[(1-Azulen­yl)methane­thiol­ato-κS](1,4,8,12-tetra­azacyclo­penta­decane-κ4N)zinc(II) perchlorate

Görls, H.; Notni, J.; Anders, E.

doi:10.1107/S1600536807047514

metal-organic compounds

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Volume 64| Part 1| January 2008| Page m203

https://doi.org/10.1107/S1600536807047514

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[(1-Azulenyl)methanethiolato-κS](1,4,8,12-tetraazacyclopentadecane-κ⁴N)zinc(II) perchlorate

Helmar Görls,^a Johannes Notni ^b and Ernst Anders ^b ^*

^aInstitut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Lessingstrasse 8, 07743 Jena, Germany, and ^bInstitut für Organische Chemie und Makromolekulare Chemie, Friedrich-Schiller-Universität Jena, Humboldtstrasse 10, 07743 Jena, Germany
^*Correspondence e-mail: goerls@xa.nlwl.uni-jena.de

(Received 12 September 2007; accepted 27 September 2007; online 18 December 2007)

In the title compound, [Zn(C₁₁H₂₆N₄)(C₁₁H₉S)]ClO₄, the Zn^II atom is five-coordinated by four N atoms from a neutral 1,4,8,12-tetraazacyclopentadecane aza-macrocycle molecule, and one S atom from an azulenylmethanethiolate ligand. Only monomers are found in the crystal. The coordination geometry can be described as trigonal bipyramidal, with the thiolate group in an equatorial position. The Zn—N and Zn—S distances are in the usual ranges for this type of complex.

Related literature

For related literature, see: Notni, Görls et al. (2006 ); Notni, Schenk et al. (2006 ); Notni et al. (2007 ); Salter et al. (2005 ); Schenk et al. (2006 ).

Experimental

Crystal data

[Zn(C₁₁H₂₆N₄)(C₁₁H₉S)]ClO₄
M_r = 552.42
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.0795 (1) Å
b = 13.7163 (3) Å
c = 23.0913 (5) Å
V = 2559.00 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.18 mm⁻¹
T = 183 (2) K
0.06 × 0.06 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
18270 measured reflections
5858 independent reflections
4978 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.138
S = 1.04
5858 reflections
295 parameters
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.65 e Å⁻³
Absolute structure: Flack (1983 ), 2541 Friedel pairs
Flack parameter: 0.002 (16)

Table 1
Selected geometric parameters (Å, °)

Zn—N4	2.134 (4)
Zn—N2	2.139 (4)
Zn—N3	2.235 (3)
Zn—N1	2.272 (4)
Zn—S	2.2804 (10)

N4—Zn—N2	130.42 (16)
N4—Zn—N3	86.95 (15)
N2—Zn—N3	85.81 (17)
N4—Zn—N1	91.17 (15)
N2—Zn—N1	80.05 (17)
N3—Zn—N1	159.70 (15)
N4—Zn—S	118.88 (11)
N2—Zn—S	110.70 (12)
N3—Zn—S	99.13 (10)
N1—Zn—S	99.46 (11)

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1990 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807047514/hy2083sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807047514/hy2083Isup2.hkl

checkCIF report

Comment top

The title compound belongs to a series of zinc thiolate complexes with azamacrocyclic ligands (Notni, Görls et al., 2006), which are potent model systems for a number of zinc enzymes (Schenk et al., 2006). These compounds possess nucleophilic p-methylthiolate or phenylmethylthiolate residues, the nucleophilicity of which is influenced by the nature of the macrocyclic ligand (Notni, Schenk et al., 2006; Notni et al., 2007). In order to gain insight into the electronic properties of the sulfur atom, azulenylmethyl derivatives were believed to allow a qualitative estimation of electron density at the thiolate sulfur employing VIS spectroscopy. However, the project failed since most of the desired complexes were elusive due to degradation processes during synthesis.

In crystalline form, the title compound is air-stable for several months. The crystal structure of the title compound contains a monovalent zinc(II) complex cation and a discrete perchlorate anion as shown in Fig. 1. Within the cation, the Zn^II atom is coordinated by four N atoms and one S atom. Whether the coordination polyhedron can be assigned to tetragonal-pyramidal or trigonal-bipyramidal type is a question, which has been discussed in detail before (Notni, Görls et al., 2006). Following the argumentation given therein, we consider the title structure being trigonal-bipyramidal since pairs of opposing short Zn—N bond lengths [2.134 (4) and 2.139 (4) Å] as well as long Zn—N bond lengths [2.235 (3) and 2.272 (4) Å] are found. This is the largest difference between short and long Zn—N bond distances found for this type of zinc complexes (Notni, Görls et al., 2006; Salter et al., 2005). The pair of long N—Zn—N bonds is considered the axis of the trigonal bipyramid, the thiolate group thus being found in the equatorial position. The Zn—S bond length of 2.280 (1)Å is within the usual range for this kind of compounds (2.27–2.32 Å). The N atoms in these complexes are chiral in nature and the absolute configuration could be determined. In analogy to similar zinc–thiolate complexes of 1,4,8,12-tetraazacyclopentadecane, the N-bound H atoms are found in (+ – – –) positions ('+' denotes the H atom being positioned at the thiolate side of the macrocycle and '–' at the opposite side).

Related literature top

For related literature, see: Notni, Görls et al. (2006); Notni, Schenk et al. (2006); Notni et al. (2007); Salter et al. (2005); Schenk et al. (2006).

Experimental top

The title compound was prepared according to the published procedure (Notni, Görls et al., 2006). A solution of zinc perchlorate hexahydrate (0.750 g, 2 mmol) and 1,4,8,12,tetraazacyclopentadecane (0.430 g, 2 mmol) in methanol (20 ml) was heated for 15 min. Then a solution of potassium hydroxide (0.112 g, 2 mmol) and 1-azulenylmethylthiol (0.350 g, 2 mmol) in methanol (5 ml) was added dropwise, whereupon a fine-crystalline precipitate of potassium perchlorate was obtained. This was filtered off, and from the remaining deep-blue solution, blue needle crystals of the title compound precipitated after 5 min which were collected on a filter funnel and dried in vacuum. Yield 66% (0.731 g). m. p. 473.5–475.5 K. Analysis, calculated for C₂₂H₃₅ClN₄O₄SZn: C 47.83, H 6.39, N 10.14, S 5.80, Cl 6.42%; Found: C 47.81, H 6.42, N 9.94, S 5.70, Cl 6.49%.

Structure description top

For related literature, see: Notni, Görls et al. (2006); Notni, Schenk et al. (2006); Notni et al. (2007); Salter et al. (2005); Schenk et al. (2006).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 40% probability level. The perchlorate anion was omitted for clarity. H atoms have been omitted except those attached to N atoms.

[(1-Azulenyl)methanethiolato-κS](1,4,8,12-tetraazacyclopentadecane-\k⁴N)zinc(II) perchlorate top

Crystal data top

[Zn(C₁₁H₂₆N₄)(C₁₁H₉S)]ClO₄	F(000) = 1160
M_r = 552.42	D_x = 1.434 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 18270 reflections
a = 8.0795 (1) Å	θ = 2.3–27.5°
b = 13.7163 (3) Å	µ = 1.18 mm⁻¹
c = 23.0913 (5) Å	T = 183 K
V = 2559.00 (8) Å³	Prism, blue
Z = 4	0.06 × 0.06 × 0.05 mm

Data collection top

Nonius KappaCCD diffractometer	4978 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.060
Graphite monochromator	θ_max = 27.5°, θ_min = 2.3°
φ and ω scans	h = −10→9
18270 measured reflections	k = −17→17
5858 independent reflections	l = −28→29

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.138	w = 1/[σ²(F_o²) + (0.0822P)² + 1.0799P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.038
5858 reflections	Δρ_max = 0.73 e Å⁻³
295 parameters	Δρ_min = −0.65 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 2541 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.002 (16)

Crystal data top

[Zn(C₁₁H₂₆N₄)(C₁₁H₉S)]ClO₄	V = 2559.00 (8) Å³
M_r = 552.42	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.0795 (1) Å	µ = 1.18 mm⁻¹
b = 13.7163 (3) Å	T = 183 K
c = 23.0913 (5) Å	0.06 × 0.06 × 0.05 mm

Data collection top

Nonius KappaCCD diffractometer	4978 reflections with I > 2σ(I)
18270 measured reflections	R_int = 0.060
5858 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.138	Δρ_max = 0.73 e Å⁻³
S = 1.04	Δρ_min = −0.65 e Å⁻³
5858 reflections	Absolute structure: Flack (1983), 2541 Friedel pairs
295 parameters	Absolute structure parameter: 0.002 (16)
0 restraints

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn	0.54052 (5)	0.85174 (3)	0.645222 (17)	0.03886 (13)
S	0.38553 (14)	0.73185 (7)	0.60351 (5)	0.0489 (2)
N1	0.5011 (5)	0.8137 (3)	0.74001 (15)	0.0618 (11)
H1C	0.4144	0.7691	0.7400	0.074*
N2	0.3875 (5)	0.9714 (3)	0.67100 (19)	0.0631 (10)
H2C	0.4580	1.0237	0.6779	0.076*
N3	0.5965 (5)	0.9402 (3)	0.56637 (15)	0.0554 (9)
H3C	0.6522	0.9965	0.5776	0.067*
N4	0.8012 (4)	0.8308 (3)	0.65356 (15)	0.0541 (9)
H4C	0.8461	0.8926	0.6589	0.065*
C1	0.4320 (9)	0.9025 (4)	0.7666 (2)	0.084 (2)
H1A	0.5223	0.9492	0.7751	0.100*
H1B	0.3767	0.8858	0.8035	0.100*
C2	0.3087 (8)	0.9488 (5)	0.7257 (3)	0.0865 (19)
H2A	0.2152	0.9035	0.7191	0.104*
H2B	0.2643	1.0093	0.7432	0.104*
C3	0.2676 (7)	1.0040 (6)	0.6259 (3)	0.095 (2)
H3A	0.1984	1.0567	0.6423	0.113*
H3B	0.1934	0.9488	0.6164	0.113*
C4	0.3464 (8)	1.0407 (5)	0.5699 (3)	0.0880 (19)
H4A	0.2574	1.0656	0.5444	0.106*
H4B	0.4193	1.0964	0.5795	0.106*
C5	0.4450 (8)	0.9681 (4)	0.5367 (2)	0.0724 (14)
H5A	0.3767	0.9092	0.5301	0.087*
H5B	0.4734	0.9959	0.4984	0.087*
C6	0.7047 (7)	0.8838 (4)	0.5260 (2)	0.0691 (14)
H6A	0.7189	0.9214	0.4897	0.083*
H6B	0.6495	0.8216	0.5161	0.083*
C7	0.8750 (7)	0.8621 (5)	0.5518 (2)	0.0780 (16)
H7A	0.9470	0.8363	0.5206	0.094*
H7B	0.9242	0.9241	0.5652	0.094*
C8	0.8765 (7)	0.7925 (4)	0.6002 (2)	0.0718 (14)
H8A	0.9925	0.7738	0.6084	0.086*
H8B	0.8163	0.7329	0.5884	0.086*
C9	0.8607 (6)	0.7707 (5)	0.7035 (2)	0.0704 (14)
H9A	0.9831	0.7722	0.7043	0.084*
H9B	0.8259	0.7023	0.6976	0.084*
C10	0.7948 (7)	0.8062 (5)	0.7619 (2)	0.0766 (16)
H10A	0.8712	0.7847	0.7929	0.092*
H10B	0.7929	0.8784	0.7620	0.092*
C11	0.6270 (9)	0.7697 (5)	0.7749 (2)	0.0811 (17)
H11A	0.6247	0.6982	0.7688	0.097*
H11B	0.6020	0.7821	0.8162	0.097*
C12	0.4652 (7)	0.6230 (3)	0.6411 (2)	0.0608 (11)
H12A	0.5863	0.6294	0.6465	0.073*
H12B	0.4135	0.6182	0.6799	0.073*
C13	0.4289 (5)	0.5323 (3)	0.60742 (18)	0.0495 (10)
C14	0.2793 (5)	0.4818 (3)	0.60754 (16)	0.0422 (8)
C15	0.1353 (6)	0.5078 (3)	0.63574 (18)	0.0547 (10)
H15A	0.1418	0.5657	0.6582	0.066*
C16	−0.0175 (7)	0.4616 (4)	0.6360 (2)	0.0653 (12)
H16A	−0.1021	0.4942	0.6571	0.078*
C17	−0.0651 (7)	0.3740 (4)	0.6098 (2)	0.0698 (13)
H17A	−0.1756	0.3537	0.6169	0.084*
C18	0.0282 (8)	0.3127 (4)	0.5746 (2)	0.0692 (13)
H18A	−0.0273	0.2558	0.5614	0.083*
C19	0.1875 (7)	0.3225 (4)	0.5565 (2)	0.0665 (13)
H19A	0.2266	0.2723	0.5317	0.080*
C20	0.2998 (6)	0.3947 (3)	0.5689 (2)	0.0546 (10)
C21	0.4628 (8)	0.4009 (4)	0.5486 (3)	0.0780 (16)
H21A	0.5143	0.3556	0.5232	0.094*
C22	0.5374 (7)	0.4838 (4)	0.5715 (3)	0.0699 (13)
H22A	0.6474	0.5042	0.5635	0.084*
Cl	0.79877 (18)	0.11964 (9)	0.68485 (6)	0.0683 (3)
O41	0.8208 (14)	0.2153 (8)	0.7006 (5)	0.091 (3)*	0.575 (13)
O42	0.6918 (15)	0.0533 (10)	0.7147 (5)	0.114 (4)*	0.575 (13)
O43	0.918 (3)	0.0559 (17)	0.6803 (12)	0.221 (9)*	0.575 (13)
O44	0.8335 (15)	0.0986 (8)	0.6292 (5)	0.122 (4)*	0.575 (13)
O41A	0.823 (3)	0.2011 (15)	0.7194 (9)	0.126 (7)*	0.425 (13)
O42A	0.6508 (15)	0.0964 (10)	0.7185 (5)	0.082 (3)*	0.425 (13)
O43A	0.961 (2)	0.0861 (11)	0.7227 (7)	0.120 (5)*	0.425 (13)
O44A	0.7107 (19)	0.1457 (11)	0.6300 (6)	0.116 (5)*	0.425 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn	0.0422 (2)	0.0405 (2)	0.0338 (2)	−0.00398 (19)	−0.00309 (18)	−0.00221 (17)
S	0.0618 (6)	0.0410 (5)	0.0440 (5)	−0.0080 (4)	−0.0168 (5)	−0.0002 (4)
N1	0.079 (3)	0.069 (2)	0.0373 (17)	−0.025 (2)	0.0085 (17)	−0.0057 (17)
N2	0.054 (2)	0.056 (2)	0.079 (3)	−0.0016 (19)	0.008 (2)	−0.015 (2)
N3	0.071 (2)	0.059 (2)	0.0365 (17)	−0.0173 (19)	−0.0119 (16)	0.0113 (15)
N4	0.0449 (16)	0.069 (2)	0.0479 (19)	−0.0047 (17)	0.0017 (15)	−0.0041 (17)
C1	0.114 (5)	0.085 (4)	0.052 (3)	−0.037 (4)	0.032 (3)	−0.025 (3)
C2	0.070 (3)	0.094 (4)	0.096 (5)	−0.003 (3)	0.027 (3)	−0.033 (4)
C3	0.055 (3)	0.107 (5)	0.121 (5)	0.022 (3)	−0.019 (3)	−0.033 (4)
C4	0.089 (4)	0.080 (4)	0.095 (5)	0.007 (3)	−0.035 (4)	0.015 (3)
C5	0.085 (4)	0.073 (3)	0.059 (3)	0.001 (3)	−0.017 (3)	0.018 (2)
C6	0.083 (3)	0.088 (4)	0.037 (2)	−0.004 (3)	0.014 (2)	0.003 (2)
C7	0.066 (3)	0.117 (5)	0.051 (3)	−0.017 (3)	0.015 (2)	−0.014 (3)
C8	0.062 (3)	0.089 (4)	0.064 (3)	−0.005 (3)	0.012 (2)	−0.008 (3)
C9	0.054 (3)	0.082 (3)	0.075 (3)	0.003 (3)	−0.024 (2)	0.008 (3)
C10	0.083 (4)	0.092 (4)	0.055 (3)	0.003 (3)	−0.032 (3)	0.001 (3)
C11	0.111 (5)	0.086 (4)	0.047 (3)	−0.019 (4)	−0.007 (3)	0.014 (3)
C12	0.086 (3)	0.044 (2)	0.053 (2)	−0.009 (2)	−0.025 (3)	0.0027 (18)
C13	0.057 (2)	0.0449 (19)	0.046 (2)	−0.0006 (18)	−0.0149 (18)	0.0022 (17)
C14	0.055 (2)	0.0375 (18)	0.0337 (17)	0.0030 (17)	−0.0042 (16)	0.0017 (15)
C15	0.075 (3)	0.050 (2)	0.038 (2)	0.008 (2)	0.002 (2)	0.0029 (18)
C16	0.067 (3)	0.075 (3)	0.054 (3)	0.004 (3)	0.012 (2)	0.005 (2)
C17	0.065 (3)	0.077 (3)	0.067 (3)	−0.011 (3)	0.007 (2)	0.017 (3)
C18	0.083 (3)	0.059 (3)	0.066 (3)	−0.022 (3)	−0.007 (3)	−0.002 (2)
C19	0.075 (3)	0.052 (2)	0.073 (3)	−0.007 (2)	−0.004 (3)	−0.012 (2)
C20	0.068 (3)	0.044 (2)	0.052 (2)	0.001 (2)	0.001 (2)	−0.0080 (18)
C21	0.064 (3)	0.067 (3)	0.103 (4)	−0.006 (3)	0.016 (3)	−0.032 (3)
C22	0.056 (2)	0.068 (3)	0.086 (3)	−0.005 (3)	−0.003 (3)	−0.005 (3)
Cl	0.0732 (7)	0.0494 (6)	0.0825 (8)	−0.0190 (5)	0.0227 (7)	−0.0145 (6)

Geometric parameters (Å, º) top

Zn—N4	2.134 (4)	C9—C10	1.530 (8)
Zn—N2	2.139 (4)	C9—H9A	0.9900
Zn—N3	2.235 (3)	C9—H9B	0.9900
Zn—N1	2.272 (4)	C10—C11	1.476 (9)
Zn—S	2.2804 (10)	C10—H10A	0.9900
S—C12	1.843 (4)	C10—H10B	0.9900
N1—C11	1.431 (8)	C11—H11A	0.9900
N1—C1	1.474 (7)	C11—H11B	0.9900
N1—H1C	0.9300	C12—C13	1.496 (6)
N2—C2	1.448 (8)	C12—H12A	0.9900
N2—C3	1.491 (8)	C12—H12B	0.9900
N2—H2C	0.9300	C13—C22	1.379 (7)
N3—C5	1.454 (7)	C13—C14	1.393 (6)
N3—C6	1.494 (7)	C14—C15	1.380 (6)
N3—H3C	0.9300	C14—C20	1.500 (6)
N4—C8	1.472 (6)	C15—C16	1.388 (7)
N4—C9	1.496 (6)	C15—H15A	0.9500
N4—H4C	0.9300	C16—C17	1.400 (8)
C1—C2	1.512 (10)	C16—H16A	0.9500
C1—H1A	0.9900	C17—C18	1.390 (8)
C1—H1B	0.9900	C17—H17A	0.9500
C2—H2A	0.9900	C18—C19	1.360 (8)
C2—H2B	0.9900	C18—H18A	0.9500
C3—C4	1.527 (10)	C19—C20	1.374 (7)
C3—H3A	0.9900	C19—H19A	0.9500
C3—H3B	0.9900	C20—C21	1.401 (8)
C4—C5	1.488 (10)	C21—C22	1.392 (7)
C4—H4A	0.9900	C21—H21A	0.9500
C4—H4B	0.9900	C22—H22A	0.9500
C5—H5A	0.9900	Cl—O43	1.31 (2)
C5—H5B	0.9900	Cl—O44	1.345 (12)
C6—C7	1.529 (8)	Cl—O41	1.373 (11)
C6—H6A	0.9900	Cl—O41A	1.39 (2)
C6—H6B	0.9900	Cl—O42	1.432 (12)
C7—C8	1.469 (8)	Cl—O42A	1.461 (11)
C7—H7A	0.9900	Cl—O44A	1.496 (15)
C7—H7B	0.9900	Cl—O43A	1.640 (16)
C8—H8A	0.9900	O43—O44	1.48 (3)
C8—H8B	0.9900

N4—Zn—N2	130.42 (16)	N4—C9—H9A	109.0
N4—Zn—N3	86.95 (15)	C10—C9—H9A	109.0
N2—Zn—N3	85.81 (17)	N4—C9—H9B	109.0
N4—Zn—N1	91.17 (15)	C10—C9—H9B	109.0
N2—Zn—N1	80.05 (17)	H9A—C9—H9B	107.8
N3—Zn—N1	159.70 (15)	C11—C10—C9	113.0 (5)
N4—Zn—S	118.88 (11)	C11—C10—H10A	109.0
N2—Zn—S	110.70 (12)	C9—C10—H10A	109.0
N3—Zn—S	99.13 (10)	C11—C10—H10B	109.0
N1—Zn—S	99.46 (11)	C9—C10—H10B	109.0
C12—S—Zn	101.15 (14)	H10A—C10—H10B	107.8
C11—N1—C1	112.6 (5)	N1—C11—C10	113.3 (4)
C11—N1—Zn	122.7 (3)	N1—C11—H11A	108.9
C1—N1—Zn	105.3 (3)	C10—C11—H11A	108.9
C11—N1—H1C	104.9	N1—C11—H11B	108.9
C1—N1—H1C	104.9	C10—C11—H11B	108.9
Zn—N1—H1C	104.9	H11A—C11—H11B	107.7
C2—N2—C3	112.8 (5)	C13—C12—S	111.1 (3)
C2—N2—Zn	109.4 (4)	C13—C12—H12A	109.4
C3—N2—Zn	114.3 (4)	S—C12—H12A	109.4
C2—N2—H2C	106.6	C13—C12—H12B	109.4
C3—N2—H2C	106.6	S—C12—H12B	109.4
Zn—N2—H2C	106.6	H12A—C12—H12B	108.0
C5—N3—C6	109.5 (4)	C22—C13—C14	108.2 (4)
C5—N3—Zn	110.9 (3)	C22—C13—C12	126.1 (4)
C6—N3—Zn	110.2 (3)	C14—C13—C12	125.7 (4)
C5—N3—H3C	108.7	C15—C14—C13	127.1 (4)
C6—N3—H3C	108.7	C15—C14—C20	125.4 (4)
Zn—N3—H3C	108.7	C13—C14—C20	107.4 (4)
C8—N4—C9	108.4 (4)	C14—C15—C16	129.4 (4)
C8—N4—Zn	112.4 (3)	C14—C15—H15A	115.3
C9—N4—Zn	117.4 (3)	C16—C15—H15A	115.3
C8—N4—H4C	105.9	C15—C16—C17	129.3 (5)
C9—N4—H4C	105.9	C15—C16—H16A	115.3
Zn—N4—H4C	105.9	C17—C16—H16A	115.3
N1—C1—C2	109.7 (4)	C18—C17—C16	128.6 (5)
N1—C1—H1A	109.7	C18—C17—H17A	115.7
C2—C1—H1A	109.7	C16—C17—H17A	115.7
N1—C1—H1B	109.7	C19—C18—C17	129.3 (5)
C2—C1—H1B	109.7	C19—C18—H18A	115.4
H1A—C1—H1B	108.2	C17—C18—H18A	115.4
N2—C2—C1	110.2 (5)	C18—C19—C20	129.2 (5)
N2—C2—H2A	109.6	C18—C19—H19A	115.4
C1—C2—H2A	109.6	C20—C19—H19A	115.4
N2—C2—H2B	109.6	C19—C20—C21	126.5 (5)
C1—C2—H2B	109.6	C19—C20—C14	128.7 (5)
H2A—C2—H2B	108.1	C21—C20—C14	104.8 (4)
N2—C3—C4	114.8 (5)	C22—C21—C20	109.2 (5)
N2—C3—H3A	108.6	C22—C21—H21A	125.4
C4—C3—H3A	108.6	C20—C21—H21A	125.4
N2—C3—H3B	108.6	C13—C22—C21	110.4 (5)
C4—C3—H3B	108.6	C13—C22—H22A	124.8
H3A—C3—H3B	107.5	C21—C22—H22A	124.8
C5—C4—C3	116.0 (5)	O43—Cl—O44	68.0 (13)
C5—C4—H4A	108.3	O43—Cl—O41	124.5 (12)
C3—C4—H4A	108.3	O44—Cl—O41	115.5 (7)
C5—C4—H4B	108.3	O43—Cl—O41A	119.0 (15)
C3—C4—H4B	108.3	O44—Cl—O41A	133.9 (10)
H4A—C4—H4B	107.4	O41—Cl—O41A	19.9 (9)
N3—C5—C4	112.5 (5)	O43—Cl—O42	93.4 (11)
N3—C5—H5A	109.1	O44—Cl—O42	116.7 (7)
C4—C5—H5A	109.1	O41—Cl—O42	123.9 (8)
N3—C5—H5B	109.1	O41A—Cl—O42	108.6 (11)
C4—C5—H5B	109.1	O43—Cl—O42A	120.1 (11)
H5A—C5—H5B	107.8	O44—Cl—O42A	129.2 (7)
N3—C6—C7	112.6 (4)	O41—Cl—O42A	100.0 (8)
N3—C6—H6A	109.1	O41A—Cl—O42A	89.0 (11)
C7—C6—H6A	109.1	O42—Cl—O42A	27.3 (6)
N3—C6—H6B	109.1	O43—Cl—O44A	116.3 (14)
C7—C6—H6B	109.1	O44—Cl—O44A	48.9 (6)
H6A—C6—H6B	107.8	O41—Cl—O44A	93.2 (8)
C8—C7—C6	115.5 (5)	O41A—Cl—O44A	111.1 (11)
C8—C7—H7A	108.4	O42—Cl—O44A	105.8 (7)
C6—C7—H7A	108.4	O42A—Cl—O44A	96.5 (7)
C8—C7—H7B	108.4	O43—Cl—O43A	42.8 (11)
C6—C7—H7B	108.4	O44—Cl—O43A	106.4 (8)
H7A—C7—H7B	107.5	O41—Cl—O43A	91.3 (8)
C7—C8—N4	113.7 (5)	O41A—Cl—O43A	78.9 (11)
C7—C8—H8A	108.8	O42—Cl—O43A	92.7 (7)
N4—C8—H8A	108.8	O42A—Cl—O43A	107.9 (7)
C7—C8—H8B	108.8	O44A—Cl—O43A	154.0 (8)
N4—C8—H8B	108.8	Cl—O43—O44	57.3 (11)
H8A—C8—H8B	107.7	Cl—O44—O43	54.7 (10)
N4—C9—C10	113.1 (5)

Experimental details

Crystal data
Chemical formula	[Zn(C₁₁H₂₆N₄)(C₁₁H₉S)]ClO₄
M_r	552.42
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	183
a, b, c (Å)	8.0795 (1), 13.7163 (3), 23.0913 (5)
V (Å³)	2559.00 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.18
Crystal size (mm)	0.06 × 0.06 × 0.05

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	18270, 5858, 4978
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.138, 1.04
No. of reflections	5858
No. of parameters	295
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.65
Absolute structure	Flack (1983), 2541 Friedel pairs
Absolute structure parameter	0.002 (16)

Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1990).

Selected geometric parameters (Å, º) top

Zn—N4	2.134 (4)	Zn—N1	2.272 (4)
Zn—N2	2.139 (4)	Zn—S	2.2804 (10)
Zn—N3	2.235 (3)

N4—Zn—N2	130.42 (16)	N3—Zn—N1	159.70 (15)
N4—Zn—N3	86.95 (15)	N4—Zn—S	118.88 (11)
N2—Zn—N3	85.81 (17)	N2—Zn—S	110.70 (12)
N4—Zn—N1	91.17 (15)	N3—Zn—S	99.13 (10)
N2—Zn—N1	80.05 (17)	N1—Zn—S	99.46 (11)

Acknowledgements

The authors gratefully acknowledge financial support from the Deutsche Forschungsgemeinschaft, SFB 436 `Metal Mediated Reactions Modelled after Nature'.

References

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