supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

sq2005 scheme

Acta Cryst. (2008). E64, m27    [ doi:10.1107/S1600536807061910 ]

(Isopropyl xanthato-[kappa]2S,S')bis(1,10-phenanthroline-[kappa]2N,N')sodium(I)

F. Li

Abstract top

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 [pi]-[pi] stacking interactions involving the phen rings help to consolidate the crystal packing (centroid-centroid distances lie in the range 3.338-3.443 Å).

Comment top

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.

Related literature top

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

Experimental top

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 top

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)].

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. Crystal packing of (I) showing π-π stacking interactions (dashed lines) along the a axis.
(Isopropyl xanthato-κ2S,S')bis(1,10-phenanthroline-κ2N,N')sodium(I) top
Crystal data top
[Na(C4H7OS2)(C12H8N2)2]F000 = 1080
Mr = 518.61Dx = 1.351 Mg m−3
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 mm−1
β = 102.557 (4)ºT = 298 (2) K
V = 2549.5 (11) Å3Block, yellow
Z = 40.23 × 0.22 × 0.16 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		4495 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 top
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 Å−3
327 parametersΔρmin = −0.22 e Å−3
102 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Na(C4H7OS2)(C12H8N2)2]V = 2549.5 (11) Å3
Mr = 518.61Z = 4
Monoclinic, P21/cMo Kα
a = 16.529 (4) ŵ = 0.26 mm−1
b = 12.153 (3) ÅT = 298 (2) K
c = 13.002 (3) Å0.23 × 0.22 × 0.16 mm
β = 102.557 (4)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		4495 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2440 reflections with I > 2σ(I)
Tmin = 0.944, Tmax = 0.960Rint = 0.043
13248 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.046102 restraints
wR(F2) = 0.127H-atom parameters constrained
S = 1.00Δρmax = 0.23 e Å−3
4495 reflectionsΔρmin = −0.22 e Å−3
327 parameters
Special details top

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) top
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) top
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, °) top
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
Table 1
Selected geometric parameters (Å, °) top
Na1—N32.470 (3)Na1—N12.523 (3)
Na1—N42.492 (3)Na1—S12.9188 (15)
Na1—N22.501 (3)Na1—S23.1265 (16)
N3—Na1—N466.79 (9)N2—Na1—S1145.46 (8)
N3—Na1—N294.11 (10)N1—Na1—S185.78 (7)
N4—Na1—N288.26 (9)N3—Na1—S2134.91 (8)
N3—Na1—N192.54 (9)N4—Na1—S285.99 (7)
N4—Na1—N1146.48 (10)N2—Na1—S2121.38 (8)
N2—Na1—N166.31 (9)N1—Na1—S2125.37 (7)
N3—Na1—S1107.62 (7)S1—Na1—S258.81 (4)
N4—Na1—S1124.66 (7)
Acknowledgements top

Any acknowledgements?

references
References top

Arnold, J. (1995). Proj. Inorg. Chem. 43, 353–358.

Janiak, C. (2000). J. Chem. Soc. Dalton Trans. pp. 3885–3896.

Sheldrick, G. M. (1990). Acta Cryst. A46, 467–473.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997a). SHELXL97. University of Göttingen, Germany.

Sheldrick, G. M. (1997b). SHELXTL. Version 5.. Bruker AXS Inc., Madison, Wisconsin, USA.

Siemens (1996). SMART and SAINT. Siemens Analytical X-Ray Instruments Inc., Madison, Wisconsin, USA.