Bis(μ-3,5-dimethyl-4H-1,2,4-triazol-4-amine-κ2N1:N2)bis­[bis­(thio­cyanato-κN)zinc]–bis­(3,5-dimethyl-4H-1,2,4-triazol-4-amine-κN1)bis­(thio­cyanato-κN)zinc (1/2)

Ge, H.-Y.; Li, B.-L.

doi:10.1107/S1600536811027887

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Pages m1100-m1101

doi:10.1107/S1600536811027887

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Bis(μ-3,5-dimethyl-4H-1,2,4-triazol-4-amine-κ²N¹:N²)bis[bis(thiocyanato-κN)zinc]–bis(3,5-dimethyl-4H-1,2,4-triazol-4-amine-κN¹)bis(thiocyanato-κN)zinc (1/2)

Hai-Yan Ge ^a and Bao-Long Li ^b ^*

^aCollege of Chemical Engineering, Taishan Medical College, Taian 271016, People's Republic of China, and ^bCollege of Chemistry, Chemical Engineering and Materials Science, The Key Laboratory of Organic Synthesis of Jiangsu Province, Soochow University, Suzhou 215123, People's Republic of China
^*Correspondence e-mail: libaolong@suda.edu.cn

(Received 17 June 2011; accepted 12 July 2011; online 16 July 2011)

In the crystal structure of the title 1:2 adduct, [Zn₂(NCS)₄(C₄H₈N₄)₂]·2[Zn(NCS)₂(C₄H₈N₄)₂] or (Ia)·2(Ib), each Zn^II atom is coordinated in a distorted tetrahedral geometry by four N atoms from two triazole rings of two 4-amino-3,5-dimethyl-1,2,4-triazole (admt) ligands and two NCS⁻ ligands. In (Ia), double N¹:N²-bridging admt ligands connect two Zn^II atoms, forming a dimer with a Zn₂(admt)₂ six-membered metallacycle located on a crystallographic inversion center. In (Ib), the admt ligands exhibit monodentate N¹-coordination modes. Weak N—H⋯N, N—H⋯S and C—H⋯S hydrogen bonds play an important role in the intermolecular packing. The S and C atoms of two thiocyanato ligands are disordered over two sets of sites in ratios of 0.57 (3):0.43 (3) and 0.63 (3):0.37 (3), respectively.

Related literature

For background to transition metal complexes of 1,2,4-triazole derivatives, see: Haasnoot (2000 ); Liu et al. (1999 , 2003 ); Zhao et al. (2002 ); Yi et al. (2004 ); Lavrenova et al. (1992 ); Zhang et al. (2007 , 2011 ). For related structures, see: Lavrenova et al. (1992); Zhang et al. (2007, 2011).

Experimental

Crystal data

[Zn₂(NCS)₄(C₄H₈N₄)₂]·2[Zn(NCS)₂(C₄H₈N₄)₂]
M_r = 1399.08
Triclinic, $[P \overline 1]$
a = 8.7665 (8) Å
b = 9.3100 (5) Å
c = 20.661 (3) Å
α = 92.560 (9)°
β = 95.926 (2)°
γ = 115.427 (6)°
V = 1507.3 (3) Å³
Z = 1
Mo Kα radiation
μ = 1.91 mm⁻¹
T = 223 K
0.34 × 0.30 × 0.14 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.564, T_max = 0.776
14831 measured reflections
5484 independent reflections
4550 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.090
S = 1.04
5484 reflections
387 parameters
30 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—N5	1.914 (3)
Zn1—N6	1.954 (3)
Zn1—N2ⁱ	2.011 (3)
Zn1—N1	2.012 (3)
Zn2—N16	1.926 (3)
Zn2—N15	1.962 (3)
Zn2—N7	1.990 (3)
Zn2—N11	2.000 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—HW1⋯S2ⁱⁱ	0.89 (2)	2.83 (3)	3.495 (3)	133 (3)
N4—HW2⋯N12	0.88 (2)	2.31 (2)	3.157 (4)	162 (3)
N10—HW3⋯N12ⁱⁱⁱ	0.85 (2)	2.47 (2)	3.251 (4)	152 (3)
N10—HW4⋯S4ⁱⁱⁱ	0.87 (2)	2.80 (2)	3.641 (4)	163 (3)
N14—HW5⋯N8^iv	0.88 (2)	2.20 (2)	3.061 (4)	167 (3)
N14—HW6⋯S3A^v	0.87 (2)	2.83 (3)	3.617 (9)	151 (3)
N14—HW6⋯S3B^v	0.87 (2)	2.83 (3)	3.542 (18)	140 (3)
C13—H13B⋯S3A^v	0.97	2.82	3.458 (7)	124
Symmetry codes: (ii) x-1, y-1, z; (iii) x, y-1, z; (iv) x-1, y, z; (v) -x+1, -y+1, -z+1.

Data collection: CrystalClear (Rigaku, 2000 ); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811027887/zq2110sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811027887/zq2110Isup2.hkl

checkCIF report

Comment top

A large number of mononuclear, oligonuclear and polynuclear transition metal complexes of 1,2,4-triazole derivatives have been synthesized and characterized due to their magnetic properties and novel topologies (Haasnoot, 2000). For 4-amino-3,5-dimethyl-1,2,4-triazole (admt), several Mn^II (Liu et al., 1999), Co^II, Ni^II (Zhao et al., 2002), Cu^II (Liu et al., 2003) and Cd^II compounds (Yi et al., 2004) were synthesized. Two Zn^II-admt compounds [Zn₂(admt)₂Cl₄] (Lavrenova et al., 1992) and [Zn₂(admt)₂I₄] (Zhang et al., 2011) were previously synthesized. Here we report the preparation and crystal structure of the title Zn^IIadduct [Zn₂(admt)₂(NCS)₄].2[Zn(admt)₂(NCS)₂] (I), containing a dimer [Zn₂(admt)₂(NCS)₄] (Ia) and two mononuclear [Zn(admt)₂(NCS)₂] (Ib) species in the same crystal structure (Fig. 1).

The molecular structure of the neutral dimer (Ia) is similar to [Zn₂(admt)₂Cl₄] (Lavrenova, et al., 1992) and [Zn₂(admt)₂I₄] (Zhang et al., 2011). Two Zn^II centers are connected by two admt ligands, resulting in a discrete Zn₂(admt)₂ six-membered metallacycle (geometric center located on a crystallographic inversion center) which represents the smallest closed cyclic structure with a 1:1 metal-to-ligand ratio (Fig. 2). One thiocyanate ligand is partially disordered over two sets of positions with site-occupancy factors of 0.57 (3) and 0.43 (3). Each Zn^II center is four-coordinated by two nitrogen donors of two admt ligands with Zn1—N1 = 2.012 (3) Å and Zn1—N2ⁱ = 2.011 (3) Å (symmetry code i: -x + 1,-y + 1,-z) and two nitrogen atoms of two thyocyanate ligands with Zn1—N5 = 1.914 (3) Å and Zn1—N6 = 1.954 (3) Å, forming a distorted tetrahedral geometry.

In the molecular structure of (Ib), a mononuclear species, the Zn^II atom is also four-coordinated by two nitrogen donors of two admt ligands with Zn2—N7 = 1.990 (3) Å and Zn2—N11 = 2.000 (3) Å and two nitrogen atoms of two thyocyante ligands with Zn2—N15 = 1.962 (3) Å and Zn2—N16 = 1.926 (3)Å, forming a distorted tetrahedral geometry. One thiocyanate ligand is also partially disordered over two sets of positions with site-occupancy factors of 0.63 (3) and 0.37 (3).

The Zn—N (triazole) and Zn—N (NCS) bond lengths in the dimer (Ia) are similar to the values in the mononuclear (Ib) and other Zn-triazole complexes (Zhang, et al., 2007 and 2011; Lavrenova, et al., 1992). The N—Zn—N bond angles in (Ia) are in the range of 103.49 (12) to 115.06 (13)°, and in the range of 103.14 (13) to 115.73 (12)° in (Ib). In comparison, the Zn/admt ratio is 1:1 in (Ia), but 1:2 in (Ib). The ligand admt, a 4-substituted 1,2,4-triazole, exhibits a N¹,N²-bidentate bridging coordination mode in (Ia), two admt ligands bridging two Zn^II atoms to form a dimer with a Zn···Zn distance of 3.6708 (8) Å. However, in the mononuclear species (Ib), admt shows a N¹ monodentate coordination mode. For a 4-substituted 1,2,4-triazole, blocking the N4 donor position through substitution, only the N¹ monodentate and N¹,N²-bidentate coordination modes are possible.

In the crystal structure of the title compound, there are hydrogen bonding interactions between amino groups NH₂ and S atoms [N4···S2ⁱⁱ (ii = x-1, y-1, z) = 3.495 (4) Å; N10···S4ⁱⁱⁱ (iii = x, y-1, z) = 3.641 (4) Å; N14···S3A^v (v = -x+1, -y+1, -z+1) = 3.617 (9) Å; N14···S3B^v= 3.542 (18) Å], and between amino groups NH₂ and the 2-position triazole N atom of (Ib) [N4···N12 = 3.157 (4) Å; N10···N12ⁱⁱⁱ = 3.251 (4) Å; N14···N8^iv (iv = x-1, y, z) = 3.061 (4) Å]. There are also weak hydrogen bonding interactions between methyl hydrogen atoms and S atoms [C13···S3A^v = 3.458 (7) Å]. No obviously π-π stacking interactions between the triazole rings were observed. These hydrogen bonding interaction stabilize the crystal structure of the title adduct (Fig. 3).

Related literature top

For background to transition metal complexes of 1,2,4-triazole derivatives, see: Haasnoot (2000); Liu et al. (1999, 2003); Zhao et al. (2002); Yi et al. (2004); Lavrenova et al. (1992); Zhang et al. (2007, 2011). For related structures, see: Lavrenova et al. (1992); Zhang et al. (2007, 2011).

Experimental top

A 15 ml aqueaous solution of 4-amino-3,5-dimethyl-1,2,4-triazole (admt) (1.0 mmol) was added to 10 ml aqueous solution Zn(NO₃)₂^.6H₂O (1.0 mmol) and KSCN (2.0 mmol) with stirring. The result solution was placed at room temperature. Colourless crystals were obtained after about one month. Anal. Calcd. for C₃₂H₄₈N₃₂S₈Zn₄: C, 27.47; H, 3.46; N, 32.05%. Found: C, 27.39; H, 3.41; N, 31.87%.

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title adduct. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius. Symmetry code (i): -x+1, -y+1, -z.
	Fig. 2. The dimeric structure of (Ia) with displacement ellipsoids drawn at the 30% probability level. Symmetry code (i): -x+1, -y+1, -z.
	Fig. 3. The mononuclear structure of (Ib) with displacement ellipsoids drawn at the 30% probability level.
	Fig. 4. A view of the hydrogen bond interactions (dashed lines) in the crystal structure pf the title compound. Symmetry codes: (ii) x-1, y-1, z; (iii) x, y-1, z; (iv) x-1, y, z; (v) -x+1, -y+1, -z+1.

Bis(µ-3,5-dimethyl-4H-1,2,4-triazol-4-amine- κ²N¹:N²)bis[bis(thiocyanato-κN)zinc]– bis(3,5-dimethyl-4H-1,2,4-triazol-4-amine- κN¹)bis(thiocyanato-κN)zinc (1/2) top

Crystal data top

[Zn₂(NCS)₄(C₄H₈N₄)₂]·2[Zn(NCS)₂(C₄H₈N₄)₂]	Z = 1
M_r = 1399.08	F(000) = 712
Triclinic, P1	D_x = 1.541 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 8.7665 (8) Å	Cell parameters from 5140 reflections
b = 9.3100 (5) Å	θ = 3.1–25.4°
c = 20.661 (3) Å	µ = 1.91 mm⁻¹
α = 92.560 (9)°	T = 223 K
β = 95.926 (2)°	Block, colourless
γ = 115.427 (6)°	0.34 × 0.30 × 0.14 mm
V = 1507.3 (3) Å³

Data collection top

Rigaku Mercury CCD diffractometer	5484 independent reflections
Radiation source: fine-focus sealed tube	4550 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.4°, θ_min = 3.1°
ω scans	h = −10→10
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −11→11
T_min = 0.564, T_max = 0.776	l = −22→24
14831 measured reflections

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0309P)² + 1.5778P] where P = (F_o² + 2F_c²)/3
5484 reflections	(Δ/σ)_max < 0.001
387 parameters	Δρ_max = 0.55 e Å⁻³
30 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[Zn₂(NCS)₄(C₄H₈N₄)₂]·2[Zn(NCS)₂(C₄H₈N₄)₂]	γ = 115.427 (6)°
M_r = 1399.08	V = 1507.3 (3) Å³
Triclinic, P1	Z = 1
a = 8.7665 (8) Å	Mo Kα radiation
b = 9.3100 (5) Å	µ = 1.91 mm⁻¹
c = 20.661 (3) Å	T = 223 K
α = 92.560 (9)°	0.34 × 0.30 × 0.14 mm
β = 95.926 (2)°

Data collection top

Rigaku Mercury CCD diffractometer	5484 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	4550 reflections with I > 2σ(I)
T_min = 0.564, T_max = 0.776	R_int = 0.034
14831 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	30 restraints
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.55 e Å⁻³
5484 reflections	Δρ_min = −0.36 e Å⁻³
387 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	Occ. (<1)
Zn1	0.41245 (5)	0.63167 (5)	0.031974 (19)	0.03212 (12)
Zn2	0.54622 (5)	0.17586 (5)	0.34171 (2)	0.03310 (12)
S1A	−0.0157 (7)	0.7863 (17)	0.0518 (4)	0.065 (2)	0.57 (3)
C5A	0.1191 (16)	0.7222 (15)	0.0350 (8)	0.0438 (11)	0.57 (3)
S1B	0.032 (2)	0.858 (2)	0.0278 (11)	0.087 (5)	0.43 (3)
C5B	0.143 (2)	0.7546 (19)	0.0296 (10)	0.0438 (11)	0.43 (3)
S3A	0.786 (2)	0.3793 (9)	0.5571 (3)	0.110 (3)	0.63 (3)
C15A	0.7285 (16)	0.3210 (15)	0.4808 (4)	0.0438 (11)	0.63 (3)
S3B	0.717 (2)	0.397 (2)	0.5555 (7)	0.111 (6)	0.37 (3)
C15B	0.690 (3)	0.329 (3)	0.4793 (7)	0.0438 (11)	0.37 (3)
S2	0.82933 (14)	0.97029 (14)	0.20364 (5)	0.0594 (3)
S4	0.80473 (14)	0.52143 (13)	0.18706 (6)	0.0549 (3)
N1	0.3658 (3)	0.4141 (3)	0.06001 (13)	0.0294 (6)
N2	0.4699 (3)	0.3396 (3)	0.04834 (13)	0.0318 (6)
N3	0.3122 (3)	0.2214 (3)	0.12156 (13)	0.0305 (6)
N4	0.2470 (4)	0.1121 (4)	0.16740 (15)	0.0408 (7)
N5	0.2201 (4)	0.6795 (4)	0.02509 (17)	0.0471 (8)
N6	0.5860 (4)	0.7776 (4)	0.10139 (16)	0.0439 (8)
N7	0.5476 (3)	−0.0370 (3)	0.33052 (14)	0.0323 (7)
N8	0.6787 (4)	−0.0591 (4)	0.36615 (14)	0.0384 (7)
N9	0.5265 (4)	−0.2668 (3)	0.29609 (14)	0.0329 (7)
N10	0.4718 (4)	−0.4100 (4)	0.25494 (17)	0.0421 (8)
N11	0.3205 (3)	0.1727 (3)	0.35209 (13)	0.0327 (7)
N12	0.2521 (4)	0.2503 (3)	0.31036 (13)	0.0343 (7)
N13	0.1194 (3)	0.1971 (3)	0.39608 (13)	0.0292 (6)
N14	0.0123 (4)	0.1907 (4)	0.44340 (15)	0.0401 (7)
N15	0.6844 (4)	0.2796 (4)	0.42611 (16)	0.0474 (8)
N16	0.6258 (4)	0.3019 (4)	0.27023 (16)	0.0446 (8)
C1	0.4354 (4)	0.2233 (4)	0.08645 (16)	0.0326 (8)
C2	0.2705 (4)	0.3398 (4)	0.10392 (15)	0.0286 (7)
C3	0.5138 (5)	0.1114 (4)	0.09104 (19)	0.0443 (9)
H3A	0.4279	0.0037	0.0764	0.066*
H3B	0.5608	0.1156	0.1361	0.066*
H3C	0.6041	0.1413	0.0637	0.066*
C4	0.1382 (5)	0.3744 (5)	0.12993 (18)	0.0405 (9)
H4C	0.1100	0.4433	0.1022	0.061*
H4D	0.1804	0.4274	0.1739	0.061*
H4E	0.0371	0.2752	0.1308	0.061*
C6	0.6884 (5)	0.8569 (4)	0.14333 (19)	0.0374 (8)
C7	0.6631 (5)	−0.1990 (4)	0.34402 (18)	0.0395 (9)
C8	0.4587 (4)	−0.1629 (4)	0.28850 (16)	0.0312 (8)
C9	0.7755 (6)	−0.2747 (6)	0.3658 (2)	0.0694 (14)
H9A	0.8615	−0.2061	0.4012	0.104*
H9B	0.8305	−0.2903	0.3295	0.104*
H9C	0.7079	−0.3773	0.3810	0.104*
C10	0.3097 (5)	−0.1893 (5)	0.2399 (2)	0.0510 (11)
H10C	0.2944	−0.0922	0.2395	0.077*
H10D	0.2083	−0.2753	0.2516	0.077*
H10E	0.3293	−0.2177	0.1968	0.077*
C11	0.1301 (4)	0.2624 (4)	0.33821 (16)	0.0286 (7)
C12	0.2390 (4)	0.1428 (4)	0.40368 (17)	0.0317 (8)
C13	0.0177 (5)	0.3329 (5)	0.31128 (17)	0.0406 (9)
H13A	0.0787	0.4160	0.2843	0.061*
H13B	−0.0168	0.3785	0.3469	0.061*
H13C	−0.0825	0.2505	0.2850	0.061*
C14	0.2714 (5)	0.0639 (5)	0.4602 (2)	0.0513 (11)
H14C	0.3331	0.0038	0.4482	0.077*
H14D	0.1638	−0.0082	0.4734	0.077*
H14E	0.3388	0.1440	0.4962	0.077*
C16	0.7019 (4)	0.3929 (4)	0.23544 (18)	0.0351 (8)
HW1	0.139 (3)	0.046 (4)	0.1524 (17)	0.042*
HW2	0.238 (5)	0.164 (4)	0.2027 (13)	0.042*
HW3	0.441 (5)	−0.481 (4)	0.2816 (15)	0.042*
HW4	0.558 (3)	−0.405 (4)	0.2359 (17)	0.042*
HW5	−0.091 (3)	0.127 (4)	0.4243 (17)	0.042*
HW6	0.036 (5)	0.290 (3)	0.4554 (18)	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0362 (2)	0.0312 (2)	0.0369 (2)	0.02067 (19)	0.01070 (18)	0.00640 (17)
Zn2	0.0314 (2)	0.0340 (2)	0.0403 (2)	0.01972 (19)	0.00779 (18)	0.00290 (18)
S1A	0.0510 (18)	0.081 (4)	0.077 (3)	0.047 (2)	−0.0059 (19)	−0.026 (3)
C5A	0.034 (3)	0.041 (2)	0.055 (2)	0.017 (2)	0.0000 (18)	−0.0045 (19)
S1B	0.078 (5)	0.085 (7)	0.111 (8)	0.067 (6)	−0.048 (6)	−0.056 (6)
C5B	0.034 (3)	0.041 (2)	0.055 (2)	0.017 (2)	0.0000 (18)	−0.0045 (19)
S3A	0.182 (8)	0.066 (2)	0.046 (2)	0.030 (4)	−0.021 (3)	−0.0143 (17)
C15A	0.034 (3)	0.041 (2)	0.055 (2)	0.017 (2)	0.0000 (18)	−0.0045 (19)
S3B	0.116 (7)	0.085 (7)	0.067 (5)	−0.018 (4)	0.038 (4)	−0.033 (4)
C15B	0.034 (3)	0.041 (2)	0.055 (2)	0.017 (2)	0.0000 (18)	−0.0045 (19)
S2	0.0541 (6)	0.0548 (7)	0.0472 (6)	0.0039 (5)	0.0093 (5)	−0.0087 (5)
S4	0.0566 (7)	0.0515 (6)	0.0570 (7)	0.0211 (5)	0.0149 (5)	0.0211 (5)
N1	0.0330 (15)	0.0278 (15)	0.0312 (15)	0.0160 (13)	0.0072 (12)	0.0035 (12)
N2	0.0374 (16)	0.0299 (15)	0.0337 (16)	0.0195 (13)	0.0074 (13)	0.0031 (13)
N3	0.0359 (16)	0.0276 (15)	0.0283 (15)	0.0133 (13)	0.0062 (13)	0.0065 (12)
N4	0.0488 (19)	0.0378 (18)	0.0341 (18)	0.0158 (16)	0.0101 (16)	0.0085 (14)
N5	0.0395 (18)	0.051 (2)	0.063 (2)	0.0297 (17)	0.0105 (16)	0.0110 (17)
N6	0.0486 (19)	0.0391 (18)	0.0459 (19)	0.0225 (16)	0.0027 (17)	−0.0032 (16)
N7	0.0350 (16)	0.0318 (16)	0.0379 (17)	0.0216 (14)	0.0051 (13)	0.0070 (13)
N8	0.0424 (17)	0.0438 (18)	0.0373 (17)	0.0281 (15)	0.0006 (14)	−0.0003 (14)
N9	0.0368 (16)	0.0293 (15)	0.0369 (16)	0.0184 (13)	0.0055 (14)	0.0043 (13)
N10	0.047 (2)	0.0292 (17)	0.054 (2)	0.0193 (16)	0.0073 (16)	0.0054 (15)
N11	0.0351 (16)	0.0395 (17)	0.0342 (16)	0.0253 (14)	0.0075 (13)	0.0078 (13)
N12	0.0366 (16)	0.0415 (17)	0.0335 (16)	0.0243 (14)	0.0082 (13)	0.0059 (13)
N13	0.0236 (14)	0.0370 (16)	0.0296 (15)	0.0140 (13)	0.0094 (12)	0.0067 (12)
N14	0.0337 (17)	0.052 (2)	0.0390 (18)	0.0202 (17)	0.0140 (14)	0.0058 (16)
N15	0.0370 (17)	0.054 (2)	0.052 (2)	0.0229 (16)	−0.0020 (16)	−0.0105 (17)
N16	0.0428 (18)	0.0456 (19)	0.053 (2)	0.0238 (16)	0.0151 (16)	0.0129 (17)
C1	0.040 (2)	0.0259 (17)	0.0331 (19)	0.0150 (16)	0.0073 (16)	0.0042 (15)
C2	0.0316 (18)	0.0267 (17)	0.0248 (17)	0.0108 (15)	0.0025 (14)	−0.0006 (14)
C3	0.064 (3)	0.038 (2)	0.044 (2)	0.032 (2)	0.017 (2)	0.0111 (17)
C4	0.042 (2)	0.046 (2)	0.041 (2)	0.0237 (18)	0.0148 (17)	0.0091 (17)
C6	0.043 (2)	0.0328 (19)	0.041 (2)	0.0175 (18)	0.0173 (19)	0.0079 (17)
C7	0.044 (2)	0.042 (2)	0.040 (2)	0.0264 (19)	0.0041 (18)	0.0049 (17)
C8	0.0326 (18)	0.0298 (18)	0.0367 (19)	0.0173 (16)	0.0095 (15)	0.0084 (16)
C9	0.075 (3)	0.070 (3)	0.079 (3)	0.056 (3)	−0.023 (3)	−0.012 (3)
C10	0.048 (2)	0.037 (2)	0.069 (3)	0.0246 (19)	−0.011 (2)	0.003 (2)
C11	0.0298 (17)	0.0305 (18)	0.0291 (18)	0.0173 (15)	0.0013 (14)	0.0021 (14)
C12	0.0267 (17)	0.0367 (19)	0.037 (2)	0.0172 (16)	0.0074 (15)	0.0097 (16)
C13	0.043 (2)	0.054 (2)	0.035 (2)	0.0311 (19)	0.0023 (17)	0.0040 (17)
C14	0.048 (2)	0.065 (3)	0.053 (3)	0.033 (2)	0.015 (2)	0.029 (2)
C16	0.0323 (19)	0.037 (2)	0.042 (2)	0.0225 (17)	0.0021 (17)	−0.0013 (17)

Geometric parameters (Å, º) top

Zn1—N5	1.914 (3)	N10—HW4	0.868 (18)
Zn1—N6	1.954 (3)	N11—C12	1.318 (4)
Zn1—N2ⁱ	2.011 (3)	N11—N12	1.395 (4)
Zn1—N1	2.012 (3)	N12—C11	1.309 (4)
Zn2—N16	1.926 (3)	N13—C12	1.344 (4)
Zn2—N15	1.962 (3)	N13—C11	1.359 (4)
Zn2—N7	1.990 (3)	N13—N14	1.410 (4)
Zn2—N11	2.000 (3)	N14—HW5	0.879 (18)
S1A—C5A	1.595 (10)	N14—HW6	0.871 (18)
C5A—N5	1.147 (10)	N16—C16	1.161 (4)
S1B—C5B	1.629 (12)	C1—C3	1.475 (5)
C5B—N5	1.173 (12)	C2—C4	1.474 (5)
S3A—C15A	1.600 (9)	C3—H3A	0.9700
C15A—N15	1.147 (8)	C3—H3B	0.9700
S3B—C15B	1.626 (13)	C3—H3C	0.9700
C15B—N15	1.158 (12)	C4—H4C	0.9700
S2—C6	1.624 (4)	C4—H4D	0.9700
S4—C16	1.615 (4)	C4—H4E	0.9700
N1—C2	1.310 (4)	C7—C9	1.485 (5)
N1—N2	1.395 (4)	C8—C10	1.485 (5)
N2—C1	1.315 (4)	C9—H9A	0.9700
N2—Zn1ⁱ	2.011 (3)	C9—H9B	0.9700
N3—C2	1.355 (4)	C9—H9C	0.9700
N3—C1	1.357 (4)	C10—H10C	0.9700
N3—N4	1.399 (4)	C10—H10D	0.9700
N4—HW1	0.889 (18)	C10—H10E	0.9700
N4—HW2	0.882 (18)	C11—C13	1.478 (5)
N6—C6	1.147 (5)	C12—C14	1.474 (5)
N7—C8	1.312 (4)	C13—H13A	0.9700
N7—N8	1.395 (4)	C13—H13B	0.9700
N8—C7	1.305 (4)	C13—H13C	0.9700
N9—C8	1.342 (4)	C14—H14C	0.9700
N9—C7	1.365 (5)	C14—H14D	0.9700
N9—N10	1.413 (4)	C14—H14E	0.9700
N10—HW3	0.853 (18)

N5—Zn1—N6	109.04 (14)	N2—C1—C3	127.0 (3)
N5—Zn1—N2ⁱ	115.00 (13)	N3—C1—C3	124.7 (3)
N6—Zn1—N2ⁱ	105.22 (12)	N1—C2—N3	108.2 (3)
N5—Zn1—N1	114.77 (12)	N1—C2—C4	127.1 (3)
N6—Zn1—N1	103.49 (12)	N3—C2—C4	124.7 (3)
N2ⁱ—Zn1—N1	108.28 (11)	C1—C3—H3A	109.5
N16—Zn2—N15	112.81 (14)	C1—C3—H3B	109.5
N16—Zn2—N7	112.84 (13)	H3A—C3—H3B	109.5
N15—Zn2—N7	106.15 (13)	C1—C3—H3C	109.5
N16—Zn2—N11	105.92 (12)	H3A—C3—H3C	109.5
N15—Zn2—N11	103.13 (12)	H3B—C3—H3C	109.5
N7—Zn2—N11	115.73 (11)	C2—C4—H4C	109.5
N5—C5A—S1A	177.3 (14)	C2—C4—H4D	109.5
N5—C5B—S1B	174.2 (18)	H4C—C4—H4D	109.5
N15—C15A—S3A	178.8 (7)	C2—C4—H4E	109.5
N15—C15B—S3B	174.4 (13)	H4C—C4—H4E	109.5
C2—N1—N2	108.0 (3)	H4D—C4—H4E	109.5
C2—N1—Zn1	127.6 (2)	N6—C6—S2	178.4 (4)
N2—N1—Zn1	122.2 (2)	N8—C7—N9	109.4 (3)
C1—N2—N1	107.5 (3)	N8—C7—C9	126.4 (4)
C1—N2—Zn1ⁱ	127.7 (2)	N9—C7—C9	124.2 (3)
N1—N2—Zn1ⁱ	122.1 (2)	N7—C8—N9	108.1 (3)
C2—N3—C1	108.1 (3)	N7—C8—C10	127.2 (3)
C2—N3—N4	129.1 (3)	N9—C8—C10	124.7 (3)
C1—N3—N4	122.8 (3)	C7—C9—H9A	109.5
N3—N4—HW1	108 (2)	C7—C9—H9B	109.5
N3—N4—HW2	109 (2)	H9A—C9—H9B	109.5
HW1—N4—HW2	103 (3)	C7—C9—H9C	109.5
C5A—N5—Zn1	164.9 (8)	H9A—C9—H9C	109.5
C5B—N5—Zn1	158.6 (10)	H9B—C9—H9C	109.5
C6—N6—Zn1	176.7 (3)	C8—C10—H10C	109.5
C8—N7—N8	108.9 (3)	C8—C10—H10D	109.5
C8—N7—Zn2	132.1 (2)	H10C—C10—H10D	109.5
N8—N7—Zn2	118.4 (2)	C8—C10—H10E	109.5
C7—N8—N7	106.2 (3)	H10C—C10—H10E	109.5
C8—N9—C7	107.5 (3)	H10D—C10—H10E	109.5
C8—N9—N10	123.4 (3)	N12—C11—N13	109.4 (3)
C7—N9—N10	128.7 (3)	N12—C11—C13	126.1 (3)
N9—N10—HW3	103 (3)	N13—C11—C13	124.5 (3)
N9—N10—HW4	108 (3)	N11—C12—N13	108.0 (3)
HW3—N10—HW4	114 (4)	N11—C12—C14	126.6 (3)
C12—N11—N12	108.5 (3)	N13—C12—C14	125.3 (3)
C12—N11—Zn2	128.6 (2)	C11—C13—H13A	109.5
N12—N11—Zn2	120.5 (2)	C11—C13—H13B	109.5
C11—N12—N11	106.4 (3)	H13A—C13—H13B	109.5
C12—N13—C11	107.6 (3)	C11—C13—H13C	109.5
C12—N13—N14	123.5 (3)	H13A—C13—H13C	109.5
C11—N13—N14	128.8 (3)	H13B—C13—H13C	109.5
N13—N14—HW5	105 (2)	C12—C14—H14C	109.5
N13—N14—HW6	106 (3)	C12—C14—H14D	109.5
HW5—N14—HW6	118 (4)	H14C—C14—H14D	109.5
C15A—N15—Zn2	163.6 (7)	C12—C14—H14E	109.5
C15B—N15—Zn2	148.3 (11)	H14C—C14—H14E	109.5
C16—N16—Zn2	167.0 (3)	H14D—C14—H14E	109.5
N2—C1—N3	108.2 (3)	N16—C16—S4	178.7 (3)

N5—Zn1—N1—C2	−39.3 (3)	N2—N1—C2—N3	1.0 (3)
N6—Zn1—N1—C2	79.4 (3)	Zn1—N1—C2—N3	−162.3 (2)
N2ⁱ—Zn1—N1—C2	−169.3 (3)	N2—N1—C2—C4	−178.2 (3)
N5—Zn1—N1—N2	159.6 (2)	Zn1—N1—C2—C4	18.5 (5)
N6—Zn1—N1—N2	−81.7 (2)	C1—N3—C2—N1	−0.8 (3)
N2ⁱ—Zn1—N1—N2	29.6 (3)	N4—N3—C2—N1	179.0 (3)
C2—N1—N2—C1	−0.8 (3)	C1—N3—C2—C4	178.5 (3)
Zn1—N1—N2—C1	163.5 (2)	N4—N3—C2—C4	−1.8 (5)
C2—N1—N2—Zn1ⁱ	162.0 (2)	N7—N8—C7—N9	−0.4 (4)
Zn1—N1—N2—Zn1ⁱ	−33.6 (3)	N7—N8—C7—C9	178.8 (4)
N16—Zn2—N7—C8	−66.9 (3)	C8—N9—C7—N8	0.8 (4)
N15—Zn2—N7—C8	169.0 (3)	N10—N9—C7—N8	173.8 (3)
N11—Zn2—N7—C8	55.3 (3)	C8—N9—C7—C9	−178.4 (4)
N16—Zn2—N7—N8	102.7 (2)	N10—N9—C7—C9	−5.4 (6)
N15—Zn2—N7—N8	−21.4 (3)	N8—N7—C8—N9	0.7 (4)
N11—Zn2—N7—N8	−135.1 (2)	Zn2—N7—C8—N9	171.0 (2)
C8—N7—N8—C7	−0.1 (4)	N8—N7—C8—C10	−178.8 (3)
Zn2—N7—N8—C7	−172.0 (2)	Zn2—N7—C8—C10	−8.4 (6)
N16—Zn2—N11—C12	−159.0 (3)	C7—N9—C8—N7	−0.9 (4)
N15—Zn2—N11—C12	−40.3 (3)	N10—N9—C8—N7	−174.3 (3)
N7—Zn2—N11—C12	75.2 (3)	C7—N9—C8—C10	178.5 (4)
N16—Zn2—N11—N12	1.3 (3)	N10—N9—C8—C10	5.1 (5)
N15—Zn2—N11—N12	120.0 (2)	N11—N12—C11—N13	0.5 (4)
N7—Zn2—N11—N12	−124.6 (2)	N11—N12—C11—C13	−178.4 (3)
C12—N11—N12—C11	−0.7 (4)	C12—N13—C11—N12	−0.2 (4)
Zn2—N11—N12—C11	−164.5 (2)	N14—N13—C11—N12	176.7 (3)
N15—Zn2—N16—C16	17.4 (14)	C12—N13—C11—C13	178.8 (3)
N7—Zn2—N16—C16	−102.9 (13)	N14—N13—C11—C13	−4.3 (5)
N11—Zn2—N16—C16	129.5 (13)	N12—N11—C12—N13	0.6 (4)
N1—N2—C1—N3	0.3 (3)	Zn2—N11—C12—N13	162.8 (2)
Zn1ⁱ—N2—C1—N3	−161.3 (2)	N12—N11—C12—C14	−179.4 (4)
N1—N2—C1—C3	179.9 (3)	Zn2—N11—C12—C14	−17.2 (5)
Zn1ⁱ—N2—C1—C3	18.3 (5)	C11—N13—C12—N11	−0.3 (4)
C2—N3—C1—N2	0.2 (4)	N14—N13—C12—N11	−177.4 (3)
N4—N3—C1—N2	−179.5 (3)	C11—N13—C12—C14	179.7 (4)
C2—N3—C1—C3	−179.3 (3)	N14—N13—C12—C14	2.6 (5)
N4—N3—C1—C3	0.9 (5)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—HW1···S2ⁱⁱ	0.89 (2)	2.83 (3)	3.495 (3)	133 (3)
N4—HW2···N12	0.88 (2)	2.31 (2)	3.157 (4)	162 (3)
N10—HW3···N12ⁱⁱⁱ	0.85 (2)	2.47 (2)	3.251 (4)	152 (3)
N10—HW4···S4ⁱⁱⁱ	0.87 (2)	2.80 (2)	3.641 (4)	163 (3)
N14—HW5···N8^iv	0.88 (2)	2.20 (2)	3.061 (4)	167 (3)
N14—HW6···S3A^v	0.87 (2)	2.83 (3)	3.617 (9)	151 (3)
N14—HW6···S3B^v	0.87 (2)	2.83 (3)	3.542 (18)	140 (3)
C13—H13B···S3A^v	0.97	2.82	3.458 (7)	124

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

Experimental details

Crystal data
Chemical formula	[Zn₂(NCS)₄(C₄H₈N₄)₂]·2[Zn(NCS)₂(C₄H₈N₄)₂]
M_r	1399.08
Crystal system, space group	Triclinic, P1
Temperature (K)	223
a, b, c (Å)	8.7665 (8), 9.3100 (5), 20.661 (3)
α, β, γ (°)	92.560 (9), 95.926 (2), 115.427 (6)
V (Å³)	1507.3 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.91
Crystal size (mm)	0.34 × 0.30 × 0.14

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.564, 0.776
No. of measured, independent and observed [I > 2σ(I)] reflections	14831, 5484, 4550
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.090, 1.04
No. of reflections	5484
No. of parameters	387
No. of restraints	30
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.36

Computer programs: CrystalClear (Rigaku, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Zn1—N5	1.914 (3)	Zn2—N16	1.926 (3)
Zn1—N6	1.954 (3)	Zn2—N15	1.962 (3)
Zn1—N2ⁱ	2.011 (3)	Zn2—N7	1.990 (3)
Zn1—N1	2.012 (3)	Zn2—N11	2.000 (3)

N5—Zn1—N6	109.04 (14)	N16—Zn2—N15	112.81 (14)
N5—Zn1—N2ⁱ	115.00 (13)	N16—Zn2—N7	112.84 (13)
N6—Zn1—N2ⁱ	105.22 (12)	N15—Zn2—N7	106.15 (13)
N5—Zn1—N1	114.77 (12)	N16—Zn2—N11	105.92 (12)
N6—Zn1—N1	103.49 (12)	N15—Zn2—N11	103.13 (12)
N2ⁱ—Zn1—N1	108.28 (11)	N7—Zn2—N11	115.73 (11)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—HW1···S2ⁱⁱ	0.889 (18)	2.83 (3)	3.495 (3)	133 (3)
N4—HW2···N12	0.882 (18)	2.31 (2)	3.157 (4)	162 (3)
N10—HW3···N12ⁱⁱⁱ	0.853 (18)	2.47 (2)	3.251 (4)	152 (3)
N10—HW4···S4ⁱⁱⁱ	0.868 (18)	2.80 (2)	3.641 (4)	163 (3)
N14—HW5···N8^iv	0.879 (18)	2.20 (2)	3.061 (4)	167 (3)
N14—HW6···S3A^v	0.871 (18)	2.83 (3)	3.617 (9)	151 (3)
N14—HW6···S3B^v	0.871 (18)	2.83 (3)	3.542 (18)	140 (3)
C13—H13B···S3A^v	0.97	2.82	3.458 (7)	123.9

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

Acknowledgements

This work was supported by the Funds of the Key Laboratory of Organic Synthesis Chemistry of Jiangsu Province and the Youth Foundation of Taishan Medical College, People's Republic of China.

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