Tris(methylammonium thiocyanurate) monohydrate

Hou, Y.; Yang, Y.

doi:10.1107/S1600536810050312

organic compounds

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ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page o44

https://doi.org/10.1107/S1600536810050312

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Tris(methylammonium thiocyanurate) monohydrate

Yimin Hou ^a and Yunxia Yang ^b ^*

^aHenan University of Traditional Chinese Medicine, Zhengzhou 450008, People's Republic of China, and ^bKey Laboratory of Polymer Materials of Gansu Province, Ministry of Education, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, Gansu, People's Republic of China
^*Correspondence e-mail: yangyx80@nwnu.edu.cn

(Received 18 November 2010; accepted 1 December 2010; online 8 December 2010)

In the title compound, 3[(CH₃)₃HN⁺]·3C₃H₂N₃S₃⁻·H₂O, two independent trithiocyanurate anions construct a planar hydrogen-bonded ribbon with two N—H⋯S hydrogen bonds linking each pair of adjacent anions in the chain. The third independent anion and the water molecule form a chain by way of N—H⋯S and O—H⋯S contacts, which propagates parallel to the ribbon. The chains and ribbons are cross-linked by O—H⋯S hydrogen bonds, generating sheets. The three independent trimethylammonium cations are contained between the sheets by way of various N—H⋯S and N—H⋯N contacts.

Related literature

For hydrogen-bond formation in the compounds of trithiocyanuric acid, see: Dean et al. (2004 ).

Experimental

Crystal data

3C₃H₁₀N⁺·3C₃H₂N₃S₃⁻·H₂O
M_r = 727.23
Triclinic, $[P \overline 1]$
a = 11.3466 (1) Å
b = 12.6474 (1) Å
c = 12.8135 (1) Å
α = 76.950 (1)°
β = 84.762 (1)°
γ = 82.274 (1)°
V = 1771.51 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.60 mm⁻¹
T = 296 K
0.55 × 0.40 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan SADABS (Bruker, 2007 ) T_min = 0.735, T_max = 0.948
14356 measured reflections
6243 independent reflections
5406 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.103
S = 1.05
6243 reflections
388 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯S3	0.86	2.57	3.284 (2)	140
O1W—H1WB⋯S9ⁱ	0.87	2.52	3.355 (2)	161
N2—H2⋯S4ⁱⁱ	0.85 (1)	2.48 (1)	3.3196 (17)	168 (2)
N3—H3⋯S6ⁱⁱⁱ	0.85 (1)	2.48 (1)	3.3203 (17)	168 (2)
N4—H4⋯S2ⁱⁱ	0.86 (1)	2.45 (1)	3.2962 (17)	169 (2)
N5—H5⋯S1ⁱⁱⁱ	0.86 (1)	2.49 (1)	3.3316 (17)	167 (2)
N7—H7⋯O1W	0.86 (1)	2.03 (1)	2.878 (3)	172 (3)
N9—H9⋯S8^iv	0.86 (1)	2.63 (1)	3.470 (2)	167 (3)
N10—H10⋯N6	0.87 (1)	1.95 (1)	2.804 (3)	168 (3)
N11—H11⋯N1	0.86 (1)	1.95 (1)	2.795 (2)	164 (3)
N12—H12⋯S7^v	0.85 (1)	2.69 (2)	3.439 (2)	148 (3)
Symmetry codes: (i) -x, -y+2, -z; (ii) -x+1, -y+1, -z+1; (iii) -x+1, -y+1, -z; (iv) -x, -y+2, -z+1; (v) x, y-1, z.

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810050312/hb5752sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810050312/hb5752Isup2.hkl

checkCIF report

Comment top

Trithiocyanuric acid, which can be regarded as the polymer of three thiourea molecules, have a strong tendency to form various hydrogen bonds (Dean et al. 2004). Here we report the crystal structure of the title ammonium water-trithiocyanurate, 3[(CH₃)₃HN⁺].3C₃H₂N₃S₃^-.H₂O, (I). In this structure, two independent trithiocyanurate anions containing S1 and S4 atoms firstly form the hydrogen-bonded ribbon parallel to (010) plane by four N—H···S hydrogen bonds, and then between two planar ribbons, there exist a totally different waving ribbon composed of the third trithiocyanurate anion and the only water molecule, in which the anion links the water molecule with varied N—H···S and O—H···S contacts (Fig. 2). With the existence of one independent O—H···S interaction between the aforementioned planar hydrogen-bonded ribbon and the waving ribbon, two planar ribbons and one waving ribbon can yield the larger hydrogen-bonded unit as shown in Fig. 3. The ammonium cations, with the existence of N—H···S and N—H···N interactions, are stably accommodated to the intervals of these separated units to form the stable crystal structure.

Related literature top

For hydrogen-bond formation in the compounds of trithiocyanuric acid, see: Dean et al. (2004).

Experimental top

Trithiocyanuric acid (0.044 g, 0.25 mmol) was dissolved in a water-ethanol (1:2 v/v) mixture and a 33% solution of trimethyl amine was added to neutralize the acid. Colorless block crystals separated after several weeks.

Structure description top

For hydrogen-bond formation in the compounds of trithiocyanuric acid, see: Dean et al. (2004).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The title compound at the 30% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Hydrogen-bonded linking pattern of the separated unit in the crystal structure of the title compound.
	Fig. 3. Packing diagram of the title compound; all hydrogen atoms bonded to carbon and carbon atoms of the trimethylammonium cations are omitted for clarity and the cations are represented with the hatched spheres.

Tris(methylammonium thiocyanurate) monohydrate top

Crystal data top

3C₃H₁₀N⁺·3C₃H₂N₃S₃⁻·H₂O	Z = 2
M_r = 727.23	F(000) = 764
Triclinic, P1	D_x = 1.363 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.3466 (1) Å	Cell parameters from 8448 reflections
b = 12.6474 (1) Å	θ = 2.4–27.6°
c = 12.8135 (1) Å	µ = 0.60 mm⁻¹
α = 76.950 (1)°	T = 296 K
β = 84.762 (1)°	Block, colorless
γ = 82.274 (1)°	0.55 × 0.40 × 0.09 mm
V = 1771.51 (3) Å³

Data collection top

Bruker APEXII CCD diffractometer	6243 independent reflections
Radiation source: fine-focus sealed tube	5406 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
phi and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan SADABS (Bruker, 2007)	h = −13→13
T_min = 0.735, T_max = 0.948	k = −15→14
14356 measured reflections	l = −15→15

Refinement top

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0524P)² + 0.8093P] where P = (F_o² + 2F_c²)/3
6243 reflections	(Δ/σ)_max = 0.002
388 parameters	Δρ_max = 0.43 e Å⁻³
12 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

3C₃H₁₀N⁺·3C₃H₂N₃S₃⁻·H₂O	γ = 82.274 (1)°
M_r = 727.23	V = 1771.51 (3) Å³
Triclinic, P1	Z = 2
a = 11.3466 (1) Å	Mo Kα radiation
b = 12.6474 (1) Å	µ = 0.60 mm⁻¹
c = 12.8135 (1) Å	T = 296 K
α = 76.950 (1)°	0.55 × 0.40 × 0.09 mm
β = 84.762 (1)°

Data collection top

Bruker APEXII CCD diffractometer	6243 independent reflections
Absorption correction: multi-scan SADABS (Bruker, 2007)	5406 reflections with I > 2σ(I)
T_min = 0.735, T_max = 0.948	R_int = 0.016
14356 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	12 restraints
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.43 e Å⁻³
6243 reflections	Δρ_min = −0.28 e Å⁻³
388 parameters

Special details top

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

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.56389 (5)	0.64769 (5)	−0.12395 (4)	0.04362 (14)
N1	0.55437 (14)	0.63614 (14)	0.08580 (12)	0.0364 (4)
C1	0.49478 (16)	0.64115 (15)	−0.00121 (15)	0.0339 (4)
O1W	0.0658 (2)	0.88067 (19)	−0.01243 (17)	0.0861 (6)
H1WA	0.1088	0.8189	−0.0116	0.129*
H1WB	0.0952	0.9280	−0.0651	0.129*
S2	0.56375 (5)	0.62637 (5)	0.29317 (4)	0.04494 (15)
N2	0.37391 (14)	0.62546 (14)	0.18974 (13)	0.0370 (4)
H2	0.335 (2)	0.624 (2)	0.2500 (12)	0.055*
C2	0.49461 (17)	0.62957 (15)	0.18250 (15)	0.0343 (4)
S3	0.16216 (5)	0.63313 (6)	0.11585 (5)	0.05253 (16)
N3	0.37320 (14)	0.64138 (14)	0.01016 (13)	0.0377 (4)
H3	0.337 (2)	0.646 (2)	−0.0466 (13)	0.057*
C3	0.30893 (17)	0.63316 (16)	0.10501 (15)	0.0364 (4)
S4	0.80586 (5)	0.34932 (6)	0.59567 (4)	0.05156 (16)
N4	0.61463 (14)	0.35390 (15)	0.49243 (13)	0.0407 (4)
H4	0.577 (2)	0.361 (2)	0.5519 (13)	0.061*
C4	0.73630 (17)	0.34937 (17)	0.48581 (16)	0.0381 (4)
S5	0.40260 (5)	0.35735 (6)	0.42068 (5)	0.05557 (17)
N5	0.61589 (15)	0.34088 (15)	0.31875 (13)	0.0404 (4)
H5	0.581 (2)	0.343 (2)	0.2620 (14)	0.061*
C5	0.54998 (17)	0.35067 (17)	0.41032 (16)	0.0380 (4)
S6	0.80673 (5)	0.33438 (7)	0.18635 (5)	0.0681 (2)
N6	0.79689 (14)	0.34433 (16)	0.39149 (13)	0.0428 (4)
C6	0.73742 (18)	0.34035 (19)	0.30705 (16)	0.0424 (5)
N10	1.04639 (17)	0.32035 (19)	0.3879 (2)	0.0643 (6)
H10	0.9696 (10)	0.331 (3)	0.398 (3)	0.096*
C10	1.0768 (4)	0.4212 (3)	0.3201 (4)	0.1236 (17)
H10A	1.0568	0.4792	0.3580	0.185*
H10B	1.0332	0.4372	0.2565	0.185*
H10C	1.1607	0.4145	0.3004	0.185*
N11	0.79117 (16)	0.68045 (18)	0.06442 (19)	0.0581 (5)
H11	0.7233 (16)	0.655 (2)	0.078 (3)	0.087*
C11	1.1012 (3)	0.2929 (4)	0.4905 (3)	0.1159 (16)
H11A	1.0825	0.3528	0.5260	0.174*
H11B	1.1860	0.2787	0.4786	0.174*
H11C	1.0711	0.2289	0.5345	0.174*
N12	0.50621 (19)	0.00292 (17)	0.28412 (18)	0.0569 (5)
H12	0.4444 (18)	−0.015 (3)	0.262 (2)	0.085*
C12	1.0776 (4)	0.2293 (4)	0.3325 (4)	0.1397 (19)
H12A	1.0415	0.2473	0.2648	0.210*
H12B	1.0489	0.1645	0.3759	0.210*
H12C	1.1626	0.2169	0.3205	0.210*
C13	0.8621 (3)	0.6173 (3)	−0.0050 (3)	0.0944 (11)
H13A	0.8258	0.6298	−0.0722	0.142*
H13B	0.8667	0.5410	0.0286	0.142*
H13C	0.9409	0.6392	−0.0175	0.142*
C14	0.8474 (3)	0.6615 (3)	0.1690 (3)	0.0917 (11)
H14A	0.7998	0.7031	0.2150	0.137*
H14B	0.9258	0.6841	0.1566	0.137*
H14C	0.8527	0.5852	0.2026	0.137*
C15	0.7683 (4)	0.7964 (3)	0.0190 (4)	0.1141 (15)
H15A	0.7320	0.8074	−0.0480	0.171*
H15B	0.8420	0.8280	0.0072	0.171*
H15C	0.7156	0.8308	0.0678	0.171*
C16	0.4718 (3)	0.0885 (2)	0.3457 (3)	0.0755 (8)
H16A	0.4210	0.0612	0.4073	0.113*
H16B	0.4300	0.1511	0.3012	0.113*
H16C	0.5420	0.1090	0.3687	0.113*
C17	0.5840 (3)	0.0438 (3)	0.1878 (3)	0.0974 (11)
H17A	0.6051	−0.0125	0.1479	0.146*
H17B	0.6551	0.0639	0.2098	0.146*
H17C	0.5423	0.1066	0.1434	0.146*
C18	0.5605 (3)	−0.0983 (2)	0.3525 (3)	0.0858 (10)
H18A	0.5062	−0.1218	0.4127	0.129*
H18B	0.6331	−0.0850	0.3776	0.129*
H18C	0.5775	−0.1541	0.3116	0.129*
N7	0.12163 (19)	0.92130 (18)	0.18856 (17)	0.0574 (5)
H7	0.107 (3)	0.916 (3)	0.1258 (13)	0.086*
S7	0.34408 (7)	0.92115 (7)	0.10863 (6)	0.0737 (2)
C7	0.2383 (2)	0.92934 (19)	0.2065 (2)	0.0538 (6)
S8	0.19623 (6)	0.96108 (6)	0.50398 (6)	0.06475 (19)
N8	0.26245 (17)	0.94371 (16)	0.30300 (17)	0.0542 (5)
C8	0.1747 (2)	0.95025 (18)	0.3790 (2)	0.0514 (5)
S9	−0.11137 (7)	0.92925 (8)	0.23683 (7)	0.0800 (2)
N9	0.05886 (18)	0.94998 (17)	0.35405 (17)	0.0529 (5)
H9	0.0012 (19)	0.964 (2)	0.3986 (19)	0.079*
C9	0.0290 (2)	0.9339 (2)	0.2601 (2)	0.0539 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0367 (3)	0.0641 (3)	0.0296 (3)	−0.0079 (2)	0.0031 (2)	−0.0103 (2)
N1	0.0296 (8)	0.0493 (10)	0.0317 (8)	−0.0075 (7)	−0.0002 (6)	−0.0106 (7)
C1	0.0329 (9)	0.0372 (10)	0.0318 (10)	−0.0057 (8)	−0.0009 (8)	−0.0073 (8)
O1W	0.0859 (15)	0.0935 (15)	0.0732 (13)	0.0028 (12)	−0.0087 (11)	−0.0124 (11)
S2	0.0367 (3)	0.0688 (4)	0.0331 (3)	−0.0108 (2)	−0.0038 (2)	−0.0153 (2)
N2	0.0309 (8)	0.0528 (10)	0.0290 (8)	−0.0096 (7)	0.0027 (6)	−0.0114 (7)
C2	0.0327 (9)	0.0379 (10)	0.0334 (10)	−0.0064 (8)	−0.0011 (8)	−0.0091 (8)
S3	0.0302 (3)	0.0844 (4)	0.0445 (3)	−0.0137 (3)	−0.0001 (2)	−0.0138 (3)
N3	0.0314 (8)	0.0541 (10)	0.0287 (8)	−0.0080 (7)	−0.0024 (7)	−0.0095 (7)
C3	0.0330 (10)	0.0435 (11)	0.0339 (10)	−0.0084 (8)	−0.0005 (8)	−0.0092 (8)
S4	0.0354 (3)	0.0880 (4)	0.0377 (3)	−0.0090 (3)	−0.0046 (2)	−0.0251 (3)
N4	0.0304 (8)	0.0639 (11)	0.0310 (9)	−0.0094 (8)	0.0018 (7)	−0.0164 (8)
C4	0.0321 (10)	0.0489 (11)	0.0354 (10)	−0.0077 (8)	−0.0004 (8)	−0.0127 (9)
S5	0.0297 (3)	0.0942 (5)	0.0464 (3)	−0.0143 (3)	0.0000 (2)	−0.0197 (3)
N5	0.0323 (8)	0.0617 (11)	0.0308 (9)	−0.0107 (8)	−0.0010 (7)	−0.0150 (8)
C5	0.0337 (10)	0.0475 (11)	0.0344 (10)	−0.0096 (8)	−0.0011 (8)	−0.0102 (8)
S6	0.0400 (3)	0.1345 (7)	0.0371 (3)	−0.0152 (3)	0.0055 (2)	−0.0340 (4)
N6	0.0305 (8)	0.0669 (12)	0.0346 (9)	−0.0093 (8)	0.0005 (7)	−0.0176 (8)
C6	0.0351 (10)	0.0594 (13)	0.0351 (11)	−0.0085 (9)	0.0001 (8)	−0.0143 (9)
N10	0.0338 (10)	0.0679 (14)	0.0813 (15)	−0.0089 (10)	0.0012 (10)	0.0042 (11)
C10	0.101 (3)	0.090 (3)	0.164 (4)	−0.046 (2)	−0.049 (3)	0.041 (3)
N11	0.0320 (9)	0.0626 (13)	0.0851 (15)	−0.0111 (9)	0.0005 (10)	−0.0259 (11)
C11	0.0499 (17)	0.194 (4)	0.083 (2)	−0.014 (2)	0.0008 (16)	0.011 (3)
N12	0.0542 (12)	0.0575 (12)	0.0608 (13)	−0.0030 (10)	−0.0084 (10)	−0.0165 (10)
C12	0.128 (4)	0.116 (3)	0.172 (5)	0.047 (3)	−0.033 (3)	−0.048 (3)
C13	0.0535 (17)	0.131 (3)	0.116 (3)	−0.0040 (18)	−0.0003 (17)	−0.068 (2)
C14	0.0481 (16)	0.145 (3)	0.091 (2)	−0.0186 (18)	−0.0029 (15)	−0.040 (2)
C15	0.092 (3)	0.065 (2)	0.185 (4)	−0.0214 (18)	−0.031 (3)	−0.011 (2)
C16	0.086 (2)	0.0609 (16)	0.082 (2)	−0.0163 (15)	0.0168 (16)	−0.0243 (15)
C17	0.097 (3)	0.110 (3)	0.072 (2)	0.010 (2)	0.0189 (18)	−0.0126 (19)
C18	0.092 (2)	0.0576 (17)	0.106 (3)	0.0014 (15)	−0.032 (2)	−0.0100 (16)
N7	0.0571 (12)	0.0642 (13)	0.0535 (12)	−0.0103 (10)	−0.0052 (10)	−0.0158 (10)
S7	0.0663 (4)	0.0802 (5)	0.0686 (4)	−0.0057 (4)	0.0147 (3)	−0.0129 (4)
C7	0.0520 (13)	0.0428 (12)	0.0649 (15)	−0.0075 (10)	0.0010 (11)	−0.0089 (11)
S8	0.0578 (4)	0.0798 (5)	0.0621 (4)	−0.0077 (3)	−0.0098 (3)	−0.0245 (3)
N8	0.0469 (11)	0.0538 (11)	0.0646 (13)	−0.0095 (9)	−0.0011 (9)	−0.0174 (10)
C8	0.0485 (13)	0.0445 (12)	0.0630 (15)	−0.0089 (10)	−0.0031 (11)	−0.0136 (11)
S9	0.0556 (4)	0.1196 (7)	0.0727 (5)	−0.0239 (4)	−0.0104 (3)	−0.0271 (5)
N9	0.0463 (11)	0.0605 (12)	0.0567 (12)	−0.0117 (9)	−0.0006 (9)	−0.0200 (10)
C9	0.0527 (14)	0.0547 (14)	0.0558 (14)	−0.0122 (11)	−0.0021 (11)	−0.0122 (11)

Geometric parameters (Å, º) top

S1—C1	1.6819 (19)	C11—H11C	0.9600
N1—C1	1.341 (2)	N12—C16	1.470 (3)
N1—C2	1.348 (2)	N12—C18	1.471 (4)
C1—N3	1.374 (2)	N12—C17	1.486 (4)
O1W—H1WA	0.8619	N12—H12	0.851 (10)
O1W—H1WB	0.8691	C12—H12A	0.9600
S2—C2	1.6723 (19)	C12—H12B	0.9600
N2—C3	1.346 (3)	C12—H12C	0.9600
N2—C2	1.371 (2)	C13—H13A	0.9600
N2—H2	0.850 (10)	C13—H13B	0.9600
S3—C3	1.6585 (19)	C13—H13C	0.9600
N3—C3	1.349 (2)	C14—H14A	0.9600
N3—H3	0.854 (10)	C14—H14B	0.9600
S4—C4	1.675 (2)	C14—H14C	0.9600
N4—C5	1.347 (3)	C15—H15A	0.9600
N4—C4	1.370 (2)	C15—H15B	0.9600
N4—H4	0.857 (10)	C15—H15C	0.9600
C4—N6	1.345 (3)	C16—H16A	0.9600
S5—C5	1.658 (2)	C16—H16B	0.9600
N5—C5	1.354 (3)	C16—H16C	0.9600
N5—C6	1.373 (3)	C17—H17A	0.9600
N5—H5	0.855 (10)	C17—H17B	0.9600
S6—C6	1.682 (2)	C17—H17C	0.9600
N6—C6	1.340 (3)	C18—H18A	0.9600
N10—C10	1.436 (4)	C18—H18B	0.9600
N10—C11	1.456 (4)	C18—H18C	0.9600
N10—C12	1.473 (5)	N7—C9	1.347 (3)
N10—H10	0.865 (10)	N7—C7	1.385 (3)
C10—H10A	0.9600	N7—H7	0.856 (10)
C10—H10B	0.9600	S7—C7	1.666 (3)
C10—H10C	0.9600	C7—N8	1.346 (3)
N11—C13	1.447 (4)	S8—C8	1.680 (3)
N11—C15	1.448 (4)	N8—C8	1.336 (3)
N11—C14	1.493 (4)	C8—N9	1.381 (3)
N11—H11	0.863 (10)	S9—C9	1.658 (3)
C11—H11A	0.9600	N9—C9	1.346 (3)
C11—H11B	0.9600	N9—H9	0.857 (10)

C1—N1—C2	119.69 (16)	C18—N12—H12	105 (2)
N1—C1—N3	118.93 (16)	C17—N12—H12	107 (2)
N1—C1—S1	122.20 (14)	N10—C12—H12A	109.5
N3—C1—S1	118.87 (14)	N10—C12—H12B	109.5
H1WA—O1W—H1WB	106.8	H12A—C12—H12B	109.5
C3—N2—C2	124.13 (16)	N10—C12—H12C	109.5
C3—N2—H2	116.5 (17)	H12A—C12—H12C	109.5
C2—N2—H2	119.1 (17)	H12B—C12—H12C	109.5
N1—C2—N2	118.82 (17)	N11—C13—H13A	109.5
N1—C2—S2	121.75 (14)	N11—C13—H13B	109.5
N2—C2—S2	119.43 (14)	H13A—C13—H13B	109.5
C3—N3—C1	124.00 (16)	N11—C13—H13C	109.5
C3—N3—H3	118.8 (18)	H13A—C13—H13C	109.5
C1—N3—H3	117.2 (18)	H13B—C13—H13C	109.5
N2—C3—N3	114.34 (17)	N11—C14—H14A	109.5
N2—C3—S3	122.95 (14)	N11—C14—H14B	109.5
N3—C3—S3	122.71 (15)	H14A—C14—H14B	109.5
C5—N4—C4	124.14 (17)	N11—C14—H14C	109.5
C5—N4—H4	117.5 (18)	H14A—C14—H14C	109.5
C4—N4—H4	118.4 (18)	H14B—C14—H14C	109.5
N6—C4—N4	119.15 (17)	N11—C15—H15A	109.5
N6—C4—S4	121.71 (15)	N11—C15—H15B	109.5
N4—C4—S4	119.14 (14)	H15A—C15—H15B	109.5
C5—N5—C6	123.76 (17)	N11—C15—H15C	109.5
C5—N5—H5	119.5 (18)	H15A—C15—H15C	109.5
C6—N5—H5	116.3 (18)	H15B—C15—H15C	109.5
N4—C5—N5	114.15 (17)	N12—C16—H16A	109.5
N4—C5—S5	122.96 (15)	N12—C16—H16B	109.5
N5—C5—S5	122.90 (15)	H16A—C16—H16B	109.5
C6—N6—C4	119.38 (17)	N12—C16—H16C	109.5
N6—C6—N5	119.31 (17)	H16A—C16—H16C	109.5
N6—C6—S6	122.21 (15)	H16B—C16—H16C	109.5
N5—C6—S6	118.48 (15)	N12—C17—H17A	109.5
C10—N10—C11	113.8 (3)	N12—C17—H17B	109.5
C10—N10—C12	110.8 (4)	H17A—C17—H17B	109.5
C11—N10—C12	109.4 (3)	N12—C17—H17C	109.5
C10—N10—H10	104 (2)	H17A—C17—H17C	109.5
C11—N10—H10	110 (2)	H17B—C17—H17C	109.5
C12—N10—H10	108 (2)	N12—C18—H18A	109.5
N10—C10—H10A	109.5	N12—C18—H18B	109.5
N10—C10—H10B	109.5	H18A—C18—H18B	109.5
H10A—C10—H10B	109.5	N12—C18—H18C	109.5
N10—C10—H10C	109.5	H18A—C18—H18C	109.5
H10A—C10—H10C	109.5	H18B—C18—H18C	109.5
H10B—C10—H10C	109.5	C9—N7—C7	123.6 (2)
C13—N11—C15	115.1 (3)	C9—N7—H7	118 (2)
C13—N11—C14	109.7 (2)	C7—N7—H7	118 (2)
C15—N11—C14	110.3 (3)	N8—C7—N7	118.7 (2)
C13—N11—H11	107 (2)	N8—C7—S7	122.06 (19)
C15—N11—H11	108 (2)	N7—C7—S7	119.2 (2)
C14—N11—H11	107 (2)	C8—N8—C7	120.0 (2)
N10—C11—H11A	109.5	N8—C8—N9	118.8 (2)
N10—C11—H11B	109.5	N8—C8—S8	123.78 (19)
H11A—C11—H11B	109.5	N9—C8—S8	117.46 (18)
N10—C11—H11C	109.5	C9—N9—C8	123.9 (2)
H11A—C11—H11C	109.5	C9—N9—H9	116 (2)
H11B—C11—H11C	109.5	C8—N9—H9	119 (2)
C16—N12—C18	111.1 (2)	N9—C9—N7	114.7 (2)
C16—N12—C17	110.3 (2)	N9—C9—S9	121.64 (19)
C18—N12—C17	112.8 (3)	N7—C9—S9	123.69 (19)
C16—N12—H12	110 (2)

C2—N1—C1—N3	1.1 (3)	N4—C4—N6—C6	−2.1 (3)
C2—N1—C1—S1	−179.13 (15)	S4—C4—N6—C6	177.44 (17)
C1—N1—C2—N2	1.6 (3)	C4—N6—C6—N5	−0.4 (3)
C1—N1—C2—S2	−178.39 (15)	C4—N6—C6—S6	179.78 (17)
C3—N2—C2—N1	−3.5 (3)	C5—N5—C6—N6	3.4 (3)
C3—N2—C2—S2	176.45 (16)	C5—N5—C6—S6	−176.76 (17)
N1—C1—N3—C3	−2.3 (3)	C9—N7—C7—N8	4.3 (4)
S1—C1—N3—C3	177.94 (16)	C9—N7—C7—S7	−175.60 (19)
C2—N2—C3—N3	2.4 (3)	N7—C7—N8—C8	−0.2 (3)
C2—N2—C3—S3	−177.34 (16)	S7—C7—N8—C8	179.74 (18)
C1—N3—C3—N2	0.6 (3)	C7—N8—C8—N9	−4.6 (3)
C1—N3—C3—S3	−179.71 (15)	C7—N8—C8—S8	176.47 (18)
C5—N4—C4—N6	1.9 (3)	N8—C8—N9—C9	6.1 (4)
C5—N4—C4—S4	−177.66 (17)	S8—C8—N9—C9	−174.96 (19)
C4—N4—C5—N5	0.9 (3)	C8—N9—C9—N7	−2.2 (3)
C4—N4—C5—S5	−179.48 (17)	C8—N9—C9—S9	177.35 (18)
C6—N5—C5—N4	−3.5 (3)	C7—N7—C9—N9	−3.1 (4)
C6—N5—C5—S5	176.84 (17)	C7—N7—C9—S9	177.44 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···S3	0.86	2.57	3.284 (2)	140
O1W—H1WB···S9ⁱ	0.87	2.52	3.355 (2)	161
N2—H2···S4ⁱⁱ	0.85 (1)	2.48 (1)	3.3196 (17)	168 (2)
N3—H3···S6ⁱⁱⁱ	0.85 (1)	2.48 (1)	3.3203 (17)	168 (2)
N4—H4···S2ⁱⁱ	0.86 (1)	2.45 (1)	3.2962 (17)	169 (2)
N5—H5···S1ⁱⁱⁱ	0.86 (1)	2.49 (1)	3.3316 (17)	167 (2)
N7—H7···O1W	0.86 (1)	2.03 (1)	2.878 (3)	172 (3)
N9—H9···S8^iv	0.86 (1)	2.63 (1)	3.470 (2)	167 (3)
N10—H10···N6	0.87 (1)	1.95 (1)	2.804 (3)	168 (3)
N11—H11···N1	0.86 (1)	1.95 (1)	2.795 (2)	164 (3)
N12—H12···S7^v	0.85 (1)	2.69 (2)	3.439 (2)	148 (3)

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

Experimental details

Crystal data
Chemical formula	3C₃H₁₀N⁺·3C₃H₂N₃S₃⁻·H₂O
M_r	727.23
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	11.3466 (1), 12.6474 (1), 12.8135 (1)
α, β, γ (°)	76.950 (1), 84.762 (1), 82.274 (1)
V (Å³)	1771.51 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.60
Crystal size (mm)	0.55 × 0.40 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan SADABS (Bruker, 2007)
T_min, T_max	0.735, 0.948
No. of measured, independent and observed [I > 2σ(I)] reflections	14356, 6243, 5406
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.103, 1.05
No. of reflections	6243
No. of parameters	388
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.28

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···S3	0.86	2.57	3.284 (2)	140
O1W—H1WB···S9ⁱ	0.87	2.52	3.355 (2)	161
N2—H2···S4ⁱⁱ	0.850 (10)	2.483 (11)	3.3196 (17)	168 (2)
N3—H3···S6ⁱⁱⁱ	0.854 (10)	2.481 (11)	3.3203 (17)	168 (2)
N4—H4···S2ⁱⁱ	0.857 (10)	2.450 (11)	3.2962 (17)	169 (2)
N5—H5···S1ⁱⁱⁱ	0.855 (10)	2.494 (12)	3.3316 (17)	167 (2)
N7—H7···O1W	0.856 (10)	2.028 (11)	2.878 (3)	172 (3)
N9—H9···S8^iv	0.857 (10)	2.631 (12)	3.470 (2)	167 (3)
N10—H10···N6	0.865 (10)	1.952 (13)	2.804 (3)	168 (3)
N11—H11···N1	0.863 (10)	1.954 (13)	2.795 (2)	164 (3)
N12—H12···S7^v	0.851 (10)	2.686 (19)	3.439 (2)	148 (3)

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

Acknowledgements

We thank Northwest Normal University for supporting this study.

References

Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconson, USA. Google Scholar
Dean, P. A. W., Jennings, M., Houle, T. M., Craig, D. C., Dance, I. G., Hook, J. M. & Scudder, M. L. (2004). CrystEngComm, 6, 543–548. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar