Di­thio­bis­(formamidinium) bis­(hydrogen sulfate)

Zouihri, H.; El Korchi, K.; Yamni, K.; Tijani, N.

doi:10.1107/S2414314618015407

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 11| November 2018| x181540

https://doi.org/10.1107/S2414314618015407

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Dithiobis(formamidinium) bis(hydrogen sulfate)

Hafid Zouihri,^a ^* Khadija El Korchi,^b Khalid Yamni ^a and Najib Tijani ^a

^aLaboratoire de Chimie des Matériaux et Biotechnologie des Produits Naturels, E.Ma.Me.P.S, Université Moulay Ismail, Faculté des Sciences, Meknès, Morocco, and ^bCenter of Nuclear Studies of Maamora (CENM) (CNESTEN), POB 1382, 10001 Kenitra, Morocco
^*Correspondence e-mail: hafid.zouihri@gmail.com

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 31 October 2018; accepted 31 October 2018; online 16 November 2018)

The crystal structure of the title salt, dithiobis(formamidinium) bis(hydrogen sulfate), C₂H₈N₄S₂²⁺·2HSO₄⁻, is built up from dithiobis(formamidinium) cations and hydrogensulfate anions. The anion is an almost regular tetrahedron. In the crystal, the anions and cations are linked by O—H⋯O and N—H⋯O hydrogen bonds, generating a three-dimensional network.

Keywords: crystal structure; dithiobis(formamidinium) salt; hydrogen bonds.

CCDC reference: 1876435

Structure description

The asymmetric unit of the title compound comprises one dithiobis(formamidinium) cation and two hydrogensulfate anions (Fig. 1). The bond distances and angles in the organic cations show no significant differences from those in a related compound involving the same organic groups (Zouihri, 2012 ). In the sulfate anion, the S—O bond lengths range from 1.436 (2) to 1.540 (2) Å. It is worth noting that the S3—O3 and S4—O7 distances are the longest because O4 and O7 are bonded to an H atom. The construction of the three-dimensional architecture (Fig. 2) is consolidated by O—H⋯O and N—H⋯O hydrogen bonds (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O6ⁱ	0.83 (2)	2.33 (3)	2.860 (3)	123 (3)
N3—H3A⋯O5	0.86 (2)	2.24 (2)	3.032 (3)	153 (3)
N3—H3A⋯O7ⁱⁱ	0.86 (2)	2.48 (3)	3.048 (3)	125 (3)
N1—H1A⋯O4	0.85 (2)	2.03 (2)	2.866 (3)	170 (3)
N1—H1B⋯O4ⁱⁱⁱ	0.85 (2)	2.14 (3)	2.813 (3)	136 (3)
N3—H3B⋯O2^iv	0.85 (2)	2.02 (2)	2.861 (3)	173 (3)
N2—H2A⋯O5^v	0.85 (2)	2.03 (2)	2.868 (3)	169 (3)
N2—H2B⋯O1	0.86 (2)	2.10 (2)	2.955 (3)	172 (3)
O3—H3⋯O1^vi	0.84 (2)	1.79 (2)	2.628 (2)	175 (5)
N4—H4B⋯O6	0.86 (2)	1.97 (2)	2.815 (3)	168 (4)
O7—H7⋯O8^vii	0.85 (2)	1.76 (2)	2.602 (3)	168 (5)
N4—H4A⋯O6ⁱ	0.83 (2)	2.33 (3)	2.860 (3)	123 (3)
N3—H3A⋯O5	0.86 (2)	2.24 (2)	3.032 (3)	153 (3)
N3—H3A⋯O7ⁱⁱ	0.86 (2)	2.48 (3)	3.048 (3)	125 (3)
N1—H1A⋯O4	0.85 (2)	2.03 (2)	2.866 (3)	170 (3)
N1—H1B⋯O4ⁱⁱⁱ	0.85 (2)	2.14 (3)	2.813 (3)	136 (3)
N3—H3B⋯O2^iv	0.85 (2)	2.02 (2)	2.861 (3)	173 (3)
N2—H2A⋯O5^v	0.85 (2)	2.03 (2)	2.868 (3)	169 (3)
N2—H2B⋯O1	0.86 (2)	2.10 (2)	2.955 (3)	172 (3)
O3—H3⋯O1^vi	0.84 (2)	1.79 (2)	2.628 (2)	175 (5)
N4—H4B⋯O6	0.86 (2)	1.97 (2)	2.815 (3)	168 (4)
O7—H7⋯O8^vii	0.85 (2)	1.76 (2)	2.602 (3)	168 (5)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x+1, y, z; (iii) -x+1, -y+1, -z+1; (iv) -x+2, -y+1, -z+1; (v) x, y-1, z; (vi) -x, -y, -z+1; (vii) -x+1, -y+2, -z.

Figure 1
Molecular view of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
Packing of the title compound. HSO₄⁻ anions are drawn as tetrahedra.

Synthesis and crystallization

Equimolar solutions of thiourea dissolved in methanol and aqueous sulfuric acid were mixed together and stirred for about 1 h. Crystals of the title compound were formed as the solvent evaporated over a few days at room temperature. They were filtered off, dried and repeatedly recrystallized as colourless prisms to enhance the purity of the product.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂H₈N₄S₂²⁺·2HO₄S⁻
M_r	346.38
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	5.1371 (2), 9.5237 (4), 12.9884 (6)
α, β, γ (°)	106.521 (2), 96.067 (2), 95.618 (2)
V (Å³)	600.32 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.83
Crystal size (mm)	0.21 × 0.17 × 0.12

Data collection
Diffractometer	Bruker X8 APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.844, 0.905
No. of measured, independent and observed [I > 2σ(I)] reflections	14082, 2892, 2625
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.100, 1.11
No. of reflections	2892
No. of parameters	203
No. of restraints	10
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.53
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1876435

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618015407/bt4077sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618015407/bt4077Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618015407/bt4077Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Dithiobis(formamidinium) bis(hydrogen sulfate) top

Crystal data top

C₂H₈N₄S₂²⁺·2HO₄S⁻	Z = 2
M_r = 346.38	F(000) = 356
Triclinic, P1	D_x = 1.916 Mg m⁻³
a = 5.1371 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.5237 (4) Å	Cell parameters from 278 reflections
c = 12.9884 (6) Å	θ = 1.2–31.2°
α = 106.521 (2)°	µ = 0.83 mm⁻¹
β = 96.067 (2)°	T = 293 K
γ = 95.618 (2)°	Prism, colourless
V = 600.32 (4) Å³	0.21 × 0.17 × 0.12 mm

Data collection top

Bruker X8 APEXII CCD area-detector diffractometer	2892 independent reflections
Radiation source: fine-focus sealed tube	2625 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω and φ scans	θ_max = 28.0°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −6→6
T_min = 0.844, T_max = 0.905	k = −12→12
14082 measured reflections	l = −17→17

Refinement top

Refinement on F²	10 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	All H-atom parameters refined
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.0418P)² + 0.7302P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
2892 reflections	Δρ_max = 0.34 e Å⁻³
203 parameters	Δρ_min = −0.53 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.

Refinement. H atoms were located from a difference map and were allowed to refine with O—H and N—H restrained to 0.86 (2) Å.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S3	0.22662 (11)	0.20042 (6)	0.54402 (4)	0.02342 (14)
S4	0.65664 (11)	0.82235 (6)	0.03004 (5)	0.02686 (14)
S1	0.98932 (13)	0.25348 (7)	0.22595 (5)	0.03335 (16)
S2	1.16936 (12)	0.46501 (7)	0.28680 (5)	0.03345 (16)
O3	−0.0718 (3)	0.19092 (19)	0.55064 (15)	0.0307 (4)
O6	0.6665 (5)	0.6659 (2)	−0.01074 (18)	0.0465 (5)
O1	0.2632 (4)	0.07584 (18)	0.45047 (15)	0.0346 (4)
O4	0.2952 (4)	0.33873 (18)	0.52202 (16)	0.0368 (4)
N2	0.6532 (5)	0.1055 (2)	0.30371 (18)	0.0327 (5)
O5	0.8279 (4)	0.8898 (2)	0.13095 (16)	0.0428 (5)
O2	0.3620 (4)	0.1912 (2)	0.64396 (17)	0.0461 (5)
N3	1.1645 (5)	0.6848 (3)	0.20735 (19)	0.0372 (5)
N1	0.6973 (4)	0.3550 (2)	0.38724 (18)	0.0298 (4)
O7	0.3693 (4)	0.8386 (3)	0.0499 (2)	0.0522 (6)
N4	0.8166 (5)	0.5039 (3)	0.1312 (2)	0.0454 (6)
O8	0.7077 (5)	0.8946 (3)	−0.05202 (18)	0.0538 (6)
C2	1.0307 (5)	0.5578 (3)	0.19805 (19)	0.0283 (5)
C1	0.7569 (5)	0.2408 (2)	0.31604 (18)	0.0250 (4)
H4A	0.744 (6)	0.418 (2)	0.117 (3)	0.047 (10)*
H3A	1.112 (6)	0.743 (3)	0.173 (2)	0.039 (8)*
H1A	0.585 (5)	0.340 (3)	0.427 (2)	0.027 (7)*
H1B	0.767 (6)	0.442 (2)	0.394 (3)	0.041 (9)*
H3B	1.303 (5)	0.715 (4)	0.254 (2)	0.051 (10)*
H2A	0.710 (6)	0.036 (3)	0.259 (2)	0.040 (8)*
H2B	0.530 (5)	0.091 (4)	0.341 (2)	0.042 (9)*
H3	−0.139 (9)	0.108 (3)	0.553 (4)	0.087 (15)*
H4B	0.749 (8)	0.553 (4)	0.091 (3)	0.073 (13)*
H7	0.329 (9)	0.925 (3)	0.057 (4)	0.081 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S3	0.0233 (3)	0.0185 (2)	0.0279 (3)	−0.00014 (18)	0.0047 (2)	0.0066 (2)
S4	0.0270 (3)	0.0264 (3)	0.0278 (3)	0.0039 (2)	0.0031 (2)	0.0091 (2)
S1	0.0396 (3)	0.0294 (3)	0.0326 (3)	0.0053 (2)	0.0146 (3)	0.0081 (2)
S2	0.0308 (3)	0.0365 (3)	0.0343 (3)	−0.0032 (2)	−0.0046 (2)	0.0182 (3)
O3	0.0252 (8)	0.0272 (8)	0.0410 (10)	0.0020 (7)	0.0101 (7)	0.0110 (7)
O6	0.0561 (13)	0.0266 (9)	0.0483 (12)	0.0042 (8)	−0.0073 (10)	0.0035 (8)
O1	0.0395 (10)	0.0209 (8)	0.0425 (10)	0.0032 (7)	0.0172 (8)	0.0040 (7)
O4	0.0423 (10)	0.0188 (8)	0.0522 (11)	0.0004 (7)	0.0196 (9)	0.0120 (7)
N2	0.0431 (12)	0.0221 (10)	0.0320 (11)	0.0024 (9)	0.0103 (9)	0.0057 (8)
O5	0.0462 (11)	0.0388 (10)	0.0338 (10)	0.0094 (9)	−0.0043 (8)	−0.0021 (8)
O2	0.0399 (11)	0.0582 (13)	0.0386 (11)	−0.0044 (9)	−0.0085 (8)	0.0207 (10)
N3	0.0403 (13)	0.0347 (11)	0.0361 (12)	−0.0055 (9)	−0.0085 (10)	0.0183 (10)
N1	0.0386 (12)	0.0211 (9)	0.0327 (11)	0.0069 (8)	0.0135 (9)	0.0086 (8)
O7	0.0286 (10)	0.0588 (14)	0.0850 (17)	0.0120 (9)	0.0161 (10)	0.0416 (13)
N4	0.0394 (13)	0.0433 (14)	0.0488 (15)	−0.0068 (11)	−0.0173 (11)	0.0188 (12)
O8	0.0746 (16)	0.0570 (13)	0.0477 (12)	0.0240 (12)	0.0308 (11)	0.0312 (11)
C2	0.0271 (11)	0.0331 (12)	0.0252 (11)	0.0022 (9)	0.0011 (9)	0.0109 (9)
C1	0.0286 (11)	0.0246 (10)	0.0239 (10)	0.0065 (8)	0.0028 (8)	0.0100 (8)

Geometric parameters (Å, º) top

S3—O2	1.436 (2)	N2—H2A	0.846 (18)
S3—O4	1.4441 (17)	N2—H2B	0.861 (18)
S3—O1	1.4803 (18)	N3—C2	1.299 (3)
S3—O3	1.5397 (18)	N3—H3A	0.858 (18)
S4—O5	1.4393 (19)	N3—H3B	0.849 (18)
S4—O6	1.440 (2)	N1—C1	1.298 (3)
S4—O8	1.456 (2)	N1—H1A	0.847 (17)
S4—O7	1.540 (2)	N1—H1B	0.845 (18)
S1—C1	1.777 (2)	O7—H7	0.851 (19)
S1—S2	2.0282 (9)	N4—C2	1.289 (3)
S2—C2	1.774 (2)	N4—H4A	0.828 (18)
O3—H3	0.840 (19)	N4—H4B	0.859 (19)
N2—C1	1.304 (3)

O2—S3—O4	114.18 (13)	H2A—N2—H2B	123 (3)
O2—S3—O1	111.76 (13)	C2—N3—H3A	123 (2)
O4—S3—O1	109.77 (11)	C2—N3—H3B	119 (2)
O2—S3—O3	108.85 (12)	H3A—N3—H3B	118 (3)
O4—S3—O3	104.91 (11)	C1—N1—H1A	117.7 (19)
O1—S3—O3	106.89 (10)	C1—N1—H1B	122 (2)
O5—S4—O6	112.33 (12)	H1A—N1—H1B	121 (3)
O5—S4—O8	112.41 (15)	S4—O7—H7	114 (3)
O6—S4—O8	110.66 (14)	C2—N4—H4A	124 (2)
O5—S4—O7	108.55 (14)	C2—N4—H4B	121 (3)
O6—S4—O7	105.97 (14)	H4A—N4—H4B	114 (4)
O8—S4—O7	106.52 (13)	N4—C2—N3	123.5 (2)
C1—S1—S2	103.40 (8)	N4—C2—S2	122.9 (2)
C2—S2—S1	104.56 (9)	N3—C2—S2	113.63 (18)
S3—O3—H3	113 (3)	N1—C1—N2	123.5 (2)
C1—N2—H2A	118 (2)	N1—C1—S1	123.21 (18)
C1—N2—H2B	119 (2)	N2—C1—S1	113.31 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O6ⁱ	0.83 (2)	2.33 (3)	2.860 (3)	123 (3)
N3—H3A···O5	0.86 (2)	2.24 (2)	3.032 (3)	153 (3)
N3—H3A···O7ⁱⁱ	0.86 (2)	2.48 (3)	3.048 (3)	125 (3)
N1—H1A···O4	0.85 (2)	2.03 (2)	2.866 (3)	170 (3)
N1—H1B···O4ⁱⁱⁱ	0.85 (2)	2.14 (3)	2.813 (3)	136 (3)
N3—H3B···O2^iv	0.85 (2)	2.02 (2)	2.861 (3)	173 (3)
N2—H2A···O5^v	0.85 (2)	2.03 (2)	2.868 (3)	169 (3)
N2—H2B···O1	0.86 (2)	2.10 (2)	2.955 (3)	172 (3)
O3—H3···O1^vi	0.84 (2)	1.79 (2)	2.628 (2)	175 (5)
N4—H4B···O6	0.86 (2)	1.97 (2)	2.815 (3)	168 (4)
O7—H7···O8^vii	0.85 (2)	1.76 (2)	2.602 (3)	168 (5)
N4—H4A···O6ⁱ	0.83 (2)	2.33 (3)	2.860 (3)	123 (3)
N3—H3A···O5	0.86 (2)	2.24 (2)	3.032 (3)	153 (3)
N3—H3A···O7ⁱⁱ	0.86 (2)	2.48 (3)	3.048 (3)	125 (3)
N1—H1A···O4	0.85 (2)	2.03 (2)	2.866 (3)	170 (3)
N1—H1B···O4ⁱⁱⁱ	0.85 (2)	2.14 (3)	2.813 (3)	136 (3)
N3—H3B···O2^iv	0.85 (2)	2.02 (2)	2.861 (3)	173 (3)
N2—H2A···O5^v	0.85 (2)	2.03 (2)	2.868 (3)	169 (3)
N2—H2B···O1	0.86 (2)	2.10 (2)	2.955 (3)	172 (3)
O3—H3···O1^vi	0.84 (2)	1.79 (2)	2.628 (2)	175 (5)
N4—H4B···O6	0.86 (2)	1.97 (2)	2.815 (3)	168 (4)
O7—H7···O8^vii	0.85 (2)	1.76 (2)	2.602 (3)	168 (5)

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

References

Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zouihri, H. (2012). Acta Cryst. E68, o257. Web of Science CrossRef IUCr Journals Google Scholar

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