Modularity and three-dimensional isostructurality of novel synthons in sulfonamide–lactam cocrystals

Bolla, G.; Mittapalli, S.; Nangia, A.

doi:10.1107/S2052252515004960

research papers

IUCrJ

Volume 2| Part 4| July 2015| Pages 389-401

ISSN: 2052-2525

doi:10.1107/S2052252515004960

CHEMISTRY | CRYSTENG

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Modularity and three-dimensional isostructurality of novel synthons in sulfonamide–lactam cocrystals

Geetha Bolla,^a Sudhir Mittapalli ^a and Ashwini Nangia ^a ^*

^aSchool of Chemistry, University of Hyderabad, Prof. C. R. Rao Road, Central University PO, Hyderabad, 500 046, India
^*Correspondence e-mail: ashwini.nangia@gmail.com

Edited by X. Zhang, Tsinghua University, China (Received 16 December 2014; accepted 11 March 2015; online 1 May 2015)

The design of novel supramolecular synthons for functional groups relevant to drugs is an essential prerequisite for applying crystal engineering in the development of novel pharmaceutical cocrystals. It has been convincingly shown over the past decade that molecular level control and modulation can influence the physicochemical properties of drug cocrystals. Whereas considerable advances have been reported on the design of cocrystals for carboxylic acids and carboxamide functional groups, the sulfonamide group, which is a cornerstone of sulfa drugs, is relatively unexplored for reproducible heterosynthon-directed crystal engineering. The occurrence of synthons and isostructurality in sulfonamide–lactam cocrystals (SO₂NH₂⋯CONH hydrogen bonding) is analyzed to define a strategy for amide-type GRAS (generally recognized as safe) coformers with sulfonamides. Three types of supramolecular synthons are identified for the N—H donor of sulfonamide hydrogen bonding to the C=O acceptor of amide. Synthon 1: catemer synthon C₂¹(4) chain motif, synthon 2: dimer–cyclic ring synthon R₂²(8)R₄²(8) motifs, and synthon 3: dimer–catemer synthon of R₂²(8)C₁¹(4)D notation. These heterosynthons of the cocrystals observed in this study are compared with the N—H⋯O dimer R₂²(8) ring and C(4) chain motifs of the individual sulfonamide structures. The X-ray crystal structures of sulfonamide–lactam cocrystals exhibit interesting isostructurality trends with the same synthon being present. One-dimensional, two-dimensional and three-dimensional isostructurality in crystal structures is associated with isosynthons and due to their recurrence, novel heterosynthons for sulfonamide cocrystals are added to the crystal engineer's toolkit. With the predominance of sulfa drugs in medicine, these new synthons provide rational strategies for the design of binary and potentially ternary cocrystals of sulfonamides.

Keywords: crystal engineering; supramolecular synthons; pharmaceutical cocrystals; isostructurality.

CCDC references: 1039188; 1039189; 1039190; 1039191; 1039192; 1039193; 1039194; 1039195; 1039196; 1039197; 1039198; 1039199; 1039200; 1053703

1. Introduction

The concept of supramolecular synthons introduced by Desiraju in 1995 (Desiraju, 1995 ; Thalladi et al., 1996 ; Reddy et al., 1996 ; Dunitz & Gavezzotti, 2012 ; Nangia & Desiraju, 1998 ) led to the identification of known and new hydrogen bond patterns in crystal engineering. Zaworotko and coworkers (Walsh et al., 2003 ) sub-classified synthons as homosynthons (those between like functional groups) and heterosynthons (hydrogen bonds between unlike groups). The past decade has witnessed immense interest in utilizing various supramolecular synthons to direct structural organization in the crystal structure. For example, acid–acid and amide–amide homosynthons are well known, while acid–pyridine and acid–amide are popular heterosynthons. The latter form of association between unlike functional groups has immediate potential in the engineering of multi-component systems, notably cocrystals (Vishweshwar et al., 2003a ,b ; Biradha & Zaworotko, 1998 ; Bis & Zaworotko, 2005 ; Bis et al., 2006 ; Vangala et al., 2005 ; Ermer & Eling, 1994 ; Reddy et al., 2006 , 2007 ; Babu et al., 2007 ; Goud et al., 2011 ; Kaur & Guru Row, 2012 )

Selected homo- and heterosynthons extracted from the literature for single and multi-component systems of sulfonamides are listed in Fig. 1. The directionality and strength of hydrogen bonding plays a major role in controlling the supramolecular assembly through complementary functional groups, which leads to the application of crystal engineering in material science and pharmaceutical solids (Childs et al., 2004 ; Trask, Motherwell & Jones, 2004 , 2005 , 2006 ; Trask, Haynes et al., 2006 ). The pairing of best-donor to best-acceptor hydrogen bonding (Etter's rules) guides cocrystal design in a majority of cases (Etter, 1982 , 1990 , 1991 ). However, as multiple functional groups come into interplay, the competition can be more complex and difficult to predict (Sarma et al., 2009 ; Aakeröy et al., 2013 ). For this reason, we examined heterosynthons of sulfonamides with the amide group in non-competing binary systems with the idea of developing a library of sulfonamide–carboxamide synthons. Whereas sulfonamide and carboxamide homosynthons have been studied, this is a report on their heterosynthons. Sulfonamides preferably form dimer and catemer synthons, whereas carboxamides more often assemble via the dimer synthon (Sanphui et al., 2010 ). A robust heterosynthon for sulfonamide group cocrystals is that with pyridine N-oxides (Goud et al., 2011), but since the latter coformers are not pharmaceutically acceptable, there is a need to develop a design strategy for sulfonamides with GRAS amides (US-FDA, 2014 ). Selected data on sulfonamides were extracted from the Cambridge Structural Database (CSD, Version 5.36, November 2014 release). With this background, benzene sulfonamides were cocrystallized with cyclic carboxamides to analyze isostructural relationships and classify the observed synthons.

Figure 1
(a) Synthons present in primary sulfonamides (homosynthons). (b) Synthon motifs present in sulfonamide cocrystals (heterosynthons) from the literature study. (c) Synthon motifs present in sulfonamide cocrystals discussed in this report (heterosynthons).

Primary sulfonamides attached to a substituted phenyl ring were selected in this exploratory cocrystal study to identify the basic heterosynthons with amides in a non-competitive environment. We were successful in obtaining cocrystals of a few benzene sulfonamides with lactams (syn amides) listed in Fig. 2. A reason to choose cyclic amides over primary amides was that the latter have syn and anti N—H donors, and together with primary sulfonamide, which also has syn and anti N—H donors, the diversity of hydrogen bond motifs may become too complex for systematic analysis. In a recent study of lactams with carboxylic acids, Moragues-Bartolome et al. (2012 ) found that 2-pyrrolidone showed a heterotetramer (CONH⋯COOH), whereas δ-valerolactam has a homotetramer synthon (CONH⋯CONH), although there were some mixed results as well (Moragues-Bartolome et al., 2012). We report in this paper isostructural pairs of cocrystals (sulfonamide–lactam) having isosynthons (similar supramolecular synthons). The lattice parameters and crystal packing of the X-ray crystal structures suggest that there are three sets of isostructural compounds and that each set has its own isosynthons. Primary sulfonamides consist of two acceptor O atoms and two donor H atoms (SO₂NH₂), and the complementary functional group lactam (HN—C=O) also has one donor and one acceptor.

Figure 2
Molecular structure of the primary sulfonamides and lactams used in this study to make binary cocrystals.

2. Experimental

2.1. Preparation of cocrystals

All the benzene sulfonamides and coformers (caprolactam, valerolactam etc.) used in this study (see Fig. 2) were purchased from Sigma–Aldrich, Hyderabad, India, and used as such without further purification. Equivalent amounts of the sulfonamide and coformer were taken in a mortar and ground with a pestle for 20–30 min using solvent-assisted grinding by adding a few drops of EtOAc. After confirming that the ground mixture is a new solid phase by powder X-ray diffraction (PXRD), the mixture was dissolved in EtOAc or EtOAc–THF. The solution was then allowed to cocrystallize at room temperature by slow evaporation. Suitable crystals for single-crystal X-ray data were obtained after 5–6 d. A summary of the grinding experiments, characterizations of cocrystals by PXRD and IR, and confirmation by single-crystal X-ray diffraction (SC-XRD) are listed in Table 1.

Table 1
Summary of characterization for sulfonamide–lactam cocrystals

$[\surd]$ = yes, × = no.

		VLM (six member lactam)			CPR (seven member lactam)
S. No.	Sulfonamides	Changes in IR	Changes in PXRD	Single crystal data	Changes in IR	Changes in PXRD	Single crystal data
1	BSA	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$
2	OTSA	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$	×
3	PTSA	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$	×
4	SNA	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$
5	2ABSA	$[\surd]$	$[\surd]$	×	$[\surd]$	$[\surd]$	$[\surd]$
6	2ClBSA	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$
7	4ClBSA	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$
8	4BrBSA	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$	$[\surd]$

2.2. BSA–VLM cocrystal (1:1)

BSA (100 mg, 0.636 mmol) and VLM (63 mg, 0.636 mmol) were ground well in a mortar and pestle for 20–30 min by adding 4–7 drops of EtOAc (liquid-assisted grinding or LAG; Shan et al., 2002 ; Trask & Jones, 2005 ; Friščić et al., 2006 ). The ground material was kept for crystallization in 5 ml of an EtOAc–THF mixture as well as in individual solvents at room temperature. Good diffraction-quality crystals were harvested under ambient conditions after 3–4 d; m.p. 79–81°C.

2.3. BSA–CPR cocrystal (1:1)

BSA (100 mg, 0.636 mmol) and CPR (72 mg, 0.636 mmol) were ground well in a mortar and pestle for 20–30 min by adding 4–7 drops of EtOAc. The ground material was kept for crystallization in 5 mL of an EtOAc–THF solvent mixture as well as in individual solvents in a 25 ml conical flask at room temperature. Good quality crystals were harvested under ambient conditions after 3–4 days; m.p. 80–83°C.

2.4. BSA–AZL (1-aza-2-cyclooctanone) cocrystal (1:1)

BSA (100 mg, 0.636 mmol) and AZL (80.87 mg, 0.636 mmol) were ground well in a mortar and pestle for 20–30 min by adding 4–7 drops of EtOAc. The ground material was kept for crystallization in 5 mL of an EtOAc–THF mixture as well as individual solvents in a 25 ml conical flask at room temperature. Good quality crystals were harvested under ambient conditions after 3–4 days; m.p. 76–81°C.

2.5. 2ClBSA–VLM, 4ClBSA–VLM cocrystal (1:1)

ClBSA isomer (100 mg, 0.521 mmol) and VLM (51.6 mg, 0.521 mmol) were ground well in a mortar and pestle for 20–30 min by adding 5 drops of EtOAc. The ground material was kept for crystallization in 5 mL of an EtOAc–THF mixture as well as individual solvents at room temperature. Single crystals were harvested under ambient conditions after 3–4 d; m.p. 80–82°C; 90–91°C

2.6. 2ClBSA–CPR, 4ClBSA–CPR cocrystal (1:1)

ClBSA isomer (100 mg, 0.521 mmol) and CPR (59 mg, 0.521 mmol) were ground well in a mortar and pestle for 20–30 min by adding 5 drops of EtOAc. The ground material was kept for crystallization in 5 mL of an EtOAc–THF mixture, as well as separate solvents at room temperature. Single crystals were harvested under ambient conditions after 3–4 d; m.p. 80–82°C; 82–83°C.

2.7. 4BrBSA–VLM cocrystal (1:1)

4BrBSA (100 mg, 0.423 mmol) and VLM (51.6 mg, 0.423 mmol) were ground well in a mortar and pestle for 20–30 min with solvent assistance by adding 4–7 drops of EtOAc. The ground material was kept for crystallization in 5 mL of an EtOAc–THF mixture, as well as individual solvents at room temperature. Single crystals were harvested under ambient conditions after 3–4 d; m.p. 92–94°C.

2.8. 4BrBSA–CPR cocrystal (1:1)

4BrBSA (100 mg, 0.423 mmol) and CPR (58.95 mg, 0.423 mmol) were ground well in a mortar aand pestle for 20–30 min through solvent-assisted grinding by adding 5 drops of EtOAc. The ground material was kept for crystallization in 5 mL of EtOAc–THF mixture as well as separate solvents. Single crystals were harvested at ambient conditions after 3–4 days; m.p. 90–92°C.

2.9. OTSA–VLM, PTSA–VLM cocrystal (1:1)

OTSA/PTSA (100 mg, 0.584 mmol) and VLM (57.89 mg, 0.584 mmol) were ground well in a mortar and pestle for 20–30 min through solvent-assisted grinding by adding 5 drops of EtOAc. The ground material was kept for crystallization in 5 mL of an EtOAc–THF mixture as well as separate solvents. Single crystals were harvested under ambient conditions after 3–4 days; m.p. 70–72°C; 74–75°C.

2.10. SNA–VLM, 2ABSA–VLM cocrystal (1:1)

SNA/2ABSA (100 mg, 0.580 mmol) and VLM (65.63 mg, 0.580 mmol) were ground well in a mortar and pestle for 20–30 min through solvent-assisted grinding by adding 5 drops of EtOAc. The ground material was kept for crystallization in 5 mL of an EtOAc–THF mixture as well as separate solvents. Single crystals were harvested at ambient conditions after 3–4 d; m.p. 95–97°C, 87–91°C.

2.11. Single-crystal X-ray diffraction

A single crystal obtained from the crystallization experiment was mounted on the goniometer of an Oxford Diffraction Gemini X-ray diffractometer equipped with an Mo Kα radiation source (λ = 0.71073 Å). Data reduction was performed using CrysAlisPro 171.33.55 software. The crystal structure was solved and refined using Olex2-1.0 with anisotropic displacement parameters for non-H atoms. H atoms were experimentally located through the difference-Fourier electron density maps in all crystal structures. Data was reduced by SAINT-Plus (Bruker, 1998 ) and further continued with SHELXTL (Sheldrick, 2008 ). A check of the final crystallographic information file (CIF) with PLATON (Spek, 2009 ) did not show any missed symmetry. X-Seed was used to prepare the figures and packing diagrams. Crystallographic parameters of all the cocrystals are summarized in Table 2. Hydrogen bond distances (see Table S1 of the supporting information ) are neutron-normalized (O—H 0.983, N—H 0.82, C—H 1.083 Å). CIF files are also deposited with the CCDC (Nos. 1039188–1039200).

Table 2
Crystallographic data summary and classification of sulfonamide–carboxamide cocrystals and isostructurality (see Table 3 for full crystallographic data)

S. No.	Cocrystal	Cell parameters (a, b, c, in Å)	Crystal system	Synthon observed
1	BSA–VLM	a = 7	Orthorhombic, P2₁2₁2₁
2	BSA–CPR	a = 7
3	4ClBSA–CPR	b = 12–13		Synthon 1
4	4BrBSA–CPR	c = 14–15		Catemer chain
5	SNA–CPR
6	4ClBSA–VLM	a = 25	Monoclinic, C2/c
7	4BrBSA–VLM	b = 7
	4BrBSA–VLM	c = 19
8	2ABSA–CPR	a = 7	Monoclinic, P2₁/n	Synthon 2
9	BSA–AZL	b = 16–17		Dimer–Cyclic ring
9	BSA–AZL	c = 12–13		Dimer–Cyclic ring
10	2ClBSA–VLM	a = 9–10	Monoclinic, P2₁/c	Synthon 3
11	2ClBSA–CPR	b = 13–14		Dimer–Catemer
11	2ClBSA–CPR	c = 10
12	PTSA–VLM	a = 5	Monoclinic, P2₁/n
		b = 16
		c = 16
13	OTSA–VLM	a = 5	Triclinic, $[P\bar 1]$
		b = 8
		c = 16

Some single-crystal diffraction data were collected at 298 K on a Bruker SMART APEX-1 CCD area-detector system equipped with a graphite monochromator, Mo Kα fine-focus sealed tube (λ = 0.71073 Å) operated at 1500 W power (40 kV, 30 mA). The frames were integrated with SAINT (Bruker, 1998) software using a narrow-frame integration algorithm. Data was corrected for absorption effects using the multi-scan method (SADABS; Bruker, 1998). The structure was solved and refined using SHELXTL (Sheldrick, 2008).

2.12. X-ray powder diffraction

Bulk samples were analyzed by X-ray powder diffraction on a Bruker AXS D8 diffractometer (Bruker-AXS, Karlsruhe, Germany). Experimental conditions: Cu Kα radiation (λ = 1.54056 Å); 40 kV; 30 mA; scanning interval 5–50° 2θ at a scan rate of 1° min⁻¹; time per step 0.5 s. The experimental PXRD patterns of the BSA, 4Cl BSA and 4Br BSA cocrystals were compared to confirm the isostructurality (Fig. S4 of the supporting information ).

2.13. Vibrational spectroscopy

A Thermo-Nicolet 6700 FT–IR spectrometer (Waltham, MA, USA) was used to record the IR spectra. IR spectra were recorded on samples dispersed in KBr pellets. For details of IR spectra see Fig. S8 and Table S4 .

3. Results and discussion

3.1. Crystal structure analysis and isostructurality

A few benzene sulfonamides (listed in Fig. 2) were selected to make cocrystals with PYR, VLM, CPR and AZL cyclic amides in a 1:1 stoichiometric ratio, which were ground mechanochemically through solvent-assisted grinding to obtain cocrystals. The resulting binary systems were analyzed with greater emphasis on VLM and CPR cocrystals since they are pharmaceutically acceptable coformers. Three types of synthons were observed: synthon 1 or the catemer motif of graph-set C₂¹(4) (Etter et al., 1990 ; Bernstein et al., 1995 ), synthon 2 which is a dimer–cyclic synthon motif of R₂²(8)R₄²(8), and synthon 3 as a dimer–catemer motif R₂²(8)C₁¹(4)D (Fig. 3). The crystal structure of BSA with AZL contains synthon 2. The crystal structures of other primary sulfonamides with AZL, PYR etc. will be discussed separately. Cocrystals of celecoxib (SO₂NH₂ drug) with odd/even homolog cyclic amides (Bolla et al., 2014 ) indicated that the odd ring size coformer (PYR, CPR) follows the heterosynthon, whereas even ring lactams (VLM, AZL) result in dimer–dimer/dimer–catemer synthons. With the aim of establishing a trend for sulfonamides, this study however did not give the previously observed synthons but resulted in different motifs. A robust and predictable functional group for sulfonamide cocrystals is pyridine N-oxide coformers (as well as P- and As-oxide) (e.g. Goud et al., 2011; Croker et al., 2012 ; Ferguson et al., 1989 ; Denise et al., 2014 ), but these are not of practical use as pharmaceuticals since they are not GRAS molecules (generally regarded as safe). The cocrystals obtained in this study and synthon classification are summarized in Fig. 3, along with crystallographic parameters in Table 2 (additional data in Table 3).

Table 3
Crystallographic parameters of the sulfonamide cocrystals with lactams of this study

	Catemer synthon
	BSA–VLM	BSA–CPR	4ClBSA–CPR	4BrBSA–CPR	SNA–CPR	4ClBSA–VLM	4BrBSA–VLM
Empirical formula	C₆H₇NO₂S·C₅H₉NO	C₆H₇NO₂S·C₆H₁₁NO	C₆H₆ClNO₂S·C₆H₁₁NO	C₆H₆BrNO₂S·C₆H₁₁NO	C₆H₈N₂O₂S·C₆H₁₁NO	C₆H₆ClNO₂S·C₅H₉NO	C₆H₆BrNO₂S·C₅H₉NO
Formula weight	256.33	270.35	304.80	349.25	285.37	290.77	335.22
Crystal system	Orthorhombic	Orthorhombic	Orthorhombic	Orthorhombic	Orthorhombic	Monoclinic	Monoclinic
Space group	P2₁2₁2₁	P2₁2₁2₁	P2₁2₁2₁	P2₁2₁2₁	P2₁2₁2₁	C2/c	C2/c
T (K)	298 (3)	298 (3)	298 (3)	298 (3)	298 (3)	298 (3)	298 (3)
a (Å)	7.1043 (5)	7.0700 (9)	7.1564 (13)	7.156 (3)	7.0957 (6)	25.701 (4)	25.914 (3)
b (Å)	12.7937 (10)	12.7624 (13)	13.369 (2)	13.538 (5)	13.1280 (13)	6.8096 (4)	6.8687 (9)
c (Å)	14.0302 (16)	14.977 (2)	15.276 (3)	15.406 (6)	15.3425 (18)	19.177 (3)	19.202 (2)
α (°)	90	90	90	90	90	90	90
β (°)	90	90	90	90	90	127.40 (2)	126.873 (2)
γ (°)	90	90	90	90	90	90	90
V (Å³)	1275.2 (2)	1351.4 (3)	1461.5 (4)	1492.5 (10)	1429.2 (3)	2666.2 (9)	2734.2(6)
D_calc (g cm⁻³)	1.335	1.329	1.385	1.554	1.326	1.449	1.629
μ (mm⁻¹)	0.253	0.242	0.409	2.899	0.235	0.445	3.161
θ range	3.59–27.83	3.96–26.72	2.84–26.31	2.00–26.38	2.64–24.65	2.66–26.31	1.96–26.35
Z/Z¹	4/1	4/1	4/1	4/1	4/1	8/1	8/1
h range	−4 → +8	−8 → +7	−8 → +7	−8 → +8	−7 → +8	−32 → +30	−32 → +32
k range	−15 → +15	−7 → +15	−12 → +16	−16 → +16	−8 → + 15	−8 → +8	−8 → +8
l range	−17 → 12	−17 → +16	−12 → +19	−19 → +19	−18 → 15	−23 → +22	−23 → +23
Reflections collected	3791	3348	4403	15 786	3692	5127	14029
Total reflections	2493	2197	2851	3029	2354	2732	2790
Observed reflections	2175	1595	1152	2405	1318	1677	2216
R₁ [I > 2σ(I)]	0.0466	0.0777	0.0896	0.0398	0.0529	0.0595	0.0348
wR₂ (all)	0.1201	0.1806	0.1141	0.0931	0.0796	0.1344	0.0939
Goodness-of-fit	1.059	1.231	0.968	1.025	0.901	1.067	1.029
X-ray diffractmeter	Oxford Gemini	Oxford Gemini	Oxford Gemini	Bruker Smart Apex	Oxford Gemini	Oxford Gemini	Bruker Smart Apex

	Dimer–cyclic synthon ring		Dimer–catemer synthon
	2ABSA–CPR	BSA–AZL	2ClBSA–VLM	2ClBSA–CPR	OTSA–VLM	PTSA–VLM
Empirical formula	C₆H₈N₂O₂S·C₆H₁₁NO	C₆H₇NO₂S·C₇H₁₃NO	C₆H₆ClNO₂S·C₅H₉NO	C₆H₆ClNO₂S·C₆H₁₁NO	C₇H₉NO₂S·C₅ H₉NO	C₇H₉NO₂S·C₅ H₉NO
Formula weight	285.37	284.36	290.77	304.80	270.35	270.35
Crystal system	Monoclinic	Monoclinic	Monoclinic	Monoclinic	Monoclinic	Triclinic
Space group	P2₁/n	P2₁/n	P2₁/c	P2₁/c	P2₁/n	P-1
T (K)	29 (3)	298 (3)	298 (3)	298 (3)	298 (3)	298 (3)
a (Å)	7.2731 (4)	7.3020 (9)	10.521 (2)	9.8782 (6)	5.3367 (6)	5.210 (3)
b (Å)	15.9052 (10)	17.189 (2)	13.7661 (12)	14.1720 (6)	15.9206 (17)	8.449 (4)
c (Å)	12.7766 (6)	12.2835 (16)	10.3407 (16)	10.8753 (6)	16.070 (3)	16.104 (8)
α (°)	90	90	90	90	90	82.894 (8)
β (°)	99.291 (5)	106.760 (2)	116.31 (2)	112.850 (7)	98.308 (12)	82.798 (8)
γ (°)	90	90	90	90	90	81.772 (8)
V (Å³)	1458.61 (14)	1476.3 (3)	1342.5 (4)	1403.00 (15)	1351.0	692.005
D_calc (g cm⁻³)	1.299	1.280	1.439	1.443	1.329	1.298
μ (mm⁻¹)	0.230	0.225	0.442	0.426	0.242	0.236
θ range	3.12–28.72	2.93–23.26	2.73–26.37	2.87–26.37	2.56–2.56	1.28–26.37
Z/Z¹	4/1	4/1	4/1	4/1	4/1	2/1
h range	−8 → +8	−8 → +8	−12 → +13	−12 → +11	−6 → +6	−6 → +6
k range	−16 → +18	−20 → +20	−15 → +17	−17 → +16	−19 → +11	−10 → +10
l range	−15 → +14	−14 → +14	−11 → +12	−13 → + 10	−14 → +20	−20 → +19
Reflections collected	5525	13 710	5058	5810	5072	7341
Total reflections	2488	2520	2731	2870	2759	2819
Observed reflections	1993	2154	2039	2483	1420	1969
R₁ [I > 2σ(I)]	0.0383	0.0597	0.0435	0.0385	0.0645	0.0504
wR₂ (all)	0.0995	0.1419	0.1144	0.1031	0.1183	0.1526
Goodness-of-fit	1.017	1.092	0.983	1.093	1.019	1.043
X-ray diffractmeter	Oxford Gemini	Bruker Smart Apex	Oxford Gemini	Oxford Gemini	Oxford Gemini	Bruker Smart Apex

Figure 3
Classification of three novel synthons in sulfonamide–lactam cocrystals. Names of the cocrystal structures are shown in the bottom row.

3.2. Synthon 1, catemer chain

Among the 13 cocrystal structures studied (Table 1), seven structures contain the sulfonamide–syn-carboxamide catemer synthon of C₂¹(4) notation. The catemer chains are assembled by sulfonamide N—H donors hydrogen bonding to the carboxamide acceptor. The structures are isostructural upon altering the auxiliary functional groups of benzene sulfonamide, such as Cl/Br/NH₂/CH₃. BSA–VLM and BSA–CPR have the same unit-cell parameters, whereas p-substituted BSA molecules (such as 4ClBSA, 4BrBSA and SNA) showed a 0.5 Å increase in the crystallographic b- and c-axis. BSA–VLM, BSA–CPR, SNA–CPR, 4ClBSA–CPR and 4BrBSA–CPR are three-dimensional isostructural. There are two more sets of isostructural cocrystals, 4ClBSA–VLM and 4BrBSA–VLM, with the same synthon.

3.2.1. BSA–VLM, BSA–CPR, SNA–CPR, 4 ClBSA–CPR and 4BrBSA–CPR (1:1)

The crystal structures of all these multi-component systems were refined in the orthorhombic space group P2₁2₁2₁. The sulfonamide NH₂ donates an N—H⋯O hydrogen bond to both sides of the carbonyl group of the lactam acceptor in the synthon 1 catemer (Fig. 4a). The hydrogen-bonded C(4) chain runs along the a-axis and in a corrugated sheet-like structure parallel to the (011) plane (Fig. 4, Fig. S1 ) and exhibits three-dimensional isostructurality in crystal packing.

Figure 4
Crystal structures of sulfonamide–lactam cocrystals with catemer synthon 1. Two-dimensional packing diagrams are drawn with the asymmetric unit showing benzene sulfonamides (in green) and lactams (in blue) (VLM, CPR).

3.2.2. ClBSA–VLM, 4BrBSA–VLM (1:1)

These two cocrystals have the catemer synthon and furthermore there is diversity in the two-dimensional packing patterns compared with the above set of five cocrystals. Both these structures are of the synthon 1 category even though they have different two-dimensional packing. The initial growth unit is the catemer hydrogen bond chain in these crystal structures. Sulfonamides and carboxamides form catemer synthon chains parallel to the b-axis (space group C2/c), which results in successive chain motifs (Fig. S1 ). The two-dimensional sheet arrangements of these isostructural cases are displayed in Fig. 4.

3.3. Synthon 2, dimer–cyclic ring

3.3.1. BSA–AZL cocrystal (1:1)

The crystal structure was refined in the monoclinic space group P2₁/n. Glide-related sulfonamide molecules are flanked between dimers of lactam through N—H⋯O (N1—H1B⋯O3: 2.12 Å, ∠158°; N1—H1A⋯O3: 2.03 Å, ∠158°) hydrogen bonds (sulfonamide NH donors) to give R₂²(8)R₄²(8) ring motif synthon 2 (Figs. 5a and b), similar to that in N-oxide cocrystals (Goud et al., 2011). The structural units extend along the a-axis in a one-dimensional pattern. The meta H atoms of BSA form C—H⋯O interactions with S=O along the a-axis (Fig. 5c) resulting in corrugated layers of sulfonamide chains separated by coformer molecules (Fig. S2 ).

Figure 5
Dimer–cyclic synthon 2 in cocrystals BSA–AZL, 2ABSA–CPR and two-dimensional layer packing. Two-dimensional packing diagrams are drawn with the asymmetric unit showing benzene sulfonamides (in green) and lactams (in blue) (VLM, CPR).

3.3.2. ABSA–CPR cocrystal (1:1)

This cocrystal is isostructural with BSA–AZL. The main synthon in 2ABSA–CPR is R₂²(8)R₄²(8) ring motifs along the a-axis (Fig. 5d) together with corrugated wave-like layers (Figs. 5d and e). The isostructurality is illustrated in Fig. S2 .

3.4. Synthon 3, dimer–catemer

3.4.1. ClBSA–VLM cocrystal (1:1)

Equimolar quantities of the components were ground and crystallized from EtOAc to give single crystals which were solved in the monoclinic space group P2₁/c. Catemer chains connect glide-related 2ClBSA molecules that assemble via homodimers of VLM through N—H⋯O (N1—H1A⋯O3 = 2.03 Å, ∠169°) hydrogen bonds in synthon 3, or dimer–catemer synthon R₂²(8)C₁¹(4)D (Figs. 6a and b). In this synthon the coformer dimers are sandwiched between sulfonamide catemer chains. Halogen bonding (Cl⋯O, Cl⋯N) provides auxiliary support to the structure (Metrangolo et al., 2005 , 2008 ; Saha & Nangia, 2007 ; Desiraju, 1989 ; Mukherjee et al., 2014 ). The catemer chains of 2ClBSA extend along the c-axis and homodimers of VLM connect adjacent chains of sulfonamides via C—H⋯O interactions to make two-dimensional stacks in the ab-plane (Fig. 6c).

Figure 6
Dimer–catemer synthon 3 in cocrystals 2ClBSA–VLM, 2ClBSA–CPR, OTSA–VLM, PTSA–VLM and two-dimensional hydrogen bond motifs. Two-dimensional packing diagrams are drawn with the asymmetric unit showing benzene sulfonamides (in green) and lactams (in blue) (VLM, CPR).

3.4.2. ClBSA–CPR cocrystal (1:1)

Cocrystal 2ClBSA–CPR is isostructural with 2ClBSA–VLM. Sulfonamide catemer chains are interlinked via discrete synthons to homodimers of CPR through N1—H1A⋯O3 hydrogen bonds (1.97 Å, ∠176°) to give synthon 3, dimer–catemer (Figs. 6a and d). The homodimers of CPR are sandwiched between chains of sulfonamide chains. These patterns grow via C—H⋯O interactions to make interestingly parachute-like cone rings (Fig. 6e).

3.4.3. OTSA–VLM cocrystal (1:1)

The OTSA molecule formed a cocrystal (monoclinic crystal system, P2₁/c space group) with VLM homodimers (N2—H2A⋯O3 = 2.26 Å, ∠175°) via a discrete (D graph set) N—H⋯O (N1—H1B⋯O3 = 2.03 Å, ∠179°) synthon along the c-axis. Such dimers are sandwiched between screw-related sulfonamide chains, similar to two previous cocrystal structures (Fig. 6f). Supportive C—H⋯O interactions make parallel stacks (Fig. 6g and Fig. S3a ).

3.4.4. PTSA–VLM cocrystal (1:1)

The crystal structure was solved in a triclinic crystal system with space group $[P\bar 1]$ . The basic supramolecular synthon of the catemer type is also present in this cocrystal (Fig. 6h), but with different unit-cell parameters (Table 3). Sulfonamide molecules form catemer chain motifs above and below the VLM homodimers (N2—H2A⋯O3; H⋯O 2.15 Å, ∠176°; Fig. 6i). The sandwich-type structure is sustained by inversion-related sulfonamide chains in AABB-type stacking (Fig. S3b ).

3.5. Isostructural and isomorphous systems

Two crystals are said to be isostructural if they have the same structure, but not necessarily the same unit-cell dimensions nor the same chemical composition, with a comparable variability in the atomic coordinates to that of the cell dimensions and chemical composition (IUCr, 2014 ). Isostructurality depicts the arrangement of different molecules in a similar way in the crystal structure, but not necessarily their unit-cell parameters (Fábián, Argay & Kálmán, 1999 ; Fábián & Kálmán, 1999 , 2004 ; Kitaigorodsky, 1961 ). Certain substituents in the molecule can be replaced with others without altering the crystal packing as well as cell values and the space group (Brink & Kroese, 1952 ; Perutz, 1956 ; Kroon et al., 1965 ; Sauer et al., 1997 ; Dikundwar et al., 2012 ). Such a functional group exchange leads to isostructural and isomorphous crystal structures (Berzelius, 1844 ; Melhado, 1980 ; Mitscherlich, 1822 ; Morrow, 1969 ). The recent literature on molecular cocrystals (Cinčić et al., 2008a ,b ; Dubey & Desiraju, 2014 ) and pharmaceutical multi-component systems, e.g. lamotrigine and olanzapine cocrystals and salts, provide examples of isostructurality (Ebenezer et al., 2011 ; Galcera et al., 2012 , 2013 ; Galcera & Molins, 2009 ; Clarke et al., 2012 ; Thakuria & Nangia, 2013 ; Chitra et al., 2012 ). The importance of isostructurality is that similar cocrystals can be designed depending on the geometry and shape and molecular composition of the starting materials. Isostructurality is also a useful guide in the crystal structure prediction of multi-component systems (Schmidt, 1971 ; Desiraju, 1989; Braga et al., 1998 ; Desiraju et al., 2011 ). Different guest molecules may be incorporated into the host lattice without substantially changing the crystal structure, i.e. isostructurality. The formation of isostructural cocrystals with the same synthon (isosynthon) and this study of sulfonamides with VLM, CPR shows how synthon similarity can lead to isostructural cocrystals (Fig. 3). There are four sets of isostructural cocrystals along with three types of synthons found in this set of cocrystals. Interestingly, a unique set of isostructural cocrystals shows isosynthons. Out of the 13 cocrystal structures in this study, four contain the dimer–catemer synthon, two result in the dimer–cyclic motif and seven gave the catemer synthon. Synthon 1 cocrystals exhibit two isostructural sets: set one of BSA–VLM, BSA–CPR, 4ClBSA–CPR, 4BrBSA–CPR, SNA–CPR and set two cocrystals 4ClBSA–CPR and 4BrBSA–CPR. These are three-dimensional isostructural systems and show isostructurality due to the Cl/Br/NH₂ exchange (functional group) and VLM/CPR (homolog; Table 4). Further, the same trend continues for synthons 2 and 3 cocrystal sets also, i.e. isostructurality for Cl/Br and VLM/CPR. Furthermore, despite changes in molecular structures, the PXRD line patterns of synthon 1 cocrystals match quite well (Fig. S4 ) confirming their isomorphous nature.

Table 4
Unit-cell similarity index ( $[\prod]$ ) of cocrystals

Cocrystal†	Crystal system/space group	Cell values	Cell values summation	$[\prod = \left\| {{a + b + c} \over {a' + b' + c'}} \right\| - 1]$
BSA–VLM^a	Orthorhombic, P2₁2₁2₁	7.104, 12.793, 14.030	33.928	0.0253
BSA–CPR^a		7.070, 12.762, 14.977	34.809	0.0253
4ClBSA–CPR^a		7.156, 13.369, 15.276	35.801	0.0082
4BrBSA–CPR^a		7.156, 13.538, 15.406	36.100	0.0082
SNA–CPR^a		7.095, 13.128, 15.342	35.566	0.0147 (SNA–CPR, 4BrBSA–CPR)
4ClBSA–VLM^b	Monoclinic, C2/c	25.701, 6.809, 19.177	51.900	0.0016
4BrBSA–VLM^b	Monoclinic, C2/c	25.914, 6.8687, 19.202	51.984	0.0016
2ClBSA–VLM^c	Monoclinic, P2₁/c	10.521, 13.7661, 10.340	34.627	0.0085
2ClBSA–CPR^c		9.878, 14.172, 10.875	34.925	0.0085
2ABSA–CPR^d		7.273, 15.905, 12.776	35.954	0.0223
BSA–AZL^d		7.302, 17.189, 12.2835	36.774	0.0223

†a, b, c, d are the different isomorphous systems as detailed in Table 1

Isostructurality was calculated on the basis of unit-cell parameters. Monoclinic and orthorhombic crystal structures show the unit-cell similarity index $[\prod]$ goes to zero (isostructurality) (see Table 2)

$[\prod = \left| {{{a + b + c} \over {a' + b' + c'}}} \right| - 1 \cong 0,]$

where a, b, c and a′, b′, c′ are orthogonalized lattice parameters of the related structures.

3.6. Classification of sulfonamide synthons

A survey of the Cambridge Structural Database (CSD, Version 5.36, 1 November 2014 update; Allen, 2002 ) furnished 220 hits of primary sulfonamides (after eliminating hydrates, solvates, salts and duplicates) and 2160 hits of secondary sulfonamides (Table 5). These reported structures were analyzed to classify the known supramolecular synthons for sulfonamides and named as the anti catemer, syn catemer, finite catemer; continuous dimers, alternative dimers (Fig. 7b), dimers making rings, finite dimers; tetramers, three point synthons, and finally a miscellaneous cluster of mixed motifs (Fig. 7, CSD refcodes are provided in Table S2 ). The presence of multiple donors/acceptors on the SO₂NH₂ group together with conformational flexibility (syn/anti) leads to many possible hydrogen bond synthons. In contrast, the syn amides are more predictable and show mainly dimer and to a lesser extent catemer synthons. The synthons in Fig. 7(c) suggest that the known heterosynthon between sulfonamide and N-oxide may be replaced by amide with the same graph set R₄²(8) to provide a crystal engineering strategy for sulfonamide–carboxamide cocrystals.

Table 5
CSD data on sulfonamides and their cocrystals

Hydrates, solvates, salts and duplicates were removed in counting statistics.

Sulfonamides	CSD hits
No. of primary sulfonamides reported	220
No. of secondary sulfonamides reported	2160
No. of primary sulfonamides cocrystals reported	33
No. of secondary sulfonamides cocrystals reported	39

Figure 7
(a) Classification of primary sulfonamide synthons reported in CSD and (b) their hydrogen bonding and frequency. (c) Synthons in cocrystals of primary sulfonamides with N-oxides and amides. The latter analysis suggests that sulfonamide–N-oxide synthons may be replaced by syn-amides to give a new strategy for sulfonamide–carboxamide cocrystals.

A CSD search for the binary systems (cocrystals) furnished 33 hits for primary sulfonamides and 39 hits for secondary sulfonamides along with the starting materials of this study (Fig. S5 ). The almost equal numbers of primary and secondary sulfonamide cocrystals means that there are no steric issues with cocrystal assembly. Among the primary sulfonamide cocrystals, there are a few N—H⋯O hydrogen-bonded structures with amides, e.g. celecoxib-valerolactam trimorphs and nicotinamide cocrystals (see Fig. 7). Among the primary sulfonamide drugs, celecoxib, furosemide, acetazolamide and hydrochlorothiazide are notable for making cocrystals with amide coformers (Bolla et al., 2014; Harriss et al., 2014 ; Ueto et al., 2012 ; Arenas-García et al., 2010 ; Sanphui & Rajput, 2014 ; Remenar et al., 2007 ), e.g. nicotinamide, isonicotinamide and picolinamide with different sulfonamide–amide synthons (see Fig. S9 ).

There are 2046 sulfonamides in the CSD but only 72 binary systems (cocrystals) in the CSD. The fewer number of sulfonamide cocrystals compared to say those for carboxylic acids and amides could be due to the enthalpy penalty for disrupting the strong sulfonamide homosynthon in the parent crystal structures with an even stronger hydrogen bond in the cocrystal. The activated oxygen acceptor of N-oxides, and to a lesser extent carboxamide functional groups, has been successfully used for sulfonamide cocrystals. The present study presents a crystal engineering approach to sulfonamide–carboxamide cocrystals analogous to the sulfonamide–pyridine-N-oxide heterosynthon.

3.7. Hirshfeld surface analysis

The Hirshfeld surface (using Crystal Explorer, Version 3.1, Hirshfeld, 1977 ; Hirshfeld & Mirsky, 1979 ; Kitaigorodsky, 1973 ; Vainshtein et al., 1982 ; Spackman & Jayatilaka, 2009 , McKinnon et al., 1998 ) translates the electron density into molecular fragments and also volume around a molecule in a manner similar to the van der Waals surface, or an outer surface of the electron density in a crystal structure. The Hirshfeld surface is related to the molecule and the proximity of its nearest neighbors and this allows easy identification of characteristic strong and weak interactions throughout the structure. It explains the nature of intermolecular interactions within a crystal structure using a two-dimensional fingerprint plot consisting of spikes and wings. The 4BrBSA–VLM cocrystal two-dimensional finger plots with all types of interactions are shown in Fig. 8 as a representative of this class. The other binary systems are shown in Fig. S6 . The strong spikes at 1.0–1.2 Å correspond to H⋯O interactions and the weak spikes between 1.2 and 1.4 Å for H⋯N hydrogen bonds. The other H⋯X, H⋯H, H⋯C interactions occur between 1.5 and 2.4 Å in the wings region. The strong H⋯O interaction is the major contributor in cocrystal structures (Fig. S7 and Table S3 ).

Figure 8
(a) Hirshfeld surfaces of the three types of the synthons present in sulfonamide–lactam cocrystals. (b) Two-dimensional fingerprint plots of the intermolecular contacts in the 4BrBSA–CPR cocrystal.

4. Conclusions

A crystal engineering strategy is described for cocrystals of an otherwise less studied but pharmaceutically very important class of sulfonamide functional group. The binary systems of benzene sulfonamide–lactam exhibit three types of heterosynthons. The N—H donor of the sulfonamide forms a hydrogen bond with the C=O acceptor in different arrangements to result in synthon 1 of the catemer chain, synthon 2 as a dimer–cyclic motif and synthon 3 as a dimer–catemer. The classification of cocrystal structures in these synthon categories now offers a design element for sulfa drug cocrystals with GRAS coformers. Interestingly, isostructural pairs of cocrystals with isosynthons are observed in this study, which not only facilitates classification but also correlates with known cocrystal structures in the CSD, e.g. the novel sulfonamide–amide synthon analogous to the reported sulfonamide–N-oxide. The cocrystals of primary sulfonamides with GRAS coformers will provide an entry to the modification of sulfa drugs via pharmaceutical cocrystals.

Supporting information

CCDC references: 1039188; 1039189; 1039190; 1039191; 1039192; 1039193; 1039194; 1039195; 1039196; 1039197; 1039198; 1039199; 1039200; 1053703

Crystal structure: contains datablocks global, 2ABSACPR, BSAAZL, 4ClBSACPR, SNACPR, 4BrBSACPR, OTSAVLM, 2ClBSACPR, BSACPR, 4ClBSAVLM, 4BrBSAVLM, PTSAVLM, 2ClBSAVLM, BSAVLM. DOI: 10.1107/S2052252515004960/zx5004sup1.cif

Structure factors: contains datablock 2ABSACPR. DOI: 10.1107/S2052252515004960/zx50042ABSACPRsup2.hkl

Structure factors: contains datablock BSAAZL. DOI: 10.1107/S2052252515004960/zx5004BSAAZLsup3.hkl

Structure factors: contains datablock BSAVLM. DOI: 10.1107/S2052252515004960/zx5004BSAVLMsup14.hkl

Structure factors: contains datablock SNACPR. DOI: 10.1107/S2052252515004960/zx5004SNACPRsup5.hkl

Structure factors: contains datablock 4BrBSACPR. DOI: 10.1107/S2052252515004960/zx50044BrBSACPRsup6.hkl

Structure factors: contains datablock OTSAVLM. DOI: 10.1107/S2052252515004960/zx5004OTSAVLMsup7.hkl

Structure factors: contains datablock 2ClBSACPR. DOI: 10.1107/S2052252515004960/zx50042ClBSACPRsup8.hkl

Structure factors: contains datablock BSACPR. DOI: 10.1107/S2052252515004960/zx5004BSACPRsup9.hkl

Structure factors: contains datablock 4ClBSAVLM. DOI: 10.1107/S2052252515004960/zx50044ClBSAVLMsup10.hkl

Structure factors: contains datablock 4BrBSAVLM. DOI: 10.1107/S2052252515004960/zx50044BrBSAVLMsup11.hkl

Structure factors: contains datablock PTSAVLM. DOI: 10.1107/S2052252515004960/zx5004PTSAVLMsup12.hkl

Structure factors: contains datablock 2ClBSAVLM. DOI: 10.1107/S2052252515004960/zx50042ClBSAVLMsup13.hkl

Structure factors: contains datablock BSAVLM. DOI: 10.1107/S2052252515004960/zx5004BSAVLMsup14.hkl

Supporting tables and figures. DOI: 10.1107/S2052252515004960/zx5004sup15.pdf

Computing details top

For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

(2ABSACPR) top

Crystal data top

C6H8N2O2S·C6H11NO	D_x = 1.299 Mg m⁻³
M_r = 285.36	Melting point: 341 K
Monoclinic, P1₂1/n1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2731 (4) Å	Cell parameters from 2272 reflections
b = 15.9052 (10) Å	θ = 3.1–28.7°
c = 12.7766 (6) Å	µ = 0.23 mm⁻¹
β = 99.291 (5)°	T = 298 K
V = 1458.60 (15) Å³	PLATE, colorles
Z = 4	0.22 × 0.21 × 0.20 mm
F(000) = 608

Data collection top

Xcalibur, Eos, Gemini diffractometer	2488 independent reflections
Radiation source: fine-focus sealed tube	1993 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ω scans	θ_max = 24.7°, θ_min = 3.0°
Absorption correction: multi-scan SADABS	h = −8→8
T_min = 0.874, T_max = 1.000	k = −16→18
5525 measured reflections	l = −15→14

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0513P)² + 0.2431P] where P = (F_o² + 2F_c²)/3
2488 reflections	(Δ/σ)_max = 0.001
179 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C6H8N2O2S·C6H11NO	V = 1458.60 (15) Å³
M_r = 285.36	Z = 4
Monoclinic, P1₂1/n1	Mo Kα radiation
a = 7.2731 (4) Å	µ = 0.23 mm⁻¹
b = 15.9052 (10) Å	T = 298 K
c = 12.7766 (6) Å	0.22 × 0.21 × 0.20 mm
β = 99.291 (5)°

Data collection top

Xcalibur, Eos, Gemini diffractometer	2488 independent reflections
Absorption correction: multi-scan SADABS	1993 reflections with I > 2σ(I)
T_min = 0.874, T_max = 1.000	R_int = 0.020
5525 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.15 e Å⁻³
2488 reflections	Δρ_min = −0.32 e Å⁻³
179 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

	x	y	z	U_iso*/U_eq
S1	0.03105 (7)	0.83445 (3)	0.15700 (4)	0.04286 (18)
O3	−0.19797 (19)	0.47718 (9)	0.56486 (11)	0.0533 (4)
O2	0.1587 (2)	0.84605 (10)	0.25335 (11)	0.0589 (4)
N3	0.0943 (2)	0.43705 (11)	0.62356 (13)	0.0507 (4)
H3A	0.1222	0.4525	0.5636	0.061*
O1	−0.1464 (2)	0.79747 (10)	0.16181 (12)	0.0603 (4)
C6	0.0484 (3)	0.74236 (12)	−0.02378 (16)	0.0451 (5)
N1	−0.0085 (3)	0.92530 (12)	0.10533 (15)	0.0484 (5)
H1A	−0.094 (3)	0.9264 (14)	0.0607 (19)	0.058*
H1B	0.094 (3)	0.9551 (14)	0.0993 (17)	0.058*
C1	0.1442 (3)	0.77321 (12)	0.07254 (15)	0.0397 (5)
C7	−0.0815 (3)	0.44355 (12)	0.63577 (16)	0.0444 (5)
N2	−0.1366 (3)	0.75970 (12)	−0.05867 (15)	0.0623 (5)
H2A	−0.1843	0.7206	−0.1015	0.075*
H2B	−0.1948	0.7615	−0.0050	0.075*
C4	0.3371 (4)	0.68114 (16)	−0.0565 (2)	0.0709 (7)
H4	0.4020	0.6502	−0.1004	0.085*
C2	0.3335 (3)	0.75770 (14)	0.10226 (18)	0.0548 (6)
H2	0.3958	0.7791	0.1660	0.066*
C12	0.2458 (3)	0.40596 (15)	0.70280 (18)	0.0571 (6)
H12A	0.3589	0.4036	0.6717	0.069*
H12B	0.2168	0.3492	0.7226	0.069*
C5	0.1519 (4)	0.69616 (14)	−0.08703 (19)	0.0616 (6)
H5	0.0927	0.6751	−0.1517	0.074*
C8	−0.1377 (3)	0.41193 (16)	0.73576 (17)	0.0586 (6)
H8A	−0.0966	0.3541	0.7468	0.070*
H8B	−0.2726	0.4124	0.7280	0.070*
C11	0.2803 (3)	0.45962 (16)	0.80099 (19)	0.0643 (6)
H11A	0.2742	0.5183	0.7800	0.077*
H11B	0.4053	0.4488	0.8379	0.077*
C9	−0.0588 (3)	0.46304 (17)	0.83262 (19)	0.0688 (7)
H9A	−0.1332	0.4525	0.8878	0.083*
H9B	−0.0708	0.5222	0.8145	0.083*
C10	0.1438 (3)	0.44484 (17)	0.87691 (18)	0.0690 (7)
H10A	0.1802	0.4797	0.9391	0.083*
H10B	0.1539	0.3866	0.8998	0.083*
C3	0.4291 (3)	0.71126 (16)	0.0386 (2)	0.0696 (7)
H3	0.5552	0.7002	0.0595	0.083*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0492 (3)	0.0467 (3)	0.0322 (3)	−0.0020 (2)	0.0050 (2)	0.0030 (2)
O3	0.0480 (8)	0.0652 (9)	0.0446 (8)	0.0006 (7)	0.0011 (7)	0.0064 (7)
O2	0.0724 (10)	0.0662 (10)	0.0335 (8)	0.0041 (8)	−0.0049 (7)	−0.0019 (7)
N3	0.0524 (10)	0.0610 (11)	0.0399 (10)	0.0056 (9)	0.0112 (8)	0.0068 (8)
O1	0.0579 (9)	0.0670 (10)	0.0602 (10)	−0.0130 (8)	0.0223 (7)	0.0016 (8)
C6	0.0564 (12)	0.0396 (10)	0.0376 (11)	−0.0034 (9)	0.0029 (9)	0.0039 (9)
N1	0.0477 (10)	0.0479 (10)	0.0468 (11)	0.0001 (9)	−0.0005 (8)	0.0035 (9)
C1	0.0449 (10)	0.0387 (10)	0.0351 (11)	−0.0035 (9)	0.0050 (8)	0.0057 (8)
C7	0.0483 (11)	0.0428 (11)	0.0419 (11)	−0.0044 (10)	0.0061 (9)	−0.0004 (10)
N2	0.0644 (12)	0.0665 (12)	0.0494 (11)	−0.0059 (10)	−0.0104 (9)	−0.0080 (10)
C4	0.0858 (19)	0.0631 (15)	0.0726 (18)	0.0115 (14)	0.0393 (15)	0.0013 (14)
C2	0.0480 (12)	0.0614 (14)	0.0538 (14)	−0.0017 (11)	0.0048 (10)	0.0040 (11)
C12	0.0512 (12)	0.0625 (14)	0.0590 (14)	0.0117 (11)	0.0131 (10)	0.0121 (12)
C5	0.0923 (19)	0.0513 (13)	0.0419 (13)	−0.0024 (13)	0.0130 (12)	−0.0046 (11)
C8	0.0512 (12)	0.0729 (15)	0.0530 (14)	−0.0060 (11)	0.0124 (10)	0.0141 (12)
C11	0.0612 (14)	0.0700 (15)	0.0572 (15)	−0.0081 (12)	−0.0037 (11)	0.0110 (13)
C9	0.0814 (17)	0.0810 (17)	0.0478 (14)	0.0121 (14)	0.0221 (12)	0.0040 (13)
C10	0.0879 (18)	0.0730 (16)	0.0430 (13)	−0.0026 (14)	0.0013 (12)	0.0024 (12)
C3	0.0549 (14)	0.0759 (17)	0.0813 (19)	0.0084 (13)	0.0213 (13)	0.0082 (15)

Geometric parameters (Å, º) top

S1—O1	1.4283 (15)	C4—H4	0.9300
S1—O2	1.4290 (14)	C2—C3	1.369 (3)
S1—N1	1.5954 (18)	C2—H2	0.9300
S1—C1	1.754 (2)	C12—C11	1.505 (3)
O3—C7	1.256 (2)	C12—H12A	0.9700
N3—C7	1.317 (2)	C12—H12B	0.9700
N3—C12	1.457 (3)	C5—H5	0.9300
N3—H3A	0.8600	C8—C9	1.514 (3)
C6—N2	1.375 (2)	C8—H8A	0.9700
C6—C5	1.399 (3)	C8—H8B	0.9700
C6—C1	1.401 (3)	C11—C10	1.514 (3)
N1—H1A	0.77 (2)	C11—H11A	0.9700
N1—H1B	0.90 (2)	C11—H11B	0.9700
C1—C2	1.390 (3)	C9—C10	1.519 (3)
C7—C8	1.490 (3)	C9—H9A	0.9700
N2—H2A	0.8631	C9—H9B	0.9700
N2—H2B	0.8626	C10—H10A	0.9700
C4—C5	1.361 (3)	C10—H10B	0.9700
C4—C3	1.375 (4)	C3—H3	0.9300

O1—S1—O2	118.80 (10)	N3—C12—H12B	109.0
O1—S1—N1	106.67 (10)	C11—C12—H12B	109.0
O2—S1—N1	106.76 (10)	H12A—C12—H12B	107.8
O1—S1—C1	108.34 (9)	C4—C5—C6	121.8 (2)
O2—S1—C1	107.32 (9)	C4—C5—H5	119.1
N1—S1—C1	108.63 (9)	C6—C5—H5	119.1
C7—N3—C12	125.74 (18)	C7—C8—C9	113.53 (19)
C7—N3—H3A	117.1	C7—C8—H8A	108.9
C12—N3—H3A	117.1	C9—C8—H8A	108.9
N2—C6—C5	120.5 (2)	C7—C8—H8B	108.9
N2—C6—C1	122.43 (19)	C9—C8—H8B	108.9
C5—C6—C1	116.96 (19)	H8A—C8—H8B	107.7
S1—N1—H1A	113.3 (17)	C12—C11—C10	114.09 (19)
S1—N1—H1B	114.7 (14)	C12—C11—H11A	108.7
H1A—N1—H1B	120 (2)	C10—C11—H11A	108.7
C2—C1—C6	120.54 (19)	C12—C11—H11B	108.7
C2—C1—S1	118.23 (15)	C10—C11—H11B	108.7
C6—C1—S1	121.22 (15)	H11A—C11—H11B	107.6
O3—C7—N3	120.19 (19)	C8—C9—C10	114.8 (2)
O3—C7—C8	121.05 (18)	C8—C9—H9A	108.6
N3—C7—C8	118.75 (18)	C10—C9—H9A	108.6
C6—N2—H2A	109.4	C8—C9—H9B	108.6
C6—N2—H2B	109.2	C10—C9—H9B	108.6
H2A—N2—H2B	109.2	H9A—C9—H9B	107.5
C5—C4—C3	120.7 (2)	C11—C10—C9	115.38 (19)
C5—C4—H4	119.7	C11—C10—H10A	108.4
C3—C4—H4	119.7	C9—C10—H10A	108.4
C3—C2—C1	120.6 (2)	C11—C10—H10B	108.4
C3—C2—H2	119.7	C9—C10—H10B	108.4
C1—C2—H2	119.7	H10A—C10—H10B	107.5
N3—C12—C11	113.09 (18)	C2—C3—C4	119.4 (2)
N3—C12—H12A	109.0	C2—C3—H3	120.3
C11—C12—H12A	109.0	C4—C3—H3	120.3

(BSAAZL) top

Crystal data top

C6H7NO2S·C7H13NO	F(000) = 608
M_r = 284.37	D_x = 1.279 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.3020 (9) Å	Cell parameters from 3397 reflections
b = 17.189 (2) Å	θ = 2.9–23.3°
c = 12.2835 (16) Å	µ = 0.23 mm⁻¹
β = 106.760 (2)°	T = 298 K
V = 1476.2 (3) Å³	PLATE, colorles
Z = 4	0.22 × 0.20 × 0.20 mm

Data collection top

CCD area detector diffractometer	2154 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.037
Graphite monochromator	θ_max = 24.7°, θ_min = 2.1°
phi and ω scans	h = −8→8
13710 measured reflections	k = −20→20
2520 independent reflections	l = −14→14

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0573P)² + 0.8349P] where P = (F_o² + 2F_c²)/3
2520 reflections	(Δ/σ)_max < 0.001
184 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C6H7NO2S·C7H13NO	V = 1476.2 (3) Å³
M_r = 284.37	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.3020 (9) Å	µ = 0.23 mm⁻¹
b = 17.189 (2) Å	T = 298 K
c = 12.2835 (16) Å	0.22 × 0.20 × 0.20 mm
β = 106.760 (2)°

Data collection top

CCD area detector diffractometer	2154 reflections with I > 2σ(I)
13710 measured reflections	R_int = 0.037
2520 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.26 e Å⁻³
2520 reflections	Δρ_min = −0.27 e Å⁻³
184 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
S1	0.38938 (11)	0.14789 (5)	0.32694 (6)	0.0614 (3)
O3	0.6840 (3)	0.53498 (12)	0.94445 (16)	0.0631 (5)
N2	0.3761 (3)	0.56077 (15)	0.8646 (2)	0.0566 (6)
C7	0.5577 (4)	0.57061 (15)	0.8708 (2)	0.0519 (7)
N1	0.4595 (4)	0.06644 (16)	0.3858 (2)	0.0624 (7)
C1	0.2838 (4)	0.20092 (15)	0.4165 (2)	0.0509 (7)
C6	0.3969 (5)	0.24554 (18)	0.5024 (2)	0.0649 (8)
H6	0.5285	0.2473	0.5140	0.078*
O1	0.5566 (4)	0.18886 (15)	0.3219 (2)	0.0918 (8)
C2	0.0897 (4)	0.19751 (18)	0.4000 (3)	0.0649 (8)
H2	0.0131	0.1669	0.3422	0.078*
O2	0.2438 (4)	0.13196 (16)	0.22504 (17)	0.0936 (8)
C13	0.2123 (4)	0.5940 (2)	0.7798 (3)	0.0677 (8)
H13A	0.2483	0.6442	0.7562	0.081*
H13B	0.1099	0.6026	0.8142	0.081*
C12	0.1394 (4)	0.5429 (2)	0.6764 (3)	0.0764 (10)
H12A	0.0416	0.5712	0.6200	0.092*
H12B	0.0791	0.4974	0.6979	0.092*
C8	0.6142 (4)	0.62429 (18)	0.7904 (3)	0.0678 (8)
H8A	0.7423	0.6434	0.8265	0.081*
H8B	0.5286	0.6687	0.7760	0.081*
C10	0.4123 (5)	0.5781 (2)	0.5924 (3)	0.0832 (10)
H10A	0.3448	0.6273	0.5867	0.100*
H10B	0.4280	0.5668	0.5182	0.100*
C9	0.6104 (5)	0.5875 (2)	0.6774 (3)	0.0773 (10)
H9A	0.6696	0.5366	0.6922	0.093*
H9B	0.6881	0.6190	0.6424	0.093*
C11	0.2909 (6)	0.5156 (2)	0.6214 (3)	0.0867 (11)
H11A	0.3745	0.4791	0.6726	0.104*
H11B	0.2272	0.4876	0.5523	0.104*
C3	0.0098 (5)	0.2398 (2)	0.4696 (3)	0.0812 (10)
H3	−0.1215	0.2380	0.4589	0.097*
C4	0.1229 (7)	0.2846 (2)	0.5545 (3)	0.0874 (11)
H4	0.0684	0.3133	0.6013	0.105*
C5	0.3157 (7)	0.2872 (2)	0.5707 (3)	0.0856 (11)
H5	0.3921	0.3177	0.6288	0.103*
H1A	0.556 (4)	0.0704 (17)	0.437 (3)	0.055 (9)*
H1B	0.367 (4)	0.0358 (18)	0.394 (2)	0.063 (9)*
H2A	0.350 (4)	0.5300 (17)	0.910 (3)	0.056 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0675 (5)	0.0681 (5)	0.0491 (4)	0.0087 (4)	0.0176 (3)	0.0095 (3)
O3	0.0502 (11)	0.0787 (14)	0.0541 (11)	0.0043 (10)	0.0050 (9)	0.0086 (10)
N2	0.0512 (14)	0.0715 (16)	0.0477 (13)	0.0044 (12)	0.0155 (11)	0.0093 (12)
C7	0.0542 (16)	0.0519 (15)	0.0465 (15)	−0.0030 (13)	0.0093 (13)	−0.0062 (12)
N1	0.0509 (15)	0.0663 (17)	0.0639 (17)	0.0013 (13)	0.0072 (14)	0.0031 (13)
C1	0.0572 (16)	0.0496 (15)	0.0417 (14)	0.0015 (12)	0.0077 (12)	0.0096 (12)
C6	0.0689 (19)	0.0658 (19)	0.0542 (17)	−0.0071 (15)	0.0086 (15)	0.0034 (15)
O1	0.0985 (18)	0.0885 (17)	0.1086 (19)	−0.0026 (14)	0.0617 (15)	0.0215 (14)
C2	0.0614 (19)	0.071 (2)	0.0570 (17)	−0.0012 (15)	0.0087 (14)	0.0009 (15)
O2	0.1033 (18)	0.118 (2)	0.0458 (12)	0.0350 (15)	−0.0006 (12)	−0.0055 (12)
C13	0.0514 (17)	0.086 (2)	0.0670 (19)	0.0184 (15)	0.0195 (14)	0.0105 (17)
C12	0.0546 (18)	0.103 (3)	0.0623 (19)	−0.0069 (17)	0.0027 (15)	0.0138 (18)
C8	0.0568 (18)	0.0632 (19)	0.080 (2)	−0.0092 (14)	0.0139 (16)	0.0119 (16)
C10	0.102 (3)	0.093 (3)	0.0595 (19)	0.012 (2)	0.0313 (19)	0.0084 (18)
C9	0.070 (2)	0.095 (2)	0.076 (2)	0.0144 (18)	0.0355 (18)	0.0293 (19)
C11	0.103 (3)	0.089 (3)	0.062 (2)	−0.014 (2)	0.014 (2)	−0.0165 (18)
C3	0.074 (2)	0.091 (3)	0.087 (3)	0.0150 (19)	0.037 (2)	0.014 (2)
C4	0.134 (4)	0.073 (2)	0.069 (2)	0.017 (2)	0.051 (2)	0.0041 (19)
C5	0.122 (3)	0.074 (2)	0.0550 (19)	−0.013 (2)	0.015 (2)	−0.0068 (17)

Geometric parameters (Å, º) top

S1—O2	1.416 (2)	C12—C11	1.526 (5)
S1—O1	1.426 (2)	C12—H12A	0.9700
S1—N1	1.591 (3)	C12—H12B	0.9700
S1—C1	1.768 (3)	C8—C9	1.517 (5)
O3—C7	1.250 (3)	C8—H8A	0.9700
N2—C7	1.317 (3)	C8—H8B	0.9700
N2—C13	1.457 (3)	C10—C11	1.500 (5)
N2—H2A	0.83 (3)	C10—C9	1.529 (5)
C7—C8	1.495 (4)	C10—H10A	0.9700
N1—H1A	0.80 (3)	C10—H10B	0.9700
N1—H1B	0.88 (3)	C9—H9A	0.9700
C1—C6	1.372 (4)	C9—H9B	0.9700
C1—C2	1.374 (4)	C11—H11A	0.9700
C6—C5	1.363 (5)	C11—H11B	0.9700
C6—H6	0.9300	C3—C4	1.365 (5)
C2—C3	1.375 (4)	C3—H3	0.9300
C2—H2	0.9300	C4—C5	1.364 (5)
C13—C12	1.511 (5)	C4—H4	0.9300
C13—H13A	0.9700	C5—H5	0.9300
C13—H13B	0.9700

O2—S1—O1	119.42 (17)	H12A—C12—H12B	107.5
O2—S1—N1	107.04 (17)	C7—C8—C9	114.3 (3)
O1—S1—N1	106.66 (16)	C7—C8—H8A	108.7
O2—S1—C1	107.39 (14)	C9—C8—H8A	108.7
O1—S1—C1	107.74 (14)	C7—C8—H8B	108.7
N1—S1—C1	108.17 (13)	C9—C8—H8B	108.7
C7—N2—C13	126.6 (3)	H8A—C8—H8B	107.6
C7—N2—H2A	118 (2)	C11—C10—C9	114.9 (3)
C13—N2—H2A	116 (2)	C11—C10—H10A	108.5
O3—C7—N2	120.0 (3)	C9—C10—H10A	108.5
O3—C7—C8	119.6 (2)	C11—C10—H10B	108.5
N2—C7—C8	120.4 (3)	C9—C10—H10B	108.5
S1—N1—H1A	112 (2)	H10A—C10—H10B	107.5
S1—N1—H1B	114.8 (19)	C8—C9—C10	115.6 (3)
H1A—N1—H1B	119 (3)	C8—C9—H9A	108.4
C6—C1—C2	120.3 (3)	C10—C9—H9A	108.4
C6—C1—S1	119.5 (2)	C8—C9—H9B	108.4
C2—C1—S1	120.2 (2)	C10—C9—H9B	108.4
C5—C6—C1	119.7 (3)	H9A—C9—H9B	107.4
C5—C6—H6	120.2	C10—C11—C12	116.0 (3)
C1—C6—H6	120.2	C10—C11—H11A	108.3
C1—C2—C3	119.3 (3)	C12—C11—H11A	108.3
C1—C2—H2	120.3	C10—C11—H11B	108.3
C3—C2—H2	120.3	C12—C11—H11B	108.3
N2—C13—C12	113.0 (3)	H11A—C11—H11B	107.4
N2—C13—H13A	109.0	C4—C3—C2	120.1 (3)
C12—C13—H13A	109.0	C4—C3—H3	119.9
N2—C13—H13B	109.0	C2—C3—H3	119.9
C12—C13—H13B	109.0	C5—C4—C3	120.1 (3)
H13A—C13—H13B	107.8	C5—C4—H4	119.9
C13—C12—C11	115.2 (3)	C3—C4—H4	119.9
C13—C12—H12A	108.5	C6—C5—C4	120.4 (3)
C11—C12—H12A	108.5	C6—C5—H5	119.8
C13—C12—H12B	108.5	C4—C5—H5	119.8
C11—C12—H12B	108.5

(4ClBSACPR) top

Crystal data top

C6H6ClNO2S·C6H11NO	D_x = 1.385 Mg m⁻³
M_r = 304.79	Melting point: 355 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
a = 7.1564 (13) Å	Cell parameters from 543 reflections
b = 13.369 (2) Å	θ = 2.8–26.3°
c = 15.276 (3) Å	µ = 0.41 mm⁻¹
V = 1461.5 (5) Å³	T = 297 K
Z = 4	PLATE, colorles
F(000) = 640	0.23 × 0.20 × 0.20 mm

Data collection top

Xcalibur, Eos, Gemini diffractometer	2851 independent reflections
Radiation source: fine-focus sealed tube	1152 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.082
ω scans	θ_max = 26.4°, θ_min = 3.1°
Absorption correction: multi-scan SADABS	h = −8→7
T_min = 0.333, T_max = 1.000	k = −12→16
4403 measured reflections	l = −12→19

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.090	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.114	w = 1/[σ²(F_o²) + (0.0114P)²] where P = (F_o² + 2F_c²)/3
S = 0.97	(Δ/σ)_max < 0.001
2851 reflections	Δρ_max = 0.25 e Å⁻³
178 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.11 (15)

Crystal data top

C6H6ClNO2S·C6H11NO	V = 1461.5 (5) Å³
M_r = 304.79	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.1564 (13) Å	µ = 0.41 mm⁻¹
b = 13.369 (2) Å	T = 297 K
c = 15.276 (3) Å	0.23 × 0.20 × 0.20 mm

Data collection top

Xcalibur, Eos, Gemini diffractometer	2851 independent reflections
Absorption correction: multi-scan SADABS	1152 reflections with I > 2σ(I)
T_min = 0.333, T_max = 1.000	R_int = 0.082
4403 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.090	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.114	Δρ_max = 0.25 e Å⁻³
S = 0.97	Δρ_min = −0.25 e Å⁻³
2851 reflections	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
178 parameters	Absolute structure parameter: 0.11 (15)
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
S3	0.0196 (3)	0.35614 (15)	0.88356 (14)	0.0535 (6)
Cl1	0.5566 (3)	0.07660 (16)	0.67777 (13)	0.0877 (8)
O2	0.0844 (6)	0.4564 (3)	0.8748 (3)	0.0713 (16)
O3	−0.0805 (7)	1.1190 (3)	0.9736 (3)	0.0632 (17)
C7	0.0056 (12)	1.0508 (6)	0.9436 (5)	0.054 (2)
C6	0.0971 (10)	0.1977 (5)	0.7767 (4)	0.0458 (19)
H6	−0.0304	0.1844	0.7780	0.055*
C3	0.4741 (11)	0.2386 (5)	0.7731 (5)	0.055 (2)
H3	0.6014	0.2523	0.7714	0.066*
C4	0.4035 (11)	0.1560 (5)	0.7312 (4)	0.048 (2)
O1	−0.1687 (6)	0.3320 (4)	0.8608 (3)	0.0827 (19)
C2	0.3530 (10)	0.3013 (5)	0.8181 (4)	0.052 (2)
H2	0.3983	0.3579	0.8464	0.063*
C5	0.2143 (11)	0.1350 (5)	0.7310 (4)	0.055 (2)
H5	0.1675	0.0801	0.7009	0.066*
C1	0.1653 (9)	0.2791 (5)	0.8203 (4)	0.0382 (18)
N1	0.0459 (9)	0.3254 (4)	0.9837 (4)	0.0539 (19)
H1A	0.005 (11)	0.273 (4)	1.002 (5)	0.065*
H1B	0.167 (8)	0.349 (5)	1.003 (4)	0.065*
N2	0.1869 (9)	1.0380 (4)	0.9556 (4)	0.065 (2)
H2A	0.2385	1.0812	0.9896	0.078*
C8	−0.0874 (10)	0.9702 (6)	0.8853 (5)	0.072 (2)
H8A	−0.2174	0.9883	0.8768	0.086*
H8B	−0.0275	0.9711	0.8284	0.086*
C10	0.1078 (11)	0.8120 (6)	0.9053 (6)	0.078 (3)
H10A	0.0981	0.7442	0.9275	0.093*
H10B	0.1291	0.8076	0.8427	0.093*
C12	0.3120 (11)	0.9637 (7)	0.9210 (6)	0.092 (3)
H12A	0.4381	0.9809	0.9387	0.110*
H12B	0.3075	0.9672	0.8576	0.110*
C9	−0.0795 (11)	0.8652 (6)	0.9207 (5)	0.083 (3)
H9A	−0.1781	0.8262	0.8936	0.099*
H9B	−0.1039	0.8672	0.9831	0.099*
C11	0.2757 (12)	0.8613 (7)	0.9469 (6)	0.094 (3)
H11A	0.2595	0.8598	1.0100	0.112*
H11B	0.3854	0.8216	0.9333	0.112*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S3	0.0373 (13)	0.0552 (14)	0.0680 (14)	0.0072 (12)	0.0053 (11)	0.0000 (13)
Cl1	0.095 (2)	0.0763 (14)	0.0922 (16)	0.0242 (15)	0.0284 (15)	−0.0156 (15)
O2	0.067 (4)	0.044 (3)	0.103 (4)	0.018 (3)	0.016 (3)	0.021 (3)
O3	0.060 (4)	0.050 (4)	0.080 (4)	0.002 (3)	0.014 (3)	−0.019 (3)
C7	0.036 (6)	0.056 (6)	0.071 (6)	−0.028 (5)	−0.006 (5)	0.007 (5)
C6	0.035 (5)	0.053 (5)	0.050 (5)	−0.013 (4)	−0.001 (4)	0.009 (4)
C3	0.040 (5)	0.059 (5)	0.066 (5)	−0.006 (5)	0.006 (5)	−0.012 (5)
C4	0.056 (6)	0.043 (5)	0.045 (5)	0.014 (5)	0.007 (4)	0.005 (4)
O1	0.026 (3)	0.108 (5)	0.114 (5)	0.014 (3)	−0.007 (3)	−0.023 (4)
C2	0.050 (6)	0.057 (5)	0.049 (5)	0.001 (5)	0.001 (4)	−0.014 (5)
C5	0.068 (6)	0.042 (5)	0.054 (5)	−0.010 (5)	−0.005 (5)	−0.016 (5)
C1	0.032 (5)	0.038 (5)	0.044 (4)	−0.005 (4)	0.000 (4)	−0.004 (4)
N1	0.049 (5)	0.045 (4)	0.068 (5)	−0.011 (4)	0.018 (4)	0.007 (4)
N2	0.055 (5)	0.039 (4)	0.100 (5)	0.009 (4)	−0.019 (4)	−0.024 (4)
C8	0.046 (5)	0.072 (6)	0.097 (7)	−0.011 (5)	0.002 (5)	−0.002 (6)
C10	0.079 (7)	0.050 (5)	0.104 (7)	−0.003 (6)	0.007 (6)	0.004 (5)
C12	0.044 (6)	0.079 (7)	0.152 (10)	0.003 (6)	−0.015 (6)	−0.012 (8)
C9	0.065 (7)	0.072 (7)	0.112 (8)	−0.027 (6)	−0.007 (5)	−0.011 (6)
C11	0.075 (8)	0.068 (7)	0.138 (8)	0.018 (7)	−0.037 (6)	0.003 (7)

Geometric parameters (Å, º) top

S3—O2	1.424 (5)	N1—H1A	0.82 (6)
S3—O1	1.429 (5)	N1—H1B	0.97 (6)
S3—N1	1.595 (6)	N2—C12	1.438 (8)
S3—C1	1.756 (7)	N2—H2A	0.8600
Cl1—C4	1.730 (7)	C8—C9	1.505 (8)
O3—C7	1.192 (8)	C8—H8A	0.9700
C7—N2	1.321 (8)	C8—H8B	0.9700
C7—C8	1.549 (9)	C10—C11	1.512 (10)
C6—C1	1.366 (8)	C10—C9	1.535 (9)
C6—C5	1.375 (8)	C10—H10A	0.9700
C6—H6	0.9300	C10—H10B	0.9700
C3—C4	1.373 (8)	C12—C11	1.449 (9)
C3—C2	1.388 (8)	C12—H12A	0.9700
C3—H3	0.9300	C12—H12B	0.9700
C4—C5	1.383 (9)	C9—H9A	0.9700
C2—C1	1.376 (8)	C9—H9B	0.9700
C2—H2	0.9300	C11—H11A	0.9700
C5—H5	0.9300	C11—H11B	0.9700

O2—S3—O1	119.8 (3)	C12—N2—H2A	114.7
O2—S3—N1	107.1 (3)	C9—C8—C7	115.2 (7)
O1—S3—N1	106.6 (3)	C9—C8—H8A	108.5
O2—S3—C1	107.9 (3)	C7—C8—H8A	108.5
O1—S3—C1	107.1 (3)	C9—C8—H8B	108.5
N1—S3—C1	107.8 (3)	C7—C8—H8B	108.5
O3—C7—N2	123.6 (8)	H8A—C8—H8B	107.5
O3—C7—C8	122.1 (7)	C11—C10—C9	115.3 (6)
N2—C7—C8	114.3 (8)	C11—C10—H10A	108.4
C1—C6—C5	121.0 (7)	C9—C10—H10A	108.4
C1—C6—H6	119.5	C11—C10—H10B	108.4
C5—C6—H6	119.5	C9—C10—H10B	108.4
C4—C3—C2	119.2 (7)	H10A—C10—H10B	107.5
C4—C3—H3	120.4	N2—C12—C11	116.1 (8)
C2—C3—H3	120.4	N2—C12—H12A	108.2
C3—C4—C5	121.6 (7)	C11—C12—H12A	108.2
C3—C4—Cl1	118.7 (7)	N2—C12—H12B	108.2
C5—C4—Cl1	119.7 (7)	C11—C12—H12B	108.2
C1—C2—C3	119.4 (7)	H12A—C12—H12B	107.4
C1—C2—H2	120.3	C8—C9—C10	114.2 (7)
C3—C2—H2	120.3	C8—C9—H9A	108.7
C6—C5—C4	118.2 (7)	C10—C9—H9A	108.7
C6—C5—H5	120.9	C8—C9—H9B	108.7
C4—C5—H5	120.9	C10—C9—H9B	108.7
C6—C1—C2	120.6 (7)	H9A—C9—H9B	107.6
C6—C1—S3	121.6 (6)	C12—C11—C10	116.1 (8)
C2—C1—S3	117.8 (6)	C12—C11—H11A	108.3
S3—N1—H1A	121 (5)	C10—C11—H11A	108.3
S3—N1—H1B	108 (4)	C12—C11—H11B	108.3
H1A—N1—H1B	120 (7)	C10—C11—H11B	108.3
C7—N2—C12	130.5 (7)	H11A—C11—H11B	107.4
C7—N2—H2A	114.7

(SNACPR) top

Crystal data top

C6H8N2O2S·C6H11NO	D_x = 1.326 Mg m⁻³
M_r = 285.36	Melting point: 368 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
a = 7.0957 (6) Å	Cell parameters from 831 reflections
b = 13.1280 (13) Å	θ = 2.7–24.7°
c = 15.3425 (18) Å	µ = 0.24 mm⁻¹
V = 1429.2 (2) Å³	T = 298 K
Z = 4	PLATE, colorles
F(000) = 608	0.22 × 0.20 × 0.20 mm

Data collection top

Xcalibur, Eos, Gemini diffractometer	2354 independent reflections
Radiation source: fine-focus sealed tube	1318 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ω scans	θ_max = 24.7°, θ_min = 2.7°
Absorption correction: multi-scan SADABS	h = −7→8
T_min = 0.667, T_max = 1.000	k = −8→15
3692 measured reflections	l = −18→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.0117P)²] where P = (F_o² + 2F_c²)/3
S = 0.90	(Δ/σ)_max < 0.001
2354 reflections	Δρ_max = 0.18 e Å⁻³
179 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (14)

Crystal data top

C6H8N2O2S·C6H11NO	V = 1429.2 (2) Å³
M_r = 285.36	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.0957 (6) Å	µ = 0.24 mm⁻¹
b = 13.1280 (13) Å	T = 298 K
c = 15.3425 (18) Å	0.22 × 0.20 × 0.20 mm

Data collection top

Xcalibur, Eos, Gemini diffractometer	2354 independent reflections
Absorption correction: multi-scan SADABS	1318 reflections with I > 2σ(I)
T_min = 0.667, T_max = 1.000	R_int = 0.042
3692 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.080	Δρ_max = 0.18 e Å⁻³
S = 0.90	Δρ_min = −0.21 e Å⁻³
2354 reflections	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
179 parameters	Absolute structure parameter: 0.03 (14)
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
C11	0.1350 (6)	0.8611 (4)	0.0600 (3)	0.0805 (15)
H11A	0.1392	0.8645	−0.0031	0.097*
H11B	0.0275	0.8195	0.0761	0.097*
S1	0.90765 (16)	0.13847 (9)	0.87588 (9)	0.0599 (3)
O1	1.1072 (3)	0.1426 (2)	0.8626 (2)	0.0811 (10)
O3	0.4913 (4)	1.1203 (2)	0.0183 (2)	0.0694 (9)
N3	0.2251 (5)	1.0426 (3)	0.0533 (2)	0.0660 (11)
H3A	0.1666	1.0888	0.0242	0.079*
O2	0.8131 (4)	0.0430 (2)	0.8621 (2)	0.0735 (9)
C4	0.6531 (7)	0.3859 (3)	0.7083 (3)	0.0562 (13)
C3	0.8468 (6)	0.3754 (4)	0.7166 (3)	0.0591 (13)
H3	0.9266	0.4201	0.6875	0.071*
C5	0.5389 (6)	0.3167 (3)	0.7511 (3)	0.0640 (14)
H5	0.4088	0.3224	0.7459	0.077*
C6	0.6134 (6)	0.2399 (3)	0.8012 (3)	0.0583 (13)
H6	0.5342	0.1944	0.8297	0.070*
N1	0.8708 (5)	0.1686 (3)	0.9750 (3)	0.0589 (12)
H1A	0.899 (6)	0.224 (3)	0.997 (3)	0.071*
H1B	0.759 (5)	0.148 (3)	0.999 (2)	0.071*
N2	0.5796 (6)	0.4620 (3)	0.6575 (2)	0.0828 (13)
H2A	0.6504	0.5161	0.6592	0.099*
H2B	0.4693	0.4781	0.6780	0.099*
C1	0.8058 (6)	0.2308 (3)	0.8090 (3)	0.0462 (11)
C7	0.4103 (7)	1.0499 (4)	0.0552 (3)	0.0565 (12)
C2	0.9211 (6)	0.3000 (3)	0.7672 (3)	0.0542 (12)
H2	1.0511	0.2951	0.7736	0.065*
C9	0.4958 (7)	0.8638 (4)	0.0672 (3)	0.0813 (15)
H9A	0.6011	0.8224	0.0865	0.098*
H9B	0.5021	0.8679	0.0041	0.098*
C8	0.5188 (6)	0.9689 (4)	0.1037 (3)	0.0744 (15)
H8A	0.6516	0.9866	0.1029	0.089*
H8B	0.4780	0.9686	0.1641	0.089*
C12	0.1071 (6)	0.9650 (3)	0.0948 (3)	0.0763 (15)
H12A	−0.0242	0.9837	0.0875	0.092*
H12B	0.1336	0.9644	0.1568	0.092*
C10	0.3129 (7)	0.8098 (3)	0.0924 (3)	0.0804 (15)
H10A	0.3166	0.7409	0.0696	0.096*
H10B	0.3070	0.8051	0.1554	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C11	0.081 (3)	0.064 (3)	0.096 (4)	−0.013 (3)	−0.008 (3)	−0.006 (4)
S1	0.0530 (6)	0.0473 (6)	0.0794 (9)	0.0085 (7)	−0.0003 (7)	0.0010 (9)
O1	0.0404 (15)	0.084 (2)	0.119 (3)	0.0153 (18)	0.0020 (17)	0.014 (3)
O3	0.0709 (19)	0.0444 (18)	0.093 (2)	−0.0027 (18)	0.0158 (18)	0.007 (2)
N3	0.058 (2)	0.046 (2)	0.094 (3)	0.006 (2)	−0.011 (2)	0.016 (3)
O2	0.079 (2)	0.0400 (16)	0.102 (2)	0.0026 (17)	−0.006 (2)	−0.005 (2)
C4	0.069 (3)	0.051 (3)	0.048 (3)	−0.001 (3)	−0.011 (2)	−0.006 (3)
C3	0.056 (3)	0.063 (3)	0.058 (3)	−0.007 (3)	0.008 (2)	0.003 (3)
C5	0.046 (3)	0.062 (3)	0.085 (4)	−0.003 (3)	−0.016 (3)	0.003 (3)
C6	0.043 (3)	0.052 (3)	0.080 (4)	−0.008 (2)	−0.007 (2)	0.005 (3)
N1	0.065 (2)	0.047 (2)	0.064 (3)	−0.001 (2)	0.001 (2)	0.004 (2)
N2	0.093 (3)	0.069 (3)	0.086 (3)	0.011 (3)	−0.006 (3)	0.007 (3)
C1	0.047 (2)	0.045 (3)	0.046 (3)	0.006 (2)	−0.004 (2)	−0.002 (3)
C7	0.052 (3)	0.051 (3)	0.067 (3)	0.012 (3)	−0.005 (3)	−0.002 (3)
C2	0.044 (2)	0.060 (3)	0.059 (3)	0.008 (3)	−0.001 (2)	0.000 (3)
C9	0.086 (3)	0.061 (3)	0.097 (4)	0.032 (4)	−0.003 (3)	0.002 (4)
C8	0.049 (3)	0.075 (3)	0.100 (4)	0.011 (3)	−0.003 (3)	0.007 (4)
C12	0.057 (3)	0.064 (3)	0.107 (4)	−0.003 (3)	−0.006 (3)	0.002 (4)
C10	0.101 (4)	0.046 (3)	0.094 (4)	0.004 (3)	0.007 (4)	0.005 (3)

Geometric parameters (Å, º) top

C11—C12	1.478 (6)	C6—C1	1.376 (5)
C11—C10	1.514 (5)	C6—H6	0.9300
C11—H11A	0.9700	N1—H1A	0.83 (4)
C11—H11B	0.9700	N1—H1B	0.91 (3)
S1—O1	1.431 (2)	N2—H2A	0.8706
S1—O2	1.437 (3)	N2—H2B	0.8693
S1—N1	1.593 (4)	C1—C2	1.380 (5)
S1—C1	1.745 (4)	C7—C8	1.510 (5)
O3—C7	1.227 (5)	C2—H2	0.9300
N3—C7	1.318 (5)	C9—C8	1.499 (6)
N3—C12	1.465 (5)	C9—C10	1.528 (5)
N3—H3A	0.8600	C9—H9A	0.9700
C4—N2	1.370 (5)	C9—H9B	0.9700
C4—C5	1.383 (5)	C8—H8A	0.9700
C4—C3	1.387 (5)	C8—H8B	0.9700
C3—C2	1.364 (5)	C12—H12A	0.9700
C3—H3	0.9300	C12—H12B	0.9700
C5—C6	1.373 (5)	C10—H10A	0.9700
C5—H5	0.9300	C10—H10B	0.9700

C12—C11—C10	113.8 (4)	C6—C1—C2	119.4 (4)
C12—C11—H11A	108.8	C6—C1—S1	121.5 (3)
C10—C11—H11A	108.8	C2—C1—S1	119.0 (3)
C12—C11—H11B	108.8	O3—C7—N3	120.8 (4)
C10—C11—H11B	108.8	O3—C7—C8	121.3 (4)
H11A—C11—H11B	107.7	N3—C7—C8	117.9 (4)
O1—S1—O2	118.3 (2)	C3—C2—C1	120.8 (4)
O1—S1—N1	106.8 (2)	C3—C2—H2	119.6
O2—S1—N1	106.3 (2)	C1—C2—H2	119.6
O1—S1—C1	107.5 (2)	C8—C9—C10	115.1 (4)
O2—S1—C1	109.03 (19)	C8—C9—H9A	108.5
N1—S1—C1	108.7 (2)	C10—C9—H9A	108.5
C7—N3—C12	127.7 (4)	C8—C9—H9B	108.5
C7—N3—H3A	116.2	C10—C9—H9B	108.5
C12—N3—H3A	116.2	H9A—C9—H9B	107.5
N2—C4—C5	121.7 (4)	C9—C8—C7	114.1 (4)
N2—C4—C3	120.1 (5)	C9—C8—H8A	108.7
C5—C4—C3	118.1 (4)	C7—C8—H8A	108.7
C2—C3—C4	120.5 (4)	C9—C8—H8B	108.7
C2—C3—H3	119.8	C7—C8—H8B	108.7
C4—C3—H3	119.8	H8A—C8—H8B	107.6
C6—C5—C4	121.5 (4)	N3—C12—C11	114.1 (4)
C6—C5—H5	119.2	N3—C12—H12A	108.7
C4—C5—H5	119.2	C11—C12—H12A	108.7
C5—C6—C1	119.6 (4)	N3—C12—H12B	108.7
C5—C6—H6	120.2	C11—C12—H12B	108.7
C1—C6—H6	120.2	H12A—C12—H12B	107.6
S1—N1—H1A	124 (4)	C11—C10—C9	114.8 (4)
S1—N1—H1B	117 (2)	C11—C10—H10A	108.6
H1A—N1—H1B	108 (4)	C9—C10—H10A	108.6
C4—N2—H2A	111.0	C11—C10—H10B	108.6
C4—N2—H2B	108.3	C9—C10—H10B	108.6
H2A—N2—H2B	108.0	H10A—C10—H10B	107.6

(4BrBSACPR) top

Crystal data top

C6H6BrNO2S·C6H11NO	D_x = 1.554 Mg m⁻³
M_r = 349.25	Melting point: 363 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
a = 7.156 (3) Å	Cell parameters from 3565 reflections
b = 13.538 (5) Å	θ = 2.6–20.1°
c = 15.406 (6) Å	µ = 2.90 mm⁻¹
V = 1492.3 (9) Å³	T = 298 K
Z = 4	PLATE, colorles
F(000) = 712	0.22 × 0.20 × 0.20 mm

Data collection top

CCD area detector diffractometer	2405 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.057
Graphite monochromator	θ_max = 26.4°, θ_min = 2.0°
phi and ω scans	h = −8→8
15786 measured reflections	k = −16→16
3029 independent reflections	l = −19→19

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.093	w = 1/[σ²(F_o²) + (0.0368P)² + 0.1698P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
3029 reflections	Δρ_max = 0.46 e Å⁻³
184 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.018 (11)

Crystal data top

C6H6BrNO2S·C6H11NO	V = 1492.3 (9) Å³
M_r = 349.25	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.156 (3) Å	µ = 2.90 mm⁻¹
b = 13.538 (5) Å	T = 298 K
c = 15.406 (6) Å	0.22 × 0.20 × 0.20 mm

Data collection top

CCD area detector diffractometer	2405 reflections with I > 2σ(I)
15786 measured reflections	R_int = 0.057
3029 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.093	Δρ_max = 0.46 e Å⁻³
S = 1.02	Δρ_min = −0.23 e Å⁻³
3029 reflections	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
184 parameters	Absolute structure parameter: 0.018 (11)
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
Br	1.06812 (7)	0.57142 (4)	0.17536 (3)	0.0783 (2)
S1	0.51258 (13)	0.85223 (8)	0.38623 (7)	0.0535 (3)
O2	0.3242 (4)	0.8284 (3)	0.3656 (2)	0.0826 (11)
C2	0.5904 (5)	0.6967 (3)	0.2777 (2)	0.0499 (9)
H2	0.4628	0.6838	0.2782	0.060*
O1	0.5740 (4)	0.9520 (2)	0.3772 (2)	0.0722 (8)
O3	1.0804 (4)	0.3851 (2)	0.97299 (19)	0.0658 (8)
C7	0.9938 (6)	0.4547 (3)	0.9408 (3)	0.0538 (10)
C4	0.8969 (5)	0.6561 (3)	0.2329 (2)	0.0494 (9)
C6	0.8509 (5)	0.7955 (3)	0.3230 (3)	0.0534 (9)
H6	0.8987	0.8488	0.3540	0.064*
N1	0.5439 (6)	0.8229 (3)	0.4860 (2)	0.0564 (9)
C12	0.6865 (7)	0.5376 (4)	0.9179 (4)	0.0802 (15)
H12A	0.5591	0.5213	0.9340	0.096*
H12B	0.6944	0.5350	0.8551	0.096*
C10	0.8940 (8)	0.6866 (3)	0.9025 (4)	0.0803 (15)
H10A	0.8698	0.6895	0.8406	0.096*
H10B	0.9062	0.7540	0.9231	0.096*
C1	0.6596 (5)	0.7767 (3)	0.3234 (3)	0.0456 (8)
C5	0.9678 (6)	0.7358 (3)	0.2773 (3)	0.0566 (10)
H5	1.0953	0.7488	0.2760	0.068*
C3	0.7081 (6)	0.6364 (3)	0.2317 (2)	0.0536 (10)
H3	0.6613	0.5831	0.2003	0.064*
C8	1.0852 (6)	0.5294 (3)	0.8836 (3)	0.0651 (11)
H8A	1.0259	0.5271	0.8270	0.078*
H8B	1.2151	0.5109	0.8759	0.078*
C9	1.0780 (8)	0.6342 (3)	0.9166 (3)	0.0745 (13)
H9A	1.1758	0.6718	0.8882	0.089*
H9B	1.1050	0.6338	0.9783	0.089*
N2	0.8108 (5)	0.4630 (3)	0.9539 (3)	0.0706 (12)
C11	0.7264 (8)	0.6401 (4)	0.9465 (4)	0.0852 (16)
H11A	0.7472	0.6400	1.0087	0.102*
H11B	0.6173	0.6806	0.9351	0.102*
H1B	0.525 (6)	0.773 (3)	0.495 (3)	0.045 (14)*
H1A	0.662 (6)	0.841 (3)	0.507 (3)	0.060 (13)*
H2A	0.764 (6)	0.413 (3)	0.979 (3)	0.064 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0896 (4)	0.0694 (3)	0.0759 (3)	0.0173 (3)	0.0210 (3)	−0.0139 (3)
S1	0.0395 (5)	0.0528 (5)	0.0681 (6)	0.0072 (4)	0.0024 (5)	−0.0021 (5)
O2	0.0397 (16)	0.100 (3)	0.108 (3)	0.0112 (16)	−0.0044 (16)	−0.021 (2)
C2	0.042 (2)	0.056 (2)	0.052 (2)	−0.0043 (19)	−0.0039 (18)	0.0051 (17)
O1	0.0761 (19)	0.0488 (17)	0.092 (2)	0.0170 (15)	0.0176 (17)	0.0098 (14)
O3	0.0651 (17)	0.0500 (16)	0.082 (2)	0.0012 (15)	−0.0087 (17)	0.0108 (14)
C7	0.055 (2)	0.044 (2)	0.063 (2)	−0.0067 (18)	0.000 (2)	−0.0002 (18)
C4	0.054 (3)	0.048 (2)	0.046 (2)	0.0043 (19)	0.0045 (18)	−0.0008 (16)
C6	0.049 (2)	0.052 (2)	0.059 (2)	−0.0033 (17)	−0.003 (2)	−0.013 (2)
N1	0.056 (3)	0.046 (2)	0.067 (2)	−0.0012 (19)	0.0105 (19)	−0.0053 (18)
C12	0.051 (3)	0.070 (3)	0.119 (4)	0.004 (2)	0.005 (3)	0.014 (3)
C10	0.098 (4)	0.050 (2)	0.094 (4)	−0.005 (3)	0.010 (3)	0.013 (2)
C1	0.0398 (19)	0.049 (2)	0.048 (2)	0.0001 (15)	−0.0010 (18)	0.0058 (19)
C5	0.040 (2)	0.069 (3)	0.062 (2)	0.0010 (19)	0.0007 (18)	−0.009 (2)
C3	0.067 (3)	0.047 (2)	0.047 (2)	−0.012 (2)	−0.0047 (19)	−0.0039 (18)
C8	0.052 (2)	0.074 (3)	0.069 (3)	−0.005 (2)	0.006 (2)	0.004 (2)
C9	0.079 (3)	0.065 (3)	0.080 (3)	−0.023 (3)	−0.007 (3)	0.012 (2)
N2	0.056 (2)	0.056 (2)	0.099 (3)	−0.0046 (19)	0.014 (2)	0.022 (2)
C11	0.088 (4)	0.071 (3)	0.097 (4)	0.026 (3)	0.017 (3)	−0.002 (3)

Geometric parameters (Å, º) top

Br—C4	1.898 (4)	C4—C5	1.374 (5)
S1—O2	1.422 (3)	C4—C3	1.377 (6)
S1—O1	1.427 (3)	C6—C5	1.360 (5)
S1—N1	1.602 (4)	C6—C1	1.392 (5)
S1—C1	1.757 (4)	C12—N2	1.456 (6)
C2—C3	1.371 (6)	C12—C11	1.483 (7)
C2—C1	1.383 (5)	C10—C9	1.511 (7)
O3—C7	1.232 (5)	C10—C11	1.515 (7)
C7—N2	1.329 (6)	C8—C9	1.508 (6)
C7—C8	1.492 (6)

O2—S1—O1	119.0 (2)	C5—C6—C1	119.9 (4)
O2—S1—N1	106.9 (2)	N2—C12—C11	114.7 (5)
O1—S1—N1	106.5 (2)	C9—C10—C11	115.5 (4)
O2—S1—C1	108.2 (2)	C2—C1—C6	119.5 (4)
O1—S1—C1	108.21 (18)	C2—C1—S1	121.4 (3)
N1—S1—C1	107.49 (19)	C6—C1—S1	119.0 (3)
C3—C2—C1	120.7 (4)	C6—C5—C4	119.8 (4)
O3—C7—N2	120.0 (4)	C2—C3—C4	118.7 (4)
O3—C7—C8	122.3 (4)	C7—C8—C9	115.0 (4)
N2—C7—C8	117.7 (4)	C8—C9—C10	115.0 (4)
C5—C4—C3	121.4 (4)	C7—N2—C12	127.1 (4)
C5—C4—Br	117.9 (3)	C12—C11—C10	114.1 (5)
C3—C4—Br	120.7 (3)

(OTSAVLM) top

Crystal data top

C7H9NO2S·C5H9NO	D_x = 1.329 Mg m⁻³
M_r = 270.34	Melting point: 343 K
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 5.3367 (6) Å	Cell parameters from 735 reflections
b = 15.9206 (17) Å	θ = 2.6–26.3°
c = 16.070 (3) Å	µ = 0.24 mm⁻¹
β = 98.308 (12)°	T = 298 K
V = 1351.0 (3) Å³	PLATE, colorles
Z = 4	0.22 × 0.20 × 0.20 mm
F(000) = 576

Data collection top

Xcalibur, Eos, Gemini diffractometer	2759 independent reflections
Radiation source: fine-focus sealed tube	1420 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.067
ω scans	θ_max = 26.4°, θ_min = 2.6°
Absorption correction: multi-scan SADABS	h = −6→6
T_min = 0.755, T_max = 1.000	k = −19→11
5072 measured reflections	l = −14→20

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0264P)²] where P = (F_o² + 2F_c²)/3
2759 reflections	(Δ/σ)_max < 0.001
170 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C7H9NO2S·C5H9NO	V = 1351.0 (3) Å³
M_r = 270.34	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.3367 (6) Å	µ = 0.24 mm⁻¹
b = 15.9206 (17) Å	T = 298 K
c = 16.070 (3) Å	0.22 × 0.20 × 0.20 mm
β = 98.308 (12)°

Data collection top

Xcalibur, Eos, Gemini diffractometer	2759 independent reflections
Absorption correction: multi-scan SADABS	1420 reflections with I > 2σ(I)
T_min = 0.755, T_max = 1.000	R_int = 0.067
5072 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.21 e Å⁻³
2759 reflections	Δρ_min = −0.24 e Å⁻³
170 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
S1	0.21166 (16)	0.62191 (5)	0.22403 (6)	0.0519 (3)
O1	0.4643 (4)	0.63090 (14)	0.26693 (16)	0.0674 (7)
N1	0.0300 (5)	0.63558 (19)	0.29386 (19)	0.0519 (8)
H1B	−0.142 (6)	0.6375 (19)	0.270 (2)	0.062*
H1A	0.071 (6)	0.608 (2)	0.340 (2)	0.062*
O2	0.1267 (5)	0.67551 (15)	0.15492 (16)	0.0756 (8)
C6	0.3592 (7)	0.4596 (2)	0.2264 (2)	0.0591 (10)
H6	0.4935	0.4790	0.2650	0.071*
C1	0.1792 (6)	0.5159 (2)	0.1901 (2)	0.0450 (8)
C2	−0.0255 (6)	0.4890 (2)	0.1329 (2)	0.0561 (9)
C5	0.3448 (8)	0.3759 (3)	0.2070 (3)	0.0780 (12)
H5	0.4691	0.3389	0.2311	0.094*
C4	0.1447 (10)	0.3478 (3)	0.1515 (3)	0.0837 (13)
H4	0.1301	0.2910	0.1384	0.100*
C3	−0.0337 (8)	0.4028 (3)	0.1153 (3)	0.0807 (13)
H3	−0.1670	0.3822	0.0770	0.097*
C7	−0.2302 (7)	0.5456 (3)	0.0899 (2)	0.0835 (13)
H7A	−0.2841	0.5834	0.1304	0.125*
H7B	−0.3714	0.5122	0.0652	0.125*
H7C	−0.1657	0.5772	0.0468	0.125*
O3	0.2324 (4)	0.52137 (14)	0.42358 (14)	0.0557 (7)
N2	0.3028 (5)	0.39875 (16)	0.49027 (17)	0.0488 (7)
H2A	0.4360	0.4209	0.5183	0.059*
C8	0.1675 (6)	0.4473 (2)	0.4342 (2)	0.0432 (8)
C9	−0.0668 (6)	0.4125 (2)	0.3845 (2)	0.0495 (9)
H9A	−0.0685	0.4275	0.3259	0.059*
H9B	−0.2122	0.4389	0.4034	0.059*
C11	−0.0199 (6)	0.2893 (2)	0.4793 (2)	0.0649 (11)
H11A	−0.0413	0.2290	0.4825	0.078*
H11B	−0.1287	0.3156	0.5151	0.078*
C12	0.2510 (6)	0.3118 (2)	0.5098 (2)	0.0582 (10)
H12A	0.2862	0.3033	0.5702	0.070*
H12B	0.3617	0.2751	0.4836	0.070*
C10	−0.0955 (7)	0.3178 (2)	0.3903 (2)	0.0667 (11)
H10A	−0.2701	0.3022	0.3714	0.080*
H10B	0.0101	0.2904	0.3541	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0399 (5)	0.0461 (5)	0.0694 (7)	−0.0035 (4)	0.0071 (5)	0.0066 (5)
O1	0.0331 (13)	0.0648 (16)	0.103 (2)	−0.0082 (12)	0.0054 (13)	−0.0125 (15)
N1	0.0356 (16)	0.059 (2)	0.060 (2)	0.0025 (15)	0.0014 (16)	−0.0034 (15)
O2	0.0841 (19)	0.0597 (16)	0.083 (2)	0.0004 (14)	0.0125 (15)	0.0323 (15)
C6	0.055 (2)	0.051 (2)	0.067 (3)	0.0044 (19)	−0.002 (2)	0.005 (2)
C1	0.042 (2)	0.049 (2)	0.044 (2)	−0.0017 (17)	0.0068 (17)	0.0022 (17)
C2	0.056 (2)	0.067 (3)	0.045 (2)	0.001 (2)	0.0045 (19)	−0.006 (2)
C5	0.089 (3)	0.059 (3)	0.084 (3)	0.020 (2)	0.007 (3)	0.008 (2)
C4	0.103 (4)	0.064 (3)	0.084 (4)	0.001 (3)	0.015 (3)	−0.018 (3)
C3	0.082 (3)	0.085 (3)	0.070 (3)	−0.013 (3)	−0.006 (2)	−0.026 (3)
C7	0.064 (3)	0.115 (4)	0.062 (3)	0.011 (3)	−0.024 (2)	−0.003 (3)
O3	0.0553 (15)	0.0478 (15)	0.0601 (17)	−0.0090 (12)	−0.0047 (12)	0.0014 (12)
N2	0.0392 (16)	0.0479 (18)	0.055 (2)	−0.0017 (14)	−0.0066 (14)	−0.0025 (15)
C8	0.0371 (19)	0.051 (2)	0.041 (2)	0.0009 (18)	0.0046 (17)	−0.0084 (19)
C9	0.043 (2)	0.059 (2)	0.044 (2)	−0.0045 (17)	−0.0035 (17)	−0.0055 (18)
C11	0.062 (3)	0.050 (2)	0.080 (3)	−0.0144 (19)	0.003 (2)	0.002 (2)
C12	0.063 (3)	0.049 (2)	0.061 (3)	0.0006 (19)	0.0023 (19)	0.0023 (19)
C10	0.056 (2)	0.068 (3)	0.071 (3)	−0.011 (2)	−0.006 (2)	−0.009 (2)

Geometric parameters (Å, º) top

S1—O2	1.422 (2)	C7—H7B	0.9600
S1—O1	1.430 (2)	C7—H7C	0.9600
S1—N1	1.600 (3)	O3—C8	1.248 (4)
S1—C1	1.775 (3)	N2—C8	1.320 (4)
N1—H1B	0.95 (3)	N2—C12	1.456 (4)
N1—H1A	0.86 (3)	N2—H2A	0.8600
C6—C5	1.368 (5)	C8—C9	1.489 (4)
C6—C1	1.380 (4)	C9—C10	1.519 (5)
C6—H6	0.9300	C9—H9A	0.9700
C1—C2	1.389 (4)	C9—H9B	0.9700
C2—C3	1.401 (5)	C11—C10	1.498 (5)
C2—C7	1.504 (5)	C11—C12	1.501 (4)
C5—C4	1.364 (5)	C11—H11A	0.9700
C5—H5	0.9300	C11—H11B	0.9700
C4—C3	1.361 (5)	C12—H12A	0.9700
C4—H4	0.9300	C12—H12B	0.9700
C3—H3	0.9300	C10—H10A	0.9700
C7—H7A	0.9600	C10—H10B	0.9700

O2—S1—O1	119.24 (15)	H7B—C7—H7C	109.5
O2—S1—N1	108.01 (16)	C8—N2—C12	127.0 (3)
O1—S1—N1	105.83 (16)	C8—N2—H2A	116.5
O2—S1—C1	108.95 (16)	C12—N2—H2A	116.5
O1—S1—C1	106.66 (15)	O3—C8—N2	120.7 (3)
N1—S1—C1	107.62 (15)	O3—C8—C9	120.4 (3)
S1—N1—H1B	111.7 (19)	N2—C8—C9	118.9 (3)
S1—N1—H1A	115 (2)	C8—C9—C10	114.8 (3)
H1B—N1—H1A	118 (3)	C8—C9—H9A	108.6
C5—C6—C1	121.5 (4)	C10—C9—H9A	108.6
C5—C6—H6	119.2	C8—C9—H9B	108.6
C1—C6—H6	119.2	C10—C9—H9B	108.6
C6—C1—C2	120.9 (3)	H9A—C9—H9B	107.5
C6—C1—S1	117.1 (3)	C10—C11—C12	110.7 (3)
C2—C1—S1	121.9 (3)	C10—C11—H11A	109.5
C1—C2—C3	115.7 (3)	C12—C11—H11A	109.5
C1—C2—C7	124.7 (3)	C10—C11—H11B	109.5
C3—C2—C7	119.6 (4)	C12—C11—H11B	109.5
C4—C5—C6	118.8 (4)	H11A—C11—H11B	108.1
C4—C5—H5	120.6	N2—C12—C11	111.1 (3)
C6—C5—H5	120.6	N2—C12—H12A	109.4
C3—C4—C5	120.1 (4)	C11—C12—H12A	109.4
C3—C4—H4	119.9	N2—C12—H12B	109.4
C5—C4—H4	119.9	C11—C12—H12B	109.4
C4—C3—C2	123.0 (4)	H12A—C12—H12B	108.0
C4—C3—H3	118.5	C11—C10—C9	110.1 (3)
C2—C3—H3	118.5	C11—C10—H10A	109.6
C2—C7—H7A	109.5	C9—C10—H10A	109.6
C2—C7—H7B	109.5	C11—C10—H10B	109.6
H7A—C7—H7B	109.5	C9—C10—H10B	109.6
C2—C7—H7C	109.5	H10A—C10—H10B	108.2
H7A—C7—H7C	109.5

(2ClBSACPR) top

Crystal data top

C6H6ClNO2S·C6H11NO	D_x = 1.443 Mg m⁻³
M_r = 304.79	Melting point: 355 K
Monoclinic, P1₂1/c1	Mo Kα radiation, λ = 0.71073 Å
a = 9.8782 (6) Å	Cell parameters from 2558 reflections
b = 14.1720 (6) Å	θ = 3.7–28.9°
c = 10.8753 (6) Å	µ = 0.43 mm⁻¹
β = 112.850 (7)°	T = 298 K
V = 1402.98 (12) Å³	BLOCK, colorles
Z = 4	0.22 × 0.22 × 0.20 mm
F(000) = 640

Data collection top

Xcalibur, Eos, Gemini diffractometer	2870 independent reflections
Radiation source: fine-focus sealed tube	2483 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 26.4°, θ_min = 2.9°
Absorption correction: multi-scan SADABS	h = −12→11
T_min = 0.876, T_max = 1.000	k = −17→16
5810 measured reflections	l = −13→10

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0514P)² + 0.3887P] where P = (F_o² + 2F_c²)/3
2870 reflections	(Δ/σ)_max < 0.001
178 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

C6H6ClNO2S·C6H11NO	V = 1402.98 (12) Å³
M_r = 304.79	Z = 4
Monoclinic, P1₂1/c1	Mo Kα radiation
a = 9.8782 (6) Å	µ = 0.43 mm⁻¹
b = 14.1720 (6) Å	T = 298 K
c = 10.8753 (6) Å	0.22 × 0.22 × 0.20 mm
β = 112.850 (7)°

Data collection top

Xcalibur, Eos, Gemini diffractometer	2870 independent reflections
Absorption correction: multi-scan SADABS	2483 reflections with I > 2σ(I)
T_min = 0.876, T_max = 1.000	R_int = 0.021
5810 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.25 e Å⁻³
2870 reflections	Δρ_min = −0.48 e Å⁻³
178 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
S1	0.88136 (5)	0.24056 (3)	0.00962 (4)	0.03143 (14)
Cl1	1.11885 (6)	0.31602 (4)	−0.10232 (6)	0.05419 (18)
O3	0.53802 (18)	0.37511 (10)	0.98172 (13)	0.0492 (4)
O2	0.80116 (16)	0.25905 (10)	−0.12931 (13)	0.0427 (3)
N1	0.7628 (2)	0.23340 (13)	0.07521 (18)	0.0398 (4)
H1A	0.689 (3)	0.2760 (17)	0.045 (2)	0.048*
H1B	0.797 (3)	0.2214 (17)	0.155 (2)	0.048*
N2	0.39497 (19)	0.47318 (11)	0.82491 (15)	0.0422 (4)
H2A	0.4202	0.5170	0.8843	0.051*
C1	0.99475 (18)	0.34009 (12)	0.08009 (16)	0.0301 (4)
C7	0.4489 (2)	0.38834 (13)	0.86453 (18)	0.0370 (4)
O1	0.97322 (16)	0.15904 (9)	0.04756 (16)	0.0488 (4)
C6	0.9817 (2)	0.38791 (13)	0.18640 (17)	0.0388 (4)
H6	0.9127	0.3683	0.2197	0.047*
C2	1.0992 (2)	0.37035 (13)	0.03259 (18)	0.0361 (4)
C12	0.2965 (2)	0.50019 (16)	0.6900 (2)	0.0490 (5)
H12A	0.2686	0.5657	0.6907	0.059*
H12B	0.2079	0.4624	0.6637	0.059*
C5	1.0706 (3)	0.46446 (15)	0.2428 (2)	0.0507 (5)
H5	1.0612	0.4964	0.3138	0.061*
C9	0.4531 (2)	0.31855 (15)	0.6516 (2)	0.0447 (5)
H9A	0.5545	0.3396	0.6875	0.054*
H9B	0.4504	0.2569	0.6119	0.054*
C10	0.3633 (3)	0.38646 (16)	0.5430 (2)	0.0531 (6)
H10A	0.2626	0.3643	0.5054	0.064*
H10B	0.4005	0.3852	0.4726	0.064*
C8	0.4020 (2)	0.30847 (14)	0.76585 (19)	0.0441 (5)
H8A	0.2956	0.3044	0.7293	0.053*
H8B	0.4403	0.2499	0.8125	0.053*
C3	1.1882 (2)	0.44687 (15)	0.0899 (2)	0.0498 (5)
H3	1.2582	0.4668	0.0580	0.060*
C11	0.3639 (3)	0.48789 (16)	0.5881 (2)	0.0521 (5)
H11A	0.4644	0.5105	0.6258	0.063*
H11B	0.3103	0.5266	0.5109	0.063*
C4	1.1723 (3)	0.49336 (15)	0.1947 (2)	0.0542 (6)
H4	1.2316	0.5451	0.2331	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0345 (2)	0.0300 (2)	0.0307 (2)	−0.00041 (17)	0.01362 (18)	−0.00086 (16)
Cl1	0.0570 (3)	0.0622 (4)	0.0593 (3)	0.0006 (3)	0.0400 (3)	−0.0022 (3)
O3	0.0688 (10)	0.0419 (8)	0.0327 (7)	0.0099 (7)	0.0151 (7)	−0.0008 (6)
O2	0.0435 (7)	0.0539 (8)	0.0287 (7)	−0.0061 (6)	0.0117 (6)	−0.0045 (6)
N1	0.0392 (9)	0.0446 (9)	0.0378 (9)	−0.0019 (7)	0.0175 (7)	0.0043 (7)
N2	0.0559 (10)	0.0352 (8)	0.0331 (8)	0.0062 (7)	0.0143 (7)	−0.0044 (7)
C1	0.0310 (8)	0.0289 (8)	0.0281 (8)	0.0030 (7)	0.0088 (7)	0.0039 (7)
C7	0.0460 (10)	0.0360 (10)	0.0344 (9)	−0.0002 (8)	0.0215 (8)	−0.0013 (8)
O1	0.0524 (8)	0.0315 (7)	0.0640 (9)	0.0074 (6)	0.0242 (7)	0.0019 (6)
C6	0.0451 (10)	0.0395 (10)	0.0304 (9)	0.0010 (8)	0.0129 (8)	−0.0006 (8)
C2	0.0335 (9)	0.0368 (9)	0.0375 (9)	0.0034 (7)	0.0133 (8)	0.0051 (8)
C12	0.0503 (12)	0.0453 (12)	0.0444 (11)	0.0120 (9)	0.0107 (9)	−0.0003 (9)
C5	0.0599 (13)	0.0414 (11)	0.0405 (11)	0.0000 (10)	0.0083 (10)	−0.0094 (9)
C9	0.0466 (11)	0.0471 (11)	0.0435 (11)	0.0016 (9)	0.0208 (9)	−0.0121 (9)
C10	0.0668 (14)	0.0595 (14)	0.0351 (10)	−0.0040 (11)	0.0219 (10)	−0.0057 (10)
C8	0.0582 (12)	0.0341 (10)	0.0415 (11)	−0.0034 (9)	0.0211 (9)	−0.0052 (8)
C3	0.0379 (11)	0.0472 (12)	0.0591 (13)	−0.0066 (9)	0.0132 (10)	0.0095 (10)
C11	0.0651 (14)	0.0502 (12)	0.0368 (11)	−0.0015 (11)	0.0151 (10)	0.0048 (9)
C4	0.0515 (13)	0.0397 (11)	0.0553 (13)	−0.0097 (10)	0.0031 (10)	−0.0033 (10)

Geometric parameters (Å, º) top

S1—O1	1.4274 (14)	C12—H12A	0.9700
S1—O2	1.4315 (14)	C12—H12B	0.9700
S1—N1	1.5934 (17)	C5—C4	1.363 (3)
S1—C1	1.7791 (18)	C5—H5	0.9300
Cl1—C2	1.7334 (19)	C9—C10	1.514 (3)
O3—C7	1.250 (2)	C9—C8	1.519 (3)
N1—H1A	0.91 (2)	C9—H9A	0.9700
N1—H1B	0.81 (2)	C9—H9B	0.9700
N2—C7	1.318 (2)	C10—C11	1.518 (3)
N2—C12	1.462 (2)	C10—H10A	0.9700
N2—H2A	0.8600	C10—H10B	0.9700
C1—C2	1.389 (2)	C8—H8A	0.9700
C1—C6	1.389 (2)	C8—H8B	0.9700
C7—C8	1.504 (3)	C3—C4	1.376 (3)
C6—C5	1.381 (3)	C3—H3	0.9300
C6—H6	0.9300	C11—H11A	0.9700
C2—C3	1.383 (3)	C11—H11B	0.9700
C12—C11	1.508 (3)	C4—H4	0.9300

O1—S1—O2	118.84 (9)	C6—C5—H5	119.9
O1—S1—N1	108.32 (9)	C10—C9—C8	114.67 (18)
O2—S1—N1	106.41 (9)	C10—C9—H9A	108.6
O1—S1—C1	107.09 (8)	C8—C9—H9A	108.6
O2—S1—C1	107.90 (8)	C10—C9—H9B	108.6
N1—S1—C1	107.86 (9)	C8—C9—H9B	108.6
S1—N1—H1A	114.9 (15)	H9A—C9—H9B	107.6
S1—N1—H1B	114.5 (17)	C9—C10—C11	114.99 (17)
H1A—N1—H1B	118 (2)	C9—C10—H10A	108.5
C7—N2—C12	126.44 (16)	C11—C10—H10A	108.5
C7—N2—H2A	116.8	C9—C10—H10B	108.5
C12—N2—H2A	116.8	C11—C10—H10B	108.5
C2—C1—C6	118.80 (17)	H10A—C10—H10B	107.5
C2—C1—S1	121.26 (14)	C7—C8—C9	113.88 (17)
C6—C1—S1	119.93 (14)	C7—C8—H8A	108.8
O3—C7—N2	120.35 (17)	C9—C8—H8A	108.8
O3—C7—C8	120.97 (17)	C7—C8—H8B	108.8
N2—C7—C8	118.68 (17)	C9—C8—H8B	108.8
C5—C6—C1	120.27 (19)	H8A—C8—H8B	107.7
C5—C6—H6	119.9	C4—C3—C2	119.5 (2)
C1—C6—H6	119.9	C4—C3—H3	120.3
C3—C2—C1	120.54 (18)	C2—C3—H3	120.3
C3—C2—Cl1	118.01 (15)	C12—C11—C10	113.55 (19)
C1—C2—Cl1	121.42 (14)	C12—C11—H11A	108.9
N2—C12—C11	113.33 (18)	C10—C11—H11A	108.9
N2—C12—H12A	108.9	C12—C11—H11B	108.9
C11—C12—H12A	108.9	C10—C11—H11B	108.9
N2—C12—H12B	108.9	H11A—C11—H11B	107.7
C11—C12—H12B	108.9	C5—C4—C3	120.8 (2)
H12A—C12—H12B	107.7	C5—C4—H4	119.6
C4—C5—C6	120.1 (2)	C3—C4—H4	119.6
C4—C5—H5	119.9

(BSACPR) top

Crystal data top

C6H7NO2S·C6H11NO	D_x = 1.329 Mg m⁻³
M_r = 270.34	Melting point: 353 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
a = 7.0700 (9) Å	Cell parameters from 1165 reflections
b = 12.7624 (13) Å	θ = 4.0–26.7°
c = 14.977 (2) Å	µ = 0.24 mm⁻¹
V = 1351.4 (3) Å³	T = 298 K
Z = 4	PLATE, colorles
F(000) = 576	0.22 × 0.20 × 0.20 mm

Data collection top

Xcalibur, Eos, Gemini diffractometer	2197 independent reflections
Radiation source: fine-focus sealed tube	1595 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ω scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan SADABS	h = −8→7
T_min = 0.788, T_max = 1.000	k = −7→15
3348 measured reflections	l = −17→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.078	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.181	w = 1/[σ²(F_o²) + (0.0352P)² + 2.5208P] where P = (F_o² + 2F_c²)/3
S = 1.23	(Δ/σ)_max < 0.001
2197 reflections	Δρ_max = 0.37 e Å⁻³
169 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.0 (2)

Crystal data top

C6H7NO2S·C6H11NO	V = 1351.4 (3) Å³
M_r = 270.34	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.0700 (9) Å	µ = 0.24 mm⁻¹
b = 12.7624 (13) Å	T = 298 K
c = 14.977 (2) Å	0.22 × 0.20 × 0.20 mm

Data collection top

Xcalibur, Eos, Gemini diffractometer	2197 independent reflections
Absorption correction: multi-scan SADABS	1595 reflections with I > 2σ(I)
T_min = 0.788, T_max = 1.000	R_int = 0.039
3348 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.078	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.181	Δρ_max = 0.37 e Å⁻³
S = 1.23	Δρ_min = −0.24 e Å⁻³
2197 reflections	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
169 parameters	Absolute structure parameter: 0.0 (2)
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
S1	0.9052 (3)	0.65992 (13)	0.85943 (13)	0.0524 (5)
O3	−0.0036 (7)	0.3842 (3)	0.5082 (4)	0.0641 (15)
O1	1.0954 (7)	0.6811 (4)	0.8374 (4)	0.0775 (17)
N1	0.8857 (10)	0.6723 (4)	0.9646 (5)	0.0551 (16)
N2	0.2566 (10)	0.4789 (5)	0.5098 (5)	0.078 (2)
H2A	0.3203	0.4215	0.5094	0.094*
O2	0.8294 (8)	0.5611 (3)	0.8371 (4)	0.0693 (16)
C1	0.7647 (10)	0.7583 (5)	0.8109 (4)	0.0435 (17)
C6	0.8499 (10)	0.8423 (6)	0.7703 (4)	0.0527 (17)
H6	0.9810	0.8473	0.7675	0.063*
C5	0.7369 (13)	0.9193 (6)	0.7339 (5)	0.066 (2)
H5	0.7921	0.9769	0.7062	0.079*
C4	0.5473 (12)	0.9116 (7)	0.7381 (6)	0.071 (3)
H4	0.4724	0.9639	0.7132	0.085*
C7	0.0729 (12)	0.4691 (5)	0.5108 (6)	0.064 (2)
C3	0.4644 (11)	0.8276 (7)	0.7785 (5)	0.068 (2)
H3	0.3333	0.8233	0.7819	0.082*
C2	0.5738 (11)	0.7495 (6)	0.8142 (5)	0.060 (2)
H2	0.5177	0.6912	0.8404	0.072*
C11	0.3443 (14)	0.6399 (7)	0.5866 (7)	0.094 (3)
H11A	0.4467	0.6905	0.5869	0.113*
H11B	0.3599	0.5961	0.6390	0.113*
C12	0.3665 (13)	0.5750 (7)	0.5093 (9)	0.109 (4)
H12A	0.4992	0.5569	0.5035	0.131*
H12B	0.3315	0.6154	0.4570	0.131*
C10	0.1627 (13)	0.6987 (6)	0.5965 (6)	0.076 (3)
H10A	0.1544	0.7498	0.5487	0.092*
H10B	0.1661	0.7369	0.6524	0.092*
C8	−0.0411 (12)	0.5691 (6)	0.5152 (8)	0.090 (3)
H8A	−0.0103	0.6114	0.4634	0.108*
H8B	−0.1742	0.5511	0.5112	0.108*
C9	−0.0129 (13)	0.6327 (7)	0.5950 (7)	0.085 (3)
H9A	−0.0103	0.5864	0.6463	0.102*
H9B	−0.1214	0.6786	0.6018	0.102*
H1A	0.785 (13)	0.646 (7)	0.988 (7)	0.102*
H1B	0.906 (14)	0.730 (7)	0.975 (7)	0.102*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0468 (10)	0.0466 (8)	0.0640 (12)	0.0048 (9)	0.0053 (10)	−0.0008 (10)
O3	0.064 (3)	0.044 (3)	0.085 (4)	−0.001 (3)	−0.014 (3)	−0.006 (3)
O1	0.046 (3)	0.082 (4)	0.105 (5)	0.010 (3)	0.016 (3)	0.013 (3)
N1	0.058 (4)	0.038 (3)	0.070 (4)	0.000 (3)	−0.011 (3)	0.005 (3)
N2	0.055 (4)	0.044 (4)	0.135 (7)	0.004 (3)	0.008 (5)	−0.016 (4)
O2	0.084 (4)	0.046 (3)	0.078 (4)	0.003 (3)	0.008 (3)	−0.014 (3)
C1	0.043 (5)	0.056 (4)	0.032 (4)	−0.001 (3)	−0.008 (3)	−0.002 (3)
C6	0.045 (4)	0.066 (4)	0.046 (4)	−0.004 (4)	0.007 (3)	0.007 (4)
C5	0.076 (6)	0.066 (5)	0.055 (6)	−0.008 (5)	−0.002 (5)	0.016 (4)
C4	0.071 (8)	0.072 (6)	0.068 (6)	0.008 (5)	−0.031 (5)	0.012 (5)
C7	0.063 (6)	0.044 (4)	0.085 (6)	0.006 (4)	−0.011 (5)	−0.018 (4)
C3	0.044 (5)	0.091 (6)	0.070 (6)	0.001 (5)	−0.016 (4)	0.005 (5)
C2	0.048 (5)	0.063 (4)	0.068 (5)	−0.009 (4)	−0.010 (4)	0.011 (4)
C11	0.079 (6)	0.068 (5)	0.136 (9)	−0.019 (5)	−0.002 (6)	−0.010 (6)
C12	0.067 (7)	0.069 (6)	0.191 (12)	−0.010 (5)	0.019 (8)	−0.036 (7)
C10	0.092 (7)	0.061 (4)	0.077 (6)	−0.004 (5)	0.005 (6)	−0.023 (4)
C8	0.063 (6)	0.065 (5)	0.141 (10)	0.015 (4)	−0.015 (6)	−0.025 (6)
C9	0.075 (6)	0.075 (6)	0.105 (8)	0.009 (5)	0.012 (5)	−0.037 (5)

Geometric parameters (Å, º) top

S1—O2	1.410 (5)	C7—C8	1.511 (10)
S1—O1	1.410 (5)	C3—C2	1.370 (10)
S1—N1	1.589 (7)	C3—H3	0.9300
S1—C1	1.758 (7)	C2—H2	0.9300
O3—C7	1.212 (8)	C11—C12	1.433 (13)
N1—H1A	0.86 (9)	C11—C10	1.494 (12)
N1—H1B	0.76 (8)	C11—H11A	0.9700
N2—C7	1.305 (9)	C11—H11B	0.9700
N2—C12	1.451 (10)	C12—H12A	0.9700
N2—H2A	0.8600	C12—H12B	0.9700
C1—C2	1.356 (10)	C10—C9	1.500 (11)
C1—C6	1.372 (9)	C10—H10A	0.9700
C6—C5	1.379 (10)	C10—H10B	0.9700
C6—H6	0.9300	C8—C9	1.458 (12)
C5—C4	1.345 (11)	C8—H8A	0.9700
C5—H5	0.9300	C8—H8B	0.9700
C4—C3	1.364 (11)	C9—H9A	0.9700
C4—H4	0.9300	C9—H9B	0.9700

O2—S1—O1	118.6 (3)	C3—C2—H2	120.4
O2—S1—N1	106.9 (3)	C12—C11—C10	117.6 (9)
O1—S1—N1	107.2 (4)	C12—C11—H11A	107.9
O2—S1—C1	109.0 (3)	C10—C11—H11A	107.9
O1—S1—C1	107.7 (3)	C12—C11—H11B	107.9
N1—S1—C1	106.9 (3)	C10—C11—H11B	107.9
S1—N1—H1A	116 (7)	H11A—C11—H11B	107.2
S1—N1—H1B	106 (8)	C11—C12—N2	115.2 (9)
H1A—N1—H1B	116 (10)	C11—C12—H12A	108.5
C7—N2—C12	127.9 (7)	N2—C12—H12A	108.5
C7—N2—H2A	116.0	C11—C12—H12B	108.5
C12—N2—H2A	116.0	N2—C12—H12B	108.5
C2—C1—C6	121.2 (7)	H12A—C12—H12B	107.5
C2—C1—S1	119.2 (6)	C11—C10—C9	115.4 (6)
C6—C1—S1	119.6 (6)	C11—C10—H10A	108.4
C1—C6—C5	118.5 (7)	C9—C10—H10A	108.4
C1—C6—H6	120.7	C11—C10—H10B	108.4
C5—C6—H6	120.7	C9—C10—H10B	108.4
C4—C5—C6	120.5 (8)	H10A—C10—H10B	107.5
C4—C5—H5	119.8	C9—C8—C7	115.7 (8)
C6—C5—H5	119.8	C9—C8—H8A	108.4
C5—C4—C3	120.4 (8)	C7—C8—H8A	108.4
C5—C4—H4	119.8	C9—C8—H8B	108.4
C3—C4—H4	119.8	C7—C8—H8B	108.4
O3—C7—N2	122.0 (7)	H8A—C8—H8B	107.4
O3—C7—C8	121.2 (8)	C8—C9—C10	116.0 (8)
N2—C7—C8	116.7 (7)	C8—C9—H9A	108.3
C4—C3—C2	120.2 (7)	C10—C9—H9A	108.3
C4—C3—H3	119.9	C8—C9—H9B	108.3
C2—C3—H3	119.9	C10—C9—H9B	108.3
C1—C2—C3	119.2 (7)	H9A—C9—H9B	107.4
C1—C2—H2	120.4

(4ClBSAVLM) top

Crystal data top

C6H6ClNO2S·C5H9NO	D_x = 1.449 Mg m⁻³
M_r = 290.76	Melting point: 363 K
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 25.701 (4) Å	Cell parameters from 1025 reflections
b = 6.8096 (4) Å	θ = 2.7–26.3°
c = 19.177 (3) Å	µ = 0.45 mm⁻¹
β = 127.40 (2)°	T = 297 K
V = 2666.3 (6) Å³	PLATE
Z = 8	0.22 × 0.20 × 0.20 mm
F(000) = 1216

Data collection top

Xcalibur, Eos, Gemini diffractometer	2732 independent reflections
Radiation source: fine-focus sealed tube	1677 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ω scans	θ_max = 26.4°, θ_min = 2.7°
Absorption correction: multi-scan SADABS	h = −32→30
T_min = 0.844, T_max = 1.000	k = −8→8
5127 measured reflections	l = −23→22

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0486P)²] where P = (F_o² + 2F_c²)/3
2732 reflections	(Δ/σ)_max < 0.001
169 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C6H6ClNO2S·C5H9NO	V = 2666.3 (6) Å³
M_r = 290.76	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 25.701 (4) Å	µ = 0.45 mm⁻¹
b = 6.8096 (4) Å	T = 297 K
c = 19.177 (3) Å	0.22 × 0.20 × 0.20 mm
β = 127.40 (2)°

Data collection top

Xcalibur, Eos, Gemini diffractometer	2732 independent reflections
Absorption correction: multi-scan SADABS	1677 reflections with I > 2σ(I)
T_min = 0.844, T_max = 1.000	R_int = 0.043
5127 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.27 e Å⁻³
2732 reflections	Δρ_min = −0.38 e Å⁻³
169 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
S1	0.16418 (4)	0.16415 (12)	0.08089 (6)	0.0460 (3)
Cl1	−0.00099 (5)	0.68185 (17)	0.14868 (7)	0.0780 (4)
O3	0.20659 (12)	0.9636 (3)	0.79188 (15)	0.0587 (7)
O1	0.13721 (13)	−0.0290 (3)	0.06081 (17)	0.0665 (7)
N2	0.19285 (13)	0.6912 (4)	0.84382 (18)	0.0490 (7)
H2A	0.2174	0.6308	0.8343	0.059*
C1	0.11457 (15)	0.3131 (4)	0.09443 (19)	0.0388 (7)
N1	0.23469 (14)	0.1540 (4)	0.17504 (19)	0.0473 (8)
H1A	0.2575 (17)	0.251 (5)	0.186 (2)	0.057*
H1B	0.2308 (16)	0.120 (5)	0.213 (2)	0.057*
C7	0.18276 (15)	0.8793 (5)	0.8239 (2)	0.0414 (8)
C2	0.12843 (16)	0.5096 (4)	0.1121 (2)	0.0454 (8)
H2	0.1615	0.5658	0.1124	0.054*
C5	0.02822 (17)	0.3436 (5)	0.1073 (2)	0.0558 (9)
H5	−0.0061	0.2893	0.1046	0.067*
C4	0.04376 (16)	0.5395 (5)	0.1269 (2)	0.0481 (8)
O2	0.17318 (12)	0.2594 (3)	0.02267 (15)	0.0593 (7)
C6	0.06435 (16)	0.2295 (5)	0.0916 (2)	0.0508 (9)
H6	0.0550	0.0966	0.0791	0.061*
C8	0.14281 (18)	0.9907 (5)	0.8431 (2)	0.0559 (9)
H8A	0.1134	1.0774	0.7940	0.067*
H8B	0.1719	1.0722	0.8944	0.067*
C3	0.09319 (16)	0.6229 (5)	0.1294 (2)	0.0497 (8)
H3	0.1030	0.7554	0.1428	0.060*
C10	0.14434 (18)	0.7008 (5)	0.9207 (2)	0.0555 (9)
H10A	0.1192	0.6229	0.9331	0.067*
H10B	0.1819	0.7547	0.9756	0.067*
C11	0.16699 (18)	0.5738 (5)	0.8803 (2)	0.0578 (10)
H11A	0.2008	0.4852	0.9244	0.069*
H11B	0.1306	0.4950	0.8341	0.069*
C9	0.10283 (18)	0.8639 (5)	0.8592 (2)	0.0596 (10)
H9A	0.0865	0.9429	0.8843	0.071*
H9B	0.0656	0.8099	0.8041	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0600 (6)	0.0403 (5)	0.0533 (5)	0.0038 (4)	0.0425 (5)	−0.0008 (4)
Cl1	0.0590 (6)	0.1005 (8)	0.0823 (7)	0.0162 (6)	0.0469 (6)	−0.0150 (6)
O3	0.0755 (17)	0.0565 (14)	0.0664 (16)	−0.0120 (13)	0.0548 (15)	−0.0072 (12)
O1	0.0878 (19)	0.0430 (14)	0.0893 (19)	−0.0110 (13)	0.0646 (17)	−0.0178 (13)
N2	0.0567 (18)	0.0414 (16)	0.0651 (19)	0.0096 (13)	0.0455 (17)	0.0011 (13)
C1	0.0409 (19)	0.0375 (18)	0.0385 (18)	0.0013 (14)	0.0243 (16)	0.0011 (13)
N1	0.055 (2)	0.0468 (17)	0.0545 (19)	0.0087 (14)	0.0408 (17)	0.0086 (15)
C7	0.0422 (19)	0.044 (2)	0.0386 (18)	−0.0015 (15)	0.0251 (16)	−0.0044 (15)
C2	0.047 (2)	0.0433 (19)	0.056 (2)	0.0021 (16)	0.0359 (18)	0.0034 (16)
C5	0.043 (2)	0.068 (2)	0.065 (2)	−0.0016 (19)	0.0373 (19)	0.0023 (19)
C4	0.042 (2)	0.059 (2)	0.0411 (19)	0.0105 (18)	0.0246 (17)	−0.0003 (16)
O2	0.0809 (18)	0.0635 (15)	0.0573 (15)	0.0092 (13)	0.0543 (15)	0.0087 (12)
C6	0.052 (2)	0.0448 (19)	0.059 (2)	−0.0034 (17)	0.0359 (19)	−0.0002 (16)
C8	0.073 (2)	0.046 (2)	0.064 (2)	0.0189 (18)	0.050 (2)	0.0114 (17)
C3	0.049 (2)	0.0406 (18)	0.060 (2)	0.0012 (16)	0.0335 (19)	−0.0016 (16)
C10	0.062 (2)	0.061 (2)	0.061 (2)	0.0044 (19)	0.046 (2)	0.0058 (18)
C11	0.070 (3)	0.045 (2)	0.066 (2)	0.0030 (18)	0.045 (2)	0.0063 (17)
C9	0.058 (2)	0.072 (2)	0.065 (2)	0.010 (2)	0.046 (2)	0.001 (2)

Geometric parameters (Å, º) top

S1—O2	1.426 (2)	C5—C4	1.378 (5)
S1—O1	1.427 (2)	C5—H5	0.9300
S1—N1	1.604 (3)	C4—C3	1.365 (4)
S1—C1	1.768 (3)	C6—H6	0.9300
Cl1—C4	1.738 (3)	C8—C9	1.511 (5)
O3—C7	1.241 (4)	C8—H8A	0.9700
N2—C7	1.316 (4)	C8—H8B	0.9700
N2—C11	1.461 (4)	C3—H3	0.9300
N2—H2A	0.8600	C10—C9	1.495 (5)
C1—C2	1.373 (4)	C10—C11	1.495 (5)
C1—C6	1.381 (4)	C10—H10A	0.9700
N1—H1A	0.82 (3)	C10—H10B	0.9700
N1—H1B	0.83 (3)	C11—H11A	0.9700
C7—C8	1.491 (4)	C11—H11B	0.9700
C2—C3	1.375 (4)	C9—H9A	0.9700
C2—H2	0.9300	C9—H9B	0.9700
C5—C6	1.377 (5)

O2—S1—O1	119.42 (15)	C1—C6—H6	120.1
O2—S1—N1	106.94 (15)	C7—C8—C9	114.5 (3)
O1—S1—N1	107.19 (16)	C7—C8—H8A	108.6
O2—S1—C1	109.17 (14)	C9—C8—H8A	108.6
O1—S1—C1	107.05 (15)	C7—C8—H8B	108.6
N1—S1—C1	106.37 (14)	C9—C8—H8B	108.6
C7—N2—C11	127.2 (3)	H8A—C8—H8B	107.6
C7—N2—H2A	116.4	C4—C3—C2	119.5 (3)
C11—N2—H2A	116.4	C4—C3—H3	120.2
C2—C1—C6	120.5 (3)	C2—C3—H3	120.2
C2—C1—S1	119.6 (2)	C9—C10—C11	109.7 (3)
C6—C1—S1	119.9 (2)	C9—C10—H10A	109.7
S1—N1—H1A	113 (2)	C11—C10—H10A	109.7
S1—N1—H1B	110 (2)	C9—C10—H10B	109.7
H1A—N1—H1B	117 (4)	C11—C10—H10B	109.7
O3—C7—N2	121.6 (3)	H10A—C10—H10B	108.2
O3—C7—C8	120.5 (3)	N2—C11—C10	111.4 (3)
N2—C7—C8	117.9 (3)	N2—C11—H11A	109.3
C1—C2—C3	119.8 (3)	C10—C11—H11A	109.3
C1—C2—H2	120.1	N2—C11—H11B	109.3
C3—C2—H2	120.1	C10—C11—H11B	109.3
C6—C5—C4	118.9 (3)	H11A—C11—H11B	108.0
C6—C5—H5	120.5	C10—C9—C8	109.8 (3)
C4—C5—H5	120.5	C10—C9—H9A	109.7
C3—C4—C5	121.4 (3)	C8—C9—H9A	109.7
C3—C4—Cl1	119.8 (3)	C10—C9—H9B	109.7
C5—C4—Cl1	118.8 (3)	C8—C9—H9B	109.7
C5—C6—C1	119.8 (3)	H9A—C9—H9B	108.2
C5—C6—H6	120.1

(4BrBSAVLM) top

Crystal data top

C6H6BrNO2S·C5H9NO	D_x = 1.629 Mg m⁻³
M_r = 335.22	Melting point: 367 K
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 25.914 (3) Å	Cell parameters from 4015 reflections
b = 6.8687 (9) Å	θ = 2.7–25.4°
c = 19.202 (2) Å	µ = 3.16 mm⁻¹
β = 126.873 (2)°	T = 298 K
V = 2734.1 (6) Å³	PLATE, colorles
Z = 8	0.22 × 0.20 × 0.20 mm
F(000) = 1360

Data collection top

CCD area detector diffractometer	2216 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
Graphite monochromator	θ_max = 26.4°, θ_min = 2.0°
phi and ω scans	h = −32→32
14029 measured reflections	k = −8→8
2790 independent reflections	l = −23→23

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0541P)² + 0.8825P] where P = (F_o² + 2F_c²)/3
2790 reflections	(Δ/σ)_max < 0.001
175 parameters	Δρ_max = 0.56 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

C6H6BrNO2S·C5H9NO	V = 2734.1 (6) Å³
M_r = 335.22	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 25.914 (3) Å	µ = 3.16 mm⁻¹
b = 6.8687 (9) Å	T = 298 K
c = 19.202 (2) Å	0.22 × 0.20 × 0.20 mm
β = 126.873 (2)°

Data collection top

CCD area detector diffractometer	2216 reflections with I > 2σ(I)
14029 measured reflections	R_int = 0.030
2790 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.56 e Å⁻³
2790 reflections	Δρ_min = −0.39 e Å⁻³
175 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
Br1	−0.003156 (14)	0.69679 (5)	0.14703 (2)	0.07718 (16)
S1	0.16814 (3)	0.16446 (9)	0.08449 (4)	0.04800 (18)
O1	0.14262 (10)	−0.0289 (3)	0.06658 (13)	0.0690 (5)
N2	0.19222 (12)	0.3131 (3)	0.34335 (16)	0.0533 (6)
O3	0.20743 (10)	0.0431 (3)	0.29329 (12)	0.0617 (5)
C7	0.18364 (12)	0.1262 (4)	0.32543 (15)	0.0440 (5)
N1	0.23788 (12)	0.1604 (4)	0.17853 (15)	0.0510 (5)
C1	0.11787 (12)	0.3130 (3)	0.09613 (15)	0.0431 (5)
C4	0.04600 (11)	0.5392 (4)	0.12539 (15)	0.0492 (6)
O2	0.17723 (10)	0.2564 (3)	0.02588 (12)	0.0622 (5)
C5	0.03196 (13)	0.3442 (4)	0.10870 (19)	0.0588 (7)
H5	−0.0017	0.2903	0.1069	0.071*
C6	0.06871 (13)	0.2296 (4)	0.09456 (19)	0.0551 (6)
H6	0.0604	0.0970	0.0840	0.066*
C10	0.14516 (15)	0.3028 (4)	0.42200 (19)	0.0596 (7)
H10A	0.1825	0.2517	0.4766	0.072*
H10B	0.1200	0.3793	0.4343	0.072*
C2	0.13035 (12)	0.5088 (3)	0.11092 (16)	0.0491 (6)
H2	0.1629	0.5643	0.1105	0.059*
C3	0.09429 (13)	0.6235 (4)	0.12650 (17)	0.0532 (6)
H3	0.1028	0.7559	0.1375	0.064*
C8	0.14546 (14)	0.0129 (4)	0.34662 (19)	0.0586 (7)
H8A	0.1749	−0.0650	0.3981	0.070*
H8B	0.1170	−0.0756	0.2990	0.070*
C11	0.16695 (14)	0.4302 (4)	0.38022 (18)	0.0607 (7)
H11A	0.1309	0.5075	0.3346	0.073*
H11B	0.2002	0.5186	0.4234	0.073*
C9	0.10520 (15)	0.1386 (5)	0.3626 (2)	0.0667 (8)
H9A	0.0682	0.1897	0.3077	0.080*
H9B	0.0896	0.0605	0.3885	0.080*
H1A	0.2336 (13)	0.127 (4)	0.2156 (18)	0.059 (8)*
H1B	0.2591 (15)	0.271 (4)	0.190 (2)	0.066 (9)*
H2A	0.2102 (13)	0.365 (4)	0.3314 (18)	0.053 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0590 (2)	0.1037 (3)	0.0761 (2)	0.01633 (16)	0.04444 (19)	−0.01461 (16)
S1	0.0623 (4)	0.0435 (3)	0.0554 (4)	0.0047 (3)	0.0445 (3)	−0.0004 (3)
O1	0.0909 (14)	0.0480 (10)	0.0923 (14)	−0.0075 (10)	0.0678 (13)	−0.0169 (10)
N2	0.0642 (14)	0.0494 (14)	0.0668 (15)	−0.0107 (10)	0.0502 (13)	−0.0004 (10)
O3	0.0793 (13)	0.0598 (11)	0.0699 (12)	0.0112 (9)	0.0576 (11)	0.0079 (9)
C7	0.0466 (13)	0.0466 (14)	0.0430 (12)	0.0008 (11)	0.0290 (11)	0.0034 (10)
N1	0.0607 (14)	0.0504 (13)	0.0586 (14)	0.0128 (11)	0.0447 (12)	0.0088 (10)
C1	0.0467 (13)	0.0456 (14)	0.0446 (12)	0.0062 (10)	0.0315 (11)	0.0044 (10)
C4	0.0433 (13)	0.0624 (16)	0.0445 (13)	0.0126 (11)	0.0277 (11)	0.0028 (11)
O2	0.0821 (13)	0.0688 (11)	0.0610 (11)	0.0116 (10)	0.0565 (11)	0.0079 (9)
C5	0.0530 (15)	0.0697 (18)	0.0695 (18)	0.0036 (13)	0.0452 (15)	0.0058 (14)
C6	0.0597 (16)	0.0467 (13)	0.0700 (17)	−0.0023 (12)	0.0449 (15)	−0.0006 (12)
C10	0.0682 (18)	0.0629 (17)	0.0658 (17)	0.0011 (13)	0.0498 (16)	−0.0024 (13)
C2	0.0520 (14)	0.0454 (13)	0.0612 (15)	−0.0007 (11)	0.0400 (13)	0.0010 (11)
C3	0.0564 (15)	0.0450 (13)	0.0634 (16)	0.0061 (11)	0.0387 (14)	−0.0016 (12)
C8	0.0753 (18)	0.0506 (15)	0.0666 (16)	−0.0187 (13)	0.0515 (15)	−0.0091 (12)
C11	0.0800 (19)	0.0451 (15)	0.0711 (18)	−0.0009 (13)	0.0528 (17)	−0.0027 (12)
C9	0.0657 (18)	0.0780 (19)	0.0761 (19)	−0.0168 (15)	0.0530 (16)	−0.0058 (15)

Geometric parameters (Å, º) top

Br1—C4	1.898 (2)	C1—C2	1.373 (3)
S1—O2	1.4280 (18)	C1—C6	1.380 (3)
S1—O1	1.431 (2)	C4—C3	1.367 (4)
S1—N1	1.616 (2)	C4—C5	1.374 (4)
S1—C1	1.771 (2)	C5—C6	1.382 (4)
N2—C7	1.313 (3)	C10—C9	1.493 (4)
N2—C11	1.461 (3)	C10—C11	1.507 (4)
O3—C7	1.242 (3)	C2—C3	1.385 (3)
C7—C8	1.494 (3)	C8—C9	1.520 (4)

O2—S1—O1	119.48 (12)	C6—C1—S1	119.82 (18)
O2—S1—N1	106.60 (13)	C3—C4—C5	121.9 (2)
O1—S1—N1	107.35 (13)	C3—C4—Br1	118.89 (19)
O2—S1—C1	109.04 (11)	C5—C4—Br1	119.23 (19)
O1—S1—C1	107.23 (11)	C4—C5—C6	118.9 (2)
N1—S1—C1	106.45 (11)	C1—C6—C5	119.7 (2)
C7—N2—C11	127.6 (2)	C9—C10—C11	110.0 (2)
O3—C7—N2	121.5 (2)	C1—C2—C3	119.8 (2)
O3—C7—C8	120.2 (2)	C4—C3—C2	119.0 (2)
N2—C7—C8	118.3 (2)	C7—C8—C9	113.9 (2)
C2—C1—C6	120.7 (2)	N2—C11—C10	111.0 (2)
C2—C1—S1	119.39 (18)	C10—C9—C8	109.8 (2)

(PTSAVLM) top

Crystal data top

C7H9NO2S·C5H9NO	F(000) = 288
M_r = 270.34	D_x = 1.298 Mg m⁻³
Triclinic, P1	Melting point: 347 K
a = 5.210 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.449 (4) Å	Cell parameters from 1964 reflections
c = 16.104 (8) Å	θ = 2.5–23.8°
α = 82.894 (8)°	µ = 0.24 mm⁻¹
β = 82.798 (8)°	T = 298 K
γ = 81.772 (8)°	PLATE, colorles
V = 692.0 (6) Å³	0.22 × 0.20 × 0.20 mm
Z = 2

Data collection top

CCD area detector diffractometer	1969 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 26.4°, θ_min = 1.3°
phi and ω scans	h = −6→6
7341 measured reflections	k = −10→10
2819 independent reflections	l = −20→19

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0881P)² + 0.0472P] where P = (F_o² + 2F_c²)/3
2819 reflections	(Δ/σ)_max = 0.001
176 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C7H9NO2S·C5H9NO	γ = 81.772 (8)°
M_r = 270.34	V = 692.0 (6) Å³
Triclinic, P1	Z = 2
a = 5.210 (3) Å	Mo Kα radiation
b = 8.449 (4) Å	µ = 0.24 mm⁻¹
c = 16.104 (8) Å	T = 298 K
α = 82.894 (8)°	0.22 × 0.20 × 0.20 mm
β = 82.798 (8)°

Data collection top

CCD area detector diffractometer	1969 reflections with I > 2σ(I)
7341 measured reflections	R_int = 0.023
2819 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.43 e Å⁻³
2819 reflections	Δρ_min = −0.15 e Å⁻³
176 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
S1	1.10112 (11)	0.19293 (7)	0.72741 (4)	0.0619 (3)
O3	0.8702 (3)	0.41356 (19)	0.91796 (10)	0.0688 (5)
N2	0.7568 (4)	0.6588 (2)	0.95856 (14)	0.0597 (5)
C8	0.7356 (4)	0.5482 (3)	0.91038 (14)	0.0537 (5)
N1	0.8887 (4)	0.1678 (3)	0.80706 (15)	0.0599 (5)
C1	1.0056 (4)	0.3814 (3)	0.67244 (14)	0.0535 (5)
O2	1.0896 (4)	0.0718 (2)	0.67443 (13)	0.0934 (7)
O1	1.3393 (3)	0.2030 (2)	0.76034 (15)	0.0947 (7)
C12	0.6188 (5)	0.8210 (3)	0.95606 (18)	0.0737 (7)
H12A	0.7382	0.8964	0.9311	0.088*
H12B	0.5601	0.8456	1.0132	0.088*
C4	0.8259 (5)	0.6833 (3)	0.59678 (16)	0.0682 (7)
C11	0.3906 (6)	0.8430 (4)	0.9073 (2)	0.0909 (9)
H11A	0.2450	0.8012	0.9425	0.109*
H11B	0.3405	0.9571	0.8924	0.109*
C6	1.1026 (5)	0.5156 (3)	0.68710 (19)	0.0790 (8)
H6	1.2325	0.5064	0.7227	0.095*
C2	0.8195 (6)	0.3973 (3)	0.61818 (17)	0.0821 (8)
H2	0.7526	0.3073	0.6062	0.099*
C10	0.4426 (7)	0.7627 (4)	0.8306 (2)	0.1003 (11)
H10A	0.5719	0.8144	0.7922	0.120*
H10B	0.2837	0.7751	0.8036	0.120*
C9	0.5402 (5)	0.5845 (3)	0.84744 (16)	0.0707 (7)
H9A	0.3924	0.5270	0.8677	0.085*
H9B	0.6190	0.5450	0.7949	0.085*
C5	1.0095 (6)	0.6651 (3)	0.64949 (19)	0.0792 (8)
H5	1.0762	0.7554	0.6611	0.095*
C7	0.7207 (7)	0.8483 (4)	0.5574 (2)	0.1055 (11)
H7A	0.8460	0.9213	0.5573	0.158*
H7B	0.5606	0.8866	0.5893	0.158*
H7C	0.6889	0.8415	0.5006	0.158*
C3	0.7320 (7)	0.5486 (4)	0.5813 (2)	0.0975 (10)
H3	0.6047	0.5589	0.5447	0.117*
H1A	0.756 (5)	0.158 (3)	0.7922 (15)	0.054 (7)*
H1B	0.885 (5)	0.240 (3)	0.8399 (16)	0.071 (9)*
H2A	0.850 (5)	0.637 (3)	0.9921 (16)	0.058 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0507 (4)	0.0481 (4)	0.0836 (5)	0.0045 (2)	−0.0138 (3)	0.0001 (3)
O3	0.0761 (11)	0.0595 (10)	0.0727 (11)	0.0114 (8)	−0.0338 (9)	−0.0121 (8)
N2	0.0561 (12)	0.0552 (12)	0.0694 (13)	0.0057 (9)	−0.0288 (11)	−0.0061 (10)
C8	0.0486 (12)	0.0555 (13)	0.0563 (13)	−0.0016 (10)	−0.0154 (10)	0.0003 (11)
N1	0.0556 (13)	0.0507 (12)	0.0747 (15)	−0.0055 (9)	−0.0215 (11)	0.0014 (10)
C1	0.0452 (11)	0.0502 (12)	0.0630 (14)	0.0000 (9)	−0.0085 (10)	−0.0021 (10)
O2	0.1218 (17)	0.0521 (10)	0.1003 (14)	0.0137 (10)	−0.0043 (12)	−0.0214 (10)
O1	0.0483 (10)	0.0814 (13)	0.1487 (18)	−0.0023 (8)	−0.0358 (11)	0.0282 (12)
C12	0.0704 (16)	0.0559 (14)	0.0935 (19)	0.0117 (12)	−0.0284 (14)	−0.0057 (13)
C4	0.0780 (17)	0.0606 (15)	0.0592 (14)	0.0017 (12)	−0.0071 (13)	0.0070 (11)
C11	0.087 (2)	0.0695 (18)	0.114 (2)	0.0168 (14)	−0.0433 (18)	−0.0013 (17)
C6	0.0770 (18)	0.0620 (16)	0.105 (2)	−0.0155 (13)	−0.0459 (16)	0.0058 (14)
C2	0.111 (2)	0.0632 (17)	0.0815 (18)	−0.0175 (15)	−0.0445 (17)	−0.0033 (14)
C10	0.116 (3)	0.093 (2)	0.089 (2)	0.0324 (18)	−0.0550 (19)	−0.0051 (17)
C9	0.0697 (16)	0.0709 (16)	0.0732 (16)	0.0026 (12)	−0.0332 (13)	−0.0021 (13)
C5	0.091 (2)	0.0518 (15)	0.098 (2)	−0.0144 (13)	−0.0275 (17)	0.0037 (14)
C7	0.127 (3)	0.077 (2)	0.100 (2)	0.0079 (18)	−0.025 (2)	0.0254 (17)
C3	0.123 (3)	0.082 (2)	0.094 (2)	−0.0061 (18)	−0.067 (2)	0.0120 (17)

Geometric parameters (Å, º) top

S1—O2	1.423 (2)	C4—C7	1.516 (3)
S1—O1	1.426 (2)	C11—C10	1.459 (4)
S1—N1	1.600 (2)	C11—H11A	0.9700
S1—C1	1.762 (2)	C11—H11B	0.9700
O3—C8	1.249 (3)	C6—C5	1.381 (4)
N2—C8	1.311 (3)	C6—H6	0.9300
N2—C12	1.452 (3)	C2—C3	1.381 (4)
N2—H2A	0.76 (3)	C2—H2	0.9300
C8—C9	1.500 (3)	C10—C9	1.521 (4)
N1—H1A	0.78 (3)	C10—H10A	0.9700
N1—H1B	0.85 (3)	C10—H10B	0.9700
C1—C6	1.362 (3)	C9—H9A	0.9700
C1—C2	1.366 (3)	C9—H9B	0.9700
C12—C11	1.483 (4)	C5—H5	0.9300
C12—H12A	0.9700	C7—H7A	0.9600
C12—H12B	0.9700	C7—H7B	0.9600
C4—C5	1.337 (4)	C7—H7C	0.9600
C4—C3	1.362 (4)	C3—H3	0.9300

O2—S1—O1	119.81 (13)	H11A—C11—H11B	107.8
O2—S1—N1	107.32 (14)	C1—C6—C5	120.5 (2)
O1—S1—N1	106.20 (14)	C1—C6—H6	119.7
O2—S1—C1	108.18 (12)	C5—C6—H6	119.7
O1—S1—C1	107.38 (11)	C1—C2—C3	119.2 (3)
N1—S1—C1	107.36 (10)	C1—C2—H2	120.4
C8—N2—C12	127.3 (2)	C3—C2—H2	120.4
C8—N2—H2A	117.7 (19)	C11—C10—C9	112.7 (2)
C12—N2—H2A	115.0 (19)	C11—C10—H10A	109.1
O3—C8—N2	120.9 (2)	C9—C10—H10A	109.1
O3—C8—C9	120.4 (2)	C11—C10—H10B	109.1
N2—C8—C9	118.7 (2)	C9—C10—H10B	109.1
S1—N1—H1A	110.0 (17)	H10A—C10—H10B	107.8
S1—N1—H1B	110.7 (17)	C8—C9—C10	113.6 (2)
H1A—N1—H1B	116 (3)	C8—C9—H9A	108.8
C6—C1—C2	118.7 (2)	C10—C9—H9A	108.8
C6—C1—S1	120.85 (19)	C8—C9—H9B	108.8
C2—C1—S1	120.30 (19)	C10—C9—H9B	108.8
N2—C12—C11	112.7 (2)	H9A—C9—H9B	107.7
N2—C12—H12A	109.1	C4—C5—C6	121.6 (3)
C11—C12—H12A	109.1	C4—C5—H5	119.2
N2—C12—H12B	109.1	C6—C5—H5	119.2
C11—C12—H12B	109.1	C4—C7—H7A	109.5
H12A—C12—H12B	107.8	C4—C7—H7B	109.5
C5—C4—C3	117.7 (2)	H7A—C7—H7B	109.5
C5—C4—C7	121.2 (3)	C4—C7—H7C	109.5
C3—C4—C7	121.1 (3)	H7A—C7—H7C	109.5
C10—C11—C12	112.8 (3)	H7B—C7—H7C	109.5
C10—C11—H11A	109.0	C4—C3—C2	122.3 (3)
C12—C11—H11A	109.0	C4—C3—H3	118.9
C10—C11—H11B	109.0	C2—C3—H3	118.9
C12—C11—H11B	109.0

(2ClBSAVLM) top

Crystal data top

C6H6ClNO2S·C5H9NO	D_x = 1.439 Mg m⁻³
M_r = 290.76	Melting point: 353 K
Monoclinic, P1₂1/c1	Mo Kα radiation, λ = 0.71073 Å
a = 10.521 (2) Å	Cell parameters from 1920 reflections
b = 13.7661 (12) Å	θ = 3.7–28.8°
c = 10.3407 (16) Å	µ = 0.44 mm⁻¹
β = 116.31 (2)°	T = 298 K
V = 1342.5 (3) Å³	BLOCK, colorles
Z = 4	0.22 × 0.22 × 0.20 mm
F(000) = 608

Data collection top

Xcalibur, Eos, Gemini diffractometer	2731 independent reflections
Radiation source: fine-focus sealed tube	2039 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ω scans	θ_max = 26.4°, θ_min = 2.7°
Absorption correction: multi-scan SADABS	h = −12→13
T_min = 0.707, T_max = 1.000	k = −15→17
5058 measured reflections	l = −11→12

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0596P)²] where P = (F_o² + 2F_c²)/3
2731 reflections	(Δ/σ)_max < 0.001
169 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C6H6ClNO2S·C5H9NO	V = 1342.5 (3) Å³
M_r = 290.76	Z = 4
Monoclinic, P1₂1/c1	Mo Kα radiation
a = 10.521 (2) Å	µ = 0.44 mm⁻¹
b = 13.7661 (12) Å	T = 298 K
c = 10.3407 (16) Å	0.22 × 0.22 × 0.20 mm
β = 116.31 (2)°

Data collection top

Xcalibur, Eos, Gemini diffractometer	2731 independent reflections
Absorption correction: multi-scan SADABS	2039 reflections with I > 2σ(I)
T_min = 0.707, T_max = 1.000	R_int = 0.038
5058 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.38 e Å⁻³
2731 reflections	Δρ_min = −0.36 e Å⁻³
169 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
S1	0.19111 (6)	0.19966 (4)	0.48704 (5)	0.03615 (18)
Cl1	0.05379 (7)	0.11264 (4)	0.16036 (6)	0.0540 (2)
O1	0.26755 (18)	0.20526 (11)	0.64070 (15)	0.0487 (4)
O2	0.05885 (17)	0.24899 (11)	0.41564 (16)	0.0495 (4)
C1	0.1601 (2)	0.07383 (14)	0.4485 (2)	0.0328 (5)
N1	0.2947 (2)	0.24040 (14)	0.4250 (2)	0.0437 (5)
H1B	0.257 (3)	0.2485 (18)	0.335 (3)	0.052*
H1A	0.372 (3)	0.2141 (19)	0.462 (3)	0.052*
O3	0.54379 (19)	0.12661 (13)	0.55417 (18)	0.0610 (5)
C2	0.1944 (2)	0.01049 (17)	0.5627 (2)	0.0437 (6)
H2	0.2366	0.0337	0.6569	0.052*
N2	0.5607 (2)	0.00213 (15)	0.6987 (2)	0.0525 (5)
H2A	0.5325	−0.0349	0.6242	0.063*
C5	0.0690 (3)	−0.06037 (17)	0.2835 (3)	0.0506 (6)
H5	0.0269	−0.0842	0.1896	0.061*
C6	0.0966 (2)	0.03718 (16)	0.3083 (2)	0.0387 (5)
C3	0.1659 (3)	−0.08749 (19)	0.5367 (3)	0.0584 (7)
H3	0.1888	−0.1300	0.6137	0.070*
C4	0.1040 (3)	−0.12237 (18)	0.3982 (3)	0.0590 (7)
H4	0.0857	−0.1885	0.3819	0.071*
C8	0.5756 (3)	0.09436 (19)	0.6778 (3)	0.0504 (6)
C10	0.6294 (4)	0.1197 (2)	0.9393 (3)	0.0769 (9)
H10A	0.6889	0.1581	1.0231	0.092*
H10B	0.5329	0.1226	0.9282	0.092*
C12	0.5869 (3)	−0.0445 (2)	0.8350 (3)	0.0620 (7)
H12A	0.6321	−0.1069	0.8412	0.074*
H12B	0.4972	−0.0561	0.8377	0.074*
C11	0.6794 (3)	0.0165 (3)	0.9618 (3)	0.0742 (9)
H11A	0.7765	0.0137	0.9747	0.089*
H11B	0.6774	−0.0089	1.0484	0.089*
C9	0.6348 (3)	0.1615 (2)	0.8064 (3)	0.0674 (8)
H9A	0.5818	0.2219	0.7810	0.081*
H9B	0.7325	0.1765	0.8291	0.081*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0502 (4)	0.0291 (3)	0.0311 (3)	0.0002 (3)	0.0198 (3)	−0.0019 (2)
Cl1	0.0700 (5)	0.0501 (4)	0.0350 (3)	−0.0103 (3)	0.0170 (3)	−0.0051 (2)
O1	0.0696 (12)	0.0471 (9)	0.0308 (8)	−0.0030 (9)	0.0235 (8)	−0.0062 (7)
O2	0.0581 (11)	0.0373 (9)	0.0523 (10)	0.0128 (8)	0.0236 (9)	0.0027 (7)
C1	0.0346 (11)	0.0276 (10)	0.0395 (11)	0.0007 (9)	0.0194 (9)	0.0012 (9)
N1	0.0544 (13)	0.0405 (11)	0.0349 (10)	−0.0103 (10)	0.0185 (10)	0.0001 (8)
O3	0.0692 (13)	0.0589 (11)	0.0577 (11)	0.0052 (10)	0.0307 (9)	0.0064 (9)
C2	0.0449 (13)	0.0395 (12)	0.0484 (13)	0.0034 (11)	0.0223 (11)	0.0068 (10)
N2	0.0594 (14)	0.0497 (12)	0.0456 (11)	0.0039 (11)	0.0207 (10)	−0.0017 (9)
C5	0.0541 (16)	0.0360 (12)	0.0662 (15)	−0.0100 (12)	0.0308 (13)	−0.0136 (12)
C6	0.0379 (12)	0.0357 (11)	0.0459 (13)	−0.0037 (10)	0.0216 (10)	−0.0026 (9)
C3	0.0583 (17)	0.0398 (13)	0.0824 (19)	0.0068 (13)	0.0360 (14)	0.0222 (13)
C4	0.0581 (17)	0.0299 (12)	0.093 (2)	−0.0039 (12)	0.0375 (15)	−0.0035 (13)
C8	0.0419 (14)	0.0527 (15)	0.0562 (16)	0.0052 (12)	0.0214 (12)	−0.0011 (12)
C10	0.087 (2)	0.082 (2)	0.0587 (18)	0.002 (2)	0.0297 (16)	−0.0146 (16)
C12	0.0659 (18)	0.0641 (17)	0.0532 (15)	0.0105 (15)	0.0239 (14)	0.0097 (13)
C11	0.073 (2)	0.090 (2)	0.0475 (15)	0.0098 (18)	0.0159 (14)	0.0012 (15)
C9	0.0657 (19)	0.0590 (17)	0.075 (2)	−0.0006 (16)	0.0296 (16)	−0.0106 (15)

Geometric parameters (Å, º) top

S1—O2	1.4254 (16)	C5—H5	0.9300
S1—O1	1.4299 (16)	C3—C4	1.370 (4)
S1—N1	1.592 (2)	C3—H3	0.9300
S1—C1	1.775 (2)	C4—H4	0.9300
Cl1—C6	1.735 (2)	C8—C9	1.508 (3)
C1—C2	1.380 (3)	C10—C11	1.497 (4)
C1—C6	1.395 (3)	C10—C9	1.514 (4)
N1—H1B	0.84 (3)	C10—H10A	0.9700
N1—H1A	0.81 (3)	C10—H10B	0.9700
O3—C8	1.251 (3)	C12—C11	1.497 (4)
C2—C3	1.382 (3)	C12—H12A	0.9700
C2—H2	0.9300	C12—H12B	0.9700
N2—C8	1.309 (3)	C11—H11A	0.9700
N2—C12	1.460 (3)	C11—H11B	0.9700
N2—H2A	0.8600	C9—H9A	0.9700
C5—C4	1.373 (4)	C9—H9B	0.9700
C5—C6	1.374 (3)

O2—S1—O1	119.27 (10)	C5—C4—H4	119.8
O2—S1—N1	108.00 (11)	O3—C8—N2	121.0 (2)
O1—S1—N1	106.29 (11)	O3—C8—C9	120.2 (2)
O2—S1—C1	107.98 (10)	N2—C8—C9	118.8 (2)
O1—S1—C1	105.00 (10)	C11—C10—C9	110.5 (3)
N1—S1—C1	110.12 (10)	C11—C10—H10A	109.6
C2—C1—C6	118.9 (2)	C9—C10—H10A	109.6
C2—C1—S1	118.18 (16)	C11—C10—H10B	109.6
C6—C1—S1	122.81 (15)	C9—C10—H10B	109.6
S1—N1—H1B	115.1 (17)	H10A—C10—H10B	108.1
S1—N1—H1A	112.1 (19)	N2—C12—C11	111.7 (2)
H1B—N1—H1A	117 (3)	N2—C12—H12A	109.3
C1—C2—C3	119.9 (2)	C11—C12—H12A	109.3
C1—C2—H2	120.1	N2—C12—H12B	109.3
C3—C2—H2	120.1	C11—C12—H12B	109.3
C8—N2—C12	126.9 (2)	H12A—C12—H12B	107.9
C8—N2—H2A	116.5	C12—C11—C10	110.4 (2)
C12—N2—H2A	116.5	C12—C11—H11A	109.6
C4—C5—C6	119.5 (2)	C10—C11—H11A	109.6
C4—C5—H5	120.2	C12—C11—H11B	109.6
C6—C5—H5	120.2	C10—C11—H11B	109.6
C5—C6—C1	120.8 (2)	H11A—C11—H11B	108.1
C5—C6—Cl1	118.02 (18)	C8—C9—C10	113.6 (2)
C1—C6—Cl1	121.17 (17)	C8—C9—H9A	108.8
C4—C3—C2	120.4 (2)	C10—C9—H9A	108.8
C4—C3—H3	119.8	C8—C9—H9B	108.8
C2—C3—H3	119.8	C10—C9—H9B	108.8
C3—C4—C5	120.4 (2)	H9A—C9—H9B	107.7
C3—C4—H4	119.8

(BSAVLM) top

Crystal data top

C6H7NO2S·C5H9NO	D_x = 1.335 Mg m⁻³
M_r = 256.32	Melting point: 352 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
a = 7.1043 (5) Å	Cell parameters from 1374 reflections
b = 12.7937 (10) Å	θ = 3.6–27.8°
c = 14.0302 (16) Å	µ = 0.25 mm⁻¹
V = 1275.2 (2) Å³	T = 298 K
Z = 4	PLATE, colorles
F(000) = 544	0.22 × 0.20 × 0.20 mm

Data collection top

Xcalibur, Eos, Gemini diffractometer	2493 independent reflections
Radiation source: fine-focus sealed tube	2175 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 26.4°, θ_min = 2.9°
Absorption correction: multi-scan SADABS	h = −4→8
T_min = 0.679, T_max = 1.000	k = −15→15
3791 measured reflections	l = −17→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.120	w = 1/[σ²(F_o²) + (0.0594P)² + 0.2685P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2493 reflections	Δρ_max = 0.25 e Å⁻³
160 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (12)

Crystal data top

C6H7NO2S·C5H9NO	V = 1275.2 (2) Å³
M_r = 256.32	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.1043 (5) Å	µ = 0.25 mm⁻¹
b = 12.7937 (10) Å	T = 298 K
c = 14.0302 (16) Å	0.22 × 0.20 × 0.20 mm

Data collection top

Xcalibur, Eos, Gemini diffractometer	2493 independent reflections
Absorption correction: multi-scan SADABS	2175 reflections with I > 2σ(I)
T_min = 0.679, T_max = 1.000	R_int = 0.025
3791 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.120	Δρ_max = 0.25 e Å⁻³
S = 1.06	Δρ_min = −0.24 e Å⁻³
2493 reflections	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
160 parameters	Absolute structure parameter: −0.01 (12)
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
S1	0.09979 (9)	0.66876 (5)	0.35518 (6)	0.0479 (2)
O2	−0.0932 (3)	0.69509 (18)	0.34129 (19)	0.0701 (7)
C1	0.2366 (4)	0.7664 (2)	0.29907 (19)	0.0400 (6)
N1	0.1392 (4)	0.6744 (2)	0.4676 (2)	0.0536 (6)
H1A	0.243 (5)	0.647 (3)	0.484 (3)	0.064*
H1B	0.114 (5)	0.732 (3)	0.489 (3)	0.064*
O1	0.1650 (4)	0.56864 (17)	0.32366 (19)	0.0672 (7)
C6	0.4304 (4)	0.7576 (2)	0.3012 (2)	0.0493 (7)
H6	0.4877	0.6997	0.3287	0.059*
C4	0.4533 (5)	0.9224 (3)	0.2214 (2)	0.0611 (9)
H4	0.5273	0.9753	0.1957	0.073*
C2	0.1514 (4)	0.8530 (2)	0.2593 (2)	0.0488 (7)
H2	0.0209	0.8591	0.2596	0.059*
C3	0.2607 (5)	0.9305 (3)	0.2191 (2)	0.0571 (8)
H3	0.2040	0.9880	0.1905	0.069*
C5	0.5370 (4)	0.8361 (3)	0.2618 (3)	0.0648 (9)
H5	0.6675	0.8308	0.2625	0.078*
O3	0.0223 (3)	−0.11055 (17)	0.49917 (18)	0.0627 (6)
N2	0.2865 (4)	−0.0211 (2)	0.4788 (2)	0.0569 (7)
H2A	0.3463	−0.0769	0.4947	0.068*
C7	0.1024 (5)	−0.0281 (2)	0.47661 (19)	0.0468 (6)
C8	−0.0072 (6)	0.0650 (3)	0.4470 (3)	0.0718 (10)
H8A	−0.0990	0.0805	0.4962	0.086*
H8B	−0.0759	0.0480	0.3893	0.086*
C11	0.4012 (6)	0.0702 (3)	0.4577 (3)	0.0807 (11)
H11A	0.4743	0.0889	0.5135	0.097*
H11B	0.4883	0.0536	0.4066	0.097*
C10	0.2857 (13)	0.1574 (5)	0.4298 (8)	0.220 (6)
H10A	0.3255	0.2153	0.4697	0.264*
H10B	0.3246	0.1749	0.3655	0.264*
C9	0.1069 (11)	0.1609 (4)	0.4291 (6)	0.152 (3)
H9A	0.0694	0.1879	0.3673	0.182*
H9B	0.0692	0.2124	0.4761	0.182*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0358 (3)	0.0397 (3)	0.0682 (5)	−0.0044 (3)	0.0010 (3)	−0.0019 (3)
O2	0.0330 (10)	0.0707 (14)	0.1068 (19)	−0.0073 (10)	−0.0080 (12)	0.0053 (13)
C1	0.0353 (13)	0.0443 (15)	0.0403 (14)	−0.0009 (12)	0.0009 (11)	−0.0022 (12)
N1	0.0528 (15)	0.0441 (13)	0.0639 (16)	−0.0006 (13)	0.0097 (13)	0.0057 (13)
O1	0.0668 (14)	0.0453 (11)	0.0894 (17)	−0.0056 (11)	0.0060 (13)	−0.0154 (11)
C6	0.0383 (15)	0.0501 (15)	0.0595 (18)	0.0040 (13)	0.0017 (13)	0.0067 (14)
C4	0.064 (2)	0.062 (2)	0.057 (2)	−0.0070 (17)	0.0116 (16)	0.0095 (16)
C2	0.0399 (15)	0.0538 (17)	0.0526 (16)	0.0088 (12)	−0.0051 (13)	0.0031 (14)
C3	0.069 (2)	0.0525 (18)	0.0498 (18)	0.0071 (17)	0.0030 (17)	0.0114 (15)
C5	0.0399 (16)	0.079 (2)	0.075 (2)	−0.0058 (17)	0.0091 (15)	0.011 (2)
O3	0.0593 (14)	0.0482 (12)	0.0807 (16)	−0.0039 (11)	0.0135 (12)	0.0037 (11)
N2	0.0517 (16)	0.0493 (15)	0.0697 (18)	0.0006 (12)	−0.0102 (13)	0.0039 (13)
C7	0.0556 (17)	0.0424 (14)	0.0424 (14)	0.0061 (15)	0.0016 (14)	−0.0017 (12)
C8	0.075 (2)	0.060 (2)	0.081 (3)	0.0233 (19)	−0.006 (2)	0.0070 (18)
C11	0.078 (3)	0.077 (2)	0.087 (3)	−0.031 (2)	−0.004 (2)	0.004 (2)
C10	0.148 (7)	0.095 (4)	0.417 (15)	−0.060 (5)	−0.117 (9)	0.137 (7)
C9	0.154 (6)	0.056 (3)	0.245 (8)	0.035 (4)	0.057 (6)	0.060 (4)

Geometric parameters (Å, º) top

S1—O2	1.425 (2)	O3—C7	1.239 (3)
S1—O1	1.432 (2)	N2—C7	1.312 (4)
S1—N1	1.604 (3)	N2—C11	1.454 (4)
S1—C1	1.768 (3)	N2—H2A	0.8600
C1—C2	1.380 (4)	C7—C8	1.483 (4)
C1—C6	1.382 (4)	C8—C9	1.492 (7)
N1—H1A	0.85 (4)	C8—H8A	0.9700
N1—H1B	0.82 (4)	C8—H8B	0.9700
C6—C5	1.373 (5)	C11—C10	1.439 (8)
C6—H6	0.9300	C11—H11A	0.9700
C4—C3	1.373 (5)	C11—H11B	0.9700
C4—C5	1.376 (5)	C10—C9	1.271 (9)
C4—H4	0.9300	C10—H10A	0.9700
C2—C3	1.380 (5)	C10—H10B	0.9700
C2—H2	0.9300	C9—H9A	0.9700
C3—H3	0.9300	C9—H9B	0.9700
C5—H5	0.9300

O2—S1—O1	118.70 (15)	C11—N2—H2A	116.2
O2—S1—N1	106.96 (16)	O3—C7—N2	120.7 (3)
O1—S1—N1	106.72 (16)	O3—C7—C8	120.9 (3)
O2—S1—C1	107.52 (14)	N2—C7—C8	118.4 (3)
O1—S1—C1	108.47 (14)	C7—C8—C9	115.0 (4)
N1—S1—C1	108.07 (13)	C7—C8—H8A	108.5
C2—C1—C6	120.7 (3)	C9—C8—H8A	108.5
C2—C1—S1	120.4 (2)	C7—C8—H8B	108.5
C6—C1—S1	118.7 (2)	C9—C8—H8B	108.5
S1—N1—H1A	113 (3)	H8A—C8—H8B	107.5
S1—N1—H1B	111 (3)	C10—C11—N2	111.0 (4)
H1A—N1—H1B	118 (4)	C10—C11—H11A	109.4
C5—C6—C1	118.8 (3)	N2—C11—H11A	109.4
C5—C6—H6	120.6	C10—C11—H11B	109.4
C1—C6—H6	120.6	N2—C11—H11B	109.4
C3—C4—C5	120.1 (3)	H11A—C11—H11B	108.0
C3—C4—H4	120.0	C9—C10—C11	126.8 (5)
C5—C4—H4	120.0	C9—C10—H10A	105.6
C3—C2—C1	119.6 (3)	C11—C10—H10A	105.6
C3—C2—H2	120.2	C9—C10—H10B	105.6
C1—C2—H2	120.2	C11—C10—H10B	105.6
C4—C3—C2	119.8 (3)	H10A—C10—H10B	106.1
C4—C3—H3	120.1	C10—C9—C8	120.9 (5)
C2—C3—H3	120.1	C10—C9—H9A	107.1
C6—C5—C4	120.9 (3)	C8—C9—H9A	107.1
C6—C5—H5	119.5	C10—C9—H9B	107.1
C4—C5—H5	119.5	C8—C9—H9B	107.1
C7—N2—C11	127.5 (3)	H9A—C9—H9B	106.8
C7—N2—H2A	116.2

Experimental details

	(2ABSACPR)	(BSAAZL)	(4ClBSACPR)	(SNACPR)
Crystal data
Chemical formula	C6H8N2O2S·C6H11NO	C6H7NO2S·C7H13NO	C6H6ClNO2S·C6H11NO	C6H8N2O2S·C6H11NO
M_r	285.36	284.37	304.79	285.36
Crystal system, space group	Monoclinic, P1₂1/n1	Monoclinic, P2₁/n	Orthorhombic, P2₁2₁2₁	Orthorhombic, P2₁2₁2₁
Temperature (K)	298	298	297	298
a, b, c (Å)	7.2731 (4), 15.9052 (10), 12.7766 (6)	7.3020 (9), 17.189 (2), 12.2835 (16)	7.1564 (13), 13.369 (2), 15.276 (3)	7.0957 (6), 13.1280 (13), 15.3425 (18)
α, β, γ (°)	90, 99.291 (5), 90	90, 106.760 (2), 90	90, 90, 90	90, 90, 90
V (Å³)	1458.60 (15)	1476.2 (3)	1461.5 (5)	1429.2 (2)
Z	4	4	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	0.23	0.23	0.41	0.24
Crystal size (mm)	0.22 × 0.21 × 0.20	0.22 × 0.20 × 0.20	0.23 × 0.20 × 0.20	0.22 × 0.20 × 0.20

Data collection
Diffractometer	Xcalibur, Eos, Gemini diffractometer	CCD area detector diffractometer	Xcalibur, Eos, Gemini diffractometer	Xcalibur, Eos, Gemini diffractometer
Absorption correction	Multi-scan SADABS	–	Multi-scan SADABS	Multi-scan SADABS
T_min, T_max	0.874, 1.000	–	0.333, 1.000	0.667, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5525, 2488, 1993	13710, 2520, 2154	4403, 2851, 1152	3692, 2354, 1318
R_int	0.020	0.037	0.082	0.042
(sin θ/λ)_max (Å⁻¹)	0.588	0.588	0.625	0.588

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.100, 1.02	0.060, 0.142, 1.09	0.090, 0.114, 0.97	0.053, 0.080, 0.90
No. of reflections	2488	2520	2851	2354
No. of parameters	179	184	178	179
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	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)	0.15, −0.32	0.26, −0.27	0.25, −0.25	0.18, −0.21
Absolute structure	?	?	Flack H D (1983), Acta Cryst. A39, 876-881	Flack H D (1983), Acta Cryst. A39, 876-881
Absolute structure parameter	?	?	0.11 (15)	0.03 (14)

	(4BrBSACPR)	(OTSAVLM)	(2ClBSACPR)	(BSACPR)
Crystal data
Chemical formula	C6H6BrNO2S·C6H11NO	C7H9NO2S·C5H9NO	C6H6ClNO2S·C6H11NO	C6H7NO2S·C6H11NO
M_r	349.25	270.34	304.79	270.34
Crystal system, space group	Orthorhombic, P2₁2₁2₁	Monoclinic, P2₁/n	Monoclinic, P1₂1/c1	Orthorhombic, P2₁2₁2₁
Temperature (K)	298	298	298	298
a, b, c (Å)	7.156 (3), 13.538 (5), 15.406 (6)	5.3367 (6), 15.9206 (17), 16.070 (3)	9.8782 (6), 14.1720 (6), 10.8753 (6)	7.0700 (9), 12.7624 (13), 14.977 (2)
α, β, γ (°)	90, 90, 90	90, 98.308 (12), 90	90, 112.850 (7), 90	90, 90, 90
V (Å³)	1492.3 (9)	1351.0 (3)	1402.98 (12)	1351.4 (3)
Z	4	4	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	2.90	0.24	0.43	0.24
Crystal size (mm)	0.22 × 0.20 × 0.20	0.22 × 0.20 × 0.20	0.22 × 0.22 × 0.20	0.22 × 0.20 × 0.20

Data collection
Diffractometer	CCD area detector diffractometer	Xcalibur, Eos, Gemini diffractometer	Xcalibur, Eos, Gemini diffractometer	Xcalibur, Eos, Gemini diffractometer
Absorption correction	–	Multi-scan SADABS	Multi-scan SADABS	Multi-scan SADABS
T_min, T_max	–	0.755, 1.000	0.876, 1.000	0.788, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15786, 3029, 2405	5072, 2759, 1420	5810, 2870, 2483	3348, 2197, 1595
R_int	0.057	0.067	0.021	0.039
(sin θ/λ)_max (Å⁻¹)	0.625	0.625	0.625	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.093, 1.02	0.065, 0.118, 1.02	0.039, 0.103, 1.09	0.078, 0.181, 1.23
No. of reflections	3029	2759	2870	2197
No. of parameters	184	170	178	169
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	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)	0.46, −0.23	0.21, −0.24	0.25, −0.48	0.37, −0.24
Absolute structure	Flack H D (1983), Acta Cryst. A39, 876-881	?	?	Flack H D (1983), Acta Cryst. A39, 876-881
Absolute structure parameter	0.018 (11)	?	?	0.0 (2)

	(4ClBSAVLM)	(4BrBSAVLM)	(PTSAVLM)	(2ClBSAVLM)
Crystal data
Chemical formula	C6H6ClNO2S·C5H9NO	C6H6BrNO2S·C5H9NO	C7H9NO2S·C5H9NO	C6H6ClNO2S·C5H9NO
M_r	290.76	335.22	270.34	290.76
Crystal system, space group	Monoclinic, C2/c	Monoclinic, C2/c	Triclinic, P1	Monoclinic, P1₂1/c1
Temperature (K)	297	298	298	298
a, b, c (Å)	25.701 (4), 6.8096 (4), 19.177 (3)	25.914 (3), 6.8687 (9), 19.202 (2)	5.210 (3), 8.449 (4), 16.104 (8)	10.521 (2), 13.7661 (12), 10.3407 (16)
α, β, γ (°)	90, 127.40 (2), 90	90, 126.873 (2), 90	82.894 (8), 82.798 (8), 81.772 (8)	90, 116.31 (2), 90
V (Å³)	2666.3 (6)	2734.1 (6)	692.0 (6)	1342.5 (3)
Z	8	8	2	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	0.45	3.16	0.24	0.44
Crystal size (mm)	0.22 × 0.20 × 0.20	0.22 × 0.20 × 0.20	0.22 × 0.20 × 0.20	0.22 × 0.22 × 0.20

Data collection
Diffractometer	Xcalibur, Eos, Gemini diffractometer	CCD area detector diffractometer	CCD area detector diffractometer	Xcalibur, Eos, Gemini diffractometer
Absorption correction	Multi-scan SADABS	–	–	Multi-scan SADABS
T_min, T_max	0.844, 1.000	–	–	0.707, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5127, 2732, 1677	14029, 2790, 2216	7341, 2819, 1969	5058, 2731, 2039
R_int	0.043	0.030	0.023	0.038
(sin θ/λ)_max (Å⁻¹)	0.625	0.625	0.625	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.134, 1.07	0.035, 0.094, 1.03	0.050, 0.153, 1.04	0.044, 0.114, 0.98
No. of reflections	2732	2790	2819	2731
No. of parameters	169	175	176	169
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	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)	0.27, −0.38	0.56, −0.39	0.43, −0.15	0.38, −0.36
Absolute structure	?	?	?	?
Absolute structure parameter	?	?	?	?

	(BSAVLM)
Crystal data
Chemical formula	C6H7NO2S·C5H9NO
M_r	256.32
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	7.1043 (5), 12.7937 (10), 14.0302 (16)
α, β, γ (°)	90, 90, 90
V (Å³)	1275.2 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.22 × 0.20 × 0.20

Data collection
Diffractometer	Xcalibur, Eos, Gemini diffractometer
Absorption correction	Multi-scan SADABS
T_min, T_max	0.679, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	3791, 2493, 2175
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.120, 1.06
No. of reflections	2493
No. of parameters	160
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.24
Absolute structure	Flack H D (1983), Acta Cryst. A39, 876-881
Absolute structure parameter	−0.01 (12)

Computer programs: SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).

Acknowledgements

GB and SM thank the UGC for a fellowship. We thank the DST-SERB scheme on APIs (SR/S1/OC 37/2011), JC Bose Fellowship (SR/S2/JCB-06/2009) and CSIR project on Pharmaceutical Cocrystals (01-2410/10/EMR-II) for funding. UGC and DST (UPE and PURSE funding) are thanked for providing instrumentation and infrastructure facilities.

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IUCrJ

Volume 2| Part 4| July 2015| Pages 389-401

ISSN: 2052-2525

doi:10.1107/S2052252515004960

CHEMISTRY | CRYSTENG

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

Modularity and three-dimensional isostructurality of novel synthons in sulfonamide–lactam cocrystals

1. Introduction

2. Experimental

2.1. Preparation of cocrystals

2.2. BSA–VLM cocrystal (1:1)

2.3. BSA–CPR cocrystal (1:1)

2.4. BSA–AZL (1-aza-2-cyclooctanone) cocrystal (1:1)

2.5. 2ClBSA–VLM, 4ClBSA–VLM cocrystal (1:1)

2.6. 2ClBSA–CPR, 4ClBSA–CPR cocrystal (1:1)

2.7. 4BrBSA–VLM cocrystal (1:1)

2.8. 4BrBSA–CPR cocrystal (1:1)

2.9. OTSA–VLM, PTSA–VLM cocrystal (1:1)

2.10. SNA–VLM, 2ABSA–VLM cocrystal (1:1)

2.11. Single-crystal X-ray diffraction

2.12. X-ray powder diffraction

2.13. Vibrational spectroscopy

3. Results and discussion

3.1. Crystal structure analysis and isostructurality

3.2. Synthon 1, catemer chain

3.2.1. BSA–VLM, BSA–CPR, SNA–CPR, 4 ClBSA–CPR and 4BrBSA–CPR (1:1)

3.2.2. ClBSA–VLM, 4BrBSA–VLM (1:1)

3.3. Synthon 2, dimer–cyclic ring

3.3.1. BSA–AZL cocrystal (1:1)

3.3.2. ABSA–CPR cocrystal (1:1)

3.4. Synthon 3, dimer–catemer

3.4.1. ClBSA–VLM cocrystal (1:1)

3.4.2. ClBSA–CPR cocrystal (1:1)

3.4.3. OTSA–VLM cocrystal (1:1)

3.4.4. PTSA–VLM cocrystal (1:1)

3.5. Isostructural and isomorphous systems

3.6. Classification of sulfonamide synthons

3.7. Hirshfeld surface analysis

4. Conclusions

Supporting information

Acknowledgements

References

research papers