Supra­molecular inter­actions in a 1:1 co-crystal of acridine and 3-chloro­thio­phene-2-carb­oxy­lic acid

Prajina, O.; Thomas Muthiah, P.; Perdih, F.

doi:10.1107/S2056989016005685

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ISSN: 2056-9890

Volume 72| Part 5| May 2016| Pages 659-662

doi:10.1107/S2056989016005685

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Supramolecular interactions in a 1:1 co-crystal of acridine and 3-chlorothiophene-2-carboxylic acid

Olakkandiyil Prajina,^a Packianathan Thomas Muthiah ^a ^* and Franc Perdih ^b

^aSchool of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, Tamilnadu, India, and ^bFaculty of Chemistry and Chemical Technology, University of Ljubljana, Vecna pot 113, PO Box 537, SI-1000 Ljubljana, Slovenia
^*Correspondence e-mail: tommtrichy@yahoo.co.in

Edited by P. C. Healy, Griffith University, Australia (Received 31 March 2016; accepted 6 April 2016; online 8 April 2016)

In the title co-crystal, C₅H₃ClO₂S·C₁₃H₉N, the components interact with each other via an O—H⋯N hydrogen bond. Acridine–acridine stacking, thiophene–thiophene stacking and acridine–thiophene C—H⋯π interactions also occur in the crystal.

Keywords: crystal structure; 3-chlorothiophene-2-carboxylic acid; acridine.

CCDC reference: 1472507

1. Chemical context

Co-crystals are solids in which two or more molecules crystallize together and interact through non-covalent interactions (Odiase et al., 2015 ). The study of non-covalent interactions in co-crystals not only adds to our knowledge but also has an undeniable relevance in the context of their pharmaceutical and biological interest (Chakraborty et al., 2014 ; Desiraju, 1989 ). The main interactions concerned are various hydrogen bonding, π–π and C—H⋯π interactions (Aakeröy et al., 2010 ). The acridine molecule is a component present in antihelminthic agents which are used in animals (Durchheimer et al., 1980 ). Acridine derivatives also show in vitro activity against protozoa (Ngadi et al., 1993 ). The acridine group is a well known intercalator interacting with nucleobase pairs (Raju et al., 2016 ; Nafisi et al., 2007 ; Sazhnikov et al., 2013 ). Acridine dyes are also widely used (Solovyeva et al., 2014 , Yasarawan et al., 2011 ). Halogenated thiophene carboxylic acid derivatives are the building blocks of many commercially available insecticides (Hull et al., 2007 ). We extended our study on supramolecular architectures in acridine molecules with the investigation of the title co-crystal with 3-chlorothiophene-2-carboxylic acid (3TPC).

2. Structural commentary

The compound (1) is a 1:1 co-crystal of 3TPC and acridine. The internal angle at N1 [C6—N1—C18 = 119.30 (15)°] and bond lengths [C18—N1 = 1.346 (2) and C6—N1 = 1.354 (2) Å] agree with those reported for neutral acridine structures (Aghabozorg et al., 2011 ; Binder et al., 1982 ; Goeta et al., 2002 ). The two external bond angles at the carbon atom of the carboxyl group are 124.13 (17) and 110.75 (15)°. The high discrepancy between these two angles is typical of an unionized carboxyl group. The C=O distance of 1.316 (2) Å and C—OH distance of 1.199 (2) Å are also typical of the carboxyl group. These values also agree with the carboxylic acids reported in the literature (Kowalska et al., 2015 ; Sienkiewicz-Gromiuk et al., 2016 ). The dihedral angle between the carboxylic acid group and the thiophene ring is 9.01 (13)°. The bond distances and angles involving the thiophene ring agree with those in structures reported earlier (Zhang et al., 2014 ).

3. Supramolecular features

The 3TPC and acridine moieties are linked by an O—H⋯N hydrogen-bonding interaction between (O1—H1) of the carboxyl group and the acridine nitrogen atom (N1) (Table 1 and Fig. 1). This O—H⋯N hydrogen bond is reminiscent of the frequently used supramolecular synthon in crystal engineering involving a carboxylic acid and a pyridine molecule (Seaton, 2014 ; Lemmerer & Bernstein, 2010 ; Thomas et al., 2010 ). A similar type of supramolecular synthon is observed in a series of nine co-crystals involving acridine and benzoic acids (Kowalska et al., 2015). This supramolecular synthon is also present in the co-crystal of 5-chlorothiophene-2-carboxylic acid and acridine reported from our laboratory (Jennifer & Muthiah, 2014 ). This co-crystal and the title co-crystal differ only in the position of chlorine in the thiophene ring. The hydrogen-bonded units are linked via π–π stacking interactions between the aromatic systems of acridine molecules [Cg1⋯Cg1ⁱ = 3.6419 (9), Cg1⋯Cg1ⁱⁱ = 3.7526 (9), Cg1⋯Cg2ⁱⁱ = 3.7293 (12), Cg2⋯Cg3ⁱ = 3.6748 (12) and Cg2⋯Cg3ⁱⁱ = 3.7298 (12) Å where Cg1 is the centroid of the N1/C6/C11/C12/C13/C18 ring, Cg2 is the centroid of the C6–C11 ring and Cg3 is the centroid of the C13–C18 ring; symmetry codes: (i) −x, 2 − y,1 − z; (ii) 1 − x, 2 − y,1 − z] and between the thiophene rings [Cg7⋯Cg7ⁱⁱⁱ = 3.7611 (12) Å where Cg7 is the centroid of the thiophene ring; symmetry code: (iii) 1 − x, 1 − y, −z]. The crystal structure also features C—H⋯π interactions, forming a three-dimensional supramolecular architecture (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

Cg7 is the centroid of the thiophene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.83	2.615 (2)	159
C9—H9⋯Cg7ⁱ	0.93	2.94	3.773 (2)	150
Symmetry code: (i) -x+1, -y+1, -z+1.

Figure 1
The asymmetric unit of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The dashed line represents the O—H⋯N hydrogen bond.

Figure 2
A view of the O—H⋯N hydrogen bonds (purple dashed lines), π–π stacking (acridine–acridine and thiophene–thiophene; red dashed lines) and C—H⋯π interactions between the acridine C—H group and the π-system of thiophene (green dashed lines).

4. Database survey

The crystal structures of a number of acridine co-crystals, acridinium salts and their metal complexes have been investigated in a variety of crystalline environments such as diphenic acid–acridine (1:1) (Shaameri et al., 2001a ), 4,4′-bis(hydroxyazobenzene)–acridine (Chakraborty et al., 2014), orcinol–acridine (1:2) and orcinol–acridine (1:1) co-crystal hydrate (Mukherjee et al., 2011 ), acridinium isophthalate (Shaameri et al., 2001b ) and acridinium 6-carboxypyridine-2- carboxylate monohydrate (Derikvand et al., 2011 ). A variety of metal complexes of acridine have also been reported (Ha, 2010 , 2012 ; Sloufova & Slouf, 2000 , 2001 ).

5. Synthesis and crystallization

To 10 ml of a hot methanol solution of 3TPC (40.6 mg, 25 mmol) were added 10 ml of a hot methanolic solution of acridine (44.8 mg, 25 mmol). The resulting solution was warmed over a water bath for half an hour and then kept at room temperature for crystallization. After a week yellow plate-like crystals of (1) were obtained.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were readily located in difference Fourier maps and were subsequently treated as riding atoms in geometrically idealized positions, with C—H = 0.93 and O—H = 0.82 Å, and with U_iso(H) = kU_eq(C, O), where k = 1.5 for hydroxy and 1.2 for all other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₅H₃ClO₂S·C₁₃H₉N
M_r	341.80
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	7.3371 (4), 8.3286 (5), 13.3819 (8)
α, β, γ (°)	107.577 (5), 97.706 (5), 93.953 (5)
V (Å³)	767.32 (8)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.39
Crystal size (mm)	0.60 × 0.30 × 0.10

Data collection
Diffractometer	Agilent SuperNova Dual Source diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013 )
T_min, T_max	0.813, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7182, 3516, 2722
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.109, 1.02
No. of reflections	3516
No. of parameters	209
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.23
Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2008 ), PLATON (Spek, 2009) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1472507

Crystal structure: contains datablock I. DOI: 10.1107/S2056989016005685/hg5473sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989016005685/hg5473Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989016005685/hg5473Isup3.cml

checkCIF report

Chemical context top

Co-crystals are solids in which two or more molecules crystallize in one crystal lattice through non-covalent interactions (Odiase et al., 2015). The study of non-covalent interactions in co-crystals not only adds to our knowledge but also has an undeniable relevance in the context of their pharmaceutical and biological interest (Chakraborty et al., 2014; Desiraju, 1989). The main interactions concerned are various hydrogen bonding, π–π and C—H···π interactions (Aakeröy et al., 2010). The acridine molecule is a component present in antihelminthic agents which are used in animals (Durchheimer et al., 1980). Acridine derivatives also show in vitro activity against protozoa (Ngadi et al., 1993). The acridine group is a well known intercalator interacting with nucleobase pairs (Raju et al., 2016; Nafisi et al., 2007; Sazhnikov et al., 2013). Acridine dyes are also widely used (Solovyeva et al., 2014, Yasarawan et al., 2011). Halogenated thiophene carboxylic acid derivatives are the building blocks of many commercially available insecticides (Hull et al., 2007). We extended our study on supramolecular architectures in acridine molecules with the investigation of the title co-crystal with 3-chlorothiophene-2-carboxylic acid.

Structural commentary top

The compound (1) is a 1:1 co-crystal of 3TPC and acridine. The internal angle at N1 [C6—N1—C18 = 119.30 (15)°] and bond lengths [C18—N1 = 1.346 (2) and C6—N1 = 1.354 (2) Å] agree with those reported for neutral acridine structures (Aghabozorg et al., 2011; Binder et al., 1982; Goeta et al., 2002). The two external bond angles at the carbon atom of the carboxyl group are 124.13 (17) and 110.75 (15)°. The high discrepancy between these two angles is typical of an unionized carboxyl group. The C═O distance of 1.316 (2) Å and C—OH distance of 1.199 (2) Å are also typical of the carboxyl group. These values also agree with the carboxylic acids reported in the literature (Kowalska et al., 2015; Sienkiewicz-Gromiuk et al., 2016). The bond distances and angles involving the thiophene ring agree with those in structures reported earlier (Zhang et al., 2014).

Supramolecular features top

3TPC and acridine are interconnected via O—H···N hydrogen-bonding interactions between (O1—H1) of the carboxyl group and the acridine nitrogen atom (N1) (Table 1 and Fig. 1). This O—H···N hydrogen bond is reminiscent of the frequently used supramolecular synthon in crystal engineering involving a carboxylic acid and a pyridine (Seaton, 2014; Lemmerer & Bernstein, 2010; Thomas et al., 2010). A similar type of supramolecular synthon is observed in a series of nine co-crystals involving acridine and benzoic acids (Kowalska et al., 2015). This supramolecular synthon is also present in the co-crystal 5TPCACR (1:1) reported from our laboratory (Jennifer & Muthiah, 2014). This co-crystal and the title co-crystal differ only in the position of chlorine in the thiophene ring. The hydrogen-bonded units are stabilized via π–π stacking interactions between the aromatic systems of acridine molecules [Cg1···Cg1ⁱ = 3.6419 (9), Cg1···Cg1ⁱⁱ = 3.7526 (9), Cg1···Cg2ⁱⁱ = 3.7293 (12), Cg2···Cg3ⁱ = 3.6748 (12) and Cg2···Cg3ⁱⁱ = 3.7298 (12) Å where Cg1 is the centroid of the N1/C6/C11/C12/C13/C18 ring, Cg2 is the centroid of the C6–C11 ring and Cg3 is the centroid of the C13–C18 ring; symmetry codes: (i) -x ,2 - y,1 - z; (ii) 1 - x, 2 - y,1 - z] and between the thiophene rings [Cg7···Cg7ⁱⁱⁱ = 3.7611 (12) Å where Cg7 is the centroid of the thiophene ring; symmetry code: (iii) 1 - x, 1 - y, -z]. The crystal structure is further stabilized by C—H···π interactions, forming a supramolecular architecture (Fig. 2).

Database survey top

The crystal structures of a number of acridine co-crystals, acridinium salts and their metal complexes have been investigated in a variety of crystalline environments: Diphenic acid–acridine (1:1) (Shaameri et al., 2001a), 4,4′-bis(hydroxyazobenzene)–acridine (Chakraborty et al., 2014), orcinol–acridine (1:2) and orcinol–acridine (1:1) co-crystal hydrate (Mukherjee et al., 2011), acridinium isophthalate (Shaameri et al., 2001b) and acridinium 6-carboxypyridine-2- carboxylate monohydrate (Derikvand et al., 2011). A variety of metal complexes of acridine have also been reported (Ha, 2010, 2012; Sloufova & Slouf, 2000, 2001).

Synthesis and crystallization top

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were readily located in difference Fourier maps and were subsequently treated as riding atoms in geometrically idealized positions, with C—H = 0.93 and O—H = 0.82 Å , and with U_iso(H) = kU_eq(C, O), where k = 1.5 for hydroxy and 1.2 for all other H atoms.

Structure description top

The compound (1) is a 1:1 co-crystal of 3TPC and acridine. The internal angle at N1 [C6—N1—C18 = 119.30 (15)°] and bond lengths [C18—N1 = 1.346 (2) and C6—N1 = 1.354 (2) Å] agree with those reported for neutral acridine structures (Aghabozorg et al., 2011; Binder et al., 1982; Goeta et al., 2002). The two external bond angles at the carbon atom of the carboxyl group are 124.13 (17) and 110.75 (15)°. The high discrepancy between these two angles is typical of an unionized carboxyl group. The C═O distance of 1.316 (2) Å and C—OH distance of 1.199 (2) Å are also typical of the carboxyl group. These values also agree with the carboxylic acids reported in the literature (Kowalska et al., 2015; Sienkiewicz-Gromiuk et al., 2016). The bond distances and angles involving the thiophene ring agree with those in structures reported earlier (Zhang et al., 2014).

Synthesis and crystallization top

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were readily located in difference Fourier maps and were subsequently treated as riding atoms in geometrically idealized positions, with C—H = 0.93 and O—H = 0.82 Å , and with U_iso(H) = kU_eq(C, O), where k = 1.5 for hydroxy and 1.2 for all other H atoms.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The asymmetric unit of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The dashed line represents the O—H···N hydrogen bond.
	Fig. 2. A view of the O—H···N hydrogen bonds (purple dashed lines), π–π stacking (acridine–acridine and thiophene–thiophene; red dashed lines) and C—H···π interactions between the acridine C—H group and the π-system of thiophene (green dashed lines).

Acridine–3-chlorothiophene-2-carboxylic acid (1/1) top

Crystal data top

C₅H₃ClO₂S·C₁₃H₉N	Z = 2
M_r = 341.80	F(000) = 352
Triclinic, P1	D_x = 1.479 Mg m⁻³
a = 7.3371 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.3286 (5) Å	Cell parameters from 2635 reflections
c = 13.3819 (8) Å	θ = 3.9–29.2°
α = 107.577 (5)°	µ = 0.39 mm⁻¹
β = 97.706 (5)°	T = 293 K
γ = 93.953 (5)°	Plate, yellow
V = 767.32 (8) Å³	0.60 × 0.30 × 0.10 mm

Data collection top

Agilent SuperNova Dual Source diffractometer with an Atlas detector	3516 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2722 reflections with I > 2σ(I)
Detector resolution: 10.4933 pixels mm^-1	R_int = 0.022
ω scans	θ_max = 27.5°, θ_min = 2.8°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	h = −9→8
T_min = 0.813, T_max = 1.000	k = −10→10
7182 measured reflections	l = −17→17

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.109	w = 1/[σ²(F_o²) + (0.0488P)² + 0.133P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
3516 reflections	Δρ_max = 0.21 e Å⁻³
209 parameters	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₅H₃ClO₂S·C₁₃H₉N	γ = 93.953 (5)°
M_r = 341.80	V = 767.32 (8) Å³
Triclinic, P1	Z = 2
a = 7.3371 (4) Å	Mo Kα radiation
b = 8.3286 (5) Å	µ = 0.39 mm⁻¹
c = 13.3819 (8) Å	T = 293 K
α = 107.577 (5)°	0.60 × 0.30 × 0.10 mm
β = 97.706 (5)°

Data collection top

Agilent SuperNova Dual Source diffractometer with an Atlas detector	3516 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	2722 reflections with I > 2σ(I)
T_min = 0.813, T_max = 1.000	R_int = 0.022
7182 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.02	Δρ_max = 0.21 e Å⁻³
3516 reflections	Δρ_min = −0.23 e Å⁻³
209 parameters

Special details top

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

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

	x	y	z	U_iso*/U_eq
Cl1	0.21228 (7)	0.16757 (7)	−0.02749 (4)	0.05748 (17)
S1	0.69521 (6)	0.48402 (6)	0.14957 (4)	0.04516 (15)
O1	0.42177 (19)	0.63242 (19)	0.26579 (11)	0.0581 (4)
H1	0.3486	0.6911	0.2968	0.087*
O2	0.16569 (18)	0.49072 (19)	0.15614 (11)	0.0569 (4)
N1	0.26273 (19)	0.85354 (18)	0.39993 (11)	0.0390 (3)
C1	0.3309 (2)	0.5158 (2)	0.18026 (14)	0.0392 (4)
C2	0.4606 (2)	0.4179 (2)	0.11735 (13)	0.0366 (4)
C3	0.4277 (2)	0.2754 (2)	0.03048 (14)	0.0403 (4)
C4	0.5886 (3)	0.2201 (3)	−0.00919 (16)	0.0499 (5)
H4	0.5890	0.1248	−0.0675	0.060*
C5	0.7426 (3)	0.3226 (3)	0.04802 (16)	0.0512 (5)
H5	0.8614	0.3061	0.0331	0.061*
C6	0.2995 (2)	0.8560 (2)	0.50232 (14)	0.0367 (4)
C7	0.3599 (2)	0.7110 (2)	0.52526 (16)	0.0451 (4)
H7	0.3756	0.6162	0.4701	0.054*
C8	0.3948 (3)	0.7096 (3)	0.62689 (17)	0.0508 (5)
H8	0.4331	0.6131	0.6407	0.061*
C9	0.3742 (3)	0.8518 (3)	0.71176 (16)	0.0505 (5)
H9	0.3994	0.8485	0.7811	0.061*
C10	0.3179 (3)	0.9933 (3)	0.69378 (15)	0.0470 (5)
H10	0.3050	1.0864	0.7508	0.056*
C11	0.2784 (2)	1.0008 (2)	0.58805 (14)	0.0374 (4)
C12	0.2206 (2)	1.1415 (2)	0.56483 (14)	0.0406 (4)
H12	0.2070	1.2375	0.6197	0.049*
C13	0.1826 (2)	1.1413 (2)	0.45997 (15)	0.0397 (4)
C14	0.1250 (3)	1.2834 (3)	0.43165 (18)	0.0521 (5)
H14	0.1088	1.3814	0.4843	0.063*
C15	0.0936 (3)	1.2765 (3)	0.3283 (2)	0.0606 (6)
H15	0.0577	1.3706	0.3104	0.073*
C16	0.1148 (3)	1.1285 (3)	0.24777 (19)	0.0631 (6)
H16	0.0921	1.1263	0.1773	0.076*
C17	0.1677 (3)	0.9888 (3)	0.27050 (16)	0.0528 (5)
H17	0.1788	0.8915	0.2159	0.063*
C18	0.2061 (2)	0.9916 (2)	0.37835 (14)	0.0398 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0514 (3)	0.0565 (3)	0.0477 (3)	−0.0036 (2)	0.0025 (2)	−0.0040 (2)
S1	0.0407 (3)	0.0458 (3)	0.0437 (3)	0.00472 (19)	0.00429 (19)	0.0075 (2)
O1	0.0474 (8)	0.0552 (9)	0.0509 (8)	0.0084 (7)	0.0069 (6)	−0.0141 (7)
O2	0.0397 (8)	0.0638 (10)	0.0539 (9)	0.0063 (6)	0.0081 (6)	−0.0012 (7)
N1	0.0361 (8)	0.0383 (8)	0.0363 (8)	0.0043 (6)	0.0094 (6)	0.0008 (7)
C1	0.0435 (10)	0.0365 (10)	0.0355 (9)	0.0045 (7)	0.0057 (7)	0.0085 (8)
C2	0.0401 (9)	0.0374 (10)	0.0318 (9)	0.0077 (7)	0.0050 (7)	0.0096 (8)
C3	0.0442 (10)	0.0398 (10)	0.0339 (9)	0.0052 (7)	0.0035 (7)	0.0082 (8)
C4	0.0549 (12)	0.0478 (12)	0.0415 (10)	0.0136 (9)	0.0119 (9)	0.0027 (9)
C5	0.0465 (11)	0.0576 (13)	0.0505 (12)	0.0165 (9)	0.0154 (9)	0.0132 (10)
C6	0.0282 (8)	0.0371 (10)	0.0405 (10)	0.0006 (6)	0.0098 (7)	0.0049 (8)
C7	0.0423 (10)	0.0379 (10)	0.0516 (11)	0.0065 (8)	0.0148 (8)	0.0057 (9)
C8	0.0464 (11)	0.0514 (12)	0.0594 (13)	0.0073 (9)	0.0118 (9)	0.0227 (11)
C9	0.0502 (11)	0.0574 (13)	0.0436 (11)	−0.0018 (9)	0.0069 (8)	0.0175 (10)
C10	0.0491 (11)	0.0457 (11)	0.0376 (10)	−0.0037 (8)	0.0092 (8)	0.0015 (9)
C11	0.0303 (8)	0.0360 (9)	0.0386 (9)	−0.0029 (7)	0.0078 (7)	0.0016 (8)
C12	0.0339 (9)	0.0341 (10)	0.0432 (10)	−0.0011 (7)	0.0092 (7)	−0.0038 (8)
C13	0.0273 (8)	0.0377 (10)	0.0497 (11)	−0.0001 (7)	0.0074 (7)	0.0074 (8)
C14	0.0380 (10)	0.0440 (12)	0.0718 (14)	0.0030 (8)	0.0063 (9)	0.0158 (11)
C15	0.0440 (11)	0.0639 (15)	0.0809 (17)	0.0051 (10)	0.0024 (11)	0.0366 (14)
C16	0.0498 (12)	0.0863 (18)	0.0580 (14)	0.0021 (11)	0.0013 (10)	0.0343 (14)
C17	0.0444 (11)	0.0654 (14)	0.0438 (11)	0.0043 (9)	0.0050 (8)	0.0116 (10)
C18	0.0278 (8)	0.0465 (11)	0.0405 (10)	0.0012 (7)	0.0059 (7)	0.0075 (8)

Geometric parameters (Å, º) top

Cl1—C3	1.7207 (18)	C8—H8	0.9300
S1—C5	1.692 (2)	C9—C10	1.352 (3)
S1—C2	1.7261 (17)	C9—H9	0.9300
O1—C1	1.316 (2)	C10—C11	1.427 (3)
O1—H1	0.8200	C10—H10	0.9300
O2—C1	1.199 (2)	C11—C12	1.379 (2)
N1—C18	1.346 (2)	C12—C13	1.393 (2)
N1—C6	1.354 (2)	C12—H12	0.9300
C1—C2	1.478 (3)	C13—C14	1.421 (3)
C2—C3	1.368 (3)	C13—C18	1.426 (3)
C3—C4	1.408 (3)	C14—C15	1.355 (3)
C4—C5	1.353 (3)	C14—H14	0.9300
C4—H4	0.9300	C15—C16	1.404 (3)
C5—H5	0.9300	C15—H15	0.9300
C6—C7	1.418 (2)	C16—C17	1.357 (3)
C6—C11	1.426 (2)	C16—H16	0.9300
C7—C8	1.354 (3)	C17—C18	1.426 (3)
C7—H7	0.9300	C17—H17	0.9300
C8—C9	1.405 (3)

C5—S1—C2	92.22 (9)	C8—C9—H9	119.6
C1—O1—H1	109.5	C9—C10—C11	120.52 (19)
C18—N1—C6	119.31 (15)	C9—C10—H10	119.7
O2—C1—O1	125.12 (18)	C11—C10—H10	119.7
O2—C1—C2	124.13 (17)	C12—C11—C6	118.43 (16)
O1—C1—C2	110.75 (15)	C12—C11—C10	123.13 (17)
C3—C2—C1	130.54 (16)	C6—C11—C10	118.44 (17)
C3—C2—S1	109.54 (14)	C11—C12—C13	120.66 (17)
C1—C2—S1	119.91 (13)	C11—C12—H12	119.7
C2—C3—C4	113.99 (17)	C13—C12—H12	119.7
C2—C3—Cl1	124.70 (15)	C12—C13—C14	122.99 (18)
C4—C3—Cl1	121.31 (15)	C12—C13—C18	117.77 (16)
C5—C4—C3	111.64 (19)	C14—C13—C18	119.23 (17)
C5—C4—H4	124.2	C15—C14—C13	120.2 (2)
C3—C4—H4	124.2	C15—C14—H14	119.9
C4—C5—S1	112.61 (15)	C13—C14—H14	119.9
C4—C5—H5	123.7	C14—C15—C16	120.6 (2)
S1—C5—H5	123.7	C14—C15—H15	119.7
N1—C6—C7	119.41 (16)	C16—C15—H15	119.7
N1—C6—C11	121.65 (16)	C17—C16—C15	121.5 (2)
C7—C6—C11	118.94 (16)	C17—C16—H16	119.2
C8—C7—C6	120.47 (19)	C15—C16—H16	119.2
C8—C7—H7	119.8	C16—C17—C18	119.8 (2)
C6—C7—H7	119.8	C16—C17—H17	120.1
C7—C8—C9	120.91 (19)	C18—C17—H17	120.1
C7—C8—H8	119.5	N1—C18—C17	119.21 (18)
C9—C8—H8	119.5	N1—C18—C13	122.18 (16)
C10—C9—C8	120.73 (18)	C17—C18—C13	118.61 (17)
C10—C9—H9	119.6

O2—C1—C2—C3	−7.7 (3)	C7—C6—C11—C12	179.62 (14)
O1—C1—C2—C3	171.99 (17)	N1—C6—C11—C10	179.36 (15)
O2—C1—C2—S1	170.91 (14)	C7—C6—C11—C10	−0.4 (2)
O1—C1—C2—S1	−9.4 (2)	C9—C10—C11—C12	179.99 (16)
C5—S1—C2—C3	0.03 (13)	C9—C10—C11—C6	0.0 (3)
C5—S1—C2—C1	−178.87 (14)	C6—C11—C12—C13	0.5 (2)
C1—C2—C3—C4	178.94 (16)	C10—C11—C12—C13	−179.48 (15)
S1—C2—C3—C4	0.2 (2)	C11—C12—C13—C14	−179.16 (15)
C1—C2—C3—Cl1	−1.6 (3)	C11—C12—C13—C18	−0.2 (2)
S1—C2—C3—Cl1	179.68 (10)	C12—C13—C14—C15	178.67 (17)
C2—C3—C4—C5	−0.4 (2)	C18—C13—C14—C15	−0.2 (3)
Cl1—C3—C4—C5	−179.89 (13)	C13—C14—C15—C16	0.9 (3)
C3—C4—C5—S1	0.4 (2)	C14—C15—C16—C17	−0.3 (3)
C2—S1—C5—C4	−0.25 (16)	C15—C16—C17—C18	−1.1 (3)
C18—N1—C6—C7	−179.75 (14)	C6—N1—C18—C17	179.93 (15)
C18—N1—C6—C11	0.5 (2)	C6—N1—C18—C13	−0.2 (2)
N1—C6—C7—C8	−179.02 (16)	C16—C17—C18—N1	−178.39 (17)
C11—C6—C7—C8	0.7 (2)	C16—C17—C18—C13	1.8 (3)
C6—C7—C8—C9	−0.7 (3)	C12—C13—C18—N1	0.1 (2)
C7—C8—C9—C10	0.3 (3)	C14—C13—C18—N1	179.06 (14)
C8—C9—C10—C11	0.0 (3)	C12—C13—C18—C17	179.95 (15)
N1—C6—C11—C12	−0.6 (2)	C14—C13—C18—C17	−1.1 (2)

Hydrogen-bond geometry (Å, º) top

Cg7 is the centroid of the thiophene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.83	2.615 (2)	159
C9—H9···Cg7ⁱ	0.93	2.94	3.773 (2)	150

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg7 is the centroid of the thiophene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.83	2.615 (2)	159.2
C9—H9···Cg7ⁱ	0.93	2.94	3.773 (2)	150

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₅H₃ClO₂S·C₁₃H₉N
M_r	341.80
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.3371 (4), 8.3286 (5), 13.3819 (8)
α, β, γ (°)	107.577 (5), 97.706 (5), 93.953 (5)
V (Å³)	767.32 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.60 × 0.30 × 0.10

Data collection
Diffractometer	Agilent SuperNova Dual Source diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013)
T_min, T_max	0.813, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7182, 3516, 2722
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.109, 1.02
No. of reflections	3516
No. of parameters	209
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.23

Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Acknowledgements

OKP thanks the UGC–SAP and UGC–BSR India for the award of an RFSMS. PTM is thankful to the UGC, New Delhi, for a UGC–BSR one-time grant to Faculty. FP thanks the Slovenian Research Agency for financial support (P1–0230-0175), as well as the EN–FIST Centre of Excellence, Slovenia, for use of the SuperNova diffractometer

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Volume 72| Part 5| May 2016| Pages 659-662

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

Supra­molecular inter­actions in a 1:1 co-crystal of acridine and 3-chloro­thio­phene-2-carb­­oxy­lic acid

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Supramolecular interactions in a 1:1 co-crystal of acridine and 3-chlorothiophene-2-carboxylic acid

3. Supramolecular features