Tris(N-ethyl-N-phenyl­di­thio­carbamato-S,S')­cobalt(III)

The crystal and molecular structure of the title mononuclear Co^III complex, [Co(EtPhdtc)₃] (EtPhdtc is N-ethyl-N-phenyl­di­thio­carbamate, C₉H₁₀NS₂), has been studied by single-crystal X-ray diffraction methods at 293 (2) K.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.013 Å
• R factor = 0.058
• wR factor = 0.185
• Data-to-parameter ratio = 16.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.47
         From the CIF: _reflns_number_total               6560
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         6941
         Completeness (_total/calc)             94.51%
          Alert C: < 95% complete

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.47
         From the CIF: _reflns_number_total               6560
         From the CIF: _diffrn_reflns_limit_ max hkl    1.   14.   18.
         From the CIF: _diffrn_reflns_limit_ min hkl   -9.  -14.  -18.
         TEST1: Expected hkl limits for theta max
         Calculated maximum hkl   13.   14.   18.
         Calculated minimum hkl  -13.  -14.  -18.
          ALERT: Expected hkl max differ from CIF values


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

The title compound, (I), was prepared in an exchange reaction between a chloroform solution of commercially manufactured vulcanization ultra-accelerator [Zn(EtPhdtc)₃] (commercial designation Vulkacit P Extra; EtPhdtc is N-ethyl-N-phenyldithiocarbamate) (Debnath, 1995) and an aqueous solution of cobalt(II) sulfate. The bond lengths in (I) are consistent with average values quoted in the usual sources (International Tables for Crystallography, 1992, Vol. C, Table 9.5.1.1).

S2. Experimental

[Co(EtPhdtc)₃] was prepared by the reaction of a chloroform solution of [Zn(EtPhdtc)₂] and the an aqueous solution of cobalt(II) sulfate at room temperature. The dark-brown product was recrystallized from chloroform.

S3. Refinement

Since the crystal diffracted very weakly, not all data to 25° in θ were collected. As a result, the completeness of the data is just 81.1% to 25° in θ.

Computing details

Data collection: P2₁ Diffractometer Control Software (Syntex, 1973); cell refinement: P2₁ Diffractometer Control Software; data reduction: XP21 (Pavelčík, 1993); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1965); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The structure of tris(N-ethyl-N-phenyldithiocarbamato-S,S')cobalt(III) with displacement ellipsoids drawn at the 30% probability level.

(I)

Crystal data

[Co(C9H10NS2)3]	Z = 2
Mr = 647.83	F(000) = 672
Triclinic, P1	Dx = 1.419 Mg m^−3
a = 10.193 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.159 (2) Å	Cell parameters from 25 reflections
c = 14.253 (3) Å	θ = 3.8–9.1°
α = 105.14 (3)°	µ = 1.00 mm^−1
β = 103.09 (3)°	T = 293 K
γ = 92.30 (3)°	Prism, dark brown
V = 1515.7 (5) Å^3	0.6 × 0.3 × 0.3 mm

Data collection

Syntex P21 diffractometer	2593 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.082
Graphite monochromator	θmax = 27.5°, θmin = 1.5°
θ–2θ scans	h = −9→1
Absorption correction: ψ scan (North et al., 1968)	k = −14→14
Tmin = 0.544, Tmax = 0.741	l = −18→18
6616 measured reflections	3 standard reflections every 100 reflections
6560 independent reflections	intensity decay: 15%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.185	H-atom parameters not refined
S = 0.86	w = 1/[σ^2(Fo^2) + (0.1151P)^2] where P = (Fo^2 + 2Fc^2)/3
5379 reflections	(Δ/σ)max < 0.001
334 parameters	Δρmax = 0.40 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

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

	x	y	z	Uiso*/Ueq
Co1	0.64828 (9)	0.65023 (8)	0.32829 (6)	0.0384 (3)
S1	0.78397 (18)	0.58530 (16)	0.22191 (12)	0.0454 (5)
S2	0.51704 (19)	0.49444 (16)	0.20370 (13)	0.0484 (5)
S3	0.57138 (18)	0.80940 (16)	0.26716 (12)	0.0436 (5)
S4	0.4765 (2)	0.70615 (17)	0.40057 (13)	0.0506 (5)
S5	0.71916 (19)	0.52763 (16)	0.42927 (13)	0.0492 (5)
S6	0.81504 (19)	0.77472 (15)	0.45267 (12)	0.0421 (5)
N1	0.6539 (6)	0.3912 (5)	0.0674 (4)	0.0546 (17)
N2	0.3695 (6)	0.9005 (6)	0.3467 (4)	0.0529 (16)
N3	0.9210 (6)	0.6522 (5)	0.5865 (4)	0.0420 (14)
C1	0.6522 (7)	0.4758 (6)	0.1519 (4)	0.0407 (17)
C2	0.5309 (9)	0.3088 (9)	0.0062 (6)	0.075 (3)
H1	0.5221	0.3047	−0.0638	0.050*
H2	0.4522	0.3439	0.0254	0.050*
C3	0.5341 (11)	0.1835 (10)	0.0179 (8)	0.104 (4)
H3	0.6059	0.1449	−0.0079	0.050*
H4	0.4492	0.1351	−0.0183	0.050*
H5	0.5492	0.1876	0.0877	0.050*
C4	0.7761 (8)	0.3672 (6)	0.0341 (5)	0.0463 (19)
C5	0.7961 (9)	0.4007 (7)	−0.0469 (5)	0.059 (2)
H6	0.7335	0.4448	−0.0785	0.050*
C6	0.9084 (11)	0.3698 (8)	−0.0823 (6)	0.074 (3)
H7	0.9222	0.3929	−0.1378	0.050*
C7	0.9997 (9)	0.3046 (8)	−0.0352 (7)	0.076 (3)
H8	1.0765	0.2841	−0.0581	0.050*
C8	0.9783 (9)	0.2698 (8)	0.0453 (6)	0.072 (3)
H9	1.0397	0.2240	0.0761	0.050*
C9	0.8678 (9)	0.3015 (8)	0.0812 (5)	0.068 (2)
H10	0.8545	0.2789	0.1369	0.050*
C11	0.4579 (7)	0.8165 (6)	0.3379 (5)	0.0423 (17)
C12	0.2829 (11)	0.9099 (9)	0.4176 (7)	0.079 (3)
H11	0.2744	0.9972	0.4467	0.050*
H12	0.3259	0.8758	0.4715	0.050*
C13	0.1479 (14)	0.8436 (13)	0.3701 (10)	0.123 (4)
H13	0.1098	0.8684	0.3109	0.050*
H14	0.0909	0.8636	0.4161	0.050*
H15	0.1542	0.7553	0.3522	0.050*
C14	0.3595 (7)	0.9895 (7)	0.2897 (6)	0.052 (2)
C15	0.4148 (8)	1.1113 (8)	0.3364 (6)	0.066 (2)
H16	0.4606	1.1345	0.4038	0.050*
C16	0.4019 (9)	1.1993 (8)	0.2823 (9)	0.080 (3)
H17	0.4389	1.2816	0.3129	0.050*
C17	0.3356 (11)	1.1637 (10)	0.1854 (9)	0.079 (3)
H18	0.3271	1.2225	0.1492	0.050*
C18	0.2810 (10)	1.0461 (10)	0.1390 (6)	0.074 (3)
H19	0.2342	1.0243	0.0719	0.050*
C19	0.2944 (8)	0.9576 (7)	0.1910 (6)	0.056 (2)
H20	0.2587	0.8753	0.1583	0.050*
C21	0.8312 (7)	0.6529 (6)	0.5028 (5)	0.0415 (17)
C22	0.9275 (8)	0.5437 (7)	0.6247 (6)	0.060 (2)
H21	1.0192	0.5432	0.6628	0.050*
H22	0.9061	0.4689	0.5686	0.050*
C23	0.8321 (10)	0.5410 (8)	0.6901 (6)	0.074 (3)
H23	0.8514	0.6156	0.7450	0.050*
H24	0.8430	0.4695	0.7157	0.050*
H25	0.7406	0.5360	0.6516	0.050*
C24	1.0062 (7)	0.7627 (6)	0.6470 (4)	0.0403 (17)
C25	1.1381 (10)	0.7797 (8)	0.6428 (7)	0.076 (3)
H26	1.1722	0.7206	0.5978	0.050*
C26	1.2190 (9)	0.8822 (10)	0.7040 (8)	0.097 (4)
H27	1.3088	0.8914	0.7007	0.050*
C27	1.1745 (10)	0.9710 (8)	0.7691 (7)	0.076 (3)
H28	1.2315	1.0416	0.8095	0.050*
C28	1.0449 (10)	0.9551 (8)	0.7742 (6)	0.069 (2)
H29	1.0122	1.0147	0.8198	0.050*
C29	0.9610 (8)	0.8521 (7)	0.7131 (6)	0.060 (2)
H30	0.8714	0.8432	0.7169	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0397 (6)	0.0366 (5)	0.0328 (5)	0.0136 (4)	0.0027 (4)	0.0029 (4)
S1	0.0400 (12)	0.0466 (10)	0.0402 (9)	0.0128 (8)	0.0044 (8)	−0.0007 (8)
S2	0.0438 (12)	0.0475 (10)	0.0431 (10)	0.0095 (9)	0.0015 (8)	0.0009 (8)
S3	0.0433 (12)	0.0466 (10)	0.0409 (9)	0.0196 (8)	0.0104 (8)	0.0096 (8)
S4	0.0534 (13)	0.0560 (11)	0.0453 (10)	0.0174 (9)	0.0160 (9)	0.0140 (8)
S5	0.0549 (13)	0.0379 (9)	0.0446 (10)	0.0096 (8)	−0.0039 (9)	0.0071 (8)
S6	0.0474 (12)	0.0366 (9)	0.0359 (9)	0.0082 (8)	0.0025 (8)	0.0051 (7)
N1	0.056 (4)	0.053 (4)	0.036 (3)	0.012 (3)	−0.006 (3)	−0.009 (3)
N2	0.051 (4)	0.061 (4)	0.052 (4)	0.028 (3)	0.020 (3)	0.014 (3)
N3	0.045 (4)	0.034 (3)	0.039 (3)	0.015 (3)	−0.002 (3)	0.005 (2)
C1	0.039 (4)	0.039 (4)	0.032 (3)	0.014 (3)	−0.006 (3)	0.001 (3)
C2	0.080 (7)	0.075 (6)	0.050 (5)	0.003 (5)	0.011 (4)	−0.012 (4)
C3	0.106 (9)	0.096 (8)	0.106 (8)	−0.006 (7)	0.062 (7)	−0.007 (6)
C4	0.052 (5)	0.043 (4)	0.035 (4)	0.014 (4)	0.009 (3)	−0.003 (3)
C5	0.073 (6)	0.057 (5)	0.044 (4)	0.022 (4)	0.012 (4)	0.010 (4)
C6	0.102 (8)	0.065 (5)	0.053 (5)	0.008 (5)	0.021 (5)	0.010 (4)
C7	0.067 (7)	0.074 (6)	0.076 (6)	0.014 (5)	0.030 (5)	−0.006 (5)
C8	0.067 (7)	0.085 (6)	0.060 (5)	0.032 (5)	0.013 (5)	0.015 (5)
C9	0.081 (7)	0.079 (6)	0.043 (4)	0.034 (5)	0.016 (4)	0.012 (4)
C11	0.038 (4)	0.045 (4)	0.036 (3)	0.010 (3)	0.004 (3)	−0.001 (3)
C12	0.085 (8)	0.087 (7)	0.083 (6)	0.057 (6)	0.038 (6)	0.032 (5)
C13	0.096 (10)	0.163 (12)	0.162 (12)	0.048 (9)	0.072 (9)	0.093 (10)
C14	0.043 (5)	0.052 (5)	0.061 (5)	0.028 (4)	0.017 (4)	0.006 (4)
C15	0.046 (5)	0.065 (6)	0.067 (5)	0.015 (4)	−0.003 (4)	−0.004 (4)
C16	0.049 (6)	0.052 (5)	0.141 (9)	0.013 (4)	0.035 (6)	0.019 (6)
C17	0.076 (7)	0.075 (7)	0.119 (9)	0.035 (6)	0.054 (7)	0.053 (7)
C18	0.081 (7)	0.090 (7)	0.058 (5)	0.030 (6)	0.027 (5)	0.022 (5)
C19	0.064 (6)	0.046 (4)	0.059 (5)	0.020 (4)	0.019 (4)	0.010 (4)
C21	0.042 (4)	0.037 (4)	0.039 (4)	0.008 (3)	0.002 (3)	0.005 (3)
C22	0.060 (6)	0.049 (4)	0.061 (5)	0.011 (4)	−0.013 (4)	0.020 (4)
C23	0.094 (7)	0.058 (5)	0.066 (5)	0.003 (5)	0.007 (5)	0.025 (4)
C24	0.035 (5)	0.051 (4)	0.034 (3)	0.010 (3)	0.005 (3)	0.013 (3)
C25	0.071 (7)	0.065 (6)	0.080 (6)	0.004 (5)	0.033 (5)	−0.013 (5)
C26	0.037 (6)	0.098 (8)	0.128 (9)	−0.007 (5)	0.019 (6)	−0.011 (7)
C27	0.062 (7)	0.059 (5)	0.084 (6)	−0.008 (5)	0.006 (5)	−0.006 (5)
C28	0.059 (6)	0.061 (5)	0.071 (5)	0.005 (4)	0.013 (5)	−0.010 (4)
C29	0.045 (6)	0.063 (5)	0.059 (5)	0.013 (4)	0.011 (4)	−0.005 (4)

Geometric parameters (Å, º)

Co1—S2	2.256 (2)	C2—C3	1.452 (14)
Co1—S4	2.255 (2)	C4—C5	1.357 (10)
Co1—S5	2.259 (2)	C4—C9	1.373 (10)
Co1—S6	2.263 (2)	C5—C6	1.373 (12)
Co1—S3	2.267 (2)	C6—C7	1.369 (12)
Co1—S1	2.279 (2)	C7—C8	1.361 (12)
S1—C1	1.708 (7)	C8—C9	1.361 (11)
S2—C1	1.700 (7)	C12—C13	1.460 (15)
S3—C11	1.689 (7)	C14—C19	1.358 (10)
S4—C11	1.694 (7)	C14—C15	1.380 (10)
S5—C21	1.709 (7)	C15—C16	1.391 (13)
S6—C21	1.690 (7)	C16—C17	1.338 (13)
N1—C1	1.326 (8)	C17—C18	1.338 (13)
N1—C4	1.442 (9)	C18—C19	1.374 (11)
N1—C2	1.473 (10)	C22—C23	1.497 (12)
N2—C11	1.327 (8)	C24—C25	1.367 (11)
N2—C14	1.431 (9)	C24—C29	1.355 (9)
N2—C12	1.473 (11)	C25—C26	1.351 (12)
N3—C21	1.332 (7)	C26—C27	1.340 (12)
N3—C24	1.427 (8)	C27—C28	1.346 (12)
N3—C22	1.449 (9)	C28—C29	1.369 (11)
S2—Co1—S4	93.33 (8)	N1—C2—C3	112.1 (8)
S2—Co1—S5	94.74 (7)	C5—C4—C9	120.2 (7)
S4—Co1—S5	92.41 (8)	C5—C4—N1	120.7 (6)
S2—Co1—S6	166.96 (7)	C9—C4—N1	118.9 (7)
S4—Co1—S6	96.57 (8)	C4—C5—C6	120.4 (7)
S5—Co1—S6	76.43 (7)	C5—C6—C7	119.2 (8)
S2—Co1—S3	96.76 (7)	C8—C7—C6	120.2 (8)
S4—Co1—S3	76.09 (7)	C9—C8—C7	120.6 (8)
S5—Co1—S3	164.15 (7)	C8—C9—C4	119.4 (8)
S6—Co1—S3	93.84 (7)	N2—C11—S3	124.8 (6)
S2—Co1—S1	76.13 (7)	N2—C11—S4	124.3 (6)
S4—Co1—S1	166.80 (7)	S3—C11—S4	110.9 (4)
S5—Co1—S1	96.32 (8)	N2—C12—C13	112.6 (8)
S6—Co1—S1	95.09 (8)	C19—C14—C15	119.0 (8)
S3—Co1—S1	97.00 (8)	C19—C14—N2	121.5 (7)
C1—S1—Co1	86.3 (2)	C15—C14—N2	119.5 (7)
C1—S2—Co1	87.2 (2)	C14—C15—C16	119.8 (8)
C11—S3—Co1	86.4 (2)	C17—C16—C15	119.0 (8)
C11—S4—Co1	86.6 (2)	C16—C17—C18	122.0 (9)
C21—S5—Co1	86.3 (2)	C17—C18—C19	119.8 (8)
C21—S6—Co1	86.6 (2)	C14—C19—C18	120.4 (7)
C1—N1—C4	122.7 (6)	N3—C21—S6	125.2 (5)
C1—N1—C2	121.1 (6)	N3—C21—S5	124.1 (5)
C4—N1—C2	116.0 (5)	S6—C21—S5	110.7 (3)
C11—N2—C14	120.5 (6)	N3—C22—C23	112.7 (7)
C11—N2—C12	122.1 (6)	C25—C24—C29	117.7 (7)
C14—N2—C12	117.4 (6)	C25—C24—N3	120.9 (6)
C21—N3—C24	120.8 (5)	C29—C24—N3	121.4 (7)
C21—N3—C22	121.6 (5)	C26—C25—C24	120.1 (8)
C24—N3—C22	117.4 (5)	C25—C26—C27	122.4 (9)
N1—C1—S1	124.7 (6)	C28—C27—C26	118.1 (8)
N1—C1—S2	124.9 (5)	C27—C28—C29	120.6 (7)
S1—C1—S2	110.3 (3)	C24—C29—C28	121.2 (8)