Cytosinium hydrogen selenite.

In the crystal structure of the title salt, C4H6N3O(+)·HSeO3 (-), systematic name 6-amino-2-methyl-idene-2,3-di-hydro-pyrim-idin-1-ium hydrogen selenite, the hydrogenselenite anions and the cytosinium cations are linked via N-H⋯O, N-H⋯Se, O-H⋯O, O-H··Se and C-H⋯O hydrogen bonds, forming a three-dimensional framework.

Related literature

For the crystal structure of cytosine, see: Barker & Marsh (1964 ▶), and of cytosine monohydrate, see: Jeffrey & Kinoshita (1963 ▶). For examples of some inorganic cytosinium salts, see: Mandel (1977 ▶); Bagieu-Beucher (1990 ▶). For examples of the structures of cytosinium salts of organic acids, see: Gdaniec et al. (1989 ▶); Smith et al. (2005 ▶). For examples of the structure of the hydrogenselenite anion, see: Richie & Harrison (2003 ▶); Wang et al. (2006 ▶); Chomnilpan et al. (1981 ▶).

Experimental

Crystal data

C4H6N3O+·HSeO3 −

M = 240.09

Orthorhombic,

a = 7.0051 (3) Å

b = 8.6342 (2) Å

c = 12.7131 (3) Å

V = 768.93 (4) Å3

Z = 4

Mo Kα radiation

μ = 4.86 mm−1

T = 293 K

0.20 × 0.15 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (Blessing, 1995 ▶) T min = 0.295, T max = 0.369

4568 measured reflections

1494 independent reflections

1283 reflections with I > 2σ(I)

R int = 0.067

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.098

S = 1.04

1494 reflections

125 parameters

7 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.46 e Å−3

Δρmin = −0.49 e Å−3

Absolute structure: Flack parameter determined using 518 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▶)

Absolute structure parameter: −0.02 (3)

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL2013 and PLATON.

Crystal structure: contains datablock(s) Global, I. DOI: 10.1107/S1600536814001275/su2689sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814001275/su2689Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814001275/su2689Isup3.cml

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

C4H6N3O+·HSeO3−	Dx = 2.074 Mg m−3
Mr = 240.09	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca21	Cell parameters from 5415 reflections
a = 7.0051 (3) Å	θ = 3.8–29.5°
b = 8.6342 (2) Å	µ = 4.86 mm−1
c = 12.7131 (3) Å	T = 293 K
V = 768.93 (4) Å3	Prism, colourless
Z = 4	0.20 × 0.15 × 0.10 mm
F(000) = 472

Nonius KappaCCD diffractometer	1494 independent reflections
Radiation source: fine-focus sealed tube	1283 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
ω – θ scans	θmax = 26.0°, θmin = 3.8°
Absorption correction: multi-scan (Blessing, 1995)	h = −8→8
Tmin = 0.295, Tmax = 0.369	k = −10→10
4568 measured reflections	l = −14→15

Refinement on F2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.042	w = 1/[σ2(Fo2) + (0.0404P)2 + 0.8215P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.098	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.46 e Å−3
1494 reflections	Δρmin = −0.49 e Å−3
125 parameters	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
7 restraints	Extinction coefficient: 0.018 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack parameter determined using 518 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.02 (3)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
O1	0.9370 (10)	0.0316 (8)	0.0502 (5)	0.050 (2)
N1	0.8269 (12)	−0.0384 (8)	0.2127 (7)	0.0392 (19)
H1A	0.832 (17)	−0.134 (5)	0.194 (8)	0.047*
N2	0.8534 (12)	0.2200 (8)	0.1669 (6)	0.0363 (17)
H2A	0.885 (14)	0.300 (8)	0.130 (7)	0.044*
N3	0.7775 (19)	0.4148 (8)	0.2818 (10)	0.047 (3)
H3A	0.732 (17)	0.455 (9)	0.337 (5)	0.056*
H3B	0.817 (16)	0.489 (8)	0.245 (6)	0.056*
C1	0.8779 (14)	0.0666 (10)	0.1365 (8)	0.037 (2)
C2	0.7901 (14)	0.2661 (10)	0.2619 (8)	0.036 (2)
C3	0.7485 (14)	0.1527 (10)	0.3383 (8)	0.041 (2)
H3	0.7088	0.1799	0.4056	0.049*
C4	0.7686 (17)	0.0029 (10)	0.3095 (8)	0.041 (2)
H4	0.7413	−0.0742	0.3583	0.049*
Se1	0.43127 (11)	0.36795 (7)	0.02452 (11)	0.0378 (4)
O2	0.2460 (11)	0.3114 (7)	−0.0579 (6)	0.0444 (16)
H2	0.147 (10)	0.350 (12)	−0.038 (10)	0.067*
O3	0.3461 (15)	0.3439 (7)	0.1431 (6)	0.054 (2)
O4	0.4180 (9)	0.5615 (6)	0.0084 (8)	0.0432 (19)

	U11	U22	U33	U12	U13	U23
O1	0.063 (4)	0.039 (3)	0.048 (6)	0.004 (3)	0.007 (3)	−0.006 (3)
N1	0.051 (5)	0.022 (3)	0.045 (5)	0.001 (3)	−0.005 (4)	0.003 (3)
N2	0.051 (4)	0.023 (4)	0.035 (4)	0.000 (3)	−0.001 (3)	0.004 (3)
N3	0.062 (8)	0.029 (3)	0.049 (5)	0.002 (5)	0.004 (5)	−0.004 (4)
C1	0.038 (5)	0.024 (4)	0.047 (6)	−0.001 (4)	−0.004 (4)	−0.004 (4)
C2	0.043 (7)	0.030 (4)	0.035 (6)	0.004 (4)	−0.002 (5)	−0.001 (4)
C3	0.050 (6)	0.036 (5)	0.036 (5)	−0.004 (4)	0.000 (4)	−0.002 (4)
C4	0.045 (6)	0.035 (5)	0.042 (6)	−0.003 (4)	−0.003 (5)	0.009 (4)
Se1	0.0425 (5)	0.0233 (4)	0.0475 (5)	0.0031 (3)	−0.0018 (7)	−0.0008 (7)
O2	0.046 (4)	0.035 (3)	0.053 (4)	0.002 (3)	−0.002 (3)	−0.009 (3)
O3	0.098 (6)	0.022 (3)	0.041 (4)	0.005 (3)	−0.001 (4)	0.002 (3)
O4	0.052 (3)	0.023 (3)	0.055 (5)	−0.001 (2)	0.003 (4)	−0.001 (3)

O1—C1	1.211 (11)	N3—H3B	0.84 (3)
N1—C4	1.345 (14)	C2—C3	1.409 (13)
N1—C1	1.374 (13)	C3—C4	1.352 (12)
N1—H1A	0.85 (3)	C3—H3	0.9300
N2—C2	1.346 (11)	C4—H4	0.9300
N2—C1	1.391 (11)	Se1—O3	1.634 (8)
N2—H2A	0.86 (3)	Se1—O4	1.686 (6)
N3—C2	1.312 (12)	Se1—O2	1.738 (7)
N3—H3A	0.84 (3)	O2—H2	0.81 (3)
C4—N1—C1	123.3 (7)	N3—C2—C3	122.2 (10)
C4—N1—H1A	121 (7)	N2—C2—C3	118.7 (8)
C1—N1—H1A	115 (7)	C4—C3—C2	117.2 (9)
C2—N2—C1	124.9 (8)	C4—C3—H3	121.4
C2—N2—H2A	110 (7)	C2—C3—H3	121.4
C1—N2—H2A	125 (7)	N1—C4—C3	122.2 (8)
C2—N3—H3A	126 (6)	N1—C4—H4	118.9
C2—N3—H3B	128 (6)	C3—C4—H4	118.9
H3A—N3—H3B	106 (5)	O3—Se1—O4	102.6 (4)
O1—C1—N1	124.3 (9)	O3—Se1—O2	104.3 (5)
O1—C1—N2	122.1 (9)	O4—Se1—O2	99.4 (4)
N1—C1—N2	113.6 (8)	Se1—O2—H2	110 (9)
N3—C2—N2	119.0 (9)
C4—N1—C1—O1	177.3 (10)	C1—N2—C2—C3	1.5 (15)
C4—N1—C1—N2	−3.4 (14)	N3—C2—C3—C4	−179.2 (12)
C2—N2—C1—O1	−179.4 (10)	N2—C2—C3—C4	−2.4 (15)
C2—N2—C1—N1	1.3 (13)	C1—N1—C4—C3	2.7 (17)
C1—N2—C2—N3	178.4 (10)	C2—C3—C4—N1	0.4 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Se1i	0.85 (3)	3.04 (6)	3.789 (9)	148 (9)
N1—H1A···O3i	0.85 (3)	1.93 (3)	2.785 (10)	176 (10)
N2—H2A···O4ii	0.86 (3)	1.97 (5)	2.798 (12)	160 (10)
N3—H3A···Se1iii	0.84 (3)	3.06 (3)	3.896 (12)	174 (7)
N3—H3A···O2iii	0.84 (3)	2.42 (7)	3.126 (12)	141 (8)
N3—H3A···O4iii	0.84 (3)	2.42 (4)	3.196 (17)	152 (8)
N3—H3B···O3ii	0.84 (3)	1.95 (4)	2.772 (12)	166 (12)
O2—H2···Se1iv	0.81 (3)	2.97 (6)	3.691 (7)	149 (10)
O2—H2···O4iv	0.81 (3)	1.87 (3)	2.682 (10)	180 (14)
C3—H3···O1v	0.93	2.46	3.168 (12)	133
C4—H4···O2vi	0.93	2.31	3.196 (11)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Se1i	0.85 (3)	3.04 (6)	3.789 (9)	148 (9)
N1—H1A⋯O3i	0.85 (3)	1.93 (3)	2.785 (10)	176 (10)
N2—H2A⋯O4ii	0.86 (3)	1.97 (5)	2.798 (12)	160 (10)
N3—H3A⋯Se1iii	0.84 (3)	3.06 (3)	3.896 (12)	174 (7)
N3—H3A⋯O2iii	0.84 (3)	2.42 (7)	3.126 (12)	141 (8)
N3—H3A⋯O4iii	0.84 (3)	2.42 (4)	3.196 (17)	152 (8)
N3—H3B⋯O3ii	0.84 (3)	1.95 (4)	2.772 (12)	166 (12)
O2—H2⋯Se1iv	0.81 (3)	2.97 (6)	3.691 (7)	149 (10)
O2—H2⋯O4iv	0.81 (3)	1.87 (3)	2.682 (10)	180 (14)
C3—H3⋯O1v	0.93	2.46	3.168 (12)	133
C4—H4⋯O2vi	0.93	2.31	3.196 (11)	159

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