Accessing the rich carbon nitride materials chemistry by heat treatments of ammonium thiocyanate, NH₄SCN

Carbon nitride materials include functional materials, and their chemical diversity and complexity are becoming increasingly appreciated. Heating of NH₄SCN leads to a range of new carbon nitride compounds, which have been structurally characterized by single-crystal X-ray diffraction. Heating at ambient pressure to 175°C leads to guanidinium thiocyanate, H₆CN₃SCN (1), and when maintaining that temperature for about 12 h a water-insoluble carbon nitride product is formed, which is a co-crystal between melamine and melamium thiocyanate, [H₆C₃N₆]·[H₁₀C₆N₁₁]⁺·[SCN]⁻ (2). In situ powder X-ray diffraction measurements of this material reveal a gradual transformation from (2), via two intermediate products, to a final melon-like end product. The first of these forms between 350 and 400°C, and is an adduct of melam and melamium thiocyanate, [H₉C₆N₁₁]·2[H₁₀C₆N₁₁]⁺·2[SCN]⁻ (3). The second forms between 400 and 480°C, and is identified as melem, 2,5,8-triamino-tri-s-triazine, H₆C₆N₁₀ (4). On heating of (2) in a sealed ampoule to 600°C, various crystals were obtained and six crystal structures were determined from the batch: 1,3,5-triazine-2,4,6-triamino, H₆C₃N₆ (5), 1,3,5-triazine-2,4-diamino, H₅C₃N₅ (6), 1,1′,3,3′,5,5′-triazine-2,2′,4,4′-tetraamino, H₈C₆N₁₀ (7), 2[H₆C₃N₆]·[H₁₀C₆N₁₁]⁺·[SCN]⁻ (8) and 2[H₆C₃N₆]·[H₇C₃N₆]⁺·[SCN]⁻ (9). Finally, a recrystallized decomposition product was found to be [H₆C₃N₆]·[H₇C₃N₆]⁺·[SCN]⁻·[H₂O] (10).

Computing details

Data collection: Apex2 (Bruker-Nonius, 2006) for (1). Cell refinement: Saint+ (Bruker-Nonius, 2006) for (1); SAINT v7.23A (Bruker, 2003) for (7). Data reduction: Saint+ (Bruker-Nonius, 2006) for (1); SAINT v7.23A (Bruker, 2003) for (7). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for (1); ShelXT (Sheldrick, 2015) for (3). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for (1); SHELXL (Sheldrick, 2015) for (2), (3), (10); SHELXL (Sheldrick, 2008) for (7). Molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) for (1); Olex2 (Dolomanov et al., 2009) for (2), (3), (7), (10). Software used to prepare material for publication: WinGX publication routines (Farrugia, 1999) for (1); Olex2 (Dolomanov et al., 2009) for (2), (3), (7), (10).

(1)

Crystal data

CH6N3·CNS	Z = 4
Mr = 118.16	F(000) = 248
Triclinic, P1	Dx = 1.385 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9149 (2) Å	Cell parameters from 4126 reflections
b = 7.0012 (1) Å	θ = 5.4–30.3°
c = 12.3713 (3) Å	µ = 0.45 mm^−1
α = 90.881 (1)°	T = 100 K
β = 104.312 (1)°	Block, colorless
γ = 101.783 (1)°	0.4 × 0.2 × 0.15 mm
V = 566.74 (2) Å^3

Data collection

Bruker X8 APEX-II diffractometer	2946 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.028
Detector resolution: 8.333 pixels mm^-1	θmax = 30.3°, θmin = 5.2°
φ–scans and ω–scans	h = −9→9
10559 measured reflections	k = −9→9
3358 independent reflections	l = −17→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.028	w = 1/[σ^2(Fo^2) + (0.0345P)^2 + 0.1355P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.073	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.34 e Å^−3
3358 reflections	Δρmin = −0.23 e Å^−3
127 parameters

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
S1	0.30634 (4)	0.09222 (4)	0.18451 (2)	0.02259 (8)
N1	−0.10593 (16)	−0.04369 (16)	0.18671 (8)	0.0251 (2)
C1	0.06338 (18)	0.01223 (16)	0.18419 (8)	0.0196 (2)
S2	0.27220 (4)	0.56264 (4)	0.41160 (2)	0.02008 (7)
N2	−0.11364 (15)	0.45179 (15)	0.25730 (8)	0.0235 (2)
C2	0.04475 (17)	0.49779 (16)	0.32144 (8)	0.0183 (2)
N11	0.28326 (14)	0.07546 (15)	0.45830 (7)	0.01961 (18)
H11A	0.2937	−0.0298	0.4223	0.024*
H11B	0.2973	0.1885	0.4278	0.024*
N10	0.22496 (15)	−0.10672 (15)	0.60463 (8)	0.02152 (19)
H10A	0.2011	−0.1148	0.6712	0.026*
H10B	0.2348	−0.2119	0.5683	0.026*
N12	0.23124 (15)	0.22191 (15)	0.61375 (8)	0.02180 (19)
H12A	0.2074	0.2138	0.6804	0.026*
H12B	0.2453	0.3352	0.5835	0.026*
C10	0.24603 (14)	0.06367 (16)	0.55911 (8)	0.01600 (19)
N21	0.34328 (15)	0.60124 (16)	0.14441 (7)	0.0233 (2)
H21A	0.3499	0.4954	0.1814	0.028*
H21B	0.374	0.7167	0.181	0.028*
N20	0.27987 (16)	0.74633 (15)	−0.02284 (8)	0.0230 (2)
H20A	0.2446	0.7369	−0.0964	0.028*
H20B	0.3106	0.8618	0.0137	0.028*
C20	0.28667 (15)	0.58657 (17)	0.03296 (8)	0.0179 (2)
N22	0.24046 (15)	0.41257 (15)	−0.02200 (8)	0.02242 (19)
H22A	0.2052	0.403	−0.0956	0.027*
H22B	0.245	0.3067	0.0151	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.02838 (14)	0.02036 (15)	0.02027 (13)	0.00626 (11)	0.00766 (10)	0.00187 (10)
N1	0.0337 (5)	0.0236 (5)	0.0190 (4)	0.0059 (4)	0.0087 (4)	0.0016 (4)
C1	0.0330 (5)	0.0148 (5)	0.0126 (4)	0.0076 (4)	0.0065 (4)	0.0020 (4)
S2	0.02227 (13)	0.01926 (14)	0.01836 (12)	0.00407 (10)	0.00490 (9)	0.00078 (9)
N2	0.0299 (5)	0.0221 (5)	0.0180 (4)	0.0058 (4)	0.0047 (3)	0.0017 (4)
C2	0.0275 (5)	0.0143 (5)	0.0154 (4)	0.0056 (4)	0.0088 (4)	0.0027 (4)
N11	0.0247 (4)	0.0205 (5)	0.0160 (4)	0.0076 (4)	0.0073 (3)	0.0026 (3)
N10	0.0278 (5)	0.0193 (5)	0.0194 (4)	0.0069 (4)	0.0080 (3)	0.0038 (3)
N12	0.0280 (5)	0.0185 (5)	0.0211 (4)	0.0041 (4)	0.0111 (4)	−0.0006 (3)
C10	0.0135 (4)	0.0180 (5)	0.0156 (4)	0.0033 (3)	0.0023 (3)	0.0003 (4)
N21	0.0341 (5)	0.0226 (5)	0.0142 (4)	0.0076 (4)	0.0068 (3)	0.0019 (3)
N20	0.0343 (5)	0.0192 (5)	0.0168 (4)	0.0086 (4)	0.0068 (4)	0.0036 (3)
C20	0.0184 (4)	0.0208 (5)	0.0162 (4)	0.0052 (4)	0.0069 (3)	0.0019 (4)
N22	0.0301 (5)	0.0187 (5)	0.0173 (4)	0.0042 (4)	0.0049 (3)	0.0002 (3)

Geometric parameters (Å, º)

S1—C1	1.6579 (12)	N12—H12A	0.88
N1—C1	1.1645 (16)	N12—H12B	0.88
S2—C2	1.6581 (11)	N21—C20	1.3331 (13)
N2—C2	1.1625 (14)	N21—H21A	0.88
N11—C10	1.3348 (13)	N21—H21B	0.88
N11—H11A	0.88	N20—C20	1.3263 (15)
N11—H11B	0.88	N20—H20A	0.88
N10—C10	1.3235 (14)	N20—H20B	0.88
N10—H10A	0.88	C20—N22	1.3253 (15)
N10—H10B	0.88	N22—H22A	0.88
N12—C10	1.3237 (14)	N22—H22B	0.88
N1—C1—S1	178.39 (9)	N12—C10—N11	120.19 (10)
N2—C2—S2	179.22 (10)	C20—N21—H21A	120
C10—N11—H11A	120	C20—N21—H21B	120
C10—N11—H11B	120	H21A—N21—H21B	120
H11A—N11—H11B	120	C20—N20—H20A	120
C10—N10—H10A	120	C20—N20—H20B	120
C10—N10—H10B	120	H20A—N20—H20B	120
H10A—N10—H10B	120	N22—C20—N20	120.07 (9)
C10—N12—H12A	120	N22—C20—N21	119.94 (10)
C10—N12—H12B	120	N20—C20—N21	119.98 (10)
H12A—N12—H12B	120	C20—N22—H22A	120
N10—C10—N12	120.02 (9)	C20—N22—H22B	120
N10—C10—N11	119.78 (10)	H22A—N22—H22B	120

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···S2^i	0.88	2.83	3.6101 (10)	149
N11—H11B···S2	0.88	2.67	3.4812 (10)	154
N10—H10A···N1^ii	0.88	2.36	3.1259 (14)	146
N10—H10A···N2^ii	0.88	2.54	3.0601 (14)	119
N10—H10B···S2^i	0.88	2.58	3.4194 (10)	161
N12—H12A···N1^ii	0.88	2.21	3.0187 (14)	152
N12—H12B···S2	0.88	2.7	3.5046 (10)	153
N21—H21A···S1	0.88	2.78	3.5717 (11)	151
N21—H21B···S1^iii	0.88	2.76	3.5350 (11)	147
N20—H20A···N2^iv	0.88	2.25	3.0390 (13)	149
N20—H20B···S1^iii	0.88	2.65	3.4458 (10)	151
N22—H22A···N2^iv	0.88	2.27	3.0509 (14)	148
N22—H22A···N1^v	0.88	2.63	3.0996 (14)	115
N22—H22B···S1	0.88	2.6	3.4326 (10)	159

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

(2)

Crystal data

CNS·C6H10N11·C3H6N6	Z = 2
Mr = 420.47	F(000) = 436
Triclinic, P1	Dx = 1.596 Mg m^−3
a = 9.8299 (11) Å	Cell parameters from 1147 reflections
b = 9.8507 (11) Å	θ = 2.2–19°
c = 10.2105 (12) Å	µ = 0.08 mm^−1
α = 64.634 (4)°	T = 15 K
β = 78.716 (5)°	Irregular
γ = 87.703 (4)°	0.05 × 0.04 × 0.03 mm
V = 875.04 (18) Å^3

Data collection

Synchrotron diffractometer	3650 reflections with I > 2σ(I)
phi–scan	Rint = 0.136
Absorption correction: multi-scan SADABS-2004/1 (Bruker,2004) was used for absorption correction. R(int) was 0.0321 before and 0.0251 after correction. The Ratio of minimum to maximum transmission is 0.8867. The λ/2 correction factor is 0.0015.	θmax = 21.7°, θmin = 1.9°
	h = −16→16
17124 measured reflections	k = −16→16
7199 independent reflections	l = −17→17

Refinement

Refinement on F^2	207 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.081	H-atom parameters constrained
wR(F^2) = 0.265	w = 1/[σ^2(Fo^2) + (0.1212P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
7199 reflections	Δρmax = 1.45 e Å^−3
262 parameters	Δρmin = −1.00 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
S1	0.82945 (10)	0.96987 (9)	0.07245 (11)	0.0160 (2)
C10	0.6860 (4)	0.8676 (4)	0.1726 (4)	0.0158 (7)
N18	0.5870 (4)	0.7874 (3)	0.2462 (4)	0.0196 (6)
N6	0.7008 (3)	0.4700 (3)	−0.0454 (3)	0.0096 (5)
N7	0.5562 (3)	0.5306 (3)	−0.2238 (3)	0.0094 (5)
N3	0.5196 (3)	0.7851 (3)	−0.3639 (3)	0.0098 (5)
H3	0.5430	0.8789	−0.3864	0.012*
N2	0.3826 (3)	0.8843 (3)	−0.5386 (3)	0.0091 (5)
N9	0.2514 (3)	0.7146 (3)	−0.5895 (3)	0.0094 (5)
N5	0.7898 (3)	0.6623 (3)	−0.0130 (3)	0.0126 (6)
H5A	0.8293	0.5953	0.0562	0.015*
H5B	0.8004	0.7586	−0.0356	0.015*
N11	0.6052 (3)	0.2855 (3)	−0.0877 (3)	0.0140 (6)
H11A	0.6452	0.2168	−0.0199	0.017*
H11B	0.5539	0.2585	−0.1350	0.017*
N4	0.6566 (3)	0.7270 (3)	−0.1915 (3)	0.0097 (5)
N8	0.3956 (3)	0.6221 (3)	−0.4133 (3)	0.0095 (5)
H8	0.4309	0.5453	−0.3480	0.011*
C3	0.5790 (3)	0.6737 (3)	−0.2534 (4)	0.0086 (5)
C5	0.6224 (3)	0.4311 (3)	−0.1187 (4)	0.0092 (5)
C4	0.7136 (3)	0.6180 (3)	−0.0840 (3)	0.0088 (5)
N10	0.2742 (3)	0.4585 (3)	−0.4612 (3)	0.0108 (5)
H10A	0.2174	0.4395	−0.5087	0.013*
H10B	0.3107	0.3840	−0.3949	0.013*
C1	0.2946 (3)	0.8524 (3)	−0.6121 (4)	0.0096 (6)
C2	0.4297 (3)	0.7640 (3)	−0.4403 (3)	0.0080 (5)
N1	0.2481 (3)	0.9693 (3)	−0.7162 (3)	0.0156 (6)
H1A	0.1918	0.9546	−0.7666	0.019*
H1B	0.2736	1.0614	−0.7347	0.019*
C6	0.3048 (3)	0.5991 (3)	−0.4896 (4)	0.0084 (5)
N13	0.9803 (3)	0.1911 (3)	0.3578 (3)	0.0100 (5)
N16	0.9403 (3)	0.4503 (3)	0.2123 (3)	0.0083 (5)
N15	1.0825 (3)	0.3865 (3)	0.3937 (3)	0.0089 (5)
N17	1.0437 (3)	0.6329 (3)	0.2509 (3)	0.0094 (5)
H17A	1.0955	0.6600	0.2976	0.011*
H17B	1.0060	0.7017	0.1810	0.011*
N12	0.8504 (3)	0.2586 (3)	0.1778 (3)	0.0147 (6)
H12A	0.8115	0.3264	0.1085	0.018*
H12B	0.8392	0.1626	0.1997	0.018*
C8	1.0547 (3)	0.2408 (3)	0.4270 (3)	0.0081 (5)
N14	1.1073 (3)	0.1349 (3)	0.5386 (3)	0.0134 (6)
H14A	1.0920	0.0389	0.5625	0.016*
H14B	1.1569	0.1617	0.5874	0.016*
C9	1.0221 (3)	0.4861 (3)	0.2861 (3)	0.0075 (5)
C7	0.9270 (3)	0.3017 (3)	0.2506 (3)	0.0090 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0213 (4)	0.0097 (3)	0.0186 (4)	−0.0037 (3)	−0.0081 (4)	−0.0055 (3)
C10	0.0196 (16)	0.0117 (12)	0.0184 (16)	−0.0002 (12)	−0.0094 (15)	−0.0062 (12)
N18	0.0212 (16)	0.0165 (12)	0.0216 (16)	−0.0015 (13)	−0.0050 (15)	−0.0081 (12)
N6	0.0141 (13)	0.0062 (9)	0.0102 (12)	−0.0007 (10)	−0.0061 (12)	−0.0035 (9)
N7	0.0106 (12)	0.0070 (9)	0.0108 (12)	−0.0011 (9)	−0.0048 (11)	−0.0030 (9)
N3	0.0138 (12)	0.0054 (9)	0.0140 (13)	0.0007 (9)	−0.0101 (12)	−0.0046 (9)
N2	0.0112 (12)	0.0062 (9)	0.0131 (12)	−0.0004 (9)	−0.0072 (11)	−0.0051 (9)
N9	0.0109 (12)	0.0058 (9)	0.0143 (13)	−0.0010 (9)	−0.0054 (12)	−0.0057 (9)
N5	0.0195 (14)	0.0082 (10)	0.0144 (13)	0.0008 (11)	−0.0104 (13)	−0.0059 (10)
N11	0.0206 (15)	0.0076 (10)	0.0167 (14)	−0.0010 (11)	−0.0091 (14)	−0.0054 (10)
N4	0.0131 (13)	0.0070 (9)	0.0112 (12)	0.0007 (10)	−0.0073 (12)	−0.0037 (9)
N8	0.0117 (12)	0.0044 (8)	0.0150 (13)	0.0002 (9)	−0.0088 (12)	−0.0039 (9)
C3	0.0102 (13)	0.0060 (10)	0.0109 (13)	−0.0014 (10)	−0.0033 (13)	−0.0041 (10)
C5	0.0124 (14)	0.0065 (10)	0.0094 (13)	−0.0007 (11)	−0.0032 (13)	−0.0034 (10)
C4	0.0106 (13)	0.0083 (10)	0.0084 (13)	0.0002 (10)	−0.0038 (12)	−0.0037 (10)
N10	0.0107 (12)	0.0077 (9)	0.0176 (13)	−0.0015 (10)	−0.0074 (12)	−0.0068 (10)
C1	0.0103 (13)	0.0069 (10)	0.0130 (14)	−0.0014 (10)	−0.0065 (13)	−0.0037 (10)
C2	0.0095 (13)	0.0068 (10)	0.0111 (13)	−0.0013 (10)	−0.0051 (12)	−0.0054 (10)
N1	0.0227 (15)	0.0063 (9)	0.0207 (15)	−0.0018 (11)	−0.0159 (14)	−0.0032 (10)
C6	0.0075 (13)	0.0061 (10)	0.0131 (14)	−0.0014 (10)	−0.0033 (12)	−0.0050 (10)
N13	0.0171 (13)	0.0048 (9)	0.0101 (12)	−0.0016 (10)	−0.0085 (12)	−0.0024 (9)
N16	0.0125 (12)	0.0045 (8)	0.0087 (11)	−0.0012 (9)	−0.0054 (11)	−0.0021 (9)
N15	0.0128 (12)	0.0051 (8)	0.0108 (12)	−0.0010 (9)	−0.0074 (11)	−0.0031 (9)
N17	0.0142 (13)	0.0036 (8)	0.0116 (12)	−0.0025 (9)	−0.0068 (12)	−0.0023 (9)
N12	0.0266 (16)	0.0049 (9)	0.0180 (14)	−0.0007 (11)	−0.0159 (14)	−0.0049 (10)
C8	0.0119 (14)	0.0044 (9)	0.0083 (13)	−0.0025 (10)	−0.0047 (12)	−0.0016 (10)
N14	0.0224 (15)	0.0047 (9)	0.0146 (13)	−0.0013 (10)	−0.0125 (13)	−0.0018 (9)
C9	0.0109 (13)	0.0048 (9)	0.0079 (13)	−0.0009 (10)	−0.0044 (12)	−0.0025 (10)
C7	0.0127 (14)	0.0063 (10)	0.0097 (13)	−0.0018 (10)	−0.0061 (13)	−0.0033 (10)

Geometric parameters (Å, º)

S1—C10	1.648 (4)	N8—C6	1.377 (3)
C10—N18	1.185 (5)	N10—H10A	0.8800
N6—C5	1.340 (3)	N10—H10B	0.8800
N6—C4	1.341 (4)	N10—C6	1.322 (3)
N7—C3	1.328 (3)	C1—N1	1.327 (4)
N7—C5	1.362 (4)	N1—H1A	0.8800
N3—H3	0.8800	N1—H1B	0.8800
N3—C3	1.401 (4)	N13—C8	1.343 (3)
N3—C2	1.363 (3)	N13—C7	1.348 (4)
N2—C1	1.374 (3)	N16—C9	1.352 (3)
N2—C2	1.321 (4)	N16—C7	1.348 (3)
N9—C1	1.348 (4)	N15—C8	1.352 (3)
N9—C6	1.333 (4)	N15—C9	1.344 (4)
N5—H5A	0.8800	N17—H17A	0.8800
N5—H5B	0.8800	N17—H17B	0.8800
N5—C4	1.337 (3)	N17—C9	1.347 (3)
N11—H11A	0.8800	N12—H12A	0.8800
N11—H11B	0.8800	N12—H12B	0.8800
N11—C5	1.340 (4)	N12—C7	1.347 (3)
N4—C3	1.328 (3)	C8—N14	1.350 (4)
N4—C4	1.361 (4)	N14—H14A	0.8800
N8—H8	0.8800	N14—H14B	0.8800
N8—C2	1.347 (3)
N18—C10—S1	176.4 (3)	N1—C1—N9	116.9 (2)
C5—N6—C4	115.3 (2)	N2—C2—N3	118.1 (2)
C3—N7—C5	114.5 (2)	N2—C2—N8	123.7 (2)
C3—N3—H3	116.4	N8—C2—N3	118.3 (2)
C2—N3—H3	116.4	C1—N1—H1A	120.0
C2—N3—C3	127.2 (2)	C1—N1—H1B	120.0
C2—N2—C1	114.0 (2)	H1A—N1—H1B	120.0
C6—N9—C1	115.8 (2)	N9—C6—N8	121.1 (2)
H5A—N5—H5B	120.0	N10—C6—N9	121.5 (2)
C4—N5—H5A	120.0	N10—C6—N8	117.4 (2)
C4—N5—H5B	120.0	C8—N13—C7	113.8 (2)
H11A—N11—H11B	120.0	C7—N16—C9	114.2 (2)
C5—N11—H11A	120.0	C9—N15—C8	114.7 (2)
C5—N11—H11B	120.0	H17A—N17—H17B	120.0
C3—N4—C4	113.6 (2)	C9—N17—H17A	120.0
C2—N8—H8	120.5	C9—N17—H17B	120.0
C2—N8—C6	118.9 (2)	H12A—N12—H12B	120.0
C6—N8—H8	120.5	C7—N12—H12A	120.0
N7—C3—N3	118.8 (2)	C7—N12—H12B	120.0
N4—C3—N7	127.1 (3)	N13—C8—N15	125.8 (2)
N4—C3—N3	114.1 (2)	N13—C8—N14	116.5 (2)
N6—C5—N7	124.2 (2)	N14—C8—N15	117.6 (2)
N6—C5—N11	119.1 (3)	C8—N14—H14A	120.0
N11—C5—N7	116.6 (2)	C8—N14—H14B	120.0
N6—C4—N4	125.1 (2)	H14A—N14—H14B	120.0
N5—C4—N6	117.6 (3)	N15—C9—N16	125.1 (2)
N5—C4—N4	117.3 (2)	N15—C9—N17	117.2 (2)
H10A—N10—H10B	120.0	N17—C9—N16	117.7 (2)
C6—N10—H10A	120.0	N16—C7—N13	126.2 (2)
C6—N10—H10B	120.0	N12—C7—N13	116.5 (2)
N9—C1—N2	126.5 (3)	N12—C7—N16	117.2 (2)
N1—C1—N2	116.6 (2)
C3—N7—C5—N6	2.2 (5)	C2—N2—C1—N9	2.1 (5)
C3—N7—C5—N11	−178.4 (3)	C2—N2—C1—N1	−177.6 (3)
C3—N3—C2—N2	178.5 (3)	C2—N8—C6—N9	0.4 (5)
C3—N3—C2—N8	−2.7 (5)	C2—N8—C6—N10	179.6 (3)
C3—N4—C4—N6	3.0 (5)	C6—N9—C1—N2	−2.9 (5)
C3—N4—C4—N5	−178.0 (3)	C6—N9—C1—N1	176.8 (3)
C5—N6—C4—N5	179.4 (3)	C6—N8—C2—N3	180.0 (3)
C5—N6—C4—N4	−1.6 (5)	C6—N8—C2—N2	−1.3 (5)
C5—N7—C3—N3	177.7 (3)	C8—N13—C7—N16	−1.3 (5)
C5—N7—C3—N4	−0.5 (5)	C8—N13—C7—N12	−179.6 (3)
C4—N6—C5—N7	−1.2 (5)	C8—N15—C9—N16	−0.6 (5)
C4—N6—C5—N11	179.4 (3)	C8—N15—C9—N17	178.5 (3)
C4—N4—C3—N7	−1.9 (5)	C9—N16—C7—N13	3.8 (5)
C4—N4—C3—N3	179.9 (3)	C9—N16—C7—N12	−178.0 (3)
C1—N2—C2—N3	178.8 (3)	C9—N15—C8—N13	3.6 (5)
C1—N2—C2—N8	0.1 (5)	C9—N15—C8—N14	−177.2 (3)
C1—N9—C6—N8	1.5 (5)	C7—N13—C8—N15	−2.7 (5)
C1—N9—C6—N10	−177.7 (3)	C7—N13—C8—N14	178.1 (3)
C2—N3—C3—N7	5.5 (5)	C7—N16—C9—N15	−2.7 (5)
C2—N3—C3—N4	−176.1 (3)	C7—N16—C9—N17	178.1 (3)

(3)

Crystal data

C6H9.67N11	F(000) = 491
Mr = 235.91	Dx = 1.484 Mg m^−3
Monoclinic, P21/c	Ag Kα radiation, λ = 0.56086 Å
a = 3.534 (3) Å	Cell parameters from 796 reflections
b = 28.13 (2) Å	θ = 3.0–16.1°
c = 10.698 (5) Å	µ = 0.07 mm^−1
β = 97.025 (13)°	T = 100 K
V = 1055.5 (13) Å^3	Block, clear light colourless
Z = 4	0.05 × 0.03 × 0.03 mm

Data collection

Bruker Apex2 CCD diffractometer	Rint = 0.130
Absorption correction: multi-scan SADABS	θmax = 16.3°, θmin = 1.1°
Tmin = 0.501, Tmax = 0.997	h = −3→3
8793 measured reflections	k = −28→28
1107 independent reflections	l = −10→10
759 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.064	w = 1/[σ^2(Fo^2) + (0.2P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.214	(Δ/σ)max < 0.001
S = 1.14	Δρmax = 0.58 e Å^−3
1107 reflections	Δρmin = −0.43 e Å^−3
155 parameters	Extinction correction: SHELXL-2016/6 (Sheldrick 2016), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
129 restraints	Extinction coefficient: 0.077 (16)
Primary atom site location: dual

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	Occ. (<1)
N1	0.9670 (15)	0.44535 (17)	1.0947 (4)	0.0275 (14)
H1A	1.031364	0.474847	1.098073	0.033*
H1B	1.021949	0.427416	1.159513	0.033*
N2	0.6904 (14)	0.38091 (16)	0.9882 (4)	0.0194 (13)
N3	0.4184 (15)	0.31835 (15)	0.8762 (4)	0.0205 (13)
H3	0.493944	0.302543	0.943485	0.025*
N4	0.2323 (14)	0.24557 (17)	0.7933 (4)	0.0189 (13)
N5	0.0352 (15)	0.17506 (16)	0.7038 (4)	0.0263 (14)
H5A	−0.083839	0.158583	0.643613	0.032*
H5B	0.148711	0.161046	0.769340	0.032*
N6	−0.1396 (14)	0.24109 (17)	0.5904 (4)	0.0175 (12)
N7	−0.3003 (14)	0.31069 (16)	0.4870 (4)	0.0237 (14)
H7A	−0.414274	0.294757	0.424857	0.028*
H7B	−0.296438	0.341232	0.484017	0.028*
N8	0.0511 (14)	0.31569 (16)	0.6800 (4)	0.0208 (13)
H8	0.052202	0.346208	0.675152	0.025*	0.6667
N9	0.4039 (15)	0.39239 (17)	0.7786 (4)	0.0247 (13)
N10	0.4300 (17)	0.46508 (18)	0.6876 (5)	0.0422 (17)
H10A	0.496255	0.494509	0.689170	0.051*
H10B	0.307823	0.453124	0.620502	0.051*
N11	0.7057 (15)	0.45759 (16)	0.8914 (4)	0.0227 (13)
C1	0.7813 (17)	0.4273 (2)	0.9886 (5)	0.0190 (14)
C2	0.5042 (18)	0.3661 (2)	0.8802 (5)	0.0202 (15)
C3	0.2273 (17)	0.2925 (2)	0.7787 (5)	0.0168 (14)
C4	0.0437 (18)	0.2214 (2)	0.6955 (5)	0.0183 (15)
C5	−0.1304 (17)	0.2881 (2)	0.5876 (5)	0.0180 (14)
C6	0.5162 (19)	0.4382 (2)	0.7886 (5)	0.0269 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.039 (4)	0.017 (3)	0.024 (3)	−0.004 (3)	−0.005 (2)	0.003 (2)
N2	0.024 (3)	0.014 (3)	0.020 (3)	−0.001 (2)	0.001 (2)	−0.002 (2)
N3	0.033 (4)	0.014 (3)	0.014 (3)	−0.001 (2)	0.001 (2)	−0.0003 (19)
N4	0.021 (3)	0.017 (3)	0.017 (3)	0.001 (2)	−0.003 (2)	−0.0013 (19)
N5	0.042 (4)	0.012 (3)	0.021 (3)	−0.002 (3)	−0.011 (2)	0.000 (2)
N6	0.021 (3)	0.018 (3)	0.013 (2)	0.000 (2)	0.001 (2)	−0.0018 (19)
N7	0.036 (4)	0.015 (3)	0.019 (3)	0.001 (2)	−0.005 (2)	−0.001 (2)
N8	0.027 (3)	0.016 (3)	0.019 (3)	0.000 (2)	0.002 (2)	0.001 (2)
N9	0.032 (4)	0.019 (3)	0.021 (3)	0.006 (3)	−0.003 (2)	0.004 (2)
N10	0.066 (5)	0.020 (3)	0.037 (3)	−0.003 (3)	−0.008 (3)	0.012 (2)
N11	0.030 (3)	0.014 (3)	0.025 (3)	0.003 (2)	0.004 (2)	0.0041 (19)
C1	0.017 (4)	0.017 (3)	0.024 (3)	0.005 (3)	0.004 (3)	−0.002 (2)
C2	0.024 (4)	0.018 (3)	0.020 (3)	0.002 (3)	0.005 (3)	0.001 (2)
C3	0.017 (4)	0.021 (3)	0.014 (3)	−0.002 (3)	0.007 (2)	−0.002 (2)
C4	0.027 (4)	0.015 (3)	0.013 (3)	−0.001 (3)	0.003 (3)	0.000 (2)
C5	0.019 (4)	0.023 (3)	0.012 (3)	−0.001 (3)	0.003 (2)	0.001 (2)
C6	0.036 (5)	0.019 (3)	0.025 (3)	0.009 (3)	0.003 (3)	0.006 (2)

Geometric parameters (Å, º)

N1—H1A	0.8600	N6—C5	1.324 (7)
N1—H1B	0.8600	N7—H7A	0.8600
N1—C1	1.340 (7)	N7—H7B	0.8600
N2—C1	1.345 (7)	N7—C5	1.328 (7)
N2—C2	1.325 (7)	N8—H8	0.8600
N3—H3	0.8600	N8—C3	1.328 (7)
N3—C2	1.376 (7)	N8—C5	1.355 (7)
N3—C3	1.379 (7)	N9—C2	1.327 (7)
N4—C3	1.330 (8)	N9—C6	1.349 (8)
N4—C4	1.353 (7)	N10—H10A	0.8600
N5—H5A	0.8600	N10—H10B	0.8600
N5—H5B	0.8600	N10—C6	1.323 (7)
N5—C4	1.306 (7)	N11—C1	1.345 (7)
N6—C4	1.347 (7)	N11—C6	1.332 (8)
H1A—N1—H1B	120.0	C6—N10—H10B	120.0
C1—N1—H1A	120.0	C6—N11—C1	114.3 (5)
C1—N1—H1B	120.0	N1—C1—N2	117.5 (5)
C2—N2—C1	113.6 (5)	N1—C1—N11	116.5 (5)
C2—N3—H3	115.7	N11—C1—N2	126.0 (5)
C2—N3—C3	128.6 (5)	N2—C2—N3	114.7 (5)
C3—N3—H3	115.7	N2—C2—N9	126.4 (6)
C3—N4—C4	114.2 (5)	N9—C2—N3	118.9 (5)
H5A—N5—H5B	120.0	N4—C3—N3	115.8 (5)
C4—N5—H5A	120.0	N4—C3—N8	125.4 (5)
C4—N5—H5B	120.0	N8—C3—N3	118.8 (5)
C5—N6—C4	114.8 (5)	N5—C4—N4	117.6 (5)
H7A—N7—H7B	120.0	N5—C4—N6	117.0 (5)
C5—N7—H7A	120.0	N6—C4—N4	125.4 (5)
C5—N7—H7B	120.0	N6—C5—N7	119.1 (5)
C3—N8—H8	122.2	N6—C5—N8	124.5 (5)
C3—N8—C5	115.7 (5)	N7—C5—N8	116.4 (5)
C5—N8—H8	122.2	N10—C6—N9	116.5 (6)
C2—N9—C6	114.9 (5)	N10—C6—N11	118.8 (6)
H10A—N10—H10B	120.0	N11—C6—N9	124.7 (5)
C6—N10—H10A	120.0

(7)

Crystal data

C6H8N10	F(000) = 228
Mr = 220.22	Dx = 1.536 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.0320 (12) Å	Cell parameters from 604 reflections
b = 7.7960 (16) Å	θ = 4.0–20.7°
c = 10.531 (2) Å	µ = 0.11 mm^−1
β = 105.90 (3)°	T = 100 K
V = 476.29 (18) Å^3	Block, orange
Z = 2	0.2 × 0.2 × 0.2 mm

Data collection

CCD area detector diffractometer	Rint = 0.115
Graphite monochromator	θmax = 23.3°, θmin = 3.3°
phi and ω scans	h = −6→6
4325 measured reflections	k = −8→8
677 independent reflections	l = −11→11
367 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.058	w = 1/[σ^2(Fo^2) + (0.0973P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.165	(Δ/σ)max < 0.001
S = 0.92	Δρmax = 0.31 e Å^−3
677 reflections	Δρmin = −0.32 e Å^−3
74 parameters	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.13 (2)

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	0.2409 (6)	0.4501 (4)	0.8758 (3)	0.0304 (11)
N3	0.1162 (6)	0.1688 (4)	0.9191 (3)	0.0276 (11)
N5	0.4522 (6)	0.2936 (4)	1.0647 (3)	0.0288 (11)
N2	−0.0854 (6)	0.3283 (5)	0.7412 (4)	0.0379 (12)
H2A	−0.1847	0.2435	0.7181	0.045*
H2B	−0.1037	0.4226	0.6936	0.045*
N4	0.3279 (6)	0.0250 (4)	1.1024 (3)	0.0297 (11)
H4A	0.2327	−0.0622	1.0796	0.036*
H4B	0.4439	0.0191	1.1742	0.036*
C2	0.0918 (7)	0.3139 (6)	0.8480 (4)	0.0302 (13)
C4	0.2960 (7)	0.1674 (5)	1.0275 (4)	0.0256 (12)
C6	0.4118 (7)	0.4286 (5)	0.9834 (4)	0.0245 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.024 (2)	0.026 (2)	0.033 (2)	−0.0093 (19)	−0.0067 (19)	−0.0015 (18)
N3	0.023 (2)	0.024 (2)	0.030 (2)	−0.0020 (17)	−0.0020 (18)	0.0065 (18)
N5	0.025 (2)	0.022 (2)	0.034 (2)	−0.0024 (19)	−0.0020 (17)	0.0019 (19)
N2	0.028 (2)	0.031 (2)	0.042 (2)	−0.0134 (19)	−0.012 (2)	0.0073 (19)
N4	0.025 (2)	0.026 (2)	0.031 (2)	−0.0052 (17)	−0.0039 (18)	0.0039 (18)
C2	0.025 (3)	0.027 (3)	0.031 (3)	−0.003 (2)	−0.005 (2)	0.006 (2)
C4	0.027 (3)	0.019 (3)	0.030 (3)	−0.002 (2)	0.006 (2)	0.002 (2)
C6	0.020 (2)	0.019 (3)	0.029 (2)	0.0007 (19)	0.000 (2)	−0.001 (2)

Geometric parameters (Å, º)

N1—C2	1.370 (5)	N5—C6	1.336 (5)
N1—C6	1.318 (5)	N2—C2	1.327 (5)
N3—C2	1.343 (5)	N4—C4	1.345 (5)
N3—C4	1.342 (5)	C6—C6^i	1.513 (8)
N5—C4	1.344 (5)
C6—N1—C2	113.5 (4)	N3—C4—N5	125.5 (4)
C4—N3—C2	114.9 (4)	N3—C4—N4	117.2 (4)
C6—N5—C4	113.6 (4)	N5—C4—N4	117.2 (4)
N3—C2—N1	124.6 (4)	N1—C6—N5	127.9 (4)
N2—C2—N1	116.4 (4)	N1—C6—C6^i	116.1 (5)
N2—C2—N3	118.9 (4)	N5—C6—C6^i	116.0 (5)
C2—N1—C6—N5	−0.2 (7)	C4—N5—C6—N1	0.6 (6)
C2—N1—C6—C6^i	177.6 (5)	C4—N5—C6—C6^i	−177.2 (5)
C2—N3—C4—N5	−2.8 (6)	C6—N1—C2—N3	−1.9 (6)
C2—N3—C4—N4	179.9 (4)	C6—N1—C2—N2	179.4 (4)
C4—N3—C2—N1	3.3 (6)	C6—N5—C4—N3	1.0 (6)
C4—N3—C2—N2	−178.1 (4)	C6—N5—C4—N4	178.3 (4)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N4^ii	0.88	3.10	3.709 (5)	128

Symmetry code: (ii) −x, −y, −z+2.

(10)

Crystal data

H2O·CNS·C3H6N6·C3H7N6	Z = 4
Mr = 329.38	F(000) = 688
Triclinic, P1	Dx = 1.551 Mg m^−3
a = 11.1348 (9) Å	Cu Kα radiation, λ = 1.54178 Å
b = 12.1287 (11) Å	Cell parameters from 2499 reflections
c = 13.1868 (12) Å	θ = 3.8–56.2°
α = 63.474 (6)°	µ = 2.32 mm^−1
β = 71.339 (7)°	T = 100 K
γ = 63.549 (6)°	Irregular, clear dark black
V = 1410.2 (2) Å^3	0.31 × 0.22 × 0.14 mm

Data collection

Bruker Apex2 CCD diffractometer	Rint = 0.033
Absorption correction: multi-scan SADABS-2004/1 (Bruker,2004) was used for absorption correction. R(int) was 0.0321 before and 0.0251 after correction. The Ratio of minimum to maximum transmission is 0.8867. The λ/2 correction factor is 0.0015.	θmax = 51.5°, θmin = 3.8°
Tmin = 0.887, Tmax = 1.000	h = −10→9
4143 measured reflections	k = −10→11
2169 independent reflections	l = −9→13
1753 reflections with I > 2σ(I)

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.074	H-atom parameters constrained
wR(F^2) = 0.229	w = 1/[σ^2(Fo^2) + (0.159P)^2 + 1.9008P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
2169 reflections	Δρmax = 0.47 e Å^−3
318 parameters	Δρmin = −0.55 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
O1	−0.5376 (5)	1.4448 (5)	0.1562 (3)	0.0385 (14)*
H1A	−0.454701	1.443619	0.132912	0.058*
H1B	−0.568024	1.448460	0.101286	0.058*
O2	0.5161 (5)	0.4348 (5)	0.7015 (4)	0.0469 (15)*
H2A	0.553375	0.403895	0.646134	0.070*
H2B	0.435497	0.492981	0.689078	0.070*
S2A	0.18425 (17)	0.75443 (16)	0.16595 (13)	0.0284 (7)
C2A	0.1812 (6)	0.8211 (6)	0.2519 (5)	0.0229 (18)*
N2A	0.1783 (5)	0.8684 (5)	0.3131 (4)	0.0285 (15)
S1A	−0.21515 (19)	1.15041 (18)	0.16044 (14)	0.0367 (8)
C1A	−0.2066 (7)	1.2068 (7)	0.2485 (5)	0.0255 (18)*
N1A	−0.1974 (5)	1.2455 (5)	0.3114 (5)	0.0287 (15)
N1	−0.3722 (5)	0.5866 (5)	0.5019 (4)	0.0214 (15)
N2	−0.1588 (5)	0.6060 (5)	0.3961 (4)	0.0197 (15)
N3	−0.3526 (5)	0.7992 (5)	0.4030 (4)	0.0198 (14)
N4	−0.1864 (6)	0.4050 (5)	0.4908 (4)	0.0315 (16)
H4A	−0.236468	0.356431	0.534698	0.038*
H4B	−0.100461	0.367348	0.466213	0.038*
N5	−0.5540 (5)	0.7729 (5)	0.5045 (4)	0.0302 (16)
H5A	−0.592097	0.858979	0.486344	0.036*
H5B	−0.602571	0.722498	0.547079	0.036*
N6	−0.1469 (5)	0.8121 (5)	0.3032 (4)	0.0221 (15)
H6A	−0.183534	0.898265	0.284911	0.027*
H6B	−0.060664	0.775278	0.278664	0.027*
C1	−0.2406 (7)	0.5351 (7)	0.4617 (5)	0.0206 (18)*
C2	−0.2215 (7)	0.7379 (7)	0.3677 (5)	0.0170 (17)*
C3	−0.4232 (7)	0.7190 (7)	0.4677 (5)	0.0205 (17)*
C11	0.3931 (7)	0.2680 (7)	0.0519 (5)	0.0192 (17)*
C12	0.2073 (7)	0.4500 (7)	0.0578 (5)	0.0194 (17)*
C13	0.1897 (7)	0.2492 (7)	0.1487 (5)	0.0197 (18)*
N11	0.3201 (5)	0.1880 (5)	0.1156 (4)	0.0181 (15)
N12	0.3409 (5)	0.4009 (5)	0.0208 (4)	0.0219 (15)
N13	0.1245 (5)	0.3809 (5)	0.1210 (4)	0.0187 (14)
N14	0.5235 (5)	0.2136 (5)	0.0159 (4)	0.0268 (15)
H14A	0.572428	0.263612	−0.026492	0.032*
H14B	0.561111	0.127479	0.034374	0.032*
N15	0.1153 (5)	0.1743 (5)	0.2145 (4)	0.0228 (15)
H15A	0.152763	0.087937	0.234424	0.027*
H15B	0.028731	0.211008	0.238116	0.027*
N16	0.1519 (6)	0.5805 (5)	0.0302 (4)	0.0284 (16)
H16A	0.202325	0.629402	−0.010066	0.034*
H16B	0.064876	0.617664	0.052323	0.034*
C21	0.2196 (7)	0.3512 (7)	0.8399 (5)	0.0177 (17)*
C22	0.4099 (7)	0.1567 (7)	0.8391 (5)	0.0174 (17)*
C23	0.2023 (7)	0.1493 (7)	0.9346 (5)	0.0191 (17)*
N21	0.1403 (5)	0.2812 (5)	0.9040 (4)	0.0200 (15)
N22	0.3344 (5)	0.0835 (5)	0.9025 (4)	0.0214 (15)
N23	0.3526 (5)	0.2928 (5)	0.8036 (4)	0.0174 (14)
H23	0.402189	0.341191	0.757549	0.021*
N24	0.1246 (5)	0.0770 (5)	0.9985 (4)	0.0251 (15)
H24A	0.037385	0.115808	1.018641	0.030*
H24B	0.160513	−0.009582	1.020617	0.030*
N25	0.5391 (5)	0.1038 (5)	0.8036 (4)	0.0246 (15)
H25A	0.577432	0.017746	0.821955	0.030*
H25B	0.587525	0.154385	0.761435	0.030*
N26	0.1682 (5)	0.4818 (5)	0.8076 (4)	0.0193 (14)
H26A	0.081590	0.521860	0.828644	0.023*
H26B	0.220648	0.528200	0.765168	0.023*
N31	−0.6979 (5)	1.0688 (5)	0.4281 (4)	0.0231 (15)
N32	−0.8911 (5)	1.2666 (5)	0.4266 (4)	0.0217 (15)
N33	−0.6785 (5)	1.2782 (5)	0.3262 (4)	0.0210 (15)*
H33	−0.628880	1.326550	0.279747	0.025*
N34	−0.4929 (5)	1.0881 (5)	0.3284 (4)	0.0225 (15)
H34A	−0.455472	1.001832	0.347770	0.027*
H34B	−0.443542	1.137679	0.285678	0.027*
N35	−0.9056 (5)	1.0623 (5)	0.5229 (4)	0.0257 (15)
H35A	−0.870311	0.975935	0.542545	0.031*
H35B	−0.992095	1.100818	0.545431	0.031*
N36	−0.8636 (6)	1.4672 (5)	0.3280 (4)	0.0234 (15)
H36A	−0.950454	1.507067	0.348353	0.028*
H36B	−0.811459	1.513913	0.285257	0.028*
C31	−0.8288 (7)	1.1340 (7)	0.4595 (5)	0.0199 (17)*
C32	−0.8117 (6)	1.3377 (7)	0.3615 (5)	0.0177 (17)*
C33	−0.6200 (7)	1.1418 (6)	0.3628 (5)	0.0176 (17)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S2A	0.0336 (13)	0.0177 (12)	0.0278 (11)	−0.0125 (9)	0.0007 (9)	−0.0033 (8)
N2A	0.030 (4)	0.016 (3)	0.029 (3)	−0.009 (3)	0.005 (3)	−0.004 (3)
S1A	0.0473 (14)	0.0348 (14)	0.0308 (11)	−0.0279 (10)	−0.0001 (10)	−0.0049 (9)
N1A	0.028 (4)	0.016 (3)	0.033 (3)	−0.012 (3)	0.006 (3)	−0.004 (3)
N1	0.025 (3)	0.008 (3)	0.024 (3)	−0.005 (3)	0.001 (3)	−0.004 (2)
N2	0.023 (3)	0.011 (4)	0.021 (3)	−0.005 (3)	−0.002 (3)	−0.004 (2)
N3	0.028 (4)	0.013 (3)	0.018 (3)	−0.013 (3)	0.002 (3)	−0.003 (2)
N4	0.032 (4)	0.008 (4)	0.040 (3)	−0.007 (3)	0.004 (3)	−0.002 (3)
N5	0.023 (4)	0.020 (4)	0.036 (3)	−0.011 (3)	0.007 (3)	−0.005 (3)
N6	0.018 (3)	0.017 (3)	0.027 (3)	−0.010 (3)	0.004 (3)	−0.005 (3)
N11	0.022 (3)	0.010 (3)	0.023 (3)	−0.007 (3)	−0.001 (3)	−0.007 (3)
N12	0.026 (4)	0.013 (4)	0.024 (3)	−0.007 (3)	−0.007 (3)	−0.003 (2)
N13	0.021 (3)	0.007 (4)	0.024 (3)	−0.002 (3)	−0.002 (3)	−0.006 (2)
N14	0.020 (3)	0.020 (3)	0.032 (3)	−0.010 (3)	0.006 (3)	−0.007 (3)
N15	0.017 (3)	0.009 (3)	0.034 (3)	−0.001 (3)	0.004 (3)	−0.010 (3)
N16	0.030 (4)	0.015 (4)	0.033 (3)	−0.012 (3)	0.003 (3)	−0.004 (3)
N21	0.025 (3)	0.007 (4)	0.020 (3)	−0.006 (3)	−0.002 (3)	0.000 (2)
N22	0.029 (4)	0.015 (3)	0.020 (3)	−0.013 (3)	0.000 (3)	−0.004 (2)
N23	0.019 (3)	0.011 (3)	0.018 (3)	−0.009 (3)	0.004 (3)	−0.003 (2)
N24	0.025 (3)	0.009 (3)	0.027 (3)	−0.004 (3)	0.000 (3)	0.001 (2)
N25	0.027 (4)	0.015 (3)	0.031 (3)	−0.011 (3)	0.004 (3)	−0.010 (3)
N26	0.018 (3)	0.005 (3)	0.028 (3)	−0.002 (3)	−0.002 (3)	−0.003 (2)
N31	0.028 (3)	0.016 (3)	0.022 (3)	−0.006 (3)	0.000 (3)	−0.008 (3)
N32	0.026 (3)	0.011 (4)	0.021 (3)	−0.003 (3)	−0.001 (3)	−0.005 (2)
N34	0.023 (4)	0.008 (3)	0.031 (3)	−0.008 (3)	0.001 (3)	−0.003 (2)
N35	0.029 (3)	0.008 (3)	0.032 (3)	−0.008 (3)	0.000 (3)	−0.003 (3)
N36	0.029 (3)	0.008 (3)	0.026 (3)	−0.005 (3)	−0.003 (3)	−0.001 (2)

Geometric parameters (Å, º)

O1—H1A	0.8699	N15—H15B	0.8800
O1—H1B	0.8699	N16—H16A	0.8800
O2—H2A	0.8700	N16—H16B	0.8800
O2—H2B	0.8701	C21—N21	1.328 (8)
S2A—C2A	1.647 (8)	C21—N23	1.356 (8)
C2A—N2A	1.166 (8)	C21—N26	1.327 (8)
S1A—C1A	1.633 (8)	C22—N22	1.321 (8)
C1A—N1A	1.167 (8)	C22—N23	1.383 (8)
N1—C1	1.342 (8)	C22—N25	1.310 (8)
N1—C3	1.345 (8)	C23—N21	1.348 (8)
N2—C1	1.359 (8)	C23—N22	1.355 (8)
N2—C2	1.351 (8)	C23—N24	1.333 (8)
N3—C2	1.344 (8)	N23—H23	0.8800
N3—C3	1.342 (8)	N24—H24A	0.8800
N4—H4A	0.8800	N24—H24B	0.8800
N4—H4B	0.8800	N25—H25A	0.8800
N4—C1	1.327 (8)	N25—H25B	0.8800
N5—H5A	0.8800	N26—H26A	0.8800
N5—H5B	0.8800	N26—H26B	0.8800
N5—C3	1.330 (8)	N31—C31	1.342 (8)
N6—H6A	0.8800	N31—C33	1.343 (8)
N6—H6B	0.8800	N32—C31	1.354 (8)
N6—C2	1.324 (8)	N32—C32	1.340 (8)
C11—N11	1.358 (8)	N33—H33	0.8800
C11—N12	1.353 (8)	N33—C32	1.358 (8)
C11—N14	1.324 (8)	N33—C33	1.386 (8)
C12—N12	1.346 (8)	N34—H34A	0.8800
C12—N13	1.349 (8)	N34—H34B	0.8800
C12—N16	1.333 (8)	N34—C33	1.291 (7)
C13—N11	1.332 (8)	N35—H35A	0.8800
C13—N13	1.352 (8)	N35—H35B	0.8800
C13—N15	1.331 (8)	N35—C31	1.319 (8)
N14—H14A	0.8800	N36—H36A	0.8800
N14—H14B	0.8800	N36—H36B	0.8800
N15—H15A	0.8800	N36—C32	1.315 (8)
H1A—O1—H1B	109.5	N21—C21—N23	121.5 (6)
H2A—O2—H2B	109.5	N26—C21—N21	120.0 (6)
N2A—C2A—S2A	179.6 (6)	N26—C21—N23	118.5 (6)
N1A—C1A—S1A	178.5 (6)	N22—C22—N23	120.6 (6)
C1—N1—C3	114.9 (5)	N25—C22—N22	121.5 (6)
C2—N2—C1	114.7 (5)	N25—C22—N23	117.9 (6)
C3—N3—C2	114.9 (6)	N21—C23—N22	126.3 (6)
H4A—N4—H4B	120.0	N24—C23—N21	116.7 (6)
C1—N4—H4A	120.0	N24—C23—N22	116.9 (6)
C1—N4—H4B	120.0	C21—N21—C23	115.6 (6)
H5A—N5—H5B	120.0	C22—N22—C23	116.1 (6)
C3—N5—H5A	120.0	C21—N23—C22	119.7 (5)
C3—N5—H5B	120.0	C21—N23—H23	120.2
H6A—N6—H6B	120.0	C22—N23—H23	120.2
C2—N6—H6A	120.0	C23—N24—H24A	120.0
C2—N6—H6B	120.0	C23—N24—H24B	120.0
N1—C1—N2	124.8 (6)	H24A—N24—H24B	120.0
N4—C1—N1	117.1 (6)	C22—N25—H25A	120.0
N4—C1—N2	118.0 (6)	C22—N25—H25B	120.0
N3—C2—N2	125.0 (6)	H25A—N25—H25B	120.0
N6—C2—N2	117.4 (6)	C21—N26—H26A	120.0
N6—C2—N3	117.6 (6)	C21—N26—H26B	120.0
N3—C3—N1	125.6 (6)	H26A—N26—H26B	120.0
N5—C3—N1	116.2 (6)	C31—N31—C33	116.9 (6)
N5—C3—N3	118.2 (6)	C32—N32—C31	116.1 (5)
N12—C11—N11	124.3 (6)	C32—N33—H33	119.8
N14—C11—N11	118.4 (6)	C32—N33—C33	120.4 (6)
N14—C11—N12	117.3 (6)	C33—N33—H33	119.8
N12—C12—N13	126.8 (6)	H34A—N34—H34B	120.0
N16—C12—N12	116.3 (6)	C33—N34—H34A	120.0
N16—C12—N13	116.9 (6)	C33—N34—H34B	120.0
N11—C13—N13	126.3 (6)	H35A—N35—H35B	120.0
N15—C13—N11	117.3 (6)	C31—N35—H35A	120.0
N15—C13—N13	116.4 (6)	C31—N35—H35B	120.0
C13—N11—C11	115.2 (6)	H36A—N36—H36B	120.0
C12—N12—C11	114.3 (5)	C32—N36—H36A	120.0
C12—N13—C13	113.0 (5)	C32—N36—H36B	120.0
C11—N14—H14A	120.0	N31—C31—N32	126.0 (6)
C11—N14—H14B	120.0	N35—C31—N31	116.9 (6)
H14A—N14—H14B	120.0	N35—C31—N32	117.0 (6)
C13—N15—H15A	120.0	N32—C32—N33	120.9 (6)
C13—N15—H15B	120.0	N36—C32—N32	120.0 (6)
H15A—N15—H15B	120.0	N36—C32—N33	119.1 (6)
C12—N16—H16A	120.0	N31—C33—N33	119.5 (6)
C12—N16—H16B	120.0	N34—C33—N31	121.4 (6)
H16A—N16—H16B	120.0	N34—C33—N33	119.0 (6)
C1—N1—C3—N3	−3.1 (9)	N21—C21—N23—C22	−3.9 (9)
C1—N1—C3—N5	178.8 (5)	N21—C23—N22—C22	3.0 (9)
C1—N2—C2—N3	2.6 (9)	N22—C22—N23—C21	4.1 (9)
C1—N2—C2—N6	−179.6 (5)	N22—C23—N21—C21	−2.8 (9)
C2—N2—C1—N1	−3.0 (9)	N23—C21—N21—C23	3.2 (9)
C2—N2—C1—N4	178.6 (5)	N23—C22—N22—C23	−3.5 (9)
C2—N3—C3—N1	2.7 (9)	N24—C23—N21—C21	−179.7 (5)
C2—N3—C3—N5	−179.2 (5)	N24—C23—N22—C22	179.9 (5)
C3—N1—C1—N2	3.3 (9)	N25—C22—N22—C23	179.7 (5)
C3—N1—C1—N4	−178.4 (5)	N25—C22—N23—C21	−179.0 (5)
C3—N3—C2—N2	−2.4 (9)	N26—C21—N21—C23	−178.6 (5)
C3—N3—C2—N6	179.8 (5)	N26—C21—N23—C22	177.8 (5)
N11—C11—N12—C12	−0.4 (9)	C31—N31—C33—N33	−3.6 (9)
N11—C13—N13—C12	−3.0 (9)	C31—N31—C33—N34	179.9 (5)
N12—C11—N11—C13	−0.9 (9)	C31—N32—C32—N33	3.7 (9)
N12—C12—N13—C13	1.4 (9)	C31—N32—C32—N36	−178.5 (5)
N13—C12—N12—C11	0.2 (9)	C32—N32—C31—N31	−3.6 (10)
N13—C13—N11—C11	2.9 (9)	C32—N32—C31—N35	−179.5 (5)
N14—C11—N11—C13	−179.8 (5)	C32—N33—C33—N31	3.9 (9)
N14—C11—N12—C12	178.5 (5)	C32—N33—C33—N34	−179.5 (5)
N15—C13—N11—C11	−177.8 (5)	C33—N31—C31—N32	3.6 (9)
N15—C13—N13—C12	177.7 (5)	C33—N31—C31—N35	179.4 (5)
N16—C12—N12—C11	179.3 (5)	C33—N33—C32—N32	−4.0 (9)
N16—C12—N13—C13	−177.7 (5)	C33—N33—C32—N36	178.1 (5)