Tris­(allyl­thio­urea-κS)­chloro­zinc(II) chloride

The title complex, [ZnCl(C₄H₈N₂S)₃]Cl, comprises [ZnCl(ATU)₃]⁺ cations (ATU is allyl­thio­urea) and Cl⁻ anions, both of which lie on threefold axes. The three S atoms of the allyl­thio­urea mol­ecules and one Cl atom coordinate the Zn atom in a tetrahedral arrangement. The crystal packing is mainly determined by weak N—H...Cl hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• R factor = 0.037
• wR factor = 0.093
• Data-to-parameter ratio = 29.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.66 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Zn1    -   Cl1     ..       9.20 su
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.29
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         10
PLAT362_ALERT_2_C Short  C(sp3)-C(sp2) Bond  C2     -   C3     ...       1.40 Ang.
PLAT368_ALERT_2_C Short  C(sp2)-C(sp2) Bond  C3     -   C4     ...       1.21 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           30.00
           From the CIF: _reflns_number_total               2190
           Count of symmetry unique reflns         1108
           Completeness (_total/calc)            197.65%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1082
           Fraction of Friedel pairs measured     0.977
           Are heavy atom types Z>Si present        yes

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 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: XSCANS (Bruker, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SIR97 (Altomare at al., 1999); program(s) used to refine structure: SHELXTL (Bruker, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: WinGX (Farrugia, 1999).

(I)

Crystal data

[ZnCl(C12H24N6S3)3]Cl	Dx = 1.424 Mg m^−3
Mr = 484.82	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 46 reflections
Hall symbol: R 3	θ = 5.0–12.5°
a = 11.0498 (4) Å	µ = 1.61 mm^−1
c = 16.0416 (11) Å	T = 293 K
V = 1696.24 (15) Å^3	Prism, colourless
Z = 3	0.45 × 0.40 × 0.31 mm
F(000) = 750

Data collection

Bruker P4 diffractometer	1849 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
Graphite monochromator	θmax = 30.0°, θmin = 2.5°
/w scans	h = −14→14
Absorption correction: psi scan (XSCANS; Bruker, 1996)	k = −15→15
Tmin = 0.522, Tmax = 0.607	l = −22→22
2412 measured reflections	3 standard reflections every 97 reflections
2190 independent reflections	intensity decay: 0.2%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.0548P)^2 + 0.0198P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.093	(Δ/σ)max < 0.001
S = 1.01	Δρmax = 0.41 e Å^−3
2190 reflections	Δρmin = −0.33 e Å^−3
74 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0156 (10)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1082 Friedel pairs?
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.002 (15)

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	1.0000	1.0000	0.76824 (3)	0.04186 (19)
Cl1	1.0000	1.0000	0.91219 (8)	0.0470 (3)
Cl2	1.0000	1.0000	0.52817 (8)	0.0438 (3)
S1	0.77973 (9)	0.83072 (9)	0.72199 (6)	0.0530 (2)
N1	0.8124 (3)	0.6755 (3)	0.83790 (18)	0.0528 (7)
H1A	0.7893	0.5972	0.8618	0.063*
H1B	0.8825	0.7514	0.8561	0.063*
C1	0.7402 (3)	0.6791 (3)	0.7730 (2)	0.0430 (6)
N2	0.6332 (3)	0.5586 (3)	0.7476 (2)	0.0579 (8)
H2A	0.6116	0.4859	0.7773	0.069*
C2	0.5494 (6)	0.5397 (5)	0.6734 (4)	0.0950 (19)
H2B	0.5062	0.5972	0.6788	0.114*
H2C	0.6111	0.5735	0.6255	0.114*
C3	0.4443 (8)	0.4015 (7)	0.6579 (5)	0.108 (2)
H3A	0.3840	0.3619	0.7029	0.130*
C4	0.4137 (8)	0.3217 (8)	0.5996 (5)	0.114 (3)
H4A	0.4668	0.3501	0.5511	0.137*
H4B	0.3370	0.2319	0.6034	0.137*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0404 (2)	0.0404 (2)	0.0447 (3)	0.02022 (12)	0.000	0.000
Cl1	0.0504 (4)	0.0504 (4)	0.0401 (6)	0.0252 (2)	0.000	0.000
Cl2	0.0417 (4)	0.0417 (4)	0.0479 (6)	0.0209 (2)	0.000	0.000
S1	0.0501 (5)	0.0429 (4)	0.0572 (5)	0.0166 (4)	−0.0135 (4)	0.0092 (4)
N1	0.0594 (17)	0.0457 (14)	0.0445 (14)	0.0196 (13)	−0.0105 (12)	0.0072 (12)
C1	0.0388 (15)	0.0409 (16)	0.0475 (16)	0.0187 (13)	−0.0008 (13)	0.0039 (12)
N2	0.0484 (16)	0.0420 (15)	0.0747 (19)	0.0162 (13)	−0.0191 (14)	0.0080 (14)
C2	0.089 (3)	0.058 (2)	0.121 (4)	0.024 (2)	−0.058 (3)	0.011 (3)
C3	0.105 (4)	0.081 (4)	0.120 (5)	0.032 (3)	−0.061 (4)	−0.005 (3)
C4	0.124 (5)	0.094 (4)	0.121 (5)	0.053 (4)	−0.062 (5)	−0.032 (4)

Geometric parameters (Å, º)

Zn1—Cl1	2.3092 (13)	N2—C2	1.458 (5)
Zn1—S1	2.3283 (9)	N2—H2A	0.8600
Zn1—S1^i	2.3283 (8)	C2—C3	1.404 (8)
Zn1—S1^ii	2.3283 (8)	C2—H2B	0.9700
S1—C1	1.713 (3)	C2—H2C	0.9700
N1—C1	1.325 (4)	C3—C4	1.211 (9)
N1—H1A	0.8600	C3—H3A	0.9300
N1—H1B	0.8600	C4—H4A	0.9300
C1—N2	1.327 (4)	C4—H4B	0.9300
Cl1—Zn1—S1	108.58 (3)	C1—N2—H2A	117.3
Cl1—Zn1—S1^i	108.58 (3)	C2—N2—H2A	117.3
S1—Zn1—S1^i	110.34 (3)	C3—C2—N2	114.9 (4)
Cl1—Zn1—S1^ii	108.58 (3)	C3—C2—H2B	108.5
S1—Zn1—S1^ii	110.34 (3)	N2—C2—H2B	108.5
S1^i—Zn1—S1^ii	110.34 (3)	C3—C2—H2C	108.5
C1—S1—Zn1	106.65 (11)	N2—C2—H2C	108.5
C1—N1—H1A	120.0	H2B—C2—H2C	107.5
C1—N1—H1B	120.0	C4—C3—C2	135.0 (9)
H1A—N1—H1B	120.0	C4—C3—H3A	112.5
N1—C1—N2	117.3 (3)	C2—C3—H3A	112.5
N1—C1—S1	122.8 (3)	C3—C4—H4A	120.0
N2—C1—S1	119.9 (2)	C3—C4—H4B	120.0
C1—N2—C2	125.3 (3)	H4A—C4—H4B	120.0
Cl1—Zn1—S1—C1	−51.22 (12)	N1—C1—N2—C2	−174.3 (5)
S1^i—Zn1—S1—C1	−170.12 (12)	S1—C1—N2—C2	5.6 (6)
S1^ii—Zn1—S1—C1	67.68 (14)	C1—N2—C2—C3	178.1 (5)
Zn1—S1—C1—N1	12.8 (3)	N2—C2—C3—C4	−124.4 (9)
Zn1—S1—C1—N2	−167.1 (3)

Symmetry codes: (i) −x+y+1, −x+2, z; (ii) −y+2, x−y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl2^iii	0.86	2.53	3.308 (3)	151
N1—H1B···Cl1	0.86	2.54	3.338 (3)	154
N2—H2A···Cl2^iii	0.86	2.46	3.255 (3)	154

Symmetry code: (iii) x−1/3, y−2/3, z+1/3.