Crystal structure of catena-poly[calcium-di-μ3-benzoato-κ6O,O′:O-μ2-(dimethyl sulfoxide)-κ2O:O]

Voronova, A.S.; Petrusenko, S.R.; Goreshnik, E.

doi:10.1107/S2056989015012487

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Volume 71| Part 8| August 2015| Pages 906-909

https://doi.org/10.1107/S2056989015012487

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Crystal structure of catena-poly[calcium-di-μ₃-benzoato-κ⁶O,O′:O-μ₂-(dimethyl sulfoxide)-κ²O:O]

Anna S. Voronova,^a Svitlana R. Petrusenko ^a ^* and Evgeny Goreshnik ^b

^aDepartment of Inorganic Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska str. 64/13, 01601 Kyiv, Ukraine, and ^bDepartment of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia
^*Correspondence e-mail: spetrusenko@yahoo.com

Edited by G. Smith, Queensland University of Technology, Australia (Received 8 May 2015; accepted 29 June 2015; online 8 July 2015)

In the title complex, [Ca(C₇H₅O₂)₂(C₂H₆OS)]_n, the Ca²⁺ ion (site symmetry m..) is surrounded by eight O atoms, six from two bridging–chelating tridentate benzoate carboxyl groups and two from a bridging dimethyl sulfoxide molecule (point group symmetry m..), giving an irregular coordination geometry [Ca—O bond length range = 2.345 (2)–2.524 (2) Å]. One-dimensional coordination complex chains extending parallel to c are generated in which the triply μ₂-O-bridged Ca²⁺ cations are separated by 3.6401 (5) Å. In the crystal, weak intrachain C—H⋯π hydrogen bonds are present between the methyl H atoms of the dimethyl sulfoxide molecules as donors and the aromatic rings as acceptors [C—H⋯Cg = 3.790 (4) Å].

Keywords: crystal structure; calcium benzoate; coordination polymer; C—H⋯π interactions.

CCDC reference: 1409468

1. Chemical context

Compounds of benzoic acid with calcium are of special interest due to their wide-ranging applications, for example as a preservative in the food industry, in cosmetics and in medicine. In spite of that, the crystal structures of such compounds have been poorly investigated. Searches of the Cambridge Structural Database (CSD; Version 5.35, November 2013 + 2 updates; Groom & Allen, 2014 ) for simple calcium benzoate complexes revealed only three results: [Ca(benz)₂(dmf)(H₂O)]_n (Yano et al., 2001 ), {[Ca(benz)(H₂O)₃]⁺ (benz)⁻}_n (Senkovska & Thewalt, 2005 ) and [Ca(benz)₂(Hbenz)(H₂O)]_n (Azizov et al., 2011 ) (where benz = benzoate).

Here we report the synthesis of a new calcium benzoate–dimethyl sulfoxide complex, [Ca(benz)₂(dmso)]_n, which was obtained as a by-product of an attempted synthesis of an Mn/Cu heterometallic complex (in crystalline form available for X-ray analysis) from the system: Mn–Cu–(bhz–sal)–CaO–KSCN–dmso (in open air), where manganese and copper were used as unactivated metal powders, bhz = benzohydrazide and sal = salicylaldehyde. The investigation of the system was carried out as a part of systematic research on the elaboration the `direct synthesis' approach to both homo- and heterometallic coordination compounds (Babich et al., 1996 ; Buvaylo et al., 2005 ; Vassilyeva et al., 1997 ). It is worth noting that an alternative method of synthesis using a classical reaction between calcium oxide and benzoic acid in dmso, affords the same complex in good yield (up to 90%), but does not give X-ray quality crystals. The crystal structure of the title complex, [Ca(benz)₂(dmso)]_n, is reported herein.

2. Structural commentary

The asymmetric unit of [Ca(benz)₂(dmso)]_n comprises one Ca²⁺ cation (site symmetry m..), one benzoate ligand and half of a dmso molecule, the other half being generated by mirror symetry. The irregular CaO₈ coordination polyhedron consists of six O atom donors from two O,O′ chelating-bridging benzoate carboxyl groups with the same coordination modes, [2.1₁1₁₂] in the Harris notation (Coxall et al., 2000 ), and two from μ₂-bridging dmso molecules (Fig. 1). The coordination geometry deviates strongly from ideal, the Ca—O bond lengths varying from 2.345 (2) to 2.524 (2) Å (Table 1) and the O—Ca—O angles from 52.19 (7) to 156.06 (8)°. The bridging Ca1—O1ⁱ and Ca1—O1ⁱⁱ (carboxyl) bond lengths are considerably shorter than the chelate ones, as is usually observed in polymeric benzoates. For the title complex, the bond-valence index [BVS (Ca)] (Allmann, 1975 ) is 2.03.

Table 1
Selected bond lengths (Å)

Ca1—O1ⁱ	2.345 (2)	Ca1—O3	2.494 (3)
Ca1—O1ⁱⁱ	2.345 (2)	Ca1—O3^iv	2.516 (3)
Ca1—O2ⁱⁱⁱ	2.481 (2)	Ca1—O1ⁱⁱⁱ	2.524 (2)
Ca1—O2	2.481 (2)	Ca1—O1	2.524 (2)
Symmetry codes: (i) $[-x+1, -y, z+{\script{1\over 2}}]$ ; (ii) $[x, -y, z+{\script{1\over 2}}]$ ; (iii) -x+1, y, z; (iv) $[-x+1, -y, z-{\script{1\over 2}}]$ .

Figure 1
A fragment of the [Ca(benz)₂(dmso)]_n chain with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. For symmetry codes, see Table 1

3. Supramolecular features

The triple-O-bridged CaO₈ polyhedra form one-dimensional coordination polymeric chains which extend parallel to the c-axis direction (Figs. 2–4 ). The Ca⋯Caⁱ and Ca1⋯Ca1^iv separation in the chain is 3.6401 (5) Å [symmetry code (iv): −x + 1, −y, z − $[{1\over 2}]$ ]. To the best of our knowledge, this is the first Ca carboxylate polymer based on non-centrosymmetric bridges (μ-η²:η¹)₂. For bridging modes in coordination polymeric structures, reference should be made to Deacon et al. (2007 ) and Busskamp et al. (2007 ). The polymer chains in the title compound are additionally stabilized by weak C—H⋯π interactions between the methyl groups of the dmso molecule and the benzoate rings (centroid Cg) (Table 2, Figs. 3 and 4).

Table 2
C—H⋯π interactions (Å, °)

Cg is the centroid of the benzoate ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯Cg	0.96	2.84	3.790 (4)	169

Figure 2
Bridging interactions observed in the title complex polymer which extends along the c- axis direction. Phenyl rings and H atoms have been omitted for clarity.

Figure 3
C—H⋯π hydrogen bonds involving a dmso donor as found in the title complex. For symmetry codes, see Table 1

Figure 4
Packing of the molecular chains viewed down the chain direction (the crystallographic c axis). C—H⋯π bonds are shown as dashed lines.

4. Synthesis and crystallization

Calcium oxide (0.056 g, 1 mmol) and benzoic acid (0.244 g, 2 mmol) were added to 20 ml of dmso and stirred magnetically for ca 5 h at 323 K, after which the solution was filtered. The white precipitate which formed after one day was collected and dried in air; yield: 0.4 g (90%). Elemental analysis for C₁₆H₁₆CaO₅S (M_r = 360.43). Calculated: Ca, 11.12%; found: Ca, 11.0%. IR (KBr, cm⁻¹): 1603 (s), 1562 (s), 1405 (s), 1024 (s), 721 (s). Crystals suitable for X-ray analysis were obtained by slow evaporation at room temperature of a solution which was the product from the reaction between manganese powder (0.05 g, 1 mmol), copper powder (0.06 g, 1 mmol), benzohydrazide (0.409 g, 3 mmol), salicylaldehyde (0.314 ml, 3 mmol), CaO (0.168 g, 3 mmol), KSCN (0.291 g, 3 mmol) and dmso (20 ml). The reaction was carried out at 353 K with magnetic stirring for eight hours, after which undissolved products were filtered off.

5. Refinement details

Crystal data, data collection and structure refinement details are given in Table 3. Hydrogen atoms were placed in calculated positions [C—H_aromatic = 0.95; C—H_methyl = 0.99 Å] and were allowed to ride in the refinements, with U_iso(H) = 1.2U_eq(aromatic C) or 1.5U_eq(methyl C). Although not of relevance in this crystal involving achiral molecules, the Flack absolute structure parameter (Flack, 1983 ) was determined as 0.04 (8) by classical fit to all intensities and 0.07 (3) from 557 selected quotients (Parsons et al., 2013 ).

Table 3
Experimental details

Crystal data
Chemical formula	[Ca(C₇H₅O₂)₂(C₂H₆OS)]
M_r	360.43
Crystal system, space group	Orthorhombic, Cmc2₁
Temperature (K)	200
a, b, c (Å)	25.531 (2), 9.5351 (8), 6.9330 (4)
V (Å³)	1687.7 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.52
Crystal size (mm)	0.22 × 0.15 × 0.11

Data collection
Diffractometer	Rigaku Mercury CCD
Absorption correction	Multi-scan (Blessing, 1995 )
T_min, T_max	0.798, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	3704, 1897, 1676
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.683

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.103, 1.13
No. of reflections	1897
No. of parameters	109
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.39
Absolute structure	Flack x determined using 557 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013)
Absolute structure parameter	0.07 (3)
Computer programs: CrystalClear (Rigaku, 1999 ), SIR92 (Altomare et al., 1993 )., SHELXL97 (Sheldrick, 2008 ), DIAMOND (Brandenburg & Putz, 2006 ) and WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1409468

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989015012487/zs2334sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015012487/zs2334Isup2.hkl

checkCIF report

Computing details top

Data collection: CrystalClear (Rigaku, 1999); cell refinement: CrystalClear (Rigaku, 1999); data reduction: CrystalClear (Rigaku, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1993).; program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: WinGX (Farrugia, 2012).

catena-Poly[calcium-di-µ₃-benzoato-κ⁶O,O':O-µ₂-(dimethyl sulfoxide)-κ²O:O] top

Crystal data top

[Ca(C₇H₅O₂)₂(C₂H₆OS)]	D_x = 1.418 Mg m⁻³
M_r = 360.43	Mo Kα radiation, λ = 0.71069 Å
Orthorhombic, Cmc2₁	Cell parameters from 1872 reflections
a = 25.531 (2) Å	θ = 2.3–28.7°
b = 9.5351 (8) Å	µ = 0.52 mm⁻¹
c = 6.9330 (4) Å	T = 200 K
V = 1687.7 (2) Å³	Block, colorless
Z = 4	0.22 × 0.15 × 0.11 mm
F(000) = 752

Data collection top

Rigaku Mercury CCD (2x2 bin mode) diffractometer	1897 independent reflections
Graphite monochromator	1676 reflections with I > 2σ(I)
Detector resolution: 14.7059 pixels mm^-1	R_int = 0.025
dtprofit.ref scans	θ_max = 29.0°, θ_min = 2.3°
Absorption correction: multi-scan (Blessing, 1995)	h = −34→26
T_min = 0.798, T_max = 0.951	k = −12→6
3704 measured reflections	l = −9→9

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)] = 0.044	H-atom parameters constrained
wR(F²) = 0.103	w = 1/[σ²(F_o²) + (0.040P)² + 0.7932P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max < 0.001
1897 reflections	Δρ_max = 0.59 e Å⁻³
109 parameters	Δρ_min = −0.39 e Å⁻³
1 restraint	Absolute structure: Flack x determined using 557 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.07 (3)

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
Ca1	0.5000	0.05825 (7)	0.36175 (11)	0.0325 (2)
O1	0.44205 (8)	0.06089 (19)	0.0668 (3)	0.0388 (5)
O2	0.43213 (9)	0.2334 (2)	0.2748 (4)	0.0509 (6)
O3	0.5000	0.1724 (3)	0.6855 (5)	0.0414 (7)
C1	0.41769 (12)	0.1682 (3)	0.1275 (5)	0.0375 (7)
C2	0.37045 (12)	0.2146 (3)	0.0171 (5)	0.0388 (7)
C3	0.35274 (13)	0.1367 (4)	−0.1381 (7)	0.0589 (10)
H3	0.3695	0.0533	−0.1704	0.071*
C4	0.31036 (16)	0.1818 (5)	−0.2452 (8)	0.0756 (13)
H4	0.2988	0.1289	−0.3495	0.091*
C5	0.28529 (14)	0.3044 (4)	−0.1984 (7)	0.0624 (11)
H5	0.2567	0.3340	−0.2707	0.075*
C6	0.30222 (15)	0.3831 (4)	−0.0461 (7)	0.0584 (11)
H6	0.2855	0.4669	−0.0160	0.070*
C7	0.34453 (12)	0.3375 (3)	0.0639 (6)	0.0464 (8)
H7	0.3555	0.3900	0.1695	0.056*
C8	0.44725 (16)	0.4090 (3)	0.6588 (6)	0.0560 (10)
H8A	0.4146	0.3721	0.7051	0.084*
H8B	0.4493	0.3964	0.5217	0.084*
H8C	0.4494	0.5071	0.6889	0.084*
S1	0.5000	0.31863 (10)	0.77164 (16)	0.0444 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca1	0.0504 (4)	0.0257 (3)	0.0214 (4)	0.000	0.000	0.0005 (3)
O1	0.0472 (11)	0.0343 (11)	0.0349 (13)	0.0085 (8)	0.0000 (10)	−0.0033 (9)
O2	0.0720 (14)	0.0427 (12)	0.0381 (13)	0.0142 (11)	−0.0139 (13)	−0.0064 (11)
O3	0.069 (2)	0.0218 (12)	0.0333 (17)	0.000	0.000	−0.0020 (12)
C1	0.0515 (17)	0.0302 (14)	0.0307 (17)	0.0017 (13)	0.0019 (13)	0.0022 (12)
C2	0.0421 (15)	0.0389 (16)	0.0353 (17)	0.0002 (13)	0.0011 (13)	0.0042 (14)
C3	0.0556 (18)	0.060 (2)	0.061 (2)	0.0180 (16)	−0.014 (2)	−0.022 (2)
C4	0.067 (2)	0.086 (3)	0.074 (3)	0.020 (2)	−0.031 (2)	−0.022 (3)
C5	0.0483 (19)	0.069 (2)	0.070 (3)	0.0101 (19)	−0.0107 (18)	0.010 (2)
C6	0.0478 (19)	0.045 (2)	0.082 (3)	0.0097 (16)	0.0054 (19)	0.003 (2)
C7	0.0483 (17)	0.0390 (17)	0.052 (2)	0.0063 (14)	0.0025 (16)	−0.0028 (16)
C8	0.083 (3)	0.0357 (15)	0.049 (2)	0.0096 (17)	0.005 (2)	−0.0010 (17)
S1	0.0829 (8)	0.0257 (5)	0.0244 (6)	0.000	0.000	−0.0015 (4)

Geometric parameters (Å, º) top

Ca1—O1ⁱ	2.345 (2)	C1—C2	1.496 (4)
Ca1—O1ⁱⁱ	2.345 (2)	C2—C3	1.383 (5)
Ca1—O2ⁱⁱⁱ	2.481 (2)	C2—C7	1.384 (4)
Ca1—O2	2.481 (2)	C3—C4	1.381 (5)
Ca1—O3	2.494 (3)	C3—H3	0.9300
Ca1—O3^iv	2.516 (3)	C4—C5	1.371 (5)
Ca1—O1ⁱⁱⁱ	2.524 (2)	C4—H4	0.9300
Ca1—O1	2.524 (2)	C5—C6	1.365 (6)
Ca1—C1ⁱⁱⁱ	2.855 (3)	C5—H5	0.9300
Ca1—C1	2.855 (3)	C6—C7	1.392 (5)
Ca1—Ca1ⁱ	3.6401 (5)	C6—H6	0.9300
Ca1—Ca1^iv	3.6401 (5)	C7—H7	0.9300
O1—C1	1.269 (3)	C8—S1	1.780 (4)
O1—Ca1^iv	2.345 (2)	C8—H8A	0.9600
O2—C1	1.251 (4)	C8—H8B	0.9600
O3—S1	1.517 (3)	C8—H8C	0.9600
O3—Ca1ⁱ	2.516 (3)	S1—C8ⁱⁱⁱ	1.780 (4)

O1ⁱ—Ca1—O1ⁱⁱ	78.22 (11)	C1ⁱⁱⁱ—Ca1—Ca1ⁱ	130.82 (7)
O1ⁱ—Ca1—O2ⁱⁱⁱ	91.88 (8)	C1—Ca1—Ca1ⁱ	130.82 (7)
O1ⁱⁱ—Ca1—O2ⁱⁱⁱ	156.06 (8)	O1ⁱ—Ca1—Ca1^iv	115.44 (6)
O1ⁱ—Ca1—O2	156.06 (8)	O1ⁱⁱ—Ca1—Ca1^iv	115.44 (6)
O1ⁱⁱ—Ca1—O2	91.88 (8)	O2ⁱⁱⁱ—Ca1—Ca1^iv	88.51 (6)
O2ⁱⁱⁱ—Ca1—O2	88.60 (12)	O2—Ca1—Ca1^iv	88.51 (6)
O1ⁱ—Ca1—O3	70.48 (7)	O3—Ca1—Ca1^iv	171.90 (7)
O1ⁱⁱ—Ca1—O3	70.48 (7)	O3^iv—Ca1—Ca1^iv	43.17 (8)
O2ⁱⁱⁱ—Ca1—O3	85.70 (8)	O1ⁱⁱⁱ—Ca1—Ca1^iv	39.79 (5)
O2—Ca1—O3	85.70 (8)	O1—Ca1—Ca1^iv	39.79 (5)
O1ⁱ—Ca1—O3^iv	82.59 (8)	C1ⁱⁱⁱ—Ca1—Ca1^iv	64.56 (7)
O1ⁱⁱ—Ca1—O3^iv	82.59 (8)	C1—Ca1—Ca1^iv	64.56 (7)
O2ⁱⁱⁱ—Ca1—O3^iv	118.06 (7)	Ca1ⁱ—Ca1—Ca1^iv	144.47 (4)
O2—Ca1—O3^iv	118.06 (7)	C1—O1—Ca1^iv	154.2 (2)
O3—Ca1—O3^iv	144.93 (11)	C1—O1—Ca1	91.54 (19)
O1ⁱ—Ca1—O1ⁱⁱⁱ	97.25 (7)	Ca1^iv—O1—Ca1	96.69 (7)
O1ⁱⁱ—Ca1—O1ⁱⁱⁱ	149.97 (5)	C1—O2—Ca1	94.01 (18)
O2ⁱⁱⁱ—Ca1—O1ⁱⁱⁱ	52.19 (7)	S1—O3—Ca1	139.05 (18)
O2—Ca1—O1ⁱⁱⁱ	101.88 (8)	S1—O3—Ca1ⁱ	127.75 (19)
O3—Ca1—O1ⁱⁱⁱ	136.43 (6)	Ca1—O3—Ca1ⁱ	93.19 (9)
O3^iv—Ca1—O1ⁱⁱⁱ	67.37 (7)	O2—C1—O1	121.8 (3)
O1ⁱ—Ca1—O1	149.97 (5)	O2—C1—C2	120.6 (3)
O1ⁱⁱ—Ca1—O1	97.25 (7)	O1—C1—C2	117.6 (3)
O2ⁱⁱⁱ—Ca1—O1	101.88 (8)	O2—C1—Ca1	60.08 (16)
O2—Ca1—O1	52.19 (7)	O1—C1—Ca1	62.08 (16)
O3—Ca1—O1	136.43 (6)	C2—C1—Ca1	173.4 (2)
O3^iv—Ca1—O1	67.37 (7)	C3—C2—C7	118.8 (3)
O1ⁱⁱⁱ—Ca1—O1	71.78 (10)	C3—C2—C1	120.2 (3)
O1ⁱ—Ca1—C1ⁱⁱⁱ	93.35 (8)	C7—C2—C1	121.1 (3)
O1ⁱⁱ—Ca1—C1ⁱⁱⁱ	170.72 (8)	C4—C3—C2	120.4 (3)
O2ⁱⁱⁱ—Ca1—C1ⁱⁱⁱ	25.91 (8)	C4—C3—H3	119.8
O2—Ca1—C1ⁱⁱⁱ	97.39 (9)	C2—C3—H3	119.8
O3—Ca1—C1ⁱⁱⁱ	110.58 (8)	C5—C4—C3	120.3 (4)
O3^iv—Ca1—C1ⁱⁱⁱ	92.57 (8)	C5—C4—H4	119.9
O1ⁱⁱⁱ—Ca1—C1ⁱⁱⁱ	26.38 (7)	C3—C4—H4	119.9
O1—Ca1—C1ⁱⁱⁱ	88.11 (8)	C6—C5—C4	120.2 (4)
O1ⁱ—Ca1—C1	170.72 (8)	C6—C5—H5	119.9
O1ⁱⁱ—Ca1—C1	93.35 (8)	C4—C5—H5	119.9
O2ⁱⁱⁱ—Ca1—C1	97.39 (9)	C5—C6—C7	119.9 (3)
O2—Ca1—C1	25.91 (8)	C5—C6—H6	120.1
O3—Ca1—C1	110.58 (8)	C7—C6—H6	120.1
O3^iv—Ca1—C1	92.57 (8)	C2—C7—C6	120.4 (3)
O1ⁱⁱⁱ—Ca1—C1	88.11 (8)	C2—C7—H7	119.8
O1—Ca1—C1	26.38 (7)	C6—C7—H7	119.8
C1ⁱⁱⁱ—Ca1—C1	94.77 (13)	S1—C8—H8A	109.5
O1ⁱ—Ca1—Ca1ⁱ	43.52 (5)	S1—C8—H8B	109.5
O1ⁱⁱ—Ca1—Ca1ⁱ	43.52 (5)	H8A—C8—H8B	109.5
O2ⁱⁱⁱ—Ca1—Ca1ⁱ	115.90 (7)	S1—C8—H8C	109.5
O2—Ca1—Ca1ⁱ	115.90 (7)	H8A—C8—H8C	109.5
O3—Ca1—Ca1ⁱ	43.63 (7)	H8B—C8—H8C	109.5
O3^iv—Ca1—Ca1ⁱ	101.29 (8)	O3—S1—C8ⁱⁱⁱ	105.78 (14)
O1ⁱⁱⁱ—Ca1—Ca1ⁱ	140.76 (5)	O3—S1—C8	105.78 (14)
O1—Ca1—Ca1ⁱ	140.76 (5)	C8ⁱⁱⁱ—S1—C8	98.4 (3)

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

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the benzoate ring.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···Cg	0.96	2.84	3.790 (4)	169

Acknowledgements

This work was partly supported by the State Fund for Fundamental Research of Ukraine (project 54.3/005).

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