2,4-Diamino-5-(4-chloro-phen-yl)-6-ethyl-pyrimidin-1-ium 2-propanamido-benzoate.

In the title salt, C(12)H(14)ClN(4) (+)·C(10)H(10)NO(3) (-), zwitterionic N-H⋯O inter-actions form an R(2) (2)(8) ring. The crystal structure is stabilized by N-H⋯O and N-H⋯N hydrogen bonds involving two different eight-membered rings. An N-H⋯O inter-action occurs between the pyrimidine ring (donor) and carboxyl-ate group (acceptor) while the other ring is formed by N-H⋯N inter-actions, which form a dimer between two symmetry-related salts. An intra-molecular N-H⋯O hydrogen bond forms a six-membered ring in the benzoate. Inter-molecular C-H⋯O inter-actions are also observed.

Related literature

For amino­pyrimidine carboxyl­ates, see: Chinnakali et al. (1999 ▶); Lynch & Jones (2004 ▶); Stanley et al. (2005 ▶). For amino­pyrimidine and benzoic acid adducts, see: Balasub­ram­ani et al. (2005 ▶, 2006 ▶); Thanigaimani et al. (2006 ▶, 2007 ▶). For hydrogen bonding in mol­ecular recognition and crystal engin­eering, see: Desiraju (1989 ▶). For puckering and asymmetry parameters, see: Cremer & Pople, (1975 ▶); Nardelli (1995 ▶).

Experimental

Crystal data

C12H14ClN4 +·C10H10NO3 −

M = 441.91

Monoclinic,

a = 22.144 (3) Å

b = 9.4915 (14) Å

c = 21.844 (3) Å

β = 99.071 (3)°

V = 4533.7 (12) Å3

Z = 8

Mo Kα radiation

μ = 0.20 mm−1

T = 293 K

0.50 × 0.45 × 0.42 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

17933 measured reflections

5077 independent reflections

2719 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.088

wR(F 2) = 0.228

S = 1.06

5077 reflections

281 parameters

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811035501/ff2025sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035501/ff2025Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811035501/ff2025Isup3.cml

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

C12H14ClN4+·C10H10NO3−	F(000) = 1856
Mr = 441.91	Dx = 1.295 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.144 (3) Å	Cell parameters from 17933 reflections
b = 9.4915 (14) Å	θ = 1.9–28.0°
c = 21.844 (3) Å	µ = 0.20 mm−1
β = 99.071 (3)°	T = 293 K
V = 4533.7 (12) Å3	Block, colorless
Z = 8	0.50 × 0.45 × 0.42 mm

Bruker SMART APEX CCD area-detector diffractometer	2719 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
graphite	θmax = 28.0°, θmin = 1.9°
ω scans	h = −28→29
17933 measured reflections	k = −10→12
5077 independent reflections	l = −28→28

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)] = 0.088	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.228	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.1005P)2 + 1.940P] where P = (Fo2 + 2Fc2)/3
5077 reflections	(Δ/σ)max = 0.002
281 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.24 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	0.62790 (7)	−0.12826 (18)	0.25493 (7)	0.1465 (7)
O1	0.25218 (12)	0.3854 (3)	0.05381 (12)	0.0926 (9)
O2	0.25430 (14)	0.2607 (4)	0.13892 (13)	0.1067 (11)
O3	0.37717 (11)	0.3960 (3)	0.33389 (11)	0.0809 (7)
N1	0.43891 (11)	0.3633 (3)	−0.01402 (11)	0.0567 (7)
N2	0.34901 (13)	0.3749 (3)	−0.08192 (12)	0.0708 (8)
H2A	0.3626	0.4469	−0.0994	0.085*
H2B	0.3130	0.3430	−0.0953	0.085*
N3	0.36043 (12)	0.2008 (3)	−0.00894 (12)	0.0640 (7)
H3	0.3237	0.1738	−0.0228	0.077*
N4	0.52835 (12)	0.3481 (3)	0.05255 (12)	0.0654 (7)
H4A	0.5399	0.4220	0.0348	0.078*
H4B	0.5525	0.3093	0.0825	0.078*
N5	0.32811 (13)	0.3417 (3)	0.23743 (12)	0.0763 (9)
H5	0.2990	0.2900	0.2188	0.092*
C2	0.38321 (14)	0.3137 (3)	−0.03469 (14)	0.0567 (8)
C4	0.39373 (15)	0.1283 (4)	0.03825 (14)	0.0620 (9)
C5	0.45211 (14)	0.1711 (3)	0.06071 (13)	0.0562 (8)
C6	0.47322 (14)	0.2937 (3)	0.03366 (13)	0.0544 (8)
C7	0.49398 (15)	0.0933 (4)	0.10941 (14)	0.0590 (8)
C8	0.51370 (18)	−0.0416 (4)	0.09988 (16)	0.0780 (10)
H8	0.4995	−0.0873	0.0627	0.094*
C9	0.5542 (2)	−0.1100 (4)	0.1447 (2)	0.0925 (13)
H9	0.5666	−0.2014	0.1378	0.111*
C10	0.57609 (18)	−0.0431 (5)	0.19934 (18)	0.0828 (11)
C11	0.55717 (17)	0.0894 (5)	0.21009 (16)	0.0770 (11)
H11	0.5722	0.1341	0.2473	0.092*
C12	0.51563 (16)	0.1586 (4)	0.16609 (15)	0.0676 (9)
H12	0.5021	0.2484	0.1742	0.081*
C13	0.36238 (19)	0.0048 (4)	0.06172 (18)	0.0857 (12)
H13A	0.3875	−0.0302	0.0990	0.103*
H13B	0.3238	0.0360	0.0729	0.103*
C14	0.3503 (3)	−0.1118 (5)	0.0168 (3)	0.1222 (18)
H14A	0.3300	−0.1870	0.0348	0.183*
H14B	0.3883	−0.1455	0.0064	0.183*
H14C	0.3247	−0.0788	−0.0200	0.183*
C15	0.33329 (14)	0.4293 (4)	0.13458 (15)	0.0596 (8)
C16	0.36330 (15)	0.5078 (4)	0.09550 (16)	0.0663 (9)
H16	0.3467	0.5132	0.0537	0.080*
C17	0.41712 (16)	0.5788 (4)	0.11626 (18)	0.0754 (10)
H17	0.4364	0.6313	0.0891	0.090*
C18	0.44141 (17)	0.5700 (4)	0.17795 (19)	0.0833 (11)
H18	0.4777	0.6169	0.1927	0.100*
C19	0.41304 (16)	0.4932 (4)	0.21807 (18)	0.0774 (10)
H19	0.4303	0.4888	0.2597	0.093*
C20	0.35892 (15)	0.4216 (4)	0.19784 (15)	0.0620 (8)
C21	0.27569 (16)	0.3551 (4)	0.10749 (16)	0.0687 (9)
C22	0.33649 (17)	0.3327 (4)	0.29967 (16)	0.0758 (10)
C23	0.2921 (2)	0.2325 (7)	0.3252 (2)	0.1161 (17)
H23A	0.2583	0.2126	0.2924	0.139*
H23B	0.3131	0.1442	0.3363	0.139*
C24	0.2684 (5)	0.2828 (11)	0.3771 (4)	0.247 (6)
H24A	0.2412	0.2139	0.3898	0.371*
H24B	0.2465	0.3689	0.3665	0.371*
H24C	0.3014	0.2999	0.4104	0.371*

	U11	U22	U33	U12	U13	U23
Cl1	0.1356 (12)	0.1739 (14)	0.1179 (10)	0.0501 (10)	−0.0176 (8)	0.0603 (10)
O1	0.0793 (17)	0.122 (2)	0.0646 (15)	−0.0330 (16)	−0.0247 (13)	0.0108 (15)
O2	0.097 (2)	0.132 (3)	0.0758 (17)	−0.0575 (19)	−0.0334 (15)	0.0152 (17)
O3	0.0685 (15)	0.104 (2)	0.0626 (14)	0.0039 (14)	−0.0119 (12)	−0.0153 (14)
N1	0.0503 (14)	0.0625 (16)	0.0522 (14)	−0.0062 (13)	−0.0077 (11)	0.0027 (12)
N2	0.0611 (16)	0.0756 (19)	0.0667 (17)	−0.0151 (15)	−0.0177 (14)	0.0160 (15)
N3	0.0519 (15)	0.0730 (19)	0.0613 (16)	−0.0176 (14)	−0.0093 (12)	0.0036 (14)
N4	0.0542 (15)	0.0687 (18)	0.0675 (17)	−0.0089 (14)	−0.0082 (13)	0.0185 (14)
N5	0.0629 (17)	0.100 (2)	0.0574 (17)	−0.0223 (17)	−0.0183 (14)	−0.0015 (16)
C2	0.0562 (19)	0.0574 (19)	0.0522 (17)	−0.0120 (16)	−0.0045 (15)	−0.0012 (15)
C4	0.062 (2)	0.067 (2)	0.0534 (18)	−0.0103 (17)	−0.0020 (15)	0.0032 (16)
C5	0.0576 (18)	0.061 (2)	0.0484 (16)	−0.0032 (16)	0.0024 (14)	0.0017 (14)
C6	0.0513 (17)	0.060 (2)	0.0494 (17)	−0.0062 (16)	0.0014 (14)	−0.0001 (14)
C7	0.0579 (18)	0.065 (2)	0.0528 (18)	−0.0041 (16)	0.0051 (15)	0.0059 (15)
C8	0.098 (3)	0.072 (3)	0.061 (2)	0.006 (2)	0.005 (2)	0.0003 (18)
C9	0.116 (4)	0.078 (3)	0.085 (3)	0.033 (3)	0.020 (3)	0.019 (2)
C10	0.075 (2)	0.104 (3)	0.068 (2)	0.014 (2)	0.005 (2)	0.026 (2)
C11	0.072 (2)	0.099 (3)	0.055 (2)	−0.005 (2)	−0.0049 (18)	0.009 (2)
C12	0.069 (2)	0.073 (2)	0.058 (2)	0.0008 (18)	0.0028 (17)	0.0016 (17)
C13	0.081 (3)	0.089 (3)	0.080 (2)	−0.021 (2)	−0.009 (2)	0.016 (2)
C14	0.132 (4)	0.085 (3)	0.139 (4)	−0.026 (3)	−0.013 (4)	0.007 (3)
C15	0.0490 (17)	0.063 (2)	0.0607 (19)	0.0016 (16)	−0.0089 (15)	−0.0106 (16)
C16	0.061 (2)	0.076 (2)	0.0568 (18)	−0.0003 (18)	−0.0051 (16)	−0.0004 (17)
C17	0.055 (2)	0.084 (3)	0.084 (3)	−0.0058 (19)	0.0027 (18)	0.006 (2)
C18	0.061 (2)	0.090 (3)	0.091 (3)	−0.017 (2)	−0.013 (2)	0.002 (2)
C19	0.065 (2)	0.086 (3)	0.071 (2)	−0.012 (2)	−0.0202 (18)	0.000 (2)
C20	0.0519 (18)	0.066 (2)	0.0625 (19)	−0.0002 (17)	−0.0091 (15)	−0.0040 (17)
C21	0.062 (2)	0.078 (2)	0.060 (2)	−0.0134 (19)	−0.0081 (17)	−0.0059 (19)
C22	0.065 (2)	0.095 (3)	0.061 (2)	0.008 (2)	−0.0099 (18)	−0.005 (2)
C23	0.100 (3)	0.174 (5)	0.073 (3)	−0.012 (3)	0.009 (2)	0.015 (3)
C24	0.312 (13)	0.252 (10)	0.206 (9)	−0.147 (10)	0.126 (9)	−0.044 (8)

Cl1—C10	1.734 (4)	C10—C11	1.357 (6)
O1—C21	1.240 (4)	C11—C12	1.387 (5)
O2—C21	1.265 (4)	C11—H11	0.9300
O3—C22	1.232 (4)	C12—H12	0.9300
N1—C2	1.331 (4)	C13—C14	1.475 (6)
N1—C6	1.360 (4)	C13—H13A	0.9700
N2—C2	1.315 (4)	C13—H13B	0.9700
N2—H2A	0.8600	C14—H14A	0.9600
N2—H2B	0.8600	C14—H14B	0.9600
N3—C2	1.345 (4)	C14—H14C	0.9600
N3—C4	1.356 (4)	C15—C16	1.380 (5)
N3—H3	0.8600	C15—C20	1.410 (4)
N4—C6	1.330 (4)	C15—C21	1.495 (5)
N4—H4A	0.8600	C16—C17	1.382 (5)
N4—H4B	0.8600	C16—H16	0.9300
N5—C22	1.346 (4)	C17—C18	1.372 (5)
N5—C20	1.405 (4)	C17—H17	0.9300
N5—H5	0.8600	C18—C19	1.366 (5)
C4—C5	1.370 (4)	C18—H18	0.9300
C4—C13	1.494 (5)	C19—C20	1.388 (5)
C5—C6	1.417 (4)	C19—H19	0.9300
C5—C7	1.492 (4)	C22—C23	1.534 (6)
C7—C8	1.379 (5)	C23—C24	1.406 (9)
C7—C12	1.400 (4)	C23—H23A	0.9700
C8—C9	1.381 (5)	C23—H23B	0.9700
C8—H8	0.9300	C24—H24A	0.9600
C9—C10	1.372 (6)	C24—H24B	0.9600
C9—H9	0.9300	C24—H24C	0.9600
C2—N1—C6	117.6 (3)	C14—C13—H13B	108.8
C2—N2—H2A	120.0	C4—C13—H13B	108.8
C2—N2—H2B	120.0	H13A—C13—H13B	107.7
H2A—N2—H2B	120.0	C13—C14—H14A	109.5
C2—N3—C4	121.8 (3)	C13—C14—H14B	109.5
C2—N3—H3	119.1	H14A—C14—H14B	109.5
C4—N3—H3	119.1	C13—C14—H14C	109.5
C6—N4—H4A	120.0	H14A—C14—H14C	109.5
C6—N4—H4B	120.0	H14B—C14—H14C	109.5
H4A—N4—H4B	120.0	C16—C15—C20	118.4 (3)
C22—N5—C20	130.8 (3)	C16—C15—C21	118.3 (3)
C22—N5—H5	114.6	C20—C15—C21	123.4 (3)
C20—N5—H5	114.6	C15—C16—C17	122.3 (3)
N2—C2—N1	119.9 (3)	C15—C16—H16	118.8
N2—C2—N3	118.2 (3)	C17—C16—H16	118.8
N1—C2—N3	121.9 (3)	C18—C17—C16	118.5 (4)
N3—C4—C5	119.4 (3)	C18—C17—H17	120.8
N3—C4—C13	115.6 (3)	C16—C17—H17	120.8
C5—C4—C13	125.0 (3)	C19—C18—C17	120.9 (3)
C4—C5—C6	116.6 (3)	C19—C18—H18	119.5
C4—C5—C7	123.6 (3)	C17—C18—H18	119.5
C6—C5—C7	119.7 (3)	C18—C19—C20	121.2 (3)
N4—C6—N1	115.1 (3)	C18—C19—H19	119.4
N4—C6—C5	122.4 (3)	C20—C19—H19	119.4
N1—C6—C5	122.5 (3)	C19—C20—N5	123.1 (3)
C8—C7—C12	118.2 (3)	C19—C20—C15	118.7 (3)
C8—C7—C5	121.9 (3)	N5—C20—C15	118.1 (3)
C12—C7—C5	119.9 (3)	O1—C21—O2	122.7 (3)
C7—C8—C9	121.0 (4)	O1—C21—C15	118.0 (3)
C7—C8—H8	119.5	O2—C21—C15	119.2 (3)
C9—C8—H8	119.5	O3—C22—N5	123.6 (4)
C10—C9—C8	120.0 (4)	O3—C22—C23	122.0 (3)
C10—C9—H9	120.0	N5—C22—C23	114.4 (3)
C8—C9—H9	120.0	C24—C23—C22	115.1 (6)
C11—C10—C9	120.2 (4)	C24—C23—H23A	108.5
C11—C10—Cl1	120.0 (3)	C22—C23—H23A	108.5
C9—C10—Cl1	119.9 (4)	C24—C23—H23B	108.5
C10—C11—C12	120.5 (4)	C22—C23—H23B	108.5
C10—C11—H11	119.7	H23A—C23—H23B	107.5
C12—C11—H11	119.7	C23—C24—H24A	109.5
C11—C12—C7	120.0 (4)	C23—C24—H24B	109.5
C11—C12—H12	120.0	H24A—C24—H24B	109.5
C7—C12—H12	120.0	C23—C24—H24C	109.5
C14—C13—C4	114.0 (4)	H24A—C24—H24C	109.5
C14—C13—H13A	108.8	H24B—C24—H24C	109.5
C4—C13—H13A	108.8
C6—N1—C2—N2	−178.0 (3)	C10—C11—C12—C7	−1.6 (5)
C6—N1—C2—N3	1.5 (5)	C8—C7—C12—C11	1.9 (5)
C4—N3—C2—N2	177.3 (3)	C5—C7—C12—C11	−176.4 (3)
C4—N3—C2—N1	−2.2 (5)	N3—C4—C13—C14	67.1 (5)
C2—N3—C4—C5	0.3 (5)	C5—C4—C13—C14	−112.8 (4)
C2—N3—C4—C13	−179.6 (3)	C20—C15—C16—C17	−0.1 (5)
N3—C4—C5—C6	2.0 (5)	C21—C15—C16—C17	−179.3 (3)
C13—C4—C5—C6	−178.1 (3)	C15—C16—C17—C18	0.2 (6)
N3—C4—C5—C7	−175.7 (3)	C16—C17—C18—C19	−0.2 (6)
C13—C4—C5—C7	4.2 (5)	C17—C18—C19—C20	0.1 (6)
C2—N1—C6—N4	−179.8 (3)	C18—C19—C20—N5	−179.8 (3)
C2—N1—C6—C5	1.0 (4)	C18—C19—C20—C15	0.0 (6)
C4—C5—C6—N4	178.1 (3)	C22—N5—C20—C19	10.9 (6)
C7—C5—C6—N4	−4.1 (5)	C22—N5—C20—C15	−168.9 (4)
C4—C5—C6—N1	−2.7 (5)	C16—C15—C20—C19	0.0 (5)
C7—C5—C6—N1	175.0 (3)	C21—C15—C20—C19	179.2 (3)
C4—C5—C7—C8	63.2 (5)	C16—C15—C20—N5	179.9 (3)
C6—C5—C7—C8	−114.4 (4)	C21—C15—C20—N5	−1.0 (5)
C4—C5—C7—C12	−118.5 (4)	C16—C15—C21—O1	−11.5 (5)
C6—C5—C7—C12	63.9 (4)	C20—C15—C21—O1	169.3 (3)
C12—C7—C8—C9	−0.7 (5)	C16—C15—C21—O2	165.7 (3)
C5—C7—C8—C9	177.6 (3)	C20—C15—C21—O2	−13.5 (5)
C7—C8—C9—C10	−0.9 (6)	C20—N5—C22—O3	−2.3 (6)
C8—C9—C10—C11	1.3 (6)	C20—N5—C22—C23	179.6 (4)
C8—C9—C10—Cl1	−178.9 (3)	O3—C22—C23—C24	44.3 (8)
C9—C10—C11—C12	−0.1 (6)	N5—C22—C23—C24	−137.5 (7)
Cl1—C10—C11—C12	−179.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O2	0.86	1.89	2.605 (4)	140
N2—H2A···O3i	0.86	2.15	2.977 (4)	163
N4—H4A···N1ii	0.86	2.16	2.988 (4)	163
N3—H3···O1iii	0.86	1.80	2.660 (4)	178
C14—H14C···O1iii	0.96	2.53	3.323 (6)	140
N2—H2B···O2iii	0.86	1.91	2.746 (4)	164
N4—H4B···O3iv	0.86	2.35	3.017 (3)	134

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5⋯O2	0.86	1.89	2.605 (4)	140
N2—H2A⋯O3i	0.86	2.15	2.977 (4)	163
N4—H4A⋯N1ii	0.86	2.16	2.988 (4)	163
N3—H3⋯O1iii	0.86	1.80	2.660 (4)	178
C14—H14C⋯O1iii	0.96	2.53	3.323 (6)	140
N2—H2B⋯O2iii	0.86	1.91	2.746 (4)	164
N4—H4B⋯O3iv	0.86	2.35	3.017 (3)	134

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