Bis(adeninium) bis-(hydrogensulfate) sulfate.

The title compound, 2C5H7N5(2+)·2HSO4(-)·SO4(2-), was synthesized from adenine and sulfuric acid. The asymmetric unit contains two diprotonated adeninium cations, two bis-ulfate anions and one sulfate anion. The crystal structure is stabilized by classical N-H⋯O and O-H⋯O hydrogen bonds, and weak C-H⋯O and C-H⋯N hydrogen bonds, generating a three-dimensional network.

Related literature

For background to the title compound, see: Biradha et al. (2010 ▶); Guenifa et al. (2009 ▶); Zeghouan et al. (2012 ▶). For related structures, see: Bendjeddou et al. (2003 ▶); Fun et al. (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

2C5H7N5 +·2HSO4 −·SO4 2−

M = 564.54

Monoclinic,

a = 26.370 (5) Å

b = 8.970 (2) Å

c = 20.350 (4) Å

β = 126.184 (10)°

V = 3885.2 (15) Å3

Z = 8

Mo Kα radiation

μ = 0.48 mm−1

T = 120 K

0.3 × 0.3 × 0.2 mm

Data collection

Nonius KappaCCD diffractometer

5681 measured reflections

5681 independent reflections

3989 reflections with I > 2σ(I)

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.131

S = 1.07

5681 reflections

352 parameters

12 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.09 e Å−3

Δρmin = −0.60 e Å−3

Data collection: KappaCCD Reference Manual (Nonius, 1998 ▶); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶), PARST97 (Nardelli, 1995 ▶), Mercury (Macrae et al., 2006 ▶) and POVRay (Persistence of Vision Team, 2004 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812044728/xu5635sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812044728/xu5635Isup2.hkl

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

2C5H7N5+·2HSO4−·SO42−	F(000) = 2320
Mr = 564.54	Dx = 1.93 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5681 reflections
a = 26.370 (5) Å	θ = 3–30.0°
b = 8.970 (2) Å	µ = 0.48 mm−1
c = 20.350 (4) Å	T = 120 K
β = 126.184 (10)°	Needle, colourless
V = 3885.2 (15) Å3	0.3 × 0.3 × 0.2 mm
Z = 8

Nonius KappaCCD diffractometer	3989 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 30.0°, θmin = 3.0°
ω scans	h = 0→37
5681 measured reflections	k = 0→12
5681 independent reflections	l = −28→23

Refinement on F2	12 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.043	w = 1/[σ2(Fo2) + (0.0749P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.131	(Δ/σ)max = 0.001
S = 1.07	Δρmax = 1.09 e Å−3
5681 reflections	Δρmin = −0.60 e Å−3
352 parameters

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 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
N1A	0.20719 (9)	0.0944 (2)	0.05345 (11)	0.0164 (5)
N2A	0.27322 (9)	0.0677 (2)	0.19479 (12)	0.0196 (6)
N3A	0.18368 (9)	0.3217 (2)	−0.01909 (11)	0.0177 (5)
N7A	0.28666 (9)	0.4136 (2)	0.19011 (11)	0.0161 (5)
N9A	0.23914 (9)	0.5305 (2)	0.07420 (11)	0.0171 (5)
C2A	0.17772 (10)	0.1776 (3)	−0.01588 (13)	0.0177 (6)
C4A	0.22262 (10)	0.3823 (2)	0.05632 (13)	0.0145 (6)
C5A	0.25287 (10)	0.3085 (2)	0.12903 (13)	0.0149 (6)
C6A	0.24601 (10)	0.1527 (2)	0.12997 (13)	0.0153 (6)
C8A	0.27706 (10)	0.5455 (2)	0.15458 (14)	0.0172 (6)
N1B	0.05771 (9)	0.5676 (2)	0.20961 (12)	0.0179 (5)
N2B	−0.01182 (9)	0.5628 (2)	0.06749 (12)	0.0172 (5)
N3B	0.08777 (9)	0.7852 (2)	0.29107 (12)	0.0206 (6)
N7B	−0.02158 (9)	0.9017 (2)	0.08688 (12)	0.0168 (5)
N9B	0.03572 (9)	1.0065 (2)	0.20639 (12)	0.0196 (6)
C2B	0.09047 (11)	0.6417 (3)	0.28198 (14)	0.0203 (7)
C4B	0.04770 (10)	0.8566 (3)	0.21910 (13)	0.0164 (6)
C5B	0.01143 (10)	0.7901 (2)	0.14346 (13)	0.0154 (6)
C6B	0.01706 (10)	0.6360 (2)	0.13545 (13)	0.0154 (6)
C8B	−0.00578 (10)	1.0302 (3)	0.12637 (13)	0.0179 (6)
S2	0.12525 (3)	0.26071 (6)	0.38069 (3)	0.0165 (2)
O5	0.08129 (8)	0.35729 (19)	0.39253 (10)	0.0234 (5)
O6	0.12578 (9)	0.1108 (2)	0.40732 (12)	0.0339 (6)
O7	0.09306 (9)	0.2668 (2)	0.29303 (11)	0.0294 (6)
O8	0.18679 (8)	0.3294 (2)	0.42607 (11)	0.0332 (6)
S3	0.11514 (3)	0.24895 (6)	0.13708 (3)	0.0156 (2)
O9	0.17374 (8)	0.3204 (2)	0.20016 (10)	0.0253 (5)
O10	0.05962 (7)	0.30655 (18)	0.12953 (10)	0.0202 (5)
O11	0.12193 (8)	0.08329 (18)	0.16194 (10)	0.0213 (5)
O12	0.10420 (8)	0.24888 (17)	0.05736 (9)	0.0179 (4)
S1	0.13614 (3)	0.77672 (6)	0.08987 (3)	0.0152 (2)
O1	0.09098 (8)	0.90674 (18)	0.05182 (10)	0.0216 (5)
O2	0.19547 (7)	0.81613 (18)	0.10101 (10)	0.0204 (5)
O3	0.14779 (8)	0.74736 (17)	0.16871 (9)	0.0191 (5)
O4	0.10611 (7)	0.64802 (18)	0.03559 (9)	0.0201 (5)
H1A	0.2012 (12)	−0.0058 (19)	0.0530 (15)	0.0240*
H2A	0.15110	0.12780	−0.06510	0.0210*
H7A	0.3078 (11)	0.393 (3)	0.2428 (10)	0.0240*
H8A	0.29440	0.63500	0.18200	0.0210*
H9A	0.2268 (12)	0.602 (2)	0.0373 (13)	0.0240*
H21A	0.2959 (11)	0.105 (3)	0.2450 (11)	0.0240*
H22A	0.2669 (12)	−0.0326 (19)	0.1924 (15)	0.0240*
H1B	0.0625 (12)	0.4704 (19)	0.2105 (16)	0.0240*
H2B	0.11700	0.58560	0.32890	0.0240*
H7B	−0.0488 (10)	0.891 (3)	0.0315 (10)	0.0240*
H8B	−0.02120	1.12300	0.10210	0.0210*
H9B	0.0541 (11)	1.081 (2)	0.2402 (13)	0.0240*
H21B	−0.0057 (12)	0.4657 (19)	0.0680 (16)	0.0240*
H22B	−0.0407 (10)	0.611 (3)	0.0202 (12)	0.0240*
H5	0.0918 (12)	0.357 (3)	0.4403 (11)	0.0300*
H11	0.1146 (13)	0.026 (3)	0.1202 (13)	0.0300*

	U11	U22	U33	U12	U13	U23
N1A	0.0185 (9)	0.0135 (9)	0.0155 (9)	−0.0025 (7)	0.0091 (8)	−0.0015 (7)
N2A	0.0237 (10)	0.0134 (9)	0.0181 (10)	−0.0018 (8)	0.0103 (9)	0.0027 (8)
N3A	0.0184 (9)	0.0176 (9)	0.0161 (9)	−0.0003 (8)	0.0096 (8)	0.0000 (7)
N7A	0.0170 (9)	0.0137 (9)	0.0151 (9)	−0.0006 (7)	0.0081 (8)	−0.0010 (7)
N9A	0.0192 (9)	0.0114 (9)	0.0176 (9)	0.0011 (7)	0.0092 (8)	0.0022 (7)
C2A	0.0167 (10)	0.0194 (11)	0.0158 (11)	−0.0008 (9)	0.0089 (9)	−0.0038 (8)
C4A	0.0153 (10)	0.0132 (10)	0.0150 (10)	0.0004 (8)	0.0090 (9)	0.0019 (8)
C5A	0.0155 (10)	0.0135 (10)	0.0140 (10)	−0.0015 (8)	0.0078 (9)	−0.0014 (8)
C6A	0.0157 (10)	0.0135 (10)	0.0169 (11)	−0.0006 (8)	0.0098 (9)	−0.0011 (8)
C8A	0.0169 (10)	0.0131 (10)	0.0206 (11)	0.0006 (8)	0.0106 (10)	−0.0011 (8)
N1B	0.0173 (9)	0.0137 (9)	0.0185 (10)	0.0014 (7)	0.0083 (8)	0.0004 (7)
N2B	0.0200 (9)	0.0117 (9)	0.0166 (9)	0.0004 (7)	0.0090 (8)	−0.0016 (7)
N3B	0.0204 (10)	0.0216 (10)	0.0159 (9)	0.0004 (8)	0.0085 (8)	−0.0001 (8)
N7B	0.0160 (9)	0.0132 (9)	0.0178 (10)	0.0007 (7)	0.0081 (8)	0.0006 (7)
N9B	0.0195 (10)	0.0148 (9)	0.0217 (10)	−0.0024 (8)	0.0106 (9)	−0.0054 (8)
C2B	0.0183 (11)	0.0223 (12)	0.0175 (11)	0.0008 (9)	0.0090 (10)	0.0019 (9)
C4B	0.0160 (10)	0.0168 (11)	0.0172 (11)	−0.0009 (8)	0.0102 (9)	−0.0033 (8)
C5B	0.0142 (10)	0.0140 (10)	0.0173 (10)	−0.0011 (8)	0.0090 (9)	0.0002 (8)
C6B	0.0155 (10)	0.0143 (10)	0.0182 (11)	−0.0002 (8)	0.0110 (9)	0.0021 (8)
C8B	0.0168 (10)	0.0170 (11)	0.0210 (11)	−0.0003 (9)	0.0118 (10)	−0.0005 (9)
S2	0.0199 (3)	0.0132 (3)	0.0163 (3)	0.0007 (2)	0.0107 (2)	−0.0011 (2)
O5	0.0289 (9)	0.0221 (9)	0.0216 (9)	0.0104 (7)	0.0162 (8)	0.0040 (7)
O6	0.0460 (12)	0.0167 (9)	0.0509 (12)	0.0040 (8)	0.0351 (11)	0.0044 (8)
O7	0.0392 (11)	0.0308 (10)	0.0184 (9)	0.0032 (8)	0.0171 (8)	−0.0005 (7)
O8	0.0261 (9)	0.0396 (11)	0.0318 (10)	−0.0102 (8)	0.0160 (9)	−0.0156 (9)
S3	0.0160 (3)	0.0147 (3)	0.0138 (3)	0.0010 (2)	0.0076 (2)	−0.0010 (2)
O9	0.0218 (8)	0.0263 (9)	0.0206 (9)	−0.0052 (7)	0.0086 (7)	−0.0057 (7)
O10	0.0217 (8)	0.0174 (8)	0.0230 (8)	0.0054 (7)	0.0141 (7)	0.0024 (7)
O11	0.0288 (9)	0.0144 (8)	0.0202 (9)	0.0053 (7)	0.0142 (8)	0.0019 (6)
O12	0.0215 (8)	0.0173 (8)	0.0137 (7)	−0.0002 (6)	0.0098 (7)	−0.0006 (6)
S1	0.0166 (3)	0.0123 (2)	0.0142 (3)	−0.0005 (2)	0.0078 (2)	−0.0011 (2)
O1	0.0240 (8)	0.0167 (8)	0.0180 (8)	0.0063 (7)	0.0091 (7)	0.0021 (6)
O2	0.0212 (8)	0.0141 (8)	0.0258 (9)	−0.0035 (6)	0.0139 (7)	−0.0023 (7)
O3	0.0252 (8)	0.0175 (8)	0.0132 (8)	0.0008 (6)	0.0105 (7)	0.0007 (6)
O4	0.0246 (8)	0.0145 (8)	0.0208 (8)	−0.0061 (7)	0.0132 (7)	−0.0058 (6)

S2—O7	1.4553 (19)	N2A—H22A	0.911 (18)
S2—O8	1.448 (2)	N7A—H7A	0.888 (17)
S2—O5	1.576 (2)	N9A—H9A	0.89 (2)
S2—O6	1.447 (2)	N1B—C6B	1.376 (3)
S3—O10	1.473 (2)	N1B—C2B	1.362 (3)
S3—O9	1.451 (2)	N2B—C6B	1.296 (3)
S3—O12	1.4705 (18)	N3B—C2B	1.308 (3)
S3—O11	1.5457 (17)	N3B—C4B	1.358 (3)
S1—O3	1.4683 (18)	N7B—C5B	1.379 (3)
S1—O2	1.485 (2)	N7B—C8B	1.324 (3)
S1—O1	1.513 (2)	N9B—C8B	1.338 (3)
S1—O4	1.4653 (17)	N9B—C4B	1.371 (3)
O5—H5	0.84 (2)	N1B—H1B	0.880 (18)
O11—H11	0.91 (3)	N2B—H22B	0.91 (2)
N1A—C2A	1.363 (3)	N2B—H21B	0.885 (18)
N1A—C6A	1.365 (3)	N7B—H7B	0.916 (17)
N2A—C6A	1.311 (3)	N9B—H9B	0.87 (2)
N3A—C4A	1.358 (3)	C4A—C5A	1.368 (3)
N3A—C2A	1.308 (3)	C5A—C6A	1.411 (3)
N7A—C8A	1.331 (3)	C2A—H2A	0.9300
N7A—C5A	1.386 (3)	C8A—H8A	0.9300
N9A—C4A	1.379 (3)	C4B—C5B	1.379 (3)
N9A—C8A	1.328 (3)	C5B—C6B	1.410 (3)
N1A—H1A	0.912 (18)	C2B—H2B	0.9300
N2A—H21A	0.89 (2)	C8B—H8B	0.9300
O7—S2—O8	112.88 (14)	C2B—N1B—H1B	118.0 (17)
O5—S2—O7	102.56 (12)	H21B—N2B—H22B	121 (2)
O5—S2—O8	108.50 (11)	C6B—N2B—H21B	119.9 (17)
O5—S2—O6	107.40 (14)	C6B—N2B—H22B	119.1 (16)
O6—S2—O8	113.41 (13)	C8B—N7B—H7B	125.1 (17)
O6—S2—O7	111.33 (11)	C5B—N7B—H7B	126.9 (17)
O9—S3—O12	112.90 (13)	C8B—N9B—H9B	120.8 (13)
O9—S3—O11	106.15 (11)	C4B—N9B—H9B	130.1 (14)
O9—S3—O10	114.29 (11)	N1A—C2A—N3A	125.5 (2)
O11—S3—O12	105.67 (10)	N3A—C4A—C5A	126.71 (18)
O10—S3—O11	106.70 (12)	N9A—C4A—C5A	106.83 (18)
O10—S3—O12	110.47 (11)	N3A—C4A—N9A	126.46 (19)
O1—S1—O4	108.04 (10)	C4A—C5A—C6A	119.78 (19)
O3—S1—O4	110.72 (10)	N7A—C5A—C6A	132.96 (19)
O1—S1—O2	109.55 (11)	N7A—C5A—C4A	107.26 (16)
O1—S1—O3	106.93 (12)	N1A—C6A—C5A	112.32 (18)
O2—S1—O4	110.76 (12)	N1A—C6A—N2A	121.42 (18)
O2—S1—O3	110.73 (11)	N2A—C6A—C5A	126.3 (2)
S2—O5—H5	114 (2)	N7A—C8A—N9A	110.04 (18)
S3—O11—H11	108.5 (17)	N3A—C2A—H2A	117.00
C2A—N1A—C6A	123.81 (19)	N1A—C2A—H2A	117.00
C2A—N3A—C4A	111.84 (18)	N7A—C8A—H8A	125.00
C5A—N7A—C8A	107.59 (18)	N9A—C8A—H8A	125.00
C4A—N9A—C8A	108.28 (17)	N1B—C2B—N3B	125.5 (2)
C6A—N1A—H1A	113.5 (16)	N9B—C4B—C5B	106.44 (19)
C2A—N1A—H1A	122.7 (16)	N3B—C4B—C5B	125.8 (2)
H21A—N2A—H22A	114 (2)	N3B—C4B—N9B	127.7 (2)
C6A—N2A—H22A	123.1 (16)	C4B—C5B—C6B	120.1 (2)
C6A—N2A—H21A	122.3 (17)	N7B—C5B—C4B	107.33 (18)
C5A—N7A—H7A	123.7 (17)	N7B—C5B—C6B	132.3 (2)
C8A—N7A—H7A	128.6 (17)	N1B—C6B—N2B	122.07 (18)
C4A—N9A—H9A	124.8 (13)	N2B—C6B—C5B	125.8 (2)
C8A—N9A—H9A	126.9 (13)	N1B—C6B—C5B	112.17 (18)
C2B—N1B—C6B	123.68 (19)	N7B—C8B—N9B	109.8 (2)
C2B—N3B—C4B	112.6 (2)	N3B—C2B—H2B	117.00
C5B—N7B—C8B	107.93 (19)	N1B—C2B—H2B	117.00
C4B—N9B—C8B	108.5 (2)	N9B—C8B—H8B	125.00
C6B—N1B—H1B	118.3 (17)	N7B—C8B—H8B	125.00

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O4i	0.84 (2)	1.74 (2)	2.580 (2)	174 (3)
O11—H11···O1ii	0.91 (3)	1.56 (2)	2.457 (2)	166 (4)
N1A—H1A···O2ii	0.912 (18)	1.92 (2)	2.760 (3)	151 (3)
N1A—H1A···O6iii	0.912 (18)	2.58 (2)	3.050 (3)	112.5 (18)
N1B—H1B···O7	0.880 (18)	2.28 (2)	3.027 (3)	142 (2)
N1B—H1B···O10	0.880 (18)	2.18 (2)	2.870 (3)	136 (2)
N2A—H21A···O3iv	0.89 (2)	1.96 (2)	2.796 (3)	156 (2)
N2A—H22A···O2ii	0.911 (18)	2.17 (2)	2.884 (3)	135 (2)
N2A—H22A···O9iv	0.911 (18)	2.22 (2)	2.814 (3)	122 (2)
N2B—H21B···O10	0.885 (18)	2.01 (3)	2.760 (3)	142 (3)
N2B—H21B···O4v	0.885 (18)	2.43 (3)	2.829 (3)	108 (2)
N2B—H22B···O12v	0.91 (2)	1.94 (2)	2.817 (3)	162 (2)
N7A—H7A···O3iv	0.888 (17)	1.96 (2)	2.757 (2)	149 (2)
N7A—H7A···O11vi	0.888 (17)	2.42 (2)	2.937 (3)	117 (2)
N7B—H7B···O1vii	0.916 (17)	2.28 (2)	2.858 (3)	121 (2)
N7B—H7B···O12v	0.916 (17)	1.97 (2)	2.763 (3)	145 (2)
N9A—H9A···O8viii	0.89 (2)	1.95 (2)	2.767 (3)	152.3 (18)
N9B—H9B···O7ix	0.87 (2)	1.920 (19)	2.775 (3)	166 (2)
C2A—H2A···O6iii	0.93	2.21	2.913 (3)	131
C2A—H2A···N3Bviii	0.93	2.49	3.189 (3)	132
C8B—H8B···O10ix	0.93	2.48	2.999 (3)	115
C8B—H8B···O1vii	0.93	2.54	2.983 (3)	109

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O4i	0.84 (2)	1.74 (2)	2.580 (2)	174 (3)
O11—H11⋯O1ii	0.91 (3)	1.56 (2)	2.457 (2)	166 (4)
N1A—H1A⋯O2ii	0.912 (18)	1.92 (2)	2.760 (3)	151 (3)
N1B—H1B⋯O7	0.880 (18)	2.28 (2)	3.027 (3)	142 (2)
N1B—H1B⋯O10	0.880 (18)	2.18 (2)	2.870 (3)	136 (2)
N2A—H21A⋯O3iii	0.89 (2)	1.96 (2)	2.796 (3)	156 (2)
N2A—H22A⋯O2ii	0.911 (18)	2.17 (2)	2.884 (3)	135 (2)
N2A—H22A⋯O9iii	0.911 (18)	2.22 (2)	2.814 (3)	122 (2)
N2B—H21B⋯O10	0.885 (18)	2.01 (3)	2.760 (3)	142 (3)
N2B—H22B⋯O12iv	0.91 (2)	1.94 (2)	2.817 (3)	162 (2)
N7A—H7A⋯O3iii	0.888 (17)	1.96 (2)	2.757 (2)	149 (2)
N7B—H7B⋯O1v	0.916 (17)	2.28 (2)	2.858 (3)	121 (2)
N7B—H7B⋯O12iv	0.916 (17)	1.97 (2)	2.763 (3)	145 (2)
N9A—H9A⋯O8vi	0.89 (2)	1.95 (2)	2.767 (3)	152.3 (18)
N9B—H9B⋯O7vii	0.87 (2)	1.920 (19)	2.775 (3)	166 (2)
C2A—H2A⋯O6viii	0.93	2.21	2.913 (3)	131
C2A—H2A⋯N3B vi	0.93	2.49	3.189 (3)	132

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