A seven-coordinated tin(IV) complex: dichloro­[2,6-diacetyl­pyridine bis­(S-benzyl­dithio­carbazato-κ⁵S,N,N′,N′′,S′]tin(IV)

The penta­dentate ligand 2,6-diacetypyridine bis­(S-benzyl­dithio­carbazate) reacts with SnCl₂·2H₂O and atmospheric O₂ to form a seven-coordinated Sn^IV complex. The asymmetric unit of the title compound, [Sn(C₂₅H₂₃N₅S₄)Cl₂], consists of one half-mol­ecule. One Cl, Sn, N of the pyridine ring and the para-C,H atoms lie on a twofold axis. The Sn^IV ion is seven-coordinated with a distorted penta­dentate bipyramidal geometry. The dithio­carbazate ligand coordinates as a dianionic penta­gonal ligand through the pyridine N atom, the two imine N atoms and the two thio­carbazate S atoms, forming the penta­gonal plane; the two chloride ions are in axial positions. The complex was also characterized by ¹¹⁹Sn Mössbauer and IR spectroscopies.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.031
• wR factor = 0.058
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       3.37
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Sn1    -   S1      ..       5.68 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C8
PLAT331_ALERT_2_C Small Average Phenyl C-C Dist.   C8     -C13           1.36 Ang.

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

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

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Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: Mercury (Bruno et al., 2002) and PLATON (Spek, 2003); software used to prepare material for publication: enCIFer (Allen et al., 2004).

(2,6-diacetylpyridine bis(S-benzyldithiocarbazate-κ⁵N,N,N,S,S) dichloro tin(IV)

Crystal data

[Sn(C25H23N5S4)Cl2]	F(000) = 1424
Mr = 711.31	Dx = 1.645 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5552 reflections
a = 7.6309 (5) Å	θ = 2.6–30.9°
b = 15.724 (1) Å	µ = 1.39 mm^−1
c = 23.972 (2) Å	T = 291 K
β = 93.235 (1)°	Prism, orange
V = 2871.7 (3) Å^3	0.29 × 0.14 × 0.04 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2541 independent reflections
Radiation source: fine-focus sealed tube	2120 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: analytical (SHELXTL/PC; Sheldrick 1997b)	h = −9→9
Tmin = 0.709, Tmax = 0.947	k = −18→18
11652 measured reflections	l = −28→28

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.059	H-atom parameters constrained
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0249P)^2] where P = (Fo^2 + 2Fc^2)/3
2541 reflections	(Δ/σ)max = 0.020
170 parameters	Δρmax = 0.79 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

Experimental. IR spectra were recorded on a Nicolet 5ZDX-FT spectrophotometer in the 4000–400 cm^-1 range using KBr discs. ¹¹⁹Sn Mössbauer spectrum was obtained using a conventional apparatus with ⁵⁷Co as source of γ-radiation, kept at room temperature. The experimental uncertainty in the measured values of isomer shift (δ) and quadrupole splintting (Δ) parameters were ± 0,06 mm s^-1 and ± 0,05 mm s^-1, respectively.

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	1.0000	0.204623 (18)	0.2500	0.03962 (11)
Cl1	1.27143 (11)	0.19030 (5)	0.30539 (4)	0.0599 (2)
S1	0.91544 (11)	0.33200 (5)	0.30880 (4)	0.0559 (2)
S2	0.67661 (12)	0.34998 (5)	0.39805 (4)	0.0596 (3)
N1	1.0000	0.0600 (2)	0.2500	0.0397 (8)
N2	0.8359 (3)	0.15076 (15)	0.32089 (10)	0.0437 (6)
N3	0.7488 (3)	0.20077 (16)	0.35757 (10)	0.0478 (6)
C1	0.9020 (4)	0.01760 (19)	0.28541 (12)	0.0427 (7)
C2	0.8981 (4)	−0.07047 (19)	0.28577 (13)	0.0524 (9)
H2	0.8277	−0.0995	0.3098	0.063*
C3	1.0000	−0.1143 (3)	0.2500	0.0568 (13)
H3	1.0000	−0.1734	0.2500	0.068*
C4	0.8051 (4)	0.0706 (2)	0.32325 (13)	0.0459 (8)
C5	0.6787 (5)	0.0323 (2)	0.36134 (15)	0.0749 (12)
H5A	0.7415	0.0115	0.3944	0.090*
H5B	0.6176	−0.0138	0.3427	0.090*
H5C	0.5958	0.0748	0.3715	0.090*
C6	0.7814 (4)	0.2815 (2)	0.35334 (12)	0.0470 (8)
C7	0.5417 (4)	0.2784 (2)	0.43654 (14)	0.0620 (10)
H7A	0.4743	0.2417	0.4108	0.074*
H7B	0.6154	0.2429	0.4613	0.074*
C8	0.4205 (4)	0.3303 (2)	0.46989 (14)	0.0500 (8)
C9	0.2500 (5)	0.3410 (2)	0.45177 (15)	0.0631 (10)
H9	0.2081	0.3166	0.4182	0.076*
C10	0.1384 (5)	0.3882 (3)	0.4834 (2)	0.0783 (12)
H10	0.0215	0.3951	0.4710	0.094*
C11	0.1984 (6)	0.4244 (3)	0.5321 (2)	0.0839 (13)
H11	0.1236	0.4567	0.5529	0.101*
C12	0.3664 (6)	0.4134 (3)	0.54999 (17)	0.0921 (14)
H12	0.4070	0.4373	0.5838	0.111*
C13	0.4793 (5)	0.3672 (2)	0.51927 (15)	0.0752 (12)
H13	0.5960	0.3610	0.5320	0.090*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.04154 (18)	0.03567 (18)	0.04215 (19)	0.000	0.00677 (13)	0.000
Cl1	0.0516 (5)	0.0657 (6)	0.0616 (6)	−0.0022 (4)	−0.0051 (4)	0.0016 (4)
S1	0.0636 (6)	0.0422 (5)	0.0640 (6)	−0.0058 (4)	0.0225 (5)	−0.0078 (4)
S2	0.0688 (6)	0.0505 (5)	0.0616 (6)	−0.0008 (4)	0.0212 (5)	−0.0134 (4)
N1	0.043 (2)	0.0329 (19)	0.044 (2)	0.000	0.0047 (17)	0.000
N2	0.0476 (16)	0.0399 (16)	0.0443 (16)	−0.0002 (12)	0.0089 (13)	−0.0041 (12)
N3	0.0528 (16)	0.0453 (16)	0.0464 (16)	−0.0022 (14)	0.0144 (13)	−0.0054 (13)
C1	0.0421 (18)	0.0405 (18)	0.0457 (19)	−0.0025 (14)	0.0025 (15)	0.0009 (15)
C2	0.053 (2)	0.041 (2)	0.064 (2)	−0.0061 (16)	0.0086 (17)	0.0076 (17)
C3	0.057 (3)	0.036 (3)	0.077 (4)	0.000	0.006 (3)	0.000
C4	0.0485 (19)	0.042 (2)	0.047 (2)	−0.0070 (15)	0.0069 (16)	0.0019 (15)
C5	0.089 (3)	0.053 (2)	0.086 (3)	−0.016 (2)	0.042 (2)	0.000 (2)
C6	0.0466 (19)	0.051 (2)	0.0440 (19)	0.0014 (15)	0.0057 (15)	−0.0071 (16)
C7	0.069 (2)	0.059 (2)	0.059 (2)	0.0010 (18)	0.0186 (19)	−0.0049 (18)
C8	0.056 (2)	0.050 (2)	0.045 (2)	0.0035 (16)	0.0126 (17)	0.0021 (16)
C9	0.063 (3)	0.067 (2)	0.059 (2)	−0.003 (2)	0.002 (2)	0.0089 (19)
C10	0.054 (2)	0.076 (3)	0.106 (4)	0.011 (2)	0.018 (3)	0.028 (3)
C11	0.092 (3)	0.078 (3)	0.087 (3)	0.027 (3)	0.044 (3)	0.009 (3)
C12	0.115 (4)	0.100 (4)	0.062 (3)	0.026 (3)	0.016 (3)	−0.022 (2)
C13	0.066 (3)	0.096 (3)	0.063 (3)	0.019 (2)	−0.001 (2)	−0.017 (2)

Geometric parameters (Å, º)

Sn1—N1	2.274 (3)	C3—H3	0.9300
Sn1—N2^i	2.327 (2)	C4—C5	1.491 (4)
Sn1—N2	2.327 (2)	C5—H5A	0.9600
Sn1—Cl1^i	2.4070 (8)	C5—H5B	0.9600
Sn1—Cl1	2.4070 (8)	C5—H5C	0.9600
Sn1—S1	2.5528 (8)	C7—C8	1.498 (4)
Sn1—S1^i	2.5528 (8)	C7—H7A	0.9700
S1—C6	1.715 (3)	C7—H7B	0.9700
S2—C6	1.745 (3)	C8—C9	1.359 (4)
S2—C7	1.813 (3)	C8—C13	1.371 (4)
N1—C1^i	1.340 (3)	C9—C10	1.387 (5)
N1—C1	1.340 (3)	C9—H9	0.9300
N2—C4	1.285 (4)	C10—C11	1.355 (5)
N2—N3	1.378 (3)	C10—H10	0.9300
N3—C6	1.299 (4)	C11—C12	1.340 (5)
C1—C2	1.385 (4)	C11—H11	0.9300
C1—C4	1.463 (4)	C12—C13	1.372 (5)
C2—C3	1.374 (4)	C12—H12	0.9300
C2—H2	0.9300	C13—H13	0.9300
C3—C2^i	1.374 (4)
N1—Sn1—N2^i	68.65 (6)	C2^i—C3—H3	120.1
N1—Sn1—N2	68.65 (6)	N2—C4—C1	115.5 (3)
N2^i—Sn1—N2	137.31 (12)	N2—C4—C5	123.3 (3)
N1—Sn1—Cl1^i	84.63 (2)	C1—C4—C5	121.2 (3)
N2^i—Sn1—Cl1^i	92.58 (6)	C4—C5—H5A	109.5
N2—Sn1—Cl1^i	83.51 (6)	C4—C5—H5B	109.5
N1—Sn1—Cl1	84.63 (2)	H5A—C5—H5B	109.5
N2^i—Sn1—Cl1	83.51 (6)	C4—C5—H5C	109.5
N2—Sn1—Cl1	92.58 (6)	H5A—C5—H5C	109.5
Cl1^i—Sn1—Cl1	169.26 (4)	H5B—C5—H5C	109.5
N1—Sn1—S1	141.68 (2)	N3—C6—S1	128.7 (2)
N2^i—Sn1—S1	148.44 (6)	N3—C6—S2	117.3 (2)
N2—Sn1—S1	73.69 (6)	S1—C6—S2	114.01 (18)
Cl1^i—Sn1—S1	98.14 (3)	C8—C7—S2	108.6 (2)
Cl1—Sn1—S1	90.30 (3)	C8—C7—H7A	110.0
N1—Sn1—S1^i	141.68 (2)	S2—C7—H7A	110.0
N2^i—Sn1—S1^i	73.69 (6)	C8—C7—H7B	110.0
N2—Sn1—S1^i	148.44 (6)	S2—C7—H7B	110.0
Cl1^i—Sn1—S1^i	90.30 (3)	H7A—C7—H7B	108.4
Cl1—Sn1—S1^i	98.14 (3)	C9—C8—C13	119.0 (3)
S1—Sn1—S1^i	76.64 (4)	C9—C8—C7	120.4 (3)
C6—S1—Sn1	99.14 (11)	C13—C8—C7	120.6 (3)
C6—S2—C7	102.85 (15)	C8—C9—C10	119.9 (4)
C1^i—N1—C1	120.3 (3)	C8—C9—H9	120.1
C1^i—N1—Sn1	119.85 (17)	C10—C9—H9	120.1
C1—N1—Sn1	119.85 (17)	C11—C10—C9	120.5 (4)
C4—N2—N3	115.8 (3)	C11—C10—H10	119.7
C4—N2—Sn1	119.8 (2)	C9—C10—H10	119.7
N3—N2—Sn1	123.86 (17)	C12—C11—C10	119.5 (4)
C6—N3—N2	114.0 (2)	C12—C11—H11	120.2
N1—C1—C2	121.0 (3)	C10—C11—H11	120.2
N1—C1—C4	115.4 (3)	C11—C12—C13	121.0 (4)
C2—C1—C4	123.6 (3)	C11—C12—H12	119.5
C3—C2—C1	118.9 (3)	C13—C12—H12	119.5
C3—C2—H2	120.5	C8—C13—C12	120.2 (4)
C1—C2—H2	120.5	C8—C13—H13	119.9
C2—C3—C2^i	119.9 (4)	C12—C13—H13	119.9
C2—C3—H3	120.1

Symmetry code: (i) −x+2, y, −z+1/2.