A 1:2 co-crystal of 2,2′-di­thiodi­benzoic acid and benzoic acid: crystal structure, Hirshfeld surface analysis and computational study

Tan, S.L.; Tiekink, E.R.T.

doi:10.1107/S2056989018017097

A 1:2 co-crystal of 2,2′-dithiodibenzoic acid and benzoic acid: crystal structure, Hirshfeld surface analysis and computational study

The asymmetric unit of the title 1:2 co-crystal has a half molecule of twofold symmetric dithiodibenzoic acid and a full molecule of benzoic acid. These are connected into three-molecule aggregates via hydroxy-O—H

O(hydroxy) hydrogen bonds.

Keywords: crystal structure; dithiodibenzoic acid; benzoic acid; hydrogen bonding; computational chemistry.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989018017097/hb7790sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989018017097/hb7790Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989018017097/hb7790Isup3.cml Supplementary material

CCDC reference: 1882556

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.002 Å
R factor = 0.039
wR factor = 0.109
Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.338 Check

Alert level G
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         12 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         13 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   2 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015b); program(s) used to refine structure: SHELXL (Sheldrick, 2015a); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

2,2'-Dithiodibenzoic acid–benzoic acid (1/2) top

Crystal data top

C₁₄H₁₀O₄S₂·2C₇H₆O₂	F(000) = 1144
M_r = 550.58	D_x = 1.477 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
a = 8.2311 (1) Å	Cell parameters from 18092 reflections
b = 13.3220 (2) Å	θ = 3.9–76.2°
c = 22.7038 (3) Å	µ = 2.41 mm⁻¹
β = 95.864 (2)°	T = 100 K
V = 2476.55 (6) Å³	Prism, colourless
Z = 4	0.20 × 0.11 × 0.06 mm

Data collection top

XtaLAB Synergy, Dualflex, AtlasS2 diffractometer	2589 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2511 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.039
Detector resolution: 5.2558 pixels mm^-1	θ_max = 76.2°, θ_min = 3.9°
ω scans	h = −10→10
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2018)	k = −16→16
T_min = 0.643, T_max = 1.000	l = −28→28
32177 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.109	w = 1/[σ²(F_o²) + (0.0597P)² + 4.0853P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2589 reflections	Δρ_max = 0.66 e Å⁻³
180 parameters	Δρ_min = −0.49 e Å⁻³
0 restraints

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
S1	0.50125 (5)	0.53534 (3)	0.29507 (2)	0.01870 (14)
O1	0.29643 (16)	0.49404 (10)	0.46525 (5)	0.0239 (3)
H1o	0.328 (3)	0.544 (2)	0.4890 (12)	0.042 (7)*
O2	0.46078 (15)	0.57402 (9)	0.40809 (5)	0.0213 (3)
O3	0.52518 (17)	0.72548 (10)	0.48274 (6)	0.0260 (3)
H3o	0.502 (4)	0.676 (2)	0.4589 (13)	0.053 (8)*
O4	0.35583 (16)	0.64485 (9)	0.53788 (5)	0.0237 (3)
C1	0.3639 (2)	0.50608 (12)	0.41556 (7)	0.0179 (3)
C2	0.3123 (2)	0.43148 (12)	0.36912 (7)	0.0175 (3)
C3	0.3622 (2)	0.43865 (12)	0.31172 (7)	0.0172 (3)
C4	0.3046 (2)	0.36819 (13)	0.26917 (7)	0.0192 (3)
H4	0.336143	0.372512	0.231068	0.023*
C5	0.2004 (2)	0.29140 (13)	0.28321 (8)	0.0213 (4)
H5	0.162961	0.244879	0.254423	0.026*
C6	0.1519 (2)	0.28379 (13)	0.33971 (8)	0.0220 (4)
H6	0.083137	0.232083	0.349054	0.026*
C7	0.2070 (2)	0.35389 (13)	0.38213 (8)	0.0208 (3)
H7	0.173415	0.349359	0.419926	0.025*
C8	0.4462 (2)	0.71641 (13)	0.53011 (7)	0.0195 (3)
C9	0.4761 (2)	0.79789 (13)	0.57426 (7)	0.0196 (3)
C10	0.4020 (2)	0.79189 (13)	0.62667 (7)	0.0212 (4)
H10	0.331481	0.739174	0.632630	0.025*
C11	0.4340 (2)	0.86479 (14)	0.66992 (8)	0.0234 (4)
H11	0.384929	0.860972	0.704986	0.028*
C12	0.5395 (2)	0.94372 (14)	0.66082 (8)	0.0238 (4)
H12	0.561938	0.992032	0.690087	0.029*
C13	0.6111 (2)	0.95056 (14)	0.60843 (8)	0.0247 (4)
H13	0.680059	1.004025	0.602298	0.030*
C14	0.5801 (2)	0.87766 (13)	0.56496 (8)	0.0225 (4)
H14	0.628625	0.882052	0.529801	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0254 (2)	0.0140 (2)	0.0171 (2)	−0.00272 (14)	0.00424 (16)	−0.00104 (13)
O1	0.0350 (7)	0.0198 (6)	0.0178 (6)	−0.0079 (5)	0.0079 (5)	−0.0026 (5)
O2	0.0281 (6)	0.0181 (6)	0.0184 (6)	−0.0062 (5)	0.0054 (5)	−0.0024 (4)
O3	0.0380 (8)	0.0203 (6)	0.0212 (6)	−0.0079 (5)	0.0110 (5)	−0.0048 (5)
O4	0.0312 (7)	0.0193 (6)	0.0212 (6)	−0.0069 (5)	0.0062 (5)	−0.0025 (5)
C1	0.0218 (8)	0.0153 (8)	0.0169 (8)	0.0010 (6)	0.0027 (6)	0.0012 (6)
C2	0.0211 (8)	0.0132 (8)	0.0181 (8)	0.0005 (6)	0.0006 (6)	−0.0002 (6)
C3	0.0202 (8)	0.0120 (7)	0.0193 (8)	0.0003 (6)	0.0014 (6)	0.0006 (6)
C4	0.0221 (8)	0.0171 (8)	0.0184 (8)	−0.0002 (6)	0.0023 (6)	−0.0014 (6)
C5	0.0238 (8)	0.0159 (8)	0.0238 (8)	−0.0017 (6)	−0.0001 (6)	−0.0037 (6)
C6	0.0247 (8)	0.0147 (8)	0.0266 (9)	−0.0039 (7)	0.0022 (7)	0.0002 (6)
C7	0.0258 (8)	0.0169 (8)	0.0201 (8)	−0.0012 (7)	0.0033 (6)	0.0016 (6)
C8	0.0228 (8)	0.0173 (8)	0.0186 (8)	−0.0006 (6)	0.0027 (6)	0.0008 (6)
C9	0.0238 (8)	0.0163 (8)	0.0184 (8)	0.0008 (6)	0.0010 (6)	−0.0004 (6)
C10	0.0233 (8)	0.0186 (8)	0.0219 (8)	−0.0009 (6)	0.0030 (6)	0.0011 (6)
C11	0.0269 (9)	0.0235 (9)	0.0200 (8)	0.0015 (7)	0.0033 (7)	−0.0016 (7)
C12	0.0279 (9)	0.0197 (8)	0.0232 (9)	0.0015 (7)	−0.0006 (7)	−0.0048 (7)
C13	0.0276 (9)	0.0183 (8)	0.0282 (9)	−0.0035 (7)	0.0026 (7)	−0.0012 (7)
C14	0.0272 (9)	0.0198 (8)	0.0212 (8)	−0.0028 (7)	0.0051 (7)	−0.0008 (7)

Geometric parameters (Å, º) top

S1—S1ⁱ	2.0446 (8)	C6—H6	0.9300
S1—C3	1.7889 (17)	C6—C7	1.384 (2)
O1—H1o	0.88 (3)	C7—H7	0.9300
O1—C1	1.317 (2)	C8—C9	1.481 (2)
O2—C1	1.229 (2)	C9—C10	1.393 (2)
O3—H3o	0.87 (3)	C9—C14	1.395 (2)
O3—C8	1.318 (2)	C10—H10	0.9300
O4—C8	1.233 (2)	C10—C11	1.387 (2)
C1—C2	1.479 (2)	C11—H11	0.9300
C2—C3	1.409 (2)	C11—C12	1.393 (3)
C2—C7	1.400 (2)	C12—H12	0.9300
C3—C4	1.395 (2)	C12—C13	1.383 (3)
C4—H4	0.9300	C13—H13	0.9300
C4—C5	1.393 (2)	C13—C14	1.390 (3)
C5—H5	0.9300	C14—H14	0.9300
C5—C6	1.385 (2)

C3—S1—S1ⁱ	105.68 (6)	C6—C7—H7	119.4
C1—O1—H1o	107.9 (18)	O3—C8—C9	115.08 (15)
C8—O3—H3o	110 (2)	O4—C8—O3	122.88 (16)
O1—C1—C2	114.38 (14)	O4—C8—C9	122.04 (15)
O2—C1—O1	122.96 (15)	C10—C9—C8	118.64 (16)
O2—C1—C2	122.65 (15)	C10—C9—C14	120.14 (16)
C3—C2—C1	121.58 (15)	C14—C9—C8	121.19 (15)
C7—C2—C1	119.01 (15)	C9—C10—H10	120.1
C7—C2—C3	119.38 (15)	C11—C10—C9	119.78 (17)
C2—C3—S1	119.84 (12)	C11—C10—H10	120.1
C4—C3—S1	121.18 (13)	C10—C11—H11	120.0
C4—C3—C2	118.96 (15)	C10—C11—C12	119.96 (17)
C3—C4—H4	119.7	C12—C11—H11	120.0
C5—C4—C3	120.63 (16)	C11—C12—H12	119.9
C5—C4—H4	119.7	C13—C12—C11	120.29 (17)
C4—C5—H5	119.7	C13—C12—H12	119.9
C6—C5—C4	120.52 (16)	C12—C13—H13	120.0
C6—C5—H5	119.7	C12—C13—C14	120.09 (17)
C5—C6—H6	120.3	C14—C13—H13	120.0
C7—C6—C5	119.36 (16)	C9—C14—H14	120.1
C7—C6—H6	120.3	C13—C14—C9	119.73 (16)
C2—C7—H7	119.4	C13—C14—H14	120.1
C6—C7—C2	121.15 (16)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O4	0.88 (3)	1.74 (3)	2.6134 (17)	170 (2)
O3—H3O···O2	0.86 (3)	1.79 (3)	2.6535 (18)	178 (4)
C7—H7···O3ⁱⁱ	0.93	2.57	3.329 (2)	139
C14—H14···O1ⁱⁱⁱ	0.93	2.59	3.395 (2)	145

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

Interaction energies (kJ mol^-1) for selected close contacts top

Contact	E_{electrostatic}	E_polarization	E_dispersion	E_{exchange-repulsion}	E_total	Symmetry operation
O3—H3···O2/O1—H1···O4	-126.1	-29.0	-13.1	153.0	-71.7	1 - x, 1 - y, 1 - z
Cg1(C2–C7)···Cg2(C9–C14)	-0.1	-1.5	-41.8	25.5	-21.7	- x, - y, - z
Cg1(C2–C7)···Cg2(C9–C14)	-4.2	-1.3	-30.1	20.8	-18.7	-1/2 + x, 1/2 + y, z
C6—H6···S1	-10.2	-2.0	-13.5	15.8	-14.2	1/2 + x, 1/2 + y, z
C14—H14···O1/C7—H7···O3	-3.6	-0.9	-13.6	14.8	-7.1	1/2 - x, 1/2 - y, 1 - z

Percentage contributions of selected interatomic contacts to the Hirshfeld surface for (I) and for the the individual TDBA and BA molecules top

Contact		Percentage contribution
	overall	TDBA	BA
H···H	37.0	32.3	41.5
O···H/H···O	21.2	25.3	25.1
S···H/H···S	9.2	12.4	2.1
C···H/H···C	15.3	14.9	12.8
C···C	9.5	9.3	8.7

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A 1:2 co-crystal of 2,2′-di­thiodi­benzoic acid and benzoic acid: crystal structure, Hirshfeld surface analysis and computational study

Supporting information

Key indicators

checkCIF/PLATON results

A 1:2 co-crystal of 2,2′-dithiodibenzoic acid and benzoic acid: crystal structure, Hirshfeld surface analysis and computational study