Crystal structure of 4-amino-5-chloro-2,6-di­methyl­pyrimidinium thio­phene-2,5-di­carboxyl­ate

Rajam, A.; Thomas Muthiah, P.; Butcher, R.J.; Zeller, M.

doi:10.1107/S2056989016010148

research communications

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Volume 72| Part 7| July 2016| Pages 1043-1046

https://doi.org/10.1107/S2056989016010148

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Crystal structure of 4-amino-5-chloro-2,6-dimethylpyrimidinium thiophene-2,5-dicarboxylate

Ammaiyappan Rajam,^a Packianathan Thomas Muthiah,^a ^* Ray J. Butcher ^b and Matthias Zeller ^c

^aSchool of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, Tamilnadu, India, ^bDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA, and ^cDepartment of Chemistry, Youngstown State University, 1 University Plaza, Youngstown, OH 44555, USA
^*Correspondence e-mail: tommtrichy@yahoo.co.in

Edited by A. J. Lough, University of Toronto, Canada (Received 21 May 2016; accepted 21 June 2016; online 24 June 2016)

In the title salt, C₆H₉ClN₃⁺·C₆H₃O₄S⁻, the cations and anions are linked via O—H⋯O and N—H⋯O hydrogen bonds, forming R₆⁶(37) ring motifs that are interconnected with each other, producing sheets. Separate parallel inversion-related sheets are linked through N—H⋯N and π–π stacking interactions [centroid–centroid distance = 3.5414 (13) Å], forming double layers parallel to (101). Weak C—H⋯O and C—H⋯S hydrogen bonds, as well as C—H⋯π interactions, connect the double layers into a three-dimensional network.

Keywords: crystal structure; crystal salts; hydrogen-bonding patterns; base-pairing; π–π stacking; C—H⋯π interactions.

CCDC reference: 1486940

1. Chemical context

In crystal engineering, non-covalent interactions, such as hydrogen bonding, play a key role in molecular recognition processes (Desiraju, 1989 ). Pyrimidine derivatives have gained considerable importance because of their remarkable biological properties, for example as anti-fungal, antiviral, anticancer and anti-allergenic agents (Ding et al., 2004 ). Thiophenecarboxylic acid and its derivatives have attracted attention because of their wide range of pharmacological properties and numerous applications, such as the preparation of DNA hybridization indicators, single-molecule magnets, photoluminescence materials and the treatment of osteoporosis as inhibitors of bone resorption in the tissue culture (Bharti et al., 2003 ; Taş et al., 2014 ; Boulsourani et al., 2011 ). The present study investigates the hydrogen-bonding patterns in 4-amino-5-chloro-2,6-dimethylpyrimidinium thiophene-2,5-dicarboxylate (I).

2. Structural commentary

The asymmetric unit of C₆H₉ClN₃⁺·C₆H₃O₄S⁻, (I), contains one 4-amino-5-chloro-2,6-dimethylpyrimidinium cation and one thiophene-2,5-dicarboxylate anion (Fig. 1). Protonation of the pyrimidine occurs at atom N1, leading to a C2B—N1B—C6B angle of 122.5 (2)° which an increase of ca 3.8° compared to the C2B—N3B—C4B angle 118.7 (2)° involving the unprotonated N3 atom.

Figure 1
The asymmetric unit of the title compound, showing 30% probability displacement ellipsoids. The dashed line indicates a hydrogen bond.

3. Supramolecular features

The carboxylate group of the thiophene-2,5-dicarboxylate anion interacts with the protonated N1 atom of the pyrimidinium moiety with a single point heterosynthon via N—H⋯O hydrogen bonds (Table 1). In addition, the components are connected through O—H⋯O and N—H⋯O hydrogen bonds (Table 1) to form an R₆⁶(37) ring graph set motif. This motif includes anions connected by O—H.·O hydrogen bonds along [10 $[\overline{1}]$ ] and involves the cations along [010] to form a 2D sheet (Fig. 2). Two separate 2D sheets (which are indicated in red and yellow in Fig. 3) are interconnected by a self-complementary base pair between the pyrimidinium moiety through N—H⋯N hydrogen bond interactions with an R₂²(8) ring graph set motif and π–π stacking interactions between the pyrimidinium ring and the thiophene ring with an observed interplanar distance of 3.4188 (10) Å, a centroid-to-centroid (Cg1–Cg2) distance of 3.5414 (13) Å (where Cg1 is the centroid of the ring N1B/C2B–C6B and Cg2 is the centroid of the ring S1A/C2A–C5A) and slip angle (the angle between the centroid vector and the normal to the plane) of 18.0°; these are typical aromatic stacking values (Hunter, 1994 ). Through these interactions, parallel inversion-related sheets are connected into double layers parallel to (101). In addition, weak C—H⋯O, C—H⋯S and C—H⋯π intermolecular interactions connect the double layers into a three-dimensional network (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the S1A/C2A–C5A ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3A—H3A⋯O2Aⁱ	1.04 (4)	1.44 (4)	2.475 (2)	176 (4)
N1B—H1B⋯O1A	0.85 (3)	1.87 (3)	2.719 (3)	178 (3)
N4B—H4B1⋯N3Bⁱⁱ	0.86 (3)	2.40 (3)	3.218 (3)	158 (3)
N4B—H4B2⋯O4Aⁱⁱⁱ	0.94 (3)	1.86 (3)	2.784 (3)	170 (3)
C7B—H7BB⋯S1A^iv	0.98	2.86	3.807 (2)	164
C8B—H8BB⋯O3A^v	0.98	2.53	3.281 (3)	134
C8B—H8BC⋯O2A^vi	0.98	2.47	3.301 (3)	143
C7B—H7BB⋯Cg^iv	0.98	2.69	3.556 (3)	148
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) -x+2, -y+1, -z+1; (v) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (vi) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
Packing diagram for (I)

, viewed along the a axis, showing a single sheet formed by O—H⋯O and N—H⋯O hydrogen bonds. Symmetry codes are given in Table 1

. Dashed lines represent hydrogen bonds.

Figure 3
A view along the b axis, showing double layers (indicated in red and yellow) formed by hydrogen bonds and π–π stacking interactions. The weak C—H⋯O and C—H⋯S hydrogen bonds connect the double layers to form a three-dimensional network. Dotted lines represent N—H⋯N, C—H⋯O and C—H⋯S interactions. Solid lines indicate the stacking interactions.

4. Database survey

The crystal structures of aminopyrimidine derivatives (Schwalbe & Williams, 1982 ) and aminopyrimidine carboxylates (Hu et al., 2002 ), have been reported. Several co-crystals/salts of aminopyrimidine derivatives have been reported from our laboratory including co-crystals/salts of aminopyrimidines with carboxylic acid (Muthiah et al., 2006 ; Devi & Muthiah, 2007 ; Subashini et al., 2008 ; Thanigaimani et al., 2009 ; Ebenezer & Muthiah, 2010 , 2012 ; Ebenezer et al., 2011 ), aminopyrimidines–thiophenecarboxylic acid (Jegan Jennifer et al., 2014 ), the crystal structure of 2-amino-4,6-dimethoxypyrimidiniumthiophene-2-carboxylate (Rajam et al., 2015 ) and metal complexes with 4-amino-5-chloro-2,6-dimethylpyrimidine (Karthikeyan et al., 2016 )

5. Synthesis and crystallization

A hot DMF solution of 4-amino-5-chloro-2,6-dimethylpyrimidine (39 mg, Alfa Aesar) and thiophene-2,5-dicarboxylic acid (43 mg, Alfa Aesar) were mixed and warmed for half an hour over a water bath. The mixture was cooled slowly and kept at room temperature. After a few days colourless plate-like crystals were obtained.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The N—H and O—H H atoms were located in difference Fourier maps and refined isotropically. All other H atoms were placed in calculated positions and refined using a riding-model approximation with C—H = 0.95 Å (CH) or 0.98 Å (CH₃). Isotropic displacement parameters for these atoms were set to 1.2 (CH) or 1.5 (CH₃) times U_eq of the parent atom. Idealized Me H atoms were refined as rotating groups. There are larger than expected residual density peaks close to the Cl and S atoms but these are not chemically sensible and are assumed to be related to the quality of the crystal.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₉ClN₃⁺·C₆H₃O₄S⁻
M_r	329.76
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	7.9948 (3), 11.3928 (4), 15.7757 (6)
β (°)	98.520 (2)
V (Å³)	1421.04 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.44
Crystal size (mm)	0.23 × 0.19 × 0.06

Data collection
Diffractometer	Bruker AXS D8 Quest CMOS
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.424, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	10749, 3911, 2862
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.185, 1.10
No. of reflections	3911
No. of parameters	208
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.59, −0.69
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SIR92 (Altomare et al., 1993 ), SHELXL2014 (Sheldrick, 2015 ), SHELXLE (Hübschle et al., 2011 ), Mercury (Macrae et al., 2008 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1486940

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016010148/lh5814sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016010148/lh5814Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989016010148/lh5814Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015) and SHELXLE (Hübschle et al., 2011); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).

4-Amino-5-chloro-2,6-dimethylpyrimidinium thiophene-2,5-dicarboxylate top

Crystal data top

C₆H₉ClN₃⁺·C₆H₃O₄S⁻	F(000) = 680
M_r = 329.76	D_x = 1.541 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.9948 (3) Å	Cell parameters from 6601 reflections
b = 11.3928 (4) Å	θ = 3.1–30.0°
c = 15.7757 (6) Å	µ = 0.44 mm⁻¹
β = 98.520 (2)°	T = 100 K
V = 1421.04 (9) Å³	Plate, colourless
Z = 4	0.23 × 0.19 × 0.06 mm

Data collection top

Bruker AXS D8 Quest CMOS diffractometer	3911 independent reflections
Radiation source: I-mu-S microsource X-ray tube	2862 reflections with I > 2σ(I)
Laterally graded multilayer (Goebel) mirror monochromator	R_int = 0.053
ω and φ scans	θ_max = 30.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −11→9
T_min = 0.424, T_max = 0.746	k = −15→16
10749 measured 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)] = 0.060	Hydrogen site location: mixed
wR(F²) = 0.185	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.1146P)²] where P = (F_o² + 2F_c²)/3
3911 reflections	(Δ/σ)_max < 0.001
208 parameters	Δρ_max = 1.59 e Å⁻³
0 restraints	Δρ_min = −0.69 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
S1A	0.83375 (7)	0.63795 (4)	0.43028 (4)	0.01808 (18)
O1A	0.6790 (2)	0.57301 (14)	0.58125 (10)	0.0252 (4)
O2A	0.6743 (2)	0.75418 (14)	0.63699 (10)	0.0218 (4)
O3A	1.0617 (2)	0.81066 (15)	0.26723 (10)	0.0227 (4)
H3A	1.110 (5)	0.780 (3)	0.214 (2)	0.060 (11)*
O4A	0.9244 (3)	0.63757 (15)	0.25678 (12)	0.0309 (4)
C1A	0.7104 (3)	0.6802 (2)	0.58237 (14)	0.0178 (4)
C2A	0.7953 (3)	0.7287 (2)	0.51203 (14)	0.0187 (4)
C3A	0.8446 (3)	0.84283 (19)	0.49963 (15)	0.0204 (5)
H3AA	0.8325	0.9054	0.5381	0.024*
C4A	0.9151 (3)	0.85594 (18)	0.42313 (15)	0.0199 (5)
H4AA	0.9568	0.9282	0.4046	0.024*
C5A	0.9166 (3)	0.75252 (19)	0.37866 (14)	0.0182 (4)
C6A	0.9689 (3)	0.7288 (2)	0.29484 (14)	0.0198 (5)
Cl1B	0.43554 (7)	0.14586 (5)	0.77201 (3)	0.02236 (18)
N1B	0.6246 (2)	0.34003 (17)	0.60286 (13)	0.0206 (4)
H1B	0.639 (4)	0.413 (3)	0.5956 (19)	0.031 (7)*
N3B	0.6059 (2)	0.14982 (16)	0.54703 (13)	0.0205 (4)
N4B	0.5127 (3)	−0.00013 (17)	0.62434 (14)	0.0242 (4)
H4B1	0.512 (4)	−0.043 (3)	0.5793 (19)	0.040 (9)*
H4B2	0.478 (4)	−0.039 (3)	0.671 (2)	0.045 (9)*
C2B	0.6450 (3)	0.2616 (2)	0.54118 (15)	0.0204 (5)
C4B	0.5460 (3)	0.1121 (2)	0.61845 (15)	0.0205 (5)
C5B	0.5201 (3)	0.1938 (2)	0.68398 (14)	0.0196 (4)
C6B	0.5592 (3)	0.3099 (2)	0.67489 (15)	0.0191 (4)
C7B	0.7142 (3)	0.3044 (2)	0.46395 (15)	0.0235 (5)
H7BA	0.6941	0.2453	0.4185	0.035*
H7BB	0.8360	0.3181	0.4787	0.035*
H7BC	0.6579	0.3778	0.4439	0.035*
C8B	0.5357 (3)	0.4046 (2)	0.73702 (15)	0.0250 (5)
H8BA	0.4198	0.4019	0.7502	0.037*
H8BB	0.5563	0.4810	0.7120	0.037*
H8BC	0.6156	0.3931	0.7898	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.0222 (3)	0.0148 (3)	0.0193 (3)	−0.00038 (18)	0.0096 (2)	−0.00055 (19)
O1A	0.0324 (9)	0.0188 (8)	0.0273 (9)	−0.0044 (7)	0.0142 (7)	0.0021 (7)
O2A	0.0242 (8)	0.0230 (8)	0.0207 (8)	−0.0008 (6)	0.0118 (6)	−0.0003 (6)
O3A	0.0267 (8)	0.0229 (8)	0.0217 (8)	−0.0026 (7)	0.0140 (7)	−0.0021 (7)
O4A	0.0445 (11)	0.0221 (9)	0.0308 (10)	−0.0068 (7)	0.0212 (8)	−0.0064 (7)
C1A	0.0186 (9)	0.0192 (10)	0.0164 (10)	0.0001 (8)	0.0054 (8)	−0.0009 (8)
C2A	0.0169 (9)	0.0197 (10)	0.0207 (10)	0.0010 (8)	0.0064 (8)	−0.0006 (9)
C3A	0.0234 (11)	0.0193 (10)	0.0199 (11)	−0.0029 (8)	0.0078 (9)	−0.0015 (8)
C4A	0.0208 (10)	0.0183 (11)	0.0218 (11)	−0.0040 (8)	0.0076 (9)	−0.0013 (8)
C5A	0.0166 (9)	0.0184 (10)	0.0210 (11)	−0.0010 (8)	0.0081 (8)	−0.0002 (8)
C6A	0.0212 (10)	0.0203 (11)	0.0197 (11)	0.0030 (8)	0.0089 (8)	0.0015 (9)
Cl1B	0.0281 (3)	0.0207 (3)	0.0200 (3)	−0.0013 (2)	0.0090 (2)	−0.0002 (2)
N1B	0.0218 (9)	0.0168 (9)	0.0239 (10)	−0.0020 (7)	0.0055 (8)	0.0024 (8)
N3B	0.0225 (9)	0.0188 (10)	0.0212 (10)	0.0004 (7)	0.0059 (8)	0.0018 (7)
N4B	0.0349 (11)	0.0171 (10)	0.0227 (10)	0.0003 (8)	0.0116 (9)	0.0000 (8)
C2B	0.0165 (9)	0.0210 (11)	0.0235 (11)	0.0009 (8)	0.0021 (8)	0.0015 (9)
C4B	0.0183 (10)	0.0215 (11)	0.0228 (11)	0.0013 (8)	0.0071 (8)	0.0006 (9)
C5B	0.0201 (10)	0.0187 (10)	0.0207 (11)	0.0003 (8)	0.0050 (8)	0.0002 (9)
C6B	0.0176 (9)	0.0163 (10)	0.0233 (11)	0.0006 (8)	0.0026 (8)	−0.0003 (9)
C7B	0.0240 (10)	0.0208 (11)	0.0273 (12)	0.0000 (9)	0.0094 (9)	0.0024 (10)
C8B	0.0327 (12)	0.0177 (11)	0.0256 (12)	0.0009 (9)	0.0078 (10)	−0.0044 (9)

Geometric parameters (Å, º) top

S1A—C2A	1.716 (2)	N1B—H1B	0.85 (3)
S1A—C5A	1.722 (2)	N3B—C2B	1.318 (3)
O1A—C1A	1.247 (3)	N3B—C4B	1.358 (3)
O2A—C1A	1.269 (3)	N4B—C4B	1.312 (3)
O3A—C6A	1.306 (3)	N4B—H4B1	0.86 (3)
O3A—H3A	1.04 (4)	N4B—H4B2	0.94 (3)
O4A—C6A	1.226 (3)	C2B—C7B	1.492 (3)
C1A—C2A	1.490 (3)	C4B—C5B	1.429 (3)
C2A—C3A	1.381 (3)	C5B—C6B	1.372 (3)
C3A—C4A	1.414 (3)	C6B—C8B	1.488 (3)
C3A—H3AA	0.9500	C7B—H7BA	0.9800
C4A—C5A	1.372 (3)	C7B—H7BB	0.9800
C4A—H4AA	0.9500	C7B—H7BC	0.9800
C5A—C6A	1.470 (3)	C8B—H8BA	0.9800
Cl1B—C5B	1.721 (2)	C8B—H8BB	0.9800
N1B—C2B	1.348 (3)	C8B—H8BC	0.9800
N1B—C6B	1.363 (3)

C2A—S1A—C5A	91.32 (10)	H4B1—N4B—H4B2	115 (3)
C6A—O3A—H3A	109 (2)	N3B—C2B—N1B	122.3 (2)
O1A—C1A—O2A	126.5 (2)	N3B—C2B—C7B	119.5 (2)
O1A—C1A—C2A	117.76 (19)	N1B—C2B—C7B	118.2 (2)
O2A—C1A—C2A	115.72 (19)	N4B—C4B—N3B	117.9 (2)
C3A—C2A—C1A	128.7 (2)	N4B—C4B—C5B	122.1 (2)
C3A—C2A—S1A	111.97 (17)	N3B—C4B—C5B	120.0 (2)
C1A—C2A—S1A	119.24 (16)	C6B—C5B—C4B	119.5 (2)
C2A—C3A—C4A	112.3 (2)	C6B—C5B—Cl1B	120.89 (18)
C2A—C3A—H3AA	123.9	C4B—C5B—Cl1B	119.55 (17)
C4A—C3A—H3AA	123.9	N1B—C6B—C5B	116.8 (2)
C5A—C4A—C3A	112.36 (19)	N1B—C6B—C8B	117.9 (2)
C5A—C4A—H4AA	123.8	C5B—C6B—C8B	125.2 (2)
C3A—C4A—H4AA	123.8	C2B—C7B—H7BA	109.5
C4A—C5A—C6A	130.0 (2)	C2B—C7B—H7BB	109.5
C4A—C5A—S1A	112.08 (16)	H7BA—C7B—H7BB	109.5
C6A—C5A—S1A	117.83 (16)	C2B—C7B—H7BC	109.5
O4A—C6A—O3A	125.4 (2)	H7BA—C7B—H7BC	109.5
O4A—C6A—C5A	119.7 (2)	H7BB—C7B—H7BC	109.5
O3A—C6A—C5A	114.8 (2)	C6B—C8B—H8BA	109.5
C2B—N1B—C6B	122.5 (2)	C6B—C8B—H8BB	109.5
C2B—N1B—H1B	121 (2)	H8BA—C8B—H8BB	109.5
C6B—N1B—H1B	116 (2)	C6B—C8B—H8BC	109.5
C2B—N3B—C4B	118.7 (2)	H8BA—C8B—H8BC	109.5
C4B—N4B—H4B1	118 (2)	H8BB—C8B—H8BC	109.5
C4B—N4B—H4B2	127 (2)

O1A—C1A—C2A—C3A	−179.2 (2)	C4B—N3B—C2B—N1B	−1.3 (3)
O2A—C1A—C2A—C3A	2.2 (3)	C4B—N3B—C2B—C7B	178.83 (19)
O1A—C1A—C2A—S1A	3.9 (3)	C6B—N1B—C2B—N3B	−1.3 (3)
O2A—C1A—C2A—S1A	−174.75 (16)	C6B—N1B—C2B—C7B	178.6 (2)
C5A—S1A—C2A—C3A	0.03 (18)	C2B—N3B—C4B—N4B	−177.9 (2)
C5A—S1A—C2A—C1A	177.43 (18)	C2B—N3B—C4B—C5B	2.5 (3)
C1A—C2A—C3A—C4A	−177.4 (2)	N4B—C4B—C5B—C6B	179.2 (2)
S1A—C2A—C3A—C4A	−0.4 (3)	N3B—C4B—C5B—C6B	−1.2 (3)
C2A—C3A—C4A—C5A	0.6 (3)	N4B—C4B—C5B—Cl1B	−2.4 (3)
C3A—C4A—C5A—C6A	176.1 (2)	N3B—C4B—C5B—Cl1B	177.20 (17)
C3A—C4A—C5A—S1A	−0.6 (3)	C2B—N1B—C6B—C5B	2.4 (3)
C2A—S1A—C5A—C4A	0.31 (18)	C2B—N1B—C6B—C8B	−177.5 (2)
C2A—S1A—C5A—C6A	−176.79 (17)	C4B—C5B—C6B—N1B	−1.2 (3)
C4A—C5A—C6A—O4A	−162.8 (2)	Cl1B—C5B—C6B—N1B	−179.59 (16)
S1A—C5A—C6A—O4A	13.7 (3)	C4B—C5B—C6B—C8B	178.8 (2)
C4A—C5A—C6A—O3A	17.1 (3)	Cl1B—C5B—C6B—C8B	0.4 (3)
S1A—C5A—C6A—O3A	−166.44 (16)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the S1A/C2A–C5A ring.

D—H···A	D—H	H···A	D···A	D—H···A
O3A—H3A···O2Aⁱ	1.04 (4)	1.44 (4)	2.475 (2)	176 (4)
N1B—H1B···O1A	0.85 (3)	1.87 (3)	2.719 (3)	178 (3)
N4B—H4B1···N3Bⁱⁱ	0.86 (3)	2.40 (3)	3.218 (3)	158 (3)
N4B—H4B2···O4Aⁱⁱⁱ	0.94 (3)	1.86 (3)	2.784 (3)	170 (3)
C7B—H7BB···S1A^iv	0.98	2.86	3.807 (2)	164
C8B—H8BB···O3A^v	0.98	2.53	3.281 (3)	134
C8B—H8BC···O2A^vi	0.98	2.47	3.301 (3)	143
C7B—H7BB···Cg^iv	0.98	2.69	3.556 (3)	148

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

Acknowledgements

PTM is thankful to the UGC, New Delhi, for a UGC–BSR one-time grant to Faculty. The authors wish to acknowledge the United States National Science Foundation (grant No. 1337296) for funds to purchase the diffractometer.

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of 4-amino-5-chloro-2,6-di­methyl­pyrimidinium thio­phene-2,5-di­carboxyl­ate

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structure of 4-amino-5-chloro-2,6-dimethylpyrimidinium thiophene-2,5-dicarboxylate

3. Supramolecular features