Tetrakis(1,3-di­methyl­imidazolidinium-2-di­thio­carboxyl­ate-κS)­zinc(II) diperchlorate

The title compound, [Zn(C₆H₁₀N₂S₂)₄](ClO₄)₂, containing four inner-salt ligands, is considered to retain an inner-salt structure in the crystal structure, where the planes of the carbenium and the di­thio­carboxyl­ate moieties are nearly perpendicular to each other [85 (2)°]. The asymmetric unit consists of one-half of the complex mol­ecule, as the complex has twofold crystallographic symmetry. The backbone C—C bond length [N₂C—CS₂ = 1.488 (7) Å] is significantly shorter than that of a normal C—C single bond.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.083
• wR factor = 0.173
• Data-to-parameter ratio = 21.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT244_ALERT_4_C Low Solvent  U(eq) as Compared to Neighbors ....        Cl1
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          8

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

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

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Computing details

Data collection: SMART-W2K/NT (Bruker, 2003); cell refinement: SMART; data reduction: SAINT-W2K/NT (Bruker, 2003); program(s) used to solve structure: SHELXTL-NT (Bruker, 2003); program(s) used to refine structure: SHELXTL-NT; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL-NT.

Tetrakis(1,3-dimethylimidazolidinium-2-dithiocarboxylate-κS)zinc perchlorate

Crystal data

[Zn(C6H10N2S2)4](ClO4)2	F(000) = 1984
Mr = 961.39	Dx = 1.551 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 8876 reflections
a = 28.6778 (10) Å	θ = 2.3–27.8°
b = 11.3532 (4) Å	µ = 1.18 mm^−1
c = 12.6453 (5) Å	T = 298 K
V = 4117.1 (3) Å^3	Cubic, red
Z = 4	0.42 × 0.25 × 0.22 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	4933 independent reflections
Radiation source: fine-focus sealed tube	4577 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
Detector resolution: 8.366 pixels mm^-1	θmax = 27.9°, θmin = 1.9°
φ and ω scans	h = −37→37
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −14→14
Tmin = 0.636, Tmax = 0.781	l = −7→16
27560 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)] = 0.083	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.173	H-atom parameters constrained
S = 1.31	w = 1/[σ^2(Fo^2) + (0.0365P)^2 + 12.633P] where P = (Fo^2 + 2Fc^2)/3
4933 reflections	(Δ/σ)max < 0.001
235 parameters	Δρmax = 0.68 e Å^−3
0 restraints	Δρmin = −0.42 e Å^−3

Special details

Experimental. none

Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 20.7669 (0.1220) x + 7.4132 (0.0414) y + 2.8065 (0.0407) z = 4.1180 (0.0555)

* 0.0000 (0.0000) S1 * 0.0000 (0.0000) C1 * 0.0000 (0.0000) S2

Rms deviation of fitted atoms = 0.0000

- 4.4149 (0.1656) x - 6.0062 (0.0551) y + 10.5527 (0.0491) z = 5.4119 (0.0888)

Angle to previous plane (with approximate e.s.d.) = 87.21 (0.36)

* 0.0000 (0.0000) N1 * 0.0000 (0.0000) C2 * 0.0000 (0.0000) N2

Rms deviation of fitted atoms = 0.0000

17.2392 (0.1605) x + 7.3065 (0.0472) y + 5.9911 (0.0201) z = 6.2089 (0.0106)

Angle to previous plane (with approximate e.s.d.) = 87.84 (1/3)

* 0.0000 (0.0000) S3 * 0.0000 (0.0000) C7 * 0.0000 (0.0000) S4

Rms deviation of fitted atoms = 0.0000

- 7.1005 (0.1924) x - 6.1447 (0.0641) y + 10.1617 (0.0317) z = 6.8530 (0.0270)

Angle to previous plane (with approximate e.s.d.) = 83.31 (0.36)

* 0.0000 (0.0000) N3 * 0.0000 (0.0000) C8 * 0.0000 (0.0000) N4

Rms deviation of fitted atoms = 0.0000

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	0.0000	0.24834 (7)	0.7500	0.0370 (2)
S1	0.04589 (4)	0.35234 (11)	0.87614 (10)	0.0426 (3)
S2	0.06616 (5)	0.48584 (13)	0.67356 (11)	0.0532 (4)
S3	0.06389 (5)	0.15031 (12)	0.66921 (11)	0.0471 (3)
S4	0.04831 (6)	0.01933 (14)	0.87377 (13)	0.0602 (4)
N1	0.09481 (15)	0.6255 (4)	0.9085 (4)	0.0467 (10)
N2	0.15086 (14)	0.5054 (4)	0.8636 (4)	0.0487 (11)
N3	0.15755 (16)	−0.0146 (4)	0.7756 (4)	0.0569 (12)
N4	0.11174 (19)	−0.1240 (4)	0.6775 (4)	0.0602 (13)
C1	0.07224 (16)	0.4553 (4)	0.7992 (4)	0.0362 (10)
C2	0.10609 (15)	0.5287 (4)	0.8582 (4)	0.0364 (10)
C3	0.1361 (2)	0.6778 (6)	0.9585 (5)	0.0636 (17)
C4	0.1754 (2)	0.5969 (6)	0.9225 (6)	0.0644 (17)
C5	0.0486 (2)	0.6753 (5)	0.9188 (5)	0.0567 (14)
C6	0.1751 (2)	0.4133 (6)	0.8062 (6)	0.0690 (18)
C7	0.07492 (17)	0.0479 (4)	0.7624 (4)	0.0408 (11)
C8	0.11540 (18)	−0.0299 (4)	0.7369 (4)	0.0436 (11)
C9	0.1889 (2)	−0.1070 (6)	0.7368 (6)	0.073 (2)
C10	0.1572 (3)	−0.1836 (6)	0.6701 (6)	0.081 (2)
C11	0.1732 (2)	0.0798 (6)	0.8435 (6)	0.0743 (19)
C12	0.0700 (3)	−0.1684 (6)	0.6278 (6)	0.078 (2)
H3A	0.1333	0.6780	1.0349	0.076*
H3B	0.1411	0.7579	0.9341	0.076*
H4A	0.1973	0.6385	0.8777	0.077*
H4B	0.1919	0.5640	0.9825	0.077*
H5A	0.0279	0.6379	0.8693	0.085*
H5B	0.0498	0.7583	0.9044	0.085*
H5C	0.0373	0.6629	0.9894	0.085*
H6A	0.1529	0.3577	0.7792	0.103*
H6B	0.1964	0.3738	0.8530	0.103*
H6C	0.1922	0.4474	0.7485	0.103*
H11A	0.1942	0.1298	0.8051	0.112*
H11B	0.1889	0.0473	0.9038	0.112*
H11C	0.1468	0.1249	0.8667	0.112*
H9A	0.2022	−0.1514	0.7949	0.088*
H9B	0.2139	−0.0738	0.6945	0.088*
H10A	0.1679	−0.1871	0.5975	0.098*
H10B	0.1555	−0.2630	0.6983	0.098*
H12A	0.0629	−0.2450	0.6556	0.116*
H12B	0.0748	−0.1739	0.5528	0.116*
H12C	0.0445	−0.1159	0.6419	0.116*
Cl1	0.23770 (5)	0.83606 (13)	1.07541 (13)	0.0573 (4)
O1	0.2002 (3)	0.9039 (7)	1.0482 (7)	0.169 (4)
O2	0.2700 (2)	0.8983 (7)	1.1308 (7)	0.153 (4)
O3	0.2569 (3)	0.7753 (7)	0.9892 (6)	0.143 (3)
O4	0.2208 (3)	0.7476 (7)	1.1370 (7)	0.158 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0338 (4)	0.0327 (4)	0.0445 (4)	0.000	−0.0029 (3)	0.000
S1	0.0423 (6)	0.0433 (6)	0.0421 (6)	−0.0118 (5)	−0.0048 (5)	0.0034 (5)
S2	0.0625 (8)	0.0533 (8)	0.0437 (7)	−0.0128 (7)	−0.0119 (6)	0.0065 (6)
S3	0.0494 (7)	0.0424 (7)	0.0494 (7)	0.0144 (5)	0.0058 (6)	0.0106 (6)
S4	0.0652 (9)	0.0567 (9)	0.0587 (9)	0.0084 (7)	0.0134 (7)	0.0126 (7)
N1	0.044 (2)	0.043 (2)	0.052 (3)	−0.0040 (19)	−0.006 (2)	−0.011 (2)
N2	0.033 (2)	0.049 (2)	0.064 (3)	−0.0048 (19)	−0.006 (2)	−0.009 (2)
N3	0.046 (2)	0.052 (3)	0.074 (3)	0.012 (2)	−0.003 (2)	0.005 (2)
N4	0.072 (3)	0.042 (2)	0.067 (3)	0.022 (2)	0.001 (3)	−0.010 (2)
C1	0.037 (2)	0.031 (2)	0.040 (2)	0.0039 (18)	−0.0028 (19)	−0.0073 (19)
C2	0.034 (2)	0.036 (2)	0.040 (2)	−0.0051 (18)	−0.0009 (19)	0.0032 (19)
C3	0.067 (4)	0.064 (4)	0.060 (4)	−0.026 (3)	−0.003 (3)	−0.021 (3)
C4	0.051 (3)	0.060 (4)	0.082 (4)	−0.020 (3)	−0.018 (3)	−0.001 (3)
C5	0.065 (4)	0.049 (3)	0.055 (3)	0.002 (3)	0.005 (3)	−0.006 (3)
C6	0.043 (3)	0.065 (4)	0.099 (5)	0.011 (3)	−0.007 (3)	−0.009 (4)
C7	0.044 (3)	0.032 (2)	0.046 (3)	0.0035 (19)	−0.007 (2)	0.000 (2)
C8	0.051 (3)	0.036 (2)	0.043 (3)	0.009 (2)	0.003 (2)	0.010 (2)
C9	0.055 (4)	0.062 (4)	0.103 (6)	0.023 (3)	0.020 (4)	0.027 (4)
C10	0.093 (5)	0.071 (4)	0.080 (5)	0.048 (4)	0.021 (4)	0.002 (4)
C11	0.059 (4)	0.072 (4)	0.093 (5)	−0.001 (3)	−0.011 (4)	0.002 (4)
C12	0.114 (6)	0.056 (4)	0.062 (4)	0.017 (4)	−0.024 (4)	−0.009 (3)
Cl1	0.0600 (8)	0.0472 (7)	0.0646 (9)	−0.0074 (6)	−0.0106 (7)	0.0025 (7)
O1	0.173 (7)	0.122 (6)	0.211 (9)	0.046 (5)	−0.121 (7)	−0.013 (6)
O2	0.085 (4)	0.131 (6)	0.243 (9)	0.005 (4)	−0.050 (5)	−0.104 (6)
O3	0.145 (6)	0.158 (7)	0.126 (6)	−0.039 (5)	0.034 (5)	−0.064 (5)
O4	0.210 (9)	0.125 (6)	0.138 (6)	−0.024 (6)	0.043 (6)	0.050 (5)

Geometric parameters (Å, º)

S1—Zn1	2.3811 (13)	C7—C8	1.494 (7)
S3—Zn1	2.3747 (13)	C7—S4	1.635 (5)
Zn1—S3^i	2.3747 (13)	C7—S3	1.685 (5)
Zn1—S1^i	2.3811 (13)	C8—N4	1.309 (7)
C1—C2	1.481 (6)	C8—N3	1.315 (7)
C1—S2	1.636 (5)	C11—N3	1.444 (8)
C1—S1	1.698 (5)	C11—H11A	0.9600
C2—N1	1.310 (6)	C11—H11B	0.9600
C2—N2	1.313 (6)	C11—H11C	0.9600
C3—N1	1.469 (7)	C9—N3	1.465 (7)
C3—C4	1.523 (9)	C9—C10	1.514 (11)
C3—H3A	0.9700	C9—H9A	0.9700
C3—H3B	0.9700	C9—H9B	0.9700
C4—N2	1.459 (7)	C10—N4	1.472 (7)
C4—H4A	0.9700	C10—H10A	0.9700
C4—H4B	0.9700	C10—H10B	0.9700
C5—N1	1.448 (7)	C12—N4	1.444 (9)
C5—H5A	0.9600	C12—H12A	0.9600
C5—H5B	0.9600	C12—H12B	0.9600
C5—H5C	0.9600	C12—H12C	0.9600
C6—N2	1.451 (7)	Cl1—O2	1.360 (6)
C6—H6A	0.9600	Cl1—O4	1.361 (7)
C6—H6B	0.9600	Cl1—O1	1.366 (7)
C6—H6C	0.9600	Cl1—O3	1.403 (7)
Zn1···S2	3.4358 (15)	S2···Zn1^i	3.4358 (15)
Zn1···S4	3.3361 (15)	S4···Zn1^i	3.3361 (15)
C1—S1—Zn1	101.75 (16)	N3—C8—C7	123.8 (5)
C7—S3—Zn1	99.65 (18)	N3—C11—H11A	109.5
S3—Zn1—S3^i	124.10 (7)	N3—C11—H11B	109.5
S3—Zn1—S1	95.41 (5)	H11A—C11—H11B	109.5
S3^i—Zn1—S1	111.75 (4)	N3—C11—H11C	109.5
S3—Zn1—S1^i	111.75 (4)	H11A—C11—H11C	109.5
S3^i—Zn1—S1^i	95.41 (5)	H11B—C11—H11C	109.5
S1—Zn1—S1^i	120.55 (7)	N3—C9—C10	103.3 (5)
C2—C1—S2	116.1 (4)	N3—C9—H9A	111.1
C2—C1—S1	113.0 (3)	C10—C9—H9A	111.1
S2—C1—S1	130.9 (3)	N3—C9—H9B	111.1
N1—C2—N2	112.6 (4)	C10—C9—H9B	111.1
N1—C2—C1	123.7 (4)	H9A—C9—H9B	109.1
N2—C2—C1	123.6 (4)	N4—C10—C9	103.4 (5)
N1—C3—C4	102.9 (4)	N4—C10—H10A	111.1
N1—C3—H3A	111.2	C9—C10—H10A	111.1
C4—C3—H3A	111.2	N4—C10—H10B	111.1
N1—C3—H3B	111.2	C9—C10—H10B	111.1
C4—C3—H3B	111.2	H10A—C10—H10B	109.0
H3A—C3—H3B	109.1	N4—C12—H12A	109.5
N2—C4—C3	103.0 (4)	N4—C12—H12B	109.5
N2—C4—H4A	111.2	H12A—C12—H12B	109.5
C3—C4—H4A	111.2	N4—C12—H12C	109.5
N2—C4—H4B	111.2	H12A—C12—H12C	109.5
C3—C4—H4B	111.2	H12B—C12—H12C	109.5
H4A—C4—H4B	109.1	O2—Cl1—O4	109.3 (6)
N1—C5—H5A	109.5	O2—Cl1—O1	111.9 (5)
N1—C5—H5B	109.5	O4—Cl1—O1	106.3 (6)
H5A—C5—H5B	109.5	O2—Cl1—O3	112.8 (5)
N1—C5—H5C	109.5	O4—Cl1—O3	102.8 (5)
H5A—C5—H5C	109.5	O1—Cl1—O3	113.0 (6)
H5B—C5—H5C	109.5	C2—N1—C5	126.7 (4)
N2—C6—H6A	109.5	C2—N1—C3	110.5 (4)
N2—C6—H6B	109.5	C5—N1—C3	122.8 (5)
H6A—C6—H6B	109.5	C2—N2—C6	126.0 (5)
N2—C6—H6C	109.5	C2—N2—C4	110.8 (5)
H6A—C6—H6C	109.5	C6—N2—C4	122.5 (5)
H6B—C6—H6C	109.5	C8—N3—C11	127.2 (5)
C8—C7—S4	115.5 (4)	C8—N3—C9	110.1 (5)
C8—C7—S3	113.8 (4)	C11—N3—C9	122.7 (5)
S4—C7—S3	130.7 (3)	C8—N4—C12	127.0 (5)
N4—C8—N3	113.2 (5)	C8—N4—C10	109.9 (6)
N4—C8—C7	122.9 (5)	C12—N4—C10	123.1 (5)
S2—C1—C2—N1	91.9 (5)	N4—C8—N3—C11	179.9 (6)
S1—C1—C2—N1	−87.9 (5)	C7—C8—N3—C11	−3.2 (9)
S2—C1—C2—N2	−86.5 (5)	N4—C8—N3—C9	2.1 (7)
S1—C1—C2—N2	93.7 (5)	C7—C8—N3—C9	179.0 (5)
N1—C3—C4—N2	−3.8 (6)	C10—C9—N3—C8	−1.9 (7)
S4—C7—C8—N4	94.6 (6)	C10—C9—N3—C11	−179.9 (6)
S3—C7—C8—N4	−84.6 (6)	N3—C8—N4—C12	176.8 (6)
S4—C7—C8—N3	−82.0 (6)	C7—C8—N4—C12	−0.1 (9)
S3—C7—C8—N3	98.9 (5)	N3—C8—N4—C10	−1.3 (7)
N3—C9—C10—N4	1.1 (7)	C7—C8—N4—C10	−178.2 (5)
N2—C2—N1—C5	−179.4 (5)	C9—C10—N4—C8	0.0 (7)
C1—C2—N1—C5	2.1 (8)	C9—C10—N4—C12	−178.2 (6)
N2—C2—N1—C3	−1.3 (6)	C2—C1—S1—Zn1	−176.1 (3)
C1—C2—N1—C3	−179.8 (5)	S2—C1—S1—Zn1	4.2 (4)
C4—C3—N1—C2	3.3 (7)	C8—C7—S3—Zn1	−178.5 (3)
C4—C3—N1—C5	−178.5 (5)	S4—C7—S3—Zn1	2.4 (4)
N1—C2—N2—C6	−172.2 (6)	C7—S3—Zn1—S3^i	−45.40 (17)
C1—C2—N2—C6	6.3 (9)	C7—S3—Zn1—S1	75.50 (18)
N1—C2—N2—C4	−1.5 (7)	C7—S3—Zn1—S1^i	−158.52 (18)
C1—C2—N2—C4	177.0 (5)	C1—S1—Zn1—S3	72.91 (16)
C3—C4—N2—C2	3.4 (7)	C1—S1—Zn1—S3^i	−156.99 (16)
C3—C4—N2—C6	174.5 (6)	C1—S1—Zn1—S1^i	−46.30 (16)

Symmetry code: (i) −x, y, −z+3/2.