Ammonium 4,6-dioxo-2-sulfanylidene-1,3-diazinan-5-ide.

In the title salt, NH(4) (+)·C(4)H(3)N(2)O(2)S(-), the asymmetric unit comprises two half-occupied ammonium positions and a 4,6-dioxo-2-sulfanylidene-1,3-diazinan-5-ide anion. The anion shows C(2) as well as C(s) symmetry and is present in its diketonic tautomeric form. Intra-cyclic angles span a range from 116.64 (9)-124.67 (9)°. Inter-molecular N-H⋯O hydrogen bonds connect the cations and anions to form a three-dimensional network.

Related literature

For the crystal structures of 2-thio­barbituric acid, its hydrate and several of its tautomeric forms, see: Calas & Martinez (1967 ▶); Chierotti et al. (2010 ▶). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

NH4 +·C4H3N2O2S−

M = 161.19

Monoclinic,

a = 11.3308 (4) Å

b = 3.9396 (1) Å

c = 14.6945 (5) Å

β = 98.644 (1)°

V = 648.49 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.44 mm−1

T = 200 K

0.53 × 0.19 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.876, T max = 1.000

6071 measured reflections

1604 independent reflections

1476 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.023

wR(F 2) = 0.067

S = 1.10

1604 reflections

116 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); 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: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811016722/bq2297sup1.cif

Supplementary material file. DOI: 10.1107/S1600536811016722/bq2297Isup2.cdx

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811016722/bq2297Isup3.hkl

Supplementary material file. DOI: 10.1107/S1600536811016722/bq2297Isup4.cml

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

NH4+·C4H3N2O2S−	F(000) = 336
Mr = 161.19	Dx = 1.651 Mg m−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 1604 reflections
a = 11.3308 (4) Å	θ = 3.1–28.3°
b = 3.9396 (1) Å	µ = 0.44 mm−1
c = 14.6945 (5) Å	T = 200 K
β = 98.644 (1)°	Rod, colourless
V = 648.49 (4) Å3	0.53 × 0.19 × 0.08 mm
Z = 4

Bruker APEXII CCD diffractometer	1604 independent reflections
Radiation source: fine-focus sealed tube	1476 reflections with I > 2σ(I)
graphite	Rint = 0.017
φ and ω scans	θmax = 28.3°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→15
Tmin = 0.876, Tmax = 1.000	k = −4→5
6071 measured reflections	l = −16→19

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.067	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ2(Fo2) + (0.0357P)2 + 0.2247P] where P = (Fo2 + 2Fc2)/3
1604 reflections	(Δ/σ)max = 0.001
116 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

	x	y	z	Uiso*/Ueq
S1	0.25562 (2)	1.03184 (7)	0.667084 (17)	0.01875 (10)
O1	0.05012 (7)	0.4191 (2)	0.39646 (5)	0.02247 (19)
O2	0.44635 (7)	0.7956 (3)	0.39645 (6)	0.0262 (2)
N1	0.34683 (8)	0.8796 (3)	0.51685 (6)	0.01740 (19)
H71	0.4077 (15)	0.978 (4)	0.5427 (12)	0.027 (4)*
N2	0.15417 (8)	0.7040 (2)	0.51663 (6)	0.01649 (19)
H72	0.0908 (14)	0.678 (4)	0.5433 (10)	0.024 (4)*
C1	0.25140 (9)	0.8614 (3)	0.56115 (7)	0.0151 (2)
C2	0.14770 (9)	0.5599 (3)	0.42919 (7)	0.0160 (2)
C3	0.24801 (9)	0.5883 (3)	0.38550 (7)	0.0182 (2)
H3	0.2466	0.4960	0.3256	0.022*
C4	0.35073 (9)	0.7513 (3)	0.42884 (7)	0.0177 (2)
N90	0.5000	0.4019 (4)	0.2500	0.0202 (3)
H901	0.5638 (14)	0.272 (4)	0.2710 (11)	0.034 (4)*
H902	0.4821 (15)	0.527 (4)	0.2944 (11)	0.031 (4)*
N91	0.0000	0.9763 (4)	0.2500	0.0234 (3)
H911	0.0284 (17)	1.109 (5)	0.2961 (13)	0.048 (5)*
H912	0.0539 (19)	0.853 (6)	0.2290 (15)	0.064 (6)*

	U11	U22	U33	U12	U13	U23
S1	0.01756 (15)	0.02527 (16)	0.01378 (14)	0.00002 (10)	0.00348 (10)	−0.00417 (9)
O1	0.0173 (4)	0.0325 (4)	0.0175 (4)	−0.0085 (3)	0.0023 (3)	−0.0039 (3)
O2	0.0176 (4)	0.0417 (5)	0.0209 (4)	−0.0090 (4)	0.0085 (3)	−0.0104 (4)
N1	0.0138 (4)	0.0247 (5)	0.0139 (4)	−0.0039 (4)	0.0025 (3)	−0.0034 (4)
N2	0.0136 (4)	0.0234 (5)	0.0130 (4)	−0.0027 (3)	0.0037 (3)	−0.0001 (3)
C1	0.0153 (4)	0.0169 (5)	0.0131 (4)	0.0005 (4)	0.0020 (4)	0.0017 (4)
C2	0.0159 (4)	0.0190 (5)	0.0127 (5)	−0.0013 (4)	0.0007 (4)	0.0012 (4)
C3	0.0184 (5)	0.0237 (5)	0.0128 (5)	−0.0030 (4)	0.0031 (4)	−0.0022 (4)
C4	0.0167 (5)	0.0228 (5)	0.0141 (4)	−0.0014 (4)	0.0043 (4)	−0.0012 (4)
N90	0.0193 (6)	0.0243 (7)	0.0170 (6)	0.000	0.0032 (5)	0.000
N91	0.0251 (7)	0.0260 (7)	0.0204 (7)	0.000	0.0074 (6)	0.000

S1—C1	1.6893 (10)	N2—H72	0.874 (16)
O1—C2	1.2656 (13)	C2—C3	1.3914 (15)
O2—C4	1.2592 (13)	C3—C4	1.3963 (14)
N1—C1	1.3452 (14)	C3—H3	0.9500
N1—C4	1.3955 (13)	N90—H901	0.902 (17)
N1—H71	0.832 (17)	N90—H902	0.866 (17)
N2—C1	1.3453 (13)	N91—H911	0.88 (2)
N2—C2	1.3965 (13)	N91—H912	0.87 (2)
C1—N1—C4	124.67 (9)	O1—C2—N2	116.73 (10)
C1—N1—H71	118.4 (12)	C3—C2—N2	117.27 (9)
C4—N1—H71	116.9 (12)	C2—C3—C4	120.62 (10)
C1—N2—C2	124.11 (9)	C2—C3—H3	119.7
C1—N2—H72	120.3 (10)	C4—C3—H3	119.7
C2—N2—H72	115.5 (10)	O2—C4—N1	116.68 (9)
N1—C1—N2	116.64 (9)	O2—C4—C3	126.64 (10)
N1—C1—S1	120.74 (8)	N1—C4—C3	116.68 (9)
N2—C1—S1	122.62 (8)	H901—N90—H902	109.4 (14)
O1—C2—C3	125.99 (10)	H911—N91—H912	114.2 (19)
C4—N1—C1—N2	0.76 (16)	O1—C2—C3—C4	179.77 (11)
C4—N1—C1—S1	−178.90 (8)	N2—C2—C3—C4	0.82 (16)
C2—N2—C1—N1	0.48 (16)	C1—N1—C4—O2	178.58 (11)
C2—N2—C1—S1	−179.87 (8)	C1—N1—C4—C3	−1.12 (16)
C1—N2—C2—O1	179.70 (10)	C2—C3—C4—O2	−179.40 (12)
C1—N2—C2—C3	−1.25 (16)	C2—C3—C4—N1	0.27 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H71···O2i	0.832 (17)	1.971 (17)	2.8025 (12)	179.0 (16)
N2—H72···O1ii	0.874 (16)	1.976 (16)	2.8483 (12)	175.7 (15)
N90—H901···S1iii	0.902 (17)	2.426 (16)	3.3252 (8)	174.8 (14)
N90—H902···O2	0.866 (17)	1.927 (17)	2.7929 (12)	177.7 (16)
N91—H911···O1iv	0.88 (2)	1.90 (2)	2.7622 (13)	166.0 (18)
N91—H912···O1v	0.87 (2)	2.66 (2)	3.0669 (15)	110.0 (16)
N91—H912···S1vi	0.87 (2)	2.62 (2)	3.3069 (3)	136.0 (19)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H71⋯O2i	0.832 (17)	1.971 (17)	2.8025 (12)	179.0 (16)
N2—H72⋯O1ii	0.874 (16)	1.976 (16)	2.8483 (12)	175.7 (15)
N90—H901⋯S1iii	0.902 (17)	2.426 (16)	3.3252 (8)	174.8 (14)
N90—H902⋯O2	0.866 (17)	1.927 (17)	2.7929 (12)	177.7 (16)
N91—H911⋯O1iv	0.88 (2)	1.90 (2)	2.7622 (13)	166.0 (18)
N91—H912⋯O1v	0.87 (2)	2.66 (2)	3.0669 (15)	110.0 (16)
N91—H912⋯S1vi	0.87 (2)	2.62 (2)	3.3069 (3)	136.0 (19)

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