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The pentadentate ligand 2,6-diacetypyridine bis(S-benzyldithiocarbazate) reacts with SnCl2·2H2O and atmospheric O2 to form a seven-coordinated SnIV 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 SnIV 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.
Supporting information
CCDC reference: 283750
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (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
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)
top
Crystal data top
[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) Å3 | 0.29 × 0.14 × 0.04 mm |
Z = 4 | |
Data collection top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0249P)2] where P = (Fo2 + 2Fc2)/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 top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
Sn1—N1 | 2.274 (3) | C3—H3 | 0.9300 |
Sn1—N2i | 2.327 (2) | C4—C5 | 1.491 (4) |
Sn1—N2 | 2.327 (2) | C5—H5A | 0.9600 |
Sn1—Cl1i | 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—S1i | 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—C1i | 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—C2i | 1.374 (4) | | |
| | | |
N1—Sn1—N2i | 68.65 (6) | C2i—C3—H3 | 120.1 |
N1—Sn1—N2 | 68.65 (6) | N2—C4—C1 | 115.5 (3) |
N2i—Sn1—N2 | 137.31 (12) | N2—C4—C5 | 123.3 (3) |
N1—Sn1—Cl1i | 84.63 (2) | C1—C4—C5 | 121.2 (3) |
N2i—Sn1—Cl1i | 92.58 (6) | C4—C5—H5A | 109.5 |
N2—Sn1—Cl1i | 83.51 (6) | C4—C5—H5B | 109.5 |
N1—Sn1—Cl1 | 84.63 (2) | H5A—C5—H5B | 109.5 |
N2i—Sn1—Cl1 | 83.51 (6) | C4—C5—H5C | 109.5 |
N2—Sn1—Cl1 | 92.58 (6) | H5A—C5—H5C | 109.5 |
Cl1i—Sn1—Cl1 | 169.26 (4) | H5B—C5—H5C | 109.5 |
N1—Sn1—S1 | 141.68 (2) | N3—C6—S1 | 128.7 (2) |
N2i—Sn1—S1 | 148.44 (6) | N3—C6—S2 | 117.3 (2) |
N2—Sn1—S1 | 73.69 (6) | S1—C6—S2 | 114.01 (18) |
Cl1i—Sn1—S1 | 98.14 (3) | C8—C7—S2 | 108.6 (2) |
Cl1—Sn1—S1 | 90.30 (3) | C8—C7—H7A | 110.0 |
N1—Sn1—S1i | 141.68 (2) | S2—C7—H7A | 110.0 |
N2i—Sn1—S1i | 73.69 (6) | C8—C7—H7B | 110.0 |
N2—Sn1—S1i | 148.44 (6) | S2—C7—H7B | 110.0 |
Cl1i—Sn1—S1i | 90.30 (3) | H7A—C7—H7B | 108.4 |
Cl1—Sn1—S1i | 98.14 (3) | C9—C8—C13 | 119.0 (3) |
S1—Sn1—S1i | 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) |
C1i—N1—C1 | 120.3 (3) | C8—C9—H9 | 120.1 |
C1i—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—C2i | 119.9 (4) | C12—C13—H13 | 119.9 |
C2—C3—H3 | 120.1 | | |
Symmetry code: (i) −x+2, y, −z+1/2. |
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