4-Amidino­pyridinium hexa­chlorido­stannate(IV) dihydrate

Ghallab, R.; Bougueria, H.; Merazig, H.

doi:10.1107/S241431462200195X

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 3| March 2022| x220195

https://doi.org/10.1107/S241431462200195X

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4-Amidinopyridinium hexachloridostannate(IV) dihydrate

Rochdi Ghallab,^a ^* Hassiba Bougueria ^b and Hocine Merazig ^a

^aEnvironmental Molecular and Structural Chemistry Research Unit, University of Constantine-1, 25000, Constantine, Algeria, and ^bCentre Universitaire Abdelhafid Boussouf - Mila, Algeria
^*Correspondence e-mail: rochdi.ghallab@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 12 January 2022; accepted 18 February 2022; online 3 March 2022)

In the title hydrated molecular salt {systematic name: 4-[amino(iminiumyl)methyl]pyridin-1-ium hexachloridostannate(IV) dihydrate}, (C₆H₉N₃)[SnCl₆]·2H₂O, the tin atom lies on a crystallographic inversion centre and the organic cation shows whole-molecule disorder. Numerous N—H⋯O, N—H⋯Cl and O—H⋯Cl hydrogen bonds link the components in the crystal.

Keywords: crystal structure; hexachloridostannate(IV); 4-amidinopyridinium.

CCDC reference: 2153109

Structure description

The title hydrated molecular salt, with formula (C₆H₉N₃)·[SnCl₆]·2H₂O, crystallizes in the triclinic space group P $[\overline{1}]$ . The asymmetric unit is constituted by a Sn_0.5Cl₃ fragment (Sn site symmetry $[\overline{1}]$ ), a 4-amidinopyridinium cation (twice protonated at N1 and N2) and a water molecule, as shown in Fig. 1.

Figure 1
The molecular structure showing 30% displacement ellipsoids.

The cation shows whole-molecule disorder about an inversion centre and the water molecule is disordered over adjacent positions (O⋯O = 1.13 Å) and there is also static disorder of two of the chloride ions of the anion. With the exception of Cl3, where the occupancy ratio is 0.67/0.33 (for Cl3A/Cl3B), each disordered atom is shared between two crystallographic sites with occupancies of 0.50. There are no abnormalities in the bond lengths and angles and they are comparable to those of similar types (Liu et al., 2011 ; Ghallab et al., 2020 ).

In the extended structure, cationic and anionic layers occur, with water molecules intercalating between them as shown in the projection of the structure onto the ac and bc planes (Figs. 2 and 3). Cohesion in the crystal is ensured by numerous hydrogen bonds (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1WAⁱ	0.86	1.96	2.760 (15)	154
N1—H1⋯O1WBⁱ	0.86	1.87	2.649 (15)	149
N2—H2A⋯Cl2ⁱⁱ	0.86	2.68	3.431 (11)	147
N3—H3A⋯O1WAⁱⁱⁱ	0.86	2.13	2.961 (16)	162
N3—H3A⋯O1WBⁱⁱⁱ	0.86	1.96	2.795 (16)	163
N3—H3B⋯Cl1A^iv	0.86	2.69	3.093 (16)	110
N3—H3B⋯Cl3B^iv	0.86	2.56	3.420 (16)	175
O1WA—H1WA⋯Cl2^v	0.85	2.77	3.415 (8)	134
O1WA—H1WB⋯Cl3A^vi	0.85	2.41	3.154 (9)	147
O1WB—H1WC⋯Cl1A^v	0.85	2.60	3.305 (10)	142
O1WB—H1WC⋯Cl1B^v	0.85	2.36	3.085 (10)	144
O1WB—H1WC⋯Cl1A^vii	0.85	2.69	3.251 (12)	124
O1WB—H1WC⋯Cl1B^vii	0.85	2.83	3.396 (13)	126
C1—H1A⋯Cl3A^viii	0.93	2.67	3.561 (17)	161
C1—H1A⋯Cl3B^viii	0.93	2.43	3.356 (17)	174
C5—H5⋯Cl1A^vii	0.93	2.80	3.674 (12)	157
C5—H5⋯Cl1B^vii	0.93	2.56	3.385 (12)	149
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) x, y+1, z+1; (vi) x, y+2, z+1; (vii) ; (viii) .

Figure 2
Projection of the crystal packing on the ac plane.

Figure 3
Projection of the crystal packing on the bc plane.

Synthesis and crystallization

Following the method of preparation described in the literature (Bouchene et al., 2018 ), the compound was synthesized via the aqueous technique. A millimeter-sized transparent crystal was formed after three months of slow evaporation at ambient temperature.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The disordered atoms were treated with constraints on distances and angles (by the SAME command and PART options). With the exception of Cl3, where the ratio is 0.67/0.33, each disordered atom is shared between two crystallographic sites with occupancy rates of 0.50.

Table 2
Experimental details

Crystal data
Chemical formula	(C₆H₉N₃)[SnCl₆]·2H₂O
M_r	490.58
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	7.4224 (13), 7.4518 (11), 8.4986 (16)
α, β, γ (°)	105.726 (7), 97.426 (9), 112.383 (7)
V (Å³)	403.85 (12)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	2.57
Crystal size (mm)	0.17 × 0.13 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.676, 0.754
No. of measured, independent and observed [I > 2σ(I)] reflections	10469, 2442, 1889
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.085, 1.15
No. of reflections	2442
No. of parameters	154
No. of restraints	53
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.22, −1.35
Computer programs: APEX2 and SAINT (Bruker, 2016), olex2.solve (Bourhis et al., 2015 ), SHELXL (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2153109

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S241431462200195X/hb4399sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431462200195X/hb4399Isup2.hkl

checkCIF report

Computing details top

Data collection: SAINT (Bruker, 2016); cell refinement: APEX2 (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: olex2.solve (Bourhis et al., 2015); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

4-[Amino(iminiumyl)methyl]pyridin-1-ium hexachloridostannate(IV) dihydrate top

Crystal data top

(C₆H₉N₃)[SnCl₆]·2H₂O	Z = 1
M_r = 490.58	F(000) = 238
Triclinic, P1	D_x = 2.017 Mg m⁻³
a = 7.4224 (13) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.4518 (11) Å	Cell parameters from 1889 reflections
c = 8.4986 (16) Å	θ = 5.0–30.5°
α = 105.726 (7)°	µ = 2.57 mm⁻¹
β = 97.426 (9)°	T = 296 K
γ = 112.383 (7)°	Block, colourless
V = 403.85 (12) Å³	0.17 × 0.13 × 0.11 mm

Data collection top

Bruker APEXII CCD diffractometer	1889 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.028
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 30.5°, θ_min = 5.0°
T_min = 0.676, T_max = 0.754	h = −10→10
10469 measured reflections	k = −10→10
2442 independent reflections	l = −12→12

Refinement top

Refinement on F²	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.0167P)² + 0.8036P] where P = (F_o² + 2F_c²)/3
S = 1.15	(Δ/σ)_max < 0.001
2442 reflections	Δρ_max = 1.22 e Å⁻³
154 parameters	Δρ_min = −1.35 e Å⁻³
53 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	Occ. (<1)
Sn1	0.000000	0.500000	0.500000	0.04673 (15)
Cl2	−0.0563 (2)	0.39683 (16)	0.19228 (11)	0.0675 (4)
Cl1B	0.2964 (10)	0.7987 (8)	0.5355 (8)	0.0640 (13)	0.5
Cl3B	0.2133 (9)	0.3209 (8)	0.5250 (8)	0.0607 (14)	0.33
Cl1A	0.3472 (10)	0.7539 (8)	0.5316 (7)	0.0612 (12)	0.5
Cl3A	0.1294 (5)	0.2493 (4)	0.4986 (4)	0.0711 (9)	0.67
C3	0.470 (3)	1.475 (3)	0.998 (2)	0.039 (3)	0.5
C4	0.5060 (13)	1.6621 (11)	1.1133 (9)	0.0462 (19)	0.5
H4	0.465642	1.667299	1.212925	0.055*	0.5
C5	0.5998 (16)	1.8390 (14)	1.0820 (13)	0.062 (2)	0.5
H5	0.618436	1.965008	1.157590	0.074*	0.5
N1	0.666 (2)	1.8325 (16)	0.9421 (16)	0.081 (3)	0.5
H1	0.734961	1.946420	0.927815	0.097*	0.5
C1	0.625 (3)	1.6494 (18)	0.8222 (18)	0.088 (5)	0.5
H1A	0.661958	1.646634	0.721374	0.105*	0.5
C2	0.5291 (16)	1.4684 (15)	0.8517 (10)	0.059 (2)	0.5
H2	0.504299	1.342167	0.772395	0.071*	0.5
C6	0.3621 (14)	1.2750 (14)	1.0199 (13)	0.053 (2)	0.5
N2	0.227 (2)	1.1247 (14)	0.8868 (15)	0.099 (4)	0.5
H2A	0.153059	1.008127	0.895028	0.119*	0.5
H2B	0.211066	1.142421	0.790976	0.119*	0.5
N3	0.397 (2)	1.2666 (18)	1.1621 (18)	0.089 (5)	0.5
H3A	0.329233	1.154902	1.180199	0.106*	0.5
H3B	0.488756	1.372373	1.243683	0.106*	0.5
O1WA	0.0858 (13)	1.8847 (11)	1.1795 (10)	0.069 (2)	0.5
H1WA	0.119362	1.785736	1.167388	0.103*	0.5
H1WB	0.101422	1.945036	1.284078	0.103*	0.5
O1WB	0.2372 (18)	1.8798 (12)	1.1997 (9)	0.091 (3)	0.5
H1WC	0.297336	1.913349	1.302646	0.137*	0.5
H1WD	0.110355	1.828348	1.187657	0.137*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.0750 (3)	0.02256 (16)	0.02323 (16)	0.00466 (17)	0.00409 (16)	0.00756 (12)
Cl2	0.1091 (10)	0.0438 (5)	0.0264 (4)	0.0154 (6)	0.0077 (5)	0.0086 (4)
Cl1B	0.064 (3)	0.046 (2)	0.0547 (17)	−0.0007 (15)	−0.0018 (17)	0.0211 (17)
Cl3B	0.067 (4)	0.051 (3)	0.056 (2)	0.025 (2)	−0.004 (2)	0.019 (2)
Cl1A	0.072 (3)	0.0429 (19)	0.0492 (14)	0.0061 (14)	0.0161 (18)	0.0157 (13)
Cl3A	0.111 (3)	0.0488 (14)	0.0504 (13)	0.0290 (14)	0.0200 (16)	0.0222 (12)
C3	0.041 (10)	0.040 (8)	0.038 (3)	0.018 (7)	0.013 (5)	0.018 (4)
C4	0.057 (5)	0.041 (4)	0.033 (3)	0.014 (4)	0.012 (3)	0.013 (3)
C5	0.058 (6)	0.048 (5)	0.073 (6)	0.019 (5)	0.020 (5)	0.017 (4)
N1	0.096 (9)	0.065 (6)	0.116 (9)	0.038 (6)	0.054 (8)	0.064 (7)
C1	0.137 (12)	0.087 (9)	0.092 (9)	0.067 (10)	0.081 (8)	0.058 (8)
C2	0.083 (7)	0.075 (6)	0.039 (4)	0.053 (6)	0.023 (4)	0.017 (4)
C6	0.049 (6)	0.045 (4)	0.064 (6)	0.019 (4)	0.018 (5)	0.020 (4)
N2	0.120 (10)	0.042 (4)	0.094 (8)	0.009 (6)	0.017 (7)	0.005 (5)
N3	0.094 (9)	0.045 (6)	0.092 (9)	−0.005 (6)	−0.006 (7)	0.037 (6)
O1WA	0.094 (6)	0.049 (4)	0.053 (4)	0.014 (4)	0.029 (4)	0.023 (3)
O1WB	0.133 (8)	0.045 (4)	0.044 (4)	−0.006 (5)	−0.005 (5)	0.018 (3)

Geometric parameters (Å, º) top

Sn1—Cl2	2.4470 (10)	C3—C4	1.372 (15)
Sn1—Cl2ⁱ	2.4470 (10)	C3—C2	1.366 (15)
Sn1—Cl1Bⁱ	2.371 (6)	C3—C6	1.48 (2)
Sn1—Cl1B	2.371 (6)	C4—C5	1.354 (10)
Sn1—Cl3Bⁱ	2.451 (7)	C5—N1	1.339 (11)
Sn1—Cl3B	2.451 (7)	N1—C1	1.358 (12)
Sn1—Cl1A	2.475 (7)	C1—C2	1.374 (12)
Sn1—Cl1Aⁱ	2.475 (7)	C6—N2	1.306 (14)
Sn1—Cl3Aⁱ	2.402 (4)	C6—N3	1.226 (16)
Sn1—Cl3A	2.402 (4)

Cl2—Sn1—Cl2ⁱ	180.0	Cl1B—Sn1—Cl3Aⁱ	78.11 (14)
Cl2—Sn1—Cl3Bⁱ	87.17 (16)	Cl3B—Sn1—Cl3Bⁱ	180.0
Cl2ⁱ—Sn1—Cl3Bⁱ	92.83 (16)	Cl3B—Sn1—Cl1Aⁱ	105.72 (16)
Cl2—Sn1—Cl3B	92.83 (16)	Cl3Bⁱ—Sn1—Cl1Aⁱ	74.28 (16)
Cl2ⁱ—Sn1—Cl3B	87.17 (16)	Cl3A—Sn1—Cl2	89.55 (8)
Cl2ⁱ—Sn1—Cl1A	90.98 (14)	Cl3Aⁱ—Sn1—Cl2	90.45 (8)
Cl2—Sn1—Cl1A	89.02 (14)	Cl3A—Sn1—Cl1A	88.16 (12)
Cl2—Sn1—Cl1Aⁱ	90.98 (14)	Cl3Aⁱ—Sn1—Cl1A	91.84 (12)
Cl2ⁱ—Sn1—Cl1Aⁱ	89.02 (14)	Cl3Aⁱ—Sn1—Cl3A	180.0
Cl1B—Sn1—Cl2ⁱ	89.79 (15)	C4—C3—C6	123.3 (12)
Cl1B—Sn1—Cl2	90.21 (15)	C2—C3—C4	119.7 (15)
Cl1Bⁱ—Sn1—Cl2	89.79 (15)	C2—C3—C6	117.0 (12)
Cl1Bⁱ—Sn1—Cl2ⁱ	90.21 (15)	C5—C4—C3	120.1 (10)
Cl1Bⁱ—Sn1—Cl1B	180.0	N1—C5—C4	120.0 (9)
Cl1B—Sn1—Cl3B	87.92 (17)	C5—N1—C1	121.3 (9)
Cl1Bⁱ—Sn1—Cl3B	92.08 (17)	N1—C1—C2	119.2 (10)
Cl1Bⁱ—Sn1—Cl3Bⁱ	87.92 (17)	C3—C2—C1	119.5 (11)
Cl1B—Sn1—Cl3Bⁱ	92.08 (17)	N2—C6—C3	116.5 (11)
Cl1B—Sn1—Cl1Aⁱ	166.23 (14)	N3—C6—C3	118.0 (11)
Cl1Bⁱ—Sn1—Cl1Aⁱ	13.77 (14)	N3—C6—N2	125.4 (11)
Cl1Bⁱ—Sn1—Cl3Aⁱ	101.89 (14)

C5—N1—C1—C2	−6 (3)	C2—C3—C6—N2	−42 (2)
C1—N1—C5—C4	6 (2)	C2—C3—C6—N3	142.5 (16)
N1—C1—C2—C3	2 (3)	C4—C3—C6—N2	135.9 (17)
C1—C2—C3—C4	0 (3)	C4—C3—C6—N3	−40 (3)
C1—C2—C3—C6	178.1 (16)	C2—C3—C4—C5	0 (3)
C6—C3—C4—C5	−177.7 (14)	C3—C4—C5—N1	−3 (2)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1WAⁱⁱ	0.86	1.96	2.760 (15)	154
N1—H1···O1WBⁱⁱ	0.86	1.87	2.649 (15)	149
N2—H2A···Cl2ⁱ	0.86	2.68	3.431 (11)	147
N3—H3A···O1WAⁱⁱⁱ	0.86	2.13	2.961 (16)	162
N3—H3A···O1WBⁱⁱⁱ	0.86	1.96	2.795 (16)	163
N3—H3B···Cl1A^iv	0.86	2.69	3.093 (16)	110
N3—H3B···Cl3B^iv	0.86	2.56	3.420 (16)	175
O1WA—H1WA···Cl2^v	0.85	2.77	3.415 (8)	134
O1WA—H1WB···Cl3A^vi	0.85	2.41	3.154 (9)	147
O1WB—H1WC···Cl1A^v	0.85	2.60	3.305 (10)	142
O1WB—H1WC···Cl1B^v	0.85	2.36	3.085 (10)	144
O1WB—H1WC···Cl1A^vii	0.85	2.69	3.251 (12)	124
O1WB—H1WC···Cl1B^vii	0.85	2.83	3.396 (13)	126
C1—H1A···Cl3A^viii	0.93	2.67	3.561 (17)	161
C1—H1A···Cl3B^viii	0.93	2.43	3.356 (17)	174
C5—H5···Cl1A^vii	0.93	2.80	3.674 (12)	157
C5—H5···Cl1B^vii	0.93	2.56	3.385 (12)	149

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+4, −z+2; (iii) x, y−1, z; (iv) −x+1, −y+2, −z+2; (v) x, y+1, z+1; (vi) x, y+2, z+1; (vii) −x+1, −y+3, −z+2; (viii) −x+1, −y+2, −z+1.

Acknowledgements

Thanks are due to DRSDT–Algeria for support.

Funding information

Funding for this research was provided by: Unité de recherche de chimie de l'environnement, moléculaire et structurale UR.CHEMS; Direction Générale de la Recherche Scientifique et du Developpement Technologique DGRSDT Algérie.

References

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