Bis(2-amino-5-bromo-pyridinium) fumarate dihydrate.

In the title compound, 2C(5)H(6)BrN(2) (+)·C(4)H(2)O(4) (2-)·2H(2)O, the complete fumarate dianion is generated by crystallographic inversion symmetry. The cation is approximately planar, with a maximum deviation of 0.036 (1) Å. In the anion, the carboxyl-ate group is twisted slightly away from the attached plane; the dihedral angle between carboxyl-ate and (E)-but-2-ene planes is 6.11 (14)°. In the crystal, the carboxyl-ate O atoms form bifurcated (N-H⋯O and C-H⋯O) and N-H⋯O hydrogen bonds with the cations. The crystal packing is stabilized by R(2) (2)(8) ring motifs which are generated by pairs of N-H⋯O hydrogen bonds. The crystal structure is further consolidated by water mol-ecules via O(water)-H⋯O and N-H⋯O(water) hydrogen bonds. The components are linked by these inter-actions into three-dimensional network.

Related literature

For details of hydrogen bonding, see: Goswami & Ghosh (1997 ▶); Goswami et al. (1998 ▶). For applications of fumaric acid, see: Batchelor et al. (2000 ▶). For related structures, see: Büyükgüngör et al. (2004 ▶); Büyükgüngör & Odabąsoğlu (20065); Hemamalini & Fun, (2010); Quah et al. (2008 ▶; 2010). 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 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

2C5H6BrN2 +·C4H2O4 2−·H2O

M = 498.14

Monoclinic,

a = 8.3717 (1) Å

b = 16.5354 (2) Å

c = 6.7846 (1) Å

β = 108.336 (1)°

V = 891.50 (2) Å3

Z = 2

Mo Kα radiation

μ = 4.59 mm−1

T = 100 K

0.39 × 0.15 × 0.12 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.271, T max = 0.618

15040 measured reflections

3942 independent reflections

3252 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.059

S = 1.03

3942 reflections

138 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.54 e Å−3

Δρmin = −0.39 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/S1600536810030989/bt5312sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030989/bt5312Isup2.hkl

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

2C5H6BrN2+·C4H2O42−·2H2O	F(000) = 496
Mr = 498.14	Dx = 1.856 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5779 reflections
a = 8.3717 (1) Å	θ = 2.6–34.6°
b = 16.5354 (2) Å	µ = 4.59 mm−1
c = 6.7846 (1) Å	T = 100 K
β = 108.336 (1)°	Block, colourless
V = 891.50 (2) Å3	0.39 × 0.15 × 0.12 mm
Z = 2

Bruker SMART APEXII CCD area-detector diffractometer	3942 independent reflections
Radiation source: fine-focus sealed tube	3252 reflections with I > 2σ(I)
graphite	Rint = 0.028
φ and ω scans	θmax = 35.2°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −13→12
Tmin = 0.271, Tmax = 0.618	k = −26→23
15040 measured reflections	l = −10→10

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.059	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0265P)2 + 0.2048P] where P = (Fo2 + 2Fc2)/3
3942 reflections	(Δ/σ)max = 0.001
138 parameters	Δρmax = 0.54 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems 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
Br1	0.741696 (15)	1.042853 (7)	0.08809 (2)	0.01677 (4)
N1	0.78272 (13)	0.79718 (7)	0.17705 (16)	0.01325 (19)
H1N1	0.712 (2)	0.7551 (11)	0.133 (3)	0.022 (4)*
N2	0.99471 (14)	0.70859 (7)	0.34946 (18)	0.0152 (2)
H2N2	1.091 (3)	0.7028 (12)	0.426 (3)	0.031 (5)*
H1N2	0.926 (2)	0.6673 (12)	0.296 (3)	0.036 (5)*
C1	0.72188 (15)	0.87250 (8)	0.11482 (19)	0.0142 (2)
H1A	0.6112	0.8790	0.0301	0.017*
C2	0.82285 (16)	0.93842 (8)	0.1764 (2)	0.0139 (2)
C3	0.99045 (15)	0.92827 (8)	0.3065 (2)	0.0148 (2)
H3A	1.0606	0.9729	0.3486	0.018*
C4	1.04836 (15)	0.85246 (8)	0.36957 (19)	0.0144 (2)
H4A	1.1575	0.8455	0.4585	0.017*
C5	0.94285 (15)	0.78397 (8)	0.30010 (18)	0.0127 (2)
O1W	0.34331 (12)	0.71054 (7)	0.61811 (17)	0.0206 (2)
H2W1	0.392 (3)	0.6972 (13)	0.729 (3)	0.038 (6)*
H1W1	0.396 (3)	0.7487 (15)	0.594 (4)	0.043 (6)*
O1	0.55652 (11)	0.67725 (5)	0.02333 (15)	0.01630 (18)
O2	0.75988 (11)	0.58655 (6)	0.15601 (16)	0.01766 (18)
C6	0.48381 (16)	0.53893 (7)	−0.0202 (2)	0.0139 (2)
H6AA	0.3763	0.5537	−0.1026	0.017*
C7	0.61164 (15)	0.60438 (7)	0.06033 (19)	0.0127 (2)

	U11	U22	U33	U12	U13	U23
Br1	0.01516 (6)	0.01024 (6)	0.02259 (7)	0.00028 (4)	0.00262 (4)	0.00195 (5)
N1	0.0112 (4)	0.0107 (5)	0.0165 (5)	−0.0015 (4)	0.0023 (4)	−0.0004 (4)
N2	0.0124 (5)	0.0108 (5)	0.0201 (5)	−0.0002 (4)	0.0017 (4)	0.0006 (4)
C1	0.0128 (5)	0.0124 (5)	0.0161 (5)	0.0000 (4)	0.0027 (4)	0.0010 (4)
C2	0.0137 (5)	0.0103 (5)	0.0170 (5)	0.0005 (4)	0.0040 (4)	0.0008 (4)
C3	0.0129 (5)	0.0123 (5)	0.0182 (6)	−0.0025 (4)	0.0035 (4)	−0.0017 (4)
C4	0.0117 (5)	0.0129 (6)	0.0162 (5)	−0.0016 (4)	0.0011 (4)	−0.0019 (4)
C5	0.0111 (5)	0.0128 (5)	0.0139 (5)	−0.0003 (4)	0.0036 (4)	−0.0005 (4)
O1W	0.0163 (5)	0.0189 (5)	0.0221 (5)	−0.0039 (4)	−0.0003 (4)	0.0050 (4)
O1	0.0134 (4)	0.0097 (4)	0.0228 (5)	0.0004 (3)	0.0014 (3)	−0.0001 (3)
O2	0.0120 (4)	0.0126 (4)	0.0245 (5)	0.0001 (3)	0.0002 (3)	−0.0001 (4)
C6	0.0112 (5)	0.0111 (5)	0.0176 (5)	−0.0005 (4)	0.0016 (4)	−0.0011 (4)
C7	0.0130 (5)	0.0105 (5)	0.0138 (5)	−0.0010 (4)	0.0030 (4)	−0.0001 (4)

Br1—C2	1.8832 (13)	C3—H3A	0.9300
N1—C5	1.3556 (15)	C4—C5	1.4223 (17)
N1—C1	1.3616 (16)	C4—H4A	0.9300
N1—H1N1	0.899 (18)	O1W—H2W1	0.77 (2)
N2—C5	1.3278 (16)	O1W—H1W1	0.81 (2)
N2—H2N2	0.81 (2)	O1—C7	1.2863 (15)
N2—H1N2	0.89 (2)	O2—C7	1.2416 (14)
C1—C2	1.3620 (17)	C6—C6i	1.326 (2)
C1—H1A	0.9300	C6—C7	1.4990 (17)
C2—C3	1.4130 (17)	C6—H6AA	0.9300
C3—C4	1.3635 (18)
C5—N1—C1	122.64 (11)	C2—C3—H3A	120.3
C5—N1—H1N1	119.8 (11)	C3—C4—C5	120.37 (11)
C1—N1—H1N1	117.5 (12)	C3—C4—H4A	119.8
C5—N2—H2N2	116.7 (14)	C5—C4—H4A	119.8
C5—N2—H1N2	119.8 (13)	N2—C5—N1	119.22 (11)
H2N2—N2—H1N2	123.4 (19)	N2—C5—C4	122.97 (11)
N1—C1—C2	120.10 (11)	N1—C5—C4	117.81 (11)
N1—C1—H1A	119.9	H2W1—O1W—H1W1	105 (2)
C2—C1—H1A	120.0	C6i—C6—C7	123.34 (14)
C1—C2—C3	119.67 (12)	C6i—C6—H6AA	118.3
C1—C2—Br1	120.62 (9)	C7—C6—H6AA	118.3
C3—C2—Br1	119.71 (9)	O2—C7—O1	124.24 (11)
C4—C3—C2	119.37 (11)	O2—C7—C6	120.03 (11)
C4—C3—H3A	120.3	O1—C7—C6	115.72 (11)
C5—N1—C1—C2	−0.12 (18)	C1—N1—C5—N2	−178.04 (12)
N1—C1—C2—C3	−0.51 (19)	C1—N1—C5—C4	1.59 (17)
N1—C1—C2—Br1	178.98 (9)	C3—C4—C5—N2	177.11 (13)
C1—C2—C3—C4	−0.42 (19)	C3—C4—C5—N1	−2.50 (18)
Br1—C2—C3—C4	−179.92 (10)	C6i—C6—C7—O2	6.0 (2)
C2—C3—C4—C5	1.93 (19)	C6i—C6—C7—O1	−173.89 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1	0.902 (18)	1.815 (18)	2.7136 (14)	174.1 (19)
N2—H2N2···O1Wii	0.82 (2)	2.11 (2)	2.9143 (16)	169.7 (19)
N2—H1N2···O2	0.893 (19)	1.946 (19)	2.8348 (15)	173.2 (19)
O1W—H2W1···O1iii	0.77 (2)	2.07 (2)	2.8213 (15)	169 (2)
O1W—H1W1···O1iv	0.82 (3)	1.99 (3)	2.7865 (14)	167 (3)
C3—H3A···O2v	0.93	2.41	3.3089 (17)	162.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1	0.902 (18)	1.815 (18)	2.7136 (14)	174.1 (19)
N2—H2N2⋯O1Wi	0.82 (2)	2.11 (2)	2.9143 (16)	169.7 (19)
N2—H1N2⋯O2	0.893 (19)	1.946 (19)	2.8348 (15)	173.2 (19)
O1W—H2W1⋯O1ii	0.77 (2)	2.07 (2)	2.8213 (15)	169 (2)
O1W—H1W1⋯O1iii	0.82 (3)	1.99 (3)	2.7865 (14)	167 (3)
C3—H3A⋯O2iv	0.93	2.41	3.3089 (17)	162

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