2-Amino­pyrimidin-1-ium 4-methyl­benzene­sulfonate

Tabatabaee, M.; Noozari, N.

doi:10.1107/S1600536811018198

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1457

doi:10.1107/S1600536811018198

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2-Aminopyrimidin-1-ium 4-methylbenzenesulfonate

Masoumeh Tabatabaee ^a ^* and Najmeh Noozari ^a

^aDepartment of Chemistry, Yazd Branch, IslamicAzad University, Yazd, Iran.
^*Correspondence e-mail: tabatabaee45m@yahoo.com

(Received 29 April 2011; accepted 13 May 2011; online 20 May 2011)

In the crystal structure of the title compound, C₄H₆N₃⁺·C₇H₇O₃S⁻, intermolecular N—H⋯O hydrogen bonds link the cations and anions into chains along [100]. Additional stabilization is provided by weak C—H⋯O hydrogen bonds. An intermolecular π–π stacking interaction with a centroid–centroid distance of 3.6957 (7) Å is also observed. The H atoms of the methyl group were refined as disordered over two sets of sites with equal occupancies

Related literature

For related structures, see: Tabatabaee et al. (2010 , 2011 ).

Experimental

Crystal data

C₄H₆N₃⁺·C₇H₇O₃S⁻
M_r = 267.30
Monoclinic, P 2₁ /n
a = 6.2567 (3) Å
b = 13.3756 (6) Å
c = 15.2512 (7) Å
β = 101.335 (1)°
V = 1251.43 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 100 K
0.50 × 0.36 × 0.32 mm

Data collection

Bruker SMART APEXII diffractometer
12275 measured reflections
3617 independent reflections
3160 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.088
S = 1.04
3617 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.88	1.79	2.674 (1)	176
N3—H3B⋯O1ⁱ	0.88	2.03	2.835 (1)	151
N3—H3C⋯O2	0.88	2.08	2.902 (1)	155
C10—H10A⋯O3ⁱⁱ	0.95	2.46	3.1035 (14)	124
C11—H11A⋯O3ⁱⁱⁱ	0.95	2.56	3.3629 (14)	143
Symmetry codes: (i) x+1, y, z; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811018198/lh5246sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811018198/lh5246Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811018198/lh5246Isup3.cml

checkCIF report

Comment top

The treatment of sulfonylchloride compounds with amines at room temperature leads to the corresponding sulfonamides (Tabatabaee et al., 2010, 2011). The title compound was obtained as a side product from the reaction of 4-methylbenzenesulfonyl chloride and 2-amino-pyrimidine in CH₂Cl₂ under reflux conditions. The compound was formed due to the hydrolysis of 4-methylbenzenesulfonyl chloride to 4-methylbenzenesulfonic acid and an H atom being transferred to an imine nitrogen atom of 2-amino-pyrimidine molecule. The molecular structure of the title compound is shown in Fig. 1. The H atoms of the methyl group are disordered over two sets of sites with equal occupancies. In the crystal, cations and anions are linked into one dimensional chains parallel to [100] (Fig. 2) by intermolecular N—H··· O hydrogen bonds and further stabilization is provided by weak C—H··· O hydrogen bonds. There is an intermolecular π···π stacking interaction involving pyrimidine and benzene rings with a centroid to centroid distance of 3.6957 (7)Å.

Related literature top

For related structures, see: Tabatabaee et al. (2010, 2011).

Experimental top

A solution of 2-amino-pyrimidine (0.095 g, 1 mmol) in CH₂Cl₂ (30 ml) was treated with 4-methylbenzenesulfonyl chloride (0.190 g, 1 mmol) and the pH of reaction mixture was adjusted to 8 with sodium carbonate solution (10%). The reaction mixture was refluxed. the solid crude was filtered. The clear filtrate solution was kept at 277K to give the colorless single crystals of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with ellipsoids drawn at the 50% probabilty level.
	Fig. 2. Part of a hydrogen-bonded (dashed lines ) chain along [100].

2-Aminopyrimidin-1-ium 4-methylbenzenesulfonate top

Crystal data top

C₄H₆N₃⁺·C₇H₇O₃S⁻	F(000) = 560
M_r = 267.30	D_x = 1.419 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5926 reflections
a = 6.2567 (3) Å	θ = 2.7–34.6°
b = 13.3756 (6) Å	µ = 0.26 mm⁻¹
c = 15.2512 (7) Å	T = 100 K
β = 101.335 (1)°	Prism, colourless
V = 1251.43 (10) Å³	0.50 × 0.36 × 0.32 mm
Z = 4

Data collection top

Bruker SMART APEXII diffractometer	3160 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 30.0°, θ_min = 2.0°
ω scans	h = −8→8
12275 measured reflections	k = −18→18
3617 independent reflections	l = −21→21

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: difference Fourier map
wR(F²) = 0.088	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0496P)² + 0.3689P] where P = (F_o² + 2F_c²)/3
3617 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₄H₆N₃⁺·C₇H₇O₃S⁻	V = 1251.43 (10) Å³
M_r = 267.30	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.2567 (3) Å	µ = 0.26 mm⁻¹
b = 13.3756 (6) Å	T = 100 K
c = 15.2512 (7) Å	0.50 × 0.36 × 0.32 mm
β = 101.335 (1)°

Data collection top

Bruker SMART APEXII diffractometer	3160 reflections with I > 2σ(I)
12275 measured reflections	R_int = 0.021
3617 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.04	Δρ_max = 0.45 e Å⁻³
3617 reflections	Δρ_min = −0.38 e Å⁻³
163 parameters

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	Occ. (<1)
S1	0.28924 (4)	0.172328 (19)	0.105904 (16)	0.01392 (8)
O1	0.28421 (13)	0.21695 (6)	0.19437 (5)	0.01877 (17)
O2	0.51293 (13)	0.15402 (6)	0.09590 (5)	0.01855 (16)
O3	0.14528 (13)	0.08711 (6)	0.08830 (5)	0.01966 (17)
C1	0.18525 (17)	0.26582 (8)	0.02687 (7)	0.01501 (19)
C2	−0.03778 (18)	0.27159 (8)	−0.00789 (7)	0.0183 (2)
H2A	−0.1349	0.2244	0.0096	0.022*
C3	−0.1167 (2)	0.34700 (9)	−0.06827 (8)	0.0220 (2)
H3A	−0.2687	0.3509	−0.0919	0.026*
C4	0.0232 (2)	0.41735 (9)	−0.09488 (8)	0.0236 (2)
C5	0.2456 (2)	0.41027 (9)	−0.05918 (8)	0.0254 (2)
H5A	0.3429	0.4576	−0.0764	0.031*
C6	0.3277 (2)	0.33500 (9)	0.00123 (8)	0.0213 (2)
H6A	0.4797	0.3309	0.0248	0.026*
C7	−0.0643 (3)	0.49831 (10)	−0.16093 (9)	0.0348 (3)
H7A	−0.1992	0.4752	−0.1997	0.052*	0.50
H7B	0.0438	0.5140	−0.1975	0.052*	0.50
H7C	−0.0944	0.5584	−0.1286	0.052*	0.50
H7D	0.0326	0.5565	−0.1508	0.052*	0.50
H7E	−0.2103	0.5178	−0.1530	0.052*	0.50
H7F	−0.0721	0.4734	−0.2219	0.052*	0.50
N1	0.61962 (15)	0.31572 (7)	0.29233 (6)	0.01640 (18)
H1A	0.5121	0.2804	0.2612	0.020*
N2	0.99877 (15)	0.33985 (7)	0.33945 (6)	0.01665 (18)
N3	0.86604 (16)	0.21369 (8)	0.23970 (7)	0.0210 (2)
H3B	1.0008	0.1961	0.2382	0.025*
H3C	0.7560	0.1808	0.2076	0.025*
C8	0.82865 (17)	0.29000 (8)	0.29050 (7)	0.0154 (2)
C9	0.57354 (18)	0.39454 (8)	0.34102 (7)	0.0177 (2)
H9A	0.4264	0.4116	0.3415	0.021*
C10	0.73953 (18)	0.44934 (8)	0.38933 (7)	0.0179 (2)
H10A	0.7132	0.5064	0.4228	0.022*
C11	0.95194 (17)	0.41679 (8)	0.38686 (7)	0.0170 (2)
H11A	1.0701	0.4525	0.4217	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01196 (12)	0.01471 (13)	0.01493 (13)	−0.00058 (8)	0.00229 (9)	−0.00101 (8)
O1	0.0151 (4)	0.0257 (4)	0.0156 (3)	−0.0016 (3)	0.0034 (3)	−0.0040 (3)
O2	0.0135 (4)	0.0209 (4)	0.0214 (4)	0.0022 (3)	0.0038 (3)	−0.0016 (3)
O3	0.0186 (4)	0.0161 (4)	0.0234 (4)	−0.0036 (3)	0.0017 (3)	0.0011 (3)
C1	0.0159 (5)	0.0137 (4)	0.0158 (4)	0.0009 (4)	0.0039 (4)	−0.0015 (4)
C2	0.0171 (5)	0.0189 (5)	0.0186 (5)	0.0003 (4)	0.0028 (4)	−0.0008 (4)
C3	0.0225 (5)	0.0222 (5)	0.0200 (5)	0.0044 (4)	0.0006 (4)	−0.0002 (4)
C4	0.0361 (7)	0.0172 (5)	0.0175 (5)	0.0044 (5)	0.0056 (4)	0.0002 (4)
C5	0.0324 (6)	0.0185 (5)	0.0274 (6)	−0.0025 (5)	0.0107 (5)	0.0029 (4)
C6	0.0191 (5)	0.0203 (5)	0.0252 (5)	−0.0023 (4)	0.0063 (4)	0.0008 (4)
C7	0.0563 (9)	0.0225 (6)	0.0245 (6)	0.0088 (6)	0.0054 (6)	0.0064 (5)
N1	0.0124 (4)	0.0201 (4)	0.0166 (4)	−0.0024 (3)	0.0026 (3)	−0.0015 (3)
N2	0.0138 (4)	0.0189 (4)	0.0169 (4)	−0.0014 (3)	0.0021 (3)	−0.0005 (3)
N3	0.0145 (4)	0.0258 (5)	0.0231 (5)	−0.0018 (4)	0.0043 (3)	−0.0087 (4)
C8	0.0138 (5)	0.0182 (5)	0.0145 (4)	−0.0008 (4)	0.0035 (3)	0.0012 (4)
C9	0.0163 (5)	0.0193 (5)	0.0180 (5)	0.0028 (4)	0.0048 (4)	0.0016 (4)
C10	0.0191 (5)	0.0164 (5)	0.0186 (5)	0.0010 (4)	0.0044 (4)	0.0000 (4)
C11	0.0165 (5)	0.0169 (5)	0.0168 (5)	−0.0029 (4)	0.0013 (4)	0.0003 (4)

Geometric parameters (Å, º) top

S1—O3	1.4449 (8)	C7—H7C	0.9800
S1—O2	1.4580 (8)	C7—H7D	0.9800
S1—O1	1.4814 (8)	C7—H7E	0.9800
S1—C1	1.7697 (11)	C7—H7F	0.9800
C1—C6	1.3930 (15)	N1—C9	1.3529 (14)
C1—C2	1.3941 (15)	N1—C8	1.3579 (14)
C2—C3	1.3895 (16)	N1—H1A	0.8800
C2—H2A	0.9500	N2—C11	1.3233 (14)
C3—C4	1.3985 (18)	N2—C8	1.3500 (14)
C3—H3A	0.9500	N3—C8	1.3296 (14)
C4—C5	1.3946 (19)	N3—H3B	0.8800
C4—C7	1.5067 (17)	N3—H3C	0.8800
C5—C6	1.3929 (17)	C9—C10	1.3631 (15)
C5—H5A	0.9500	C9—H9A	0.9500
C6—H6A	0.9500	C10—C11	1.4060 (15)
C7—H7A	0.9800	C10—H10A	0.9500
C7—H7B	0.9800	C11—H11A	0.9500

O3—S1—O2	115.10 (5)	H7B—C7—H7D	56.3
O3—S1—O1	111.29 (5)	H7C—C7—H7D	56.3
O2—S1—O1	110.83 (5)	C4—C7—H7E	109.5
O3—S1—C1	107.38 (5)	H7A—C7—H7E	56.3
O2—S1—C1	106.22 (5)	H7B—C7—H7E	141.1
O1—S1—C1	105.36 (5)	H7C—C7—H7E	56.3
C6—C1—C2	120.29 (10)	H7D—C7—H7E	109.5
C6—C1—S1	119.39 (8)	C4—C7—H7F	109.5
C2—C1—S1	120.31 (8)	H7A—C7—H7F	56.3
C3—C2—C1	119.41 (11)	H7B—C7—H7F	56.3
C3—C2—H2A	120.3	H7C—C7—H7F	141.1
C1—C2—H2A	120.3	H7D—C7—H7F	109.5
C2—C3—C4	121.30 (11)	H7E—C7—H7F	109.5
C2—C3—H3A	119.4	C9—N1—C8	121.24 (9)
C4—C3—H3A	119.4	C9—N1—H1A	119.4
C5—C4—C3	118.33 (11)	C8—N1—H1A	119.4
C5—C4—C7	120.89 (12)	C11—N2—C8	116.81 (10)
C3—C4—C7	120.78 (12)	C8—N3—H3B	120.0
C6—C5—C4	121.14 (11)	C8—N3—H3C	120.0
C6—C5—H5A	119.4	H3B—N3—H3C	120.0
C4—C5—H5A	119.4	N3—C8—N2	119.44 (10)
C5—C6—C1	119.52 (11)	N3—C8—N1	119.13 (10)
C5—C6—H6A	120.2	N2—C8—N1	121.43 (10)
C1—C6—H6A	120.2	N1—C9—C10	119.59 (10)
C4—C7—H7A	109.5	N1—C9—H9A	120.2
C4—C7—H7B	109.5	C10—C9—H9A	120.2
H7A—C7—H7B	109.5	C9—C10—C11	116.28 (10)
C4—C7—H7C	109.5	C9—C10—H10A	121.9
H7A—C7—H7C	109.5	C11—C10—H10A	121.9
H7B—C7—H7C	109.5	N2—C11—C10	124.57 (10)
C4—C7—H7D	109.5	N2—C11—H11A	117.7
H7A—C7—H7D	141.1	C10—C11—H11A	117.7

O3—S1—C1—C6	−152.15 (9)	C7—C4—C5—C6	−179.36 (12)
O2—S1—C1—C6	−28.51 (10)	C4—C5—C6—C1	−0.34 (18)
O1—S1—C1—C6	89.14 (9)	C2—C1—C6—C5	0.24 (17)
O3—S1—C1—C2	29.29 (10)	S1—C1—C6—C5	−178.32 (9)
O2—S1—C1—C2	152.94 (9)	C11—N2—C8—N3	178.22 (10)
O1—S1—C1—C2	−89.42 (9)	C11—N2—C8—N1	−2.14 (15)
C6—C1—C2—C3	−0.06 (16)	C9—N1—C8—N3	−178.11 (10)
S1—C1—C2—C3	178.49 (9)	C9—N1—C8—N2	2.25 (16)
C1—C2—C3—C4	−0.03 (17)	C8—N1—C9—C10	−0.06 (16)
C2—C3—C4—C5	−0.07 (18)	N1—C9—C10—C11	−1.95 (15)
C2—C3—C4—C7	179.54 (11)	C8—N2—C11—C10	−0.04 (16)
C3—C4—C5—C6	0.25 (18)	C9—C10—C11—N2	2.07 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.88	1.79	2.674 (1)	176
N3—H3B···O1ⁱ	0.88	2.03	2.835 (1)	151
N3—H3C···O2	0.88	2.08	2.902 (1)	155
C10—H10A···O3ⁱⁱ	0.95	2.46	3.1035 (14)	124
C11—H11A···O3ⁱⁱⁱ	0.95	2.56	3.3629 (14)	143

Symmetry codes: (i) x+1, y, z; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+3/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₄H₆N₃⁺·C₇H₇O₃S⁻
M_r	267.30
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	6.2567 (3), 13.3756 (6), 15.2512 (7)
β (°)	101.335 (1)
V (Å³)	1251.43 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.50 × 0.36 × 0.32

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	12275, 3617, 3160
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.088, 1.04
No. of reflections	3617
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.38

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.88	1.79	2.674 (1)	176
N3—H3B···O1ⁱ	0.88	2.03	2.835 (1)	151
N3—H3C···O2	0.88	2.08	2.902 (1)	155
C10—H10A···O3ⁱⁱ	0.95	2.46	3.1035 (14)	124
C11—H11A···O3ⁱⁱⁱ	0.95	2.56	3.3629 (14)	143

Symmetry codes: (i) x+1, y, z; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+3/2, y+1/2, −z+1/2.

Acknowledgements

This research was supported by the Islamic Azad University, Yazd Branch.

References

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