Bis(2-carb­oxy­quinolinium) hexa­chlorido­stan­nate(IV) dihydrate

Benhamada, M.S.E.; Benlatreche, T.; Ghallab, R.; Dénès, G.; Merazig, H.

doi:10.1107/S2414314624008265

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 9| Part 8| August 2024| x240826

https://doi.org/10.1107/S2414314624008265

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Bis(2-carboxyquinolinium) hexachloridostannate(IV) dihydrate

Mohamed Siradj Eddine Benhamada,^a ^* Tarek Benlatreche,^a Rochdi Ghallab,^b George Dénès ^c and Hocine Merazig ^a

^aEnvironmental Molecular and Structural Chemistry Research Unit, University of Constantine-1, 25000, Constantine, Algeria, ^bEcole Nationale Polytechnique de Constantine (ENPC), Laboratoire de Technologie des Matériaux Avancés, Algeria, and ^cLaboratory of Solid State Chemistry and Mössbauer Spectroscopy, Department of Chemistry and Biochemistry, Concordia University, 7141 Sherbrooke St. West, Monreal, H4B 1R6 QC, Canada
^*Correspondence e-mail: mbenhamada@hotmail.fr

Edited by M. Weil, Vienna University of Technology, Austria (Received 8 July 2024; accepted 21 August 2024; online 30 August 2024)

In the hydrated title salt, (C₁₀H₈NO₂)₂[SnCl₆]·2H₂O, the tin(IV) atom is located about a center of inversion. In the crystal structure, the organic cation, the octahedral inorganic anion and the water molecule of crystallization interact through O—H⋯O, N—H⋯O and O—H⋯Cl hydrogen bonds, supplemented by weak π–π stacking between neighboring cations, and C—Cl⋯π interactions.

Keywords: crystal structure; [SnCl₆]^2– anion; hydrogen-bonding; π–π stacking.

CCDC reference: 2378953

Structure description

The crystal structure determination of the title compound, (I), was undertaken as part of studies of organic–inorganic hybrid materials, which may exhibit various interesting physical properties such as dielectric characteristics (Hajlaoui et al., 2013 ).

The asymmetric unit of (I) comprises half of an octahedral [SnCl₆]^2– anion (the whole anion being completed by inversion symmetry), one 2-carboxyquinolinium cation, and a water molecule of crystallization (Fig. 1).

Figure 1
View of the molecular entities in (I) with the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. [Symmetry code: (i) −x, −y, −z].

The Sn^IV atom is coordinated by six chlorine atoms, forming a slightly distorted octahedron. The lengths of the Sn—Cl bonds in the hexachloridostannate(IV) anion range from 2.4180 (3) to 2.4406 (3) Å and the Cl—Sn—Cl bond angles deviate only by approximately 1° from ideal values, similar to those reported in the literature (Ghallab et al., 2020 ; Rademeyer, 2004 ; Billing et al., 2007 ).

In the 2-carboxyquinolinium cation, the C—C bond lengths range from 1.364 (2) to 1.5029 (15) Å and the C—N bond lengths are 1.3282 (14) and 1.3649 (17) Å; the angles vary between 115.14 (10) (N1—C2—C1) and 126.71 (11)° (O1—C—O2). These values are similar compared with related cations with protonated aromatic N atoms (Gelmboldt et al., 2007 ; Smith et al., 2004 , 2008 ). The cation in (I) is not planar, as indicated by a dihedral angle between the quinoline ring and the carboxy group of 11.61 (9)°.

Apart from Coulombic forces, the cohesion in the crystal structure is ensured by classical hydrogen bonds between the carboxyl group as donor and the water molecule as acceptor groups, and by interactions between the protonated quinoline N atom and the non-protonated O atom of the carboxyl group of a neighboring molecule. Further interactions involve the water molecule and the hexachloridostannate anion (Table 1, Fig. 2). There are also π–π stacking interactions between neighboring cations [3.7898 (8) Å, slippage 1.678 Å; Fig. 3a] and Cl⋯π interactions [3.5633 (6) Å; Fig. 3b].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3	0.82	1.75	2.5684 (14)	176
N1—H1A⋯O2ⁱ	0.832 (17)	2.028 (17)	2.8348 (13)	163.4 (15)
O3—H3A⋯Cl1	0.85	2.46	3.2048 (11)	146
O3—H3B⋯Cl2ⁱⁱ	0.85	2.61	3.3708 (11)	150
Symmetry codes: (i) ; (ii) .

Figure 2
O—H⋯O, N—H⋯O and O—H⋯Cl hydrogen-bonding interactions in the crystal structure of (I) indicated by dashed lines. Symmetry codes refer to Table 1

Figure 3
(a) π–π stacking interactions and (b) Cl⋯π interactions in the crystal structure of (I).

Synthesis and crystallization

Tin(II) chloride dihydrate (SnCl₂·2H₂O) was mixed with quinaldic acid (C₁₀H₇NO₂) in a 1:2 molar ratio, along with a few drops of hydrochloric acid in distilled water. The mixture was refluxed for one h at 343 K. After two weeks of slow solvent evaporation at room temperature, colorless single crystals suitable for X-ray analysis were obtained.

Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 2. The H atom bound to the N atom was refined freely. 14 reflections were omitted from the refinement because they were obstructed from the beam stop.

Table 2
Experimental details

Crystal data
Chemical formula	(C₁₀H₈NO₂)[SnCl₆]·2H₂O
M_r	715.77
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	8.3220 (4), 9.2704 (4), 9.4248 (4)
α, β, γ (°)	108.101 (2), 99.515 (2), 99.749 (2)
V (Å³)	662.46 (5)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	1.61
Crystal size (mm)	0.10 × 0.09 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.851, 0.879
No. of measured, independent and observed [I > 2σ(I)] reflections	19467, 3262, 3199
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.013, 0.033, 1.08
No. of reflections	3262
No. of parameters	168
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.25
Computer programs: APEX2 and SAINT (Bruker, 2013 ), OLEX2.solve (Bourhis et al., 2015 ), SHELXL (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2378953

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314624008265/wm4218sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314624008265/wm4218Isup4.hkl

checkCIF report

Computing details top

Bis(2-carboxyquinolinium) hexachloridostannate(IV) dihydrate top

Crystal data top

(C₁₀H₈NO₂)[SnCl₆]·2H₂O	Z = 1
M_r = 715.77	F(000) = 354
Triclinic, P1	D_x = 1.794 Mg m⁻³
a = 8.3220 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.2704 (4) Å	Cell parameters from 9611 reflections
c = 9.4248 (4) Å	θ = 3.7–48.2°
α = 108.101 (2)°	µ = 1.61 mm⁻¹
β = 99.515 (2)°	T = 296 K
γ = 99.749 (2)°	Plate, yellow
V = 662.46 (5) Å³	0.10 × 0.09 × 0.08 mm

Data collection top

Bruker APEXII CCD diffractometer	3199 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.015
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 28.3°, θ_min = 4.8°
T_min = 0.851, T_max = 0.879	h = −11→11
19467 measured reflections	k = −12→12
3262 independent reflections	l = −12→12

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.013	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.033	w = 1/[σ²(F_o²) + (0.013P)² + 0.3169P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
3262 reflections	Δρ_max = 0.41 e Å⁻³
168 parameters	Δρ_min = −0.25 e Å⁻³

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
Sn1	0.000000	0.000000	0.000000	0.01307 (3)
Cl1	0.12549 (3)	0.26567 (3)	0.17700 (3)	0.01985 (6)
Cl2	−0.27553 (3)	0.05974 (3)	−0.01450 (3)	0.02261 (6)
Cl3	−0.03577 (4)	−0.08014 (3)	0.21592 (3)	0.02122 (6)
O2	0.82893 (11)	0.48826 (10)	0.04894 (9)	0.02362 (17)
O1	0.70770 (11)	0.47285 (12)	0.24138 (10)	0.02734 (19)
H1	0.625567	0.421382	0.171718	0.041*
O3	0.44565 (12)	0.30407 (12)	0.03220 (12)	0.0316 (2)
H3A	0.358189	0.328438	0.058776	0.047*
H3B	0.438485	0.207555	0.016123	0.047*
N1	1.12611 (12)	0.62982 (11)	0.25392 (11)	0.01629 (17)
C2	0.98812 (14)	0.60663 (12)	0.30529 (12)	0.0171 (2)
C1	0.83151 (14)	0.51554 (13)	0.18355 (13)	0.0183 (2)
C3	0.99422 (16)	0.66408 (14)	0.46178 (13)	0.0213 (2)
H3	0.897184	0.649793	0.497561	0.026*
C6	1.28072 (14)	0.70531 (13)	0.34788 (13)	0.0181 (2)
C9	1.59120 (17)	0.85434 (15)	0.54706 (16)	0.0299 (3)
H9	1.696466	0.902964	0.612341	0.036*
C8	1.57523 (16)	0.79829 (15)	0.38631 (16)	0.0277 (3)
H8	1.670263	0.812255	0.347661	0.033*
C7	1.42258 (15)	0.72382 (14)	0.28635 (14)	0.0230 (2)
H7	1.413118	0.686630	0.180899	0.028*
C5	1.29308 (15)	0.76284 (13)	0.50879 (13)	0.0208 (2)
C10	1.45388 (17)	0.83779 (15)	0.60721 (14)	0.0274 (3)
H10	1.465775	0.875747	0.712974	0.033*
C4	1.14626 (16)	0.74234 (14)	0.56255 (13)	0.0230 (2)
H4	1.151849	0.782030	0.667260	0.028*
H1A	1.119 (2)	0.5947 (19)	0.160 (2)	0.026 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.01189 (5)	0.01279 (5)	0.01377 (5)	0.00232 (3)	0.00262 (3)	0.00407 (4)
Cl1	0.02182 (13)	0.01429 (11)	0.01922 (12)	0.00029 (9)	0.00555 (10)	0.00173 (9)
Cl2	0.01509 (12)	0.02717 (14)	0.02324 (13)	0.00878 (10)	0.00250 (10)	0.00457 (11)
Cl3	0.02591 (13)	0.02106 (13)	0.01886 (12)	0.00433 (10)	0.00618 (10)	0.01006 (10)
O2	0.0205 (4)	0.0291 (4)	0.0164 (4)	0.0005 (3)	0.0033 (3)	0.0045 (3)
O1	0.0201 (4)	0.0358 (5)	0.0226 (4)	−0.0002 (4)	0.0071 (3)	0.0077 (4)
O3	0.0207 (4)	0.0325 (5)	0.0368 (5)	−0.0007 (4)	0.0106 (4)	0.0069 (4)
N1	0.0185 (4)	0.0158 (4)	0.0123 (4)	0.0036 (3)	0.0020 (3)	0.0028 (3)
C2	0.0197 (5)	0.0152 (5)	0.0164 (5)	0.0049 (4)	0.0035 (4)	0.0053 (4)
C1	0.0182 (5)	0.0175 (5)	0.0187 (5)	0.0047 (4)	0.0046 (4)	0.0051 (4)
C3	0.0257 (6)	0.0217 (5)	0.0175 (5)	0.0074 (4)	0.0075 (4)	0.0063 (4)
C6	0.0196 (5)	0.0150 (5)	0.0167 (5)	0.0038 (4)	0.0005 (4)	0.0037 (4)
C9	0.0239 (6)	0.0260 (6)	0.0301 (6)	0.0012 (5)	−0.0089 (5)	0.0069 (5)
C8	0.0201 (6)	0.0267 (6)	0.0330 (7)	0.0044 (5)	0.0023 (5)	0.0084 (5)
C7	0.0210 (6)	0.0235 (6)	0.0213 (5)	0.0036 (4)	0.0029 (4)	0.0051 (5)
C5	0.0258 (6)	0.0164 (5)	0.0164 (5)	0.0044 (4)	−0.0003 (4)	0.0037 (4)
C10	0.0310 (7)	0.0246 (6)	0.0188 (5)	0.0035 (5)	−0.0053 (5)	0.0042 (5)
C4	0.0326 (6)	0.0216 (5)	0.0132 (5)	0.0078 (5)	0.0035 (4)	0.0039 (4)

Geometric parameters (Å, º) top

Sn1—Cl3	2.4180 (3)	C2—C1	1.5029 (15)
Sn1—Cl3ⁱ	2.4180 (3)	C3—C4	1.3758 (17)
Sn1—Cl1	2.4370 (3)	C3—H3	0.9300
Sn1—Cl1ⁱ	2.4370 (3)	C6—C7	1.4067 (17)
Sn1—Cl2ⁱ	2.4406 (3)	C6—C5	1.4220 (15)
Sn1—Cl2	2.4406 (3)	C9—C10	1.364 (2)
O2—C1	1.2099 (14)	C9—C8	1.4155 (19)
O1—C1	1.3026 (14)	C9—H9	0.9300
O1—H1	0.8200	C8—C7	1.3715 (17)
O3—H3A	0.8511	C8—H8	0.9300
O3—H3B	0.8496	C7—H7	0.9300
N1—C2	1.3282 (14)	C5—C4	1.4041 (18)
N1—C6	1.3649 (14)	C5—C10	1.4171 (17)
N1—H1A	0.832 (17)	C10—H10	0.9300
C2—C3	1.3927 (15)	C4—H4	0.9300

Cl3—Sn1—Cl3ⁱ	179.999 (12)	O1—C1—C2	112.24 (10)
Cl3—Sn1—Cl1	89.336 (10)	C4—C3—C2	118.86 (11)
Cl3ⁱ—Sn1—Cl1	90.665 (10)	C4—C3—H3	120.6
Cl3—Sn1—Cl1ⁱ	90.663 (10)	C2—C3—H3	120.6
Cl3ⁱ—Sn1—Cl1ⁱ	89.336 (10)	N1—C6—C7	120.61 (10)
Cl1—Sn1—Cl1ⁱ	180.0	N1—C6—C5	117.83 (10)
Cl3—Sn1—Cl2ⁱ	91.121 (10)	C7—C6—C5	121.56 (11)
Cl3ⁱ—Sn1—Cl2ⁱ	88.879 (10)	C10—C9—C8	120.70 (12)
Cl1—Sn1—Cl2ⁱ	90.704 (10)	C10—C9—H9	119.6
Cl1ⁱ—Sn1—Cl2ⁱ	89.295 (10)	C8—C9—H9	119.6
Cl3—Sn1—Cl2	88.879 (10)	C7—C8—C9	121.41 (12)
Cl3ⁱ—Sn1—Cl2	91.121 (10)	C7—C8—H8	119.3
Cl1—Sn1—Cl2	89.295 (10)	C9—C8—H8	119.3
Cl1ⁱ—Sn1—Cl2	90.706 (10)	C8—C7—C6	118.11 (11)
Cl2ⁱ—Sn1—Cl2	180.0	C8—C7—H7	120.9
C1—O1—H1	109.5	C6—C7—H7	120.9
H3A—O3—H3B	109.4	C4—C5—C10	123.20 (11)
C2—N1—C6	123.38 (10)	C4—C5—C6	118.68 (11)
C2—N1—H1A	118.5 (11)	C10—C5—C6	118.11 (11)
C6—N1—H1A	118.2 (11)	C9—C10—C5	120.10 (12)
N1—C2—C3	120.58 (10)	C9—C10—H10	120.0
N1—C2—C1	115.14 (10)	C5—C10—H10	120.0
C3—C2—C1	124.29 (10)	C3—C4—C5	120.63 (11)
O2—C1—O1	126.71 (11)	C3—C4—H4	119.7
O2—C1—C2	121.05 (10)	C5—C4—H4	119.7

C6—N1—C2—C3	1.99 (16)	N1—C6—C7—C8	−178.90 (11)
C6—N1—C2—C1	−177.71 (10)	C5—C6—C7—C8	0.58 (18)
N1—C2—C1—O2	−11.11 (16)	N1—C6—C5—C4	−1.35 (16)
C3—C2—C1—O2	169.20 (11)	C7—C6—C5—C4	179.15 (11)
N1—C2—C1—O1	168.63 (10)	N1—C6—C5—C10	178.41 (10)
C3—C2—C1—O1	−11.06 (16)	C7—C6—C5—C10	−1.09 (17)
N1—C2—C3—C4	−1.40 (17)	C8—C9—C10—C5	0.5 (2)
C1—C2—C3—C4	178.27 (11)	C4—C5—C10—C9	−179.70 (12)
C2—N1—C6—C7	178.92 (11)	C6—C5—C10—C9	0.55 (18)
C2—N1—C6—C5	−0.58 (16)	C2—C3—C4—C5	−0.54 (18)
C10—C9—C8—C7	−1.0 (2)	C10—C5—C4—C3	−177.86 (12)
C9—C8—C7—C6	0.47 (19)	C6—C5—C4—C3	1.89 (17)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3	0.82	1.75	2.5684 (14)	176
N1—H1A···O2ⁱⁱ	0.832 (17)	2.028 (17)	2.8348 (13)	163.4 (15)
O3—H3A···Cl1	0.85	2.46	3.2048 (11)	146
O3—H3B···Cl2ⁱ	0.85	2.61	3.3708 (11)	150
C3—H3···Cl1ⁱⁱⁱ	0.93	2.97	3.6014 (12)	127
C7—H7···O2ⁱⁱ	0.93	2.58	3.2850 (15)	133
C7—H7···O3ⁱⁱ	0.93	2.51	3.3144 (16)	146

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

Acknowledgements

Thanks are due to DRSDT-Algeria.

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