When solvent becomes reactant: a study of 6-amino­thio­cytosine derivatives

The dissolution of 6-amino­thio­cytosine in common solvents (such as methanol, dimethyl sulfoxide and di­chloro­methane) under alkaline conditions is shown to afford new com­pounds with a 6-amino­thio­cytosine skeleton: 2,2′-disulfanediylbis(pyrimidine-4,6-di­amine) (1), C₈H₁₀N₈S₂, 2,2′-[methane­diylbis(sulfanedi­yl)]bis­(pyrimidine-4,6-di­amine) (2), C₉H₁₂N₈S₂, 2-[(meth­oxy­meth­yl)sul­fan­yl]pyrimidine-4,6-di­amine (3), C₆H₁₀N₄OS, and poly[(μ-4,6-di­amino­pyrimidine-2-sulfinato)potassium(I)] (4), [K(C₄H₅N₄O₂S)]_n. The crystal architectures of these com­pounds are found to be strongly influenced by extensive hydrogen-bond networks, although some individual features are also observed. Specifically, 1 is characterized by very short C—H...N hydrogen bonds, 2 features apparently weak and long C—H...π, C—H...S and π–π contacts as the greatest contributors to stabilization energy, while 3 contains ribbons of mol­ecules formed by centrosymmetric dimers of two types, and 4 is characterized by layers with principal structural units com­prising distorted six-mol­ecule rings. The inter­molecular inter­actions in 1–4 are characterized in terms of their geometry, topology and energy, and the corresponding results are confirmed and visualized using Hirshfeld surface analysis.

Computing details

For all structures, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

2,2'-Disulfanediylbis(pyrimidine-4,6-diamine) (1)

Crystal data

C8H10N8S2	F(000) = 584
Mr = 282.36	Dx = 1.580 Mg m^−3
Monoclinic, Cc	Cu Kα radiation, λ = 1.54184 Å
a = 12.3766 (3) Å	Cell parameters from 4768 reflections
b = 10.7745 (2) Å	θ = 5.5–75.9°
c = 9.2050 (2) Å	µ = 4.06 mm^−1
β = 104.777 (2)°	T = 130 K
V = 1186.90 (5) Å^3	Block, colourless
Z = 4	0.1 × 0.05 × 0.05 mm

Data collection

Rigaku SuperNova Single Source diffractometer with an Atlas detector	1888 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	1877 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.019
Detector resolution: 10.5357 pixels mm^-1	θmax = 76.1°, θmin = 5.5°
ω scans	h = −12→15
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −13→13
Tmin = 0.745, Tmax = 1.000	l = −11→10
5026 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.022	w = 1/[σ^2(Fo^2) + (0.0346P)^2 + 0.7075P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.059	(Δ/σ)max = 0.001
S = 1.07	Δρmax = 0.17 e Å^−3
1888 reflections	Δρmin = −0.23 e Å^−3
163 parameters	Absolute structure: Flack x determined using 640 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
2 restraints	Absolute structure parameter: 0.009 (12)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.39810 (18)	0.3677 (2)	0.7728 (2)	0.0200 (5)
C2	0.4850 (2)	0.3070 (2)	0.7476 (3)	0.0168 (5)
N3	0.59186 (18)	0.3384 (2)	0.7809 (2)	0.0188 (5)
C4	0.6147 (2)	0.4502 (2)	0.8530 (3)	0.0200 (5)
N4	0.72210 (19)	0.4869 (2)	0.8878 (3)	0.0271 (5)
H4A	0.7381	0.5499	0.9415	0.051*
H4B	0.7748	0.4366	0.8715	0.041*
C5	0.5316 (2)	0.5212 (3)	0.8914 (3)	0.0222 (5)
H5	0.5519	0.5956	0.9512	0.024*
C6	0.4227 (2)	0.4764 (3)	0.8498 (3)	0.0216 (5)
N6	0.3364 (2)	0.5349 (3)	0.8837 (3)	0.0304 (6)
H6A	0.2739	0.4987	0.8657	0.065*
H6B	0.3414	0.6072	0.9284	0.047*
S7	0.43925 (5)	0.15767 (6)	0.66919 (6)	0.02028 (15)
S8	0.56246 (5)	0.09561 (5)	0.57967 (6)	0.01759 (14)
C9	0.5211 (2)	0.1481 (2)	0.3882 (3)	0.0153 (5)
N10	0.60815 (18)	0.15691 (19)	0.3296 (2)	0.0173 (4)
C11	0.5831 (2)	0.1969 (2)	0.1838 (3)	0.0188 (5)
N11	0.66782 (19)	0.2082 (2)	0.1191 (3)	0.0245 (5)
H11A	0.7292	0.1903	0.1664	0.032*
H11B	0.6478	0.2439	0.0230	0.037*
C12	0.4727 (2)	0.2237 (2)	0.1063 (3)	0.0204 (5)
H12	0.4588	0.2503	−0.0009	0.022*
C13	0.3900 (2)	0.2067 (2)	0.1810 (3)	0.0179 (5)
N13	0.27969 (18)	0.2211 (2)	0.1104 (3)	0.0216 (5)
H13A	0.2637	0.2688	0.0358	0.026*
H13B	0.2365	0.2227	0.1690	0.019*
N14	0.41375 (18)	0.1695 (2)	0.3267 (2)	0.0172 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0160 (11)	0.0260 (11)	0.0175 (11)	0.0002 (8)	0.0031 (8)	0.0021 (9)
C2	0.0183 (12)	0.0209 (12)	0.0103 (11)	0.0003 (9)	0.0018 (9)	0.0008 (9)
N3	0.0165 (11)	0.0207 (10)	0.0185 (11)	−0.0009 (8)	0.0032 (9)	−0.0011 (8)
C4	0.0200 (13)	0.0191 (12)	0.0188 (13)	−0.0003 (10)	0.0009 (10)	0.0005 (10)
N4	0.0186 (12)	0.0242 (11)	0.0369 (14)	−0.0016 (9)	0.0043 (10)	−0.0096 (10)
C5	0.0196 (13)	0.0204 (12)	0.0253 (14)	0.0013 (10)	0.0033 (10)	−0.0029 (10)
C6	0.0204 (13)	0.0232 (13)	0.0201 (13)	0.0053 (11)	0.0033 (10)	0.0027 (10)
N6	0.0223 (12)	0.0318 (14)	0.0375 (14)	0.0046 (10)	0.0082 (10)	−0.0066 (11)
S7	0.0183 (3)	0.0246 (3)	0.0193 (3)	−0.0059 (2)	0.0073 (2)	−0.0033 (2)
S8	0.0163 (3)	0.0194 (3)	0.0163 (3)	0.0008 (2)	0.0028 (2)	0.0014 (2)
C9	0.0160 (12)	0.0136 (11)	0.0154 (12)	−0.0017 (8)	0.0026 (9)	−0.0009 (9)
N10	0.0143 (10)	0.0195 (10)	0.0175 (11)	0.0004 (7)	0.0028 (8)	0.0009 (8)
C11	0.0173 (12)	0.0194 (11)	0.0201 (12)	−0.0004 (9)	0.0054 (10)	−0.0008 (9)
N11	0.0157 (11)	0.0355 (13)	0.0236 (11)	0.0018 (9)	0.0071 (9)	0.0075 (10)
C12	0.0184 (12)	0.0242 (12)	0.0176 (11)	0.0021 (11)	0.0029 (9)	0.0024 (10)
C13	0.0173 (12)	0.0159 (11)	0.0187 (12)	0.0009 (8)	0.0015 (9)	−0.0018 (9)
N13	0.0163 (11)	0.0291 (11)	0.0186 (10)	0.0045 (9)	0.0030 (8)	0.0026 (9)
N14	0.0154 (10)	0.0195 (10)	0.0171 (10)	0.0009 (8)	0.0048 (8)	−0.0006 (8)

Geometric parameters (Å, º)

N1—C2	1.329 (3)	S8—C9	1.797 (2)
N1—C6	1.362 (4)	C9—N14	1.325 (3)
C2—N3	1.323 (3)	C9—N10	1.325 (3)
C2—S7	1.795 (3)	N10—C11	1.368 (3)
N3—C4	1.370 (3)	C11—N11	1.337 (4)
C4—N4	1.345 (3)	C11—C12	1.402 (3)
C4—C5	1.398 (4)	N11—H11A	0.7975
N4—H4A	0.8334	N11—H11B	0.9377
N4—H4B	0.8901	C12—C13	1.383 (4)
C5—C6	1.390 (4)	C12—H12	0.9996
C5—H5	0.9688	C13—N14	1.358 (3)
C6—N6	1.345 (4)	C13—N13	1.363 (3)
N6—H6A	0.8441	N13—H13A	0.8403
N6—H6B	0.8756	N13—H13B	0.8503
S7—S8	2.0231 (9)
C2—N1—C6	115.5 (2)	C9—S8—S7	103.87 (9)
N3—C2—N1	129.8 (2)	N14—C9—N10	130.1 (2)
N3—C2—S7	121.1 (2)	N14—C9—S8	118.5 (2)
N1—C2—S7	108.96 (19)	N10—C9—S8	111.33 (17)
C2—N3—C4	114.0 (2)	C9—N10—C11	114.7 (2)
N4—C4—N3	116.3 (2)	N11—C11—N10	117.3 (2)
N4—C4—C5	121.7 (2)	N11—C11—C12	121.9 (2)
N3—C4—C5	122.0 (2)	N10—C11—C12	120.8 (2)
C4—N4—H4A	116.8	C11—N11—H11A	118.8
C4—N4—H4B	120.2	C11—N11—H11B	114.1
H4A—N4—H4B	121.5	H11A—N11—H11B	126.9
C6—C5—C4	117.7 (2)	C13—C12—C11	117.9 (2)
C6—C5—H5	122.5	C13—C12—H12	124.5
C4—C5—H5	119.7	C11—C12—H12	117.5
N6—C6—N1	116.0 (2)	N14—C13—N13	116.3 (2)
N6—C6—C5	123.0 (3)	N14—C13—C12	121.9 (2)
N1—C6—C5	121.0 (2)	N13—C13—C12	121.7 (2)
C6—N6—H6A	118.7	C13—N13—H13A	117.2
C6—N6—H6B	124.2	C13—N13—H13B	114.5
H6A—N6—H6B	117.1	H13A—N13—H13B	116.8
C2—S7—S8	105.47 (9)	C9—N14—C13	114.5 (2)
C6—N1—C2—N3	−3.0 (4)	S7—S8—C9—N14	−24.5 (2)
C6—N1—C2—S7	172.07 (18)	S7—S8—C9—N10	156.64 (15)
N1—C2—N3—C4	0.5 (4)	N14—C9—N10—C11	1.6 (4)
S7—C2—N3—C4	−174.02 (19)	S8—C9—N10—C11	−179.77 (17)
C2—N3—C4—N4	−179.3 (2)	C9—N10—C11—N11	179.6 (2)
C2—N3—C4—C5	2.0 (4)	C9—N10—C11—C12	−0.8 (3)
N4—C4—C5—C6	179.5 (2)	N11—C11—C12—C13	178.5 (3)
N3—C4—C5—C6	−1.9 (4)	N10—C11—C12—C13	−1.0 (4)
C2—N1—C6—N6	−176.2 (2)	C11—C12—C13—N14	2.4 (4)
C2—N1—C6—C5	2.9 (4)	C11—C12—C13—N13	−174.7 (2)
C4—C5—C6—N6	178.3 (3)	N10—C9—N14—C13	−0.3 (4)
C4—C5—C6—N1	−0.7 (4)	S8—C9—N14—C13	−178.87 (17)
N3—C2—S7—S8	−20.8 (2)	N13—C13—N14—C9	175.5 (2)
N1—C2—S7—S8	163.70 (15)	C12—C13—N14—C9	−1.8 (4)

2,2'-[Methanediylbis(sulfanediyl)]bis(pyrimidine-4,6-diamine) (2)

Crystal data

C9H12N8S2	Dx = 1.621 Mg m^−3
Mr = 296.39	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Fdd2	Cell parameters from 3186 reflections
a = 36.9868 (10) Å	θ = 4.8–75.1°
b = 15.5842 (4) Å	µ = 4.00 mm^−1
c = 4.2131 (1) Å	T = 130 K
V = 2428.47 (11) Å^3	Needle, colourless
Z = 8	0.2 × 0.02 × 0.02 mm
F(000) = 1232

Data collection

Rigaku SuperNova Single Source diffractometer with an Atlas detector	1171 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	1153 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.019
Detector resolution: 10.5357 pixels mm^-1	θmax = 75.8°, θmin = 4.8°
ω scans	h = −46→46
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −19→13
Tmin = 0.593, Tmax = 1.000	l = −5→5
4267 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.023	w = 1/[σ^2(Fo^2) + (0.0386P)^2 + 2.5037P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.062	(Δ/σ)max = 0.001
S = 1.06	Δρmax = 0.18 e Å^−3
1171 reflections	Δρmin = −0.16 e Å^−3
88 parameters	Absolute structure: Flack x determined using 436 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.001 (12)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.33494 (5)	0.31726 (11)	0.3752 (5)	0.0233 (4)
C2	0.30593 (6)	0.32157 (14)	0.5623 (6)	0.0224 (5)
N3	0.28855 (5)	0.38998 (11)	0.6691 (7)	0.0244 (4)
C4	0.30253 (6)	0.46631 (13)	0.5759 (6)	0.0243 (5)
N4	0.28395 (6)	0.53599 (11)	0.6790 (8)	0.0319 (4)
H4A	0.2922	0.5857	0.6680	0.038*
H4B	0.2696	0.5212	0.8300	0.038*
C5	0.33268 (6)	0.47186 (13)	0.3806 (6)	0.0250 (5)
H5	0.3422	0.5257	0.3158	0.030*
C6	0.34835 (6)	0.39450 (14)	0.2836 (6)	0.0238 (4)
N6	0.37774 (5)	0.39304 (13)	0.0935 (5)	0.0290 (5)
H6A	0.3872	0.3437	0.0353	0.035*
H6B	0.3874	0.4415	0.0278	0.035*
S7	0.28927 (2)	0.21932 (3)	0.67621 (18)	0.02388 (16)
C8	0.2500	0.2500	0.9038 (9)	0.0241 (6)
H8A	0.2434	0.2024	1.0400	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0224 (8)	0.0201 (8)	0.0273 (11)	−0.0009 (7)	−0.0023 (7)	−0.0001 (8)
C2	0.0210 (10)	0.0206 (10)	0.0256 (11)	−0.0012 (8)	−0.0040 (8)	−0.0004 (8)
N3	0.0231 (8)	0.0215 (8)	0.0285 (9)	0.0007 (7)	−0.0018 (8)	−0.0003 (12)
C4	0.0246 (11)	0.0197 (11)	0.0288 (13)	0.0000 (8)	−0.0070 (9)	0.0002 (9)
N4	0.0369 (10)	0.0194 (9)	0.0393 (11)	0.0029 (7)	0.0025 (11)	0.0020 (11)
C5	0.0257 (10)	0.0200 (9)	0.0293 (13)	−0.0026 (8)	−0.0033 (9)	0.0027 (10)
C6	0.0213 (10)	0.0242 (10)	0.0260 (10)	−0.0021 (8)	−0.0041 (8)	0.0008 (9)
N6	0.0272 (9)	0.0247 (9)	0.0350 (13)	−0.0020 (7)	0.0057 (8)	0.0004 (8)
S7	0.0259 (2)	0.0174 (2)	0.0284 (3)	−0.00188 (17)	0.0009 (2)	−0.0008 (2)
C8	0.0255 (13)	0.0236 (14)	0.0232 (14)	−0.0039 (11)	0.000	0.000

Geometric parameters (Å, º)

N1—C2	1.333 (3)	C5—C6	1.398 (3)
N1—C6	1.358 (3)	C5—H5	0.9500
C2—N3	1.324 (3)	C6—N6	1.351 (3)
C2—S7	1.775 (2)	N6—H6A	0.8800
N3—C4	1.355 (3)	N6—H6B	0.8800
C4—N4	1.356 (3)	S7—C8	1.805 (2)
C4—C5	1.389 (4)	C8—S7^i	1.805 (2)
N4—H4A	0.8337	C8—H8A	0.9700
N4—H4B	0.8606
C2—N1—C6	114.67 (19)	C4—C5—H5	121.6
N3—C2—N1	129.2 (2)	C6—C5—H5	121.6
N3—C2—S7	117.56 (17)	N6—C6—N1	116.6 (2)
N1—C2—S7	113.21 (16)	N6—C6—C5	121.4 (2)
C2—N3—C4	115.0 (2)	N1—C6—C5	122.0 (2)
N3—C4—N4	114.6 (2)	C6—N6—H6A	120.0
N3—C4—C5	122.2 (2)	C6—N6—H6B	120.0
N4—C4—C5	123.1 (2)	H6A—N6—H6B	120.0
C4—N4—H4A	122.8	C2—S7—C8	100.67 (8)
C4—N4—H4B	109.6	S7^i—C8—S7	115.8 (2)
H4A—N4—H4B	121.0	S7^i—C8—H8A	108.3
C4—C5—C6	116.9 (2)	S7—C8—H8A	108.3
C6—N1—C2—N3	0.2 (4)	C2—N1—C6—N6	−179.9 (2)
C6—N1—C2—S7	179.97 (16)	C2—N1—C6—C5	0.1 (3)
N1—C2—N3—C4	−0.5 (4)	C4—C5—C6—N6	180.0 (2)
S7—C2—N3—C4	179.73 (18)	C4—C5—C6—N1	−0.1 (4)
C2—N3—C4—N4	178.2 (3)	N3—C2—S7—C8	2.5 (2)
C2—N3—C4—C5	0.5 (4)	N1—C2—S7—C8	−177.34 (18)
N3—C4—C5—C6	−0.3 (4)	C2—S7—C8—S7^i	78.08 (8)
N4—C4—C5—C6	−177.8 (3)

Symmetry code: (i) −x+1/2, −y+1/2, z.

2-[(Methoxymethyl)sulfanyl]pyrimidine-4,6-diamine (3)

Crystal data

C6H10N4OS	F(000) = 392
Mr = 186.24	Dx = 1.372 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.6783 (4) Å	Cell parameters from 921 reflections
b = 9.1691 (6) Å	θ = 4.2–26.5°
c = 11.4391 (6) Å	µ = 0.32 mm^−1
β = 97.846 (4)°	T = 295 K
V = 901.71 (9) Å^3	Block, colourless
Z = 4	0.6 × 0.5 × 0.3 mm

Data collection

Rigaku Xcalibur Eos diffractometer	1315 reflections with I > 2σ(I)
Detector resolution: 16.1544 pixels mm^-1	Rint = 0.018
ω scans	θmax = 28.3°, θmin = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −10→7
Tmin = 0.847, Tmax = 1.000	k = −11→6
3394 measured reflections	l = −14→11
1852 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.131	w = 1/[σ^2(Fo^2) + (0.0531P)^2 + 0.3948P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
1852 reflections	Δρmax = 0.35 e Å^−3
118 parameters	Δρmin = −0.33 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.8830 (2)	0.4430 (2)	0.36011 (17)	0.0470 (5)
C2	0.8219 (3)	0.4554 (3)	0.2483 (2)	0.0478 (6)
N3	0.7011 (2)	0.3863 (3)	0.19090 (18)	0.0541 (6)
C4	0.6305 (3)	0.2910 (3)	0.2572 (2)	0.0529 (7)
N4	0.5052 (3)	0.2211 (3)	0.1999 (2)	0.0780 (8)
H4A	0.4754	0.2385	0.1264	0.094*
H4B	0.4552	0.1593	0.2369	0.094*
C5	0.6844 (3)	0.2665 (3)	0.3740 (2)	0.0513 (7)
H5	0.6355	0.2001	0.4182	0.062*
C6	0.8135 (3)	0.3437 (3)	0.4236 (2)	0.0464 (6)
N6	0.8784 (3)	0.3259 (3)	0.53582 (19)	0.0598 (6)
H6A	0.9591	0.3760	0.5633	0.072*
H6B	0.8395	0.2644	0.5804	0.072*
S7	0.92576 (8)	0.57972 (10)	0.17073 (6)	0.0655 (3)
C8	0.7892 (4)	0.6153 (4)	0.0397 (3)	0.0614 (8)
H8A	0.851 (3)	0.649 (3)	−0.015 (2)	0.060 (8)*
H8B	0.744 (3)	0.523 (4)	0.012 (3)	0.075 (10)*
O9	0.6652 (2)	0.7049 (2)	0.05835 (17)	0.0638 (6)
C10	0.7096 (4)	0.8527 (4)	0.0823 (3)	0.0832 (10)
H10A	0.7651	0.8884	0.0210	0.125*
H10B	0.7754	0.8583	0.1568	0.125*
H10C	0.6184	0.9111	0.0851	0.125*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0442 (10)	0.0452 (13)	0.0521 (12)	−0.0017 (10)	0.0089 (9)	0.0011 (10)
C2	0.0426 (12)	0.0507 (16)	0.0515 (14)	0.0004 (12)	0.0118 (10)	−0.0018 (12)
N3	0.0498 (12)	0.0621 (15)	0.0517 (12)	−0.0102 (11)	0.0110 (9)	−0.0020 (11)
C4	0.0456 (13)	0.0530 (17)	0.0618 (16)	−0.0060 (13)	0.0129 (12)	−0.0064 (13)
N4	0.0707 (16)	0.088 (2)	0.0743 (16)	−0.0360 (15)	0.0059 (13)	−0.0019 (15)
C5	0.0465 (13)	0.0472 (16)	0.0621 (17)	−0.0027 (12)	0.0139 (12)	0.0060 (12)
C6	0.0449 (13)	0.0428 (15)	0.0531 (14)	0.0077 (12)	0.0123 (11)	0.0024 (12)
N6	0.0608 (13)	0.0595 (15)	0.0582 (13)	−0.0068 (12)	0.0048 (10)	0.0123 (12)
S7	0.0517 (4)	0.0788 (6)	0.0660 (5)	−0.0137 (4)	0.0081 (3)	0.0163 (4)
C8	0.0635 (18)	0.068 (2)	0.0550 (16)	−0.0069 (17)	0.0160 (14)	0.0036 (15)
O9	0.0513 (11)	0.0575 (13)	0.0821 (13)	−0.0093 (10)	0.0068 (9)	0.0057 (10)
C10	0.077 (2)	0.056 (2)	0.117 (3)	−0.0129 (18)	0.0170 (19)	0.006 (2)

Geometric parameters (Å, º)

N1—C2	1.321 (3)	C6—N6	1.339 (3)
N1—C6	1.357 (3)	N6—H6A	0.8600
C2—N3	1.321 (3)	N6—H6B	0.8600
C2—S7	1.766 (3)	S7—C8	1.809 (3)
N3—C4	1.357 (3)	C8—O9	1.393 (4)
C4—N4	1.352 (3)	C8—H8A	0.93 (3)
C4—C5	1.373 (4)	C8—H8B	0.97 (3)
N4—H4A	0.8600	O9—C10	1.426 (4)
N4—H4B	0.8600	C10—H10A	0.9600
C5—C6	1.380 (3)	C10—H10B	0.9600
C5—H5	0.9300	C10—H10C	0.9600
C2—N1—C6	115.3 (2)	C6—N6—H6A	120.0
N1—C2—N3	128.8 (2)	C6—N6—H6B	120.0
N1—C2—S7	112.16 (18)	H6A—N6—H6B	120.0
N3—C2—S7	119.00 (19)	C2—S7—C8	102.18 (14)
C2—N3—C4	114.8 (2)	O9—C8—S7	114.3 (2)
N4—C4—N3	115.4 (2)	O9—C8—H8A	115.7 (18)
N4—C4—C5	122.6 (3)	S7—C8—H8A	104.3 (17)
N3—C4—C5	122.0 (2)	O9—C8—H8B	106.3 (18)
C4—N4—H4A	120.0	S7—C8—H8B	107.9 (18)
C4—N4—H4B	120.0	H8A—C8—H8B	108 (2)
H4A—N4—H4B	120.0	C8—O9—C10	113.3 (2)
C4—C5—C6	117.8 (2)	O9—C10—H10A	109.5
C4—C5—H5	121.1	O9—C10—H10B	109.5
C6—C5—H5	121.1	H10A—C10—H10B	109.5
N6—C6—N1	115.8 (2)	O9—C10—H10C	109.5
N6—C6—C5	122.9 (2)	H10A—C10—H10C	109.5
N1—C6—C5	121.3 (2)	H10B—C10—H10C	109.5
C6—N1—C2—N3	1.3 (4)	C2—N1—C6—N6	177.4 (2)
C6—N1—C2—S7	−176.83 (17)	C2—N1—C6—C5	−2.4 (3)
N1—C2—N3—C4	0.7 (4)	C4—C5—C6—N6	−178.3 (2)
S7—C2—N3—C4	178.76 (19)	C4—C5—C6—N1	1.5 (4)
C2—N3—C4—N4	179.0 (2)	N1—C2—S7—C8	−163.8 (2)
C2—N3—C4—C5	−1.7 (4)	N3—C2—S7—C8	17.9 (2)
N4—C4—C5—C6	179.9 (3)	C2—S7—C8—O9	74.3 (3)
N3—C4—C5—C6	0.7 (4)	S7—C8—O9—C10	70.4 (3)

Poly[(µ-4,6-diaminopyrimidine-2-sulfinato)potassium(I)] (4)

Crystal data

[K(C4H5N4O2S)]	Z = 2
Mr = 212.28	F(000) = 216
Triclinic, P1	Dx = 1.872 Mg m^−3
a = 6.9631 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.035 (1) Å	Cell parameters from 1084 reflections
c = 8.0886 (10) Å	θ = 3.3–26.6°
α = 103.021 (10)°	µ = 0.94 mm^−1
β = 111.568 (11)°	T = 295 K
γ = 106.007 (10)°	Plate, yellow
V = 376.56 (9) Å^3	0.25 × 0.2 × 0.06 mm

Data collection

Rigaku Xcalibur Eos diffractometer	1507 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	1321 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
Detector resolution: 16.2413 pixels mm^-1	θmax = 27.0°, θmin = 3.2°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −10→10
Tmin = 0.853, Tmax = 1.000	l = −9→10
2466 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.090	w = 1/[σ^2(Fo^2) + (0.0408P)^2 + 0.2579P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
1507 reflections	Δρmax = 0.32 e Å^−3
109 parameters	Δρmin = −0.30 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
K1	0.70120 (9)	−0.16473 (8)	0.44579 (9)	0.03648 (19)
N1	0.6643 (3)	0.3677 (3)	0.4567 (3)	0.0254 (4)
C2	0.8070 (4)	0.2858 (3)	0.5049 (3)	0.0236 (5)
S2	0.90525 (10)	0.29667 (9)	0.75330 (8)	0.02673 (18)
O21	1.1022 (3)	0.2428 (3)	0.7880 (3)	0.0401 (5)
O22	0.7085 (3)	0.1347 (3)	0.7254 (3)	0.0429 (5)
N3	0.8766 (3)	0.1928 (3)	0.3987 (3)	0.0254 (4)
C4	0.7961 (4)	0.1866 (3)	0.2148 (3)	0.0248 (5)
N4	0.8684 (4)	0.0945 (3)	0.1045 (3)	0.0357 (5)
H41	0.9594	0.0445	0.1515	0.043*
H42	0.8233	0.0860	−0.0125	0.043*
C5	0.6507 (4)	0.2704 (3)	0.1483 (3)	0.0284 (5)
H5	0.6017	0.2706	0.0247	0.034*
C6	0.5800 (4)	0.3542 (3)	0.2707 (3)	0.0250 (5)
N6	0.4250 (4)	0.4277 (3)	0.2136 (3)	0.0336 (5)
H61	0.3849	0.4792	0.2931	0.040*
H62	0.3666	0.4228	0.0977	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.0296 (3)	0.0424 (4)	0.0442 (4)	0.0181 (3)	0.0207 (3)	0.0162 (3)
N1	0.0270 (10)	0.0333 (11)	0.0210 (10)	0.0179 (9)	0.0117 (8)	0.0104 (8)
C2	0.0240 (11)	0.0302 (12)	0.0186 (11)	0.0121 (10)	0.0099 (9)	0.0105 (9)
S2	0.0285 (3)	0.0390 (4)	0.0172 (3)	0.0195 (3)	0.0105 (2)	0.0104 (2)
O21	0.0369 (11)	0.0691 (13)	0.0300 (10)	0.0350 (10)	0.0166 (8)	0.0254 (9)
O22	0.0364 (11)	0.0623 (13)	0.0321 (10)	0.0160 (10)	0.0161 (9)	0.0247 (9)
N3	0.0292 (11)	0.0348 (11)	0.0217 (10)	0.0194 (9)	0.0145 (8)	0.0132 (8)
C4	0.0264 (12)	0.0314 (12)	0.0214 (11)	0.0127 (10)	0.0135 (10)	0.0116 (9)
N4	0.0477 (13)	0.0539 (14)	0.0262 (11)	0.0347 (12)	0.0245 (10)	0.0191 (10)
C5	0.0331 (13)	0.0375 (13)	0.0195 (11)	0.0179 (11)	0.0123 (10)	0.0133 (10)
C6	0.0250 (12)	0.0268 (12)	0.0244 (11)	0.0119 (10)	0.0105 (10)	0.0111 (9)
N6	0.0360 (12)	0.0462 (13)	0.0246 (10)	0.0286 (11)	0.0104 (9)	0.0142 (9)

Geometric parameters (Å, º)

K1—O21^i	2.7729 (19)	S2—O22	1.510 (2)
K1—O22^ii	2.782 (2)	S2—K1^ii	3.6484 (10)
K1—N3^i	2.837 (2)	O21—K1^i	2.7729 (19)
K1—O22	2.881 (2)	O22—K1^ii	2.782 (2)
K1—N3	2.965 (2)	N3—C4	1.366 (3)
K1—N6^iii	3.009 (2)	N3—K1^i	2.837 (2)
K1—N1^ii	3.086 (2)	C4—N4	1.355 (3)
K1—C2	3.372 (2)	C4—C5	1.380 (3)
K1—O21	3.372 (2)	N4—H41	0.8600
K1—S2	3.5059 (11)	N4—H42	0.8600
K1—C6^iii	3.538 (2)	C5—C6	1.385 (3)
K1—S2^ii	3.6484 (10)	C5—H5	0.9300
N1—C2	1.328 (3)	C6—N6	1.355 (3)
N1—C6	1.364 (3)	C6—K1^iv	3.538 (2)
N1—K1^ii	3.086 (2)	N6—K1^iv	3.009 (2)
C2—N3	1.322 (3)	N6—H61	0.8600
C2—S2	1.842 (2)	N6—H62	0.8600
S2—O21	1.4982 (18)
O21^i—K1—O22^ii	116.17 (6)	N3—K1—S2^ii	105.02 (4)
O21^i—K1—N3^i	60.51 (5)	N6^iii—K1—S2^ii	65.50 (4)
O22^ii—K1—N3^i	176.53 (6)	N1^ii—K1—S2^ii	45.61 (4)
O21^i—K1—O22	142.94 (6)	C2—K1—S2^ii	93.18 (4)
O22^ii—K1—O22	73.93 (6)	O21—K1—S2^ii	126.34 (4)
N3^i—K1—O22	108.03 (6)	S2—K1—S2^ii	101.55 (2)
O21^i—K1—N3	76.44 (6)	C6^iii—K1—S2^ii	86.65 (4)
O22^ii—K1—N3	82.65 (6)	C2—N1—C6	114.61 (19)
N3^i—K1—N3	95.30 (5)	C2—N1—K1^ii	101.64 (14)
O22—K1—N3	69.48 (5)	C6—N1—K1^ii	112.74 (14)
O21^i—K1—N6^iii	77.36 (6)	N3—C2—N1	129.4 (2)
O22^ii—K1—N6^iii	83.27 (6)	N3—C2—S2	117.31 (17)
N3^i—K1—N6^iii	96.67 (6)	N1—C2—S2	113.22 (16)
O22—K1—N6^iii	139.40 (6)	N3—C2—K1	60.98 (12)
N3—K1—N6^iii	140.74 (6)	N1—C2—K1	129.51 (16)
O21^i—K1—N1^ii	139.71 (6)	S2—C2—K1	78.53 (8)
O22^ii—K1—N1^ii	64.92 (5)	O21—S2—O22	108.96 (12)
N3^i—K1—N1^ii	118.14 (6)	O21—S2—C2	103.00 (10)
O22—K1—N1^ii	77.35 (5)	O22—S2—C2	99.05 (10)
N3—K1—N1^ii	138.85 (5)	O21—S2—K1	72.48 (9)
N6^iii—K1—N1^ii	62.53 (6)	O22—S2—K1	53.69 (8)
O21^i—K1—C2	99.39 (6)	C2—S2—K1	70.48 (8)
O22^ii—K1—C2	72.06 (6)	O21—S2—K1^ii	149.90 (9)
N3^i—K1—C2	107.01 (6)	O22—S2—K1^ii	44.55 (8)
O22—K1—C2	47.50 (5)	C2—S2—K1^ii	73.75 (7)
N3—K1—C2	22.95 (5)	K1—S2—K1^ii	78.45 (2)
N6^iii—K1—C2	150.79 (6)	S2—O21—K1^i	130.27 (10)
N1^ii—K1—C2	117.25 (5)	S2—O21—K1	82.46 (9)
O21^i—K1—O21	101.64 (5)	K1^i—O21—K1	78.36 (5)
O22^ii—K1—O21	111.39 (6)	S2—O22—K1^ii	113.08 (10)
N3^i—K1—O21	69.19 (5)	S2—O22—K1	101.33 (9)
O22—K1—O21	45.25 (5)	K1^ii—O22—K1	106.07 (6)
N3—K1—O21	52.51 (5)	C2—N3—C4	114.94 (19)
N6^iii—K1—O21	163.40 (5)	C2—N3—K1^i	122.60 (15)
N1^ii—K1—O21	115.57 (5)	C4—N3—K1^i	115.99 (14)
C2—K1—O21	45.76 (5)	C2—N3—K1	96.07 (14)
O21^i—K1—S2	118.06 (5)	C4—N3—K1	115.55 (14)
O22^ii—K1—S2	86.64 (5)	K1^i—N3—K1	84.70 (5)
N3^i—K1—S2	94.13 (5)	N4—C4—N3	115.8 (2)
O22—K1—S2	24.97 (4)	N4—C4—C5	122.8 (2)
N3—K1—S2	48.75 (4)	N3—C4—C5	121.3 (2)
N6^iii—K1—S2	164.28 (5)	C4—N4—H41	120.0
N1^ii—K1—S2	102.21 (4)	C4—N4—H42	120.0
C2—K1—S2	30.98 (4)	H41—N4—H42	120.0
O21—K1—S2	25.06 (3)	C4—C5—C6	118.1 (2)
O21^i—K1—C6^iii	68.84 (6)	C4—C5—H5	121.0
O22^ii—K1—C6^iii	105.28 (6)	C6—C5—H5	121.0
N3^i—K1—C6^iii	74.78 (6)	N6—C6—N1	116.3 (2)
O22—K1—C6^iii	146.15 (6)	N6—C6—C5	122.2 (2)
N3—K1—C6^iii	144.35 (6)	N1—C6—C5	121.5 (2)
N6^iii—K1—C6^iii	22.04 (5)	N6—C6—K1^iv	56.44 (13)
N1^ii—K1—C6^iii	72.25 (5)	N1—C6—K1^iv	86.70 (13)
C2—K1—C6^iii	165.77 (6)	C5—C6—K1^iv	125.28 (16)
O21—K1—C6^iii	142.22 (5)	C6—N6—K1^iv	101.52 (15)
S2—K1—C6^iii	162.28 (4)	C6—N6—H61	120.0
O21^i—K1—S2^ii	120.97 (5)	K1^iv—N6—H61	63.6
O22^ii—K1—S2^ii	22.37 (4)	C6—N6—H62	120.0
N3^i—K1—S2^ii	159.43 (5)	K1^iv—N6—H62	104.1
O22—K1—S2^ii	82.55 (4)	H61—N6—H62	120.0
C6—N1—C2—N3	−0.6 (4)	K1^ii—S2—O22—K1	113.09 (10)
K1^ii—N1—C2—N3	121.3 (2)	N1—C2—N3—C4	2.8 (4)
C6—N1—C2—S2	−176.98 (16)	S2—C2—N3—C4	179.02 (16)
K1^ii—N1—C2—S2	−55.09 (16)	K1—C2—N3—C4	121.9 (2)
C6—N1—C2—K1	−82.8 (2)	N1—C2—N3—K1^i	153.4 (2)
K1^ii—N1—C2—K1	39.12 (18)	S2—C2—N3—K1^i	−30.4 (2)
N3—C2—S2—O21	17.3 (2)	K1—C2—N3—K1^i	−87.58 (12)
N1—C2—S2—O21	−165.91 (18)	N1—C2—N3—K1	−119.1 (2)
K1—C2—S2—O21	65.82 (10)	S2—C2—N3—K1	57.16 (16)
N3—C2—S2—O22	−94.73 (19)	C2—N3—C4—N4	179.0 (2)
N1—C2—S2—O22	82.10 (19)	K1^i—N3—C4—N4	26.4 (3)
K1—C2—S2—O22	−46.17 (9)	K1—N3—C4—N4	−70.5 (2)
N3—C2—S2—K1	−48.56 (17)	C2—N3—C4—C5	−0.8 (3)
N1—C2—S2—K1	128.27 (19)	K1^i—N3—C4—C5	−153.39 (19)
N3—C2—S2—K1^ii	−131.78 (19)	K1—N3—C4—C5	109.8 (2)
N1—C2—S2—K1^ii	45.05 (16)	N4—C4—C5—C6	177.3 (2)
K1—C2—S2—K1^ii	−83.22 (4)	N3—C4—C5—C6	−2.9 (4)
O22—S2—O21—K1^i	107.82 (15)	C2—N1—C6—N6	176.7 (2)
C2—S2—O21—K1^i	3.35 (18)	K1^ii—N1—C6—N6	61.1 (2)
K1—S2—O21—K1^i	67.73 (13)	C2—N1—C6—C5	−3.5 (3)
K1^ii—S2—O21—K1^i	83.3 (2)	K1^ii—N1—C6—C5	−119.2 (2)
O22—S2—O21—K1	40.09 (9)	C2—N1—C6—K1^iv	−133.56 (18)
C2—S2—O21—K1	−64.38 (9)	K1^ii—N1—C6—K1^iv	110.81 (9)
K1^ii—S2—O21—K1	15.58 (15)	C4—C5—C6—N6	−175.0 (2)
O21—S2—O22—K1^ii	−162.75 (9)	C4—C5—C6—N1	5.2 (4)
C2—S2—O22—K1^ii	−55.56 (11)	C4—C5—C6—K1^iv	115.7 (2)
K1—S2—O22—K1^ii	−113.09 (10)	N1—C6—N6—K1^iv	66.1 (2)
O21—S2—O22—K1	−49.65 (10)	C5—C6—N6—K1^iv	−113.7 (2)
C2—S2—O22—K1	57.54 (10)

Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y, −z+1; (iii) x, y−1, z; (iv) x, y+1, z.