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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): m1317.
Published online 2009 October 7. doi:  10.1107/S1600536809039920
PMCID: PMC2970966

[2-(3,5-Dimethyl-1H-pyrazol-1-yl-κN 2)-1,10-phenanthroline-κ2 N,N′]bis­(thio­cyanato-κN)cadmium(II)

Abstract

In the title complex, [Cd(NCS)2(C17H14N4)], the CdII ion is in a distorted trigonal-bipyramidal CdN5 coordination geometry. In the crystal structure, there is a π–π stacking inter­action involving a pyrazole ring and a symmetry-related pyridine ring with a centroid–centroid distance of 3.578 (3) Å.

Related literature

For a related structure, see: Liu et al. (2008 [triangle]).

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Object name is e-65-m1317-scheme1.jpg

Experimental

Crystal data

  • [Cd(NCS)2(C17H14N4)]
  • M r = 502.88
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1317-efi1.jpg
  • a = 7.7324 (15) Å
  • b = 14.811 (3) Å
  • c = 8.7150 (17) Å
  • β = 104.006 (2)°
  • V = 968.4 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.36 mm−1
  • T = 298 K
  • 0.25 × 0.16 × 0.10 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.727, T max = 0.876
  • 5622 measured reflections
  • 3971 independent reflections
  • 3695 reflections with I > 2σ(I)
  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.082
  • S = 1.03
  • 3971 reflections
  • 255 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.90 e Å−3
  • Δρmin = −0.38 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1803 Friedel pairs
  • Flack parameter: 0.03 (3)

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809039920/lh2919sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809039920/lh2919Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This project was supported by the National Natural Science Foundation of China (No. 20971080).

supplementary crystallographic information

Comment

Derivatives of 1,10-phenanthroline play an important role in modern coordination chemistry and many complexes have been reported with these types of compounds as ligands [see e.g. Liu et al. (2008) for a closely related Cd complex]. To the best of knowledge, no crystal structures of complexes with 2-(3,5-Dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline as a ligand have been reported so far, and herein we report the crystal structure of the title compound (I).

The molecular structure of the title compound in shown in Fig. 1. The CdII ion is coordinated by five N atoms in a distorted trigonal bipyramidal environment. Generally, CdII ion assumes six atoms coordination mode and the present five coordination mode may be attributed to the chelation mode of the ligand 2-(3,5-Dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline. The non-hydrogen atoms of the 2-(3,5-Dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline ligand define a plane within 0.0705 Å with a maximum deviation of 0.189 (6) Å for atom C8. In the crystal structure, there is a π–π stacking interaction involving the pyrazole ring and a symmetry related pyridine ring with the relevant distances being Cg1···Cg2i = 3.578 (3) Å and Cg1···Cg2iperp = 3.361 Å (symmetry code: (I) -1+x, y, z; Cg1 and Cg2 are the centroids of C7-C10/N3/N6 pyrazol ring and N1/C14/15/C17-C19 pyridine ring, respectively; Cg1···Cg2iperp is the perpendicular distance from Cg1 ring to Cg2i ring).

Experimental

10 ml methanol solution of 2-(3,5-Dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline (0.0406 g, 0.148 mmol) was added to a 10 ml methanol solution containing Cd(ClO4).6H2O (0.0655 g, 0.156 mmol) and NaNCS (0.0121 g, 0.149 mmol), and the mixed soluton was stirred for a few minutes. The colorless single crystals were obtained after the filtrate had been allowed to stand at room temperature for about a week.

Refinement

All H atoms were placed in calculated positions and refined as riding with C—H = 0.96 Å, Uiso = 1.5Ueq(C) for methyl H and C—H = 0.93 Å, Uiso = 1.2Ueq(C) for other H atoms.

Figures

Fig. 1.
The molecular structure of title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Crystal data

[Cd(NCS)2(C17H14N4)]F(000) = 500
Mr = 502.88Dx = 1.725 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 2683 reflections
a = 7.7324 (15) Åθ = 2.4–24.9°
b = 14.811 (3) ŵ = 1.36 mm1
c = 8.7150 (17) ÅT = 298 K
β = 104.006 (2)°Block, colorless
V = 968.4 (3) Å30.25 × 0.16 × 0.10 mm
Z = 2

Data collection

Bruker SMART APEX CCD diffractometer3971 independent reflections
Radiation source: fine-focus sealed tube3695 reflections with I > 2σ(I)
graphiteRint = 0.021
[var phi] and ω scansθmax = 27.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −9→9
Tmin = 0.727, Tmax = 0.876k = −18→18
5622 measured reflectionsl = −11→4

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.082w = 1/[σ2(Fo2) + (0.0366P)2 + 0.2846P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.043
3971 reflectionsΔρmax = 0.90 e Å3
255 parametersΔρmin = −0.38 e Å3
1 restraintAbsolute structure: Flack (1983), 1803 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.03 (3)

Special details

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.

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

xyzUiso*/Ueq
C10.6366 (8)0.9188 (4)0.3905 (6)0.0571 (13)
H10.63460.96870.45470.069*
C20.9604 (10)0.8931 (5)0.5143 (8)0.065 (2)
H20.96580.94280.58040.078*
C30.7957 (8)0.8709 (4)0.4056 (6)0.0537 (13)
C40.7877 (6)0.7957 (3)0.3077 (5)0.0422 (10)
C50.4839 (8)0.8938 (3)0.2833 (7)0.0555 (13)
H50.37860.92590.27490.067*
C60.4893 (8)0.8186 (3)0.1861 (6)0.0426 (12)
C70.1719 (6)0.8183 (3)0.0153 (6)0.0505 (12)
C80.0992 (8)0.9038 (4)0.0664 (8)0.0646 (15)
H8A−0.01890.91400.00240.097*
H8B0.17470.95340.05430.097*
H8C0.09530.89880.17540.097*
C90.0877 (7)0.7584 (3)−0.0940 (7)0.0547 (13)
H9−0.02890.7623−0.15470.066*
C100.2094 (7)0.6895 (4)−0.0984 (6)0.0498 (12)
C110.1863 (8)0.6062 (4)−0.1965 (8)0.0699 (17)
H11A0.29610.5921−0.22400.105*
H11B0.09430.6158−0.29110.105*
H11C0.15330.5570−0.13770.105*
C120.5035 (9)0.4510 (4)0.1563 (7)0.0515 (14)
C130.7029 (6)0.6142 (3)−0.3031 (6)0.0472 (12)
C141.0787 (7)0.6191 (3)0.2318 (6)0.0537 (14)
H141.07110.56890.16640.064*
C150.9446 (6)0.7413 (3)0.3156 (5)0.0440 (10)
C161.1065 (8)0.8435 (5)0.5223 (7)0.0664 (16)
H161.21230.86030.59280.080*
C171.1048 (7)0.7655 (3)0.4256 (6)0.0519 (12)
C181.2533 (7)0.7108 (4)0.4316 (6)0.0590 (14)
H181.36090.72400.50260.071*
C191.2406 (7)0.6379 (6)0.3332 (6)0.0634 (14)
H191.33950.60180.33480.076*
Cd10.64744 (4)0.64456 (2)0.05473 (3)0.04668 (10)
N10.9318 (6)0.6684 (2)0.2214 (4)0.0444 (10)
N20.6373 (6)0.7719 (3)0.2006 (4)0.0405 (9)
N30.3643 (5)0.7057 (3)0.0005 (5)0.0476 (9)
N40.5860 (8)0.5095 (3)0.1234 (7)0.0668 (14)
N50.6979 (6)0.6273 (3)−0.1753 (5)0.0603 (12)
N60.3425 (5)0.7858 (2)0.0737 (5)0.0441 (9)
S10.3932 (3)0.36735 (13)0.2031 (2)0.0779 (5)
S20.7124 (2)0.59068 (13)−0.48295 (17)0.0695 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.076 (4)0.043 (3)0.054 (3)−0.003 (3)0.020 (3)−0.011 (2)
C20.079 (6)0.060 (3)0.053 (3)−0.016 (4)0.009 (3)−0.017 (3)
C30.062 (3)0.049 (3)0.052 (3)−0.007 (2)0.016 (2)−0.003 (2)
C40.049 (3)0.039 (2)0.041 (2)−0.0077 (19)0.016 (2)0.0044 (18)
C50.064 (4)0.043 (3)0.061 (3)0.007 (2)0.019 (3)−0.003 (2)
C60.048 (3)0.036 (2)0.046 (3)−0.002 (2)0.016 (2)0.006 (2)
C70.043 (3)0.046 (3)0.064 (3)−0.001 (2)0.016 (2)0.015 (2)
C80.053 (3)0.049 (3)0.093 (5)0.007 (2)0.019 (3)0.015 (3)
C90.041 (3)0.056 (3)0.065 (3)0.000 (2)0.008 (2)0.011 (2)
C100.045 (3)0.054 (3)0.050 (3)−0.009 (2)0.010 (2)−0.002 (2)
C110.055 (3)0.078 (4)0.074 (4)−0.010 (3)0.010 (3)−0.018 (3)
C120.053 (3)0.052 (3)0.047 (3)0.010 (3)0.007 (2)−0.008 (2)
C130.041 (3)0.042 (2)0.057 (3)−0.0006 (18)0.010 (2)0.0041 (19)
C140.058 (3)0.053 (3)0.055 (3)0.002 (2)0.022 (2)0.005 (2)
C150.044 (3)0.050 (3)0.040 (2)−0.005 (2)0.0133 (19)0.011 (2)
C160.059 (4)0.073 (4)0.059 (3)−0.016 (3)−0.003 (3)−0.001 (3)
C170.047 (3)0.056 (3)0.050 (3)−0.016 (2)0.006 (2)0.008 (2)
C180.045 (3)0.076 (4)0.050 (3)−0.010 (3)−0.001 (2)0.012 (3)
C190.049 (3)0.075 (4)0.069 (3)0.013 (4)0.019 (2)0.020 (4)
Cd10.04711 (18)0.04536 (16)0.04917 (17)−0.0017 (2)0.01472 (12)−0.0109 (2)
N10.051 (2)0.042 (3)0.0419 (19)−0.0003 (15)0.0143 (16)0.0038 (15)
N20.046 (2)0.0389 (19)0.036 (2)−0.0045 (17)0.0089 (17)−0.0002 (16)
N30.046 (2)0.049 (2)0.046 (2)−0.0052 (17)0.0088 (17)−0.0023 (18)
N40.085 (4)0.044 (3)0.074 (3)−0.007 (3)0.025 (3)−0.001 (2)
N50.072 (3)0.059 (4)0.055 (2)−0.005 (2)0.026 (2)−0.011 (2)
N60.041 (2)0.043 (2)0.050 (2)−0.0024 (16)0.0136 (17)0.0030 (17)
S10.0718 (11)0.0883 (12)0.0750 (11)−0.0273 (9)0.0203 (8)−0.0011 (9)
S20.0666 (9)0.1010 (12)0.0424 (7)0.0002 (8)0.0160 (6)0.0019 (7)

Geometric parameters (Å, °)

C1—C51.367 (8)C11—H11B0.9600
C1—C31.398 (9)C11—H11C0.9600
C1—H10.9300C12—N41.152 (8)
C2—C161.335 (11)C12—S11.611 (7)
C2—C31.429 (9)C13—N51.141 (6)
C2—H20.9300C13—S21.624 (6)
C3—C41.396 (7)C14—N11.335 (6)
C4—N21.350 (6)C14—C191.375 (8)
C4—C151.444 (7)C14—H140.9300
C5—C61.407 (7)C15—N11.346 (6)
C5—H50.9300C15—C171.416 (7)
C6—N21.316 (7)C16—C171.429 (8)
C6—N61.395 (7)C16—H160.9300
C7—C91.348 (7)C17—C181.395 (8)
C7—N61.380 (6)C18—C191.368 (9)
C7—C81.496 (8)C18—H180.9300
C8—H8A0.9600C19—H190.9300
C8—H8B0.9600Cd1—N52.148 (4)
C8—H8C0.9600Cd1—N42.174 (5)
C9—C101.396 (8)Cd1—N22.286 (4)
C9—H90.9300Cd1—N32.310 (4)
C10—N31.317 (6)Cd1—N12.350 (4)
C10—C111.486 (7)N3—N61.377 (5)
C11—H11A0.9600
C5—C1—C3121.5 (5)N1—C14—H14118.0
C5—C1—H1119.3C19—C14—H14118.0
C3—C1—H1119.3N1—C15—C17122.6 (5)
C16—C2—C3121.0 (6)N1—C15—C4118.8 (4)
C16—C2—H2119.5C17—C15—C4118.6 (4)
C3—C2—H2119.5C2—C16—C17121.8 (6)
C4—C3—C1116.0 (5)C2—C16—H16119.1
C4—C3—C2119.3 (6)C17—C16—H16119.1
C1—C3—C2124.7 (6)C18—C17—C15117.1 (5)
N2—C4—C3122.3 (5)C18—C17—C16123.9 (5)
N2—C4—C15117.5 (4)C15—C17—C16119.0 (5)
C3—C4—C15120.2 (4)C19—C18—C17120.1 (5)
C1—C5—C6118.6 (5)C19—C18—H18120.0
C1—C5—H5120.7C17—C18—H18120.0
C6—C5—H5120.7C18—C19—C14118.6 (6)
N2—C6—N6115.2 (5)C18—C19—H19120.7
N2—C6—C5120.7 (5)C14—C19—H19120.7
N6—C6—C5124.1 (5)N5—Cd1—N4104.40 (19)
C9—C7—N6106.7 (5)N5—Cd1—N2130.96 (16)
C9—C7—C8128.0 (5)N4—Cd1—N2124.53 (18)
N6—C7—C8125.4 (5)N5—Cd1—N3103.47 (16)
C7—C8—H8A109.5N4—Cd1—N399.06 (19)
C7—C8—H8B109.5N2—Cd1—N368.42 (14)
H8A—C8—H8B109.5N5—Cd1—N1103.92 (15)
C7—C8—H8C109.5N4—Cd1—N1101.66 (18)
H8A—C8—H8C109.5N2—Cd1—N171.66 (14)
H8B—C8—H8C109.5N3—Cd1—N1140.03 (13)
C7—C9—C10106.7 (5)C14—N1—C15117.5 (4)
C7—C9—H9126.7C14—N1—Cd1127.8 (3)
C10—C9—H9126.7C15—N1—Cd1114.7 (3)
N3—C10—C9111.1 (5)C6—N2—C4120.8 (4)
N3—C10—C11119.5 (5)C6—N2—Cd1121.7 (3)
C9—C10—C11129.4 (5)C4—N2—Cd1117.4 (3)
C10—C11—H11A109.5C10—N3—N6105.5 (4)
C10—C11—H11B109.5C10—N3—Cd1136.8 (4)
H11A—C11—H11B109.5N6—N3—Cd1117.3 (3)
C10—C11—H11C109.5C12—N4—Cd1158.7 (5)
H11A—C11—H11C109.5C13—N5—Cd1171.3 (4)
H11B—C11—H11C109.5N3—N6—C7110.0 (4)
N4—C12—S1178.4 (6)N3—N6—C6117.1 (4)
N5—C13—S2177.3 (5)C7—N6—C6132.9 (4)
N1—C14—C19124.1 (5)
C5—C1—C3—C4−1.3 (8)C5—C6—N2—Cd1176.5 (4)
C5—C1—C3—C2179.8 (6)C3—C4—N2—C6−1.2 (7)
C16—C2—C3—C40.7 (9)C15—C4—N2—C6−179.6 (4)
C16—C2—C3—C1179.5 (6)C3—C4—N2—Cd1−178.6 (4)
C1—C3—C4—N22.2 (7)C15—C4—N2—Cd13.0 (5)
C2—C3—C4—N2−178.8 (5)N5—Cd1—N2—C688.0 (4)
C1—C3—C4—C15−179.4 (5)N4—Cd1—N2—C6−87.5 (4)
C2—C3—C4—C15−0.5 (7)N3—Cd1—N2—C6−1.3 (4)
C3—C1—C5—C6−0.5 (9)N1—Cd1—N2—C6−179.2 (4)
C1—C5—C6—N21.6 (8)N5—Cd1—N2—C4−94.6 (4)
C1—C5—C6—N6179.3 (5)N4—Cd1—N2—C489.9 (4)
N6—C7—C9—C100.8 (6)N3—Cd1—N2—C4176.1 (4)
C8—C7—C9—C10−179.3 (5)N1—Cd1—N2—C4−1.9 (3)
C7—C9—C10—N3−1.3 (6)C9—C10—N3—N61.3 (6)
C7—C9—C10—C11179.4 (5)C11—C10—N3—N6−179.3 (4)
N2—C4—C15—N1−2.6 (6)C9—C10—N3—Cd1−170.8 (4)
C3—C4—C15—N1179.0 (4)C11—C10—N3—Cd18.6 (8)
N2—C4—C15—C17179.2 (4)N5—Cd1—N3—C1046.2 (5)
C3—C4—C15—C170.8 (6)N4—Cd1—N3—C10−61.1 (5)
C3—C2—C16—C17−1.2 (10)N2—Cd1—N3—C10175.3 (6)
N1—C15—C17—C181.0 (7)N1—Cd1—N3—C10178.4 (4)
C4—C15—C17—C18179.2 (4)N5—Cd1—N3—N6−125.2 (3)
N1—C15—C17—C16−179.3 (5)N4—Cd1—N3—N6127.5 (3)
C4—C15—C17—C16−1.2 (7)N2—Cd1—N3—N63.8 (3)
C2—C16—C17—C18−178.9 (6)N1—Cd1—N3—N66.9 (4)
C2—C16—C17—C151.5 (9)S1—C12—N4—Cd1−177 (100)
C15—C17—C18—C190.4 (8)N5—Cd1—N4—C12−114.8 (14)
C16—C17—C18—C19−179.1 (5)N2—Cd1—N4—C1261.7 (15)
C17—C18—C19—C14−1.3 (9)N3—Cd1—N4—C12−8.2 (14)
N1—C14—C19—C180.9 (9)N1—Cd1—N4—C12137.4 (14)
C19—C14—N1—C150.6 (7)S2—C13—N5—Cd1−84 (11)
C19—C14—N1—Cd1180.0 (4)N4—Cd1—N5—C1361 (3)
C17—C15—N1—C14−1.5 (6)N2—Cd1—N5—C13−115 (3)
C4—C15—N1—C14−179.7 (4)N3—Cd1—N5—C13−42 (3)
C17—C15—N1—Cd1179.0 (3)N1—Cd1—N5—C13167 (3)
C4—C15—N1—Cd10.9 (5)C10—N3—N6—C7−0.8 (5)
N5—Cd1—N1—C14−49.9 (4)Cd1—N3—N6—C7173.1 (3)
N4—Cd1—N1—C1458.3 (4)C10—N3—N6—C6179.9 (4)
N2—Cd1—N1—C14−178.9 (4)Cd1—N3—N6—C6−6.1 (5)
N3—Cd1—N1—C14178.0 (3)C9—C7—N6—N30.0 (5)
N5—Cd1—N1—C15129.5 (3)C8—C7—N6—N3−180.0 (5)
N4—Cd1—N1—C15−122.3 (3)C9—C7—N6—C6179.1 (5)
N2—Cd1—N1—C150.5 (3)C8—C7—N6—C6−0.9 (9)
N3—Cd1—N1—C15−2.5 (4)N2—C6—N6—N34.9 (6)
N6—C6—N2—C4−178.6 (4)C5—C6—N6—N3−172.8 (5)
C5—C6—N2—C4−0.8 (7)N2—C6—N6—C7−174.1 (5)
N6—C6—N2—Cd1−1.4 (6)C5—C6—N6—C78.1 (9)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH2919).

References

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  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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