Adeninium cytosinium sulfate.

In the title compound, C(5)H(6)N(5) (+)·C(4)H(6)N(3)O(+)·SO(4) (2-), the adeninium (AdH(+)) and cytosinium (CytH(+)) cations and sulfate dianion are involved in a three-dimensional hydrogen-bonding network with four different modes, viz. AdH(+)⋯AdH(+), AdH(+)⋯CytH(+), AdH(+)⋯SO(4) (2-) and CytH(+)⋯SO(4) (2-). The adeninium cations form N-H⋯N dimers through the Hoogsteen faces, generating a characteristic R(2) (2)(10) motif. This AdH(+)⋯AdH(+) hydrogen bond in combination with AdH(+)⋯CytH(+ )H-bonds leads to two-dimensional cationic ribbons parallel to the a axis. The sulfate anions inter-link the ribbons into a three-dimensional hydrogen-bonding network and thus reinforce the crystal structure.

Related literature

Nucleobases possess multiple hydrogen-bonding sites (Saenger, 1984 ▶) and so can form an abundance of aggregates through hydrogen bonds, from dimers to infinite extended species, see: Jai-nhuknan et al. (1997 ▶); Bendjeddou et al. (2003 ▶); Smith et al. (2005 ▶); Sridhar & Ravikumar (2007 ▶). For protonated nucleobases in acid-base catalysis, see: Lippert (2005 ▶). For their use in the construction of highly ordered supra­molecular nanostructures which are of inter­est for their potential applications as mol­ecular devices, see: Lehn (1995 ▶); Gottarelli et al. (2000 ▶). Bond lengths in adeninium cations are dependent on the degree of protonation, see: Hingerty et al. (1981 ▶); Langer & Huml (1978 ▶). For bond angles in neutral adenine, see: Voet & Rich (1970 ▶). For related structures with a cytosinium cation, see: Prabakaran et al. (2001 ▶); Smith et al. (2005 ▶); Sridhar & Ravikumar (2008 ▶). For graph-set motifs, see: Bernstein et al. (1995 ▶). For hydrogen bond ing, see: Jeffrey & Saenger (1991 ▶). For pKa values for cytosine, see: Stecher (1968 ▶).

Experimental

Crystal data

C5H6N5 +·C4H6N3O+·SO4 2−

M = 344.33

Monoclinic,

a = 9.180 (2) Å

b = 12.948 (3) Å

c = 11.328 (3) Å

β = 99.356 (2)°

V = 1328.6 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.29 mm−1

T = 100 K

0.39 × 0.26 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur Saphire2 CCD diffractometer

Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008 ▶) T min = 0.921, T max = 0.975

57856 measured reflections

5843 independent reflections

5061 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.088

S = 1.04

5843 reflections

232 parameters

8 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.51 e Å−3

Δρmin = −0.51 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034023/at2867sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034023/at2867Isup2.hkl

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

C5H6N5+·C4H6N3O+·SO42−	F(000) = 712
Mr = 344.33	Dx = 1.721 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 57856 reflections
a = 9.180 (2) Å	θ = 3.1–35.0°
b = 12.948 (3) Å	µ = 0.29 mm−1
c = 11.328 (3) Å	T = 100 K
β = 99.356 (2)°	Prism, colourless
V = 1328.6 (5) Å3	0.39 × 0.26 × 0.12 mm
Z = 4

Oxford Diffraction Xcalibur Saphire2 CCD diffractometer	5843 independent reflections
Radiation source: fine-focus sealed tube	5061 reflections with I > 2σ(I)
graphite	Rint = 0.026
φ and ω scans	θmax = 35.0°, θmin = 3.1°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	h = −14→14
Tmin = 0.921, Tmax = 0.975	k = −20→20
57856 measured reflections	l = −17→18

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)] = 0.027	Hydrogen site location: difference Fourier map
wR(F2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0602P)2 + 0.1819P] where P = (Fo2 + 2Fc2)/3
5843 reflections	(Δ/σ)max = 0.001
232 parameters	Δρmax = 0.51 e Å−3
8 restraints	Δρmin = −0.51 e Å−3

Experimental. CrysAlis RED (Oxford Diffraction, 2008) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid.

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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
N1A	0.89503 (7)	0.08114 (5)	0.15030 (6)	0.0102 (1)
N2A	0.93054 (8)	−0.04224 (5)	0.30191 (6)	0.0114 (2)
N3A	0.92695 (7)	0.26232 (5)	0.17622 (6)	0.0113 (2)
N7A	1.01108 (7)	0.14551 (5)	0.46688 (6)	0.0097 (1)
N9A	1.00189 (7)	0.30483 (5)	0.38697 (6)	0.0106 (2)
C2A	0.89521 (8)	0.18034 (6)	0.10957 (7)	0.0113 (2)
C4A	0.96300 (8)	0.23844 (5)	0.29397 (6)	0.0091 (2)
C5A	0.96826 (7)	0.14027 (5)	0.34460 (6)	0.0083 (2)
C6A	0.93243 (7)	0.05505 (5)	0.26787 (6)	0.0087 (1)
C8A	1.02951 (8)	0.24570 (5)	0.48772 (7)	0.0106 (2)
O5C	0.58498 (6)	0.24982 (4)	0.27802 (5)	0.0133 (2)
N1C	0.59982 (7)	0.08175 (5)	0.33878 (6)	0.0100 (1)
N2C	0.76585 (7)	0.18374 (5)	0.67114 (6)	0.0107 (2)
N3C	0.67261 (7)	0.21469 (5)	0.47342 (6)	0.0092 (1)
C2C	0.61681 (8)	0.18570 (5)	0.35794 (7)	0.0093 (2)
C4C	0.71397 (7)	0.14707 (5)	0.56532 (7)	0.0085 (2)
C5C	0.69956 (8)	0.03932 (5)	0.54009 (7)	0.0100 (2)
C6C	0.64100 (8)	0.01083 (5)	0.42725 (7)	0.0102 (2)
S1	0.27538 (2)	0.03329 (1)	0.11795 (2)	0.0083 (1)
O1	0.19268 (7)	−0.06314 (4)	0.12530 (5)	0.0137 (2)
O2	0.24941 (6)	0.10652 (4)	0.21156 (5)	0.0119 (1)
O3	0.43624 (6)	0.01038 (4)	0.13141 (5)	0.0122 (1)
O4	0.22552 (6)	0.07936 (4)	−0.00242 (5)	0.0115 (1)
H1A	0.8721 (13)	0.0315 (8)	0.0979 (9)	0.0123*
H2A	0.87069	0.19049	0.02747	0.0135*
H3A	0.9548 (13)	−0.0569 (10)	0.3778 (8)	0.0136*
H4A	0.9167 (13)	−0.0894 (8)	0.2481 (9)	0.0136*
H8A	1.05853	0.27310	0.56380	0.0127*
H9A	1.0154 (13)	0.3714 (6)	0.3849 (11)	0.0127*
H1C	0.5516 (12)	0.0640 (9)	0.2698 (8)	0.0120*
H2C	0.7866 (13)	0.1437 (9)	0.7326 (9)	0.0129*
H3C	0.6899 (12)	0.2814 (6)	0.4829 (10)	0.0111*
H4C	0.7671 (12)	0.2495 (6)	0.6843 (10)	0.0129*
H5C	0.72934	−0.00972	0.59907	0.0120*
H6C	0.62847	−0.05905	0.40948	0.0122*

	U11	U22	U33	U12	U13	U23
N1A	0.0133 (2)	0.0090 (2)	0.0078 (3)	−0.0006 (2)	−0.0001 (2)	−0.0007 (2)
N2A	0.0175 (3)	0.0066 (2)	0.0096 (3)	−0.0002 (2)	0.0010 (2)	−0.0009 (2)
N3A	0.0146 (3)	0.0097 (2)	0.0088 (3)	−0.0012 (2)	−0.0001 (2)	0.0010 (2)
N7A	0.0122 (2)	0.0085 (2)	0.0080 (3)	−0.0007 (2)	0.0007 (2)	−0.0006 (2)
N9A	0.0145 (3)	0.0070 (2)	0.0098 (3)	−0.0019 (2)	0.0008 (2)	−0.0005 (2)
C2A	0.0141 (3)	0.0104 (3)	0.0087 (3)	−0.0007 (2)	−0.0002 (2)	0.0012 (2)
C4A	0.0107 (3)	0.0076 (3)	0.0089 (3)	−0.0010 (2)	0.0009 (2)	−0.0001 (2)
C5A	0.0101 (3)	0.0070 (2)	0.0077 (3)	−0.0005 (2)	0.0010 (2)	−0.0002 (2)
C6A	0.0097 (2)	0.0080 (2)	0.0082 (3)	0.0002 (2)	0.0010 (2)	−0.0002 (2)
C8A	0.0133 (3)	0.0093 (3)	0.0089 (3)	−0.0015 (2)	0.0006 (2)	−0.0006 (2)
O5C	0.0198 (3)	0.0095 (2)	0.0093 (3)	0.0003 (2)	−0.0017 (2)	0.0021 (2)
N1C	0.0126 (2)	0.0077 (2)	0.0088 (3)	−0.0007 (2)	−0.0013 (2)	−0.0008 (2)
N2C	0.0144 (3)	0.0091 (2)	0.0079 (3)	−0.0005 (2)	−0.0006 (2)	0.0002 (2)
N3C	0.0127 (2)	0.0064 (2)	0.0078 (3)	−0.0001 (2)	−0.0007 (2)	0.0001 (2)
C2C	0.0103 (3)	0.0081 (3)	0.0089 (3)	−0.0001 (2)	0.0002 (2)	−0.0002 (2)
C4C	0.0089 (2)	0.0082 (3)	0.0084 (3)	0.0000 (2)	0.0011 (2)	0.0009 (2)
C5C	0.0116 (3)	0.0072 (3)	0.0106 (3)	−0.0002 (2)	0.0004 (2)	0.0009 (2)
C6C	0.0113 (3)	0.0075 (3)	0.0116 (3)	−0.0007 (2)	0.0013 (2)	0.0003 (2)
S1	0.0115 (1)	0.0059 (1)	0.0067 (1)	0.0002 (1)	−0.0008 (1)	0.0003 (1)
O1	0.0199 (3)	0.0090 (2)	0.0111 (3)	−0.0048 (2)	−0.0008 (2)	0.0018 (2)
O2	0.0167 (2)	0.0094 (2)	0.0097 (3)	0.0013 (2)	0.0025 (2)	−0.0014 (2)
O3	0.0123 (2)	0.0111 (2)	0.0122 (3)	0.0025 (2)	−0.0013 (2)	−0.0024 (2)
O4	0.0174 (2)	0.0083 (2)	0.0076 (2)	0.0005 (2)	−0.0016 (2)	0.0019 (2)

S1—O1	1.4706 (10)	N1C—C6C	1.3665 (12)
S1—O2	1.4706 (10)	N1C—C2C	1.3682 (12)
S1—O3	1.4895 (10)	N2C—C4C	1.3052 (12)
S1—O4	1.4905 (10)	N3C—C4C	1.3660 (12)
O5C—C2C	1.2281 (11)	N3C—C2C	1.3772 (13)
N1A—C2A	1.3649 (13)	N1C—H1C	0.864 (9)
N1A—C6A	1.3628 (12)	N2C—H4C	0.864 (8)
N2A—C6A	1.3184 (12)	N2C—H2C	0.864 (11)
N3A—C2A	1.3077 (12)	N3C—H3C	0.882 (8)
N3A—C4A	1.3568 (12)	C4A—C5A	1.3921 (12)
N7A—C8A	1.3245 (12)	C5A—C6A	1.4101 (12)
N7A—C5A	1.3787 (12)	C2A—H2A	0.9300
N9A—C4A	1.3616 (12)	C8A—H8A	0.9300
N9A—C8A	1.3634 (12)	C4C—C5C	1.4260 (12)
N1A—H1A	0.877 (10)	C5C—C6C	1.3548 (13)
N2A—H4A	0.858 (10)	C5C—H5C	0.9300
N2A—H3A	0.873 (9)	C6C—H6C	0.9300
N9A—H9A	0.872 (8)
O1—S1—O4	107.88 (3)	N3A—C4A—C5A	126.85 (6)
O1—S1—O2	111.16 (3)	N3A—C4A—N9A	127.46 (6)
O1—S1—O3	109.72 (3)	N9A—C4A—C5A	105.70 (6)
O3—S1—O4	108.98 (3)	N7A—C5A—C4A	110.74 (6)
O2—S1—O3	109.20 (3)	N7A—C5A—C6A	131.12 (6)
O2—S1—O4	109.87 (3)	C4A—C5A—C6A	118.14 (6)
C2A—N1A—C6A	123.35 (6)	N1A—C6A—N2A	120.63 (6)
C2A—N3A—C4A	112.24 (6)	N2A—C6A—C5A	125.47 (6)
C5A—N7A—C8A	103.57 (6)	N1A—C6A—C5A	113.89 (6)
C4A—N9A—C8A	106.43 (6)	N7A—C8A—N9A	113.57 (7)
C2A—N1A—H1A	118.3 (7)	N3A—C2A—H2A	117.00
C6A—N1A—H1A	118.3 (7)	N1A—C2A—H2A	117.00
H3A—N2A—H4A	122.0 (11)	N7A—C8A—H8A	123.00
C6A—N2A—H3A	118.8 (8)	N9A—C8A—H8A	123.00
C6A—N2A—H4A	118.7 (7)	O5C—C2C—N3C	121.54 (6)
C4A—N9A—H9A	128.6 (8)	O5C—C2C—N1C	122.74 (7)
C8A—N9A—H9A	124.7 (8)	N1C—C2C—N3C	115.72 (6)
C2C—N1C—C6C	122.27 (7)	N2C—C4C—N3C	118.78 (6)
C2C—N3C—C4C	124.30 (6)	N2C—C4C—C5C	123.24 (7)
C6C—N1C—H1C	121.6 (8)	N3C—C4C—C5C	117.98 (7)
C2C—N1C—H1C	115.7 (8)	C4C—C5C—C6C	117.72 (7)
C4C—N2C—H2C	121.4 (7)	N1C—C6C—C5C	121.94 (6)
H2C—N2C—H4C	117.2 (10)	C4C—C5C—H5C	121.00
C4C—N2C—H4C	120.6 (7)	C6C—C5C—H5C	121.00
C2C—N3C—H3C	114.5 (7)	C5C—C6C—H6C	119.00
C4C—N3C—H3C	120.9 (7)	N1C—C6C—H6C	119.00
N1A—C2A—N3A	125.53 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O1i	0.877 (10)	2.535 (10)	3.1036 (19)	123.3 (8)
N1A—H1A···O4i	0.877 (10)	1.928 (11)	2.7833 (17)	164.5 (11)
N1C—H1C···O3	0.864 (9)	1.877 (10)	2.7350 (17)	172.0 (11)
N2C—H2C···O1ii	0.864 (11)	1.902 (11)	2.7596 (17)	171.8 (11)
N2A—H3A···N7Aiii	0.873 (9)	2.081 (10)	2.9118 (18)	158.7 (12)
N3C—H3C···O4iv	0.882 (8)	1.835 (8)	2.7164 (17)	178.2 (11)
N2A—H4A···O5Cv	0.858 (10)	2.102 (10)	2.8368 (18)	143.3 (9)
N2C—H4C···O2iv	0.864 (8)	1.901 (8)	2.7622 (17)	174.4 (11)
N9A—H9A···O3vi	0.872 (8)	1.870 (8)	2.7364 (17)	172.5 (12)
C2A—H2A···O1i	0.9300	2.3900	3.0553 (19)	128.00
C5C—H5C···O2ii	0.9300	2.4600	3.357 (2)	161.00
C6C—H6C···N3Av	0.9300	2.5300	3.447 (2)	170.00
C8A—H8A···O5Civ	0.9300	2.4200	3.245 (2)	148.00

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1A⋯O1i	0.877 (10)	2.535 (10)	3.1036 (19)	123.3 (8)
N1A—H1A⋯O4i	0.877 (10)	1.928 (11)	2.7833 (17)	164.5 (11)
N1C—H1C⋯O3	0.864 (9)	1.877 (10)	2.7350 (17)	172.0 (11)
N2C—H2C⋯O1ii	0.864 (11)	1.902 (11)	2.7596 (17)	171.8 (11)
N2A—H3A⋯N7Aiii	0.873 (9)	2.081 (10)	2.9118 (18)	158.7 (12)
N3C—H3C⋯O4iv	0.882 (8)	1.835 (8)	2.7164 (17)	178.2 (11)
N2A—H4A⋯O5Cv	0.858 (10)	2.102 (10)	2.8368 (18)	143.3 (9)
N2C—H4C⋯O2iv	0.864 (8)	1.901 (8)	2.7622 (17)	174.4 (11)
N9A—H9A⋯O3vi	0.872 (8)	1.870 (8)	2.7364 (17)	172.5 (12)
C2A—H2A⋯O1i	0.9300	2.3900	3.0553 (19)	128.00
C5C—H5C⋯O2ii	0.9300	2.4600	3.357 (2)	161.00
C6C—H6C⋯N3Av	0.9300	2.5300	3.447 (2)	170.00
C8A—H8A⋯O5Civ	0.9300	2.4200	3.245 (2)	148.00

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