2,6-Di-amino-4-chloro-pyrimidinium 4-carb-oxy-butano-ate.

In the title mol-ecular salt, C4H6ClN4 (+)·C5H7O4 (-), the cation is essentially planar, with a maximum deviation of 0.037 (1) Å for all non-H atoms. The anions are self-assembled through O-H⋯O hydrogen bonds, forming a supra-molecular zigzag chain with graph-set notation C(8). 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 with an R 2 (2)(8) ring motif. This motif further self-organizes through N-H⋯O and O-H⋯O hydrogen bonds, generating an array of six hydrogen bonds, the rings having graph-set notation R 3 (2)(8), R 2 (2)(8), R 4 (2)(8), R 2 (2)(8) and R 3 (2)(8). In addition, another type of R 2 (2)(8) motif is formed by inversion-related pyrimidinium cations via N-H⋯N hydrogen bonds, forming a two-dimensional network parallel to (101).

Related literature

For applications of pyrimidine derivatives, see: Condon et al. (1993 ▶); Maeno et al. (1990 ▶); Gilchrist (1997 ▶). For applications of glutaric acid, see: Windholz (1976 ▶). For the conformation of glutaric acid, see: Saraswathi et al. (2001 ▶); Stanley et al. (2002 ▶). For related structures, see: Thanigaimani et al. (2012a ▶,b ▶); Thanigaimani & Mu­thiah (2010 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C4H6ClN4 +·C5H7O4 −

M = 276.68

Monoclinic,

a = 5.1582 (1) Å

b = 23.2339 (5) Å

c = 9.8858 (2) Å

β = 94.7949 (12)°

V = 1180.62 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.34 mm−1

T = 296 K

0.54 × 0.24 × 0.21 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.838, T max = 0.932

31054 measured reflections

3121 independent reflections

2402 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.099

S = 1.04

3121 reflections

187 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.27 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/S1600536814015220/sj5418sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814015220/sj5418Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814015220/sj5418Isup3.cml

CCDC reference: 1010934

Additional supporting information: crystallographic information; 3D view; checkCIF report

C4H6ClN4+·C5H7O4−	F(000) = 576
Mr = 276.68	Dx = 1.557 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9974 reflections
a = 5.1582 (1) Å	θ = 2.3–28.9°
b = 23.2339 (5) Å	µ = 0.34 mm−1
c = 9.8858 (2) Å	T = 296 K
β = 94.7949 (12)°	Block, colourless
V = 1180.62 (4) Å3	0.54 × 0.24 × 0.21 mm
Z = 4

Bruker SMART APEXII DUO CCD area-detector diffractometer	3121 independent reflections
Radiation source: fine-focus sealed tube	2402 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 29.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −7→7
Tmin = 0.838, Tmax = 0.932	k = −31→31
31054 measured reflections	l = −13→13

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0384P)2 + 0.4919P] where P = (Fo2 + 2Fc2)/3
3121 reflections	(Δ/σ)max < 0.001
187 parameters	Δρmax = 0.24 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cl1	0.16574 (11)	0.356710 (18)	0.02821 (5)	0.05343 (16)
O1	0.9550 (2)	0.61641 (5)	0.37186 (13)	0.0452 (3)
O2	0.6452 (2)	0.58299 (5)	0.49189 (13)	0.0457 (3)
O4	0.2839 (3)	0.82514 (5)	0.75083 (13)	0.0456 (3)
O3	0.1675 (3)	0.73460 (5)	0.78386 (15)	0.0566 (4)
N1	0.0480 (3)	0.51507 (5)	0.25300 (13)	0.0313 (3)
N2	0.3649 (3)	0.55724 (6)	0.13291 (16)	0.0410 (4)
N3	0.2615 (3)	0.46281 (5)	0.08966 (13)	0.0336 (3)
N4	−0.2630 (3)	0.47569 (6)	0.37842 (15)	0.0388 (3)
C1	0.2246 (3)	0.51130 (6)	0.15836 (15)	0.0306 (3)
C2	0.1140 (3)	0.41827 (6)	0.12105 (16)	0.0326 (3)
C3	−0.0637 (3)	0.41698 (6)	0.21495 (16)	0.0352 (4)
H3A	−0.1570	0.3839	0.2319	0.042*
C4	−0.0981 (3)	0.46873 (6)	0.28496 (15)	0.0306 (3)
C5	0.7825 (3)	0.62305 (6)	0.45526 (16)	0.0317 (3)
C6	0.7534 (3)	0.68300 (6)	0.51111 (17)	0.0333 (3)
H6A	0.7280	0.7095	0.4353	0.040*
H6B	0.9152	0.6935	0.5623	0.040*
C7	0.5326 (3)	0.69147 (6)	0.60184 (16)	0.0344 (4)
H7A	0.3721	0.6768	0.5565	0.041*
H7B	0.5692	0.6700	0.6854	0.041*
C8	0.5006 (3)	0.75477 (7)	0.63429 (18)	0.0371 (4)
H8A	0.6670	0.7694	0.6725	0.045*
H8B	0.4566	0.7752	0.5499	0.045*
C9	0.2995 (3)	0.76880 (6)	0.73030 (16)	0.0321 (3)
H1N4	−0.364 (4)	0.4456 (9)	0.3998 (19)	0.050 (6)*
H2N2	0.469 (4)	0.5531 (8)	0.071 (2)	0.049 (6)*
H1N2	0.341 (4)	0.5903 (9)	0.171 (2)	0.048 (5)*
H2N4	−0.282 (4)	0.5094 (9)	0.4155 (19)	0.046 (5)*
H1N1	0.023 (4)	0.5489 (9)	0.294 (2)	0.052 (6)*
H1O4	0.153 (6)	0.8363 (12)	0.805 (3)	0.092 (8)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0729 (4)	0.0304 (2)	0.0614 (3)	−0.0024 (2)	0.0322 (3)	−0.01516 (19)
O1	0.0534 (8)	0.0268 (6)	0.0612 (8)	−0.0052 (5)	0.0391 (6)	−0.0065 (5)
O2	0.0517 (8)	0.0280 (6)	0.0626 (8)	−0.0071 (5)	0.0359 (6)	−0.0052 (5)
O4	0.0556 (8)	0.0281 (6)	0.0579 (8)	0.0063 (5)	0.0328 (6)	−0.0002 (5)
O3	0.0675 (9)	0.0356 (7)	0.0734 (9)	−0.0098 (6)	0.0450 (8)	−0.0061 (6)
N1	0.0372 (8)	0.0229 (6)	0.0365 (7)	0.0004 (5)	0.0189 (6)	−0.0024 (5)
N2	0.0496 (9)	0.0274 (7)	0.0505 (9)	−0.0047 (6)	0.0301 (7)	−0.0040 (6)
N3	0.0393 (8)	0.0270 (6)	0.0370 (7)	0.0013 (5)	0.0182 (6)	−0.0028 (5)
N4	0.0454 (9)	0.0291 (7)	0.0457 (8)	−0.0021 (6)	0.0270 (7)	−0.0021 (6)
C1	0.0345 (8)	0.0266 (7)	0.0327 (8)	0.0026 (6)	0.0142 (6)	0.0015 (6)
C2	0.0394 (9)	0.0245 (7)	0.0355 (8)	0.0024 (6)	0.0117 (7)	−0.0034 (6)
C3	0.0422 (9)	0.0246 (7)	0.0411 (9)	−0.0040 (6)	0.0177 (7)	−0.0010 (6)
C4	0.0332 (8)	0.0267 (7)	0.0338 (8)	0.0014 (6)	0.0128 (6)	0.0024 (6)
C5	0.0326 (8)	0.0271 (7)	0.0376 (8)	−0.0006 (6)	0.0153 (7)	−0.0017 (6)
C6	0.0340 (8)	0.0262 (7)	0.0418 (8)	−0.0014 (6)	0.0157 (7)	−0.0046 (6)
C7	0.0371 (9)	0.0280 (7)	0.0404 (9)	0.0004 (6)	0.0166 (7)	−0.0033 (6)
C8	0.0418 (9)	0.0286 (7)	0.0439 (9)	−0.0002 (7)	0.0212 (8)	−0.0033 (7)
C9	0.0344 (8)	0.0294 (7)	0.0335 (8)	0.0017 (6)	0.0093 (7)	−0.0028 (6)

Cl1—C2	1.7321 (15)	N4—H1N4	0.91 (2)
O1—C5	1.2720 (17)	N4—H2N4	0.87 (2)
O2—C5	1.2416 (18)	C2—C3	1.358 (2)
O4—C9	1.3281 (18)	C3—C4	1.406 (2)
O4—H1O4	0.94 (3)	C3—H3A	0.9300
O3—C9	1.1982 (19)	C5—C6	1.511 (2)
N1—C1	1.3624 (18)	C6—C7	1.520 (2)
N1—C4	1.3661 (19)	C6—H6A	0.9700
N1—H1N1	0.90 (2)	C6—H6B	0.9700
N2—C1	1.325 (2)	C7—C8	1.517 (2)
N2—H2N2	0.85 (2)	C7—H7A	0.9700
N2—H1N2	0.87 (2)	C7—H7B	0.9700
N3—C2	1.3361 (19)	C8—C9	1.499 (2)
N3—C1	1.3373 (18)	C8—H8A	0.9700
N4—C4	1.3173 (19)	C8—H8B	0.9700
C9—O4—H1O4	114.7 (17)	O2—C5—C6	120.54 (13)
C1—N1—C4	121.44 (13)	O1—C5—C6	116.42 (13)
C1—N1—H1N1	119.6 (13)	C5—C6—C7	115.92 (12)
C4—N1—H1N1	118.9 (13)	C5—C6—H6A	108.3
C1—N2—H2N2	115.6 (13)	C7—C6—H6A	108.3
C1—N2—H1N2	121.9 (13)	C5—C6—H6B	108.3
H2N2—N2—H1N2	122.2 (19)	C7—C6—H6B	108.3
C2—N3—C1	115.26 (12)	H6A—C6—H6B	107.4
C4—N4—H1N4	119.0 (12)	C8—C7—C6	110.52 (12)
C4—N4—H2N4	120.4 (13)	C8—C7—H7A	109.5
H1N4—N4—H2N4	120.4 (18)	C6—C7—H7A	109.5
N2—C1—N3	118.62 (13)	C8—C7—H7B	109.5
N2—C1—N1	119.06 (14)	C6—C7—H7B	109.5
N3—C1—N1	122.32 (13)	H7A—C7—H7B	108.1
N3—C2—C3	127.27 (14)	C9—C8—C7	115.99 (13)
N3—C2—Cl1	113.61 (11)	C9—C8—H8A	108.3
C3—C2—Cl1	119.11 (12)	C7—C8—H8A	108.3
C2—C3—C4	115.95 (14)	C9—C8—H8B	108.3
C2—C3—H3A	122.0	C7—C8—H8B	108.3
C4—C3—H3A	122.0	H8A—C8—H8B	107.4
N4—C4—N1	117.81 (14)	O3—C9—O4	122.82 (14)
N4—C4—C3	124.44 (14)	O3—C9—C8	125.75 (14)
N1—C4—C3	117.75 (13)	O4—C9—C8	111.43 (13)
O2—C5—O1	123.03 (14)
C2—N3—C1—N2	179.75 (16)	C1—N1—C4—C3	−1.2 (2)
C2—N3—C1—N1	−0.4 (2)	C2—C3—C4—N4	179.39 (17)
C4—N1—C1—N2	−178.74 (16)	C2—C3—C4—N1	0.0 (2)
C4—N1—C1—N3	1.4 (2)	O2—C5—C6—C7	−5.6 (2)
C1—N3—C2—C3	−0.9 (3)	O1—C5—C6—C7	175.33 (15)
C1—N3—C2—Cl1	179.29 (12)	C5—C6—C7—C8	−171.88 (15)
N3—C2—C3—C4	1.1 (3)	C6—C7—C8—C9	−176.36 (15)
Cl1—C2—C3—C4	−179.10 (13)	C7—C8—C9—O3	1.1 (3)
C1—N1—C4—N4	179.40 (15)	C7—C8—C9—O4	−179.20 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1N4···O2i	0.91 (2)	1.99 (2)	2.7950 (19)	147.4 (18)
N2—H2N2···N3ii	0.85 (2)	2.23 (2)	3.079 (2)	176.9 (18)
N2—H1N2···O4iii	0.87 (2)	2.15 (2)	3.0140 (18)	175.5 (18)
N4—H2N4···O2iv	0.87 (2)	1.92 (2)	2.7904 (18)	175 (2)
N1—H1N1···O1iv	0.90 (2)	1.80 (2)	2.6924 (17)	177 (2)
O4—H1O4···O1v	0.94 (3)	1.67 (3)	2.5480 (15)	155 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1N4⋯O2i	0.91 (2)	1.99 (2)	2.7950 (19)	147.4 (18)
N2—H2N2⋯N3ii	0.85 (2)	2.23 (2)	3.079 (2)	176.9 (18)
N2—H1N2⋯O4iii	0.87 (2)	2.15 (2)	3.0140 (18)	175.5 (18)
N4—H2N4⋯O2iv	0.87 (2)	1.92 (2)	2.7904 (18)	175 (2)
N1—H1N1⋯O1iv	0.90 (2)	1.80 (2)	2.6924 (17)	177 (2)
O4—H1O4⋯O1v	0.94 (3)	1.67 (3)	2.5480 (15)	155 (3)

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