Bis(2,6-diamino-4-chloro-pyrimidin-1-ium) fumarate.

In the title salt, 2C4H6ClN4(+)·C4H2O4(2-), the complete fumarate dianion is generated by crystallographic inversion symmetry. The cation is essentially planar, with a maximum deviation of 0.018 (1) Å. In the anion, the carboxyl-ate group is twisted slightly away from the attached plane, the dihedral angle between the carboxyl-ate and (E)-but-2-ene planes being 12.78 (13)°. 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 R2(2)(8) ring motif. In addition, another type of R2(2)(8) motif is formed by centrosymmetrically related pyrimidinium cations via N-H⋯N hydrogen bonds. These two combined motifs form a heterotetra-mer. The crystal structure is further stabilized by stong N-H⋯O, N-H⋯Cl and weak C-H⋯O hydrogen bonds, resulting a three-dimensional network.

Related literature

For applications of pyrimidine derivatives, see: Condon et al. (1993 ▶); Maeno et al. (1990 ▶); Gilchrist (1997 ▶). For details of fumaric acid, see: Batchelor et al. (2000 ▶). For hydrogen-bonded synthons, see: Thakur & Desiraju (2008 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C4H6ClN4 +·0.5C4H2O4 2−

M = 202.61

Monoclinic,

a = 5.4478 (7) Å

b = 10.5187 (14) Å

c = 14.8171 (18) Å

β = 100.990 (4)°

V = 833.50 (18) Å3

Z = 4

Mo Kα radiation

μ = 0.43 mm−1

T = 100 K

0.71 × 0.31 × 0.17 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.749, T max = 0.931

9206 measured reflections

2984 independent reflections

2708 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.127

S = 1.08

2984 reflections

138 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.78 e Å−3

Δρmin = −0.78 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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812045308/rz5019sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812045308/rz5019Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812045308/rz5019Isup3.cml

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

C4H6ClN4+·0.5C4H2O42−	F(000) = 416
Mr = 202.61	Dx = 1.615 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6512 reflections
a = 5.4478 (7) Å	θ = 3.4–32.6°
b = 10.5187 (14) Å	µ = 0.43 mm−1
c = 14.8171 (18) Å	T = 100 K
β = 100.990 (4)°	Block, colourless
V = 833.50 (18) Å3	0.71 × 0.31 × 0.17 mm
Z = 4

Bruker SMART APEXII DUO CCD area-detector diffractometer	2984 independent reflections
Radiation source: fine-focus sealed tube	2708 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
φ and ω scans	θmax = 32.6°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
Tmin = 0.749, Tmax = 0.931	k = −15→11
9206 measured reflections	l = −22→20

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0781P)2 + 0.3432P] where P = (Fo2 + 2Fc2)/3
2984 reflections	(Δ/σ)max < 0.001
138 parameters	Δρmax = 0.78 e Å−3
1 restraint	Δρmin = −0.78 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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	0.40235 (6)	0.33920 (3)	0.76706 (2)	0.01926 (11)
N1	0.60987 (19)	0.49304 (10)	0.89510 (7)	0.0145 (2)
N2	0.94266 (19)	0.63383 (10)	0.88172 (7)	0.01248 (19)
N3	0.7774 (2)	0.62835 (11)	1.01344 (8)	0.0172 (2)
N4	1.1199 (2)	0.64457 (11)	0.75251 (8)	0.0155 (2)
C1	0.7751 (2)	0.58432 (11)	0.92934 (8)	0.0128 (2)
C2	0.9508 (2)	0.59135 (11)	0.79616 (8)	0.0121 (2)
C3	0.7835 (2)	0.49584 (11)	0.75646 (8)	0.0139 (2)
H3A	0.7827	0.4627	0.6968	0.017*
C4	0.6220 (2)	0.45442 (11)	0.81056 (8)	0.0138 (2)
O1	0.1038 (2)	0.65131 (9)	0.56049 (7)	0.0197 (2)
O2	0.2393 (2)	0.68272 (9)	0.42877 (7)	0.0196 (2)
C5	0.2377 (2)	0.62262 (11)	0.50395 (8)	0.0145 (2)
C6	0.4095 (2)	0.51141 (11)	0.52358 (8)	0.0148 (2)
H6A	0.3894	0.4547	0.5715	0.018*
H1	1.054 (4)	0.688 (2)	0.9060 (19)	0.054 (8)*
H2	0.874 (4)	0.685 (2)	1.0338 (16)	0.031 (6)*
H3	0.662 (4)	0.597 (2)	1.0383 (16)	0.035 (6)*
H4	1.118 (4)	0.629 (2)	0.7009 (16)	0.024 (5)*
H5	1.208 (4)	0.697 (2)	0.7770 (15)	0.025 (5)*

	U11	U22	U33	U12	U13	U23
Cl1	0.01810 (17)	0.01552 (16)	0.02516 (18)	−0.00602 (9)	0.00670 (12)	−0.00792 (10)
N1	0.0156 (4)	0.0128 (4)	0.0160 (5)	−0.0033 (3)	0.0054 (3)	−0.0023 (3)
N2	0.0156 (4)	0.0097 (4)	0.0130 (4)	−0.0027 (3)	0.0050 (3)	−0.0008 (3)
N3	0.0212 (5)	0.0169 (5)	0.0153 (5)	−0.0072 (4)	0.0082 (4)	−0.0037 (4)
N4	0.0205 (5)	0.0133 (4)	0.0138 (4)	−0.0028 (4)	0.0063 (4)	−0.0010 (4)
C1	0.0144 (5)	0.0103 (5)	0.0145 (5)	−0.0017 (4)	0.0047 (4)	0.0002 (4)
C2	0.0139 (5)	0.0094 (4)	0.0135 (5)	0.0008 (3)	0.0041 (4)	0.0004 (3)
C3	0.0155 (5)	0.0114 (5)	0.0154 (5)	−0.0015 (4)	0.0047 (4)	−0.0020 (4)
C4	0.0141 (5)	0.0101 (4)	0.0178 (5)	−0.0014 (4)	0.0040 (4)	−0.0022 (4)
O1	0.0235 (5)	0.0206 (5)	0.0174 (4)	0.0087 (3)	0.0096 (4)	0.0032 (3)
O2	0.0270 (5)	0.0178 (4)	0.0159 (4)	0.0112 (4)	0.0089 (4)	0.0055 (3)
C5	0.0167 (5)	0.0132 (5)	0.0138 (5)	0.0039 (4)	0.0039 (4)	0.0004 (4)
C6	0.0179 (5)	0.0126 (5)	0.0143 (5)	0.0049 (4)	0.0039 (4)	0.0023 (4)

Cl1—C4	1.7385 (12)	N4—H4	0.78 (2)
N1—C4	1.3305 (15)	N4—H5	0.77 (2)
N1—C1	1.3474 (15)	C2—C3	1.4076 (16)
N2—C2	1.3529 (15)	C3—C4	1.3695 (16)
N2—C1	1.3592 (14)	C3—H3A	0.9500
N2—H1	0.862 (10)	O1—C5	1.2482 (14)
N3—C1	1.3273 (15)	O2—C5	1.2824 (14)
N3—H2	0.81 (2)	C5—C6	1.4919 (16)
N3—H3	0.85 (2)	C6—C6i	1.334 (2)
N4—C2	1.3444 (15)	C6—H6A	0.9500
C4—N1—C1	114.99 (10)	N4—C2—C3	122.99 (11)
C2—N2—C1	120.34 (10)	N2—C2—C3	119.54 (10)
C2—N2—H1	118 (2)	C4—C3—C2	114.80 (10)
C1—N2—H1	122 (2)	C4—C3—H3A	122.6
C1—N3—H2	119.5 (17)	C2—C3—H3A	122.6
C1—N3—H3	113.3 (16)	N1—C4—C3	127.36 (11)
H2—N3—H3	127 (2)	N1—C4—Cl1	114.05 (9)
C2—N4—H4	120.1 (17)	C3—C4—Cl1	118.59 (9)
C2—N4—H5	119.4 (16)	O1—C5—O2	124.44 (11)
H4—N4—H5	120 (2)	O1—C5—C6	118.95 (11)
N3—C1—N1	119.22 (10)	O2—C5—C6	116.61 (10)
N3—C1—N2	117.81 (11)	C6i—C6—C5	122.53 (14)
N1—C1—N2	122.97 (10)	C6i—C6—H6A	118.7
N4—C2—N2	117.47 (11)	C5—C6—H6A	118.7
C4—N1—C1—N3	−179.71 (11)	N2—C2—C3—C4	0.33 (17)
C4—N1—C1—N2	−0.05 (17)	C1—N1—C4—C3	0.85 (19)
C2—N2—C1—N3	179.15 (11)	C1—N1—C4—Cl1	−178.65 (9)
C2—N2—C1—N1	−0.51 (18)	C2—C3—C4—N1	−0.99 (19)
C1—N2—C2—N4	179.70 (11)	C2—C3—C4—Cl1	178.50 (9)
C1—N2—C2—C3	0.34 (17)	O1—C5—C6—C6i	−167.18 (16)
N4—C2—C3—C4	−178.98 (11)	O2—C5—C6—C6i	12.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O2ii	0.86 (1)	1.69 (1)	2.5281 (14)	165 (3)
N3—H2···O1ii	0.81 (2)	2.12 (2)	2.9233 (15)	168 (2)
N3—H3···N1iii	0.85 (2)	2.15 (2)	3.0014 (16)	176 (2)
N4—H4···O1iv	0.78 (2)	2.08 (2)	2.8307 (16)	161 (2)
N4—H5···Cl1v	0.77 (2)	2.78 (2)	3.3671 (13)	135.0 (19)
N4—H5···O2ii	0.77 (2)	2.56 (2)	3.1458 (15)	134.2 (19)
C3—H3A···O2i	0.95	2.39	3.3085 (16)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯O2i	0.86 (1)	1.69 (1)	2.5281 (14)	165 (3)
N3—H2⋯O1i	0.81 (2)	2.12 (2)	2.9233 (15)	168 (2)
N3—H3⋯N1ii	0.85 (2)	2.15 (2)	3.0014 (16)	176 (2)
N4—H4⋯O1iii	0.78 (2)	2.08 (2)	2.8307 (16)	161 (2)
N4—H5⋯Cl1iv	0.77 (2)	2.78 (2)	3.3671 (13)	135.0 (19)
N4—H5⋯O2i	0.77 (2)	2.56 (2)	3.1458 (15)	134.2 (19)
C3—H3A⋯O2v	0.95	2.39	3.3085 (16)	162

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