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

The title compound, C(12)H(14)ClN(4) (+)·C(9)H(8)NO(3) (-), is a salt with a 1:1 ratio of cation and anion components inter-acting with each other forming an R(2) (2)(8) ring motif. The crystal structure is stabilized by hydrogen bonds (N-H⋯O) involving two different eight-membered rings. One of them is formed between the pyrimidine ring (donor) and the carboxylate group (acceptor) from the benzoate, whereas the other ring is formed by N-H⋯O interactions, which help to form a dimer between two symmetry-related salts in the unit cell. In addition, an intramolecular C-H⋯N and intermolecular C-H⋯Cl interactions help to control the molecules in the unit-cell packing.

Related literature

For related literature on amino­pyrimidine–carboxyl­ate inter­actions, see: Baker & Santi (1965 ▶); Chinnakali et al. (1999 ▶); Desiraju (1989 ▶); Hunt et al. (1980 ▶); Lynch & Jones (2004 ▶); Stanley et al. (2005 ▶). For literature on amino­pyrimidine and benzoic acid adducts, see: Thanigaimani et al. (2006 ▶, 2007 ▶); Balasubramani et al. (2005 ▶, 2006 ▶). For puckering parameters, see: Cremer & Pople, (1975 ▶); Nardelli (1995 ▶).

Experimental

Crystal data

C12H14ClN4 +·C9H8NO3 −

M = 427.89

Monoclinic,

a = 25.226 (4) Å

b = 9.0666 (16) Å

c = 20.688 (4) Å

β = 113.400 (3)°

V = 4342.5 (13) Å3

Z = 8

Mo Kα radiation

μ = 0.21 mm−1

T = 293 K

0.4 × 0.35 × 0.32 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

14400 measured reflections

3937 independent reflections

3079 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.123

S = 1.04

3937 reflections

272 parameters

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.19 e Å−3

Data collection: SMART (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/S1600536811032570/ng5209sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811032570/ng5209Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811032570/ng5209Isup3.cml

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

C12H14ClN4+·C9H8NO3−	F(000) = 1792
Mr = 427.89	Dx = 1.309 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 25.226 (4) Å	Cell parameters from 14400 reflections
b = 9.0666 (16) Å	θ = 1.8–26.2°
c = 20.688 (4) Å	µ = 0.21 mm−1
β = 113.400 (3)°	T = 293 K
V = 4342.5 (13) Å3	Block, colourless
Z = 8	0.4 × 0.35 × 0.32 mm

Bruker SMART APEX CCD area-detector diffractometer	3079 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.019
graphite	θmax = 26.2°, θmin = 1.8°
ω scans	h = −29→30
14400 measured reflections	k = −11→11
3937 independent reflections	l = −25→24

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.059P)2 + 2.2497P] where P = (Fo2 + 2Fc2)/3
3937 reflections	(Δ/σ)max < 0.001
272 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.19 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	0.09641 (3)	0.17665 (8)	0.85360 (3)	0.0916 (3)
O1	0.34974 (6)	0.30249 (17)	0.60241 (7)	0.0668 (4)
O2	0.40391 (6)	0.20074 (17)	0.70432 (7)	0.0651 (4)
O3	0.16543 (8)	0.5398 (3)	0.55466 (10)	0.1088 (7)
N1	0.06713 (6)	0.24269 (18)	0.44774 (7)	0.0487 (4)
H1	0.0925	0.2276	0.4304	0.058*
N5	0.25286 (7)	0.4296 (2)	0.58885 (9)	0.0691 (5)
H5	0.2795	0.4091	0.5742	0.083*
N2	−0.02695 (6)	0.31925 (17)	0.42880 (8)	0.0490 (4)
C2	0.01378 (8)	0.2902 (2)	0.40505 (9)	0.0473 (4)
C4	−0.01287 (7)	0.30452 (19)	0.49808 (9)	0.0449 (4)
C5	0.04201 (8)	0.2494 (2)	0.54570 (9)	0.0450 (4)
C6	0.08133 (8)	0.2183 (2)	0.51771 (9)	0.0458 (4)
N3	0.00325 (7)	0.3063 (2)	0.33758 (8)	0.0642 (5)
H3A	−0.0302	0.3358	0.3086	0.077*
H3B	0.0298	0.2873	0.3226	0.077*
N4	−0.05259 (7)	0.34253 (19)	0.52206 (8)	0.0573 (4)
H4A	−0.0856	0.3749	0.4934	0.069*
H4B	−0.0453	0.3347	0.5662	0.069*
C9	0.13931 (8)	0.1497 (2)	0.55671 (10)	0.0573 (5)
H9A	0.1505	0.1627	0.6069	0.069*
H9B	0.1678	0.1987	0.5437	0.069*
C10	0.13821 (12)	−0.0142 (3)	0.54001 (14)	0.0866 (8)
H10A	0.1758	−0.0557	0.5655	0.130*
H10B	0.1277	−0.0270	0.4904	0.130*
H10C	0.1105	−0.0630	0.5536	0.130*
C11	0.05491 (8)	0.2300 (2)	0.62204 (9)	0.0461 (4)
C12	0.05200 (10)	0.0934 (2)	0.65023 (10)	0.0615 (5)
H12	0.0415	0.0115	0.6208	0.074*
C13	0.06433 (10)	0.0761 (2)	0.72089 (11)	0.0672 (6)
H13	0.0625	−0.0165	0.7392	0.081*
C14	0.07937 (9)	0.1978 (2)	0.76379 (10)	0.0583 (5)
C15	0.08186 (10)	0.3350 (2)	0.73762 (10)	0.0624 (5)
H15	0.0916	0.4169	0.7672	0.075*
C16	0.06970 (9)	0.3503 (2)	0.66685 (10)	0.0565 (5)
H16	0.0715	0.4433	0.6489	0.068*
C17	0.26374 (9)	0.3814 (2)	0.65760 (11)	0.0597 (5)
C18	0.22574 (11)	0.4080 (3)	0.69018 (15)	0.0842 (7)
H18	0.1915	0.4589	0.6659	0.101*
C19	0.23812 (13)	0.3602 (4)	0.75731 (16)	0.0925 (8)
H19	0.2122	0.3790	0.7781	0.111*
C20	0.28810 (12)	0.2852 (3)	0.79432 (14)	0.0819 (7)
H20	0.2964	0.2536	0.8401	0.098*
C21	0.32583 (10)	0.2572 (3)	0.76267 (11)	0.0654 (6)
H21	0.3597	0.2059	0.7878	0.078*
C22	0.31507 (8)	0.3029 (2)	0.69465 (10)	0.0516 (5)
C23	0.35930 (8)	0.2663 (2)	0.66497 (10)	0.0498 (5)
C24	0.20715 (10)	0.5028 (3)	0.54250 (13)	0.0763 (7)
C25	0.21049 (12)	0.5345 (4)	0.47279 (14)	0.0992 (9)
H25A	0.1732	0.5193	0.4355	0.149*
H25B	0.2381	0.4696	0.4664	0.149*
H25C	0.2223	0.6350	0.4720	0.149*

	U11	U22	U33	U12	U13	U23
Cl1	0.1155 (6)	0.1148 (6)	0.0436 (3)	0.0138 (4)	0.0307 (3)	0.0113 (3)
O1	0.0521 (8)	0.0950 (11)	0.0544 (9)	0.0212 (8)	0.0222 (7)	0.0160 (8)
O2	0.0497 (8)	0.0881 (11)	0.0533 (8)	0.0187 (7)	0.0158 (6)	0.0105 (7)
O3	0.0666 (11)	0.1441 (18)	0.0979 (13)	0.0506 (12)	0.0139 (10)	0.0016 (12)
N1	0.0421 (8)	0.0635 (10)	0.0400 (8)	0.0054 (7)	0.0159 (6)	0.0034 (7)
N5	0.0487 (9)	0.0840 (13)	0.0700 (12)	0.0178 (9)	0.0187 (8)	0.0095 (10)
N2	0.0410 (8)	0.0601 (10)	0.0426 (8)	0.0025 (7)	0.0131 (7)	0.0051 (7)
C2	0.0437 (10)	0.0538 (11)	0.0400 (9)	−0.0003 (8)	0.0118 (8)	0.0027 (8)
C4	0.0432 (10)	0.0455 (10)	0.0449 (10)	−0.0014 (8)	0.0164 (8)	0.0034 (8)
C5	0.0461 (10)	0.0441 (10)	0.0428 (9)	0.0009 (8)	0.0156 (8)	0.0028 (8)
C6	0.0445 (10)	0.0488 (10)	0.0391 (9)	−0.0005 (8)	0.0112 (8)	−0.0002 (8)
N3	0.0499 (9)	0.1003 (14)	0.0388 (9)	0.0151 (9)	0.0136 (7)	0.0090 (8)
N4	0.0454 (9)	0.0785 (12)	0.0478 (9)	0.0105 (8)	0.0183 (7)	0.0101 (8)
C9	0.0496 (11)	0.0754 (14)	0.0418 (10)	0.0112 (10)	0.0128 (8)	0.0048 (9)
C10	0.0947 (18)	0.0754 (16)	0.0860 (17)	0.0288 (14)	0.0320 (14)	0.0133 (13)
C11	0.0449 (10)	0.0496 (11)	0.0420 (9)	0.0060 (8)	0.0154 (8)	0.0035 (8)
C12	0.0830 (15)	0.0490 (12)	0.0509 (11)	−0.0012 (10)	0.0248 (10)	0.0001 (9)
C13	0.0921 (16)	0.0565 (13)	0.0550 (12)	0.0053 (11)	0.0314 (11)	0.0141 (10)
C14	0.0613 (12)	0.0722 (14)	0.0407 (10)	0.0115 (10)	0.0194 (9)	0.0065 (10)
C15	0.0770 (14)	0.0601 (13)	0.0473 (11)	0.0038 (11)	0.0218 (10)	−0.0065 (9)
C16	0.0703 (13)	0.0474 (11)	0.0512 (11)	0.0036 (9)	0.0235 (10)	0.0034 (9)
C17	0.0486 (11)	0.0663 (13)	0.0625 (12)	0.0024 (9)	0.0204 (9)	−0.0077 (10)
C18	0.0624 (14)	0.1020 (19)	0.0919 (19)	0.0213 (13)	0.0344 (13)	−0.0068 (15)
C19	0.0876 (19)	0.121 (2)	0.0872 (19)	0.0119 (17)	0.0543 (16)	−0.0122 (17)
C20	0.0856 (18)	0.104 (2)	0.0663 (14)	0.0015 (15)	0.0405 (13)	−0.0067 (14)
C21	0.0640 (13)	0.0748 (14)	0.0574 (12)	0.0038 (11)	0.0243 (10)	−0.0023 (11)
C22	0.0447 (10)	0.0536 (11)	0.0539 (11)	−0.0036 (8)	0.0169 (8)	−0.0081 (9)
C23	0.0430 (10)	0.0543 (11)	0.0475 (11)	0.0014 (8)	0.0129 (8)	−0.0032 (9)
C24	0.0526 (13)	0.0783 (16)	0.0795 (16)	0.0147 (12)	0.0065 (11)	−0.0024 (12)
C25	0.0818 (17)	0.111 (2)	0.0846 (18)	0.0232 (16)	0.0111 (14)	0.0237 (16)

Cl1—C14	1.7433 (19)	C10—H10C	0.9600
O1—C23	1.262 (2)	C11—C12	1.383 (3)
O2—C23	1.247 (2)	C11—C16	1.383 (3)
O3—C24	1.222 (3)	C12—C13	1.377 (3)
N1—C2	1.354 (2)	C12—H12	0.9300
N1—C6	1.364 (2)	C13—C14	1.372 (3)
N1—H1	0.8600	C13—H13	0.9300
N5—C24	1.346 (3)	C14—C15	1.368 (3)
N5—C17	1.407 (3)	C15—C16	1.379 (3)
N5—H5	0.8600	C15—H15	0.9300
N2—C2	1.329 (2)	C16—H16	0.9300
N2—C4	1.339 (2)	C17—C18	1.395 (3)
C2—N3	1.321 (2)	C17—C22	1.408 (3)
C4—N4	1.328 (2)	C18—C19	1.367 (4)
C4—C5	1.433 (2)	C18—H18	0.9300
C5—C6	1.362 (3)	C19—C20	1.368 (4)
C5—C11	1.491 (2)	C19—H19	0.9300
C6—C9	1.497 (3)	C20—C21	1.376 (3)
N3—H3A	0.8600	C20—H20	0.9300
N3—H3B	0.8600	C21—C22	1.386 (3)
N4—H4A	0.8600	C21—H21	0.9300
N4—H4B	0.8600	C22—C23	1.509 (3)
C9—C10	1.523 (3)	C24—C25	1.505 (4)
C9—H9A	0.9700	C25—H25A	0.9600
C9—H9B	0.9700	C25—H25B	0.9600
C10—H10A	0.9600	C25—H25C	0.9600
C10—H10B	0.9600
C2—N1—C6	121.21 (16)	C14—C13—C12	118.9 (2)
C2—N1—H1	119.4	C14—C13—H13	120.6
C6—N1—H1	119.4	C12—C13—H13	120.6
C24—N5—C17	129.9 (2)	C15—C14—C13	121.32 (18)
C24—N5—H5	115.1	C15—C14—Cl1	119.43 (17)
C17—N5—H5	115.1	C13—C14—Cl1	119.25 (17)
C2—N2—C4	117.42 (14)	C14—C15—C16	119.05 (19)
N3—C2—N2	120.54 (16)	C14—C15—H15	120.5
N3—C2—N1	117.07 (17)	C16—C15—H15	120.5
N2—C2—N1	122.39 (16)	C15—C16—C11	121.32 (19)
N4—C4—N2	117.08 (15)	C15—C16—H16	119.3
N4—C4—C5	120.00 (16)	C11—C16—H16	119.3
N2—C4—C5	122.92 (16)	C18—C17—N5	122.7 (2)
C6—C5—C4	116.60 (16)	C18—C17—C22	119.0 (2)
C6—C5—C11	122.45 (16)	N5—C17—C22	118.38 (18)
C4—C5—C11	120.95 (16)	C19—C18—C17	120.8 (2)
C5—C6—N1	119.27 (16)	C19—C18—H18	119.6
C5—C6—C9	125.29 (16)	C17—C18—H18	119.6
N1—C6—C9	115.35 (16)	C18—C19—C20	120.9 (2)
C2—N3—H3A	120.0	C18—C19—H19	119.5
C2—N3—H3B	120.0	C20—C19—H19	119.5
H3A—N3—H3B	120.0	C19—C20—C21	118.9 (2)
C4—N4—H4A	120.0	C19—C20—H20	120.6
C4—N4—H4B	120.0	C21—C20—H20	120.6
H4A—N4—H4B	120.0	C20—C21—C22	122.3 (2)
C6—C9—C10	110.93 (18)	C20—C21—H21	118.8
C6—C9—H9A	109.5	C22—C21—H21	118.8
C10—C9—H9A	109.5	C21—C22—C17	118.07 (19)
C6—C9—H9B	109.5	C21—C22—C23	117.99 (17)
C10—C9—H9B	109.5	C17—C22—C23	123.93 (18)
H9A—C9—H9B	108.0	O2—C23—O1	123.28 (18)
C9—C10—H10A	109.5	O2—C23—C22	117.42 (17)
C9—C10—H10B	109.5	O1—C23—C22	119.29 (16)
H10A—C10—H10B	109.5	O3—C24—N5	123.6 (3)
C9—C10—H10C	109.5	O3—C24—C25	121.7 (2)
H10A—C10—H10C	109.5	N5—C24—C25	114.8 (2)
H10B—C10—H10C	109.5	C24—C25—H25A	109.5
C12—C11—C16	117.94 (17)	C24—C25—H25B	109.5
C12—C11—C5	121.79 (17)	H25A—C25—H25B	109.5
C16—C11—C5	120.26 (17)	C24—C25—H25C	109.5
C13—C12—C11	121.50 (19)	H25A—C25—H25C	109.5
C13—C12—H12	119.3	H25B—C25—H25C	109.5
C11—C12—H12	119.3
C4—N2—C2—N3	−178.21 (17)	C12—C13—C14—Cl1	−178.78 (17)
C4—N2—C2—N1	2.2 (3)	C13—C14—C15—C16	−0.9 (3)
C6—N1—C2—N3	−177.84 (17)	Cl1—C14—C15—C16	178.42 (17)
C6—N1—C2—N2	1.8 (3)	C14—C15—C16—C11	0.2 (3)
C2—N2—C4—N4	175.89 (16)	C12—C11—C16—C15	0.7 (3)
C2—N2—C4—C5	−4.6 (3)	C5—C11—C16—C15	−179.95 (19)
N4—C4—C5—C6	−177.47 (17)	C24—N5—C17—C18	−1.4 (4)
N2—C4—C5—C6	3.1 (3)	C24—N5—C17—C22	178.4 (2)
N4—C4—C5—C11	1.7 (3)	N5—C17—C18—C19	−179.5 (2)
N2—C4—C5—C11	−177.80 (16)	C22—C17—C18—C19	0.7 (4)
C4—C5—C6—N1	1.0 (3)	C17—C18—C19—C20	0.0 (5)
C11—C5—C6—N1	−178.14 (16)	C18—C19—C20—C21	−0.5 (5)
C4—C5—C6—C9	−175.26 (17)	C19—C20—C21—C22	0.2 (4)
C11—C5—C6—C9	5.6 (3)	C20—C21—C22—C17	0.5 (3)
C2—N1—C6—C5	−3.3 (3)	C20—C21—C22—C23	−179.9 (2)
C2—N1—C6—C9	173.28 (17)	C18—C17—C22—C21	−0.9 (3)
C5—C6—C9—C10	100.7 (2)	N5—C17—C22—C21	179.27 (19)
N1—C6—C9—C10	−75.7 (2)	C18—C17—C22—C23	179.5 (2)
C6—C5—C11—C12	−80.4 (2)	N5—C17—C22—C23	−0.3 (3)
C4—C5—C11—C12	100.5 (2)	C21—C22—C23—O2	−2.1 (3)
C6—C5—C11—C16	100.3 (2)	C17—C22—C23—O2	177.44 (19)
C4—C5—C11—C16	−78.8 (2)	C21—C22—C23—O1	177.81 (18)
C16—C11—C12—C13	−1.1 (3)	C17—C22—C23—O1	−2.7 (3)
C5—C11—C12—C13	179.58 (19)	C17—N5—C24—O3	−0.3 (4)
C11—C12—C13—C14	0.5 (3)	C17—N5—C24—C25	−179.4 (2)
C12—C13—C14—C15	0.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O1	0.86	1.90	2.614 (2)	140
C9—H9B···N5	0.97	2.87	3.683 (3)	142
N1—H1···O1i	0.86	1.86	2.715 (2)	177
N3—H3B···O2i	0.86	1.96	2.802 (3)	165
N3—H3A···O2ii	0.86	2.16	2.897 (2)	143
N4—H4A···O3iii	0.86	2.01	2.859 (2)	168
C10—H10B···Cl1iv	0.96	2.95	3.864 (3)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5⋯O1	0.86	1.90	2.614 (2)	140
C9—H9B⋯N5	0.97	2.87	3.683 (3)	142
N1—H1⋯O1i	0.86	1.86	2.715 (2)	177
N3—H3B⋯O2i	0.86	1.96	2.802 (3)	165
N3—H3A⋯O2ii	0.86	2.16	2.897 (2)	143
N4—H4A⋯O3iii	0.86	2.01	2.859 (2)	168
C10—H10B⋯Cl1iv	0.96	2.95	3.864 (3)	160

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