Redetermination of bis(N,N-diethyl­di­thio­carbamato-κS)­di­methyl­tin(IV) at low temperature

The title compound, [Sn(CH₃)₂(C₅H₁₀NS₂)₂], previously reported by Morris & Schlemper [J. Cryst. Mol. Struct. (1979), 9, 13–31], has been rerefined against new intensity data. Geometric parameters agree quite well. However, the positions of the hydroxyl H atoms could be determined employing the new data. Furthermore, the results of the present structure determination are of significantly higher precision. There are one and a half mol­ecules in the asymmetric unit. The Sn atom of one mol­ecule is located on a twofold rotation axis, whereas all other atoms are located in general positions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.026
• wR factor = 0.052
• Data-to-parameter ratio = 22.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_360  Alert C Short  C(sp3)-C(sp3) Bond  C(15)  -   C(16)  =       1.36 Ang.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

Perspective views of the title compound, (I), are shown in Figs. 1 and 2. The original structure was reported by Morris & Schlemper (1979), who also reported a triclinic polymorph. Lockhart et al. (1986), on the other hand, had determined the structure of an orthorhombic polymorph. The geometric parameters of both determinations agree quite well. A least-squares fit between all non-H atoms gives an r.m.s. deviation of 0.044 Å. However, the present work is of significantly improved precision and we were able to determine the positions of the H atoms. There are one and a half molecules in the asymmetric unit. The Sn atom of one molecule is located on a twofold rotation axis, whereas all other atoms are located on general positions.

S2. Experimental

In an effort to synthesize a macrocyclic tin complex, we added diethyltin dichloride, 2,4-pentanedione, ethylenediamine and sodium diethyl dithiocarbamate trihydrate to DMSO as solvent medium. From the product mixture we isolated suitable single crystals. However, we got an entirely different structure from what we expected.

S3. Refinement

All H atoms could be located unequivocally by difference Fourier synthesis and were refined with fixed individual displacement parameters [U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C_methyl)], using a riding model, with C—H = 0.99 Å or methyl C—H = 0.98 Å. One curious feature of the structure is the very short C15—C16 bond, which at 1.356 (7) Å is much shorter than a usual CH₂—CH₃ bond. We attribute this to a slight disorder of these atoms. By the way, the structure of Morris & Schlemper (1979) shows the same feature.

Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991).

Figures

	Fig. 1. Perspective view of molecule 1 of the title compound, showing the atom numbering and displacement ellipsoids at the 50% probability level.
	Fig. 2. Perspective view of molecule 2 of the title compound, showing the atom numbering and displacement ellipsoids at the 50% probability level.

bis(N,N-diethyldithiocarbamato-κS)dimethyltin(IV)

Crystal data

[Sn(CH3)2(C5H10NS2)2]	F(000) = 2712
Mr = 445.28	Dx = 1.477 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 22309 reflections
a = 27.735 (2) Å	θ = 3.5–25.2°
b = 12.3703 (7) Å	µ = 1.68 mm^−1
c = 17.8281 (12) Å	T = 293 K
β = 100.829 (6)°	Block, colourless
V = 6007.7 (7) Å^3	0.22 × 0.21 × 0.12 mm
Z = 12

Data collection

Stoe IPDS-II two-circle diffractometer	5755 independent reflections
Radiation source: fine-focus sealed tube	3910 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
ω scans	θmax = 25.8°, θmin = 3.6°
Absorption correction: multi-scan (MULABS; Spek, 1990; Blessing, 1995)	h = −33→33
Tmin = 0.708, Tmax = 0.824	k = −15→15
41948 measured reflections	l = −21→21

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.052	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.02P)^2] where P = (Fo^2 + 2Fc^2)/3
5755 reflections	(Δ/σ)max = 0.004
258 parameters	Δρmax = 0.64 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−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 (Ų)

	x	y	z	Uiso*/Ueq
Sn1	0.662828 (8)	0.541443 (16)	0.400477 (12)	0.05720 (7)
S1	0.60531 (3)	0.38492 (6)	0.40544 (6)	0.0693 (2)
S2	0.55785 (3)	0.59621 (7)	0.36857 (6)	0.0776 (3)
S3	0.72693 (3)	0.39578 (6)	0.43772 (5)	0.0643 (2)
S4	0.76803 (3)	0.60904 (7)	0.40873 (6)	0.0754 (2)
N1	0.50936 (10)	0.4111 (2)	0.36286 (16)	0.0728 (7)
N2	0.82015 (9)	0.4268 (2)	0.43167 (14)	0.0650 (7)
C1	0.66556 (15)	0.6383 (3)	0.4988 (2)	0.0979 (13)
H1A	0.6663	0.5926	0.5426	0.147*
H1B	0.6370	0.6838	0.4924	0.147*
H1C	0.6946	0.6823	0.5062	0.147*
C2	0.66033 (13)	0.5668 (3)	0.28242 (19)	0.0824 (10)
H2A	0.6593	0.4983	0.2569	0.124*
H2B	0.6890	0.6059	0.2753	0.124*
H2C	0.6315	0.6077	0.2615	0.124*
C3	0.55218 (10)	0.4619 (3)	0.37769 (17)	0.0591 (7)
C4	0.77714 (10)	0.4759 (2)	0.42664 (16)	0.0555 (7)
C5	0.50504 (14)	0.2916 (3)	0.3642 (3)	0.0938 (12)
H5A	0.4771	0.2698	0.3259	0.113*
H5B	0.5342	0.2601	0.3505	0.113*
C6	0.4991 (3)	0.2488 (4)	0.4376 (4)	0.161 (2)
H6A	0.4965	0.1715	0.4346	0.242*
H6B	0.4698	0.2782	0.4511	0.242*
H6C	0.5270	0.2685	0.4757	0.242*
C7	0.46299 (12)	0.4720 (3)	0.3396 (2)	0.0856 (11)
H7A	0.4390	0.4256	0.3084	0.103*
H7B	0.4689	0.5331	0.3085	0.103*
C8	0.44229 (16)	0.5118 (5)	0.4052 (3)	0.137 (2)
H8A	0.4123	0.5501	0.3867	0.205*
H8B	0.4654	0.5595	0.4355	0.205*
H8C	0.4358	0.4517	0.4358	0.205*
C9	0.82803 (12)	0.3117 (3)	0.4511 (2)	0.0747 (9)
H9A	0.8046	0.2894	0.4823	0.090*
H9B	0.8607	0.3027	0.4813	0.090*
C10	0.82263 (17)	0.2400 (3)	0.3824 (3)	0.1067 (14)
H10A	0.8283	0.1663	0.3984	0.160*
H10B	0.8461	0.2608	0.3517	0.160*
H10C	0.7900	0.2469	0.3529	0.160*
C11	0.86381 (12)	0.4851 (3)	0.4171 (2)	0.0862 (11)
H11A	0.8535	0.5457	0.3834	0.103*
H11B	0.8832	0.4371	0.3916	0.103*
C12	0.89494 (16)	0.5260 (5)	0.4898 (3)	0.1310 (18)
H12A	0.9229	0.5637	0.4782	0.197*
H12B	0.9059	0.4660	0.5229	0.197*
H12C	0.8759	0.5743	0.5148	0.197*
Sn2	0.5000	0.08929 (3)	0.7500	0.07005 (11)
S5	0.43799 (3)	−0.06228 (7)	0.72285 (6)	0.0796 (3)
S6	0.39645 (4)	0.15789 (8)	0.70688 (8)	0.1019 (4)
N3	0.34354 (11)	−0.0217 (3)	0.6761 (2)	0.1022 (11)
C13	0.49290 (15)	0.1449 (4)	0.8595 (2)	0.1075 (14)
H13A	0.4909	0.0842	0.8923	0.161*
H13B	0.4637	0.1878	0.8554	0.161*
H13C	0.5209	0.1881	0.8806	0.161*
C14	0.38717 (12)	0.0231 (3)	0.6996 (2)	0.0767 (9)
C15	0.29574 (19)	0.0526 (5)	0.6403 (3)	0.1252 (16)
H15A	0.3057	0.1209	0.6211	0.150*
H15B	0.2742	0.0150	0.5994	0.150*
C16	0.2738 (3)	0.0677 (6)	0.7013 (4)	0.199 (3)
H16A	0.2449	0.1112	0.6865	0.298*
H16B	0.2962	0.1036	0.7412	0.298*
H16C	0.2648	−0.0011	0.7195	0.298*
C17	0.33664 (15)	−0.1394 (3)	0.6673 (3)	0.1012 (14)
H17A	0.3075	−0.1528	0.6290	0.121*
H17B	0.3644	−0.1694	0.6484	0.121*
C18	0.3317 (2)	−0.1970 (4)	0.7377 (3)	0.139 (2)
H18A	0.3272	−0.2728	0.7270	0.208*
H18B	0.3038	−0.1695	0.7563	0.208*
H18C	0.3608	−0.1863	0.7756	0.208*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.05827 (12)	0.04909 (12)	0.06721 (13)	−0.00293 (10)	0.01937 (9)	−0.00405 (11)
S1	0.0511 (4)	0.0508 (5)	0.1068 (7)	0.0005 (3)	0.0168 (4)	0.0055 (4)
S2	0.0693 (5)	0.0584 (5)	0.1088 (7)	0.0109 (4)	0.0261 (5)	0.0077 (5)
S3	0.0535 (4)	0.0523 (5)	0.0887 (6)	−0.0057 (3)	0.0177 (4)	0.0055 (4)
S4	0.0707 (5)	0.0556 (5)	0.1026 (7)	−0.0126 (4)	0.0233 (5)	0.0037 (5)
N1	0.0582 (16)	0.0772 (19)	0.085 (2)	−0.0004 (14)	0.0182 (14)	−0.0012 (15)
N2	0.0527 (15)	0.0768 (18)	0.0679 (17)	−0.0022 (12)	0.0178 (12)	0.0115 (14)
C1	0.092 (3)	0.100 (3)	0.107 (3)	−0.014 (2)	0.030 (2)	−0.048 (2)
C2	0.079 (2)	0.099 (3)	0.073 (2)	0.0057 (19)	0.0216 (17)	0.011 (2)
C3	0.0523 (16)	0.0603 (18)	0.0673 (19)	−0.0004 (15)	0.0182 (14)	−0.0011 (16)
C4	0.0551 (17)	0.0582 (19)	0.0550 (18)	−0.0071 (14)	0.0152 (13)	0.0012 (14)
C5	0.073 (2)	0.087 (3)	0.125 (4)	−0.012 (2)	0.028 (2)	−0.016 (3)
C6	0.197 (6)	0.115 (4)	0.196 (6)	−0.010 (4)	0.102 (5)	0.038 (4)
C7	0.0535 (19)	0.110 (3)	0.091 (3)	0.0104 (19)	0.0076 (17)	0.005 (2)
C8	0.087 (3)	0.215 (6)	0.117 (4)	0.056 (3)	0.042 (3)	0.016 (4)
C9	0.066 (2)	0.079 (2)	0.082 (3)	0.0135 (17)	0.0203 (17)	0.023 (2)
C10	0.128 (4)	0.087 (3)	0.116 (4)	0.024 (2)	0.051 (3)	0.004 (3)
C11	0.0566 (19)	0.107 (3)	0.101 (3)	−0.0086 (19)	0.0282 (19)	0.017 (2)
C12	0.085 (3)	0.159 (5)	0.142 (4)	−0.041 (3)	0.004 (3)	0.005 (4)
Sn2	0.0666 (2)	0.05157 (18)	0.1002 (3)	0.000	0.03682 (18)	0.000
S5	0.0719 (6)	0.0531 (5)	0.1127 (7)	−0.0004 (4)	0.0149 (5)	−0.0077 (5)
S6	0.0725 (6)	0.0626 (6)	0.1785 (12)	0.0098 (4)	0.0442 (7)	−0.0050 (6)
N3	0.0624 (18)	0.086 (2)	0.163 (3)	−0.0019 (16)	0.0335 (19)	−0.030 (2)
C13	0.091 (3)	0.114 (3)	0.129 (4)	−0.035 (2)	0.052 (3)	−0.045 (3)
C14	0.066 (2)	0.070 (2)	0.100 (3)	0.0009 (17)	0.0327 (18)	−0.0111 (19)
C15	0.124 (4)	0.155 (5)	0.101 (3)	−0.013 (3)	0.035 (3)	−0.014 (3)
C16	0.239 (8)	0.221 (8)	0.166 (6)	−0.043 (6)	0.114 (6)	−0.039 (6)
C17	0.083 (3)	0.100 (3)	0.129 (4)	−0.027 (2)	0.040 (2)	−0.052 (3)
C18	0.177 (5)	0.104 (4)	0.158 (5)	−0.061 (3)	0.089 (4)	−0.059 (3)

Geometric parameters (Å, º)

Sn1—C1	2.113 (3)	C9—H9B	0.9700
Sn1—C2	2.116 (3)	C10—H10A	0.9600
Sn1—S1	2.5207 (8)	C10—H10B	0.9600
Sn1—S3	2.5308 (8)	C10—H10C	0.9600
S1—C3	1.746 (3)	C11—C12	1.504 (5)
S2—C3	1.680 (3)	C11—H11A	0.9700
S3—C4	1.750 (3)	C11—H11B	0.9700
S4—C4	1.688 (3)	C12—H12A	0.9600
N1—C3	1.326 (4)	C12—H12B	0.9600
N1—C5	1.483 (4)	C12—H12C	0.9600
N1—C7	1.481 (4)	Sn2—C13^i	2.114 (4)
N2—C4	1.326 (4)	Sn2—C13	2.114 (4)
N2—C9	1.472 (4)	Sn2—S5^i	2.5287 (9)
N2—C11	1.474 (4)	Sn2—S5	2.5287 (9)
C1—H1A	0.9600	S5—C14	1.748 (3)
C1—H1B	0.9600	S6—C14	1.688 (4)
C1—H1C	0.9600	N3—C14	1.325 (4)
C2—H2A	0.9600	N3—C17	1.473 (5)
C2—H2B	0.9600	N3—C15	1.641 (6)
C2—H2C	0.9600	C13—H13A	0.9600
C5—C6	1.449 (6)	C13—H13B	0.9600
C5—H5A	0.9700	C13—H13C	0.9600
C5—H5B	0.9700	C15—C16	1.356 (7)
C6—H6A	0.9600	C15—H15A	0.9700
C6—H6B	0.9600	C15—H15B	0.9700
C6—H6C	0.9600	C16—H16A	0.9600
C7—C8	1.480 (5)	C16—H16B	0.9600
C7—H7A	0.9700	C16—H16C	0.9600
C7—H7B	0.9700	C17—C18	1.471 (6)
C8—H8A	0.9600	C17—H17A	0.9700
C8—H8B	0.9600	C17—H17B	0.9700
C8—H8C	0.9600	C18—H18A	0.9600
C9—C10	1.498 (5)	C18—H18B	0.9600
C9—H9A	0.9700	C18—H18C	0.9600
C1—Sn1—C2	136.95 (17)	C9—C10—H10A	109.5
C1—Sn1—S1	109.30 (12)	C9—C10—H10B	109.5
C2—Sn1—S1	104.24 (11)	H10A—C10—H10B	109.5
C1—Sn1—S3	105.78 (13)	C9—C10—H10C	109.5
C2—Sn1—S3	104.86 (10)	H10A—C10—H10C	109.5
S1—Sn1—S3	82.06 (3)	H10B—C10—H10C	109.5
C3—S1—Sn1	94.44 (10)	N2—C11—C12	111.7 (3)
C4—S3—Sn1	95.85 (10)	N2—C11—H11A	109.3
C3—N1—C5	122.7 (3)	C12—C11—H11A	109.3
C3—N1—C7	120.9 (3)	N2—C11—H11B	109.3
C5—N1—C7	116.3 (3)	C12—C11—H11B	109.3
C4—N2—C9	123.4 (2)	H11A—C11—H11B	107.9
C4—N2—C11	121.5 (3)	C11—C12—H12A	109.5
C9—N2—C11	115.1 (3)	C11—C12—H12B	109.5
Sn1—C1—H1A	109.5	H12A—C12—H12B	109.5
Sn1—C1—H1B	109.5	C11—C12—H12C	109.5
H1A—C1—H1B	109.5	H12A—C12—H12C	109.5
Sn1—C1—H1C	109.5	H12B—C12—H12C	109.5
H1A—C1—H1C	109.5	C13^i—Sn2—C13	142.0 (3)
H1B—C1—H1C	109.5	C13^i—Sn2—S5^i	103.90 (11)
Sn1—C2—H2A	109.5	C13—Sn2—S5^i	104.04 (14)
Sn1—C2—H2B	109.5	C13^i—Sn2—S5	104.04 (14)
H2A—C2—H2B	109.5	C13—Sn2—S5	103.90 (11)
Sn1—C2—H2C	109.5	S5^i—Sn2—S5	84.29 (4)
H2A—C2—H2C	109.5	C14—S5—Sn2	94.96 (12)
H2B—C2—H2C	109.5	C14—N3—C17	122.7 (3)
N1—C3—S2	123.1 (2)	C14—N3—C15	120.7 (3)
N1—C3—S1	118.4 (2)	C17—N3—C15	115.7 (3)
S2—C3—S1	118.51 (17)	Sn2—C13—H13A	109.5
N2—C4—S4	124.1 (2)	Sn2—C13—H13B	109.5
N2—C4—S3	117.3 (2)	H13A—C13—H13B	109.5
S4—C4—S3	118.67 (17)	Sn2—C13—H13C	109.5
C6—C5—N1	113.7 (4)	H13A—C13—H13C	109.5
C6—C5—H5A	108.8	H13B—C13—H13C	109.5
N1—C5—H5A	108.8	N3—C14—S6	123.7 (3)
C6—C5—H5B	108.8	N3—C14—S5	118.0 (3)
N1—C5—H5B	108.8	S6—C14—S5	118.3 (2)
H5A—C5—H5B	107.7	C16—C15—N3	102.5 (5)
C5—C6—H6A	109.5	C16—C15—H15A	111.3
C5—C6—H6B	109.5	N3—C15—H15A	111.3
H6A—C6—H6B	109.5	C16—C15—H15B	111.3
C5—C6—H6C	109.5	N3—C15—H15B	111.3
H6A—C6—H6C	109.5	H15A—C15—H15B	109.2
H6B—C6—H6C	109.5	C15—C16—H16A	109.5
N1—C7—C8	113.2 (3)	C15—C16—H16B	109.5
N1—C7—H7A	108.9	H16A—C16—H16B	109.5
C8—C7—H7A	108.9	C15—C16—H16C	109.5
N1—C7—H7B	108.9	H16A—C16—H16C	109.5
C8—C7—H7B	108.9	H16B—C16—H16C	109.5
H7A—C7—H7B	107.7	C18—C17—N3	114.8 (4)
C7—C8—H8A	109.5	C18—C17—H17A	108.6
C7—C8—H8B	109.5	N3—C17—H17A	108.6
H8A—C8—H8B	109.5	C18—C17—H17B	108.6
C7—C8—H8C	109.5	N3—C17—H17B	108.6
H8A—C8—H8C	109.5	H17A—C17—H17B	107.6
H8B—C8—H8C	109.5	C17—C18—H18A	109.5
N2—C9—C10	113.1 (3)	C17—C18—H18B	109.5
N2—C9—H9A	109.0	H18A—C18—H18B	109.5
C10—C9—H9A	109.0	C17—C18—H18C	109.5
N2—C9—H9B	109.0	H18A—C18—H18C	109.5
C10—C9—H9B	109.0	H18B—C18—H18C	109.5
H9A—C9—H9B	107.8
C1—Sn1—S1—C3	77.56 (17)	C3—N1—C7—C8	−86.2 (5)
C2—Sn1—S1—C3	−75.03 (14)	C5—N1—C7—C8	97.0 (4)
S3—Sn1—S1—C3	−178.43 (10)	C4—N2—C9—C10	93.7 (4)
C1—Sn1—S3—C4	−80.37 (15)	C11—N2—C9—C10	−85.8 (4)
C2—Sn1—S3—C4	69.02 (15)	C4—N2—C11—C12	95.4 (4)
S1—Sn1—S3—C4	171.73 (10)	C9—N2—C11—C12	−85.2 (4)
C5—N1—C3—S2	174.3 (3)	C13^i—Sn2—S5—C14	−76.46 (16)
C7—N1—C3—S2	−2.3 (4)	C13—Sn2—S5—C14	77.52 (19)
C5—N1—C3—S1	−3.9 (4)	S5^i—Sn2—S5—C14	−179.40 (13)
C7—N1—C3—S1	179.5 (2)	C17—N3—C14—S6	177.5 (3)
Sn1—S1—C3—N1	172.3 (2)	C15—N3—C14—S6	8.9 (5)
Sn1—S1—C3—S2	−5.91 (18)	C17—N3—C14—S5	−1.5 (5)
C9—N2—C4—S4	176.8 (2)	C15—N3—C14—S5	−170.1 (3)
C11—N2—C4—S4	−3.8 (4)	Sn2—S5—C14—N3	176.5 (3)
C9—N2—C4—S3	−4.4 (4)	Sn2—S5—C14—S6	−2.6 (2)
C11—N2—C4—S3	175.0 (2)	C14—N3—C15—C16	−96.8 (6)
Sn1—S3—C4—N2	−171.8 (2)	C17—N3—C15—C16	93.8 (5)
Sn1—S3—C4—S4	7.04 (18)	C14—N3—C17—C18	85.0 (5)
C3—N1—C5—C6	91.9 (5)	C15—N3—C17—C18	−105.8 (5)
C7—N1—C5—C6	−91.4 (5)

Symmetry code: (i) −x+1, y, −z+3/2.