supplementary materials


Acta Cryst. (2010). E66, m442    [ doi:10.1107/S1600536810010147 ]

[4'-(3-Pyridyl)-2,2';6',2''-terpyridine]dithiocyanatocopper(II)

D. Hu, H. Feng and C. Hu

Abstract top

In the title compound, [Cu(NCS)2(C20H14N4)], the Cu atom is five-coordinated in a tetragonal-pyramidal geometry.

Comment top

The heterocyclic ligand 4'-(3-pyridyl)-2,2':6'2''-terpyridine was synthesized according to literature methods (Constable et al., 1992). As a excellent tridentate chelating ligand, it can furnish complexes from a large range of metal salts. The structure of the title compound, (I), obtained from copper(I) thiocyanate is shown in Fig. 1. The Cu(II) atom is chelated by a tridentate terpydine in a cis-cis configuration and two independent thiocyanate in a five-coordinate environment and shows distorted tetragonal pyramid geometry (Fig. 1). The Cu—N bonds range from 1.931 (3)Å to 2.143 (4)Å are comparable with those reported (Hou et al., 2004). In the monomer, one thiocyanate was in the apical site while the terpyridine and the other one thiocyanate were at the equatorial positions.

Related literature top

For details of the synthesis, see: Constable & Thompson (1992). For related structures, see: Feng et al. (2006); Hou et al. (2004).

Experimental top

The mixture of CuSCN (0.0125 g, 0.1 mmol), 4'-(3-pyridyl)-2,2':6'2''-terpyridine (0.0155 g, 0.05 mmol), acetonnitril (6 ml) were placed and sealed in a 10 ml Teflon-lined stainless steel reactor and heated to 140°C for 72 h, then cooled down to room temperature at a rate of 2°C per 20 min. Green block single crystals suitable for X-ray diffraction were obtained in ca. 60% yield

Refinement top

Hydrogen atoms were placed in calculated positions (C–H 0.93 Å; U(H) = 1.2UeqC) and were included in the refinement in the riding model approximation.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. ORTEP-3 plot of the title compound with the atom labeling scheme. Displacement ellipsoids are drawn at the 35% probability level. H atoms are omitted for clarity.
[4'-(3-Pyridyl)-2,2';6',2''-terpyridine]dithiocyanatocopper(II) top
Crystal data top
[Cu(NCS)2(C20H14N4)]F(000) = 996
Mr = 490.05Dx = 1.553 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2079 reflections
a = 8.2171 (6) Åθ = 2.6–21.4°
b = 23.012 (2) ŵ = 1.26 mm1
c = 11.2279 (8) ÅT = 298 K
β = 99.079 (1)°Block, green
V = 2096.5 (3) Å30.27 × 0.27 × 0.18 mm
Z = 4
Data collection top
Bruker SMART APEX area-detector
diffractometer
4781 independent reflections
Radiation source: fine-focus sealed tube3371 reflections with I > 2σ(I)
graphiteRint = 0.038
φ and ω scanθmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 105
Tmin = 0.429, Tmax = 0.805k = 2629
12626 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.160H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0832P)2]
where P = (Fo2 + 2Fc2)/3
4781 reflections(Δ/σ)max = 0.001
280 parametersΔρmax = 0.64 e Å3
0 restraintsΔρmin = 0.44 e Å3
Crystal data top
[Cu(NCS)2(C20H14N4)]V = 2096.5 (3) Å3
Mr = 490.05Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.2171 (6) ŵ = 1.26 mm1
b = 23.012 (2) ÅT = 298 K
c = 11.2279 (8) Å0.27 × 0.27 × 0.18 mm
β = 99.079 (1)°
Data collection top
Bruker SMART APEX area-detector
diffractometer
4781 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
3371 reflections with I > 2σ(I)
Tmin = 0.429, Tmax = 0.805Rint = 0.038
12626 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.059H-atom parameters constrained
wR(F2) = 0.160Δρmax = 0.64 e Å3
S = 1.07Δρmin = 0.44 e Å3
4781 reflectionsAbsolute structure: ?
280 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.35786 (5)0.135609 (18)0.69095 (4)0.04072 (18)
S10.5487 (2)0.10524 (7)0.30631 (12)0.0930 (5)
S20.69634 (16)0.05042 (5)1.01610 (12)0.0705 (4)
N10.4648 (4)0.21527 (13)0.7228 (3)0.0395 (7)
N20.1730 (3)0.18662 (12)0.6333 (3)0.0376 (7)
N30.1684 (4)0.07761 (13)0.6675 (3)0.0477 (8)
N40.4448 (5)0.12136 (17)0.5232 (4)0.0681 (11)
N50.5115 (4)0.09198 (15)0.8049 (3)0.0567 (9)
N60.4985 (4)0.30689 (15)0.3820 (3)0.0545 (9)
C10.6201 (4)0.22617 (17)0.7760 (4)0.0459 (9)
H10.68780.19500.80320.055*
C20.6827 (5)0.28129 (18)0.7918 (4)0.0517 (10)
H20.78990.28750.83060.062*
C30.5841 (5)0.32709 (17)0.7493 (4)0.0544 (11)
H30.62470.36480.75790.065*
C40.4239 (5)0.31726 (16)0.6935 (4)0.0473 (10)
H40.35560.34810.66490.057*
C50.3680 (4)0.26104 (15)0.6813 (3)0.0369 (8)
C60.1981 (4)0.24383 (15)0.6274 (3)0.0362 (8)
C70.0730 (4)0.28084 (15)0.5800 (3)0.0394 (8)
H70.09290.32040.57410.047*
C80.0849 (4)0.25821 (15)0.5408 (3)0.0378 (8)
C90.1082 (4)0.19839 (16)0.5516 (3)0.0414 (9)
H90.21160.18200.52720.050*
C100.0237 (4)0.16374 (15)0.5987 (3)0.0396 (8)
C110.0177 (5)0.10032 (16)0.6220 (4)0.0475 (10)
C120.1211 (6)0.0675 (2)0.6069 (5)0.0726 (15)
H120.22200.08390.57490.087*
C130.1112 (7)0.0091 (2)0.6397 (6)0.094 (2)
H130.20520.01400.63260.113*
C140.0431 (7)0.0137 (2)0.6833 (6)0.097 (2)
H140.05450.05290.70310.116*
C150.1769 (6)0.02138 (17)0.6969 (5)0.0661 (13)
H150.27910.00570.72800.079*
C160.4894 (5)0.36367 (19)0.4057 (4)0.0554 (11)
H160.58050.38660.37740.066*
C170.3527 (5)0.39026 (18)0.4697 (4)0.0550 (11)
H170.35140.43010.48350.066*
C180.2186 (5)0.35648 (16)0.5128 (4)0.0482 (10)
H180.12460.37340.55570.058*
C190.2235 (4)0.29699 (15)0.4923 (3)0.0374 (8)
C200.3672 (5)0.27481 (17)0.4255 (4)0.0480 (10)
H200.37200.23510.41020.058*
C220.4845 (5)0.11376 (17)0.4333 (4)0.0441 (9)
C230.5890 (5)0.07416 (16)0.8920 (4)0.0468 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0325 (3)0.0397 (3)0.0473 (3)0.00621 (19)0.0019 (2)0.00460 (19)
S10.1100 (13)0.1146 (12)0.0590 (8)0.0514 (10)0.0277 (8)0.0161 (8)
S20.0649 (8)0.0655 (8)0.0726 (8)0.0015 (6)0.0159 (6)0.0226 (6)
N10.0289 (15)0.0434 (17)0.0445 (17)0.0030 (13)0.0009 (13)0.0023 (13)
N20.0282 (15)0.0349 (15)0.0471 (18)0.0007 (12)0.0026 (13)0.0006 (13)
N30.0423 (18)0.0389 (17)0.057 (2)0.0000 (14)0.0059 (16)0.0046 (15)
N40.069 (3)0.073 (3)0.064 (3)0.017 (2)0.015 (2)0.001 (2)
N50.045 (2)0.055 (2)0.065 (2)0.0071 (17)0.0078 (18)0.0152 (17)
N60.0328 (17)0.061 (2)0.066 (2)0.0045 (16)0.0062 (16)0.0049 (17)
C10.0250 (18)0.052 (2)0.057 (2)0.0032 (16)0.0053 (17)0.0087 (18)
C20.0277 (18)0.062 (3)0.062 (3)0.0025 (18)0.0034 (18)0.004 (2)
C30.039 (2)0.045 (2)0.077 (3)0.0086 (19)0.003 (2)0.002 (2)
C40.0312 (19)0.040 (2)0.069 (3)0.0007 (17)0.0017 (18)0.0014 (18)
C50.0270 (17)0.044 (2)0.0386 (19)0.0037 (15)0.0016 (15)0.0003 (15)
C60.0280 (17)0.0418 (19)0.0378 (19)0.0031 (15)0.0021 (15)0.0020 (15)
C70.0333 (19)0.0378 (19)0.045 (2)0.0023 (15)0.0012 (16)0.0035 (15)
C80.0298 (18)0.041 (2)0.041 (2)0.0018 (15)0.0014 (15)0.0007 (15)
C90.0291 (18)0.042 (2)0.049 (2)0.0011 (16)0.0045 (16)0.0009 (16)
C100.0327 (19)0.039 (2)0.045 (2)0.0014 (16)0.0003 (16)0.0026 (16)
C110.044 (2)0.039 (2)0.055 (2)0.0036 (17)0.0060 (19)0.0045 (17)
C120.048 (3)0.057 (3)0.102 (4)0.009 (2)0.022 (3)0.015 (3)
C130.069 (3)0.052 (3)0.146 (5)0.022 (3)0.029 (4)0.024 (3)
C140.084 (4)0.047 (3)0.144 (6)0.011 (3)0.034 (4)0.033 (3)
C150.061 (3)0.042 (2)0.088 (3)0.003 (2)0.012 (3)0.014 (2)
C160.036 (2)0.063 (3)0.064 (3)0.016 (2)0.000 (2)0.015 (2)
C170.047 (2)0.041 (2)0.077 (3)0.0076 (19)0.008 (2)0.007 (2)
C180.034 (2)0.049 (2)0.057 (2)0.0013 (17)0.0050 (18)0.0067 (18)
C190.0278 (17)0.0392 (19)0.044 (2)0.0032 (15)0.0019 (15)0.0036 (15)
C200.035 (2)0.048 (2)0.057 (2)0.0032 (17)0.0060 (18)0.0001 (18)
C220.036 (2)0.044 (2)0.050 (2)0.0082 (17)0.0011 (18)0.0021 (18)
C230.036 (2)0.038 (2)0.065 (3)0.0003 (17)0.0044 (19)0.0053 (18)
Geometric parameters (Å, °) top
Cu1—N12.040 (3)C5—C61.485 (4)
Cu1—N21.948 (3)C6—C71.375 (5)
Cu1—N32.036 (3)C7—C81.403 (5)
Cu1—N42.143 (4)C7—H70.9300
Cu1—N51.931 (3)C8—C91.398 (5)
S1—C221.609 (5)C8—C191.482 (5)
S2—C231.622 (4)C9—C101.382 (5)
N1—C11.344 (4)C9—H90.9300
N1—C51.357 (4)C10—C111.485 (5)
N2—C101.335 (4)C11—C121.356 (6)
N2—C61.336 (4)C12—C131.395 (6)
N3—C151.334 (5)C12—H120.9300
N3—C111.366 (5)C13—C141.388 (7)
N4—C221.122 (5)C13—H130.9300
N5—C231.154 (5)C14—C151.353 (6)
N6—C161.333 (5)C14—H140.9300
N6—C201.334 (5)C15—H150.9300
C1—C21.370 (5)C16—C171.378 (6)
C1—H10.9300C16—H160.9300
C2—C31.369 (5)C17—C181.373 (5)
C2—H20.9300C17—H170.9300
C3—C41.384 (5)C18—C191.388 (5)
C3—H30.9300C18—H180.9300
C4—C51.373 (5)C19—C201.392 (5)
C4—H40.9300C20—H200.9300
N1—Cu1—N279.0 (1)C8—C7—H7120.4
N1—Cu1—N3155.7 (1)C9—C8—C7118.1 (3)
N1—Cu1—N495.6 (1)C9—C8—C19121.2 (3)
N1—Cu1—N597.6 (1)C7—C8—C19120.8 (3)
N2—Cu1—N379.1 (1)C10—C9—C8119.5 (3)
N2—Cu1—N498.7 (1)C10—C9—H9120.3
N2—Cu1—N5158.0 (2)C8—C9—H9120.3
N3—Cu1—N498.1 (2)N2—C10—C9120.9 (3)
N3—Cu1—N598.7 (1)N2—C10—C11113.0 (3)
N4—Cu1—N5103.2 (2)C9—C10—C11126.1 (3)
C1—N1—C5118.1 (3)C12—C11—N3121.9 (4)
C1—N1—Cu1126.7 (3)C12—C11—C10125.1 (4)
C5—N1—Cu1115.1 (2)N3—C11—C10112.9 (3)
C10—N2—C6121.1 (3)C11—C12—C13119.4 (4)
C10—N2—Cu1119.5 (2)C11—C12—H12120.3
C6—N2—Cu1119.5 (2)C13—C12—H12120.3
C15—N3—C11118.2 (3)C14—C13—C12118.0 (5)
C15—N3—Cu1126.5 (3)C14—C13—H13121.0
C11—N3—Cu1115.3 (2)C12—C13—H13121.0
C22—N4—Cu1177.4 (4)C15—C14—C13119.7 (4)
C23—N5—Cu1164.0 (4)C15—C14—H14120.2
C16—N6—C20116.9 (3)C13—C14—H14120.2
N1—C1—C2122.8 (3)N3—C15—C14122.7 (4)
N1—C1—H1118.6N3—C15—H15118.6
C2—C1—H1118.6C14—C15—H15118.6
C3—C2—C1118.6 (3)N6—C16—C17123.7 (4)
C3—C2—H2120.7N6—C16—H16118.2
C1—C2—H2120.7C17—C16—H16118.2
C2—C3—C4120.0 (4)C18—C17—C16118.4 (4)
C2—C3—H3120.0C18—C17—H17120.8
C4—C3—H3120.0C16—C17—H17120.8
C5—C4—C3118.6 (4)C17—C18—C19120.0 (4)
C5—C4—H4120.7C17—C18—H18120.0
C3—C4—H4120.7C19—C18—H18120.0
N1—C5—C4121.9 (3)C18—C19—C20116.8 (3)
N1—C5—C6113.3 (3)C18—C19—C8122.2 (3)
C4—C5—C6124.8 (3)C20—C19—C8121.0 (3)
N2—C6—C7121.2 (3)N6—C20—C19124.2 (4)
N2—C6—C5112.6 (3)N6—C20—H20117.9
C7—C6—C5126.1 (3)C19—C20—H20117.9
C6—C7—C8119.3 (3)N4—C22—S1177.1 (5)
C6—C7—H7120.4N5—C23—S2178.6 (4)
N5—Cu1—N1—C118.8 (3)N1—C5—C6—N21.7 (4)
N2—Cu1—N1—C1176.8 (3)C4—C5—C6—N2176.0 (3)
N3—Cu1—N1—C1150.6 (3)N1—C5—C6—C7178.9 (3)
N4—Cu1—N1—C185.4 (3)C4—C5—C6—C71.2 (6)
N5—Cu1—N1—C5163.6 (3)N2—C6—C7—C82.0 (5)
N2—Cu1—N1—C55.6 (2)C5—C6—C7—C8175.0 (3)
N3—Cu1—N1—C531.8 (4)C6—C7—C8—C90.1 (5)
N4—Cu1—N1—C592.2 (3)C6—C7—C8—C19178.4 (3)
N5—Cu1—N2—C1091.2 (4)C7—C8—C9—C100.7 (5)
N3—Cu1—N2—C104.8 (3)C19—C8—C9—C10179.1 (3)
N1—Cu1—N2—C10174.1 (3)C6—N2—C10—C92.3 (5)
N4—Cu1—N2—C1091.8 (3)Cu1—N2—C10—C9176.6 (3)
N5—Cu1—N2—C689.9 (4)C6—N2—C10—C11175.0 (3)
N3—Cu1—N2—C6176.3 (3)Cu1—N2—C10—C116.0 (4)
N1—Cu1—N2—C66.9 (3)C8—C9—C10—N20.4 (6)
N4—Cu1—N2—C687.1 (3)C8—C9—C10—C11176.6 (4)
N5—Cu1—N3—C1516.7 (4)C15—N3—C11—C120.3 (7)
N2—Cu1—N3—C15174.5 (4)Cu1—N3—C11—C12176.8 (4)
N1—Cu1—N3—C15148.3 (4)C15—N3—C11—C10177.2 (4)
N4—Cu1—N3—C1588.1 (4)Cu1—N3—C11—C100.0 (4)
N5—Cu1—N3—C11160.2 (3)N2—C10—C11—C12173.0 (4)
N2—Cu1—N3—C112.4 (3)C9—C10—C11—C124.1 (7)
N1—Cu1—N3—C1128.5 (5)N2—C10—C11—N33.7 (5)
N4—Cu1—N3—C1195.0 (3)C9—C10—C11—N3179.1 (4)
N2—Cu1—N5—C2315.6 (15)N3—C11—C12—C130.7 (8)
N3—Cu1—N5—C2398.2 (12)C10—C11—C12—C13175.7 (5)
N1—Cu1—N5—C2363.7 (12)C11—C12—C13—C142.1 (10)
N4—Cu1—N5—C23161.3 (12)C12—C13—C14—C152.5 (11)
C5—N1—C1—C21.3 (6)C11—N3—C15—C140.1 (8)
Cu1—N1—C1—C2178.8 (3)Cu1—N3—C15—C14176.9 (5)
N1—C1—C2—C31.5 (7)C13—C14—C15—N31.5 (10)
C1—C2—C3—C41.1 (7)C20—N6—C16—C171.2 (7)
C2—C3—C4—C50.5 (7)N6—C16—C17—C180.7 (7)
C1—N1—C5—C40.7 (5)C16—C17—C18—C190.5 (6)
Cu1—N1—C5—C4178.5 (3)C17—C18—C19—C201.2 (6)
C1—N1—C5—C6178.5 (3)C17—C18—C19—C8177.6 (4)
Cu1—N1—C5—C63.7 (4)C9—C8—C19—C18160.4 (4)
C3—C4—C5—N10.4 (6)C7—C8—C19—C1818.0 (6)
C3—C4—C5—C6177.9 (4)C9—C8—C19—C2018.2 (6)
C10—N2—C6—C73.1 (5)C7—C8—C19—C20163.3 (4)
Cu1—N2—C6—C7175.8 (3)C16—N6—C20—C190.4 (6)
C10—N2—C6—C5174.2 (3)C18—C19—C20—N60.7 (6)
Cu1—N2—C6—C56.8 (4)C8—C19—C20—N6178.0 (4)
Acknowledgements top

The authors thank Northwest Normal University for supporting this study.

references
References top

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