Literature DB >> 21588103

(N-Benzoyl-N'-phenyl-thio-urea-κS)chlorido(η-1,5-cyclo-octa-diene)rhodium(I).

P D Riekert Kotze1, Andreas Roodt, Johan A Venter, Stefanus Otto.   

Abstract

The title compound, [RhCl(C(8)H(12))(C(14)H(12)N(2)OS)], is a rhodium(I) derivative with a functionalized thio-urea ligand. Despite the presence of several heteroatoms, the thio-urea ligand coordinates only in a monodentate fashion via the S atom. The geometry of the coordination sphere is approximately square planar about the Rh(I) atom, with two bonds to the π-electrons of the 1,5-cyclo-octa-diene ligand, one bond to the Cl(-) ligand and one bond to the S atom of the thio-urea ligand. The mol-ecular structure is stabilized by intra-molecular N-H⋯O and N-H⋯Cl hydrogen bonding. Inter-molecular N-H⋯O hydrogen-bonding inter-actions lead to the formation of layers extending parallel to (011).

Entities:  

Year:  2010        PMID： 21588103      PMCID： PMC3007502          DOI： 10.1107/S1600536810029740

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


Related literature

For related Rh(I) complexes containing thio­urea ligands, see: Cauzzi et al. (1995 ▶); Kemp et al. (1996 ▶, 1997 ▶); Roodt et al. (1994 ▶). For related Rh(I) complexes containing other or similar β-diketones and π-bonding ligands, see: Bahl et al. (2000 ▶); Brink et al. (2007 ▶); Leipoldt et al. (1977 ▶, 1980 ▶); Roodt et al. (2003 ▶); Steyl et al. (2004 ▶). For structural data for the thio­urea ligand N-phenyl-N′-benzoyl­thio­urea, see: Yamin & Yusof (2003 ▶).

Experimental

Crystal data

[RhCl(C8H12)(C14H12N2OS)] M = 502.85 Triclinic, a = 6.6703 (2) Å b = 10.1665 (4) Å c = 14.9616 (5) Å α = 96.891 (2)° β = 91.588 (2)° γ = 90.616 (2)° V = 1006.78 (6) Å3 Z = 2 Mo Kα radiation μ = 1.10 mm−1 T = 100 K 0.18 × 0.17 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.827, T max = 0.917 18721 measured reflections 4980 independent reflections 4476 reflections with I > 2σ(I) R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.029 wR(F 2) = 0.103 S = 1.23 4980 reflections 253 parameters H-atom parameters constrained Δρmax = 0.77 e Å−3 Δρmin = −0.66 e Å−3 Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and publCIF (Westrip, 2010 ▶). Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810029740/wm2369sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536810029740/wm2369Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
[RhCl(C8H12)(C14H12N2OS)]Z = 2
Mr = 502.85F(000) = 512
Triclinic, P1Dx = 1.659 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.6703 (2) ÅCell parameters from 8458 reflections
b = 10.1665 (4) Åθ = 3.1–28.3°
c = 14.9616 (5) ŵ = 1.10 mm−1
α = 96.891 (2)°T = 100 K
β = 91.588 (2)°Platelet, yellow
γ = 90.616 (2)°0.18 × 0.17 × 0.08 mm
V = 1006.78 (6) Å3
Bruker APEXII CCD area-detector diffractometer4980 independent reflections
Radiation source: fine-focus sealed tube4476 reflections with I > 2σ(I)
graphiteRint = 0.032
φ– and ω–scansθmax = 28.3°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −8→8
Tmin = 0.827, Tmax = 0.917k = −13→13
18721 measured reflectionsl = −19→19
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103H-atom parameters constrained
S = 1.23w = 1/[σ2(Fo2) + (0.0511P)2 + 0.7134P] where P = (Fo2 + 2Fc2)/3
4980 reflections(Δ/σ)max = 0.001
253 parametersΔρmax = 0.77 e Å−3
0 restraintsΔρmin = −0.66 e Å−3
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.
xyzUiso*/Ueq
Rh10.63173 (3)0.78913 (2)0.637367 (14)0.01158 (9)
Cl10.56345 (11)0.95960 (7)0.75606 (5)0.01837 (16)
S10.42173 (10)0.62944 (7)0.69410 (5)0.01483 (15)
O10.6682 (3)0.5834 (2)0.97351 (14)0.0187 (4)
N20.3860 (3)0.5223 (2)0.84601 (16)0.0155 (5)
H20.42370.51720.90230.019*
N10.6287 (3)0.6887 (2)0.84822 (16)0.0147 (5)
H10.66580.75980.82430.018*
C90.2314 (4)0.4322 (3)0.80693 (18)0.0135 (5)
C80.4760 (4)0.6125 (3)0.80349 (19)0.0134 (5)
C100.0498 (4)0.4796 (3)0.77768 (19)0.0148 (5)
H100.02890.57220.78020.018*
C61.0460 (4)0.6965 (3)1.0142 (2)0.0201 (6)
H61.00270.62601.04570.024*
C12−0.0712 (4)0.2545 (3)0.7407 (2)0.0195 (6)
H12−0.17540.19380.71860.023*
C10.9224 (4)0.7406 (3)0.94780 (19)0.0142 (5)
C70.7298 (4)0.6651 (3)0.92667 (19)0.0139 (5)
C31.1740 (5)0.9028 (3)0.9235 (2)0.0290 (8)
H31.21820.97370.89260.035*
C11−0.1017 (4)0.3899 (3)0.7445 (2)0.0173 (6)
H11−0.22650.42170.72440.021*
C20.9856 (5)0.8446 (3)0.9022 (2)0.0235 (7)
H2A0.90140.87560.85720.028*
C140.2642 (4)0.2972 (3)0.80220 (19)0.0171 (6)
H140.39000.26570.82140.021*
C130.1126 (4)0.2078 (3)0.7693 (2)0.0183 (6)
H130.13430.11520.76640.022*
C190.8922 (4)0.8992 (3)0.6073 (2)0.0167 (6)
H190.92990.97400.65470.020*
C160.5920 (5)0.7470 (3)0.4355 (2)0.0183 (6)
H16A0.45130.77290.42550.022*
H16B0.63410.69130.38060.022*
C51.2327 (5)0.7560 (3)1.0342 (2)0.0233 (7)
H51.31720.72591.07950.028*
C41.2967 (5)0.8581 (3)0.9890 (2)0.0251 (7)
H41.42510.89781.00290.030*
C201.0617 (4)0.8056 (3)0.5829 (2)0.0225 (7)
H20A1.13590.78930.63860.027*
H20B1.15590.84810.54480.027*
C210.9898 (4)0.6720 (3)0.5324 (2)0.0196 (6)
H21A0.98980.67740.46680.023*
H21B1.08470.60220.54560.023*
C220.7794 (4)0.6336 (3)0.5590 (2)0.0153 (6)
H220.77190.54650.58340.018*
C180.7382 (4)0.9284 (3)0.54959 (19)0.0147 (5)
H180.68441.01990.56280.018*
C150.6023 (4)0.6668 (3)0.51368 (19)0.0150 (6)
H150.49310.59830.51210.018*
C170.7254 (4)0.8724 (3)0.4506 (2)0.0180 (6)
H17A0.86170.85090.42940.022*
H17B0.66980.94020.41490.022*
U11U22U33U12U13U23
Rh10.01211 (12)0.01013 (13)0.01270 (13)−0.00102 (8)0.00040 (8)0.00221 (9)
Cl10.0245 (3)0.0138 (3)0.0166 (3)0.0010 (3)0.0037 (3)0.0002 (3)
S10.0163 (3)0.0168 (3)0.0120 (3)−0.0051 (3)−0.0012 (2)0.0050 (3)
O10.0183 (10)0.0233 (11)0.0155 (10)−0.0071 (8)−0.0018 (8)0.0075 (9)
N20.0171 (11)0.0185 (12)0.0114 (11)−0.0064 (9)−0.0025 (9)0.0045 (10)
N10.0167 (11)0.0141 (12)0.0136 (12)−0.0049 (9)−0.0015 (9)0.0044 (9)
C90.0151 (12)0.0139 (13)0.0113 (13)−0.0044 (10)0.0008 (10)0.0015 (10)
C80.0132 (12)0.0139 (13)0.0127 (13)0.0002 (10)0.0008 (10)0.0005 (10)
C100.0177 (13)0.0135 (13)0.0139 (14)−0.0007 (10)0.0045 (10)0.0031 (11)
C60.0179 (13)0.0270 (16)0.0168 (15)−0.0051 (12)0.0011 (11)0.0086 (12)
C120.0219 (14)0.0180 (15)0.0181 (15)−0.0077 (11)−0.0011 (11)0.0013 (12)
C10.0131 (12)0.0149 (14)0.0141 (13)−0.0023 (10)0.0012 (10)0.0001 (11)
C70.0132 (12)0.0152 (14)0.0130 (13)−0.0011 (10)0.0006 (10)0.0009 (11)
C30.0285 (17)0.0246 (17)0.035 (2)−0.0126 (14)−0.0060 (14)0.0125 (15)
C110.0144 (12)0.0212 (15)0.0167 (14)−0.0019 (11)−0.0028 (11)0.0041 (12)
C20.0230 (15)0.0233 (16)0.0249 (17)−0.0072 (12)−0.0068 (12)0.0085 (13)
C140.0191 (13)0.0188 (15)0.0135 (14)−0.0010 (11)−0.0029 (11)0.0034 (11)
C130.0236 (14)0.0141 (14)0.0172 (14)−0.0024 (11)−0.0044 (11)0.0036 (11)
C190.0140 (12)0.0126 (13)0.0238 (15)−0.0043 (10)0.0036 (11)0.0023 (11)
C160.0250 (14)0.0167 (14)0.0132 (14)−0.0025 (11)0.0014 (11)0.0024 (11)
C50.0186 (14)0.0278 (17)0.0243 (16)−0.0010 (12)−0.0049 (12)0.0080 (13)
C40.0171 (14)0.0284 (18)0.0291 (18)−0.0070 (12)−0.0017 (12)0.0023 (14)
C200.0120 (13)0.0177 (15)0.0373 (19)−0.0008 (11)0.0024 (12)0.0008 (13)
C210.0142 (13)0.0163 (15)0.0281 (17)0.0030 (11)0.0040 (11)0.0014 (12)
C220.0178 (13)0.0090 (13)0.0186 (14)−0.0003 (10)0.0037 (11)−0.0005 (11)
C180.0178 (12)0.0088 (12)0.0180 (14)−0.0039 (10)0.0025 (11)0.0041 (11)
C150.0185 (13)0.0116 (13)0.0144 (14)−0.0039 (10)0.0010 (10)−0.0006 (11)
C170.0212 (14)0.0145 (14)0.0196 (15)−0.0020 (11)0.0041 (11)0.0061 (12)
Rh1—C152.105 (3)C11—H110.9500
Rh1—C222.121 (3)C2—H2A0.9500
Rh1—C192.144 (3)C14—C131.391 (4)
Rh1—C182.170 (3)C14—H140.9500
Rh1—S12.3803 (7)C13—H130.9500
Rh1—Cl12.3850 (7)C19—C181.382 (4)
S1—C81.696 (3)C19—C201.510 (4)
O1—C71.224 (3)C19—H191.0000
N2—C81.325 (4)C16—C151.504 (4)
N2—C91.436 (3)C16—C171.538 (4)
N2—H20.8800C16—H16A0.9900
N1—C81.381 (3)C16—H16B0.9900
N1—C71.385 (4)C5—C41.375 (5)
N1—H10.8800C5—H50.9500
C9—C141.386 (4)C4—H40.9500
C9—C101.388 (4)C20—C211.537 (4)
C10—C111.393 (4)C20—H20A0.9900
C10—H100.9500C20—H20B0.9900
C6—C51.388 (4)C21—C221.528 (4)
C6—C11.392 (4)C21—H21A0.9900
C6—H60.9500C21—H21B0.9900
C12—C111.388 (4)C22—C151.410 (4)
C12—C131.394 (4)C22—H221.0000
C12—H120.9500C18—C171.521 (4)
C1—C21.393 (4)C18—H181.0000
C1—C71.496 (4)C15—H151.0000
C3—C41.382 (5)C17—H17A0.9900
C3—C21.395 (4)C17—H17B0.9900
C3—H30.9500
C15—Rh1—C2238.97 (11)C14—C13—H13120.1
C15—Rh1—C1997.74 (11)C12—C13—H13120.1
C22—Rh1—C1982.06 (11)C18—C19—C20125.5 (3)
C15—Rh1—C1881.32 (11)C18—C19—Rh172.36 (16)
C22—Rh1—C1889.91 (11)C20—C19—Rh1109.79 (19)
C19—Rh1—C1837.35 (11)C18—C19—H19113.8
C15—Rh1—S185.42 (8)C20—C19—H19113.8
C22—Rh1—S189.46 (8)Rh1—C19—H19113.8
C19—Rh1—S1161.71 (9)C15—C16—C17112.8 (2)
C18—Rh1—S1159.60 (8)C15—C16—H16A109.0
C15—Rh1—Cl1160.03 (8)C17—C16—H16A109.0
C22—Rh1—Cl1160.91 (8)C15—C16—H16B109.0
C19—Rh1—Cl189.02 (8)C17—C16—H16B109.0
C18—Rh1—Cl193.19 (8)H16A—C16—H16B107.8
S1—Rh1—Cl194.05 (2)C4—C5—C6120.6 (3)
C8—S1—Rh1112.67 (10)C4—C5—H5119.7
C8—N2—C9124.8 (2)C6—C5—H5119.7
C8—N2—H2117.6C5—C4—C3119.9 (3)
C9—N2—H2117.6C5—C4—H4120.0
C8—N1—C7126.9 (2)C3—C4—H4120.0
C8—N1—H1116.5C19—C20—C21113.1 (2)
C7—N1—H1116.5C19—C20—H20A109.0
C14—C9—C10120.7 (3)C21—C20—H20A109.0
C14—C9—N2118.8 (3)C19—C20—H20B109.0
C10—C9—N2120.5 (3)C21—C20—H20B109.0
N2—C8—N1118.5 (3)H20A—C20—H20B107.8
N2—C8—S1122.2 (2)C22—C21—C20112.1 (2)
N1—C8—S1119.1 (2)C22—C21—H21A109.2
C9—C10—C11119.3 (3)C20—C21—H21A109.2
C9—C10—H10120.3C22—C21—H21B109.2
C11—C10—H10120.3C20—C21—H21B109.2
C5—C6—C1119.6 (3)H21A—C21—H21B107.9
C5—C6—H6120.2C15—C22—C21123.7 (3)
C1—C6—H6120.2C15—C22—Rh169.93 (16)
C11—C12—C13119.9 (3)C21—C22—Rh1113.40 (19)
C11—C12—H12120.1C15—C22—H22114.0
C13—C12—H12120.1C21—C22—H22114.0
C6—C1—C2120.0 (3)Rh1—C22—H22114.0
C6—C1—C7115.9 (3)C19—C18—C17122.9 (3)
C2—C1—C7123.9 (3)C19—C18—Rh170.29 (16)
O1—C7—N1121.6 (2)C17—C18—Rh1112.65 (18)
O1—C7—C1122.5 (3)C19—C18—H18114.4
N1—C7—C1115.9 (2)C17—C18—H18114.4
C4—C3—C2120.5 (3)Rh1—C18—H18114.4
C4—C3—H3119.7C22—C15—C16125.6 (2)
C2—C3—H3119.7C22—C15—Rh171.11 (16)
C12—C11—C10120.4 (3)C16—C15—Rh1111.48 (19)
C12—C11—H11119.8C22—C15—H15113.7
C10—C11—H11119.8C16—C15—H15113.7
C1—C2—C3119.2 (3)Rh1—C15—H15113.7
C1—C2—H2A120.4C18—C17—C16111.3 (2)
C3—C2—H2A120.4C18—C17—H17A109.4
C9—C14—C13119.8 (3)C16—C17—H17A109.4
C9—C14—H14120.1C18—C17—H17B109.4
C13—C14—H14120.1C16—C17—H17B109.4
C14—C13—C12119.9 (3)H17A—C17—H17B108.0
C15—Rh1—S1—C8147.13 (13)C18—C19—C20—C21−47.9 (4)
C22—Rh1—S1—C8108.32 (13)Rh1—C19—C20—C2134.1 (3)
C19—Rh1—S1—C846.3 (3)C19—C20—C21—C22−29.6 (4)
C18—Rh1—S1—C8−163.4 (2)C20—C21—C22—C1591.3 (4)
Cl1—Rh1—S1—C8−52.90 (11)C20—C21—C22—Rh110.6 (3)
C8—N2—C9—C14120.1 (3)C19—Rh1—C22—C15−112.87 (18)
C8—N2—C9—C10−62.3 (4)C18—Rh1—C22—C15−76.23 (17)
C9—N2—C8—N1−177.1 (2)S1—Rh1—C22—C1583.38 (15)
C9—N2—C8—S1−1.8 (4)Cl1—Rh1—C22—C15−175.75 (18)
C7—N1—C8—N214.4 (4)C15—Rh1—C22—C21119.1 (3)
C7—N1—C8—S1−161.1 (2)C19—Rh1—C22—C216.2 (2)
Rh1—S1—C8—N2−175.2 (2)C18—Rh1—C22—C2142.8 (2)
Rh1—S1—C8—N10.1 (2)S1—Rh1—C22—C21−157.6 (2)
C14—C9—C10—C111.0 (4)Cl1—Rh1—C22—C21−56.7 (4)
N2—C9—C10—C11−176.5 (3)C20—C19—C18—C17−2.7 (4)
C5—C6—C1—C2−0.5 (5)Rh1—C19—C18—C17−104.8 (2)
C5—C6—C1—C7176.2 (3)C20—C19—C18—Rh1102.1 (3)
C8—N1—C7—O1−12.9 (4)C15—Rh1—C18—C19−115.12 (18)
C8—N1—C7—C1164.3 (3)C22—Rh1—C18—C19−76.96 (18)
C6—C1—C7—O111.1 (4)S1—Rh1—C18—C19−165.15 (18)
C2—C1—C7—O1−172.3 (3)Cl1—Rh1—C18—C1984.20 (16)
C6—C1—C7—N1−166.1 (3)C15—Rh1—C18—C173.3 (2)
C2—C1—C7—N110.5 (4)C22—Rh1—C18—C1741.4 (2)
C13—C12—C11—C10−0.7 (4)C19—Rh1—C18—C17118.4 (3)
C9—C10—C11—C12−0.1 (4)S1—Rh1—C18—C17−46.8 (3)
C6—C1—C2—C30.5 (5)Cl1—Rh1—C18—C17−157.41 (19)
C7—C1—C2—C3−175.9 (3)C21—C22—C15—C16−2.0 (4)
C4—C3—C2—C1−0.1 (5)Rh1—C22—C15—C16103.4 (3)
C10—C9—C14—C13−1.1 (4)C21—C22—C15—Rh1−105.3 (3)
N2—C9—C14—C13176.4 (3)C17—C16—C15—C22−46.0 (4)
C9—C14—C13—C120.4 (4)C17—C16—C15—Rh135.6 (3)
C11—C12—C13—C140.5 (4)C19—Rh1—C15—C2267.06 (18)
C15—Rh1—C19—C1864.59 (18)C18—Rh1—C15—C22100.73 (17)
C22—Rh1—C19—C18100.38 (18)S1—Rh1—C15—C22−94.81 (15)
S1—Rh1—C19—C18163.5 (2)Cl1—Rh1—C15—C22175.93 (17)
Cl1—Rh1—C19—C18−96.55 (16)C22—Rh1—C15—C16−121.7 (3)
C15—Rh1—C19—C20−57.6 (2)C19—Rh1—C15—C16−54.7 (2)
C22—Rh1—C19—C20−21.8 (2)C18—Rh1—C15—C16−21.0 (2)
C18—Rh1—C19—C20−122.2 (3)S1—Rh1—C15—C16143.47 (19)
S1—Rh1—C19—C2041.2 (4)Cl1—Rh1—C15—C1654.2 (3)
Cl1—Rh1—C19—C20141.2 (2)C19—C18—C17—C1695.1 (3)
C1—C6—C5—C40.0 (5)Rh1—C18—C17—C1614.6 (3)
C6—C5—C4—C30.4 (5)C15—C16—C17—C18−32.7 (3)
C2—C3—C4—C5−0.4 (5)
D—H···AD—HH···AD···AD—H···A
N2—H2···O10.881.992.657 (3)132
N2—H2···O1i0.882.323.053 (3)141
N1—H1···Cl10.882.473.253 (3)148
Table 1

Selected bond lengths (Å)

Rh1—C152.105 (3)
Rh1—C222.121 (3)
Rh1—C192.144 (3)
Rh1—C182.170 (3)
Rh1—S12.3803 (7)
Rh1—Cl12.3850 (7)
Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯AD—HH⋯AD⋯AD—H⋯A
N2—H2⋯O10.881.992.657 (3)132
N2—H2⋯O1i0.882.323.053 (3)141
N1—H1⋯Cl10.882.473.253 (3)148

Symmetry code: (i) .

  2 in total

1.  Dicarbonyl(tropolonato)rhodium(I), a redetermination.

Authors:  Gideon Steyl; Gert J Kruger; Andreas Roodt
Journal:  Acta Crystallogr C       Date:  2004-09-04       Impact factor: 1.172

2.  A short history of SHELX.

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

1.  (N-Benzoyl-N',N'-diphenyl-thio-ureato-κ(2)S,O)(η(4)-cyclo-octa-1,5-diene)rhodium(I).

Authors:  Stefan Warsink; Andreas Roodt
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2012-07-10
  1 in total

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