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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): m27.
Published online 2007 December 6. doi:  10.1107/S1600536807061910
PMCID: PMC2914917

(Isopropyl xanthato-κ2 S,S′)bis­(1,10-phenanthroline-κ2 N,N′)sodium(I)

Abstract

The title compound, [Na(C4H7OS2)(C12H8N2)2], is monomeric, with the Na atom chelated by the S atoms of an i-propylxanthate ligand and the N atoms of two 1,10-phenanthroline (phen) ligands. The Na atom is six-coordinate in a distorted trigonal anti­prism. A number of π–π stacking inter­actions involving the phen rings help to consolidate the crystal packing (centroid–centroid distances lie in the range 3.338–3.443 Å).

Related literature

For the structures of related complexes, see: Arnold (1995 [triangle]). For a comparison of π–π stacking inter­actions, see: Janiak (2000 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-00m27-scheme1.jpg

Experimental

Crystal data

  • [Na(C4H7OS2)(C12H8N2)2]
  • M r = 518.61
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00m27-efi1.jpg
  • a = 16.529 (4) Å
  • b = 12.153 (3) Å
  • c = 13.002 (3) Å
  • β = 102.557 (4)°
  • V = 2549.5 (11) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.26 mm−1
  • T = 298 (2) K
  • 0.23 × 0.22 × 0.16 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.944, T max = 0.960
  • 13248 measured reflections
  • 4495 independent reflections
  • 2440 reflections with I > 2σ(I)
  • R int = 0.043

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.127
  • S = 1.00
  • 4495 reflections
  • 327 parameters
  • 102 restraints
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a [triangle]); molecular graphics: SHELXTL (Sheldrick, 1997b [triangle]); 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/S1600536807061910/sq2005sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807061910/sq2005Isup2.hkl

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

supplementary crystallographic information

Comment

So far only a handful of sodium chalcogenolates have been investigated in the solid state (Arnold et al., 1995). As a continuation of our interest in sulfur-containing ligands, in this paper we report the synthesis and structural characterization of the title compound, (I).

The title compound, (I), is monomeric, with the Na atom chelated by the S atoms of an i-propylxanthate ligand and the nitrogen atoms of two 1,10-phenanthroline ligands (Fig. 1). The metal is six-coordinate in a coordination polyhedron that can be described as a distorted trigonal antiprism. The plane defined by S1, N1 and N3 is essentially parallel to that defined by S2, N2 and N4 (the two planes are inclined by 7.1°) and Na is displaced by 1.35 and 1.24 Å away from these planes, respectively.

A number of π-π stacking interactions involving the phen rings help to consolidate the crystal packing (Fig. 2). The Cg···Cg (Cg = ring centroid) distances lie in the range 3.338–3.443 Å, which is normal for such interactions (Janiak, 2000) and lead to the formation of an infinite one-dimensional chain network structure along the a axis.

Experimental

To an acetonitrile solution of NaI (1.0 mmol) was added another acetonitrile solution of sodium i-propylxanthate (1.0 mmol) and phenanthroline (2.0 mmol). The resulting solution was stirred for 3.0 h at room temperature and a yellow-red solid was obtained by filtration. The product was recrystallized in acetone to give yellow-red crystals. Yield 82%. m.p.:436 K. Anal. Calcd. (%) for C28H23NaON4S2 (Mr = 518.61): C, 64.84; H, 4.47; N, 10.80. Found (%): C, 64.52; H, 4.23; N, 10.67.

Refinement

All H atoms were positioned geometrically and treated as riding on their parent atoms [C—H = 0.93Å and Uiso = 1.2*Ueq(C) for CH (aromatic), C—H = 0.96Å and Uiso = 1.5*Ueq(C) for CH3, C—H = 0.98Å and Uiso = 1.2*Ueq(C) for CH (aliphatic)].

Figures

Fig. 1.
The structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
Crystal packing of (I) showing π-π stacking interactions (dashed lines) along the a axis.

Crystal data

[Na(C4H7OS2)(C12H8N2)2]F000 = 1080
Mr = 518.61Dx = 1.351 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
a = 16.529 (4) ÅCell parameters from 2319 reflections
b = 12.153 (3) Åθ = 2.3–21.4º
c = 13.002 (3) ŵ = 0.26 mm1
β = 102.557 (4)ºT = 298 (2) K
V = 2549.5 (11) Å3Block, yellow
Z = 40.23 × 0.22 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer4495 independent reflections
Radiation source: fine-focus sealed tube2440 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.043
T = 298(2) Kθmax = 25.0º
phi and ω scansθmin = 2.1º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −16→19
Tmin = 0.944, Tmax = 0.960k = −13→14
13248 measured reflectionsl = −15→14

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.127  w = 1/[σ2(Fo2) + (0.0469P)2 + 0.6823P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
4495 reflectionsΔρmax = 0.23 e Å3
327 parametersΔρmin = −0.22 e Å3
102 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

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
Na10.24442 (7)0.42828 (10)0.49678 (9)0.0561 (4)
S10.23574 (6)0.23226 (7)0.36513 (6)0.0594 (3)
S20.26704 (6)0.19302 (7)0.59616 (6)0.0652 (3)
N10.11912 (15)0.4938 (2)0.3635 (2)0.0542 (7)
N20.16281 (16)0.5731 (2)0.5659 (2)0.0571 (7)
N30.33660 (16)0.5616 (2)0.4359 (2)0.0543 (7)
N40.36660 (15)0.4814 (2)0.6368 (2)0.0522 (7)
O10.25533 (14)0.04248 (16)0.44589 (16)0.0656 (7)
C10.0964 (2)0.4556 (3)0.2670 (3)0.0641 (10)
H10.13300.40960.24230.077*
C20.0208 (2)0.4798 (3)0.1992 (3)0.0664 (10)
H20.00790.45110.13130.080*
C3−0.0334 (2)0.5456 (3)0.2341 (3)0.0631 (10)
H3−0.08450.56170.19050.076*
C4−0.01268 (19)0.5897 (2)0.3358 (3)0.0534 (8)
C50.06533 (18)0.5611 (2)0.3984 (2)0.0481 (8)
C60.08858 (19)0.6039 (2)0.5051 (2)0.0483 (8)
C70.0332 (2)0.6737 (2)0.5417 (3)0.0569 (9)
C80.0581 (3)0.7141 (3)0.6447 (3)0.0719 (11)
H80.02360.76110.67200.086*
C90.1327 (3)0.6846 (3)0.7041 (3)0.0757 (11)
H90.15040.71160.77220.091*
C100.1822 (2)0.6135 (3)0.6620 (3)0.0680 (10)
H100.23270.59280.70450.082*
C11−0.0666 (2)0.6609 (3)0.3771 (3)0.0670 (10)
H11−0.11780.67970.33520.080*
C12−0.0449 (2)0.7008 (3)0.4744 (3)0.0708 (11)
H12−0.08110.74720.49920.085*
C130.3242 (2)0.6017 (3)0.3396 (3)0.0688 (10)
H130.27520.58270.29300.083*
C140.3786 (3)0.6699 (3)0.3027 (3)0.0802 (12)
H140.36610.69580.23380.096*
C150.4505 (3)0.6979 (3)0.3695 (3)0.0717 (11)
H150.48840.74280.34640.086*
C160.4675 (2)0.6591 (2)0.4731 (3)0.0541 (8)
C170.40810 (18)0.5912 (2)0.5034 (2)0.0455 (8)
C180.42288 (18)0.5493 (2)0.6098 (2)0.0440 (7)
C190.49649 (19)0.5806 (2)0.6811 (3)0.0514 (8)
C200.5093 (2)0.5388 (3)0.7836 (3)0.0644 (10)
H200.55700.55750.83300.077*
C210.4525 (2)0.4713 (3)0.8106 (3)0.0667 (10)
H210.46010.44360.87870.080*
C220.3821 (2)0.4440 (3)0.7342 (3)0.0647 (9)
H220.34380.39650.75320.078*
C230.5415 (2)0.6870 (3)0.5485 (3)0.0651 (10)
H230.58080.73200.52820.078*
C240.5552 (2)0.6498 (3)0.6469 (3)0.0641 (10)
H240.60380.66930.69420.077*
C250.25295 (16)0.1505 (2)0.4714 (2)0.0446 (7)
C260.2626 (2)−0.0430 (3)0.5236 (2)0.0622 (10)
H260.2900−0.01410.59280.075*
C270.1785 (3)−0.0821 (4)0.5268 (3)0.1047 (14)
H27A0.1458−0.02140.54200.157*
H27B0.1822−0.13700.58080.157*
H27C0.1529−0.11340.45990.157*
C280.3157 (3)−0.1305 (3)0.4899 (3)0.1062 (15)
H28A0.2909−0.15420.41960.159*
H28B0.3202−0.19200.53710.159*
H28C0.3699−0.10120.49130.159*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Na10.0451 (7)0.0543 (7)0.0660 (8)−0.0008 (6)0.0060 (6)−0.0073 (6)
S10.0697 (6)0.0538 (5)0.0522 (5)−0.0038 (4)0.0078 (4)0.0015 (4)
S20.0852 (7)0.0600 (5)0.0466 (5)0.0113 (5)0.0062 (4)−0.0070 (4)
N10.0462 (17)0.0547 (16)0.0613 (18)0.0053 (14)0.0110 (14)−0.0046 (14)
N20.0554 (18)0.0576 (16)0.0582 (18)0.0005 (14)0.0122 (14)−0.0064 (14)
N30.0547 (18)0.0561 (16)0.0509 (17)0.0019 (13)0.0088 (14)0.0003 (14)
N40.0458 (16)0.0530 (15)0.0581 (17)−0.0046 (13)0.0123 (13)0.0032 (14)
O10.1042 (19)0.0457 (13)0.0483 (13)0.0012 (12)0.0195 (12)−0.0033 (11)
C10.058 (2)0.067 (2)0.066 (2)0.0055 (18)0.0102 (19)−0.0034 (19)
C20.067 (3)0.067 (2)0.061 (2)−0.002 (2)0.005 (2)0.0041 (19)
C30.057 (2)0.060 (2)0.068 (2)0.0004 (19)0.0049 (19)0.0182 (19)
C40.047 (2)0.0450 (18)0.069 (2)0.0067 (16)0.0158 (17)0.0201 (17)
C50.0429 (19)0.0396 (17)0.063 (2)−0.0008 (15)0.0148 (16)0.0059 (16)
C60.050 (2)0.0354 (16)0.062 (2)−0.0004 (15)0.0191 (17)0.0068 (15)
C70.068 (2)0.0387 (18)0.071 (2)0.0048 (17)0.030 (2)0.0101 (17)
C80.101 (3)0.047 (2)0.081 (3)0.012 (2)0.048 (2)0.005 (2)
C90.102 (3)0.064 (2)0.067 (2)−0.001 (2)0.031 (2)−0.009 (2)
C100.069 (3)0.073 (2)0.063 (2)0.003 (2)0.017 (2)−0.007 (2)
C110.057 (2)0.058 (2)0.088 (3)0.0176 (18)0.021 (2)0.027 (2)
C120.075 (3)0.052 (2)0.094 (3)0.0234 (19)0.037 (2)0.018 (2)
C130.073 (3)0.072 (2)0.058 (2)0.009 (2)0.009 (2)−0.001 (2)
C140.115 (4)0.069 (3)0.059 (2)0.019 (3)0.027 (3)0.014 (2)
C150.096 (3)0.048 (2)0.084 (3)0.004 (2)0.049 (2)0.005 (2)
C160.059 (2)0.0376 (17)0.072 (2)0.0038 (16)0.0283 (19)−0.0034 (17)
C170.0429 (19)0.0378 (16)0.058 (2)0.0023 (14)0.0158 (16)−0.0065 (15)
C180.0393 (18)0.0377 (16)0.056 (2)0.0007 (14)0.0126 (15)−0.0033 (15)
C190.045 (2)0.0425 (17)0.065 (2)0.0022 (15)0.0076 (17)−0.0132 (16)
C200.063 (2)0.060 (2)0.064 (2)0.0070 (19)0.0011 (19)−0.0125 (19)
C210.080 (3)0.068 (2)0.050 (2)0.008 (2)0.011 (2)0.0039 (18)
C220.069 (3)0.060 (2)0.068 (2)−0.0030 (19)0.020 (2)0.0069 (19)
C230.058 (2)0.0467 (19)0.097 (3)−0.0148 (17)0.031 (2)−0.011 (2)
C240.047 (2)0.058 (2)0.087 (3)−0.0102 (18)0.0121 (19)−0.019 (2)
C250.0343 (17)0.0451 (17)0.0536 (18)0.0008 (13)0.0076 (14)−0.0052 (15)
C260.083 (3)0.050 (2)0.051 (2)0.0037 (18)0.0111 (19)0.0061 (16)
C270.110 (4)0.111 (3)0.095 (3)−0.022 (3)0.027 (3)0.028 (3)
C280.138 (4)0.079 (3)0.101 (3)0.039 (3)0.023 (3)0.001 (2)

Geometric parameters (Å, °)

Na1—N32.470 (3)C10—H100.9300
Na1—N42.492 (3)C11—C121.329 (5)
Na1—N22.501 (3)C11—H110.9300
Na1—N12.523 (3)C12—H120.9300
Na1—S12.9188 (15)C13—C141.383 (5)
Na1—S23.1265 (16)C13—H130.9300
S1—C251.675 (3)C14—C151.354 (5)
S2—C251.670 (3)C14—H140.9300
N1—C11.314 (4)C15—C161.397 (5)
N1—C51.357 (4)C15—H150.9300
N2—C101.315 (4)C16—C171.403 (4)
N2—C61.360 (4)C16—C231.432 (4)
N3—C131.317 (4)C17—C181.444 (4)
N3—C171.359 (3)C18—C191.412 (4)
N4—C221.316 (4)C19—C201.399 (4)
N4—C181.346 (4)C19—C241.425 (4)
O1—C251.357 (3)C20—C211.349 (4)
O1—C261.435 (3)C20—H200.9300
C1—C21.395 (4)C21—C221.396 (4)
C1—H10.9300C21—H210.9300
C2—C31.351 (4)C22—H220.9300
C2—H20.9300C23—C241.329 (4)
C3—C41.398 (4)C23—H230.9300
C3—H30.9300C24—H240.9300
C4—C51.411 (4)C26—C271.478 (5)
C4—C111.429 (4)C26—C281.504 (5)
C5—C61.452 (4)C26—H260.9800
C6—C71.405 (4)C27—H27A0.9600
C7—C81.402 (5)C27—H27B0.9600
C7—C121.431 (4)C27—H27C0.9600
C8—C91.354 (5)C28—H28A0.9600
C8—H80.9300C28—H28B0.9600
C9—C101.382 (5)C28—H28C0.9600
C9—H90.9300
N3—Na1—N466.79 (9)C4—C11—H11119.4
N3—Na1—N294.11 (10)C11—C12—C7121.3 (3)
N4—Na1—N288.26 (9)C11—C12—H12119.3
N3—Na1—N192.54 (9)C7—C12—H12119.3
N4—Na1—N1146.48 (10)N3—C13—C14125.0 (4)
N2—Na1—N166.31 (9)N3—C13—H13117.5
N3—Na1—S1107.62 (7)C14—C13—H13117.5
N4—Na1—S1124.66 (7)C15—C14—C13118.3 (4)
N2—Na1—S1145.46 (8)C15—C14—H14120.9
N1—Na1—S185.78 (7)C13—C14—H14120.9
N3—Na1—S2134.91 (8)C14—C15—C16119.9 (4)
N4—Na1—S285.99 (7)C14—C15—H15120.0
N2—Na1—S2121.38 (8)C16—C15—H15120.0
N1—Na1—S2125.37 (7)C15—C16—C17117.5 (3)
S1—Na1—S258.81 (4)C15—C16—C23123.0 (3)
C25—S1—Na191.28 (11)C17—C16—C23119.5 (3)
C25—S2—Na184.41 (11)N3—C17—C16122.5 (3)
C1—N1—C5117.4 (3)N3—C17—C18117.9 (3)
C1—N1—Na1124.5 (2)C16—C17—C18119.6 (3)
C5—N1—Na1117.4 (2)N4—C18—C19122.7 (3)
C10—N2—C6116.9 (3)N4—C18—C17118.9 (3)
C10—N2—Na1124.4 (2)C19—C18—C17118.4 (3)
C6—N2—Na1118.3 (2)C20—C19—C18117.2 (3)
C13—N3—C17116.8 (3)C20—C19—C24122.6 (3)
C13—N3—Na1124.6 (2)C18—C19—C24120.1 (3)
C17—N3—Na1118.5 (2)C21—C20—C19120.0 (3)
C22—N4—C18117.5 (3)C21—C20—H20120.0
C22—N4—Na1124.8 (2)C19—C20—H20120.0
C18—N4—Na1117.7 (2)C20—C21—C22118.5 (3)
C25—O1—C26122.0 (2)C20—C21—H21120.7
N1—C1—C2124.0 (3)C22—C21—H21120.7
N1—C1—H1118.0N4—C22—C21124.1 (3)
C2—C1—H1118.0N4—C22—H22117.9
C3—C2—C1118.7 (3)C21—C22—H22117.9
C3—C2—H2120.6C24—C23—C16121.3 (3)
C1—C2—H2120.6C24—C23—H23119.3
C2—C3—C4120.1 (3)C16—C23—H23119.3
C2—C3—H3120.0C23—C24—C19121.1 (3)
C4—C3—H3120.0C23—C24—H24119.5
C3—C4—C5117.2 (3)C19—C24—H24119.5
C3—C4—C11122.9 (3)O1—C25—S2122.1 (2)
C5—C4—C11119.9 (3)O1—C25—S1112.4 (2)
N1—C5—C4122.6 (3)S2—C25—S1125.50 (18)
N1—C5—C6118.6 (3)O1—C26—C27108.5 (3)
C4—C5—C6118.8 (3)O1—C26—C28105.7 (3)
N2—C6—C7122.8 (3)C27—C26—C28113.1 (3)
N2—C6—C5118.4 (3)O1—C26—H26109.8
C7—C6—C5118.9 (3)C27—C26—H26109.8
C8—C7—C6117.2 (3)C28—C26—H26109.8
C8—C7—C12122.9 (3)C26—C27—H27A109.5
C6—C7—C12119.9 (3)C26—C27—H27B109.5
C9—C8—C7119.6 (4)H27A—C27—H27B109.5
C9—C8—H8120.2C26—C27—H27C109.5
C7—C8—H8120.2H27A—C27—H27C109.5
C8—C9—C10118.9 (4)H27B—C27—H27C109.5
C8—C9—H9120.5C26—C28—H28A109.5
C10—C9—H9120.5C26—C28—H28B109.5
N2—C10—C9124.5 (4)H28A—C28—H28B109.5
N2—C10—H10117.7C26—C28—H28C109.5
C9—C10—H10117.7H28A—C28—H28C109.5
C12—C11—C4121.1 (3)H28B—C28—H28C109.5
C12—C11—H11119.4

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SQ2005).

References

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