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Acta Cryst. (2007). E63, m2556    [ doi:10.1107/S1600536807045096 ]

(Phenylmethanethiolato)(1,5,9-triazacyclododecane)zinc(II) thiocyanate

H. Görls, J. Notni and E. Anders

Abstract top

The title compound, [Zn(C7H7S)(C9H21N3)]SCN, features a cationic Zn complex with the metal atom in a distorted tetrahedral environment. The crystal packing is stabilized by N-H...N and N-H...S hydrogen bonds. However, one of the amino H atoms is not involved in hydrogen bonding.

Comment top

The title compound belongs to a series of cationic zinc thiolate complexes with azamacrocyclic ligands (Notni, Görls & Anders, 2006), where the crystal structure of the corresponding perchlorate salt has been published. These complexes have shown to react with heterocumulenes (COS, CS2) to give di- and trithiocarbonato complexes, respectively (Notni, Schenk et al., 2006), In the course of our efforts to elucidate the reactivity towards other heterocumulenes we also investigated the reaction with thiocyanate anion. However, no reaction was observed, but the complex precipitated as thiocyanate salt whose crystal structure is reported herein. The crystal structure of (1) consists of a Zn-complex-monocation and a discrete thiocyanato anion as shown in Fig. 1. Within the Zn-cation, the Zn atom is coordinated by three nitrogen atoms and one sulfur atom in a distorted tetrahedral arrangement, the Zn—S bond length being 2.2497 (8) Å and the Zn—N bond lengths 2.054 (3), 2.046 (3) and 2.050 (3) Å. The bond angles around Zn range from 112.04 (9) to 119.65 (9)° for S–Zn–N angles and from 101.86 (13) to 102.86 (12)° for N–Zn–N angles. The Zn–N and Zn–S distances are in accord with the corresponding distances in the other Zn complexes reported in the literature (Notni, Görls & Anders, 2006; Börzel et al., 2003; Brand et al., 2001). There are no unexpected geometrical features associated with the coordination structure of zinc ion. The hydrogen atoms of the amine-groups are all in cis-position and found on the side of the complex that bears the thiolate.

Related literature top

A series of related complexes has been prepared and characterized structurally (Notni, Görls & Anders, 2006). The complexes react with carbon disulfide to give trithiocarbonates (Notni, Schenk et al., 2006; Schenk et al., 2006), and with methyl iodide to give thioethers (Notni et al., 2007). The complexes are of importance as biomimetics for a sulfur analogue of carbonic anhydrase (Schenk et al., 2006).

For related literature, see: Börzel et al. (2003); Brand et al. (2001).

Experimental top

A sample of {(phenylmethylthiolato)(1,5,9-triazacyclododecane)}zinc(II) perchlorate (0.5 mmol, 23 mg) was placed in an NMR tube and dissolved in acetonitrile-D3 (0.5 ml) Then tetrabutylammonium thiocyanate (0.5 mmol, 15.5 mg) was added. The signals of the complex cation in the NMR spectra showed no alteration, even after prolonged standing at r. t.. After one week, a precipitate had formed, which was subjected to X-ray structural analysis.

Refinement top

The hydrogen atoms of the tree amines groups at N1, N2 and N3 were located by difference Fourier synthesis and refined isotropically. All other hydrogen atoms were calculated into idealized positions and were refined with 1.5 times the isotropic displacement parameter of the corresponding carbon atom.

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/PC (Siemens, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. Molecular structure of 1. Displacement ellipsoids are drawn at the 40% probability level. H atoms bonded to C omitted.
(Phenylmethanethiolato)(1,5,9-triazacyclododecane)zinc(II) thiocyanate top
Crystal data top
[Zn(C7H7S)(C9H21N3)]SCNZ = 4
Mr = 417.92F000 = 880
Monoclinic, CcDx = 1.406 Mg m−3
Hall symbol: C-2ycMo Kα radiation
λ = 0.71073 Å
a = 15.6005 (7) ŵ = 1.46 mm−1
b = 8.8031 (4) ÅT = 183 (2) K
c = 16.2518 (6) ÅPrism, colourless
β = 117.777 (2)º0.04 × 0.04 × 0.03 mm
V = 1974.72 (15) Å3
Data collection top
KappaCCD
diffractometer		3636 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.034
Monochromator: graphiteθmax = 27.5º
T = 183(2) Kθmin = 2.8º
φ and ω scanh = −18→20
Absorption correction: nonek = −10→11
6436 measured reflectionsl = −21→19
4132 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of
independent and constrained refinement
R[F2 > 2σ(F2)] = 0.036  w = 1/[σ2(Fo2) + (0.030P)2 + 0.6448P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.077(Δ/σ)max = 0.005
S = 1.01Δρmax = 0.33 e Å−3
4132 reflectionsΔρmin = −0.44 e Å−3
229 parametersExtinction correction: none
2 restraintsAbsolute structure: Flack (1983), 1885 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.020 (14)
Secondary atom site location: difference Fourier map
Crystal data top
[Zn(C7H7S)(C9H21N3)]SCNV = 1974.72 (15) Å3
Mr = 417.92Z = 4
Monoclinic, CcMo Kα
a = 15.6005 (7) ŵ = 1.46 mm−1
b = 8.8031 (4) ÅT = 183 (2) K
c = 16.2518 (6) Å0.04 × 0.04 × 0.03 mm
β = 117.777 (2)º
Data collection top
KappaCCD
diffractometer		4132 independent reflections
Absorption correction: none3636 reflections with I > 2σ(I)
6436 measured reflectionsRint = 0.034
Refinement top
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.077Δρmax = 0.33 e Å−3
S = 1.01Δρmin = −0.44 e Å−3
4132 reflectionsAbsolute structure: Flack (1983), 1885 Friedel pairs
229 parametersFlack parameter: 0.020 (14)
2 restraints
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 > 2sigma(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
xyzUiso*/Ueq
Zn0.19047 (2)0.28977 (4)0.83730 (2)0.02175 (10)
S10.10003 (7)0.33403 (10)0.68420 (6)0.0312 (2)
N10.1643 (2)0.0879 (3)0.8850 (2)0.0279 (7)
N20.1642 (2)0.4447 (3)0.9167 (2)0.0294 (7)
N30.3386 (2)0.2917 (3)0.8947 (2)0.0268 (6)
C10.1251 (3)0.1120 (4)0.9516 (2)0.0317 (8)
H1A0.17930.13411.01400.038*
H1B0.09300.01770.95620.038*
C20.0534 (3)0.2409 (5)0.9225 (3)0.0442 (10)
H2A0.01640.24220.85380.053*
H2B0.00690.22170.94690.053*
C30.0981 (4)0.3935 (5)0.9550 (3)0.0514 (12)
H3A0.13520.39191.02370.062*
H3B0.04560.46930.93770.062*
C40.2507 (3)0.5225 (5)0.9887 (3)0.0483 (11)
H4A0.27740.46141.04650.058*
H4B0.23100.62221.00250.058*
C50.3288 (3)0.5468 (5)0.9605 (3)0.0447 (10)
H5A0.37230.62850.99960.054*
H5B0.29840.58210.89520.054*
C60.3890 (3)0.4068 (4)0.9692 (2)0.0358 (9)
H6A0.44920.43870.96780.043*
H6B0.40780.35871.03030.043*
C70.3846 (3)0.1394 (4)0.9263 (2)0.0329 (8)
H7A0.45520.15300.96540.039*
H7B0.37460.07880.87120.039*
C80.3443 (3)0.0521 (4)0.9813 (2)0.0343 (9)
H8A0.3915−0.02751.01810.041*
H8B0.33800.12261.02570.041*
C90.2468 (3)−0.0225 (4)0.9227 (3)0.0356 (9)
H9A0.2488−0.07640.87010.043*
H9B0.2351−0.09900.96100.043*
C100.1668 (3)0.2321 (4)0.6338 (2)0.0316 (8)
H10A0.12720.23380.56530.038*
H10B0.22700.28940.64910.038*
C110.1941 (3)0.0699 (4)0.6634 (2)0.0304 (8)
C120.2855 (3)0.0175 (5)0.6836 (2)0.0454 (11)
H12A0.33230.08620.68330.054*
C130.3096 (4)−0.1364 (7)0.7047 (3)0.0615 (16)
H13A0.3726−0.17120.71860.074*
C140.2424 (5)−0.2363 (6)0.7051 (3)0.0629 (16)
H14A0.2588−0.34040.71880.076*
C150.1516 (4)−0.1863 (5)0.6857 (3)0.0472 (11)
H15A0.1053−0.25590.68620.057*
C160.1273 (3)−0.0342 (4)0.6652 (2)0.0336 (9)
H16A0.0645−0.00040.65230.040*
S1T−0.08174 (7)−0.05941 (12)0.73994 (7)0.0424 (3)
C1T−0.0051 (3)−0.1944 (4)0.7955 (3)0.0338 (9)
N1T0.0514 (3)−0.2856 (5)0.8386 (4)0.0685 (13)
H1N20.132 (3)0.517 (5)0.875 (3)0.036 (11)*
H1N10.121 (3)0.043 (5)0.843 (3)0.042 (13)*
H1N30.347 (3)0.317 (5)0.851 (3)0.046 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn0.02147 (17)0.02404 (17)0.01877 (15)0.0013 (2)0.00856 (12)0.00112 (19)
S10.0325 (5)0.0335 (5)0.0197 (4)0.0069 (4)0.0056 (3)0.0045 (4)
N10.0302 (17)0.0282 (16)0.0213 (14)−0.0070 (13)0.0085 (13)0.0004 (13)
N20.0345 (17)0.0281 (16)0.0270 (14)0.0100 (14)0.0155 (13)0.0022 (13)
N30.0234 (15)0.0374 (17)0.0220 (14)−0.0005 (13)0.0126 (12)0.0012 (13)
C10.032 (2)0.037 (2)0.0276 (17)−0.0069 (16)0.0153 (16)0.0040 (16)
C20.027 (2)0.065 (3)0.049 (2)0.0055 (19)0.0239 (19)0.017 (2)
C30.071 (3)0.045 (2)0.068 (3)0.025 (2)0.057 (3)0.015 (2)
C40.044 (3)0.056 (3)0.040 (2)0.010 (2)0.0161 (19)−0.015 (2)
C50.042 (2)0.036 (2)0.044 (2)−0.0128 (19)0.0099 (18)−0.0110 (18)
C60.0219 (18)0.042 (2)0.036 (2)−0.0085 (17)0.0076 (16)−0.0062 (17)
C70.0274 (19)0.042 (2)0.0266 (17)0.0092 (17)0.0103 (15)−0.0024 (16)
C80.035 (2)0.0323 (19)0.0262 (18)0.0118 (16)0.0064 (16)0.0037 (15)
C90.044 (2)0.0254 (17)0.0331 (19)0.0054 (16)0.0145 (17)0.0060 (15)
C100.036 (2)0.039 (2)0.0193 (16)−0.0017 (17)0.0120 (15)−0.0016 (15)
C110.035 (2)0.041 (2)0.0138 (15)0.0026 (17)0.0095 (14)−0.0029 (15)
C120.033 (2)0.073 (3)0.0224 (18)0.007 (2)0.0064 (16)−0.008 (2)
C130.054 (3)0.091 (4)0.022 (2)0.043 (3)0.003 (2)−0.007 (2)
C140.103 (5)0.055 (3)0.027 (2)0.037 (3)0.027 (3)0.009 (2)
C150.075 (3)0.038 (2)0.033 (2)0.009 (2)0.029 (2)0.0042 (18)
C160.042 (2)0.037 (2)0.0252 (17)0.0004 (17)0.0182 (16)−0.0029 (15)
S1T0.0311 (5)0.0466 (6)0.0440 (5)0.0053 (5)0.0127 (4)0.0154 (5)
C1T0.031 (2)0.0298 (19)0.048 (2)−0.0014 (17)0.0250 (19)0.0028 (17)
N1T0.061 (3)0.054 (3)0.099 (3)0.019 (2)0.045 (3)0.030 (2)
Geometric parameters (Å, °) top
Zn—N22.046 (3)C5—H5B0.9900
Zn—N32.050 (3)C6—H6A0.9900
Zn—N12.054 (3)C6—H6B0.9900
Zn—S12.2497 (8)C7—C81.520 (5)
S1—C101.831 (4)C7—H7A0.9900
N1—C11.487 (5)C7—H7B0.9900
N1—C91.497 (5)C8—C91.517 (5)
N1—H1N10.81 (4)C8—H8A0.9900
N2—C41.479 (5)C8—H8B0.9900
N2—C31.501 (5)C9—H9A0.9900
N2—H1N20.89 (4)C9—H9B0.9900
N3—C61.491 (5)C10—C111.504 (5)
N3—C71.493 (5)C10—H10A0.9900
N3—H1N30.81 (4)C10—H10B0.9900
C1—C21.506 (6)C11—C121.384 (5)
C1—H1A0.9900C11—C161.398 (5)
C1—H1B0.9900C12—C131.405 (7)
C2—C31.492 (7)C12—H12A0.9500
C2—H2A0.9900C13—C141.371 (8)
C2—H2B0.9900C13—H13A0.9500
C3—H3A0.9900C14—C151.372 (8)
C3—H3B0.9900C14—H14A0.9500
C4—C51.502 (6)C15—C161.390 (5)
C4—H4A0.9900C15—H15A0.9500
C4—H4B0.9900C16—H16A0.9500
C5—C61.516 (6)S1T—C1T1.628 (4)
C5—H5A0.9900C1T—N1T1.156 (5)
N2—Zn—N3102.86 (12)C4—C5—H5B108.7
N2—Zn—N1101.86 (13)C6—C5—H5B108.7
N3—Zn—N1102.44 (12)H5A—C5—H5B107.6
N2—Zn—S1112.04 (9)N3—C6—C5114.1 (3)
N3—Zn—S1119.65 (9)N3—C6—H6A108.7
N1—Zn—S1115.75 (9)C5—C6—H6A108.7
C10—S1—Zn102.43 (12)N3—C6—H6B108.7
C1—N1—C9111.2 (3)C5—C6—H6B108.7
C1—N1—Zn111.9 (2)H6A—C6—H6B107.6
C9—N1—Zn115.6 (2)N3—C7—C8113.1 (3)
C1—N1—H1N1104 (3)N3—C7—H7A109.0
C9—N1—H1N1104 (3)C8—C7—H7A109.0
Zn—N1—H1N1109 (3)N3—C7—H7B109.0
C4—N2—C3111.2 (3)C8—C7—H7B109.0
C4—N2—Zn115.5 (2)H7A—C7—H7B107.8
C3—N2—Zn116.1 (2)C9—C8—C7114.7 (3)
C4—N2—H1N2105 (3)C9—C8—H8A108.6
C3—N2—H1N2106 (3)C7—C8—H8A108.6
Zn—N2—H1N2101 (3)C9—C8—H8B108.6
C6—N3—C7110.1 (3)C7—C8—H8B108.6
C6—N3—Zn115.5 (2)H8A—C8—H8B107.6
C7—N3—Zn114.1 (2)N1—C9—C8113.3 (3)
C6—N3—H1N3106 (3)N1—C9—H9A108.9
C7—N3—H1N3107 (3)C8—C9—H9A108.9
Zn—N3—H1N3103 (3)N1—C9—H9B108.9
N1—C1—C2112.1 (3)C8—C9—H9B108.9
N1—C1—H1A109.2H9A—C9—H9B107.7
C2—C1—H1A109.2C11—C10—S1117.3 (3)
N1—C1—H1B109.2C11—C10—H10A108.0
C2—C1—H1B109.2S1—C10—H10A108.0
H1A—C1—H1B107.9C11—C10—H10B108.0
C3—C2—C1114.3 (4)S1—C10—H10B108.0
C3—C2—H2A108.7H10A—C10—H10B107.2
C1—C2—H2A108.7C12—C11—C16118.1 (4)
C3—C2—H2B108.7C12—C11—C10120.0 (4)
C1—C2—H2B108.7C16—C11—C10121.7 (3)
H2A—C2—H2B107.6C11—C12—C13120.6 (5)
C2—C3—N2114.9 (3)C11—C12—H12A119.7
C2—C3—H3A108.5C13—C12—H12A119.7
N2—C3—H3A108.5C14—C13—C12120.0 (5)
C2—C3—H3B108.5C14—C13—H13A120.0
N2—C3—H3B108.5C12—C13—H13A120.0
H3A—C3—H3B107.5C13—C14—C15120.2 (5)
N2—C4—C5113.3 (3)C13—C14—H14A119.9
N2—C4—H4A108.9C15—C14—H14A119.9
C5—C4—H4A108.9C14—C15—C16120.0 (5)
N2—C4—H4B108.9C14—C15—H15A120.0
C5—C4—H4B108.9C16—C15—H15A120.0
H4A—C4—H4B107.7C15—C16—C11121.0 (4)
C4—C5—C6114.3 (4)C15—C16—H16A119.5
C4—C5—H5A108.7C11—C16—H16A119.5
C6—C5—H5A108.7N1T—C1T—S1T176.7 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H1N2···N1Ti0.89 (4)2.06 (5)2.875 (6)150.00
N3—H1N3···S1Tii0.81 (5)2.75 (5)3.536 (3)165.00
Symmetry codes: (i) x, y+1, z; (ii) x+1/2, y+1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H1N2···N1Ti0.89 (4)2.06 (5)2.875 (6)150.00
N3—H1N3···S1Tii0.81 (5)2.75 (5)3.536 (3)165.00
Symmetry codes: (i) x, y+1, z; (ii) x+1/2, y+1/2, z.
Acknowledgements top

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

references
References top

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