Literature DB >> 21578198

(μ-trans-1,2-Di-4-pyridylethyl-ene-κN:N')bis-[bis-(N,N-diisopropyl-dithio-carbamato-κS,S')zinc(II)].

Hadi D Arman, Pavel Poplaukhin, Edward R T Tiekink.   

Abstract

The dinuclear title compound, [class="Chemical">Zn(2)(C(7)H(14)NS(2))(4)(C(12)<class="Chemical">span class="Species">H(10)N(2))], is centrosymmetric about the central C=C bond. The five-coordinate Zn atom is bonded to two asymmetrically chelating dithio-carbamate ligands and a pyridine N atom to define an NS(4) coordination geometry tending towards a square pyramid, with the N atom in the apical site. In the crystal structure, C-H⋯S contacts lead to supra-molecular chains.

Entities:  

Year:  2009        PMID： 21578198      PMCID： PMC2971214          DOI： 10.1107/S1600536809044250

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For background to supra­molecular polymers of zinc 1,1-dithiol­ates, see: Lai et al. (2002 ▶); Chen et al. (2006 ▶); Benson et al. (2007 ▶). For a related structure and the synthesis, see: Lai & Tiekink (2003 ▶). For additional geometrical analysis, see: Addison et al. (1984 ▶).

Experimental

Crystal data

[<span class="Chemical">Zn2(<class="Chemical">span class="CellLine">C7H14NS2)4(C12H10N2)] M = 1018.21 Triclinic, a = 8.2690 (14) Å b = 11.1640 (18) Å c = 14.156 (2) Å α = 80.806 (10)° β = 84.878 (9)° γ = 72.566 (5)° V = 1229.6 (3) Å3 Z = 1 Mo Kα radiation μ = 1.35 mm−1 T = 98 K 0.43 × 0.35 × 0.22 mm

Data collection

Rigaku AFC12K/SATURN724 diffractometer Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.810, T max = 1 9453 measured reflections 5613 independent reflections 5323 reflections with I > 2σ(I) R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.038 wR(F 2) = 0.103 S = 1.08 5613 reflections 261 parameters H-atom parameters constrained Δρmax = 0.73 e Å−3 Δρmin = −0.93 e Å−3 Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); 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: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97. Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809044250/hb5178sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536809044250/hb5178Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
[Zn2(C7H14NS2)4(C12H10N2)]Z = 1
Mr = 1018.21F(000) = 536
Triclinic, P1Dx = 1.375 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71069 Å
a = 8.2690 (14) ÅCell parameters from 4206 reflections
b = 11.1640 (18) Åθ = 2.6–40.2°
c = 14.156 (2) ŵ = 1.35 mm−1
α = 80.806 (10)°T = 98 K
β = 84.878 (9)°Block, gold
γ = 72.566 (5)°0.43 × 0.35 × 0.22 mm
V = 1229.6 (3) Å3
Rigaku AFC12K/SATURN724 diffractometer5613 independent reflections
Radiation source: fine-focus sealed tube5323 reflections with I > 2σ(I)
graphiteRint = 0.027
ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −9→10
Tmin = 0.810, Tmax = 1k = −13→14
9453 measured reflectionsl = −18→18
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103H-atom parameters constrained
S = 1.08w = 1/[σ2(Fo2) + (0.0536P)2 + 0.8556P] where P = (Fo2 + 2Fc2)/3
5613 reflections(Δ/σ)max = 0.001
261 parametersΔρmax = 0.73 e Å−3
0 restraintsΔρmin = −0.93 e Å−3
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.
xyzUiso*/Ueq
Zn0.26250 (3)0.37511 (2)0.262741 (17)0.01954 (9)
S10.50382 (7)0.25806 (5)0.35054 (4)0.02363 (13)
S20.31926 (7)0.14535 (5)0.24038 (4)0.02353 (13)
S30.18968 (7)0.47710 (5)0.10606 (4)0.02045 (12)
S40.29663 (7)0.59904 (5)0.24745 (4)0.02168 (12)
N10.6241 (2)0.01811 (18)0.31035 (14)0.0237 (4)
N20.2671 (2)0.69764 (16)0.06127 (12)0.0191 (3)
N30.0406 (2)0.39861 (17)0.34610 (13)0.0203 (3)
C10.4978 (3)0.1269 (2)0.30131 (15)0.0193 (4)
C20.7810 (3)−0.0048 (2)0.36315 (18)0.0302 (5)
H20.8458−0.09520.35870.036*
C30.7483 (4)0.0018 (3)0.46940 (19)0.0377 (6)
H3A0.70190.09060.47980.057*
H3B0.8549−0.03620.50230.057*
H3C0.6668−0.04480.49490.057*
C40.8972 (3)0.0716 (3)0.3145 (2)0.0356 (6)
H4A0.91210.06320.24620.053*
H4B1.00780.03970.34380.053*
H4C0.84670.16100.32220.053*
C50.6116 (3)−0.0926 (2)0.26693 (19)0.0300 (5)
H50.5131−0.05960.22430.036*
C60.7657 (4)−0.1476 (3)0.2036 (2)0.0455 (7)
H6A0.7888−0.07960.15640.068*
H6B0.7436−0.21120.17030.068*
H6C0.8642−0.18740.24320.068*
C70.5682 (6)−0.1896 (3)0.3430 (2)0.0585 (10)
H7A0.6630−0.22700.38560.088*
H7B0.5470−0.25630.31290.088*
H7C0.4664−0.14900.38020.088*
C80.2528 (2)0.60365 (19)0.12971 (14)0.0173 (4)
C90.3395 (3)0.7973 (2)0.08196 (16)0.0230 (4)
H90.38090.77140.14850.028*
C100.4919 (3)0.8049 (3)0.0156 (2)0.0356 (6)
H10A0.57620.72130.01990.053*
H10B0.54220.86620.03460.053*
H10C0.45580.8323−0.05040.053*
C110.2042 (3)0.9242 (2)0.0808 (2)0.0342 (6)
H11A0.16170.95350.01620.051*
H11B0.25320.98630.09960.051*
H11C0.11050.91470.12600.051*
C120.2101 (3)0.7146 (2)−0.03856 (15)0.0230 (4)
H120.23000.7958−0.07070.028*
C130.3156 (3)0.6133 (2)−0.09784 (17)0.0302 (5)
H13A0.43620.5970−0.08730.045*
H13B0.29480.6428−0.16590.045*
H13C0.28350.5349−0.07850.045*
C140.0198 (3)0.7356 (2)−0.04095 (18)0.0271 (5)
H14A−0.00690.6565−0.01530.041*
H14B−0.01550.7621−0.10720.041*
H14C−0.04050.8017−0.00190.041*
C150.0365 (3)0.3549 (2)0.44008 (17)0.0294 (5)
H150.14040.31030.46960.035*
C16−0.1129 (3)0.3724 (2)0.49564 (16)0.0297 (5)
H16−0.11010.34070.56210.036*
C17−0.2677 (3)0.4365 (2)0.45415 (15)0.0200 (4)
C18−0.2633 (3)0.4766 (2)0.35583 (15)0.0224 (4)
H18−0.36580.51650.32360.027*
C19−0.1086 (3)0.4576 (2)0.30552 (16)0.0228 (4)
H19−0.10780.48790.23890.027*
C20−0.4262 (3)0.4592 (2)0.51333 (15)0.0207 (4)
H20−0.42300.41190.57550.025*
U11U22U33U12U13U23
Zn0.01645 (14)0.02258 (14)0.01769 (14)−0.00523 (10)0.00223 (9)0.00022 (9)
S10.0225 (3)0.0227 (3)0.0275 (3)−0.0087 (2)−0.0054 (2)−0.0022 (2)
S20.0220 (3)0.0234 (3)0.0256 (3)−0.0055 (2)−0.0057 (2)−0.0041 (2)
S30.0237 (3)0.0223 (2)0.0171 (2)−0.0098 (2)0.00010 (19)−0.00222 (18)
S40.0266 (3)0.0246 (3)0.0151 (2)−0.0099 (2)−0.0018 (2)−0.00120 (18)
N10.0215 (9)0.0222 (9)0.0260 (10)−0.0062 (7)−0.0042 (7)0.0016 (7)
N20.0201 (8)0.0203 (8)0.0158 (8)−0.0052 (7)−0.0011 (7)−0.0008 (6)
N30.0180 (8)0.0230 (8)0.0184 (9)−0.0055 (7)0.0028 (7)−0.0010 (7)
C10.0183 (9)0.0232 (10)0.0165 (9)−0.0084 (8)0.0013 (7)0.0006 (7)
C20.0224 (11)0.0340 (12)0.0316 (13)−0.0067 (9)−0.0065 (9)0.0032 (10)
C30.0390 (14)0.0450 (15)0.0295 (13)−0.0128 (12)−0.0069 (11)−0.0022 (11)
C40.0227 (11)0.0472 (15)0.0392 (14)−0.0146 (11)−0.0009 (10)−0.0041 (11)
C50.0306 (12)0.0234 (11)0.0343 (13)−0.0040 (9)−0.0037 (10)−0.0054 (9)
C60.0463 (17)0.0485 (16)0.0402 (16)−0.0061 (13)0.0026 (13)−0.0187 (13)
C70.099 (3)0.0461 (18)0.0459 (18)−0.0458 (19)0.0196 (18)−0.0164 (14)
C80.0153 (9)0.0202 (9)0.0151 (9)−0.0037 (7)0.0008 (7)−0.0028 (7)
C90.0254 (11)0.0218 (10)0.0234 (11)−0.0098 (8)−0.0024 (8)−0.0015 (8)
C100.0341 (13)0.0345 (13)0.0452 (15)−0.0209 (11)0.0083 (11)−0.0099 (11)
C110.0288 (12)0.0276 (12)0.0483 (16)−0.0057 (10)−0.0019 (11)−0.0162 (11)
C120.0271 (11)0.0239 (10)0.0169 (10)−0.0066 (8)−0.0036 (8)−0.0001 (8)
C130.0356 (13)0.0348 (12)0.0190 (11)−0.0075 (10)0.0027 (9)−0.0072 (9)
C140.0249 (11)0.0269 (11)0.0293 (12)−0.0056 (9)−0.0076 (9)−0.0038 (9)
C150.0194 (10)0.0407 (13)0.0209 (11)−0.0023 (9)−0.0004 (9)0.0043 (9)
C160.0209 (11)0.0438 (14)0.0174 (11)−0.0035 (10)0.0020 (9)0.0036 (9)
C170.0182 (10)0.0221 (10)0.0209 (10)−0.0081 (8)0.0017 (8)−0.0031 (8)
C180.0175 (10)0.0281 (11)0.0187 (10)−0.0038 (8)0.0008 (8)−0.0014 (8)
C190.0192 (10)0.0289 (11)0.0183 (10)−0.0062 (8)0.0013 (8)−0.0002 (8)
C200.0197 (10)0.0262 (10)0.0162 (9)−0.0075 (8)0.0031 (8)−0.0034 (8)
Zn—N32.0621 (18)C7—H7A0.9800
Zn—S12.3655 (7)C7—H7B0.9800
Zn—S32.3662 (7)C7—H7C0.9800
Zn—S22.5320 (7)C9—C101.518 (3)
Zn—S42.5720 (7)C9—C111.519 (3)
S1—C11.734 (2)C9—H91.0000
S2—C11.719 (2)C10—H10A0.9800
S3—C81.733 (2)C10—H10B0.9800
S4—C81.727 (2)C10—H10C0.9800
N1—C11.340 (3)C11—H11A0.9800
N1—C21.490 (3)C11—H11B0.9800
N1—C51.499 (3)C11—H11C0.9800
N2—C81.335 (3)C12—C141.522 (3)
N2—C91.489 (3)C12—C131.525 (3)
N2—C121.495 (3)C12—H121.0000
N3—C151.343 (3)C13—H13A0.9800
N3—C191.344 (3)C13—H13B0.9800
C2—C31.514 (4)C13—H13C0.9800
C2—C41.520 (4)C14—H14A0.9800
C2—H21.0000C14—H14B0.9800
C3—H3A0.9800C14—H14C0.9800
C3—H3B0.9800C15—C161.384 (3)
C3—H3C0.9800C15—H150.9500
C4—H4A0.9800C16—C171.395 (3)
C4—H4B0.9800C16—H160.9500
C4—H4C0.9800C17—C181.393 (3)
C5—C71.501 (4)C17—C201.469 (3)
C5—C61.519 (4)C18—C191.383 (3)
C5—H51.0000C18—H180.9500
C6—H6A0.9800C19—H190.9500
C6—H6B0.9800C20—C20i1.330 (4)
C6—H6C0.9800C20—H200.9500
N3—Zn—S1112.29 (5)H7A—C7—H7C109.5
N3—Zn—S3107.48 (5)H7B—C7—H7C109.5
S1—Zn—S3140.23 (2)N2—C8—S4122.56 (15)
N3—Zn—S299.44 (5)N2—C8—S3122.09 (15)
S1—Zn—S273.21 (2)S4—C8—S3115.36 (12)
S3—Zn—S2100.61 (2)N2—C9—C10111.56 (18)
N3—Zn—S4100.23 (5)N2—C9—C11111.17 (18)
S1—Zn—S499.98 (2)C10—C9—C11112.7 (2)
S3—Zn—S472.47 (2)N2—C9—H9107.0
S2—Zn—S4160.31 (2)C10—C9—H9107.0
C1—S1—Zn87.45 (7)C11—C9—H9107.0
C1—S2—Zn82.55 (7)C9—C10—H10A109.5
C8—S3—Zn88.80 (7)C9—C10—H10B109.5
C8—S4—Zn82.47 (7)H10A—C10—H10B109.5
C1—N1—C2124.9 (2)C9—C10—H10C109.5
C1—N1—C5119.88 (19)H10A—C10—H10C109.5
C2—N1—C5115.18 (19)H10B—C10—H10C109.5
C8—N2—C9120.53 (17)C9—C11—H11A109.5
C8—N2—C12124.50 (18)C9—C11—H11B109.5
C9—N2—C12114.95 (16)H11A—C11—H11B109.5
C15—N3—C19117.40 (19)C9—C11—H11C109.5
C15—N3—Zn123.08 (15)H11A—C11—H11C109.5
C19—N3—Zn119.50 (14)H11B—C11—H11C109.5
N1—C1—S2122.16 (16)N2—C12—C14112.12 (18)
N1—C1—S1122.17 (16)N2—C12—C13113.96 (18)
S2—C1—S1115.67 (12)C14—C12—C13113.47 (19)
N1—C2—C3113.7 (2)N2—C12—H12105.4
N1—C2—C4113.0 (2)C14—C12—H12105.4
C3—C2—C4114.1 (2)C13—C12—H12105.4
N1—C2—H2104.9C12—C13—H13A109.5
C3—C2—H2104.9C12—C13—H13B109.5
C4—C2—H2104.9H13A—C13—H13B109.5
C2—C3—H3A109.5C12—C13—H13C109.5
C2—C3—H3B109.5H13A—C13—H13C109.5
H3A—C3—H3B109.5H13B—C13—H13C109.5
C2—C3—H3C109.5C12—C14—H14A109.5
H3A—C3—H3C109.5C12—C14—H14B109.5
H3B—C3—H3C109.5H14A—C14—H14B109.5
C2—C4—H4A109.5C12—C14—H14C109.5
C2—C4—H4B109.5H14A—C14—H14C109.5
H4A—C4—H4B109.5H14B—C14—H14C109.5
C2—C4—H4C109.5N3—C15—C16122.7 (2)
H4A—C4—H4C109.5N3—C15—H15118.7
H4B—C4—H4C109.5C16—C15—H15118.7
N1—C5—C7110.4 (2)C15—C16—C17120.0 (2)
N1—C5—C6113.3 (2)C15—C16—H16120.0
C7—C5—C6113.4 (3)C17—C16—H16120.0
N1—C5—H5106.4C18—C17—C16117.1 (2)
C7—C5—H5106.4C18—C17—C20122.64 (19)
C6—C5—H5106.4C16—C17—C20120.3 (2)
C5—C6—H6A109.5C19—C18—C17119.4 (2)
C5—C6—H6B109.5C19—C18—H18120.3
H6A—C6—H6B109.5C17—C18—H18120.3
C5—C6—H6C109.5N3—C19—C18123.3 (2)
H6A—C6—H6C109.5N3—C19—H19118.3
H6B—C6—H6C109.5C18—C19—H19118.3
C5—C7—H7A109.5C20i—C20—C17125.1 (3)
C5—C7—H7B109.5C20i—C20—H20117.4
H7A—C7—H7B109.5C17—C20—H20117.4
C5—C7—H7C109.5
N3—Zn—S1—C199.95 (9)C1—N1—C2—C4−68.5 (3)
S3—Zn—S1—C1−80.02 (8)C5—N1—C2—C4112.6 (2)
S2—Zn—S1—C16.43 (7)C1—N1—C5—C7−103.7 (3)
S4—Zn—S1—C1−154.56 (7)C2—N1—C5—C775.3 (3)
N3—Zn—S2—C1−117.11 (9)C1—N1—C5—C6128.0 (2)
S1—Zn—S2—C1−6.53 (7)C2—N1—C5—C6−53.1 (3)
S3—Zn—S2—C1132.96 (7)C9—N2—C8—S46.4 (3)
S4—Zn—S2—C165.65 (9)C12—N2—C8—S4−171.92 (16)
N3—Zn—S3—C8101.33 (9)C9—N2—C8—S3−173.29 (15)
S1—Zn—S3—C8−78.70 (7)C12—N2—C8—S38.4 (3)
S2—Zn—S3—C8−155.14 (7)Zn—S4—C8—N2−171.20 (18)
S4—Zn—S3—C85.83 (7)Zn—S4—C8—S38.52 (10)
N3—Zn—S4—C8−111.15 (9)Zn—S3—C8—N2170.53 (17)
S1—Zn—S4—C8133.82 (7)Zn—S3—C8—S4−9.19 (11)
S3—Zn—S4—C8−5.90 (7)C8—N2—C9—C10122.8 (2)
S2—Zn—S4—C866.08 (9)C12—N2—C9—C10−58.7 (2)
S1—Zn—N3—C151.8 (2)C8—N2—C9—C11−110.5 (2)
S3—Zn—N3—C15−178.20 (18)C12—N2—C9—C1167.9 (2)
S2—Zn—N3—C1577.44 (19)C8—N2—C12—C1461.8 (3)
S4—Zn—N3—C15−103.51 (19)C9—N2—C12—C14−116.6 (2)
S1—Zn—N3—C19−176.66 (15)C8—N2—C12—C13−68.8 (3)
S3—Zn—N3—C193.32 (17)C9—N2—C12—C13112.8 (2)
S2—Zn—N3—C19−101.04 (16)C19—N3—C15—C16−2.2 (4)
S4—Zn—N3—C1978.01 (16)Zn—N3—C15—C16179.3 (2)
C2—N1—C1—S2−179.16 (17)N3—C15—C16—C170.6 (4)
C5—N1—C1—S2−0.3 (3)C15—C16—C17—C182.3 (4)
C2—N1—C1—S10.7 (3)C15—C16—C17—C20−177.9 (2)
C5—N1—C1—S1179.53 (17)C16—C17—C18—C19−3.5 (3)
Zn—S2—C1—N1−170.64 (18)C20—C17—C18—C19176.7 (2)
Zn—S2—C1—S19.49 (10)C15—N3—C19—C180.9 (3)
Zn—S1—C1—N1170.04 (18)Zn—N3—C19—C18179.48 (17)
Zn—S1—C1—S2−10.09 (11)C17—C18—C19—N32.0 (4)
C1—N1—C2—C363.5 (3)C18—C17—C20—C20i−15.2 (4)
C5—N1—C2—C3−115.3 (2)C16—C17—C20—C20i164.9 (3)
D—H···AD—HH···AD···AD—H···A
C20—H20···S4ii0.952.773.545 (2)139
Table 1

Selected bond lengths (Å)

Zn—N32.0621 (18)
Zn—S12.3655 (7)
Zn—S32.3662 (7)
Zn—S22.5320 (7)
Zn—S42.5720 (7)
Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯AD—HH⋯AD⋯AD—H⋯A
C20—H20⋯S4i0.952.773.545 (2)139

Symmetry code: (i) .

  1 in total

1.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290
  1 in total
  1 in total

1.  Crystal structure of bis-[N-(2-hy-droxy-eth-yl)-N-methyl-dithio-carbamato-κ2S,S'](pyridine)-zinc(II) pyridine monosolvate and its N-ethyl analogue.

Authors:  Pavel Poplaukhin; Edward R T Tiekink
Journal:  Acta Crystallogr E Crystallogr Commun       Date:  2017-07-21
  1 in total

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