4,4′-Bipyridine–3-(thio­phen-3-yl)acrylic acid (1/2)

Rajakannu, P.; Hussain, F.; Sathiyendiran, M.

doi:10.1107/S1600536811035823

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2595

https://doi.org/10.1107/S1600536811035823

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4,4′-Bipyridine–3-(thiophen-3-yl)acrylic acid (1/2)

Palanisamy Rajakannu,^a Firasat Hussain ^a ^* and Malaichamy Sathiyendiran ^a ^*

^aDepartment of Chemistry, University of Delhi, North Campus, Delhi, India
^*Correspondence e-mail: fhussain@chemistry.du.ac.in, msathi@chemistry.du.ac.in

(Received 22 July 2011; accepted 2 September 2011; online 14 September 2011)

In the title 1/2 adduct, C₁₀H₈N₂·2C₇H₆O₂S, the dihedral angle between the pyridine rings is 18.41 (11)°. In the thiopheneacrylic acid molecules, the dihedral angles between the respective thiophene and acrylic acid units are 5.52 (17)° and 23.92 (9)°. In the crystal, the components are linked via O—H⋯N hydrogen-bonding interactions, forming units of two 3-thiopheneacrylic acid molecules and one 4,4′-bipyridine molecule.

Related literature

For the synthesis and in vitro antibacterial activity of oxazolidines, see: Srivastava et al. (2008 ). For crystal engineering co-crystal and polymorph architectures, see: Friščić & MacGillivray (2009 ); Eccles et al. (2010 ). For the supramolecular construction of molecular ladders, see: Gao et al. (2004 ); MacGillivray et al. (2008 ); Friščić & MacGillivray (2005 ). For C—H⋯O hydrogen bonds in supramolecular design, see: Desiraju (1996 ) and for C—H⋯π interactions in crystal engineering, see: Desiraju (2002 ).

Experimental

Crystal data

C₁₀H₈N₂·2C₇H₆O₂S
M_r = 464.54
Triclinic, $[P \overline 1]$
a = 7.3454 (5) Å
b = 10.7319 (8) Å
c = 15.0196 (11) Å
α = 102.518 (6)°
β = 103.648 (6)°
γ = 94.892 (6)°
V = 1111.54 (14) Å³
Z = 2
Cu Kα radiation
μ = 2.46 mm⁻¹
T = 293 K
0.37 × 0.15 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.692, T_max = 1.000
9038 measured reflections
4344 independent reflections
3498 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.132
S = 1.05
4344 reflections
291 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N1ⁱ	0.82	1.86	2.668 (2)	168
O4—H4A⋯N2ⁱⁱ	0.82	1.87	2.684 (2)	174
Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z.

Data collection: CrysAlis PRO (Oxford Diffraction 2009) $[Oxford Diffraction (2009). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ; cell refinement: CrysAlis RED (Oxford Diffraction, 2009) $[Oxford Diffraction (2009). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ; data reduction: CrysAlis RED $[Oxford Diffraction (2009). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: publCIF (Westrip, 2010 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811035823/si2368sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811035823/si2368Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811035823/si2368Isup3.cml

checkCIF report

Comment top

Supramolecular synthons that are based upon hydrogen bonds represent a prototypal tool for crystal engineering (Desiraju, 1996; 2002). Supramolecular heterosynthons formed from pyridine/amide and carboxylic acids have previously been exploited for liquid crystalline materials, two-dimensional beta networks, two-dimensional corrugated sheets and ternary supramolecules (MacGillivray et al., 2008; Gao et al., 2004; Friščić & MacGillivray, 2005; 2009). Recently, pharmaceutical molecules such as aspirin, rac-ibuprofen, and rac-flurbiprofen form heterosynthons with ditopic pyridine donors. Herein, we report co-crystal 1 synthesized and characterized by FT—IR, UV-Vis, ¹H-NMR spectroscopy, EA, DSC, and TGA.

The co-crystal 1 of the 2:1 adduct of 3-thiopheneacrylic acid with 4,4'-bipyridine was obtained by layering methanolic solution of 4,4'-bipyridyl to the methanolic solution of 3-thiopheneacrylic acid at room temperature. Each 3-thiopheneacrylic acid molecule forms a moderate intermolecular O—H···N bond with pyridine (Table 1). The 4,4'-bipyridine molecule in the adduct is non-planar with the two pyridine rings forming a dihedral angle of 18.41 (11)°. The two thiophene and the bipyridine are not coplanar and the dihedral angles between the S1 thiophene/N1 pyridine and S2 thiophene/ N2 pyridine are 30.14 (11)° and 47.64 (7)°, respectively. The heterosynthon extends to one-dimensional latterane like sheets held together by moderate π-π stacking interactions (Fig. 2). The Cg1–Cg2ⁱⁱ distance (between the N1,C8-C12 and N2,C13-C17 4,4'-bipyridine moieties) and the dihedral angle between pyridine planes α are 4.1411 (13)Å and 18.4 (1)°, respectively. [Symmetry code ii: (-1+x,y,z).

Related literature top

For the synthesis and in vitro antibacterial activity of oxazolidines, see: Srivastava et al. (2008). For the crystal engineering co-crystal and polymorph architectures, see: Friščić & MacGillivray (2009); Eccles et al. (2010). For the supramolecular construction of molecular ladders, see: Gao et al. (2004); MacGillivray et al. (2008); Friščić & MacGillivray (2005). For C—H···O hydrogen bonds in supramolecular design, see: Desiraju (1996) and for C—H···π interactions in crystal engineering, see: Desiraju (2002).

Experimental top

All starting materials and products were found to be stable towards moisture and air. Starting materials such as 4,4'-bipyridyl (bpy) and 3-thiopheneacrylic acid (taa) were procured from commercial sources and used as received. Commercial grade solvents e.g. methanol was used as received further purification. The mixture of 1:2 ratio of 4,4'-bipyridyl (100.1 mg, 0.6409 mmol) and 3-thiopheneacrylic acid (197.8 mg, 1.2828 mmol) in methanol was stirred for 3 h at room temperature. The clear solution was obtained by filtration and that solution was kept at room temperature for several days. The white colored crystals were obtained. Yield: 83% (248.3 mg, 0.5344 mmol). Anal. Calcd for C₂₄H₂₀N₂O₄S₂: C, 62.05; H, 4.34; N, 6.03; S, 13.8. Found: C, 60.93; H, 4.13; N, 5.87; S, 12.93. ¹H NMR (CDCl₃,): 8.72 (dd, J = 4.7 Hz, 4H, H^α, bpy), 7.71 (d, J = 1.54 Hz, 2H, H⁴, taa), 7.53 (dd, J = 4.7 Hz, 4H, H^β, bpy), 7.47 (dd, J = 1.32 Hz, 2H, H¹, taa), 7.29 (m, 4H, H^2,3, taa), 6.20 (d, J = 15.44 Hz, 2H, H⁵, taa).

Structure description top

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010) and PLATON (Spek, 2009).

Figures top

	Fig. 1. ORTEP view of the molecule with thermal ellipsoids drawn at 50% probability level Color code: White: C; red: O; blue: N; grey: H; yellow:S;
	Fig. 2. One-dimensional latterane like sheet formed though π-π stacking interactions between the two neighboring heterosynthons.
	Fig. 3. Synthesis of co-crystal of 4,4'-bipyridine and di(3-thiopheneacrylic acid)

4,4'-bipyridine–3-(thiophen-3-yl)acrylic acid (1/2) top

Crystal data top

C₁₀H₈N₂·2C₇H₆O₂S	Z = 2
M_r = 464.54	F(000) = 484
Triclinic, P1	D_x = 1.388 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.3454 (5) Å	Cell parameters from 3251 reflections
b = 10.7319 (8) Å	θ = 3.1–72.9°
c = 15.0196 (11) Å	µ = 2.46 mm⁻¹
α = 102.518 (6)°	T = 293 K
β = 103.648 (6)°	Plate, white
γ = 94.892 (6)°	0.37 × 0.15 × 0.10 mm
V = 1111.54 (14) Å³

Data collection top

Xcalibur, Sapphire3 diffractometer	4344 independent reflections
Radiation source: fine-focus sealed tube	3498 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 15.9853 pixels mm^-1	θ_max = 72.1°, θ_min = 3.1°
ω scans	h = −8→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −13→12
T_min = 0.692, T_max = 1.000	l = −18→13
9038 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.132	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0658P)² + 0.2003P] where P = (F_o² + 2F_c²)/3
4344 reflections	(Δ/σ)_max < 0.001
291 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₀H₈N₂·2C₇H₆O₂S	γ = 94.892 (6)°
M_r = 464.54	V = 1111.54 (14) Å³
Triclinic, P1	Z = 2
a = 7.3454 (5) Å	Cu Kα radiation
b = 10.7319 (8) Å	µ = 2.46 mm⁻¹
c = 15.0196 (11) Å	T = 293 K
α = 102.518 (6)°	0.37 × 0.15 × 0.10 mm
β = 103.648 (6)°

Data collection top

Xcalibur, Sapphire3 diffractometer	4344 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	3498 reflections with I > 2σ(I)
T_min = 0.692, T_max = 1.000	R_int = 0.027
9038 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.132	H-atom parameters constrained
S = 1.05	Δρ_max = 0.24 e Å⁻³
4344 reflections	Δρ_min = −0.32 e Å⁻³
291 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
C1	0.0548 (3)	0.0002 (2)	−0.17354 (15)	0.0547 (5)
H1	0.0689	−0.0528	−0.1316	0.066*
C2	0.1988 (3)	0.08388 (19)	−0.17968 (13)	0.0439 (4)
C3	0.1338 (3)	0.1521 (2)	−0.25031 (15)	0.0542 (5)
H3	0.2120	0.2136	−0.2645	0.065*
C4	−0.0525 (3)	0.1183 (2)	−0.29432 (16)	0.0611 (6)
H4	−0.1172	0.1531	−0.3420	0.073*
C5	0.3899 (3)	0.09887 (19)	−0.12014 (13)	0.0447 (4)
H5	0.4097	0.0504	−0.0753	0.054*
C6	0.5392 (3)	0.1746 (2)	−0.12320 (14)	0.0479 (4)
H6	0.5262	0.2230	−0.1681	0.058*
C7	0.7262 (3)	0.18356 (19)	−0.05652 (14)	0.0467 (4)
C8	0.2956 (3)	0.2219 (2)	0.08555 (15)	0.0559 (5)
H8	0.2325	0.1394	0.0762	0.067*
C9	0.4852 (3)	0.2485 (2)	0.13424 (15)	0.0508 (5)
H9	0.5459	0.1850	0.1574	0.061*
C10	0.5840 (3)	0.36980 (18)	0.14838 (13)	0.0429 (4)
C11	0.4821 (3)	0.4604 (2)	0.11311 (16)	0.0571 (5)
H11	0.5412	0.5437	0.1213	0.069*
C12	0.2929 (3)	0.4253 (2)	0.06605 (17)	0.0610 (6)
H12	0.2273	0.4872	0.0432	0.073*
C13	0.7889 (3)	0.40367 (18)	0.19703 (13)	0.0430 (4)
C14	0.8822 (3)	0.3308 (2)	0.25474 (15)	0.0537 (5)
H14	0.8163	0.2593	0.2646	0.064*
C15	1.0737 (3)	0.3656 (2)	0.29725 (16)	0.0575 (5)
H15	1.1340	0.3149	0.3347	0.069*
C16	1.0874 (3)	0.5381 (2)	0.23340 (17)	0.0595 (6)
H16	1.1565	0.6104	0.2263	0.071*
C17	0.8972 (3)	0.5096 (2)	0.18718 (16)	0.0556 (5)
H17	0.8417	0.5614	0.1494	0.067*
C18	1.2549 (3)	0.6734 (2)	0.52895 (16)	0.0584 (5)
H18	1.2472	0.5856	0.5026	0.070*
C19	1.1052 (3)	0.7401 (2)	0.51574 (13)	0.0475 (4)
C20	1.1585 (3)	0.8722 (2)	0.56515 (17)	0.0614 (6)
H20	1.0746	0.9324	0.5652	0.074*
C21	1.3461 (3)	0.9011 (2)	0.61250 (18)	0.0660 (6)
H21	1.4053	0.9830	0.6477	0.079*
C22	0.9150 (3)	0.6807 (2)	0.46025 (13)	0.0490 (5)
H22	0.8956	0.5918	0.4362	0.059*
C23	0.7683 (3)	0.7418 (2)	0.44109 (15)	0.0548 (5)
H23	0.7857	0.8303	0.4668	0.066*
C24	0.5778 (3)	0.6803 (2)	0.38173 (15)	0.0549 (5)
O1	0.7640 (2)	0.11251 (16)	−0.00462 (11)	0.0637 (4)
O2	0.8489 (2)	0.27837 (16)	−0.05983 (12)	0.0645 (4)
H2	0.9510	0.2794	−0.0227	0.097*
O3	0.4670 (2)	0.74129 (19)	0.34314 (14)	0.0809 (6)
O4	0.5423 (2)	0.55602 (16)	0.37539 (13)	0.0650 (4)
H4A	0.4325	0.5289	0.3450	0.098*
S1	−0.15372 (8)	0.00362 (7)	−0.25123 (4)	0.0671 (2)
S2	1.45740 (8)	0.76787 (7)	0.59882 (5)	0.0697 (2)
N1	0.1992 (2)	0.30804 (19)	0.05151 (13)	0.0568 (5)
N2	1.1767 (2)	0.46765 (18)	0.28753 (13)	0.0552 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0390 (10)	0.0657 (13)	0.0557 (12)	0.0000 (9)	0.0023 (8)	0.0207 (10)
C2	0.0382 (10)	0.0472 (10)	0.0429 (9)	0.0050 (8)	0.0058 (7)	0.0098 (8)
C3	0.0474 (11)	0.0583 (12)	0.0553 (12)	0.0055 (9)	0.0045 (9)	0.0213 (10)
C4	0.0512 (12)	0.0715 (14)	0.0548 (12)	0.0142 (11)	−0.0025 (9)	0.0193 (11)
C5	0.0378 (10)	0.0497 (10)	0.0448 (10)	0.0062 (8)	0.0048 (8)	0.0147 (8)
C6	0.0390 (10)	0.0518 (11)	0.0511 (11)	0.0052 (8)	0.0018 (8)	0.0200 (9)
C7	0.0358 (9)	0.0512 (11)	0.0511 (10)	0.0048 (8)	0.0049 (8)	0.0163 (9)
C8	0.0430 (11)	0.0567 (12)	0.0597 (12)	−0.0069 (9)	0.0073 (9)	0.0086 (10)
C9	0.0421 (10)	0.0491 (11)	0.0569 (11)	0.0014 (8)	0.0065 (9)	0.0130 (9)
C10	0.0351 (9)	0.0489 (10)	0.0400 (9)	0.0028 (8)	0.0049 (7)	0.0074 (8)
C11	0.0437 (11)	0.0502 (11)	0.0701 (13)	0.0020 (9)	−0.0004 (10)	0.0178 (10)
C12	0.0426 (11)	0.0653 (14)	0.0701 (14)	0.0101 (10)	0.0000 (10)	0.0208 (11)
C13	0.0338 (9)	0.0472 (10)	0.0422 (9)	0.0030 (7)	0.0039 (7)	0.0065 (8)
C14	0.0396 (10)	0.0610 (12)	0.0590 (12)	0.0026 (9)	0.0047 (9)	0.0224 (10)
C15	0.0415 (11)	0.0663 (14)	0.0609 (13)	0.0078 (10)	0.0005 (9)	0.0220 (11)
C16	0.0406 (11)	0.0591 (13)	0.0695 (14)	−0.0079 (9)	0.0010 (10)	0.0165 (11)
C17	0.0422 (11)	0.0544 (12)	0.0629 (13)	−0.0014 (9)	−0.0013 (9)	0.0186 (10)
C18	0.0406 (11)	0.0641 (13)	0.0612 (13)	0.0030 (9)	0.0058 (9)	0.0059 (10)
C19	0.0372 (10)	0.0588 (12)	0.0421 (9)	0.0004 (8)	0.0040 (7)	0.0121 (9)
C20	0.0439 (12)	0.0593 (13)	0.0700 (14)	0.0058 (10)	−0.0008 (10)	0.0101 (11)
C21	0.0461 (12)	0.0624 (14)	0.0716 (15)	−0.0046 (10)	−0.0014 (10)	0.0021 (11)
C22	0.0390 (10)	0.0576 (12)	0.0453 (10)	−0.0037 (9)	0.0036 (8)	0.0140 (9)
C23	0.0406 (11)	0.0612 (13)	0.0559 (12)	−0.0025 (9)	0.0000 (9)	0.0182 (10)
C24	0.0371 (10)	0.0682 (14)	0.0571 (12)	−0.0024 (9)	0.0027 (9)	0.0248 (10)
O1	0.0460 (8)	0.0779 (11)	0.0686 (10)	0.0059 (7)	−0.0012 (7)	0.0399 (9)
O2	0.0389 (8)	0.0669 (10)	0.0806 (11)	−0.0046 (7)	−0.0068 (7)	0.0324 (8)
O3	0.0477 (9)	0.0871 (12)	0.0997 (13)	−0.0059 (9)	−0.0160 (9)	0.0502 (11)
O4	0.0359 (8)	0.0668 (10)	0.0792 (11)	−0.0008 (7)	−0.0064 (7)	0.0169 (8)
S1	0.0359 (3)	0.0853 (4)	0.0685 (4)	−0.0024 (3)	−0.0014 (2)	0.0156 (3)
S2	0.0343 (3)	0.0880 (5)	0.0729 (4)	0.0059 (3)	−0.0003 (2)	0.0073 (3)
N1	0.0350 (9)	0.0705 (12)	0.0563 (10)	−0.0002 (8)	0.0024 (7)	0.0110 (9)
N2	0.0359 (9)	0.0640 (11)	0.0558 (10)	0.0012 (8)	0.0006 (7)	0.0089 (8)

Geometric parameters (Å, º) top

C1—C2	1.361 (3)	C13—C14	1.392 (3)
C1—S1	1.701 (2)	C14—C15	1.382 (3)
C1—H1	0.9300	C14—H14	0.9300
C2—C3	1.430 (3)	C15—N2	1.332 (3)
C2—C5	1.451 (3)	C15—H15	0.9300
C3—C4	1.351 (3)	C16—N2	1.328 (3)
C3—H3	0.9300	C16—C17	1.380 (3)
C4—S1	1.703 (3)	C16—H16	0.9300
C4—H4	0.9300	C17—H17	0.9300
C5—C6	1.324 (3)	C18—C19	1.362 (3)
C5—H5	0.9300	C18—S2	1.699 (2)
C6—C7	1.478 (3)	C18—H18	0.9300
C6—H6	0.9300	C19—C20	1.423 (3)
C7—O1	1.207 (2)	C19—C22	1.456 (3)
C7—O2	1.318 (2)	C20—C21	1.367 (3)
C8—N1	1.328 (3)	C20—H20	0.9300
C8—C9	1.385 (3)	C21—S2	1.705 (3)
C8—H8	0.9300	C21—H21	0.9300
C9—C10	1.383 (3)	C22—C23	1.315 (3)
C9—H9	0.9300	C22—H22	0.9300
C10—C11	1.395 (3)	C23—C24	1.479 (3)
C10—C13	1.485 (2)	C23—H23	0.9300
C11—C12	1.380 (3)	C24—O3	1.208 (3)
C11—H11	0.9300	C24—O4	1.315 (3)
C12—N1	1.330 (3)	O2—H2	0.8200
C12—H12	0.9300	O4—H4A	0.8200
C13—C17	1.386 (3)

C2—C1—S1	112.31 (16)	C15—C14—C13	119.4 (2)
C2—C1—H1	123.8	C15—C14—H14	120.3
S1—C1—H1	123.8	C13—C14—H14	120.3
C1—C2—C3	110.97 (18)	N2—C15—C14	123.6 (2)
C1—C2—C5	122.51 (18)	N2—C15—H15	118.2
C3—C2—C5	126.52 (18)	C14—C15—H15	118.2
C4—C3—C2	113.3 (2)	N2—C16—C17	123.3 (2)
C4—C3—H3	123.4	N2—C16—H16	118.3
C2—C3—H3	123.4	C17—C16—H16	118.3
C3—C4—S1	111.33 (17)	C16—C17—C13	120.1 (2)
C3—C4—H4	124.3	C16—C17—H17	120.0
S1—C4—H4	124.3	C13—C17—H17	120.0
C6—C5—C2	126.60 (18)	C19—C18—S2	112.62 (18)
C6—C5—H5	116.7	C19—C18—H18	123.7
C2—C5—H5	116.7	S2—C18—H18	123.7
C5—C6—C7	121.21 (18)	C18—C19—C20	111.27 (19)
C5—C6—H6	119.4	C18—C19—C22	123.4 (2)
C7—C6—H6	119.4	C20—C19—C22	125.35 (19)
O1—C7—O2	123.23 (18)	C21—C20—C19	112.8 (2)
O1—C7—C6	124.35 (18)	C21—C20—H20	123.6
O2—C7—C6	112.42 (17)	C19—C20—H20	123.6
N1—C8—C9	123.5 (2)	C20—C21—S2	111.29 (18)
N1—C8—H8	118.3	C20—C21—H21	124.4
C9—C8—H8	118.3	S2—C21—H21	124.4
C10—C9—C8	119.7 (2)	C23—C22—C19	125.7 (2)
C10—C9—H9	120.1	C23—C22—H22	117.1
C8—C9—H9	120.1	C19—C22—H22	117.1
C9—C10—C11	116.67 (18)	C22—C23—C24	124.9 (2)
C9—C10—C13	122.63 (18)	C22—C23—H23	117.6
C11—C10—C13	120.69 (18)	C24—C23—H23	117.6
C12—C11—C10	119.5 (2)	O3—C24—O4	124.2 (2)
C12—C11—H11	120.3	O3—C24—C23	121.6 (2)
C10—C11—H11	120.2	O4—C24—C23	114.25 (18)
N1—C12—C11	123.6 (2)	C7—O2—H2	109.5
N1—C12—H12	118.2	C24—O4—H4A	109.5
C11—C12—H12	118.2	C1—S1—C4	92.12 (11)
C17—C13—C14	116.54 (18)	C18—S2—C21	91.96 (11)
C17—C13—C10	121.64 (18)	C8—N1—C12	117.01 (18)
C14—C13—C10	121.82 (18)	C16—N2—C15	117.01 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1ⁱ	0.82	1.86	2.668 (2)	168
O4—H4A···N2ⁱⁱ	0.82	1.87	2.684 (2)	174

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

Experimental details

Crystal data
Chemical formula	C₁₀H₈N₂·2C₇H₆O₂S
M_r	464.54
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.3454 (5), 10.7319 (8), 15.0196 (11)
α, β, γ (°)	102.518 (6), 103.648 (6), 94.892 (6)
V (Å³)	1111.54 (14)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	2.46
Crystal size (mm)	0.37 × 0.15 × 0.10

Data collection
Diffractometer	Xcalibur, Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.692, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9038, 4344, 3498
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.132, 1.05
No. of reflections	4344
No. of parameters	291
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.32

Computer programs: CrysAlis PRO (Oxford Diffraction 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), publCIF (Westrip, 2010) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1ⁱ	0.82	1.86	2.668 (2)	168.4
O4—H4A···N2ⁱⁱ	0.82	1.87	2.684 (2)	174.1

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

Acknowledgements

The authors are grateful to the University Sophisticated Instrument Center (USIC), University of Delhi, Delhi, India, for providing the single-crystal X-ray diffractometer facility. They also thank the Department of Science & Technology for financial support.

References

Desiraju, G. R. (1996). Acc. Chem. Res. 29, 441–449. CrossRef CAS PubMed Web of Science Google Scholar
Desiraju, G. R. (2002). Acc. Chem. Res. 35, 565–573. Web of Science CrossRef PubMed CAS Google Scholar
Eccles, K. S., Elcoate, C. J., Stokes, S. P., Maguire, A. R. & Lawrence, S. E. (2010). Cryst. Growth Des. 10, 4243–4245. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Friščić, T. & MacGillivray, L. R. (2005). Supramol. Chem. 17, 47–51. Google Scholar
Friščić, T. & MacGillivray, L. R. (2009). Chem. Commun. pp. 773–775. Google Scholar
Gao, X., Friščić, T. & MacGillivray, L. R. (2004). Angew. Chem. Int. Ed. 43, 232–236. Web of Science CSD CrossRef CAS Google Scholar
MacGillivray, L. R., Papaefstathiou, G. S., Friščić, T., Hamilton, T. D., Bučar, D. K., Chu, Q., Varshney, D. B. & Georgiev, I. G. (2008). Acc. Chem. Res. 41, 280–291. Web of Science CrossRef PubMed CAS Google Scholar
Oxford Diffraction (2009). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Srivastava, B. K., Jain, M. R., Solanki, M., Soni, R., Valani, D., Gupta, S., Mishra, B., Takale, V., Kapadnis, P., Patel, H., Pandya, P., Patel, J. Z. & Patel, P. R. (2008). Eur. J. Med. Chem. pp. 683–693. Web of Science CrossRef Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar