Bis(μ-4-methyl­piperidine-1-dithio­carboxyl­ato-κ²S:S′)[bis­(4-methyl­piperidine-1-dithio­carboxyl­ato-S:S′)zinc(II)]

In the centrosymmetric title compound, [Zn₂(C₇H₁₂NS₂)₄], each Zn atom is chelated by one dithio­carboxyl­ate group, while the other dithio­carboxyl­ate ligand bridges the two Zn atoms to form a dimeric binuclear complex. The coordination geometry about each Zn atom is distorted tetra­hedral.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.043
• wR factor = 0.124
• Data-to-parameter ratio = 23.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.94

Alert level C
REFLT03_ALERT_3_C  Reflection count < 95% complete
           From the CIF: _diffrn_reflns_theta_max           28.28
           From the CIF: _diffrn_reflns_theta_full          28.28
           From the CIF: _reflns_number_total               4480
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         4740
           Completeness (_total/calc)             94.51%
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Zn1    -   S4      ..       8.79 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C4

Alert level G
ABSTM02_ALERT_3_G  The ratio of expected to reported Tmax/Tmin(RR') is < 0.75
            Tmin and Tmax reported:      0.450     0.819
            Tmin(prime) and Tmax expected:      0.592     0.773
            RR(prime) =      0.718
            Please check that your absorption correction is appropriate.

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

The structure of zinc(II) dithiocarbamate is that of a centrosymmetric dimer (Cox & Tiekink, 1997). Zinc dithiocarbamates have been studied as antioxidant additives to photographic film (Fukumoto et al., 1986) and as hydrocarbon-based lubricants (Shelkova et al., 1990). A number of other centrosymmetric dimeric zinc(II) dithiocarbamate complexes have been reported, such as the ethyl isopropyldithiocarbamate complex (Baba et al., 2001a) and the ethyl butyldithiocarbamate complex (Baba et al., 2001b).

In the title complex, (I), the asymmetric unit contains one-half of the complex molecule, which lies about a centre of symmetry. One dithiocarboxylate group behaves as a chelating bidentate ligand, coordinating through atoms S3 and S4, while the other bidentate dithiocarboxylate ligand bridges two adjacent Zn atoms through atoms S1 and S2ⁱ [symmetry code: (i) −x, 2 − y, −z] to give a centrosymmetric dimer (Fig. 1). The coordination geometry about the Zn atoms is distorted tetrahedral (Table 1).

S2. Experimental

Carbon disulfide was added to an ethanolic solution of 4-methylpiperidine with constant stirring at 273 K. After 2 h, an ethanolic solution of zinc chloride was added. [Please give brief details of quantities and volumes or concentrations] The mixture was stirred vigorously and set aside. The solid which formed was isolated, washed with an excess of ethanol and recrystallized from a dichloromethane–methanol (1/1) mixture.

S3. Refinement

All H atoms bound to carbon were refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H, C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C) for CH₂, and C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for CH₃.

Computing details

Data collection: CrysAlis RED [Or CCD?] (Oxford Diffraction, 2004); cell refinement: CrysAlis RED; data reduction: CrysAlis RED; program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Figures

Fig. 1. The structure of (I), showing the atom-numbering scheme and with displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (i) −x, 2 − y, −z.]

Bis(µ-4-methylpiperidine-1-dithiocarboxylato-κ²S:S')[bis(4- methylpiperidine-1-dithiocarboxylato-S:S')zinc(II)]

Crystal data

[Zn2(C7H12NS2)4]	Z = 1
Mr = 827.92	F(000) = 432
Triclinic, P1	Dx = 1.438 Mg m^−3
Hall symbol: -P 1	Melting point: 511 K
a = 8.1806 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.4347 (11) Å	Cell parameters from 194 reflections
c = 11.9679 (12) Å	θ = 4.2–29.4°
α = 108.808 (9)°	µ = 1.72 mm^−1
β = 107.28 (1)°	T = 293 K
γ = 101.583 (9)°	Prism, colourless
V = 955.9 (2) Å^3	0.3 × 0.2 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur2 CCD diffractometer	4480 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3095 reflections with I > 2sσ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 8.6225 pixels mm^-1	θmax = 28.3°, θmin = 4.2°
ω/2θ scans	h = −10→10
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2004)	k = −15→14
Tmin = 0.450, Tmax = 0.819	l = −13→15
7446 measured reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.124	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0674P)^2 + 0.1131P] where P = (Fo^2 + 2Fc^2)/3
4480 reflections	(Δ/σ)max < 0.001
192 parameters	Δρmax = 0.61 e Å^−3
0 restraints	Δρmin = −0.34 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
Zn1	0.05714 (5)	1.01640 (4)	0.16884 (3)	0.04582 (14)
S1	0.25445 (11)	1.04276 (7)	0.06343 (7)	0.04222 (19)
S2	0.06113 (14)	0.81258 (10)	−0.18708 (8)	0.0591 (3)
S3	−0.07059 (11)	0.81961 (8)	0.17834 (7)	0.0482 (2)
S4	0.22765 (12)	1.04734 (8)	0.38971 (8)	0.0497 (2)
N1	0.3251 (4)	0.8174 (3)	0.0088 (3)	0.0544 (7)
N2	0.0716 (4)	0.8364 (3)	0.4167 (2)	0.0484 (7)
C1	0.2232 (4)	0.8814 (3)	−0.0332 (3)	0.0409 (7)
C2	0.3192 (6)	0.6873 (4)	−0.0746 (3)	0.0721 (12)
H2A	0.4357	0.6929	−0.0810	0.086*
H2B	0.2283	0.6588	−0.1600	0.086*
C3	0.2743 (6)	0.5901 (4)	−0.0199 (4)	0.0671 (11)
H3A	0.2720	0.5056	−0.0746	0.080*
H3B	0.1544	0.5809	−0.0188	0.080*
C4	0.4108 (5)	0.6309 (3)	0.1157 (4)	0.0562 (9)
H4	0.5296	0.6363	0.1113	0.067*
C5	0.4222 (5)	0.7673 (4)	0.1981 (3)	0.0604 (10)
H5A	0.5176	0.7974	0.2820	0.072*
H5B	0.3089	0.7632	0.2093	0.072*
C6	0.4600 (5)	0.8656 (4)	0.1406 (3)	0.0613 (10)
H6A	0.4553	0.9487	0.1928	0.074*
H6B	0.5806	0.8794	0.1399	0.074*
C7	0.3691 (7)	0.5329 (5)	0.1720 (5)	0.0893 (15)
H7A	0.2522	0.5243	0.1763	0.134*
H7B	0.4597	0.5627	0.2567	0.134*
H7C	0.3690	0.4496	0.1188	0.134*
C8	0.0764 (4)	0.8951 (3)	0.3388 (3)	0.0381 (6)
C9	0.2045 (5)	0.8872 (3)	0.5498 (3)	0.0621 (10)
H9A	0.1421	0.8942	0.6079	0.074*
H9B	0.2855	0.9735	0.5734	0.074*
C10	0.3122 (5)	0.7947 (4)	0.5602 (4)	0.0662 (11)
H10A	0.3834	0.7955	0.5083	0.079*
H10B	0.3956	0.8262	0.6485	0.079*
C11	0.1944 (5)	0.6555 (4)	0.5173 (3)	0.0568 (9)
H11	0.1339	0.6547	0.5767	0.068*
C12	0.0481 (5)	0.6108 (3)	0.3836 (3)	0.0567 (9)
H12A	0.1044	0.6018	0.3219	0.068*
H12B	−0.0360	0.5257	0.3603	0.068*
C13	−0.0549 (5)	0.7057 (3)	0.3774 (3)	0.0548 (9)
H13A	−0.1427	0.6761	0.2907	0.066*
H13B	−0.1199	0.7097	0.4337	0.066*
C14	0.3047 (7)	0.5638 (5)	0.5201 (5)	0.0933 (15)
H14A	0.3729	0.5683	0.4678	0.140*
H14B	0.2248	0.4759	0.4876	0.140*
H14C	0.3864	0.5891	0.6067	0.140*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0566 (3)	0.0481 (2)	0.0463 (2)	0.02432 (18)	0.02641 (18)	0.02565 (18)
S1	0.0496 (4)	0.0402 (4)	0.0437 (4)	0.0174 (3)	0.0220 (3)	0.0203 (3)
S2	0.0805 (6)	0.0615 (6)	0.0341 (4)	0.0415 (5)	0.0145 (4)	0.0144 (4)
S3	0.0447 (4)	0.0478 (5)	0.0418 (4)	0.0077 (4)	0.0053 (3)	0.0210 (4)
S4	0.0526 (5)	0.0434 (4)	0.0436 (4)	0.0048 (4)	0.0102 (4)	0.0207 (4)
N1	0.0630 (18)	0.0558 (18)	0.0434 (14)	0.0352 (15)	0.0136 (13)	0.0160 (13)
N2	0.0536 (16)	0.0445 (15)	0.0388 (13)	0.0071 (12)	0.0094 (12)	0.0204 (12)
C1	0.0455 (17)	0.0480 (17)	0.0398 (15)	0.0236 (14)	0.0211 (13)	0.0216 (13)
C2	0.104 (3)	0.071 (3)	0.0465 (19)	0.060 (3)	0.023 (2)	0.0163 (18)
C3	0.071 (3)	0.050 (2)	0.066 (2)	0.0315 (19)	0.0150 (19)	0.0085 (18)
C4	0.055 (2)	0.055 (2)	0.066 (2)	0.0283 (17)	0.0255 (17)	0.0248 (18)
C5	0.062 (2)	0.064 (2)	0.0478 (19)	0.0295 (19)	0.0107 (16)	0.0178 (17)
C6	0.057 (2)	0.055 (2)	0.055 (2)	0.0259 (17)	0.0008 (16)	0.0170 (17)
C7	0.121 (4)	0.074 (3)	0.114 (4)	0.047 (3)	0.071 (3)	0.057 (3)
C8	0.0357 (15)	0.0410 (16)	0.0396 (15)	0.0134 (12)	0.0134 (12)	0.0194 (13)
C9	0.078 (3)	0.054 (2)	0.0340 (16)	0.0013 (19)	0.0052 (16)	0.0201 (15)
C10	0.058 (2)	0.077 (3)	0.053 (2)	0.007 (2)	0.0102 (17)	0.034 (2)
C11	0.063 (2)	0.060 (2)	0.062 (2)	0.0240 (18)	0.0315 (18)	0.0346 (18)
C12	0.072 (2)	0.0448 (18)	0.0523 (19)	0.0132 (17)	0.0262 (17)	0.0208 (16)
C13	0.0505 (19)	0.054 (2)	0.0527 (19)	0.0023 (16)	0.0123 (15)	0.0287 (17)
C14	0.104 (4)	0.101 (4)	0.113 (4)	0.062 (3)	0.053 (3)	0.063 (3)

Geometric parameters (Å, º)

Zn1—S1	2.3552 (9)	C5—H5A	0.9700
Zn1—S2^i	2.3277 (10)	C5—H5B	0.9700
Zn1—S3	2.3366 (9)	C6—H6A	0.9700
Zn1—S4	2.4630 (9)	C6—H6B	0.9700
S1—C1	1.751 (3)	C7—H7A	0.9600
S2—C1	1.722 (3)	C7—H7B	0.9600
S2—Zn1^i	2.3277 (10)	C7—H7C	0.9600
S3—C8	1.739 (3)	C9—C10	1.518 (6)
S4—C8	1.713 (3)	C9—H9A	0.9700
N1—C1	1.310 (4)	C9—H9B	0.9700
N1—C6	1.473 (4)	C10—C11	1.513 (5)
N1—C2	1.483 (4)	C10—H10A	0.9700
N2—C8	1.318 (4)	C10—H10B	0.9700
N2—C9	1.476 (4)	C11—C14	1.518 (5)
N2—C13	1.470 (4)	C11—C12	1.531 (5)
C2—C3	1.499 (6)	C11—H11	0.9800
C2—H2A	0.9700	C12—C13	1.509 (5)
C2—H2B	0.9700	C12—H12A	0.9700
C3—C4	1.524 (5)	C12—H12B	0.9700
C3—H3A	0.9700	C13—H13A	0.9700
C3—H3B	0.9700	C13—H13B	0.9700
C4—C7	1.515 (5)	C14—H14A	0.9600
C4—C5	1.519 (5)	C14—H14B	0.9600
C4—H4	0.9800	C14—H14C	0.9600
C5—C6	1.523 (5)
S2^i—Zn1—S1	106.06 (4)	C5—C6—H6B	109.6
S3—Zn1—S1	124.13 (4)	H6A—C6—H6B	108.1
S2^i—Zn1—S3	126.10 (4)	C4—C7—H7A	109.5
S2^i—Zn1—S4	106.02 (3)	C4—C7—H7B	109.5
S3—Zn1—S4	75.62 (3)	H7A—C7—H7B	109.5
S1—Zn1—S4	110.52 (3)	C4—C7—H7C	109.5
C1—S1—Zn1	102.94 (11)	H7A—C7—H7C	109.5
C1—S2—Zn1^i	96.92 (11)	H7B—C7—H7C	109.5
C8—S3—Zn1	85.21 (10)	N2—C8—S4	122.0 (2)
C8—S4—Zn1	81.84 (10)	N2—C8—S3	120.9 (2)
C1—N1—C6	125.0 (3)	S4—C8—S3	117.05 (17)
C1—N1—C2	122.7 (3)	N2—C9—C10	109.1 (3)
C6—N1—C2	112.3 (3)	N2—C9—H9A	109.9
C8—N2—C13	124.0 (3)	C10—C9—H9A	109.9
C8—N2—C9	124.1 (3)	N2—C9—H9B	109.9
C13—N2—C9	111.6 (3)	C10—C9—H9B	109.9
N1—C1—S2	121.3 (2)	H9A—C9—H9B	108.3
N1—C1—S1	120.9 (2)	C11—C10—C9	113.2 (3)
S2—C1—S1	117.77 (17)	C11—C10—H10A	108.9
N1—C2—C3	109.9 (3)	C9—C10—H10A	108.9
N1—C2—H2A	109.7	C11—C10—H10B	108.9
C3—C2—H2A	109.7	C9—C10—H10B	108.9
N1—C2—H2B	109.7	H10A—C10—H10B	107.8
C3—C2—H2B	109.7	C10—C11—C14	112.0 (3)
H2A—C2—H2B	108.2	C10—C11—C12	109.2 (3)
C2—C3—C4	112.1 (3)	C14—C11—C12	111.5 (3)
C2—C3—H3A	109.2	C10—C11—H11	108.0
C4—C3—H3A	109.2	C14—C11—H11	108.0
C2—C3—H3B	109.2	C12—C11—H11	108.0
C4—C3—H3B	109.2	C13—C12—C11	112.0 (3)
H3A—C3—H3B	107.9	C13—C12—H12A	109.2
C7—C4—C5	112.7 (3)	C11—C12—H12A	109.2
C7—C4—C3	112.9 (4)	C13—C12—H12B	109.2
C5—C4—C3	108.6 (3)	C11—C12—H12B	109.2
C7—C4—H4	107.5	H12A—C12—H12B	107.9
C5—C4—H4	107.5	N2—C13—C12	109.9 (3)
C3—C4—H4	107.5	N2—C13—H13A	109.7
C4—C5—C6	113.0 (3)	C12—C13—H13A	109.7
C4—C5—H5A	109.0	N2—C13—H13B	109.7
C6—C5—H5A	109.0	C12—C13—H13B	109.7
C4—C5—H5B	109.0	H13A—C13—H13B	108.2
C6—C5—H5B	109.0	C11—C14—H14A	109.5
H5A—C5—H5B	107.8	C11—C14—H14B	109.5
N1—C6—C5	110.3 (3)	H14A—C14—H14B	109.5
N1—C6—H6A	109.6	C11—C14—H14C	109.5
C5—C6—H6A	109.6	H14A—C14—H14C	109.5
N1—C6—H6B	109.6	H14B—C14—H14C	109.5
S2^i—Zn1—S1—C1	−143.68 (10)	C3—C4—C5—C6	−52.9 (4)
S3—Zn1—S1—C1	15.68 (11)	C1—N1—C6—C5	124.9 (4)
S4—Zn1—S1—C1	101.85 (10)	C2—N1—C6—C5	−56.5 (4)
S2^i—Zn1—S3—C8	−96.29 (11)	C4—C5—C6—N1	54.3 (4)
S1—Zn1—S3—C8	108.50 (11)	C13—N2—C8—S4	−179.7 (3)
S4—Zn1—S3—C8	3.24 (10)	C9—N2—C8—S4	−6.5 (5)
S2^i—Zn1—S4—C8	120.70 (11)	C13—N2—C8—S3	−0.3 (5)
S3—Zn1—S4—C8	−3.31 (11)	C9—N2—C8—S3	172.9 (3)
S1—Zn1—S4—C8	−124.81 (11)	Zn1—S4—C8—N2	−175.8 (3)
C6—N1—C1—S2	−176.6 (3)	Zn1—S4—C8—S3	4.84 (16)
C2—N1—C1—S2	4.9 (5)	Zn1—S3—C8—N2	175.5 (3)
C6—N1—C1—S1	6.3 (5)	Zn1—S3—C8—S4	−5.07 (16)
C2—N1—C1—S1	−172.2 (3)	C8—N2—C9—C10	−114.0 (4)
Zn1^i—S2—C1—N1	176.3 (3)	C13—N2—C9—C10	59.9 (4)
Zn1^i—S2—C1—S1	−6.54 (19)	N2—C9—C10—C11	−56.1 (4)
Zn1—S1—C1—N1	−91.1 (3)	C9—C10—C11—C14	176.1 (3)
Zn1—S1—C1—S2	91.70 (18)	C9—C10—C11—C12	52.1 (4)
C1—N1—C2—C3	−122.4 (4)	C10—C11—C12—C13	−52.2 (4)
C6—N1—C2—C3	58.9 (5)	C14—C11—C12—C13	−176.4 (3)
N1—C2—C3—C4	−58.3 (4)	C8—N2—C13—C12	112.8 (4)
C2—C3—C4—C7	−179.2 (3)	C9—N2—C13—C12	−61.1 (4)
C2—C3—C4—C5	55.0 (4)	C11—C12—C13—N2	57.0 (4)
C7—C4—C5—C6	−178.8 (3)

Symmetry code: (i) −x, −y+2, −z.