Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020090/hg2228sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020090/hg2228Isup2.hkl |
CCDC reference: 648077
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.005 Å
- R factor = 0.030
- wR factor = 0.087
- Data-to-parameter ratio = 15.3
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ....... 0.92
Author Response: This alarm is due to the crystal defect of my sample. To solve this problem, several samples were screened. The selected sample exhibited the best diffraction behavior. |
Alert level B PLAT420_ALERT_2_B D-H Without Acceptor O4 - H4A ... ?
Alert level C REFLT03_ALERT_3_C Reflection count < 95% complete From the CIF: _diffrn_reflns_theta_max 25.50 From the CIF: _diffrn_reflns_theta_full 25.50 From the CIF: _reflns_number_total 7145 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 7742 Completeness (_total/calc) 92.29% PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low .... 0.92 PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 100 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.15 Ratio PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.60 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.23 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.10 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for C19 - C20 .. 5.69 su PLAT480_ALERT_4_C Long H...A H-Bond Reported H5 .. O4 .. 2.62 Ang. PLAT732_ALERT_1_C Angle Calc 106.34(9), Rep 106.3(2) ...... 2.22 su-Ra C10 -SN1 -S1 1.555 1.555 1.555
1 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 11 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 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 6 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound (I) was prepared as an unexpected product in our work by the following procedure: A solution of Schiff base ligand, 1,5-Bis[(1E)-4-methoxybenzylidene]thiocarbonohydrazide, (0.342 g, 1 m mol) and dibutyltin dichloride (0.304 g, 1 m mol) in acetonitrile (20 ml) was heated for 8 h under reflux. The reaction mixture was then cooled and the pale yellow precipitate that had formed was filtered off. Recrystallization of the crude product from ethanol-DMF solution resulted in single crystals of (I) suitable for X-ray diffraction analysis after several days.
Slightly disorder in the ethanol was identified from the difference map. Disordered atoms were refined by applying restraints to the bond lengths [1.540 (2)Å for C35—C36 and 1.340 (2)Å for C35—O4]. All the H atoms were positioned in idealized locations and refined as riding on their carrier atoms, with O—H distances of 0.82 (hydroxyl), C—H distances of 0.93 (aryl), 0.97 (methylene) and 0.96Å (methyl) with Uiso(H) = 1.5Ueq(C) for hydroxyl and methyl, Uiso(H) = 1.2Ueq(C) for the other atoms.
Organotin complexes have attracted attention in supermolecular chemistry in recent years (Ma et al., 2005; Barbieri et al., 2001), whereas thiosemicarbazones and their complexes have a wide range of applications in biology (Casas et al., 2000). In the context of our continuous interest for the structural and biological properties of organotin compounds (Fang et al., 2001; 2006a), we report here the crystal structure of the title complex, (I). To the best of our knowledge, this is the first example of organotin complex containing C2N2S2Sn2 planar dicyclo fragment.
The structure of (I) is an unexpected product in our work. It crystallizes in space group P-1, with one half-molecule of an organotin complex [2,2,6,6-Tetra-n-butyl-2,6-dichloro-4,8-di[(1E)-4-methoxybenzylidene]ηydrazino-1,5-diaza-2,6-distanna-3,7-dithiabicyclo[3.3.0]octane], one substituted thiocarbonohydrazide ligand [1,5-Bis[(1E)-4-methoxybenzylidene]thiocarbonohydrazide] and one ethanol molecule in the asymmetric unit (Fig. 1). Part of the thiocarbonohydrazide ligand molecules were cracked to form a novel substituted C2N2S2Sn2 planar dicyclo organotin complex. The five-membered ring Sn1—S1—C1—N1A—N1 is coplanar with a mean deviation of 0.024 (3) Å. The inversion center is situated at the midpoint of N1—N1A bond, and it is by this bond that the two five-membered rings are fused together. Both of the SnIV atoms are penta-coordinated with distorted trigonal-bipyramidal geometry. C10, C14 (from butyl groups) and S1 atom occupy the equatorial plane, these equatorial atoms and relative Sn atom are nearly coplanar, the mean deviation from the plane is 0.031 (4) Å. Cl1 and N1 atoms occupy the axial positions with the N1—Sn1—Cl1 bond angle 160.11 (6)°. All the C═ N bonds exist in E-configuration, and all the bond lengths in (I) are within the expected range and agree well with literature values (Altmann et al., 1998; Fang et al., 2006).
In the crystal lattice, every two molecules of the ligand are linked by the weak hydrogen bonds N6—H6···S2i to form dimers, with the attached two ethanol molecules by the strong N5—H5···O4ii and weak C25—H25···O4ii hydrogen bonds. The molecules of organotin are linked by S···S interactions (Wang et al., 2004). and N—H···Cliii, C—H···Cliii weak hydrogen bonds involving all potential S and Cl atom donors, generating one-dimensional infinite chains parallel to the a axis, as shown in Fig. 2. The 4-methoxyphenyl rings protrude on both sides of these chains and have no special intercalations [symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x + 1, -y + 2, -z + 1; (iii) -x + 1, -y + 2, -z].
For related literature, see: Altmann et al. (1998); Barbieri et al. (2001); Casas et al. (2000); Fang et al. (2001, 2006a); Ma et al. (2005); Wang et al. (2004).
For related literature, see: Fang et al. (2006b). Comment section contains one ambiguous reference to Fang et al. (2006); should this be 2006b?
Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: APEX2; program(s) used to refine structure: APEX2; molecular graphics: APEX2; software used to prepare material for publication: APEX2 and publCIF (Westrip, 2007).
[Sn2(C4H9)4Cl2(C18H18N6O2S2)]·2C17H18N4O2S·2C2H6O | Z = 1 |
Mr = 1728.20 | F(000) = 894 |
Triclinic, P1 | Dx = 1.382 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9295 (6) Å | Cell parameters from 9573 reflections |
b = 10.3932 (7) Å | θ = 2.2–28.2° |
c = 24.015 (2) Å | µ = 0.83 mm−1 |
α = 81.439 (1)° | T = 296 K |
β = 85.350 (1)° | Block, pale yellow |
γ = 70.521 (1)° | 0.40 × 0.31 × 0.31 mm |
V = 2076.6 (3) Å3 |
Bruker APEX II area-detector diffractometer | 7145 independent reflections |
Radiation source: fine-focus sealed tube | 6432 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
φ and ω scans | θmax = 25.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −10→10 |
Tmin = 0.74, Tmax = 0.77 | k = −12→12 |
13116 measured reflections | l = −28→28 |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0547P)2 + 0.6928P] where P = (Fo2 + 2Fc2)/3 |
7145 reflections | (Δ/σ)max = 0.001 |
467 parameters | Δρmax = 0.58 e Å−3 |
2 restraints | Δρmin = −0.39 e Å−3 |
[Sn2(C4H9)4Cl2(C18H18N6O2S2)]·2C17H18N4O2S·2C2H6O | γ = 70.521 (1)° |
Mr = 1728.20 | V = 2076.6 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.9295 (6) Å | Mo Kα radiation |
b = 10.3932 (7) Å | µ = 0.83 mm−1 |
c = 24.015 (2) Å | T = 296 K |
α = 81.439 (1)° | 0.40 × 0.31 × 0.31 mm |
β = 85.350 (1)° |
Bruker APEX II area-detector diffractometer | 7145 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 6432 reflections with I > 2σ(I) |
Tmin = 0.74, Tmax = 0.77 | Rint = 0.014 |
13116 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 2 restraints |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.58 e Å−3 |
7145 reflections | Δρmin = −0.39 e Å−3 |
467 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Sn1 | 0.812698 (18) | 1.104088 (18) | −0.091670 (7) | 0.04294 (8) | |
S1 | 0.70369 (8) | 0.97683 (9) | −0.01266 (3) | 0.05509 (19) | |
S2 | 0.60672 (15) | 0.63859 (11) | 0.44775 (4) | 0.0835 (3) | |
O1 | 1.1578 (3) | 0.6447 (3) | 0.38324 (10) | 0.0870 (8) | |
O2 | 1.0079 (4) | 1.2706 (4) | 0.32703 (14) | 0.1100 (10) | |
O3 | 0.4216 (4) | 0.6818 (3) | 0.87416 (10) | 0.0846 (7) | |
O4 | 0.4485 (5) | 0.9813 (4) | 0.38112 (15) | 0.1195 (12) | |
H4A | 0.5388 | 0.9519 | 0.3676 | 0.179* | |
N1 | 1.0120 (2) | 1.0342 (2) | −0.02674 (9) | 0.0428 (5) | |
N2 | 0.8235 (2) | 0.8662 (3) | 0.08325 (9) | 0.0499 (5) | |
H2 | 0.7385 | 0.8437 | 0.0865 | 0.060* | |
N3 | 0.9227 (2) | 0.8296 (2) | 0.12835 (9) | 0.0474 (5) | |
N4 | 0.6883 (3) | 0.8739 (3) | 0.47857 (11) | 0.0608 (6) | |
N5 | 0.6294 (3) | 0.7983 (3) | 0.52189 (11) | 0.0623 (6) | |
H5 | 0.6181 | 0.8206 | 0.5554 | 0.075* | |
N6 | 0.5359 (3) | 0.6237 (3) | 0.55591 (10) | 0.0635 (7) | |
H6 | 0.5071 | 0.5548 | 0.5514 | 0.076* | |
N7 | 0.5255 (3) | 0.6639 (3) | 0.60890 (10) | 0.0609 (6) | |
Cl1 | 0.53743 (9) | 1.14405 (9) | −0.13637 (3) | 0.0652 (2) | |
C1 | 0.8556 (3) | 0.9364 (3) | 0.03407 (10) | 0.0408 (5) | |
C2 | 0.8603 (3) | 0.7939 (3) | 0.17573 (12) | 0.0564 (7) | |
H2A | 0.7561 | 0.7939 | 0.1760 | 0.068* | |
C3 | 0.9413 (3) | 0.7534 (3) | 0.22894 (12) | 0.0556 (7) | |
C4 | 1.1033 (3) | 0.7185 (3) | 0.23344 (13) | 0.0615 (8) | |
H4 | 1.1677 | 0.7184 | 0.2010 | 0.074* | |
C5 | 1.1705 (4) | 0.6837 (4) | 0.28516 (15) | 0.0696 (9) | |
H5A | 1.2801 | 0.6599 | 0.2874 | 0.084* | |
C6 | 1.0777 (4) | 0.6836 (3) | 0.33429 (14) | 0.0654 (8) | |
C7 | 0.9148 (4) | 0.7165 (4) | 0.33124 (15) | 0.0749 (10) | |
H7 | 0.8506 | 0.7157 | 0.3637 | 0.090* | |
C8 | 0.8499 (4) | 0.7509 (4) | 0.27789 (14) | 0.0722 (9) | |
H8 | 0.7406 | 0.7730 | 0.2753 | 0.087* | |
C9 | 1.0686 (6) | 0.6324 (5) | 0.43472 (16) | 0.1052 (15) | |
H9A | 0.9938 | 0.7208 | 0.4404 | 0.158* | |
H9B | 1.1396 | 0.5992 | 0.4655 | 0.158* | |
H9C | 1.0126 | 0.5688 | 0.4329 | 0.158* | |
C10 | 0.7273 (4) | 1.3153 (3) | −0.07763 (14) | 0.0602 (7) | |
H10A | 0.7475 | 1.3702 | −0.1119 | 0.072* | |
H10B | 0.6129 | 1.3418 | −0.0715 | 0.072* | |
C11 | 0.7951 (4) | 1.3536 (3) | −0.02949 (14) | 0.0634 (8) | |
H11A | 0.9084 | 1.3343 | −0.0366 | 0.076* | |
H11B | 0.7806 | 1.2959 | 0.0048 | 0.076* | |
C12 | 0.7209 (5) | 1.5024 (4) | −0.02030 (19) | 0.0827 (11) | |
H12A | 0.7444 | 1.5594 | −0.0534 | 0.099* | |
H12B | 0.6064 | 1.5237 | −0.0172 | 0.099* | |
C13 | 0.7737 (7) | 1.5411 (6) | 0.0304 (2) | 0.1180 (18) | |
H13A | 0.7333 | 1.4989 | 0.0638 | 0.177* | |
H13B | 0.7340 | 1.6393 | 0.0295 | 0.177* | |
H13C | 0.8877 | 1.5099 | 0.0304 | 0.177* | |
C14 | 0.9298 (4) | 0.9572 (3) | −0.14765 (14) | 0.0628 (8) | |
H14A | 0.9071 | 1.0019 | −0.1859 | 0.075* | |
H14B | 1.0435 | 0.9324 | −0.1435 | 0.075* | |
C15 | 0.8890 (5) | 0.8280 (4) | −0.14076 (19) | 0.0847 (11) | |
H15A | 0.9100 | 0.7834 | −0.1024 | 0.102* | |
H15B | 0.7759 | 0.8519 | −0.1460 | 0.102* | |
C16 | 0.9757 (6) | 0.7283 (5) | −0.1798 (2) | 0.0995 (14) | |
H16A | 0.9539 | 0.7737 | −0.2180 | 0.119* | |
H16B | 1.0886 | 0.7064 | −0.1748 | 0.119* | |
C17 | 0.9413 (8) | 0.5976 (5) | −0.1746 (3) | 0.130 (2) | |
H17A | 0.9435 | 0.5587 | −0.1357 | 0.194* | |
H17B | 1.0200 | 0.5345 | −0.1960 | 0.194* | |
H17C | 0.8381 | 0.6146 | −0.1888 | 0.194* | |
C18 | 1.0726 (9) | 1.3605 (7) | 0.3415 (3) | 0.151 (3) | |
H18A | 0.9978 | 1.4214 | 0.3648 | 0.226* | |
H18B | 1.0990 | 1.4131 | 0.3081 | 0.226* | |
H18C | 1.1672 | 1.3110 | 0.3620 | 0.226* | |
C19 | 0.9364 (5) | 1.2028 (4) | 0.37029 (17) | 0.0806 (10) | |
C20 | 0.9198 (5) | 1.2282 (4) | 0.4242 (2) | 0.0896 (12) | |
H20 | 0.9549 | 1.2957 | 0.4346 | 0.108* | |
C21 | 0.8485 (5) | 1.1514 (4) | 0.46519 (18) | 0.0841 (11) | |
H21 | 0.8365 | 1.1685 | 0.5025 | 0.101* | |
C22 | 0.7980 (4) | 1.0529 (3) | 0.44951 (14) | 0.0633 (8) | |
C23 | 0.8144 (4) | 1.0330 (4) | 0.39310 (15) | 0.0739 (9) | |
H23 | 0.7773 | 0.9677 | 0.3817 | 0.089* | |
C24 | 0.8832 (5) | 1.1063 (5) | 0.35441 (18) | 0.0852 (11) | |
H24 | 0.8939 | 1.0905 | 0.3170 | 0.102* | |
C25 | 0.7306 (4) | 0.9690 (3) | 0.49192 (14) | 0.0636 (8) | |
H25 | 0.7188 | 0.9863 | 0.5292 | 0.076* | |
C26 | 0.5903 (4) | 0.6915 (3) | 0.51171 (13) | 0.0595 (7) | |
C27 | 0.4748 (4) | 0.5921 (3) | 0.64858 (13) | 0.0612 (7) | |
H27 | 0.4480 | 0.5182 | 0.6402 | 0.073* | |
C28 | 0.4574 (4) | 0.6212 (3) | 0.70636 (13) | 0.0581 (7) | |
C29 | 0.4751 (5) | 0.7397 (4) | 0.72069 (14) | 0.0690 (9) | |
H29 | 0.4951 | 0.8043 | 0.6925 | 0.083* | |
C30 | 0.4635 (5) | 0.7629 (4) | 0.77620 (14) | 0.0720 (9) | |
H30 | 0.4748 | 0.8432 | 0.7852 | 0.086* | |
C31 | 0.4354 (4) | 0.6676 (4) | 0.81836 (13) | 0.0630 (8) | |
C32 | 0.4171 (4) | 0.5487 (4) | 0.80527 (14) | 0.0681 (9) | |
H32 | 0.3984 | 0.4840 | 0.8337 | 0.082* | |
C33 | 0.4268 (4) | 0.5273 (4) | 0.74950 (14) | 0.0665 (8) | |
H33 | 0.4125 | 0.4482 | 0.7406 | 0.080* | |
C34 | 0.4351 (6) | 0.8029 (4) | 0.89018 (17) | 0.0885 (12) | |
H34A | 0.5373 | 0.8102 | 0.8778 | 0.133* | |
H34B | 0.4242 | 0.7990 | 0.9304 | 0.133* | |
H34C | 0.3531 | 0.8815 | 0.8732 | 0.133* | |
C35 | 0.3503 (8) | 0.9364 (8) | 0.3557 (2) | 0.154 (3) | |
H35A | 0.2418 | 0.9881 | 0.3658 | 0.185* | |
H35B | 0.3677 | 0.8408 | 0.3706 | 0.185* | |
C36 | 0.3665 (12) | 0.9471 (10) | 0.2915 (2) | 0.201 (4) | |
H36A | 0.4087 | 1.0197 | 0.2772 | 0.302* | |
H36B | 0.2640 | 0.9667 | 0.2762 | 0.302* | |
H36C | 0.4370 | 0.8616 | 0.2807 | 0.302* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.03414 (10) | 0.04993 (13) | 0.04704 (12) | −0.01539 (8) | −0.00385 (7) | −0.00810 (8) |
S1 | 0.0380 (3) | 0.0843 (5) | 0.0499 (4) | −0.0309 (3) | −0.0072 (3) | −0.0015 (3) |
S2 | 0.1316 (9) | 0.0845 (7) | 0.0550 (5) | −0.0642 (6) | 0.0080 (5) | −0.0114 (4) |
O1 | 0.0871 (18) | 0.103 (2) | 0.0635 (15) | −0.0213 (15) | −0.0233 (13) | −0.0003 (14) |
O2 | 0.128 (3) | 0.113 (3) | 0.107 (2) | −0.072 (2) | 0.0075 (19) | −0.0039 (19) |
O3 | 0.117 (2) | 0.0871 (18) | 0.0569 (13) | −0.0421 (16) | 0.0087 (13) | −0.0187 (12) |
O4 | 0.123 (3) | 0.144 (3) | 0.108 (2) | −0.072 (3) | −0.032 (2) | 0.016 (2) |
N1 | 0.0316 (10) | 0.0512 (13) | 0.0465 (11) | −0.0142 (9) | −0.0047 (8) | −0.0061 (9) |
N2 | 0.0348 (11) | 0.0678 (15) | 0.0511 (13) | −0.0232 (10) | −0.0059 (9) | −0.0025 (11) |
N3 | 0.0385 (11) | 0.0530 (13) | 0.0531 (13) | −0.0184 (10) | −0.0079 (9) | −0.0023 (10) |
N4 | 0.0718 (17) | 0.0540 (15) | 0.0574 (15) | −0.0246 (13) | 0.0011 (12) | −0.0018 (12) |
N5 | 0.0788 (18) | 0.0582 (16) | 0.0540 (14) | −0.0292 (14) | 0.0021 (12) | −0.0066 (12) |
N6 | 0.0831 (18) | 0.0598 (16) | 0.0535 (14) | −0.0322 (14) | 0.0005 (12) | −0.0065 (12) |
N7 | 0.0720 (17) | 0.0575 (15) | 0.0530 (14) | −0.0217 (13) | 0.0003 (12) | −0.0060 (12) |
Cl1 | 0.0440 (4) | 0.0873 (6) | 0.0691 (5) | −0.0273 (4) | −0.0169 (3) | −0.0028 (4) |
C1 | 0.0319 (11) | 0.0455 (14) | 0.0467 (14) | −0.0142 (10) | −0.0009 (9) | −0.0072 (11) |
C2 | 0.0452 (15) | 0.069 (2) | 0.0595 (17) | −0.0265 (14) | −0.0058 (12) | −0.0001 (14) |
C3 | 0.0534 (16) | 0.0594 (18) | 0.0563 (17) | −0.0239 (14) | −0.0066 (12) | 0.0010 (13) |
C4 | 0.0484 (16) | 0.072 (2) | 0.0597 (18) | −0.0174 (15) | −0.0036 (13) | 0.0017 (15) |
C5 | 0.0524 (17) | 0.080 (2) | 0.072 (2) | −0.0189 (16) | −0.0111 (15) | 0.0019 (17) |
C6 | 0.070 (2) | 0.061 (2) | 0.0615 (19) | −0.0157 (16) | −0.0144 (15) | −0.0029 (15) |
C7 | 0.067 (2) | 0.088 (3) | 0.060 (2) | −0.0150 (18) | −0.0011 (15) | −0.0042 (17) |
C8 | 0.0495 (17) | 0.094 (3) | 0.068 (2) | −0.0219 (17) | −0.0037 (14) | 0.0032 (18) |
C9 | 0.124 (4) | 0.117 (4) | 0.054 (2) | −0.009 (3) | −0.013 (2) | −0.014 (2) |
C10 | 0.0494 (16) | 0.0533 (17) | 0.075 (2) | −0.0076 (13) | −0.0078 (14) | −0.0172 (15) |
C11 | 0.0637 (19) | 0.0587 (19) | 0.071 (2) | −0.0210 (15) | 0.0015 (15) | −0.0193 (15) |
C12 | 0.080 (2) | 0.068 (2) | 0.105 (3) | −0.0251 (19) | 0.010 (2) | −0.032 (2) |
C13 | 0.136 (4) | 0.119 (4) | 0.126 (4) | −0.061 (3) | 0.028 (3) | −0.074 (3) |
C14 | 0.0591 (18) | 0.067 (2) | 0.0679 (19) | −0.0245 (15) | 0.0097 (14) | −0.0247 (16) |
C15 | 0.091 (3) | 0.074 (2) | 0.099 (3) | −0.039 (2) | 0.022 (2) | −0.031 (2) |
C16 | 0.117 (4) | 0.081 (3) | 0.109 (3) | −0.036 (3) | 0.020 (3) | −0.043 (3) |
C17 | 0.165 (5) | 0.089 (3) | 0.153 (5) | −0.058 (4) | 0.020 (4) | −0.050 (3) |
C18 | 0.210 (7) | 0.126 (5) | 0.157 (5) | −0.114 (5) | −0.002 (5) | −0.002 (4) |
C19 | 0.085 (3) | 0.079 (3) | 0.077 (2) | −0.031 (2) | −0.0040 (19) | 0.006 (2) |
C20 | 0.101 (3) | 0.071 (2) | 0.112 (3) | −0.049 (2) | −0.006 (2) | −0.012 (2) |
C21 | 0.105 (3) | 0.074 (2) | 0.085 (3) | −0.046 (2) | −0.007 (2) | −0.007 (2) |
C22 | 0.0634 (18) | 0.0535 (18) | 0.074 (2) | −0.0211 (15) | −0.0047 (15) | −0.0033 (15) |
C23 | 0.080 (2) | 0.075 (2) | 0.071 (2) | −0.0339 (19) | 0.0033 (17) | −0.0082 (18) |
C24 | 0.091 (3) | 0.094 (3) | 0.077 (2) | −0.044 (2) | 0.006 (2) | −0.006 (2) |
C25 | 0.073 (2) | 0.0599 (19) | 0.0606 (18) | −0.0247 (16) | −0.0019 (15) | −0.0083 (15) |
C26 | 0.0691 (19) | 0.0536 (18) | 0.0560 (17) | −0.0225 (15) | −0.0039 (14) | −0.0010 (14) |
C27 | 0.072 (2) | 0.0545 (18) | 0.0591 (18) | −0.0241 (15) | 0.0011 (14) | −0.0068 (14) |
C28 | 0.0642 (18) | 0.0535 (18) | 0.0554 (17) | −0.0201 (14) | −0.0005 (13) | −0.0025 (13) |
C29 | 0.093 (2) | 0.059 (2) | 0.0590 (19) | −0.0350 (18) | −0.0019 (16) | 0.0014 (15) |
C30 | 0.093 (3) | 0.062 (2) | 0.069 (2) | −0.0341 (19) | 0.0013 (18) | −0.0119 (17) |
C31 | 0.0655 (19) | 0.066 (2) | 0.0561 (18) | −0.0204 (16) | 0.0046 (14) | −0.0095 (15) |
C32 | 0.084 (2) | 0.063 (2) | 0.0586 (19) | −0.0298 (18) | 0.0106 (16) | −0.0053 (15) |
C33 | 0.077 (2) | 0.059 (2) | 0.067 (2) | −0.0284 (17) | 0.0112 (16) | −0.0123 (16) |
C34 | 0.109 (3) | 0.088 (3) | 0.074 (2) | −0.034 (2) | 0.006 (2) | −0.029 (2) |
C35 | 0.147 (6) | 0.199 (8) | 0.132 (5) | −0.087 (5) | −0.043 (4) | 0.020 (5) |
C36 | 0.276 (11) | 0.247 (10) | 0.162 (7) | −0.181 (9) | 0.009 (7) | −0.060 (7) |
Sn1—C14 | 2.133 (3) | C12—H12B | 0.9700 |
Sn1—C10 | 2.140 (3) | C13—H13A | 0.9600 |
Sn1—N1 | 2.319 (2) | C13—H13B | 0.9600 |
Sn1—S1 | 2.4717 (7) | C13—H13C | 0.9600 |
Sn1—Cl1 | 2.6421 (7) | C14—C15 | 1.488 (5) |
S1—C1 | 1.732 (2) | C14—H14A | 0.9700 |
S2—C26 | 1.687 (3) | C14—H14B | 0.9700 |
O1—C6 | 1.364 (4) | C15—C16 | 1.479 (5) |
O1—C9 | 1.428 (5) | C15—H15A | 0.9700 |
O2—C18 | 1.349 (6) | C15—H15B | 0.9700 |
O2—C19 | 1.399 (5) | C16—C17 | 1.475 (6) |
O3—C31 | 1.361 (4) | C16—H16A | 0.9700 |
O3—C34 | 1.413 (5) | C16—H16B | 0.9700 |
O4—C35 | 1.343 (8) | C17—H17A | 0.9600 |
O4—H4A | 0.8200 | C17—H17B | 0.9600 |
N1—C1i | 1.309 (3) | C17—H17C | 0.9600 |
N1—N1i | 1.409 (4) | C18—H18A | 0.9600 |
N2—C1 | 1.355 (3) | C18—H18B | 0.9600 |
N2—N3 | 1.382 (3) | C18—H18C | 0.9600 |
N2—H2 | 0.8600 | C19—C20 | 1.346 (6) |
N3—C2 | 1.286 (4) | C19—C24 | 1.356 (6) |
N4—C25 | 1.260 (4) | C20—C21 | 1.419 (6) |
N4—N5 | 1.385 (4) | C20—H20 | 0.9300 |
N5—C26 | 1.329 (4) | C21—C22 | 1.358 (5) |
N5—H5 | 0.8600 | C21—H21 | 0.9300 |
N6—C26 | 1.335 (4) | C22—C23 | 1.389 (5) |
N6—N7 | 1.384 (3) | C22—C25 | 1.465 (5) |
N6—H6 | 0.8600 | C23—C24 | 1.352 (5) |
N7—C27 | 1.270 (4) | C23—H23 | 0.9300 |
C1—N1i | 1.309 (3) | C24—H24 | 0.9300 |
C2—C3 | 1.456 (4) | C25—H25 | 0.9300 |
C2—H2A | 0.9300 | C27—C28 | 1.449 (4) |
C3—C8 | 1.378 (4) | C27—H27 | 0.9300 |
C3—C4 | 1.379 (4) | C28—C29 | 1.388 (5) |
C4—C5 | 1.370 (4) | C28—C33 | 1.389 (5) |
C4—H4 | 0.9300 | C29—C30 | 1.379 (5) |
C5—C6 | 1.386 (5) | C29—H29 | 0.9300 |
C5—H5A | 0.9300 | C30—C31 | 1.377 (5) |
C6—C7 | 1.384 (5) | C30—H30 | 0.9300 |
C7—C8 | 1.397 (5) | C31—C32 | 1.382 (5) |
C7—H7 | 0.9300 | C32—C33 | 1.381 (5) |
C8—H8 | 0.9300 | C32—H32 | 0.9300 |
C9—H9A | 0.9600 | C33—H33 | 0.9300 |
C9—H9B | 0.9600 | C34—H34A | 0.9600 |
C9—H9C | 0.9600 | C34—H34B | 0.9600 |
C10—C11 | 1.507 (4) | C34—H34C | 0.9600 |
C10—H10A | 0.9700 | C35—C36 | 1.528 (7) |
C10—H10B | 0.9700 | C35—H35A | 0.9700 |
C11—C12 | 1.509 (5) | C35—H35B | 0.9700 |
C11—H11A | 0.9700 | C36—H36A | 0.9600 |
C11—H11B | 0.9700 | C36—H36B | 0.9600 |
C12—C13 | 1.493 (6) | C36—H36C | 0.9600 |
C12—H12A | 0.9700 | ||
C14—Sn1—C10 | 147.6 (2) | H14A—C14—H14B | 107.3 |
C14—Sn1—N1 | 96.5 (2) | C16—C15—C14 | 115.1 (3) |
C10—Sn1—N1 | 95.9 (2) | C16—C15—H15A | 108.5 |
C14—Sn1—S1 | 105.58 (9) | C14—C15—H15A | 108.5 |
C10—Sn1—S1 | 106.3 (2) | C16—C15—H15B | 108.5 |
N1—Sn1—S1 | 77.13 (6) | C14—C15—H15B | 108.5 |
C14—Sn1—Cl1 | 90.29 (9) | H15A—C15—H15B | 107.5 |
C10—Sn1—Cl1 | 88.08 (8) | C17—C16—C15 | 117.6 (4) |
N1—Sn1—Cl1 | 160.11 (6) | C17—C16—H16A | 107.9 |
S1—Sn1—Cl1 | 83.04 (2) | C15—C16—H16A | 107.9 |
C1—S1—Sn1 | 99.19 (9) | C17—C16—H16B | 107.9 |
C6—O1—C9 | 117.9 (3) | C15—C16—H16B | 107.9 |
C18—O2—C19 | 117.2 (4) | H16A—C16—H16B | 107.2 |
C31—O3—C34 | 118.2 (3) | C16—C17—H17A | 109.5 |
C35—O4—H4A | 109.5 | C16—C17—H17B | 109.5 |
C1i—N1—N1i | 115.5 (2) | H17A—C17—H17B | 109.5 |
C1i—N1—Sn1 | 124.44 (18) | C16—C17—H17C | 109.5 |
N1i—N1—Sn1 | 119.78 (19) | H17A—C17—H17C | 109.5 |
C1—N2—N3 | 122.2 (2) | H17B—C17—H17C | 109.5 |
C1—N2—H2 | 118.9 | O2—C18—H18A | 109.5 |
N3—N2—H2 | 118.9 | O2—C18—H18B | 109.5 |
C2—N3—N2 | 115.0 (2) | H18A—C18—H18B | 109.5 |
C25—N4—N5 | 116.5 (3) | O2—C18—H18C | 109.5 |
C26—N5—N4 | 120.1 (3) | H18A—C18—H18C | 109.5 |
C26—N5—H5 | 119.9 | H18B—C18—H18C | 109.5 |
N4—N5—H5 | 119.9 | C20—C19—C24 | 120.7 (4) |
C26—N6—N7 | 120.2 (3) | C20—C19—O2 | 124.2 (4) |
C26—N6—H6 | 119.9 | C24—C19—O2 | 115.1 (4) |
N7—N6—H6 | 119.9 | C19—C20—C21 | 119.8 (4) |
C27—N7—N6 | 115.9 (3) | C19—C20—H20 | 120.1 |
N1i—C1—N2 | 120.3 (2) | C21—C20—H20 | 120.1 |
N1i—C1—S1 | 128.1 (2) | C22—C21—C20 | 119.5 (4) |
N2—C1—S1 | 111.53 (17) | C22—C21—H21 | 120.3 |
N3—C2—C3 | 124.6 (3) | C20—C21—H21 | 120.3 |
N3—C2—H2A | 117.7 | C21—C22—C23 | 118.5 (3) |
C3—C2—H2A | 117.7 | C21—C22—C25 | 119.9 (3) |
C8—C3—C4 | 118.0 (3) | C23—C22—C25 | 121.6 (3) |
C8—C3—C2 | 117.8 (3) | C24—C23—C22 | 121.5 (4) |
C4—C3—C2 | 124.1 (3) | C24—C23—H23 | 119.2 |
C5—C4—C3 | 120.7 (3) | C22—C23—H23 | 119.2 |
C5—C4—H4 | 119.6 | C23—C24—C19 | 120.0 (4) |
C3—C4—H4 | 119.6 | C23—C24—H24 | 120.0 |
C4—C5—C6 | 121.0 (3) | C19—C24—H24 | 120.0 |
C4—C5—H5A | 119.5 | N4—C25—C22 | 120.9 (3) |
C6—C5—H5A | 119.5 | N4—C25—H25 | 119.6 |
O1—C6—C7 | 124.4 (3) | C22—C25—H25 | 119.6 |
O1—C6—C5 | 115.8 (3) | N5—C26—N6 | 116.2 (3) |
C7—C6—C5 | 119.7 (3) | N5—C26—S2 | 124.2 (2) |
C6—C7—C8 | 117.9 (3) | N6—C26—S2 | 119.6 (2) |
C6—C7—H7 | 121.0 | N7—C27—C28 | 122.4 (3) |
C8—C7—H7 | 121.0 | N7—C27—H27 | 118.8 |
C3—C8—C7 | 122.6 (3) | C28—C27—H27 | 118.8 |
C3—C8—H8 | 118.7 | C29—C28—C33 | 118.0 (3) |
C7—C8—H8 | 118.7 | C29—C28—C27 | 121.8 (3) |
O1—C9—H9A | 109.5 | C33—C28—C27 | 120.1 (3) |
O1—C9—H9B | 109.5 | C30—C29—C28 | 120.8 (3) |
H9A—C9—H9B | 109.5 | C30—C29—H29 | 119.6 |
O1—C9—H9C | 109.5 | C28—C29—H29 | 119.6 |
H9A—C9—H9C | 109.5 | C31—C30—C29 | 120.2 (3) |
H9B—C9—H9C | 109.5 | C31—C30—H30 | 119.9 |
C11—C10—Sn1 | 117.4 (2) | C29—C30—H30 | 119.9 |
C11—C10—H10A | 107.9 | O3—C31—C30 | 124.3 (3) |
Sn1—C10—H10A | 107.9 | O3—C31—C32 | 115.5 (3) |
C11—C10—H10B | 107.9 | C30—C31—C32 | 120.2 (3) |
Sn1—C10—H10B | 107.9 | C33—C32—C31 | 119.2 (3) |
H10A—C10—H10B | 107.2 | C33—C32—H32 | 120.4 |
C10—C11—C12 | 113.9 (3) | C31—C32—H32 | 120.4 |
C10—C11—H11A | 108.8 | C32—C33—C28 | 121.6 (3) |
C12—C11—H11A | 108.8 | C32—C33—H33 | 119.2 |
C10—C11—H11B | 108.8 | C28—C33—H33 | 119.2 |
C12—C11—H11B | 108.8 | O3—C34—H34A | 109.5 |
H11A—C11—H11B | 107.7 | O3—C34—H34B | 109.5 |
C13—C12—C11 | 115.5 (4) | H34A—C34—H34B | 109.5 |
C13—C12—H12A | 108.4 | O3—C34—H34C | 109.5 |
C11—C12—H12A | 108.4 | H34A—C34—H34C | 109.5 |
C13—C12—H12B | 108.4 | H34B—C34—H34C | 109.5 |
C11—C12—H12B | 108.4 | O4—C35—C36 | 116.3 (5) |
H12A—C12—H12B | 107.5 | O4—C35—H35A | 108.2 |
C12—C13—H13A | 109.5 | C36—C35—H35A | 108.2 |
C12—C13—H13B | 109.5 | O4—C35—H35B | 108.2 |
H13A—C13—H13B | 109.5 | C36—C35—H35B | 108.2 |
C12—C13—H13C | 109.5 | H35A—C35—H35B | 107.4 |
H13A—C13—H13C | 109.5 | C35—C36—H36A | 109.5 |
H13B—C13—H13C | 109.5 | C35—C36—H36B | 109.5 |
C15—C14—Sn1 | 117.1 (2) | H36A—C36—H36B | 109.5 |
C15—C14—H14A | 108.0 | C35—C36—H36C | 109.5 |
Sn1—C14—H14A | 108.0 | H36A—C36—H36C | 109.5 |
C15—C14—H14B | 108.0 | H36B—C36—H36C | 109.5 |
Sn1—C14—H14B | 108.0 |
Symmetry code: (i) −x+2, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···N7 | 0.86 | 2.26 | 2.619 (4) | 105 |
C2—H2A···Cl1ii | 0.93 | 2.70 | 3.572 (3) | 157 |
C25—H25···O4iii | 0.93 | 2.52 | 3.354 (5) | 150 |
N2—H2···Cl1ii | 0.86 | 2.62 | 3.398 (2) | 151 |
N6—H6···S2iv | 0.86 | 2.53 | 3.386 (3) | 171 |
N5—H5···O4iii | 0.86 | 2.62 | 3.379 (5) | 147 |
Symmetry codes: (ii) −x+1, −y+2, −z; (iii) −x+1, −y+2, −z+1; (iv) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Sn2(C4H9)4Cl2(C18H18N6O2S2)]·2C17H18N4O2S·2C2H6O |
Mr | 1728.20 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 8.9295 (6), 10.3932 (7), 24.015 (2) |
α, β, γ (°) | 81.439 (1), 85.350 (1), 70.521 (1) |
V (Å3) | 2076.6 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.83 |
Crystal size (mm) | 0.40 × 0.31 × 0.31 |
Data collection | |
Diffractometer | Bruker APEX II area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.74, 0.77 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13116, 7145, 6432 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.087, 1.04 |
No. of reflections | 7145 |
No. of parameters | 467 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.58, −0.39 |
Computer programs: APEX2 (Bruker, 2004), APEX2 and publCIF (Westrip, 2007).
Sn1—C14 | 2.133 (3) | Sn1—S1 | 2.4717 (7) |
Sn1—C10 | 2.140 (3) | Sn1—Cl1 | 2.6421 (7) |
Sn1—N1 | 2.319 (2) | S1—C1 | 1.732 (2) |
C14—Sn1—C10 | 147.6 (2) | N1—Sn1—S1 | 77.13 (6) |
C14—Sn1—N1 | 96.5 (2) | C14—Sn1—Cl1 | 90.29 (9) |
C10—Sn1—N1 | 95.9 (2) | C10—Sn1—Cl1 | 88.08 (8) |
C14—Sn1—S1 | 105.58 (9) | N1—Sn1—Cl1 | 160.11 (6) |
C10—Sn1—S1 | 106.3 (2) | S1—Sn1—Cl1 | 83.04 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···N7 | 0.86 | 2.26 | 2.619 (4) | 105.4 |
C2—H2A···Cl1i | 0.93 | 2.70 | 3.572 (3) | 156.5 |
C25—H25···O4ii | 0.93 | 2.52 | 3.354 (5) | 149.6 |
N2—H2···Cl1i | 0.86 | 2.62 | 3.398 (2) | 150.5 |
N6—H6···S2iii | 0.86 | 2.53 | 3.386 (3) | 170.7 |
N5—H5···O4ii | 0.86 | 2.62 | 3.379 (5) | 147.2 |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+2, −z+1; (iii) −x+1, −y+1, −z+1. |
Organotin complexes have attracted attention in supermolecular chemistry in recent years (Ma et al., 2005; Barbieri et al., 2001), whereas thiosemicarbazones and their complexes have a wide range of applications in biology (Casas et al., 2000). In the context of our continuous interest for the structural and biological properties of organotin compounds (Fang et al., 2001; 2006a), we report here the crystal structure of the title complex, (I). To the best of our knowledge, this is the first example of organotin complex containing C2N2S2Sn2 planar dicyclo fragment.
The structure of (I) is an unexpected product in our work. It crystallizes in space group P-1, with one half-molecule of an organotin complex [2,2,6,6-Tetra-n-butyl-2,6-dichloro-4,8-di[(1E)-4-methoxybenzylidene]ηydrazino-1,5-diaza-2,6-distanna-3,7-dithiabicyclo[3.3.0]octane], one substituted thiocarbonohydrazide ligand [1,5-Bis[(1E)-4-methoxybenzylidene]thiocarbonohydrazide] and one ethanol molecule in the asymmetric unit (Fig. 1). Part of the thiocarbonohydrazide ligand molecules were cracked to form a novel substituted C2N2S2Sn2 planar dicyclo organotin complex. The five-membered ring Sn1—S1—C1—N1A—N1 is coplanar with a mean deviation of 0.024 (3) Å. The inversion center is situated at the midpoint of N1—N1A bond, and it is by this bond that the two five-membered rings are fused together. Both of the SnIV atoms are penta-coordinated with distorted trigonal-bipyramidal geometry. C10, C14 (from butyl groups) and S1 atom occupy the equatorial plane, these equatorial atoms and relative Sn atom are nearly coplanar, the mean deviation from the plane is 0.031 (4) Å. Cl1 and N1 atoms occupy the axial positions with the N1—Sn1—Cl1 bond angle 160.11 (6)°. All the C═ N bonds exist in E-configuration, and all the bond lengths in (I) are within the expected range and agree well with literature values (Altmann et al., 1998; Fang et al., 2006).
In the crystal lattice, every two molecules of the ligand are linked by the weak hydrogen bonds N6—H6···S2i to form dimers, with the attached two ethanol molecules by the strong N5—H5···O4ii and weak C25—H25···O4ii hydrogen bonds. The molecules of organotin are linked by S···S interactions (Wang et al., 2004). and N—H···Cliii, C—H···Cliii weak hydrogen bonds involving all potential S and Cl atom donors, generating one-dimensional infinite chains parallel to the a axis, as shown in Fig. 2. The 4-methoxyphenyl rings protrude on both sides of these chains and have no special intercalations [symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x + 1, -y + 2, -z + 1; (iii) -x + 1, -y + 2, -z].