2-Amino-5-chloro-pyrimidin-1-ium hydrogen maleate.

In the title salt, C(4)H(5)ClN(3) (+)·C(4)H(3)O(4) (-), the 2-amino-5-chloro-pyrimidinium cation is protonated at one of its pyrimidine N atoms. In the roughly planar (r.m.s. deviation = 0.026 Å) hydrogen malate anion, an intra-molecular O-H⋯O hydrogen bond generates an S(7) ring. In the crystal, the protonated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxyl-ate O atoms of the anion via a pair of N-H⋯O hydrogen bonds, forming an R(2) (2)(8) ring motif. The ion pairs are connected via further N-H⋯O hydrogen bonds and a short C-H⋯O inter-action, forming layers lying parallel to the bc plane.

Related literature

For background to pyrimidine compounds, see: Glidewell et al. (2003 ▶); Panneerselvam et al. (2004 ▶). For details of maleic acid, see: James & Williams (1974 ▶); Bertolasi et al. (1980 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C4H5ClN3 +·C4H3O4 −

M = 245.62

Monoclinic,

a = 9.3974 (6) Å

b = 5.5167 (4) Å

c = 20.0654 (13) Å

β = 95.264 (1)°

V = 1035.86 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.37 mm−1

T = 296 K

0.42 × 0.36 × 0.13 mm

Data collection

Bruker APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.860, T max = 0.954

12808 measured reflections

3443 independent reflections

2745 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.109

S = 1.04

3443 reflections

161 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.35 e Å−3

Δρmin = −0.36 e Å−3

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

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811051646/hb6543sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811051646/hb6543Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811051646/hb6543Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C4H5ClN3+·C4H3O4−	F(000) = 504
Mr = 245.62	Dx = 1.575 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4623 reflections
a = 9.3974 (6) Å	θ = 2.8–31.4°
b = 5.5167 (4) Å	µ = 0.37 mm−1
c = 20.0654 (13) Å	T = 296 K
β = 95.264 (1)°	Block, colourless
V = 1035.86 (12) Å3	0.42 × 0.36 × 0.13 mm
Z = 4

Bruker APEXII DUO CCD diffractometer	3443 independent reflections
Radiation source: fine-focus sealed tube	2745 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 31.7°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −13→13
Tmin = 0.860, Tmax = 0.954	k = −7→8
12808 measured reflections	l = −29→29

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0515P)2 + 0.2504P] where P = (Fo2 + 2Fc2)/3
3443 reflections	(Δ/σ)max = 0.001
161 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.36 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

	x	y	z	Uiso*/Ueq
Cl1	0.07132 (4)	0.34821 (8)	0.119864 (19)	0.05434 (13)
O1	0.34314 (14)	0.1959 (2)	0.47054 (5)	0.0547 (3)
O2	0.20761 (12)	0.3832 (2)	0.39206 (5)	0.0483 (3)
O3	0.44057 (12)	0.28155 (19)	0.58566 (5)	0.0477 (3)
O4	0.43276 (11)	0.5756 (2)	0.65981 (4)	0.0456 (2)
N1	0.14846 (11)	0.8848 (2)	0.24914 (5)	0.0364 (2)
N2	0.32969 (11)	0.59171 (19)	0.27016 (5)	0.0305 (2)
N3	0.32863 (14)	0.9408 (2)	0.33347 (6)	0.0424 (3)
C1	0.26868 (12)	0.8052 (2)	0.28452 (5)	0.0307 (2)
C2	0.09165 (13)	0.7456 (3)	0.20036 (6)	0.0372 (3)
H2A	0.0086	0.7977	0.1757	0.045*
C3	0.15083 (13)	0.5224 (2)	0.18395 (6)	0.0343 (2)
C4	0.27274 (13)	0.4492 (2)	0.22009 (6)	0.0335 (2)
H4A	0.3160	0.3033	0.2104	0.040*
C5	0.26812 (14)	0.3825 (2)	0.44879 (6)	0.0351 (3)
C6	0.25815 (15)	0.6000 (2)	0.49162 (6)	0.0391 (3)
H6A	0.2049	0.7265	0.4714	0.047*
C7	0.31273 (15)	0.6453 (2)	0.55439 (6)	0.0387 (3)
H7A	0.2921	0.7985	0.5703	0.046*
C8	0.40123 (13)	0.4898 (2)	0.60285 (5)	0.0328 (2)
H1N2	0.4062 (19)	0.537 (4)	0.2941 (9)	0.048 (5)*
H1N3	0.2848 (19)	1.066 (3)	0.3469 (9)	0.047 (5)*
H2N3	0.402 (2)	0.884 (3)	0.3604 (9)	0.051 (5)*
H1O3	0.376 (3)	0.225 (5)	0.5110 (14)	0.093 (8)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0550 (2)	0.0562 (2)	0.0486 (2)	−0.00891 (17)	−0.01285 (15)	−0.01739 (16)
O1	0.0821 (8)	0.0392 (6)	0.0379 (5)	0.0180 (5)	−0.0202 (5)	−0.0097 (4)
O2	0.0577 (6)	0.0494 (6)	0.0343 (5)	0.0033 (5)	−0.0154 (4)	−0.0049 (4)
O3	0.0627 (6)	0.0412 (5)	0.0358 (4)	0.0183 (5)	−0.0148 (4)	−0.0045 (4)
O4	0.0498 (5)	0.0551 (6)	0.0298 (4)	0.0150 (5)	−0.0085 (4)	−0.0093 (4)
N1	0.0357 (5)	0.0351 (5)	0.0367 (5)	0.0036 (4)	−0.0055 (4)	−0.0018 (4)
N2	0.0331 (5)	0.0313 (5)	0.0261 (4)	0.0025 (4)	−0.0023 (3)	0.0008 (4)
N3	0.0491 (7)	0.0373 (6)	0.0376 (5)	0.0081 (5)	−0.0136 (5)	−0.0095 (5)
C1	0.0338 (5)	0.0305 (5)	0.0272 (5)	0.0001 (4)	−0.0009 (4)	0.0010 (4)
C2	0.0319 (5)	0.0412 (7)	0.0369 (6)	−0.0007 (5)	−0.0065 (4)	0.0009 (5)
C3	0.0354 (6)	0.0361 (6)	0.0306 (5)	−0.0068 (5)	−0.0023 (4)	−0.0029 (5)
C4	0.0387 (6)	0.0310 (6)	0.0306 (5)	−0.0009 (5)	0.0018 (4)	−0.0018 (4)
C5	0.0399 (6)	0.0342 (6)	0.0298 (5)	−0.0010 (5)	−0.0045 (4)	−0.0006 (4)
C6	0.0492 (7)	0.0335 (6)	0.0326 (5)	0.0106 (5)	−0.0070 (5)	0.0002 (5)
C7	0.0495 (7)	0.0335 (6)	0.0316 (5)	0.0110 (5)	−0.0039 (5)	−0.0031 (5)
C8	0.0330 (5)	0.0381 (6)	0.0265 (5)	0.0040 (5)	−0.0012 (4)	−0.0004 (4)

Cl1—C3	1.7201 (12)	N3—H1N3	0.858 (19)
O1—C5	1.3005 (16)	N3—H2N3	0.89 (2)
O1—H1O3	0.86 (3)	C2—C3	1.4027 (19)
O2—C5	1.2248 (15)	C2—H2A	0.9300
O3—C8	1.2645 (16)	C3—C4	1.3599 (17)
O4—C8	1.2475 (14)	C4—H4A	0.9300
N1—C2	1.3178 (17)	C5—C6	1.4837 (18)
N1—C1	1.3512 (15)	C6—C7	1.3393 (17)
N2—C4	1.3473 (15)	C6—H6A	0.9300
N2—C1	1.3527 (15)	C7—C8	1.4916 (17)
N2—H1N2	0.880 (18)	C7—H7A	0.9300
N3—C1	1.3192 (16)
C5—O1—H1O3	108.0 (18)	C2—C3—Cl1	120.76 (9)
C2—N1—C1	117.60 (11)	N2—C4—C3	118.81 (11)
C4—N2—C1	121.33 (10)	N2—C4—H4A	120.6
C4—N2—H1N2	117.2 (12)	C3—C4—H4A	120.6
C1—N2—H1N2	121.4 (12)	O2—C5—O1	120.36 (12)
C1—N3—H1N3	120.2 (12)	O2—C5—C6	119.16 (12)
C1—N3—H2N3	120.3 (12)	O1—C5—C6	120.46 (11)
H1N3—N3—H2N3	117.3 (16)	C7—C6—C5	131.05 (12)
N3—C1—N1	119.11 (11)	C7—C6—H6A	114.5
N3—C1—N2	119.47 (11)	C5—C6—H6A	114.5
N1—C1—N2	121.41 (10)	C6—C7—C8	130.40 (12)
N1—C2—C3	122.92 (11)	C6—C7—H7A	114.8
N1—C2—H2A	118.5	C8—C7—H7A	114.8
C3—C2—H2A	118.5	O4—C8—O3	122.95 (11)
C4—C3—C2	117.92 (11)	O4—C8—C7	116.77 (11)
C4—C3—Cl1	121.32 (10)	O3—C8—C7	120.28 (10)
C2—N1—C1—N3	179.67 (12)	C2—C3—C4—N2	0.81 (18)
C2—N1—C1—N2	0.63 (18)	Cl1—C3—C4—N2	−179.38 (9)
C4—N2—C1—N3	−179.27 (12)	O2—C5—C6—C7	179.72 (16)
C4—N2—C1—N1	−0.23 (18)	O1—C5—C6—C7	−2.0 (2)
C1—N1—C2—C3	−0.3 (2)	C5—C6—C7—C8	−0.8 (3)
N1—C2—C3—C4	−0.4 (2)	C6—C7—C8—O4	−177.01 (16)
N1—C2—C3—Cl1	179.77 (10)	C6—C7—C8—O3	2.8 (2)
C1—N2—C4—C3	−0.52 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O4i	0.881 (19)	1.810 (18)	2.6897 (14)	177.6 (19)
N3—H1N3···O1ii	0.860 (17)	2.592 (18)	3.0814 (16)	117.2 (14)
N3—H1N3···O2ii	0.860 (17)	2.128 (17)	2.9795 (16)	170.2 (16)
N3—H2N3···O3i	0.893 (18)	1.975 (18)	2.8629 (17)	172.8 (16)
O1—H1O3···O3	0.86 (3)	1.60 (3)	2.4514 (15)	179 (3)
C2—H2A···O2iii	0.93	2.39	3.3117 (17)	173

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O4i	0.881 (19)	1.810 (18)	2.6897 (14)	177.6 (19)
N3—H1N3⋯O1ii	0.860 (17)	2.592 (18)	3.0814 (16)	117.2 (14)
N3—H1N3⋯O2ii	0.860 (17)	2.128 (17)	2.9795 (16)	170.2 (16)
N3—H2N3⋯O3i	0.893 (18)	1.975 (18)	2.8629 (17)	172.8 (16)
O1—H1O3⋯O3	0.86 (3)	1.60 (3)	2.4514 (15)	179 (3)
C2—H2A⋯O2iii	0.93	2.39	3.3117 (17)	173

Symmetry codes: (i) ; (ii) ; (iii) .