried out on an Elementar (vario MICRO cube) elemental analyser. About 1 to 4 mg of each sample was placed in a tin vessel and measured at 1423 K under a helium atmosphere with addition of oxygen during the measurement.

Colourless single crystals of (Ia) were obtained by dissolving the purified starting material (400 mg) in 1-methyl-2-pyrrolidone (30 ml) under reflux and then filtering the hot solution. The solution was left for evaporation crystallization at room temperature for 54 weeks. Upon reduction of the supernatant to 5 ml, colourless single crystals of (Ia) had formed. The precipitate was isolated by filtration, washed with acetone and dried at room temperature. Spectroscopic analysis: IR (KBr, ν, cm-1): 3091 (m), 3039 (m), 2854 (m), 2613 (m), 1757 (w), 1560 (s), 1477 (m), 1375 (m), 1230 (s), 1195 (s), 1116 (s), 1043 (s), 739 (m), 719 (m), 636 (s); 1H NMR (300 MHz, d6-DMSO, δ, p.p.m.): 7.57 (s, 1H, Ar—H), 7.05 (s, 1H, Ar—H), 6.9–6.0 [s (broad), 3H, Ar—NH3+], 2.29 (s, 3H, Ar—CH3); elemental analysis, calculated for C7H8ClNO3S (%): C 37.93, H 3.64, N 6.32, S 14.47; found: C 37.67, H 3.58, N 6.16, S 14.68.

Suitable single crystals of (Ib) were obtained by treatment of the purified starting material (20 mg) with 1-methyl-2-pyrrolidone (3 ml) in an ultrasonic bath at room temperature for 30 min. After 2 d, colourless plate-shaped crystals of (Ib) were obtained. The precipitate was isolated by filtration and dried for one day at room temperature. Spectroscopic analysis: IR (KBr, ν, cm-1): 3101 (m), 3040 (m), 3017 (m), 2961 (m), 2926 (m), 2855 (m), 2833 (m), 2613 (s), 1773 (m), 1757 (m), 1734 (m), 1684 (s), 1653 (s), 1633 (m), 1591 (m), 1576 (s), 1560 (s), 1541 (s), 1522 (s), 1508 (s), 1477 (s), 1437 (m), 1375 (s), 1288 (m), 1230 (s), 1196 (s), 1165 (s), 1117 (s), 1080 (m), 1043 (s), 739 (s), 719 (s), 636 (s), 567 (s); 1H NMR (300 MHz, d6-DMSO, δ, p.p.m.): 7.57 (s, 1H, Ar—H), 7.04 (s, 1H, Ar—H), 5.00–3.50 [s (broad), 3H, Ar—NH3+], 3.32–3.27 [m, 2H, CH2 (NMP)], 2.69 [s, 3H, CH3 (NMP)], 2.28 (s, 3H, Ar—CH3), 2.19–2.15 [m, 2H, CH2 (NMP)], 1.95–1.84 [m, 2H, CH2 (NMP)]; elemental analysis, calculated for C7H8ClNO3S.C5H9NO (%): C 44.93, H 5.34, N 8.73, S 10.00; found: C 44.72, H 5.31, N 8.62, S 10.20.

Suitable single crystals of (Ic) were obtained by treatment of the purified starting material (500 mg) with dimethyl sulfoxide (3 ml) in an ultrasonic bath at room temperature for 30 min. After 3 d, colourless block-shaped crystals of (Ic) were obtained. The precipitate was isolated by filtration and dried for 1 d at room temperature. Spectroscopic analysis: IR (KBr, ν, cm-1): 3121 (m), 3086 (m), 3063 (m), 3007 (m), 2920 (m), 2853 (m), 2627 (m), 1593 (m), 1558 (s), 1549 (s), 1506 (s), 1373 (s), 1308 (m), 1290 (m), 1238 (s), 1204 (s), 1165 (s), 1117 (s), 1078 (s), 1038 (s), 1003 (s), 735(s), 721 (s), 710 (m), 637 (s), 563 (s); 1H NMR (300 MHz, d6-DMSO, δ, p.p.m.): 7.56 (s, 1H, Ar—H), 7.03 (s, 1H, Ar—H), 5.50–3.50 [s (broad), 3H, Ar—NH3+], 2.54 (s, 6H, DMSO), 2.28 (s, 3H, Ar—CH3); elemental analysis, calculated for C7H8ClNO3S.C2H6OS (%): C 36.06, H 4.71, N 4.67, S 21.39; found: C 35.90, H 4.72, N 4.52, S 21.56.

Refinement top

Compound (Ia) was refined in the nonstandard space group Ia, rather than in Cc, in order to avoid a very large monoclinic angle of β = 129.887 (1)°. N- and O-bound H atoms were taken from difference Fourier syntheses and refined. C-bound H atoms were positioned geometrically and treated as riding, with planar C—H = 0.95 Å, methyl C—H = 0.98 Å and secondary C—H = 0.99 Å, and with Uiso(H) = 1.2Ueq(Cnon-methyl) or 1.5Ueq(Cmethyl) for (Ia), (Ib) and (Ic), and with planar C—H = 0.93 Å and secondary C—H = 0.97 Å, and with Uiso(H) = 1.2Ueq(C) for (II). The H atoms on atoms C7 and C12 of (Ib) were taken from a difference synthesis and refined. The pyrrolidone ring atoms C9, C10 and C11 of (Ib) were found to be displaced from the mirror plane and so they were refined as split atoms with occupancy factors of 0.5.

Computing details top

Data collection: SMART (Siemens, 1995) for (Ia), (Ib), (Ic); SMART (Bruker, 1998) for (II). Cell refinement: SAINT (Siemens, 1995) for (Ia); SMART (Siemens, 1995) for (Ib), (Ic); SAINT (Bruker, 1998) for (II). Data reduction: SAINT (Siemens, 1995) for (Ia), (Ib), (Ic); SAINT (Bruker, 1998) for (II). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (Ia), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The molecular structure of (Ib), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. The second possible position of the disordered 1-methyl-2-pyrrolidone molecule has been omitted. Dotted lines indicate hydrogen bonds. [Please check added text]
[Figure 3] Fig. 3. The crystal packing of (Ib), viewed down [010]. Hydrogen bonds are shown as dotted lines and C-bound H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 4] Fig. 4. A section of the structure of (Ib), showing the hydrogen-bonded ladders and the stacking of the benzene groups; the view direction is [001]. Hydrogen bonds are shown as dotted lines and C-bound H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x, -y + 1/2, z; (ii) -x + 1, y + 1/2, -z + 1.]
[Figure 5] Fig. 5. The molecular structure of (Ic), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Dotted lines indicate hydrogen bonds. [Please check added text]
[Figure 6] Fig. 6. The crystal packing of (Ic), viewed down [100]. Hydrogen bonds are shown as dotted lines and C-bound H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 7] Fig. 7. A view of the ladder structure of (Ic). Hydrogen bonds are shown as dotted lines and C-bound H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x + 1, y, z; (ii) -x + 1, -y + 1, -z + 1; (iii) x - 1, y, z; (iv) -x + 2, -y + 1, -z + 1.]
[Figure 8] Fig. 8. The molecular structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Unlabelled atoms are related to labelled atoms by an inversion centre at the mid-point of the central six-membered ring (Symmetry code?).
(Ia) 2-ammonio-5-chloro-4-methylbenzenesulfonate top
Crystal data top
C7H8ClNO3SF(000) = 456
Mr = 221.65Dx = 1.683 Mg m3
Monoclinic, IaMo Kα radiation, λ = 0.71073 Å
Hall symbol: I -2yaCell parameters from 4137 reflections
a = 4.9308 (3) Åθ = 3–26°
b = 32.364 (2) ŵ = 0.65 mm1
c = 5.4922 (4) ÅT = 173 K
β = 93.654 (1)°Plate, colourless
V = 874.68 (10) Å30.40 × 0.20 × 0.06 mm
Z = 4
Data collection top
Siemens SMART 1K CCD area-detector
diffractometer
2101 independent reflections
Radiation source: normal-focus sealed tube1934 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
ω scansθmax = 28.9°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
h = 66
Tmin = 0.693, Tmax = 0.962k = 4240
5429 measured reflectionsl = 77
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)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.093 w = 1/[σ2(Fo2) + (0.055P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.002
2101 reflectionsΔρmax = 0.68 e Å3
131 parametersΔρmin = 0.51 e Å3
2 restraintsAbsolute structure: Flack (1983), with 986 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.04 (8)
Crystal data top
C7H8ClNO3SV = 874.68 (10) Å3
Mr = 221.65Z = 4
Monoclinic, IaMo Kα radiation
a = 4.9308 (3) ŵ = 0.65 mm1
b = 32.364 (2) ÅT = 173 K
c = 5.4922 (4) Å0.40 × 0.20 × 0.06 mm
β = 93.654 (1)°
Data collection top
Siemens SMART 1K CCD area-detector
diffractometer
2101 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
1934 reflections with I > 2σ(I)
Tmin = 0.693, Tmax = 0.962Rint = 0.038
5429 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.093Δρmax = 0.68 e Å3
S = 1.05Δρmin = 0.51 e Å3
2101 reflectionsAbsolute structure: Flack (1983), with 986 Friedel pairs
131 parametersAbsolute structure parameter: 0.04 (8)
2 restraints
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.72511 (17)0.54001 (2)0.53803 (15)0.0311 (2)
S10.58477 (13)0.697987 (19)0.82240 (13)0.01330 (16)
O10.7370 (4)0.67847 (6)1.0255 (4)0.0194 (4)
O20.3309 (4)0.71674 (6)0.8873 (4)0.0177 (4)
O30.7459 (4)0.72534 (6)0.6776 (4)0.0180 (4)
N10.1513 (6)0.70089 (8)0.3815 (5)0.0145 (5)
H1A0.035 (8)0.7069 (11)0.498 (8)0.027 (9)*
H1B0.045 (8)0.7007 (10)0.257 (8)0.019 (10)*
H1C0.261 (7)0.7241 (11)0.386 (6)0.022 (9)*
C10.4852 (6)0.65653 (8)0.6208 (5)0.0149 (5)
C20.2932 (6)0.66165 (9)0.4260 (5)0.0159 (6)
C30.2335 (6)0.62892 (8)0.2666 (5)0.0182 (6)
H3A0.10010.63270.13610.022*
C40.3623 (6)0.59102 (9)0.2923 (5)0.0213 (6)
C50.5519 (6)0.58663 (9)0.4883 (6)0.0195 (6)
C60.6147 (6)0.61883 (9)0.6510 (5)0.0190 (6)
H6A0.74650.61480.78270.023*
C70.2963 (7)0.55652 (10)0.1142 (6)0.0288 (7)
H7A0.46390.54670.04650.043*
H7B0.17110.56670.01820.043*
H7C0.21100.53370.19840.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0370 (4)0.0216 (4)0.0341 (5)0.0097 (4)0.0032 (3)0.0039 (3)
S10.0114 (3)0.0190 (3)0.0097 (3)0.0002 (3)0.0024 (2)0.0006 (3)
O10.0194 (10)0.0245 (10)0.0138 (9)0.0010 (9)0.0018 (7)0.0004 (8)
O20.0129 (9)0.0242 (10)0.0165 (10)0.0013 (8)0.0055 (7)0.0032 (8)
O30.0168 (10)0.0228 (10)0.0155 (10)0.0010 (8)0.0097 (8)0.0018 (8)
N10.0148 (11)0.0201 (13)0.0087 (12)0.0002 (10)0.0009 (9)0.0012 (9)
C10.0162 (13)0.0189 (14)0.0099 (13)0.0012 (11)0.0035 (10)0.0030 (11)
C20.0149 (13)0.0198 (14)0.0139 (14)0.0013 (11)0.0071 (10)0.0023 (11)
C30.0210 (15)0.0220 (14)0.0116 (13)0.0026 (12)0.0023 (11)0.0012 (10)
C40.0214 (14)0.0278 (16)0.0155 (14)0.0052 (12)0.0067 (12)0.0027 (11)
C50.0208 (14)0.0193 (14)0.0191 (14)0.0057 (11)0.0078 (12)0.0012 (11)
C60.0168 (14)0.0231 (14)0.0170 (14)0.0000 (12)0.0001 (11)0.0002 (11)
C70.037 (2)0.0242 (16)0.0250 (18)0.0003 (14)0.0002 (15)0.0068 (13)
Geometric parameters (Å, º) top
Cl1—C51.747 (3)C2—C31.394 (4)
S1—O11.449 (2)C3—C41.384 (4)
S1—O21.456 (2)C3—H3A0.9500
S1—O31.4587 (19)C4—C51.388 (4)
S1—C11.788 (3)C4—C71.506 (4)
N1—C21.463 (4)C5—C61.394 (4)
N1—H1A0.91 (4)C6—H6A0.9500
N1—H1B0.83 (4)C7—H7A0.9800
N1—H1C0.92 (4)C7—H7B0.9800
C1—C61.382 (4)C7—H7C0.9800
C1—C21.393 (4)
O1—S1—O2113.87 (12)C4—C3—C2122.2 (3)
O1—S1—O3114.25 (12)C4—C3—H3A118.9
O2—S1—O3112.78 (12)C2—C3—H3A118.9
O1—S1—C1104.93 (13)C3—C4—C5116.8 (3)
O2—S1—C1104.95 (13)C3—C4—C7120.8 (3)
O3—S1—C1104.80 (12)C5—C4—C7122.3 (3)
C2—N1—H1A113 (2)C4—C5—C6122.1 (3)
C2—N1—H1B113 (2)C4—C5—Cl1120.6 (2)
H1A—N1—H1B101 (4)C6—C5—Cl1117.3 (2)
C2—N1—H1C115 (2)C1—C6—C5120.1 (3)
H1A—N1—H1C102 (3)C1—C6—H6A120.0
H1B—N1—H1C111 (3)C5—C6—H6A120.0
C6—C1—C2118.9 (2)C4—C7—H7A109.5
C6—C1—S1118.8 (2)C4—C7—H7B109.5
C2—C1—S1122.2 (2)H7A—C7—H7B109.5
C1—C2—C3119.9 (3)C4—C7—H7C109.5
C1—C2—N1121.8 (3)H7A—C7—H7C109.5
C3—C2—N1118.4 (3)H7B—C7—H7C109.5
O1—S1—C1—C616.0 (3)N1—C2—C3—C4178.6 (3)
O2—S1—C1—C6136.3 (2)C2—C3—C4—C51.2 (4)
O3—S1—C1—C6104.7 (2)C2—C3—C4—C7179.0 (3)
O1—S1—C1—C2167.8 (2)C3—C4—C5—C60.9 (4)
O2—S1—C1—C247.5 (2)C7—C4—C5—C6179.2 (3)
O3—S1—C1—C271.5 (2)C3—C4—C5—Cl1179.8 (2)
C6—C1—C2—C30.4 (4)C7—C4—C5—Cl10.1 (4)
S1—C1—C2—C3176.6 (2)C2—C1—C6—C50.2 (4)
C6—C1—C2—N1179.2 (3)S1—C1—C6—C5176.5 (2)
S1—C1—C2—N13.0 (4)C4—C5—C6—C10.4 (4)
C1—C2—C3—C41.0 (4)Cl1—C5—C6—C1179.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3i0.91 (4)1.88 (4)2.772 (4)166 (4)
N1—H1B···O1ii0.84 (4)2.05 (4)2.831 (4)156 (3)
N1—H1C···O2iii0.93 (4)1.95 (4)2.809 (3)155 (3)
C3—H3A···O1ii0.952.373.148 (3)138
C7—H7C···Cl1iv0.983.023.925 (3)154
Symmetry codes: (i) x1, y, z; (ii) x1, y, z1; (iii) x, y+3/2, z1/2; (iv) x1/2, y+1, z.
(Ib) 2-ammonio-5-chloro-4-methylbenzenesulfonate 1-methyl-2-pyrrolidone monosolvate top
Crystal data top
C7H8ClNO3S·C5H9NOF(000) = 336
Mr = 320.79Dx = 1.465 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 196 reflections
a = 9.1917 (17) Åθ = 3–23°
b = 6.9457 (11) ŵ = 0.42 mm1
c = 11.8265 (13) ÅT = 165 K
β = 105.538 (7)°Plate, colourless
V = 727.44 (19) Å30.40 × 0.36 × 0.10 mm
Z = 2
Data collection top
Siemens SMART 1K CCD area-detector
diffractometer
2552 independent reflections
Radiation source: normal-focus sealed tube2131 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ω scansθmax = 31.9°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
h = 1313
Tmin = 0.889, Tmax = 0.959k = 1010
12236 measured reflectionsl = 1717
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)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.101 w = 1/[σ2(Fo2) + (0.05P)2 + 0.4P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
2552 reflectionsΔρmax = 0.56 e Å3
139 parametersΔρmin = 0.57 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.011 (3)
Crystal data top
C7H8ClNO3S·C5H9NOV = 727.44 (19) Å3
Mr = 320.79Z = 2
Monoclinic, P21/mMo Kα radiation
a = 9.1917 (17) ŵ = 0.42 mm1
b = 6.9457 (11) ÅT = 165 K
c = 11.8265 (13) Å0.40 × 0.36 × 0.10 mm
β = 105.538 (7)°
Data collection top
Siemens SMART 1K CCD area-detector
diffractometer
2552 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
2131 reflections with I > 2σ(I)
Tmin = 0.889, Tmax = 0.959Rint = 0.028
12236 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.101H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.56 e Å3
2552 reflectionsΔρmin = 0.57 e Å3
139 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cl10.24641 (5)0.25000.43223 (4)0.02590 (13)
S10.30567 (5)0.25000.34505 (4)0.01966 (12)
O10.20108 (17)0.25000.22981 (12)0.0361 (4)
O20.39672 (12)0.07667 (17)0.37237 (10)0.0331 (3)
O30.46344 (18)0.25000.85413 (13)0.0363 (4)
N10.42404 (18)0.25000.61528 (14)0.0209 (3)
N20.5996 (2)0.25001.04493 (15)0.0389 (5)
C10.19356 (19)0.25000.44728 (15)0.0184 (3)
C20.25958 (19)0.25000.56809 (15)0.0181 (3)
C30.1721 (2)0.25000.64635 (16)0.0203 (3)
H3A0.21990.25000.72820.024*
C40.0141 (2)0.25000.60749 (16)0.0210 (3)
C50.0503 (2)0.25000.48688 (17)0.0209 (3)
C60.03673 (19)0.25000.40712 (16)0.0205 (3)
H6A0.01090.25000.32520.025*
C70.0774 (2)0.25000.69568 (19)0.0275 (4)
C80.5852 (2)0.25000.92992 (17)0.0311 (5)
C90.7378 (3)0.2171 (5)0.9076 (2)0.0326 (7)*0.50
H9A0.77430.33580.87790.039*0.50
H9B0.73230.11280.84950.039*0.50
C100.8414 (4)0.1605 (9)1.0266 (4)0.0681 (15)0.50
H10A0.86320.02071.02930.082*0.50
H10B0.93800.23191.04250.082*0.50
C110.7555 (3)0.2134 (5)1.1153 (3)0.0381 (8)*0.50
H11A0.75840.10641.17120.046*0.50
H11B0.79920.32981.15990.046*0.50
C120.4766 (4)0.25001.0993 (2)0.0428 (6)
H1A0.470 (2)0.152 (3)0.5967 (17)0.040 (5)*
H1B0.449 (3)0.25000.691 (3)0.034 (7)*
H7A0.013 (4)0.25000.770 (3)0.055 (9)*
H7B0.143 (3)0.143 (4)0.686 (2)0.072 (8)*
H12A0.386 (4)0.25001.045 (4)0.066 (11)*
H12B0.485 (3)0.135 (4)1.148 (2)0.061 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.01538 (19)0.0323 (3)0.0308 (2)0.0000.00747 (16)0.000
S10.01513 (19)0.0293 (2)0.01538 (19)0.0000.00559 (14)0.000
O10.0222 (7)0.0704 (12)0.0160 (6)0.0000.0055 (5)0.000
O20.0315 (5)0.0361 (6)0.0377 (6)0.0113 (5)0.0197 (5)0.0052 (5)
O30.0285 (7)0.0575 (11)0.0206 (7)0.0000.0028 (6)0.000
N10.0168 (6)0.0281 (8)0.0174 (7)0.0000.0035 (5)0.000
N20.0314 (9)0.0700 (15)0.0158 (7)0.0000.0071 (7)0.000
C10.0162 (7)0.0232 (8)0.0163 (7)0.0000.0053 (6)0.000
C20.0151 (7)0.0214 (8)0.0177 (7)0.0000.0043 (6)0.000
C30.0208 (8)0.0232 (8)0.0184 (8)0.0000.0076 (6)0.000
C40.0203 (8)0.0226 (8)0.0224 (8)0.0000.0099 (7)0.000
C50.0155 (7)0.0225 (8)0.0255 (8)0.0000.0069 (6)0.000
C60.0164 (7)0.0260 (9)0.0188 (8)0.0000.0040 (6)0.000
C70.0258 (9)0.0354 (11)0.0258 (9)0.0000.0149 (8)0.000
C80.0259 (9)0.0512 (13)0.0167 (8)0.0000.0068 (7)0.000
C100.0255 (15)0.112 (4)0.060 (2)0.010 (2)0.0015 (16)0.009 (3)
C120.0562 (16)0.0487 (15)0.0338 (12)0.0000.0295 (12)0.000
Geometric parameters (Å, º) top
Cl1—C51.7443 (18)C4—C51.390 (3)
S1—O11.4421 (15)C4—C71.505 (3)
S1—O2i1.4523 (11)C5—C61.391 (3)
S1—O21.4524 (11)C6—H6A0.9500
S1—C11.7863 (18)C7—H7A0.92 (4)
O3—C81.233 (3)C7—H7B0.94 (3)
N1—C21.464 (2)C8—C91.512 (3)
N1—H1A0.86 (2)C9—C101.525 (5)
N1—H1B0.86 (3)C9—H9A0.9900
N2—C81.331 (3)C9—H9B0.9900
N2—C121.442 (3)C10—C111.518 (5)
N2—C111.474 (3)C10—H10A0.9900
C1—C61.392 (2)C10—H10B0.9900
C1—C21.395 (2)C11—H11A0.9900
C2—C31.379 (2)C11—H11B0.9900
C3—C41.400 (3)C12—H12A0.90 (4)
C3—H3A0.9500C12—H12B0.97 (3)
O1—S1—O2i114.13 (6)C1—C6—H6A120.0
O1—S1—O2114.13 (6)C4—C7—H7A109 (2)
O2i—S1—O2111.98 (10)C4—C7—H7B112.0 (16)
O1—S1—C1106.27 (8)H7A—C7—H7B109.8 (19)
O2i—S1—C1104.60 (5)O3—C8—N2124.4 (2)
O2—S1—C1104.60 (5)O3—C8—C9125.2 (2)
C2—N1—H1A115.3 (13)N2—C8—C9109.64 (19)
C2—N1—H1B110.6 (18)C8—C9—C10104.9 (2)
H1A—N1—H1B104.9 (16)C8—C9—H9A110.8
C8—N2—C12125.5 (2)C10—C9—H9A110.8
C8—N2—C11113.1 (2)C8—C9—H9B110.8
C12—N2—C11120.6 (2)C10—C9—H9B110.8
C6—C1—C2118.44 (16)H9A—C9—H9B108.8
C6—C1—S1120.11 (13)C11—C10—C9105.3 (3)
C2—C1—S1121.45 (13)C11—C10—H10A110.7
C3—C2—C1121.03 (16)C9—C10—H10A110.7
C3—C2—N1118.18 (16)C11—C10—H10B110.7
C1—C2—N1120.79 (15)C9—C10—H10B110.7
C2—C3—C4121.29 (16)H10A—C10—H10B108.8
C2—C3—H3A119.4N2—C11—C10105.0 (2)
C4—C3—H3A119.4N2—C11—H11A110.7
C5—C4—C3117.14 (16)C10—C11—H11A110.7
C5—C4—C7123.17 (17)N2—C11—H11B110.7
C3—C4—C7119.69 (17)C10—C11—H11B110.7
C4—C5—C6122.10 (16)H11A—C11—H11B108.8
C4—C5—Cl1119.63 (14)N2—C12—H12A111 (2)
C6—C5—Cl1118.28 (14)N2—C12—H12B108.0 (14)
C5—C6—C1120.00 (16)H12A—C12—H12B109.7 (19)
C5—C6—H6A120.0
O1—S1—C1—C60.0C3—C4—C5—Cl1180.0
O2i—S1—C1—C6121.07 (5)C7—C4—C5—Cl10.0
O2—S1—C1—C6121.07 (5)C4—C5—C6—C10.0
O1—S1—C1—C2180.0Cl1—C5—C6—C1180.0
O2i—S1—C1—C258.93 (5)C2—C1—C6—C50.0
O2—S1—C1—C258.93 (5)S1—C1—C6—C5180.0
C6—C1—C2—C30.0C12—N2—C8—O30.000 (1)
S1—C1—C2—C3180.0C11—N2—C8—O3169.19 (15)
C6—C1—C2—N1180.0C12—N2—C8—C9170.75 (14)
S1—C1—C2—N10.0C11—N2—C8—C91.6 (2)
C1—C2—C3—C40.0O3—C8—C9—C10160.5 (3)
N1—C2—C3—C4180.0N2—C8—C9—C1010.1 (3)
C2—C3—C4—C50.0C8—C9—C10—C1114.2 (4)
C2—C3—C4—C7180.0C8—N2—C11—C107.7 (3)
C3—C4—C5—C60.0C12—N2—C11—C10162.1 (3)
C7—C4—C5—C6180.0C9—C10—C11—N213.4 (4)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2ii0.86 (2)1.98 (2)2.785 (2)156 (2)
N1—H1B···O30.86 (3)1.90 (3)2.750 (2)169 (3)
C3—H3A···O30.952.333.112 (3)139
Symmetry code: (ii) x+1, y, z+1.
(Ic) 2-ammonio-5-chloro-4-methylbenzenesulfonate dimethyl sulfoxide monosolvate top
Crystal data top
C7H8ClNO3S·C2H6OSZ = 2
Mr = 299.78F(000) = 312
Triclinic, P1Dx = 1.583 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.0394 (12) ÅCell parameters from 131 reflections
b = 9.4441 (14) Åθ = 3–23°
c = 11.8044 (16) ŵ = 0.64 mm1
α = 71.078 (11)°T = 167 K
β = 89.466 (16)°Block, colourless
γ = 81.207 (17)°0.40 × 0.30 × 0.20 mm
V = 628.83 (18) Å3
Data collection top
Siemens SMART 1K CCD area-detector
diffractometer
3481 independent reflections
Radiation source: normal-focus sealed tube2398 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
ω scansθmax = 30.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
h = 88
Tmin = 0.779, Tmax = 0.880k = 1313
10341 measured reflectionsl = 1616
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H atoms treated by a mixture of independent and constrained refinement
S = 0.98 w = 1/[σ2(Fo2) + (0.02P)2]
where P = (Fo2 + 2Fc2)/3
3481 reflections(Δ/σ)max = 0.001
169 parametersΔρmax = 0.42 e Å3
0 restraintsΔρmin = 0.38 e Å3
Crystal data top
C7H8ClNO3S·C2H6OSγ = 81.207 (17)°
Mr = 299.78V = 628.83 (18) Å3
Triclinic, P1Z = 2
a = 6.0394 (12) ÅMo Kα radiation
b = 9.4441 (14) ŵ = 0.64 mm1
c = 11.8044 (16) ÅT = 167 K
α = 71.078 (11)°0.40 × 0.30 × 0.20 mm
β = 89.466 (16)°
Data collection top
Siemens SMART 1K CCD area-detector
diffractometer
3481 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
2398 reflections with I > 2σ(I)
Tmin = 0.779, Tmax = 0.880Rint = 0.057
10341 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.081H atoms treated by a mixture of independent and constrained refinement
S = 0.98Δρmax = 0.42 e Å3
3481 reflectionsΔρmin = 0.38 e Å3
169 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.14668 (8)0.71970 (6)1.00413 (4)0.02703 (13)
S10.34360 (8)0.37453 (5)0.71857 (4)0.01767 (12)
S21.09294 (8)0.78816 (5)0.43564 (4)0.02104 (13)
O10.1302 (2)0.33852 (14)0.76920 (12)0.0230 (3)
O20.3257 (2)0.44905 (15)0.58958 (11)0.0277 (3)
O30.5259 (2)0.24888 (14)0.75731 (12)0.0264 (3)
O40.9378 (2)0.79015 (15)0.53781 (12)0.0283 (3)
N10.7485 (3)0.5448 (2)0.65303 (16)0.0187 (4)
H1A0.825 (4)0.627 (3)0.6096 (19)0.037 (6)*
H1B0.671 (3)0.524 (2)0.5944 (17)0.027 (6)*
H1C0.841 (4)0.471 (3)0.690 (2)0.043 (8)*
C10.4130 (3)0.51526 (19)0.77669 (16)0.0166 (4)
C20.6000 (3)0.58591 (19)0.73998 (16)0.0163 (4)
C30.6475 (3)0.6974 (2)0.78443 (16)0.0191 (4)
H3A0.77600.74390.75830.023*
C40.5116 (3)0.7431 (2)0.86664 (16)0.0184 (4)
C50.3254 (3)0.6707 (2)0.90153 (16)0.0181 (4)
C60.2755 (3)0.5579 (2)0.85867 (16)0.0184 (4)
H6A0.14810.51040.88530.022*
C70.5619 (3)0.8650 (2)0.91401 (17)0.0236 (4)
H7A0.44070.95180.88820.035*
H7B0.70360.89710.88300.035*
H7C0.57420.82551.00180.035*
C80.9710 (4)0.9422 (2)0.30894 (18)0.0290 (5)
H8A0.95951.03710.32720.044*
H8B0.82110.92630.28980.044*
H8C1.06540.94790.24010.044*
C91.3261 (3)0.8693 (2)0.4644 (2)0.0294 (5)
H9A1.40530.80330.53940.044*
H9B1.27240.96940.47120.044*
H9C1.42860.87960.39830.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0267 (3)0.0333 (3)0.0273 (3)0.0044 (2)0.0093 (2)0.0186 (2)
S10.0186 (3)0.0191 (2)0.0179 (3)0.00470 (19)0.00367 (19)0.00905 (19)
S20.0235 (3)0.0171 (2)0.0237 (3)0.0033 (2)0.0050 (2)0.0084 (2)
O10.0205 (7)0.0277 (7)0.0264 (8)0.0108 (6)0.0071 (6)0.0135 (6)
O20.0372 (9)0.0320 (8)0.0173 (7)0.0114 (7)0.0039 (7)0.0103 (6)
O30.0247 (8)0.0216 (7)0.0350 (9)0.0020 (6)0.0013 (7)0.0143 (6)
O40.0363 (9)0.0219 (7)0.0295 (8)0.0086 (6)0.0159 (7)0.0107 (6)
N10.0172 (9)0.0194 (9)0.0213 (10)0.0040 (7)0.0045 (8)0.0089 (7)
C10.0178 (10)0.0155 (9)0.0158 (10)0.0001 (7)0.0004 (8)0.0051 (7)
C20.0172 (10)0.0163 (9)0.0145 (9)0.0002 (7)0.0025 (8)0.0048 (7)
C30.0171 (10)0.0187 (9)0.0205 (10)0.0053 (8)0.0036 (8)0.0042 (8)
C40.0231 (10)0.0165 (9)0.0152 (10)0.0008 (8)0.0005 (8)0.0055 (7)
C50.0191 (10)0.0206 (9)0.0146 (10)0.0007 (8)0.0024 (8)0.0074 (8)
C60.0173 (10)0.0206 (9)0.0180 (10)0.0040 (8)0.0037 (8)0.0069 (8)
C70.0271 (11)0.0209 (10)0.0265 (11)0.0048 (9)0.0032 (9)0.0123 (8)
C80.0324 (12)0.0245 (11)0.0282 (12)0.0042 (9)0.0014 (10)0.0061 (9)
C90.0239 (11)0.0314 (12)0.0385 (13)0.0037 (9)0.0024 (10)0.0193 (10)
Geometric parameters (Å, º) top
Cl1—C51.7414 (19)C3—C41.397 (3)
S1—O31.4448 (14)C3—H3A0.9500
S1—O21.4526 (14)C4—C51.395 (3)
S1—O11.4566 (14)C4—C71.502 (2)
S1—C11.7831 (18)C5—C61.390 (2)
S2—O41.5236 (14)C6—H6A0.9500
S2—C81.783 (2)C7—H7A0.9800
S2—C91.787 (2)C7—H7B0.9800
N1—C21.464 (2)C7—H7C0.9800
N1—H1A0.96 (2)C8—H8A0.9800
N1—H1B0.92 (2)C8—H8B0.9800
N1—H1C0.82 (3)C8—H8C0.9800
C1—C61.387 (2)C9—H9A0.9800
C1—C21.394 (3)C9—H9B0.9800
C2—C31.385 (2)C9—H9C0.9800
O3—S1—O2113.53 (8)C3—C4—C7121.78 (17)
O3—S1—O1113.68 (8)C6—C5—C4122.72 (18)
O2—S1—O1112.85 (8)C6—C5—Cl1117.52 (15)
O3—S1—C1106.05 (8)C4—C5—Cl1119.76 (14)
O2—S1—C1104.25 (8)C1—C6—C5119.56 (17)
O1—S1—C1105.40 (8)C1—C6—H6A120.2
O4—S2—C8105.64 (9)C5—C6—H6A120.2
O4—S2—C9104.62 (9)C4—C7—H7A109.5
C8—S2—C997.88 (10)C4—C7—H7B109.5
C2—N1—H1A111.5 (13)H7A—C7—H7B109.5
C2—N1—H1B112.5 (13)C4—C7—H7C109.5
H1A—N1—H1B104.4 (17)H7A—C7—H7C109.5
C2—N1—H1C107.8 (17)H7B—C7—H7C109.5
H1A—N1—H1C110 (2)S2—C8—H8A109.5
H1B—N1—H1C111 (2)S2—C8—H8B109.5
C6—C1—C2119.00 (16)H8A—C8—H8B109.5
C6—C1—S1119.39 (14)S2—C8—H8C109.5
C2—C1—S1121.60 (14)H8A—C8—H8C109.5
C3—C2—C1120.50 (17)H8B—C8—H8C109.5
C3—C2—N1118.82 (16)S2—C9—H9A109.5
C1—C2—N1120.67 (16)S2—C9—H9B109.5
C2—C3—C4121.77 (17)H9A—C9—H9B109.5
C2—C3—H3A119.1S2—C9—H9C109.5
C4—C3—H3A119.1H9A—C9—H9C109.5
C5—C4—C3116.45 (17)H9B—C9—H9C109.5
C5—C4—C7121.77 (17)
O3—S1—C1—C6117.15 (15)N1—C2—C3—C4179.34 (17)
O2—S1—C1—C6122.74 (15)C2—C3—C4—C50.0 (3)
O1—S1—C1—C63.70 (17)C2—C3—C4—C7179.43 (17)
O3—S1—C1—C264.14 (17)C3—C4—C5—C60.5 (3)
O2—S1—C1—C255.97 (17)C7—C4—C5—C6179.87 (17)
O1—S1—C1—C2175.01 (15)C3—C4—C5—Cl1179.77 (13)
C6—C1—C2—C30.2 (3)C7—C4—C5—Cl10.8 (3)
S1—C1—C2—C3178.53 (14)C2—C1—C6—C50.6 (3)
C6—C1—C2—N1179.61 (16)S1—C1—C6—C5178.14 (14)
S1—C1—C2—N10.9 (2)C4—C5—C6—C10.8 (3)
C1—C2—C3—C40.1 (3)Cl1—C5—C6—C1179.92 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O40.96 (3)1.74 (3)2.695 (2)173 (2)
N1—H1B···O20.93 (2)2.31 (2)3.013 (2)132 (2)
N1—H1B···O2i0.93 (2)2.10 (2)2.883 (2)141 (2)
N1—H1C···O1ii0.82 (3)2.02 (3)2.818 (2)162 (3)
C9—H9B···O4iii0.982.403.356 (3)166
C9—H9C···O3iv0.982.503.231 (3)131
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z; (iii) x+2, y+2, z+1; (iv) x+2, y+1, z+1.
(II) 2,2'-(1,4-phenylene)di(4,5-dihydroimidazolium) bis(4-aminobenzenesulfonate) dihydrate top
Crystal data top
C12H16N42+·2C6H6NO3S·2H2OF(000) = 1256
Mr = 596.68Dx = 1.469 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3721 reflections
a = 13.6306 (11) Åθ = 2.6–26.3°
b = 12.698 (1) ŵ = 0.26 mm1
c = 15.5907 (13) ÅT = 273 K
V = 2698.5 (4) Å3Block, yellow
Z = 40.15 × 0.12 × 0.10 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2346 independent reflections
Radiation source: fine-focus sealed tube1293 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
ϕ and ω scansθmax = 25.1°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
h = 1615
Tmin = 0.962, Tmax = 0.975k = 1515
11859 measured reflectionsl = 1814
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.065H atoms treated by a mixture of independent and constrained refinement
S = 0.87 w = 1/[σ2(Fo2) + (0.03P)2]
where P = (Fo2 + 2Fc2)/3
2346 reflections(Δ/σ)max = 0.002
205 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C12H16N42+·2C6H6NO3S·2H2OV = 2698.5 (4) Å3
Mr = 596.68Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 13.6306 (11) ŵ = 0.26 mm1
b = 12.698 (1) ÅT = 273 K
c = 15.5907 (13) Å0.15 × 0.12 × 0.10 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2346 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
1293 reflections with I > 2σ(I)
Tmin = 0.962, Tmax = 0.975Rint = 0.036
11859 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.065H atoms treated by a mixture of independent and constrained refinement
S = 0.87Δρmax = 0.20 e Å3
2346 reflectionsΔρmin = 0.22 e Å3
205 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.29385 (5)0.17187 (4)0.68926 (3)0.04268 (15)
O10.20809 (13)0.13745 (15)0.73632 (10)0.0679 (5)
O20.37965 (11)0.11039 (14)0.71628 (9)0.0531 (4)
O30.31226 (15)0.28328 (12)0.69388 (10)0.0693 (5)
O40.56168 (17)0.1512 (2)0.63678 (11)0.0798 (7)
N10.22286 (18)0.07637 (18)0.32274 (13)0.0625 (6)
N20.03144 (14)0.29231 (17)0.53180 (14)0.0532 (5)
N30.01574 (15)0.22747 (18)0.65337 (12)0.0518 (5)
C10.27387 (14)0.14212 (14)0.58050 (11)0.0328 (4)
C20.25558 (14)0.03947 (15)0.55480 (12)0.0364 (5)
H2A0.25330.01440.59520.044*
C30.24075 (15)0.01763 (16)0.46925 (13)0.0398 (5)
H3A0.22970.05160.45250.048*
C40.24189 (15)0.09695 (16)0.40693 (12)0.0382 (5)
C50.26048 (16)0.19923 (15)0.43453 (13)0.0390 (5)
H5A0.26220.25360.39460.047*
C60.27641 (14)0.22160 (15)0.51983 (12)0.0370 (5)
H6A0.28900.29050.53680.044*
C70.00643 (17)0.0871 (2)0.44694 (13)0.0500 (6)
H7A0.01060.14570.41140.060*
C80.00292 (15)0.10058 (19)0.53554 (13)0.0448 (5)
C90.00945 (17)0.01192 (19)0.58796 (13)0.0512 (6)
H9A0.01590.02000.64700.061*
C100.00644 (16)0.20605 (18)0.57301 (13)0.0452 (5)
C110.0181 (2)0.3855 (2)0.58421 (16)0.0643 (7)
H11A0.03700.42720.56430.077*
H11B0.07670.42890.58440.077*
C120.00190 (19)0.3391 (2)0.67338 (15)0.0623 (7)
H12A0.05330.34980.71160.075*
H12B0.06040.36940.69890.075*
H1A0.243 (2)0.128 (2)0.2778 (19)0.094 (10)*
H1B0.2187 (19)0.011 (2)0.3063 (16)0.071 (8)*
H2B0.0517 (18)0.291 (2)0.4849 (17)0.064 (8)*
H3B0.0391 (17)0.1892 (18)0.6872 (16)0.056 (8)*
H4A0.5091 (17)0.1277 (17)0.6521 (14)0.044 (7)*
H4B0.607 (2)0.150 (2)0.6692 (19)0.095 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0517 (3)0.0494 (3)0.0270 (2)0.0001 (3)0.0014 (2)0.0018 (2)
O10.0585 (10)0.1039 (13)0.0414 (9)0.0001 (11)0.0177 (8)0.0010 (9)
O20.0530 (10)0.0667 (10)0.0396 (8)0.0003 (8)0.0130 (8)0.0042 (7)
O30.1196 (16)0.0473 (9)0.0410 (9)0.0028 (9)0.0077 (10)0.0110 (8)
O40.0494 (13)0.145 (2)0.0453 (10)0.0119 (12)0.0105 (10)0.0269 (12)
N10.0962 (19)0.0564 (13)0.0349 (10)0.0215 (12)0.0015 (11)0.0022 (10)
N20.0463 (12)0.0707 (14)0.0427 (11)0.0028 (10)0.0151 (10)0.0111 (11)
N30.0507 (13)0.0696 (14)0.0352 (11)0.0060 (11)0.0058 (9)0.0097 (10)
C10.0286 (11)0.0402 (10)0.0297 (10)0.0044 (8)0.0009 (8)0.0010 (8)
C20.0378 (11)0.0349 (10)0.0365 (11)0.0005 (10)0.0009 (9)0.0060 (8)
C30.0445 (12)0.0339 (10)0.0410 (11)0.0022 (9)0.0007 (9)0.0022 (10)
C40.0415 (12)0.0445 (11)0.0287 (10)0.0043 (10)0.0008 (9)0.0018 (10)
C50.0453 (13)0.0378 (10)0.0338 (11)0.0017 (9)0.0004 (9)0.0071 (8)
C60.0439 (13)0.0320 (10)0.0350 (11)0.0015 (9)0.0012 (9)0.0033 (9)
C70.0498 (14)0.0641 (16)0.0361 (12)0.0106 (12)0.0060 (11)0.0149 (11)
C80.0336 (11)0.0646 (14)0.0364 (11)0.0081 (10)0.0055 (11)0.0086 (11)
C90.0499 (14)0.0710 (16)0.0327 (11)0.0079 (12)0.0044 (10)0.0110 (11)
C100.0287 (12)0.0691 (15)0.0380 (10)0.0062 (10)0.0045 (10)0.0133 (11)
C110.0666 (18)0.0680 (16)0.0583 (16)0.0170 (14)0.0134 (13)0.0044 (13)
C120.0607 (16)0.0752 (17)0.0511 (13)0.0083 (15)0.0016 (12)0.0010 (14)
Geometric parameters (Å, º) top
S1—O31.4386 (16)C3—C41.399 (3)
S1—O11.4477 (17)C3—H3A0.9300
S1—O21.4679 (16)C4—C51.391 (3)
S1—C11.7586 (19)C5—C61.377 (3)
O4—H4A0.81 (2)C5—H5A0.9300
O4—H4B0.80 (3)C6—H6A0.9300
N1—C41.363 (3)C7—C9i1.370 (3)
N1—H1A1.00 (3)C7—C81.398 (3)
N1—H1B0.87 (3)C7—H7A0.9300
N2—C101.315 (3)C8—C91.394 (3)
N2—C111.449 (3)C8—C101.462 (3)
N2—H2B0.78 (3)C9—C7i1.370 (3)
N3—C101.317 (3)C9—H9A0.9300
N3—C121.464 (3)C11—C121.534 (3)
N3—H3B0.78 (2)C11—H11A0.9700
C1—C61.384 (3)C11—H11B0.9700
C1—C21.386 (3)C12—H12A0.9700
C2—C31.377 (3)C12—H12B0.9700
C2—H2A0.9300
O3—S1—O1114.36 (11)C6—C5—H5A119.3
O3—S1—O2111.70 (11)C4—C5—H5A119.3
O1—S1—O2109.72 (10)C5—C6—C1120.38 (18)
O3—S1—C1106.65 (9)C5—C6—H6A119.8
O1—S1—C1107.38 (10)C1—C6—H6A119.8
O2—S1—C1106.61 (9)C9i—C7—C8120.5 (2)
H4A—O4—H4B119 (3)C9i—C7—H7A119.7
C4—N1—H1A119.8 (16)C8—C7—H7A119.7
C4—N1—H1B118.7 (18)C9—C8—C7119.1 (2)
H1A—N1—H1B116 (2)C9—C8—C10120.23 (18)
C10—N2—C11111.8 (2)C7—C8—C10120.7 (2)
C10—N2—H2B122 (2)C7i—C9—C8120.41 (19)
C11—N2—H2B126 (2)C7i—C9—H9A119.8
C10—N3—C12111.9 (2)C8—C9—H9A119.8
C10—N3—H3B127.2 (18)N2—C10—N3110.6 (2)
C12—N3—H3B120.6 (18)N2—C10—C8125.2 (2)
C6—C1—C2119.53 (17)N3—C10—C8124.2 (2)
C6—C1—S1119.90 (14)N2—C11—C12102.7 (2)
C2—C1—S1120.57 (14)N2—C11—H11A111.2
C3—C2—C1119.71 (18)C12—C11—H11A111.2
C3—C2—H2A120.1N2—C11—H11B111.2
C1—C2—H2A120.1C12—C11—H11B111.2
C2—C3—C4121.72 (18)H11A—C11—H11B109.1
C2—C3—H3A119.1N3—C12—C11101.60 (19)
C4—C3—H3A119.1N3—C12—H12A111.5
N1—C4—C5120.75 (19)C11—C12—H12A111.5
N1—C4—C3121.89 (18)N3—C12—H12B111.5
C5—C4—C3117.33 (17)C11—C12—H12B111.5
C6—C5—C4121.32 (18)H12A—C12—H12B109.3
O3—S1—C1—C61.0 (2)C9i—C7—C8—C90.2 (4)
O1—S1—C1—C6121.96 (17)C9i—C7—C8—C10179.8 (2)
O2—S1—C1—C6120.50 (17)C7—C8—C9—C7i0.2 (4)
O3—S1—C1—C2178.93 (17)C10—C8—C9—C7i179.8 (2)
O1—S1—C1—C258.07 (19)C11—N2—C10—N35.5 (3)
O2—S1—C1—C259.46 (18)C11—N2—C10—C8174.2 (2)
C6—C1—C2—C30.4 (3)C12—N3—C10—N22.4 (3)
S1—C1—C2—C3179.58 (16)C12—N3—C10—C8177.8 (2)
C1—C2—C3—C41.1 (3)C9—C8—C10—N2157.6 (2)
C2—C3—C4—N1177.0 (2)C7—C8—C10—N222.1 (3)
C2—C3—C4—C51.1 (3)C9—C8—C10—N322.8 (3)
N1—C4—C5—C6177.7 (2)C7—C8—C10—N3157.6 (2)
C3—C4—C5—C60.4 (3)C10—N2—C11—C1210.5 (3)
C4—C5—C6—C10.3 (3)C10—N3—C12—C118.6 (3)
C2—C1—C6—C50.3 (3)N2—C11—C12—N310.7 (2)
S1—C1—C6—C5179.74 (16)
Symmetry code: (i) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3ii1.00 (3)1.97 (3)2.949 (3)167 (2)
N1—H1B···O1iii0.87 (3)2.40 (3)3.174 (3)149 (2)
N1—H1B···O2iii0.87 (3)2.48 (3)3.214 (3)143 (2)
N2—H2B···O4iv0.78 (3)2.04 (3)2.756 (3)152 (2)
N3—H3B···O2v0.79 (2)2.12 (2)2.894 (3)169 (2)
O4—H4A···O20.81 (2)2.04 (2)2.822 (3)161 (2)
O4—H4B···O1vi0.80 (3)2.02 (3)2.816 (3)172 (3)
Symmetry codes: (ii) x, y+1/2, z1/2; (iii) x+1/2, y, z1/2; (iv) x1/2, y+1/2, z+1; (v) x1/2, y, z+3/2; (vi) x+1/2, y, z+3/2.

Experimental details

(Ia)(Ib)(Ic)(II)
Crystal data
Chemical formulaC7H8ClNO3SC7H8ClNO3S·C5H9NOC7H8ClNO3S·C2H6OSC12H16N42+·2C6H6NO3S·2H2O
Mr221.65320.79299.78596.68
Crystal system, space groupMonoclinic, IaMonoclinic, P21/mTriclinic, P1Orthorhombic, Pbca
Temperature (K)173165167273
a, b, c (Å)4.9308 (3), 32.364 (2), 5.4922 (4)9.1917 (17), 6.9457 (11), 11.8265 (13)6.0394 (12), 9.4441 (14), 11.8044 (16)13.6306 (11), 12.698 (1), 15.5907 (13)
α, β, γ (°)90, 93.654 (1), 9090, 105.538 (7), 9071.078 (11), 89.466 (16), 81.207 (17)90, 90, 90
V3)874.68 (10)727.44 (19)628.83 (18)2698.5 (4)
Z4224
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.650.420.640.26
Crystal size (mm)0.40 × 0.20 × 0.060.40 × 0.36 × 0.100.40 × 0.30 × 0.200.15 × 0.12 × 0.10
Data collection
DiffractometerSiemens SMART 1K CCD area-detector
diffractometer
Siemens SMART 1K CCD area-detector
diffractometer
Siemens SMART 1K CCD area-detector
diffractometer
Bruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2000)
Multi-scan
(SADABS; Sheldrick, 2000)
Multi-scan
(SADABS; Sheldrick, 2000)
Multi-scan
(SADABS; Bruker, 1998)
Tmin, Tmax0.693, 0.9620.889, 0.9590.779, 0.8800.962, 0.975
No. of measured, independent and
observed [I > 2σ(I)] reflections
5429, 2101, 1934 12236, 2552, 2131 10341, 3481, 2398 11859, 2346, 1293
Rint0.0380.0280.0570.036
(sin θ/λ)max1)0.6810.7440.7020.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.093, 1.05 0.037, 0.101, 1.01 0.036, 0.081, 0.98 0.030, 0.065, 0.87
No. of reflections2101255234812346
No. of parameters131139169205
No. of restraints2000
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.68, 0.510.56, 0.570.42, 0.380.20, 0.22
Absolute structureFlack (1983), with 986 Friedel pairs???
Absolute structure parameter0.04 (8)???

Computer programs: SMART (Siemens, 1995), SMART (Bruker, 1998), SAINT (Siemens, 1995), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) for (Ia) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3i0.91 (4)1.88 (4)2.772 (4)166 (4)
N1—H1B···O1ii0.84 (4)2.05 (4)2.831 (4)156 (3)
N1—H1C···O2iii0.93 (4)1.95 (4)2.809 (3)155 (3)
C3—H3A···O1ii0.952.373.148 (3)138
C7—H7C···Cl1iv0.983.023.925 (3)154
Symmetry codes: (i) x1, y, z; (ii) x1, y, z1; (iii) x, y+3/2, z1/2; (iv) x1/2, y+1, z.
Hydrogen-bond geometry (Å, º) for (Ib) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.86 (2)1.98 (2)2.785 (2)156 (2)
N1—H1B···O30.86 (3)1.90 (3)2.750 (2)169 (3)
C3—H3A···O30.952.333.112 (3)139
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) for (Ic) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O40.96 (3)1.74 (3)2.695 (2)173 (2)
N1—H1B···O20.93 (2)2.31 (2)3.013 (2)132 (2)
N1—H1B···O2i0.93 (2)2.10 (2)2.883 (2)141 (2)
N1—H1C···O1ii0.82 (3)2.02 (3)2.818 (2)162 (3)
C9—H9B···O4iii0.982.403.356 (3)166
C9—H9C···O3iv0.982.503.231 (3)131
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z; (iii) x+2, y+2, z+1; (iv) x+2, y+1, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3i1.00 (3)1.97 (3)2.949 (3)167 (2)
N1—H1B···O1ii0.87 (3)2.40 (3)3.174 (3)149 (2)
N1—H1B···O2ii0.87 (3)2.48 (3)3.214 (3)143 (2)
N2—H2B···O4iii0.78 (3)2.04 (3)2.756 (3)152 (2)
N3—H3B···O2iv0.79 (2)2.12 (2)2.894 (3)169 (2)
O4—H4A···O20.81 (2)2.04 (2)2.822 (3)161 (2)
O4—H4B···O1v0.80 (3)2.02 (3)2.816 (3)172 (3)
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x+1/2, y, z1/2; (iii) x1/2, y+1/2, z+1; (iv) x1/2, y, z+3/2; (v) x+1/2, y, z+3/2.
 

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