Bis-(2-amino-5-methyl-pyridinium) fumarate-fumaric acid (1/1).

In the crystal structure of the title compound, C(6)H(9)N(2) (+)·0.5C(4)H(2)O(4) (2-)·0.5C(4)H(6)O(4), the fumarate dianion and fumaric acid mol-ecule are located on inversion centres. The 2-amino-5-methyl-pyrimidinium cation inter-acts with the carboxyl-ate group of the fumarate anion through a pair of N-H⋯O hydrogen bonds, forming an R(2) (2)(8) ring motif. These motifs are centrosymmetrically paired via N-H⋯O hydrogen bonds, forming a complementary DDAA array. The carboxyl groups of the fumaric acid mol-ecules and the carboxyl-ate groups of the fumarate anions are hydrogen bonded through O-H⋯O hydrogen bonds, leading to a supra-molecular chain along [101]. The crystal structure is further stabilized by weak C-H⋯O hydrogen bonds.

Related literature

For details of fumaric acid, see: Batchelor et al. (2000 ▶). For related structures, see: Hemamalini & Fun (2010 ▶); Nahringbauer & Kvick (1977 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For DDAA arrays, see: Robert et al. (2001 ▶); Umadevi et al. (2002 ▶); Thanigaimani et al. (2007 ▶). For carbox­yl–carboxyl­ate inter­actions, see: Büyükgüngör & Odabaşoğlu (2002 ▶); Büyükgüngör et al. (2004 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C6H9N2 +·0.5C4H4O4 2−·0.5C4H2O4

M = 224.22

Triclinic,

a = 4.0366 (4) Å

b = 9.3145 (10) Å

c = 14.0077 (14) Å

α = 94.030 (3)°

β = 95.060 (3)°

γ = 90.903 (3)°

V = 523.20 (9) Å3

Z = 2

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.61 × 0.22 × 0.20 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.935, T max = 0.978

19772 measured reflections

5445 independent reflections

4852 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.110

S = 1.05

5445 reflections

147 parameters

H-atom parameters constrained

Δρmax = 0.60 e Å−3

Δρmin = −0.34 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 datablocks global, I. DOI: 10.1107/S1600536810027960/is2576sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810027960/is2576Isup2.hkl

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

C6H9N2+·0.5C4H4O42−·0.5C4H2O4	Z = 2
Mr = 224.22	F(000) = 236
Triclinic, P1	Dx = 1.423 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.0366 (4) Å	Cell parameters from 9900 reflections
b = 9.3145 (10) Å	θ = 2.7–37.6°
c = 14.0077 (14) Å	µ = 0.11 mm−1
α = 94.030 (3)°	T = 100 K
β = 95.060 (3)°	Block, colourless
γ = 90.903 (3)°	0.61 × 0.22 × 0.20 mm
V = 523.20 (9) Å3

Bruker APEXII DUO CCD area-detector diffractometer	5445 independent reflections
Radiation source: fine-focus sealed tube	4852 reflections with I > 2σ(I)
graphite	Rint = 0.019
φ and ω scans	θmax = 37.7°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −6→6
Tmin = 0.935, Tmax = 0.978	k = −15→15
19772 measured reflections	l = −24→23

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0626P)2 + 0.0878P] where P = (Fo2 + 2Fc2)/3
5445 reflections	(Δ/σ)max = 0.001
147 parameters	Δρmax = 0.60 e Å−3
0 restraints	Δρmin = −0.34 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 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
N1	0.64925 (12)	0.45378 (5)	0.20997 (3)	0.01315 (8)
H1	0.5764	0.3700	0.1870	0.016*
N2	0.31601 (12)	0.55122 (5)	0.09009 (3)	0.01504 (9)
H2A	0.2404	0.4662	0.0712	0.018*
H2B	0.2451	0.6241	0.0605	0.018*
C1	0.54215 (13)	0.56996 (5)	0.16485 (4)	0.01190 (8)
C2	0.67623 (13)	0.70674 (5)	0.20110 (4)	0.01341 (9)
H2	0.6147	0.7890	0.1706	0.016*
C3	0.89669 (13)	0.71642 (6)	0.28125 (4)	0.01392 (9)
H3	0.9845	0.8062	0.3048	0.017*
C4	0.99507 (13)	0.59304 (6)	0.32951 (4)	0.01383 (9)
C5	0.86767 (13)	0.46307 (6)	0.29027 (4)	0.01433 (9)
H5	0.9311	0.3795	0.3189	0.017*
C6	1.21690 (15)	0.60555 (7)	0.42149 (4)	0.01903 (10)
H6A	1.1001	0.6517	0.4716	0.029*
H6B	1.4123	0.6617	0.4131	0.029*
H6C	1.2803	0.5112	0.4388	0.029*
O1	0.27081 (16)	0.19332 (6)	0.39352 (4)	0.02686 (12)
O2	0.49662 (14)	0.03168 (5)	0.29314 (3)	0.02170 (10)
H2C	0.4257	0.0849	0.2522	0.033*
C7	0.42204 (15)	0.08387 (6)	0.37847 (4)	0.01544 (9)
C8	0.54504 (15)	−0.00956 (6)	0.45556 (4)	0.01586 (9)
H8	0.6889	−0.0833	0.4410	0.019*
O3	0.10076 (14)	0.26911 (5)	0.02053 (3)	0.02176 (10)
O4	0.34405 (13)	0.19338 (5)	0.15605 (3)	0.02015 (10)
C9	0.17514 (14)	0.17185 (6)	0.07482 (4)	0.01450 (9)
C10	0.06922 (15)	0.01973 (6)	0.04396 (4)	0.01504 (9)
H10	0.1014	−0.0501	0.0880	0.018*

	U11	U22	U33	U12	U13	U23
N1	0.01540 (17)	0.00928 (16)	0.01454 (17)	0.00050 (13)	−0.00023 (13)	0.00127 (13)
N2	0.01861 (19)	0.01217 (18)	0.01362 (17)	0.00003 (14)	−0.00253 (14)	0.00090 (14)
C1	0.01360 (18)	0.01021 (18)	0.01198 (18)	0.00080 (14)	0.00146 (14)	0.00086 (14)
C2	0.0165 (2)	0.00966 (18)	0.01402 (19)	0.00031 (15)	0.00102 (15)	0.00067 (14)
C3	0.01491 (19)	0.01202 (19)	0.01459 (19)	−0.00112 (15)	0.00159 (15)	−0.00077 (15)
C4	0.01274 (18)	0.0149 (2)	0.01376 (19)	0.00020 (15)	0.00090 (14)	0.00098 (15)
C5	0.01445 (19)	0.0131 (2)	0.0155 (2)	0.00149 (15)	−0.00004 (15)	0.00273 (15)
C6	0.0157 (2)	0.0245 (3)	0.0163 (2)	−0.00173 (18)	−0.00234 (16)	0.00247 (19)
O1	0.0431 (3)	0.0210 (2)	0.01696 (19)	0.0171 (2)	0.00033 (18)	0.00395 (16)
O2	0.0396 (3)	0.01464 (18)	0.01119 (16)	0.00699 (17)	0.00121 (16)	0.00307 (13)
C7	0.0220 (2)	0.01199 (19)	0.01201 (18)	0.00230 (16)	−0.00174 (16)	0.00234 (15)
C8	0.0221 (2)	0.0134 (2)	0.01226 (19)	0.00444 (17)	−0.00012 (16)	0.00316 (15)
O3	0.0348 (2)	0.01109 (17)	0.01746 (18)	−0.00270 (15)	−0.01071 (16)	0.00485 (14)
O4	0.0338 (2)	0.01254 (17)	0.01229 (16)	−0.00547 (15)	−0.00885 (15)	0.00302 (13)
C9	0.0213 (2)	0.01004 (18)	0.01138 (18)	−0.00190 (15)	−0.00325 (15)	0.00168 (14)
C10	0.0219 (2)	0.01007 (18)	0.01231 (19)	−0.00229 (16)	−0.00368 (15)	0.00215 (14)

N1—C1	1.3492 (7)	C6—H6A	0.9600
N1—C5	1.3635 (7)	C6—H6B	0.9600
N1—H1	0.8600	C6—H6C	0.9600
N2—C1	1.3271 (7)	O1—C7	1.2118 (7)
N2—H2A	0.8600	O2—C7	1.3199 (7)
N2—H2B	0.8600	O2—H2C	0.8200
C1—C2	1.4188 (8)	C7—C8	1.4903 (7)
C2—C3	1.3665 (7)	C8—C8i	1.3285 (11)
C2—H2	0.9300	C8—H8	0.9300
C3—C4	1.4184 (8)	O3—C9	1.2468 (7)
C3—H3	0.9300	O4—C9	1.2754 (6)
C4—C5	1.3671 (8)	C9—C10	1.4965 (8)
C4—C6	1.4992 (8)	C10—C10ii	1.3314 (10)
C5—H5	0.9300	C10—H10	0.9300
C1—N1—C5	123.03 (5)	C4—C5—H5	119.4
C1—N1—H1	118.5	C4—C6—H6A	109.5
C5—N1—H1	118.5	C4—C6—H6B	109.5
C1—N2—H2A	120.0	H6A—C6—H6B	109.5
C1—N2—H2B	120.0	C4—C6—H6C	109.5
H2A—N2—H2B	120.0	H6A—C6—H6C	109.5
N2—C1—N1	118.82 (5)	H6B—C6—H6C	109.5
N2—C1—C2	123.44 (5)	C7—O2—H2C	109.5
N1—C1—C2	117.73 (5)	O1—C7—O2	125.02 (5)
C3—C2—C1	119.37 (5)	O1—C7—C8	123.42 (5)
C3—C2—H2	120.3	O2—C7—C8	111.56 (5)
C1—C2—H2	120.3	C8i—C8—C7	121.87 (6)
C2—C3—C4	121.69 (5)	C8i—C8—H8	119.1
C2—C3—H3	119.2	C7—C8—H8	119.1
C4—C3—H3	119.2	O3—C9—O4	123.73 (5)
C5—C4—C3	116.88 (5)	O3—C9—C10	119.39 (5)
C5—C4—C6	121.66 (5)	O4—C9—C10	116.87 (4)
C3—C4—C6	121.41 (5)	C10ii—C10—C9	122.67 (6)
N1—C5—C4	121.22 (5)	C10ii—C10—H10	118.7
N1—C5—H5	119.4	C9—C10—H10	118.7
C5—N1—C1—N2	−176.50 (5)	C1—N1—C5—C4	−0.74 (8)
C5—N1—C1—C2	2.78 (8)	C3—C4—C5—N1	−1.74 (8)
N2—C1—C2—C3	176.95 (5)	C6—C4—C5—N1	175.74 (5)
N1—C1—C2—C3	−2.29 (8)	O1—C7—C8—C8i	10.08 (12)
C1—C2—C3—C4	−0.13 (8)	O2—C7—C8—C8i	−169.47 (8)
C2—C3—C4—C5	2.14 (8)	O3—C9—C10—C10ii	7.89 (11)
C2—C3—C4—C6	−175.35 (5)	O4—C9—C10—C10ii	−170.95 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4	0.86	1.89	2.7305 (7)	167
N2—H2A···O3	0.86	1.98	2.8334 (7)	175
N2—H2B···O3iii	0.86	2.04	2.8329 (7)	154
O2—H2C···O4	0.82	1.75	2.5618 (7)	170
C5—H5···O1iv	0.93	2.46	3.3582 (9)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4	0.86	1.89	2.7305 (7)	167
N2—H2A⋯O3	0.86	1.98	2.8334 (7)	175
N2—H2B⋯O3i	0.86	2.04	2.8329 (7)	154
O2—H2C⋯O4	0.82	1.75	2.5618 (7)	170
C5—H5⋯O1ii	0.93	2.46	3.3582 (9)	162

Symmetry codes: (i) ; (ii) .