N,N,N,N′,N′,N′-Hexa­kis­(2-hy­droxy­ethyl)butane-1,4-diaminium bis­(2-sul­fan­ylidene-1,3-di­thiole-4,5-dithiolato-κ2S4,S5)zincate

Zhang, X.; Xie, B.; Zou, L.; Wang, J.; Lin, X.

doi:10.1107/S1600536813014992

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 7| July 2013| Pages m368-m369

https://doi.org/10.1107/S1600536813014992

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N,N,N,N′,N′,N′-Hexakis(2-hydroxyethyl)butane-1,4-diaminium bis(2-sulfanylidene-1,3-dithiole-4,5-dithiolato-κ²S⁴,S⁵)zincate

Xiulan Zhang,^a,^b ^* Bin Xie,^a,^b Like Zou,^a,^b Jun Wang ^a,^b and Xiao Lin ^a,^b

^aInstitute of Functionalized Materials, Sichuan University of Science and Engineering, Zigong 643000, People's Republic of China, and ^bCollege of Chemistry and Pharmaceutical Engineering, Sichuan University of Science and Engineering, Zigong 643000, People's Republic of China
^*Correspondence e-mail: zxlsuse@sina.com

(Received 16 May 2013; accepted 31 May 2013; online 8 June 2013)

In the asymmetric unit of the title compound, (C₁₆H₃₈N₂O₆)[Zn(C₃S₅)₂], two independent cations lie across inversion centers. In one of the cations, the three symmetry-unique O—H groups are disordered over two sets of sites with refined occupancy ratios of 0.701 (9):0.299 (9), 0.671 (8):0.329 (8) and 0.566 (7):0.434 (7). In the anion, the Zn^II ion is coordinated in a distorted tetrahedral environment by four S atoms of two chelating 1,3-dithiole-2-thione-4,5-dithiolato ligands. The dihedral angle between the mean planes [maximun deviations = 0.022 (3) and 0.0656 (6) Å] of the two ligands is 87.76 (3)°. An intamolecular O—H⋯O hydrogen bond occurs in the disordered cation. In the crystal, O—H⋯O and O—H⋯S hydrogen bonds link the components into a two-dimensional network parallel to (0-11).

Related literature

For synthetic background to the title compound, see: Steimecke et al. (1982 ); Xie et al. (2009 ). For a related crystal structure, see: Zhao et al. (2011 ).

Experimental

Crystal data

(C₁₆H₃₈N₂O₆)[Zn(C₃S₅)₂]
M_r = 812.51
Triclinic, $[P \overline 1]$
a = 9.051 (5) Å
b = 13.142 (7) Å
c = 15.321 (8) Å
α = 69.803 (5)°
β = 84.566 (5)°
γ = 76.909 (6)°
V = 1665.6 (15) Å³
Z = 2
Mo Kα radiation
μ = 1.40 mm⁻¹
T = 296 K
0.21 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.757, T_max = 0.767
11410 measured reflections
7406 independent reflections
6279 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.098
S = 1.05
7406 reflections
401 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.89 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O5ⁱ	0.82	2.03	2.800 (5)	157
O2—H2⋯O5ⁱ	0.82	1.93	2.668 (5)	149
O3—H3⋯O2ⁱⁱ	0.82	2.16	2.923 (3)	154
O4—H4⋯O6ⁱ	0.82	2.07	2.887 (8)	179
O5—H5⋯O6	0.82	1.79	2.615 (9)	179
O6—H6⋯S2ⁱⁱⁱ	0.82	2.92	3.540 (8)	134
Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z; (iii) -x+1, -y+1, -z.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL2013.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536813014992/lh5618sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813014992/lh5618Isup2.hkl

checkCIF report

Comment top

The crystal structure of the title compound is presented herein. The anion is shown in Fig. 1 and the cations are shown in Figs. 3 and 4. The asymmetric unit contains two independent cations which lie across inversion centers. In one of the cations the three symmetry unique O—H groups are disordered over two sets of sites with refined occupancy ratios of 0.701 (9):0.299 (9) for O4:O4', 0.671 (8):0.329 (8) for O5:O5' and 0.567 (7):0.434 (7) for O6:O6'. In the anion, the Zn^II ion is coordinated in a distorted tetrahedral coordination environment by four S atoms of two chelating 1,3-dithiole-2-thione-4,5-dithilato ligands. The dihedral angle between the mean planes of the two ligands (with maximun deviations of 0.022 (3) for C3 and 0.0656 (6) Å for S8) is 87.76 (3)°. In the crystal, O—H···O and O—H···S hydrogen bonds link the components of the structure into a two-dimensional network parallel to (011) (Fig. 4). Only the donor H atoms of the major components of disorder have been considered. The bis(tetra-N-butylammoniun) analogue of the title compound has been reported in the literature (Zhao et al., 2011).

Related literature top

For synthetic background to the title compound, see: Steimecke et al. (1982); Xie et al. (2009). For a related crystal structure, see: Zhao et al. (2011).

Experimental top

All synthetic procedures were carried out under nitrogen using standard Schlenk techniques. The compound tdb(COPh)₂ (tdb = 4,5-dimercapto-1,3-dithiole-2-thione) was synthesized according to procedure described by Steimecke et al. (1982) and Xie et al. (2009). The quatemary ammonium salt N,N'-bis(tri(2'-hydroethyl)-1,4-butanediammonium bromide [BDA]Br₂ was obtained by the reaction of triethanolamine (30 g, 0.2 mol) and 1,4-dibromobutane (21 g, 0.1 mol) in refluxing acetone for one week. The compound tdb(COPh)₂ (0.812 g, 2 mmol) was dissolved in sodium methoxide solution at room temperature to give a dark red solution after 0.5 h. To this solution ZnCl₂.6H₂O (0.244 g, 1 mmol) was added. After stirring the reaction mixture for 1 h, [BDA]Br₂ (0.486 g, 1 mmol) was added to form a red solution. The reaction mixture was filtered off after 1 h, and the filtrate was then standed. The red crystals were obtained after two weeks.

Structure description top

For synthetic background to the title compound, see: Steimecke et al. (1982); Xie et al. (2009). For a related crystal structure, see: Zhao et al. (2011).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008).

Figures top

	Fig. 1. The anion with displacement ellipsoids shown at the 30% level.
	Fig. 2. The ordered cation with displacement ellipsoids shown at the 30% level. Unlabled atoms are related by the symmetry operator (-x + 1, -y + 2, -z + 1).
	Fig. 3. The disordered cation with displacement ellipsoids shown at the 30% level. Unlabled atoms are related by the symmetry operator (-x + 1, -y + 1, -z). The minor components are shown with dashed lines.
	Fig. 4. Part of the crystal structure with donor-acceptor distances of hydrogen bonds shown as dashed lines.

N,N,N,N',N',N'-Hexakis(2-hydroxyethyl)butane-1,4-diaminium bis(2-sulfanylidene-1,3-dithiole-4,5-dithiolato-κ²S⁴,S⁵)zincate top

Crystal data top

(C₁₆H₃₈N₂O₆)[Zn(C₃S₅)₂]	Z = 2
M_r = 812.51	F(000) = 844
Triclinic, P1	D_x = 1.620 Mg m⁻³
a = 9.051 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.142 (7) Å	Cell parameters from 6094 reflections
c = 15.321 (8) Å	θ = 2.5–28.4°
α = 69.803 (5)°	µ = 1.40 mm⁻¹
β = 84.566 (5)°	T = 296 K
γ = 76.909 (6)°	Block, red
V = 1665.6 (15) Å³	0.21 × 0.20 × 0.20 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	6279 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.017
φ and ω scans	θ_max = 28.6°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −12→11
T_min = 0.757, T_max = 0.767	k = −17→12
11410 measured reflections	l = −19→20
7406 independent reflections

Refinement top

Refinement on F²	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0483P)² + 1.1464P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
7406 reflections	Δρ_max = 0.89 e Å⁻³
401 parameters	Δρ_min = −0.61 e Å⁻³

Crystal data top

(C₁₆H₃₈N₂O₆)[Zn(C₃S₅)₂]	γ = 76.909 (6)°
M_r = 812.51	V = 1665.6 (15) Å³
Triclinic, P1	Z = 2
a = 9.051 (5) Å	Mo Kα radiation
b = 13.142 (7) Å	µ = 1.40 mm⁻¹
c = 15.321 (8) Å	T = 296 K
α = 69.803 (5)°	0.21 × 0.20 × 0.20 mm
β = 84.566 (5)°

Data collection top

Bruker SMART APEXII CCD diffractometer	7406 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	6279 reflections with I > 2σ(I)
T_min = 0.757, T_max = 0.767	R_int = 0.017
11410 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	4 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.05	Δρ_max = 0.89 e Å⁻³
7406 reflections	Δρ_min = −0.61 e Å⁻³
401 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.72260 (3)	0.31560 (2)	0.29989 (2)	0.03324 (9)
S1	1.43528 (9)	0.07781 (8)	0.13331 (7)	0.0595 (2)
S2	1.16079 (8)	0.26092 (7)	0.11098 (5)	0.04481 (17)
S3	1.19712 (7)	0.07888 (6)	0.28040 (5)	0.04110 (16)
S4	0.86527 (8)	0.38273 (6)	0.16423 (5)	0.03975 (16)
S5	0.91180 (7)	0.16205 (5)	0.37140 (4)	0.03560 (14)
S6	0.60063 (7)	0.43102 (5)	0.38427 (4)	0.03266 (14)
S7	0.49964 (7)	0.27202 (5)	0.26931 (5)	0.03467 (14)
S8	0.18379 (7)	0.36528 (5)	0.31683 (4)	0.03174 (13)
S9	0.26376 (7)	0.50500 (5)	0.40545 (4)	0.03092 (13)
S10	−0.06504 (7)	0.51276 (7)	0.38168 (6)	0.04485 (18)
C1	1.2721 (3)	0.1367 (2)	0.1725 (2)	0.0407 (6)
C2	1.0312 (3)	0.1804 (2)	0.27378 (17)	0.0298 (5)
C3	1.0134 (3)	0.2666 (2)	0.19272 (17)	0.0316 (5)
C4	0.3785 (3)	0.35788 (19)	0.32191 (16)	0.0270 (5)
C5	0.4163 (3)	0.42241 (19)	0.36549 (16)	0.0274 (5)
C6	0.1181 (3)	0.4648 (2)	0.36886 (17)	0.0304 (5)
O1	0.8411 (3)	1.0111 (2)	0.13299 (15)	0.0738 (8)
H1	0.9254	0.9745	0.1272	0.111*
O2	1.1048 (2)	0.8211 (2)	0.34668 (15)	0.0574 (6)
H2	1.0753	0.8226	0.2972	0.086*
O3	0.3905 (2)	0.79755 (19)	0.43313 (15)	0.0518 (5)
H3	0.3166	0.8242	0.3994	0.078*
N1	0.7275 (2)	0.87055 (15)	0.38146 (13)	0.0259 (4)
C15	0.5189 (3)	0.7627 (3)	0.3815 (2)	0.0452 (7)
H15A	0.5092	0.8112	0.3172	0.054*
H15B	0.5190	0.6884	0.3827	0.054*
C16	0.6697 (3)	0.76267 (19)	0.41688 (18)	0.0325 (5)
H16A	0.7460	0.7062	0.4015	0.039*
H16B	0.6623	0.7403	0.4842	0.039*
C17	0.5665 (3)	0.9539 (2)	0.49775 (17)	0.0374 (6)
H17A	0.5393	0.8826	0.5290	0.045*
H17B	0.6525	0.9572	0.5292	0.045*
C18	0.6089 (3)	0.9665 (2)	0.39676 (16)	0.0303 (5)
H18A	0.6470	1.0341	0.3688	0.036*
H18B	0.5177	0.9748	0.3642	0.036*
C19	0.7612 (3)	0.8966 (2)	0.27804 (16)	0.0332 (5)
H19A	0.6700	0.8987	0.2484	0.040*
H19B	0.8382	0.8360	0.2695	0.040*
C20	0.8147 (4)	1.0040 (3)	0.22751 (19)	0.0460 (7)
H20A	0.7379	1.0668	0.2322	0.055*
H20B	0.9072	1.0040	0.2547	0.055*
C21	0.8694 (3)	0.8543 (2)	0.43514 (17)	0.0307 (5)
H21A	0.8970	0.9258	0.4192	0.037*
H21B	0.8433	0.8310	0.5010	0.037*
C22	1.0087 (3)	0.7720 (2)	0.42009 (19)	0.0362 (5)
H22A	1.0658	0.7383	0.4771	0.043*
H22B	0.9762	0.7137	0.4066	0.043*
C12	0.6135 (5)	0.6888 (6)	0.1276 (3)	0.0924 (16)
H12A	0.6734	0.6384	0.0978	0.111*	0.701 (9)
H12B	0.5920	0.7623	0.0814	0.111*	0.701 (9)
O4	0.6950 (5)	0.6901 (5)	0.1991 (3)	0.096 (2)	0.701 (9)
H4	0.7745	0.7024	0.1711	0.144*	0.701 (9)
C14	0.2392 (5)	0.8699 (3)	0.1175 (3)	0.0687 (10)
H14A	0.3198	0.8512	0.1613	0.082*	0.671 (8)
H14B	0.2246	0.9487	0.0831	0.082*	0.671 (8)
O5	0.1091 (4)	0.8486 (4)	0.1657 (3)	0.0746 (16)	0.671 (8)
H5	0.0669	0.8126	0.1455	0.112*	0.671 (8)
C7	0.0785 (5)	0.6446 (4)	0.0908 (3)	0.0781 (12)
H7A	0.1068	0.6577	0.0258	0.094*	0.566 (7)
H7B	0.0342	0.5793	0.1131	0.094*	0.566 (7)
O6	−0.0266 (7)	0.7353 (6)	0.1000 (6)	0.132 (3)	0.566 (7)
H6	−0.0577	0.7765	0.0485	0.198*	0.566 (7)
H12C	0.6957	0.6376	0.1665	0.111*	0.299 (9)
H12D	0.6327	0.6850	0.0653	0.111*	0.299 (9)
O4'	0.6138 (17)	0.7934 (8)	0.1249 (11)	0.130 (7)	0.299 (9)
H4'	0.6945	0.8099	0.1022	0.195*	0.299 (9)
H14C	0.1848	0.8266	0.1695	0.082*	0.329 (8)
H14D	0.3292	0.8784	0.1418	0.082*	0.329 (8)
O5'	0.1495 (14)	0.9722 (7)	0.0798 (9)	0.141 (6)	0.329 (8)
H5'	0.1913	1.0077	0.0330	0.212*	0.329 (8)
H7'1	0.0479	0.7232	0.0571	0.094*	0.434 (7)
H7'2	0.1053	0.6070	0.0453	0.094*	0.434 (7)
O6'	−0.0404 (6)	0.6090 (5)	0.1422 (5)	0.074 (2)	0.434 (7)
H6'	−0.0684	0.6440	0.1781	0.111*	0.434 (7)
N2	0.3447 (3)	0.68177 (19)	0.09357 (14)	0.0369 (5)
C8	0.2173 (3)	0.6257 (3)	0.1464 (2)	0.0472 (7)
H8A	0.2575	0.5466	0.1713	0.057*
H8B	0.1861	0.6516	0.1987	0.057*
C9	0.4633 (4)	0.5148 (3)	0.0416 (2)	0.0559 (8)
H9A	0.5367	0.4913	0.0905	0.067*
H9B	0.3801	0.4769	0.0654	0.067*
C10	0.4042 (3)	0.6398 (2)	0.01308 (18)	0.0424 (6)
H10A	0.3232	0.6607	−0.0309	0.051*
H10B	0.4854	0.6765	−0.0187	0.051*
C11	0.4673 (3)	0.6526 (3)	0.1644 (2)	0.0528 (8)
H11A	0.4268	0.6852	0.2118	0.063*
H11B	0.4898	0.5728	0.1943	0.063*
C13	0.2875 (4)	0.8067 (2)	0.0507 (2)	0.0485 (7)
H13A	0.3672	0.8375	0.0103	0.058*
H13B	0.2020	0.8194	0.0119	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02578 (15)	0.03610 (17)	0.03580 (16)	−0.00251 (11)	0.00140 (11)	−0.01242 (13)
S1	0.0344 (4)	0.0688 (5)	0.0720 (5)	−0.0009 (4)	0.0130 (4)	−0.0290 (4)
S2	0.0335 (4)	0.0567 (4)	0.0376 (3)	−0.0042 (3)	0.0051 (3)	−0.0122 (3)
S3	0.0283 (3)	0.0377 (3)	0.0515 (4)	−0.0017 (3)	0.0002 (3)	−0.0112 (3)
S4	0.0327 (3)	0.0404 (4)	0.0361 (3)	−0.0009 (3)	0.0001 (3)	−0.0047 (3)
S5	0.0329 (3)	0.0352 (3)	0.0331 (3)	−0.0036 (2)	0.0006 (2)	−0.0070 (3)
S6	0.0228 (3)	0.0394 (3)	0.0415 (3)	−0.0072 (2)	−0.0022 (2)	−0.0198 (3)
S7	0.0306 (3)	0.0353 (3)	0.0433 (3)	−0.0053 (2)	0.0013 (2)	−0.0211 (3)
S8	0.0252 (3)	0.0344 (3)	0.0413 (3)	−0.0095 (2)	−0.0010 (2)	−0.0175 (3)
S9	0.0248 (3)	0.0339 (3)	0.0393 (3)	−0.0058 (2)	0.0003 (2)	−0.0191 (3)
S10	0.0227 (3)	0.0550 (4)	0.0645 (5)	−0.0040 (3)	0.0011 (3)	−0.0325 (4)
C1	0.0292 (13)	0.0487 (16)	0.0478 (15)	−0.0086 (11)	0.0008 (11)	−0.0209 (13)
C2	0.0227 (11)	0.0323 (12)	0.0376 (12)	−0.0060 (9)	−0.0006 (9)	−0.0155 (10)
C3	0.0250 (12)	0.0392 (13)	0.0336 (12)	−0.0071 (10)	−0.0013 (9)	−0.0154 (11)
C4	0.0243 (11)	0.0270 (11)	0.0302 (11)	−0.0069 (8)	0.0000 (9)	−0.0092 (9)
C5	0.0221 (11)	0.0291 (11)	0.0314 (11)	−0.0057 (8)	0.0015 (9)	−0.0108 (9)
C6	0.0245 (11)	0.0317 (12)	0.0356 (12)	−0.0057 (9)	0.0005 (9)	−0.0125 (10)
O1	0.0740 (18)	0.0860 (19)	0.0353 (11)	0.0018 (14)	0.0146 (11)	−0.0034 (11)
O2	0.0394 (12)	0.0719 (15)	0.0470 (12)	−0.0044 (10)	0.0077 (9)	−0.0093 (11)
O3	0.0262 (10)	0.0638 (14)	0.0569 (13)	−0.0061 (9)	0.0003 (9)	−0.0119 (11)
N1	0.0251 (9)	0.0245 (9)	0.0274 (9)	−0.0024 (7)	0.0012 (7)	−0.0098 (8)
C15	0.0380 (15)	0.0541 (17)	0.0509 (16)	−0.0195 (13)	0.0036 (12)	−0.0216 (14)
C16	0.0303 (12)	0.0256 (11)	0.0416 (13)	−0.0056 (9)	0.0032 (10)	−0.0123 (10)
C17	0.0383 (14)	0.0381 (14)	0.0314 (12)	0.0051 (11)	0.0017 (10)	−0.0149 (11)
C18	0.0304 (12)	0.0279 (11)	0.0297 (11)	0.0035 (9)	0.0005 (9)	−0.0124 (10)
C19	0.0318 (13)	0.0392 (13)	0.0294 (12)	−0.0043 (10)	0.0028 (9)	−0.0154 (10)
C20	0.0457 (16)	0.0521 (17)	0.0334 (13)	−0.0116 (13)	0.0064 (12)	−0.0067 (12)
C21	0.0285 (12)	0.0314 (12)	0.0326 (12)	−0.0051 (9)	−0.0015 (9)	−0.0117 (10)
C22	0.0276 (12)	0.0344 (13)	0.0438 (14)	−0.0025 (10)	−0.0024 (10)	−0.0116 (11)
C12	0.052 (2)	0.166 (5)	0.070 (3)	−0.045 (3)	−0.0022 (19)	−0.038 (3)
O4	0.063 (3)	0.174 (6)	0.073 (3)	−0.052 (3)	0.000 (2)	−0.052 (3)
C14	0.074 (3)	0.055 (2)	0.081 (3)	−0.0139 (18)	0.016 (2)	−0.032 (2)
O5	0.064 (3)	0.090 (3)	0.081 (3)	−0.011 (2)	0.019 (2)	−0.051 (3)
C7	0.050 (2)	0.100 (3)	0.085 (3)	−0.029 (2)	−0.008 (2)	−0.022 (2)
O6	0.063 (4)	0.155 (7)	0.160 (7)	−0.022 (4)	−0.014 (4)	−0.027 (6)
C12'	0.052 (2)	0.166 (5)	0.070 (3)	−0.045 (3)	−0.0022 (19)	−0.038 (3)
O4'	0.118 (12)	0.135 (14)	0.144 (14)	−0.061 (10)	0.011 (10)	−0.038 (11)
C14'	0.074 (3)	0.055 (2)	0.081 (3)	−0.0139 (18)	0.016 (2)	−0.032 (2)
O5'	0.147 (13)	0.120 (11)	0.165 (13)	−0.029 (9)	0.023 (10)	−0.064 (10)
C7'	0.050 (2)	0.100 (3)	0.085 (3)	−0.029 (2)	−0.008 (2)	−0.022 (2)
O6'	0.054 (4)	0.075 (5)	0.092 (5)	−0.017 (3)	0.008 (3)	−0.026 (4)
N2	0.0359 (12)	0.0431 (12)	0.0289 (10)	−0.0098 (9)	−0.0011 (9)	−0.0073 (9)
C8	0.0456 (17)	0.0516 (17)	0.0398 (15)	−0.0170 (13)	0.0037 (12)	−0.0064 (13)
C9	0.065 (2)	0.0458 (17)	0.0473 (17)	0.0007 (15)	−0.0007 (15)	−0.0111 (14)
C10	0.0466 (16)	0.0435 (15)	0.0310 (13)	−0.0018 (12)	−0.0026 (11)	−0.0092 (11)
C11	0.0431 (17)	0.082 (2)	0.0343 (14)	−0.0149 (16)	−0.0041 (12)	−0.0180 (15)
C13	0.0537 (18)	0.0422 (16)	0.0448 (15)	−0.0095 (13)	0.0081 (13)	−0.0111 (13)

Geometric parameters (Å, º) top

Zn1—S5	2.3384 (11)	C19—H19B	0.9700
Zn1—S4	2.3467 (11)	C20—H20A	0.9700
Zn1—S7	2.3468 (13)	C20—H20B	0.9700
Zn1—S6	2.3487 (10)	C21—C22	1.520 (3)
S1—C1	1.666 (3)	C21—H21A	0.9700
S2—C1	1.715 (3)	C21—H21B	0.9700
S2—C3	1.748 (3)	C22—H22A	0.9700
S3—C1	1.710 (3)	C22—H22B	0.9700
S3—C2	1.753 (3)	C12—O4	1.384 (5)
S4—C3	1.744 (3)	C12—C11	1.501 (5)
S5—C2	1.740 (3)	C12—H12A	0.9700
S6—C5	1.754 (3)	C12—H12B	0.9700
S7—C4	1.739 (2)	O4—H4	0.8200
S8—C6	1.726 (3)	C14—O5	1.360 (5)
S8—C4	1.751 (3)	C14—C13	1.506 (5)
S9—C6	1.730 (3)	C14—H14A	0.9700
S9—C5	1.755 (2)	C14—H14B	0.9700
S10—C6	1.653 (3)	O5—H5	0.8200
C2—C3	1.355 (4)	C7—O6	1.387 (6)
C4—C5	1.359 (3)	C7—C8	1.510 (5)
O1—C20	1.419 (4)	C7—H7A	0.9700
O1—H1	0.8200	C7—H7B	0.9700
O2—C22	1.416 (3)	O6—H6	0.8200
O2—H2	0.8200	O4'—H4'	0.8200
O3—C15	1.422 (4)	O5'—H5'	0.8200
O3—H3	0.8200	O6'—H6'	0.8200
N1—C19	1.517 (3)	N2—C11	1.517 (4)
N1—C21	1.525 (3)	N2—C8	1.524 (4)
N1—C16	1.526 (3)	N2—C10	1.525 (3)
N1—C18	1.529 (3)	N2—C13	1.526 (4)
C15—C16	1.515 (4)	C8—H8A	0.9700
C15—H15A	0.9700	C8—H8B	0.9700
C15—H15B	0.9700	C9—C9ⁱⁱ	1.511 (6)
C16—H16A	0.9700	C9—C10	1.524 (4)
C16—H16B	0.9700	C9—H9A	0.9700
C17—C17ⁱ	1.517 (5)	C9—H9B	0.9700
C17—C18	1.520 (3)	C10—H10A	0.9700
C17—H17A	0.9700	C10—H10B	0.9700
C17—H17B	0.9700	C11—H11A	0.9700
C18—H18A	0.9700	C11—H11B	0.9700
C18—H18B	0.9700	C13—H13A	0.9700
C19—C20	1.520 (4)	C13—H13B	0.9700
C19—H19A	0.9700

S5—Zn1—S4	95.39 (4)	C19—C20—H20A	110.3
S5—Zn1—S7	114.65 (5)	O1—C20—H20B	110.3
S4—Zn1—S7	112.42 (4)	C19—C20—H20B	110.3
S5—Zn1—S6	119.13 (4)	H20A—C20—H20B	108.5
S4—Zn1—S6	121.38 (4)	C22—C21—N1	117.3 (2)
S7—Zn1—S6	95.16 (4)	C22—C21—H21A	108.0
C1—S2—C3	98.74 (13)	N1—C21—H21A	108.0
C1—S3—C2	98.65 (13)	C22—C21—H21B	108.0
C3—S4—Zn1	94.44 (9)	N1—C21—H21B	108.0
C2—S5—Zn1	94.63 (9)	H21A—C21—H21B	107.2
C5—S6—Zn1	95.26 (8)	O2—C22—C21	113.1 (2)
C4—S7—Zn1	95.17 (9)	O2—C22—H22A	109.0
C6—S8—C4	98.40 (11)	C21—C22—H22A	109.0
C6—S9—C5	97.96 (12)	O2—C22—H22B	109.0
S1—C1—S3	123.13 (18)	C21—C22—H22B	109.0
S1—C1—S2	124.60 (18)	H22A—C22—H22B	107.8
S3—C1—S2	112.26 (15)	O4—C12—C11	110.5 (4)
C3—C2—S5	127.41 (19)	O4—C12—H12A	109.6
C3—C2—S3	115.23 (18)	C11—C12—H12A	109.5
S5—C2—S3	117.34 (14)	O4—C12—H12B	109.6
C2—C3—S4	127.16 (19)	C11—C12—H12B	109.6
C2—C3—S2	115.10 (19)	H12A—C12—H12B	108.1
S4—C3—S2	117.70 (15)	C12—O4—H4	100.0
C5—C4—S7	127.82 (18)	O5—C14—C13	113.3 (3)
C5—C4—S8	115.32 (18)	O5—C14—H14A	108.9
S7—C4—S8	116.85 (13)	C13—C14—H14A	108.9
C4—C5—S6	126.34 (18)	O5—C14—H14B	108.9
C4—C5—S9	115.79 (18)	C13—C14—H14B	108.9
S6—C5—S9	117.87 (14)	H14A—C14—H14B	107.7
S10—C6—S8	122.11 (15)	C14—O5—H5	112.3
S10—C6—S9	125.45 (15)	O6—C7—C8	109.5 (5)
S8—C6—S9	112.43 (13)	O6—C7—H7A	109.8
C20—O1—H1	109.5	C8—C7—H7A	109.8
C22—O2—H2	109.5	O6—C7—H7B	109.8
C15—O3—H3	109.5	C8—C7—H7B	109.8
C19—N1—C21	111.68 (18)	H7A—C7—H7B	108.2
C19—N1—C16	107.84 (18)	C7—O6—H6	109.5
C21—N1—C16	108.20 (18)	C11—N2—C8	105.6 (2)
C19—N1—C18	109.04 (17)	C11—N2—C10	111.1 (2)
C21—N1—C18	108.76 (18)	C8—N2—C10	110.7 (2)
C16—N1—C18	111.34 (18)	C11—N2—C13	112.3 (2)
O3—C15—C16	114.3 (2)	C8—N2—C13	110.9 (2)
O3—C15—H15A	108.7	C10—N2—C13	106.4 (2)
C16—C15—H15A	108.7	C7—C8—N2	115.9 (3)
O3—C15—H15B	108.7	C7—C8—H8A	108.3
C16—C15—H15B	108.7	N2—C8—H8A	108.3
H15A—C15—H15B	107.6	C7—C8—H8B	108.3
C15—C16—N1	117.8 (2)	N2—C8—H8B	108.3
C15—C16—H16A	107.9	H8A—C8—H8B	107.4
N1—C16—H16A	107.9	C9ⁱⁱ—C9—C10	109.6 (3)
C15—C16—H16B	107.9	C9ⁱⁱ—C9—H9A	109.8
N1—C16—H16B	107.9	C10—C9—H9A	109.8
H16A—C16—H16B	107.2	C9ⁱⁱ—C9—H9B	109.8
C17ⁱ—C17—C18	109.6 (3)	C10—C9—H9B	109.8
C17ⁱ—C17—H17A	109.8	H9A—C9—H9B	108.2
C18—C17—H17A	109.8	C9—C10—N2	114.5 (2)
C17ⁱ—C17—H17B	109.8	C9—C10—H10A	108.6
C18—C17—H17B	109.8	N2—C10—H10A	108.6
H17A—C17—H17B	108.2	C9—C10—H10B	108.6
C17—C18—N1	115.26 (19)	N2—C10—H10B	108.6
C17—C18—H18A	108.5	H10A—C10—H10B	107.6
N1—C18—H18A	108.5	C12—C11—N2	116.3 (3)
C17—C18—H18B	108.5	C12—C11—H11A	108.2
N1—C18—H18B	108.5	N2—C11—H11A	108.2
H18A—C18—H18B	107.5	C12—C11—H11B	108.2
N1—C19—C20	116.6 (2)	N2—C11—H11B	108.2
N1—C19—H19A	108.1	H11A—C11—H11B	107.4
C20—C19—H19A	108.1	C14—C13—N2	116.5 (3)
N1—C19—H19B	108.1	C14—C13—H13A	108.2
C20—C19—H19B	108.1	N2—C13—H13A	108.2
H19A—C19—H19B	107.3	C14—C13—H13B	108.2
O1—C20—C19	107.3 (3)	N2—C13—H13B	108.2
O1—C20—H20A	110.3	H13A—C13—H13B	107.3

C2—S3—C1—S1	−179.27 (18)	O3—C15—C16—N1	−86.4 (3)
C2—S3—C1—S2	1.05 (18)	C19—N1—C16—C15	−65.9 (3)
C3—S2—C1—S1	178.89 (19)	C21—N1—C16—C15	173.2 (2)
C3—S2—C1—S3	−1.43 (18)	C18—N1—C16—C15	53.7 (3)
Zn1—S5—C2—C3	7.0 (2)	C17ⁱ—C17—C18—N1	−172.2 (3)
Zn1—S5—C2—S3	−175.04 (12)	C19—N1—C18—C17	−178.3 (2)
C1—S3—C2—C3	−0.1 (2)	C21—N1—C18—C17	−56.3 (3)
C1—S3—C2—S5	−178.35 (15)	C16—N1—C18—C17	62.8 (3)
S5—C2—C3—S4	−0.1 (4)	C21—N1—C19—C20	−63.6 (3)
S3—C2—C3—S4	−178.16 (14)	C16—N1—C19—C20	177.6 (2)
S5—C2—C3—S2	177.16 (14)	C18—N1—C19—C20	56.6 (3)
S3—C2—C3—S2	−0.9 (3)	N1—C19—C20—O1	179.3 (2)
Zn1—S4—C3—C2	−6.8 (2)	C19—N1—C21—C22	−52.4 (3)
Zn1—S4—C3—S2	175.99 (13)	C16—N1—C21—C22	66.2 (3)
C1—S2—C3—C2	1.4 (2)	C18—N1—C21—C22	−172.8 (2)
C1—S2—C3—S4	178.98 (15)	N1—C21—C22—O2	90.2 (3)
Zn1—S7—C4—C5	−1.2 (2)	O6—C7—C8—N2	−92.6 (5)
Zn1—S7—C4—S8	177.39 (12)	C11—N2—C8—C7	178.7 (3)
C6—S8—C4—C5	3.0 (2)	C10—N2—C8—C7	−61.0 (4)
C6—S8—C4—S7	−175.81 (14)	C13—N2—C8—C7	56.8 (4)
S7—C4—C5—S6	−2.9 (3)	C9ⁱⁱ—C9—C10—N2	−172.9 (3)
S8—C4—C5—S6	178.43 (13)	C11—N2—C10—C9	59.0 (3)
S7—C4—C5—S9	176.60 (14)	C8—N2—C10—C9	−57.9 (3)
S8—C4—C5—S9	−2.0 (3)	C13—N2—C10—C9	−178.5 (3)
Zn1—S6—C5—C4	5.0 (2)	O4—C12—C11—N2	160.9 (4)
Zn1—S6—C5—S9	−174.57 (12)	C8—N2—C11—C12	174.2 (4)
C6—S9—C5—C4	0.1 (2)	C10—N2—C11—C12	54.1 (4)
C6—S9—C5—S6	179.63 (14)	C13—N2—C11—C12	−64.9 (4)
C4—S8—C6—S10	177.80 (16)	O5—C14—C13—N2	−69.8 (5)
C4—S8—C6—S9	−2.82 (16)	C11—N2—C13—C14	−51.4 (4)
C5—S9—C6—S10	−178.71 (17)	C8—N2—C13—C14	66.4 (4)
C5—S9—C6—S8	1.93 (16)	C10—N2—C13—C14	−173.1 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5ⁱⁱⁱ	0.82	2.03	2.800 (5)	157
O2—H2···O5ⁱⁱⁱ	0.82	1.93	2.668 (5)	149
O3—H3···O2^iv	0.82	2.16	2.923 (3)	154
O4—H4···O6ⁱⁱⁱ	0.82	2.07	2.887 (8)	179
O5—H5···O6	0.82	1.79	2.615 (9)	179
O6—H6···S2ⁱⁱ	0.82	2.92	3.540 (8)	134

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

Experimental details

Crystal data
Chemical formula	(C₁₆H₃₈N₂O₆)[Zn(C₃S₅)₂]
M_r	812.51
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	9.051 (5), 13.142 (7), 15.321 (8)
α, β, γ (°)	69.803 (5), 84.566 (5), 76.909 (6)
V (Å³)	1665.6 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.40
Crystal size (mm)	0.21 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.757, 0.767
No. of measured, independent and observed [I > 2σ(I)] reflections	11410, 7406, 6279
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.673

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.098, 1.05
No. of reflections	7406
No. of parameters	401
No. of restraints	4
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.89, −0.61

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5ⁱ	0.82	2.03	2.800 (5)	156.7
O2—H2···O5ⁱ	0.82	1.93	2.668 (5)	149.2
O3—H3···O2ⁱⁱ	0.82	2.16	2.923 (3)	154.0
O4—H4···O6ⁱ	0.82	2.07	2.887 (8)	179.3
O5—H5···O6	0.82	1.79	2.615 (9)	179.2
O6—H6···S2ⁱⁱⁱ	0.82	2.92	3.540 (8)	133.5

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

Acknowledgements

The authors acknowledge financial assistance from Sichuan University of Science and Engineering, the Institute of Functionalized Materials (grant No. 2009xjkpL004) and the Education Committee of Sichuan Province (Nos. 2011JY0052 and 13ZB0134).

References

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