Bis­(methane­sulfonato-κO)(5,10,15,20-tetra­phenyl­porphyrinato-κ4N,N′,N′′,N′′′)tin(IV) chloro­form tris­olvate

Singh, A.P.; Kim, H.-J.

doi:10.1107/S1600536812015875

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m626

doi:10.1107/S1600536812015875

Open

access

Bis(methanesulfonato-κO)(5,10,15,20-tetraphenylporphyrinato-κ⁴N,N′,N′′,N′′′)tin(IV) chloroform trisolvate

Atul P. Singh ^a and Hee-Joon Kim ^a ^*

^aDepartment of Applied Chemistry, Kumoh National Institute of Technology, 1 Yangho-dong, Gumi 730-701, Republic of Korea
^*Correspondence e-mail: hjk@kumoh.ac.kr

(Received 16 March 2012; accepted 11 April 2012; online 18 April 2012)

In the crystal structure of the title compound, [Sn(C₄₄H₂₈N₄)(CH₃O₃S)₂]·3CHCl₃, the Sn^IV ion is located on an inversion center and is octahedrally coordinated. The porphyrin N atoms occupy the equatorial positions while the axial positions are occupied by the O atoms of the methanesulfonate anions. The phenyl rings make dihedral angles of 77.02 (13) and 87.89 (14)° with the porphyrin ring. Of the three solvent chloroform molecules, one is disordered over a twofold rotation axis. In the crystal a three-dimensional assembly is accomplished via C—H⋯O hydrogen bonds between the H atoms of the phenyl groups in the porphyrin ring and the O atoms of the methanesulfonate ligands.

Related literature

For general background to tin(IV) porphyrin chemistry, see: Arnold & Blok (2004 ). For the preparation of related tin porphyrins, see: Kim et al. (2004 , 2005 , 2007 , 2009 ). For related structures, see: Liu et al. (1996 ); Smith et al. (1991 ).

Experimental

Crystal data

[Sn(C₄₄H₂₈N₄)(CH₃O₃S)₂]·3CHCl₃
M_r = 1279.69
Monoclinic, C 2/c
a = 25.379 (2) Å
b = 11.6269 (9) Å
c = 20.860 (3) Å
β = 120.934 (1)°
V = 5279.9 (9) Å³
Z = 4
Mo Kα radiation
μ = 1.07 mm⁻¹
T = 150 K
0.26 × 0.19 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.765, T_max = 0.848
22613 measured reflections
5192 independent reflections
4525 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.088
S = 1.04
5192 reflections
331 parameters
H-atom parameters constrained
Δρ_max = 0.91 e Å⁻³
Δρ_min = −0.86 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O2ⁱ	0.95	2.55	3.280 (4)	134
C24—H24A⋯O2ⁱⁱ	1.00	2.35	3.191 (4)	141
Symmetry codes: (i) $[-x, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812015875/wm2606sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812015875/wm2606Isup2.hkl

checkCIF report

Comment top

In tin(IV) porphyrin chemistry, a number of compounds have been synthesized through variation of the axial ligands such as hydroxide, alkoxides, halides, nitrate, perchlorate or carboxylates (Arnold & Blok, 2004). Among these compounds, hydroxido-tin(IV) porphyrins have been employed as useful precursors for the preparation of various tin(IV) prophyrin complexes bearing oxygen donor ligands preferentially (Kim et al., 2004, 2005, 2007, 2009). In this order, we have studied the reactivity behaviour of hydroxido-tin(IV) porphyrins with various acidic compounds including sulfonic acid derivatives. Here we report the synthesis, characterization and X-ray structural study of the title solvate [Sn(C₄₄H₂₈N₄)(CH₃SO₃)₂]^.3CHCl₃ or [Sn(TPP)(CH₃SO₃)₂]^.3CHCl₃ (TPP = tetraphenylporphyrinato dianion).

The characterization of the title compound has been carried out with ¹H NMR spectroscopy (see supplementary materials) as well as with X-ray crystal structure analysis. The molecular structure of Sn(TPP)(CH₃SO₃)₂ shown in Figure 1 exhibits an octahedral geometry around the tin(IV) ion (site symmetry 1). The equatorial plane is formed by four N atoms of the porphyrin ring while the axial positions are occupied by methanesulfonate groups. The methanesulfonate groups are unidentately coordinating to the tin atom. The bond lengths, Sn1—N1 = 2.074 (2), Sn1—N2 = 2.081 (2) Å and angles, N1—Sn1—N2 = 89.99 (8)°, N1—Sn1—N2ⁱ = 90.01 (8)°, N1—Sn1—N1ⁱ = 180.00 (7)° and O1—Sn1—O1ⁱ = 180.0°, associated with these atoms well corroborate the fact related to an octahedral coordination environment around the tin atom. The bond length Sn—O_{methanesulfonato} (2.1184 (18) Å) is significantly longer than Sn—O_acetato (2.086 (5) Å) in Sn(TPP)(CH₃CO₂)₂ (Liu et al., 1996), which reflects a less basic character of the methanesulfonate group than of the acetate group. On comparison with the reported Sn(TPP) complex bearing CF₃SO₃^- groups (Smith et al., 1991), this comound crystallizes as a diaqua-complex where the two water molecules are coordinating to the tin atom at the axial sites while the two CF₃SO₃^- groups act as counter anions. The comparative study of these two anionic sulfonate groups evidently reveals that the methanesulfonate anion has a more basic character than the trifluoromethanesulfonate anion.

In the crystal structure of [Sn(C₄₄H₂₈N₄)(CH₃SO₃)₂]^.3CHCl₃ the presence of intramolecular and intermolecular hydrogen bonding (which lies in the range of moderate to weak bonding) is evident. The molecular structure shows the presence of one intramolecular hydrogen bond (C11—H11A···O3 = 2.846 Å) between the phenyl H11A atom and the O3 atom of the methanesulfonato ligand. Two additional hydrogen bonds (C20—H20A···O3 = 2.626, C19—H19A···O3 = 3.012 Å) involving H19A, H20A atoms of the phenyl groups and O3 atoms of the methanesulfonato ligands form a chain structure along the b-axis (Figure 2). Further, these adjacent one-dimensional chains interact with each other via additional hydrogen bonds, resulting in two-dimensional (C8—H8A···O2 = 2.552, C8—H8A···O1 = 2.769 Å) (Figure 3) and three-dimensional (C10—H10A···O3 = 3.065 Å) (Figure 4) structural motifs. The view of three-dimensional supramolecular assembly along the b-axis (in ac-plane) displays the presence of infinite channels which are filled by chloroform molecules. The asymmetric unit is associated with two chloroform molecules present in the three-dimensional channels as free solvent molecules. Another chloroform molecules in the asymmetric unit is present in a weakly hydrogen-bonded state (C24—H24A···O3 = 2.720, C24—H24A···O2 = 2.352 Å) with the oxygen atoms of the methanesulfonato ligands of adjacent asymmetric units.

Related literature top

For general background to tin(IV) porphyrin chemistry, see: Arnold & Blok (2004). For the preparation of related tin porphyrins, see: Kim et al. (2004, 2005, 2007, 2009). For related structures, see: Liu et al. (1996); Smith et al. (1991).

Experimental top

A mixture of Sn(TPP)(OH)₂ (0.150 g, 1.96 × 10 ^-4 mol) and methanesulfonic acid (0.0376 g, 3.92 × 10 ^-4 mol) in dry chloroform (20 ml) was stirred at room temperature for 8 h. The solvent was removed and the crude material was stirred in dry hexane for 4 h. The precipitated compound was filtered and dried in vacuo. The product was further recrystallized by slow diffusion of n-hexane into a chloroform solution of the compound. Yield: 75%. Mp > 300° C. ¹H NMR (400 MHz, CDCl₃, SiMe₄): δ -0.50 (6H, s, CH₃), 7.79–7.86 (12H, Ar—H), 8.29 (8H, d, ³J_H—H = 6.56 Hz, Ar—H), 9.17 (8H, s, ⁴J_H—Sn = 14.8 Hz, β-pyrrolic H).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of [Sn(C₄₄H₂₈N₄)(CH₃SO₃)₂]^.3CHCl₃ with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity. [Symmetry codes: (A) -x, -y, -z; (B) -x, y, -z + 0.5.]
	Fig. 2. View of the one-dimensional chain along the b-axis. Hydrogen-bonding interactions are drawn with dashed lines.
	Fig. 3. View along the a-axis of the two-dimensional structure. Hydrogen-bond interactions are drawn with dashed lines.
	Fig. 4. View along b-axis of the three-dimensional structure. Hydrogen-bond interactions are drawn with dashed lines.

Bis(methanesulfonato-κO)(5,10,15,20-tetraphenylporphyrinato- κ⁴N,N'',N'',N''')tin(IV) chloroform trisolvate top

Crystal data top

[Sn(C₄₄H₂₈N₄)(CH₃O₃S)₂]·3CHCl₃	F(000) = 2568
M_r = 1279.69	D_x = 1.610 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9494 reflections
a = 25.379 (2) Å	θ = 2.5–27.6°
b = 11.6269 (9) Å	µ = 1.07 mm⁻¹
c = 20.860 (3) Å	T = 150 K
β = 120.934 (1)°	Block, violet
V = 5279.9 (9) Å³	0.26 × 0.19 × 0.16 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	5192 independent reflections
Radiation source: Turbo X-ray	4525 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.035
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −31→31
T_min = 0.765, T_max = 0.848	k = −14→14
22613 measured reflections	l = −24→25

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0404P)² + 12.8121P] where P = (F_o² + 2F_c²)/3
5192 reflections	(Δ/σ)_max < 0.001
331 parameters	Δρ_max = 0.91 e Å⁻³
0 restraints	Δρ_min = −0.86 e Å⁻³

Crystal data top

[Sn(C₄₄H₂₈N₄)(CH₃O₃S)₂]·3CHCl₃	V = 5279.9 (9) Å³
M_r = 1279.69	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 25.379 (2) Å	µ = 1.07 mm⁻¹
b = 11.6269 (9) Å	T = 150 K
c = 20.860 (3) Å	0.26 × 0.19 × 0.16 mm
β = 120.934 (1)°

Data collection top

Bruker APEXII CCD diffractometer	5192 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	4525 reflections with I > 2σ(I)
T_min = 0.765, T_max = 0.848	R_int = 0.035
22613 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0404P)² + 12.8121P] where P = (F_o² + 2F_c²)/3
5192 reflections	Δρ_max = 0.91 e Å⁻³
331 parameters	Δρ_min = −0.86 e Å⁻³

Special details top

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 > 2σ(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	U_iso*/U_eq	Occ. (<1)
Sn1	0.0000	0.0000	0.0000	0.02057 (8)
S1	0.14343 (3)	−0.07734 (6)	0.12355 (4)	0.02780 (15)
O1	0.07563 (8)	−0.07458 (16)	0.09584 (10)	0.0297 (4)
O2	0.16993 (10)	0.03546 (19)	0.14721 (12)	0.0408 (5)
O3	0.15589 (10)	−0.13277 (19)	0.07136 (12)	0.0416 (5)
N1	−0.05688 (9)	−0.08286 (17)	0.02948 (11)	0.0233 (4)
N2	0.00374 (9)	0.14274 (17)	0.06239 (11)	0.0228 (4)
C1	−0.08282 (12)	−0.1898 (2)	0.00474 (14)	0.0256 (5)
C2	−0.12325 (13)	−0.2100 (2)	0.03274 (15)	0.0299 (6)
H2A	−0.1465	−0.2779	0.0255	0.036*
C3	−0.12243 (12)	−0.1162 (2)	0.07092 (15)	0.0291 (6)
H3A	−0.1456	−0.1058	0.0946	0.035*
C4	−0.08066 (12)	−0.0349 (2)	0.06968 (14)	0.0250 (5)
C5	−0.06792 (12)	0.0747 (2)	0.10157 (14)	0.0247 (5)
C6	−0.10283 (12)	0.1116 (2)	0.13798 (14)	0.0261 (5)
C7	−0.08757 (13)	0.0719 (3)	0.20824 (15)	0.0335 (6)
H7A	−0.0543	0.0199	0.2342	0.040*
C8	−0.12063 (14)	0.1076 (3)	0.24057 (17)	0.0408 (7)
H8A	−0.1093	0.0815	0.2892	0.049*
C9	−0.16933 (15)	0.1800 (3)	0.20320 (19)	0.0429 (8)
H9A	−0.1922	0.2031	0.2254	0.051*
C10	−0.18547 (16)	0.2199 (3)	0.1334 (2)	0.0464 (8)
H10A	−0.2194	0.2706	0.1076	0.056*
C11	−0.15213 (14)	0.1861 (3)	0.10063 (17)	0.0372 (7)
H11A	−0.1632	0.2141	0.0525	0.045*
C12	−0.02762 (11)	0.1554 (2)	0.09967 (13)	0.0239 (5)
C13	−0.01197 (12)	0.2649 (2)	0.13580 (15)	0.0279 (6)
H13A	−0.0268	0.2958	0.1657	0.033*
C14	0.02779 (12)	0.3169 (2)	0.12005 (15)	0.0271 (5)
H14A	0.0460	0.3904	0.1372	0.033*
C15	0.03759 (11)	0.2412 (2)	0.07293 (14)	0.0239 (5)
C16	0.07386 (11)	0.2634 (2)	0.04160 (14)	0.0243 (5)
C17	0.10721 (12)	0.3760 (2)	0.06105 (14)	0.0248 (5)
C18	0.08175 (16)	0.4711 (3)	0.0177 (2)	0.0612 (12)
H18A	0.0417	0.4664	−0.0253	0.073*
C19	0.11340 (17)	0.5748 (3)	0.0354 (2)	0.0643 (12)
H19A	0.0947	0.6405	0.0048	0.077*
C20	0.17068 (14)	0.5828 (2)	0.09582 (18)	0.0375 (7)
H20A	0.1926	0.6534	0.1077	0.045*
C21	0.19643 (16)	0.4888 (3)	0.1391 (2)	0.0595 (11)
H21A	0.2366	0.4940	0.1819	0.071*
C22	0.16519 (15)	0.3853 (3)	0.1222 (2)	0.0525 (9)
H22A	0.1841	0.3202	0.1531	0.063*
C23	0.17079 (15)	−0.1659 (3)	0.20286 (17)	0.0421 (7)
H23A	0.2154	−0.1752	0.2265	0.063*
H23B	0.1509	−0.2414	0.1878	0.063*
H23C	0.1613	−0.1304	0.2384	0.063*
C24	0.22194 (17)	0.5661 (3)	0.3870 (2)	0.0504 (8)
H24A	0.2647	0.5432	0.4016	0.061*
Cl1	0.17224 (7)	0.51173 (11)	0.29855 (8)	0.0916 (4)
Cl2	0.20717 (7)	0.51221 (9)	0.45494 (8)	0.0788 (4)
Cl3	0.21860 (5)	0.71697 (8)	0.38628 (6)	0.0621 (3)
C25	0.0212 (4)	0.6766 (7)	0.2678 (6)	0.070 (2)	0.50
H25	0.0622	0.6907	0.3138	0.084*	0.50
Cl4	0.02877 (7)	0.75684 (14)	0.20677 (9)	0.1048 (5)
Cl5	0.0137 (3)	0.5484 (3)	0.2778 (3)	0.146 (3)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.02249 (13)	0.01973 (13)	0.02126 (13)	−0.00515 (9)	0.01251 (10)	−0.00170 (9)
S1	0.0274 (3)	0.0302 (3)	0.0260 (3)	0.0002 (3)	0.0140 (3)	0.0005 (3)
O1	0.0265 (9)	0.0327 (10)	0.0275 (10)	−0.0020 (8)	0.0122 (8)	0.0053 (8)
O2	0.0397 (12)	0.0418 (11)	0.0446 (12)	−0.0139 (10)	0.0244 (10)	−0.0095 (10)
O3	0.0509 (13)	0.0439 (12)	0.0353 (11)	0.0098 (10)	0.0259 (10)	0.0010 (9)
N1	0.0262 (11)	0.0218 (10)	0.0237 (11)	−0.0053 (8)	0.0140 (9)	−0.0017 (8)
N2	0.0259 (11)	0.0218 (10)	0.0241 (11)	−0.0060 (8)	0.0152 (9)	−0.0030 (8)
C1	0.0266 (13)	0.0231 (12)	0.0258 (13)	−0.0050 (10)	0.0126 (11)	0.0008 (10)
C2	0.0332 (14)	0.0280 (13)	0.0348 (15)	−0.0083 (11)	0.0220 (12)	−0.0005 (11)
C3	0.0315 (14)	0.0304 (14)	0.0322 (14)	−0.0073 (11)	0.0213 (12)	−0.0028 (11)
C4	0.0256 (13)	0.0277 (12)	0.0233 (13)	−0.0044 (10)	0.0137 (11)	0.0011 (10)
C5	0.0261 (13)	0.0280 (13)	0.0212 (12)	−0.0025 (10)	0.0131 (11)	0.0002 (10)
C6	0.0280 (13)	0.0268 (13)	0.0277 (13)	−0.0093 (10)	0.0173 (11)	−0.0062 (10)
C7	0.0316 (14)	0.0431 (16)	0.0285 (14)	−0.0044 (12)	0.0174 (12)	0.0006 (12)
C8	0.0428 (17)	0.0565 (19)	0.0331 (16)	−0.0188 (15)	0.0267 (14)	−0.0111 (14)
C9	0.0468 (18)	0.0452 (18)	0.056 (2)	−0.0129 (15)	0.0406 (17)	−0.0177 (15)
C10	0.0442 (18)	0.0385 (17)	0.068 (2)	0.0040 (14)	0.0366 (18)	0.0015 (16)
C11	0.0398 (16)	0.0370 (16)	0.0408 (17)	0.0028 (13)	0.0250 (14)	0.0057 (13)
C12	0.0270 (13)	0.0249 (12)	0.0202 (12)	−0.0012 (10)	0.0124 (10)	0.0002 (10)
C13	0.0297 (13)	0.0272 (13)	0.0290 (14)	−0.0026 (11)	0.0167 (12)	−0.0045 (11)
C14	0.0305 (13)	0.0211 (12)	0.0286 (13)	−0.0039 (10)	0.0143 (11)	−0.0027 (10)
C15	0.0235 (12)	0.0222 (12)	0.0230 (12)	−0.0034 (10)	0.0098 (10)	−0.0005 (10)
C16	0.0247 (12)	0.0220 (12)	0.0249 (13)	−0.0036 (10)	0.0119 (11)	0.0006 (10)
C17	0.0272 (13)	0.0219 (12)	0.0293 (13)	−0.0052 (10)	0.0174 (11)	−0.0025 (10)
C18	0.0387 (18)	0.0378 (18)	0.063 (2)	−0.0121 (15)	−0.0052 (17)	0.0162 (17)
C19	0.049 (2)	0.0291 (16)	0.074 (3)	−0.0094 (15)	0.0023 (19)	0.0189 (17)
C20	0.0394 (16)	0.0238 (13)	0.0507 (18)	−0.0099 (12)	0.0242 (15)	−0.0067 (13)
C21	0.0374 (18)	0.0354 (18)	0.063 (2)	−0.0132 (14)	−0.0052 (17)	0.0039 (16)
C22	0.0418 (18)	0.0301 (16)	0.052 (2)	−0.0078 (13)	0.0004 (16)	0.0109 (14)
C23	0.0398 (17)	0.0498 (18)	0.0309 (15)	0.0100 (14)	0.0140 (13)	0.0115 (14)
C24	0.056 (2)	0.053 (2)	0.055 (2)	0.0161 (17)	0.0373 (18)	0.0061 (17)
Cl1	0.0975 (10)	0.0843 (9)	0.0691 (8)	−0.0046 (7)	0.0257 (7)	−0.0116 (6)
Cl2	0.1253 (11)	0.0547 (6)	0.0981 (9)	0.0140 (6)	0.0872 (9)	0.0121 (5)
Cl3	0.0740 (6)	0.0512 (5)	0.0733 (6)	0.0138 (5)	0.0466 (6)	0.0105 (5)
C25	0.059 (5)	0.060 (5)	0.083 (7)	−0.006 (3)	0.031 (5)	−0.009 (4)
Cl4	0.0796 (9)	0.1124 (11)	0.1096 (11)	0.0073 (8)	0.0395 (8)	0.0276 (9)
Cl5	0.169 (6)	0.0757 (16)	0.248 (8)	0.053 (3)	0.146 (6)	0.069 (3)

Geometric parameters (Å, º) top

Sn1—N1	2.074 (2)	C12—C13	1.427 (4)
Sn1—N1ⁱ	2.074 (2)	C13—C14	1.354 (4)
Sn1—N2ⁱ	2.081 (2)	C13—H13A	0.9500
Sn1—N2	2.081 (2)	C14—C15	1.433 (4)
Sn1—O1	2.1184 (18)	C14—H14A	0.9500
Sn1—O1ⁱ	2.1185 (18)	C15—C16	1.400 (4)
S1—O3	1.434 (2)	C16—C1ⁱ	1.394 (4)
S1—O2	1.440 (2)	C16—C17	1.498 (3)
S1—O1	1.5077 (19)	C17—C18	1.363 (4)
S1—C23	1.760 (3)	C17—C22	1.369 (4)
N1—C1	1.377 (3)	C18—C19	1.389 (5)
N1—C4	1.378 (3)	C18—H18A	0.9500
N2—C12	1.377 (3)	C19—C20	1.352 (5)
N2—C15	1.380 (3)	C19—H19A	0.9500
C1—C16ⁱ	1.394 (4)	C20—C21	1.353 (4)
C1—C2	1.437 (4)	C20—H20A	0.9500
C2—C3	1.344 (4)	C21—C22	1.383 (4)
C2—H2A	0.9500	C21—H21A	0.9500
C3—C4	1.431 (3)	C22—H22A	0.9500
C3—H3A	0.9500	C23—H23A	0.9800
C4—C5	1.397 (4)	C23—H23B	0.9800
C5—C12	1.403 (3)	C23—H23C	0.9800
C5—C6	1.496 (4)	C24—Cl1	1.733 (4)
C6—C11	1.386 (4)	C24—Cl2	1.756 (4)
C6—C7	1.388 (4)	C24—Cl3	1.756 (4)
C7—C8	1.383 (4)	C24—H24A	1.0000
C7—H7A	0.9500	C25—Cl5	1.530 (9)
C8—C9	1.361 (5)	C25—Cl4	1.667 (10)
C8—H8A	0.9500	C25—Cl4ⁱⁱ	1.858 (9)
C9—C10	1.374 (5)	C25—H25	1.0000
C9—H9A	0.9500	Cl4—C25ⁱⁱ	1.858 (9)
C10—C11	1.390 (4)	Cl5—Cl5ⁱⁱ	0.999 (10)
C10—H10A	0.9500	Cl5—C25ⁱⁱ	1.745 (9)
C11—H11A	0.9500

N1—Sn1—N1ⁱ	180.00 (7)	C6—C11—C10	120.1 (3)
N1—Sn1—N2ⁱ	90.01 (8)	C6—C11—H11A	119.9
N1ⁱ—Sn1—N2ⁱ	89.99 (8)	C10—C11—H11A	119.9
N1—Sn1—N2	89.99 (8)	N2—C12—C5	125.8 (2)
N1ⁱ—Sn1—N2	90.01 (8)	N2—C12—C13	108.0 (2)
N2ⁱ—Sn1—N2	180.0	C5—C12—C13	126.2 (2)
N1—Sn1—O1	87.77 (8)	C14—C13—C12	108.1 (2)
N1ⁱ—Sn1—O1	92.23 (8)	C14—C13—H13A	126.0
N2ⁱ—Sn1—O1	89.52 (8)	C12—C13—H13A	126.0
N2—Sn1—O1	90.48 (8)	C13—C14—C15	107.8 (2)
N1—Sn1—O1ⁱ	92.23 (8)	C13—C14—H14A	126.1
N1ⁱ—Sn1—O1ⁱ	87.77 (8)	C15—C14—H14A	126.1
N2ⁱ—Sn1—O1ⁱ	90.47 (8)	N2—C15—C16	125.7 (2)
N2—Sn1—O1ⁱ	89.53 (8)	N2—C15—C14	107.8 (2)
O1—Sn1—O1ⁱ	180.0	C16—C15—C14	126.5 (2)
O3—S1—O2	115.02 (13)	C1ⁱ—C16—C15	126.3 (2)
O3—S1—O1	111.86 (12)	C1ⁱ—C16—C17	117.0 (2)
O2—S1—O1	110.60 (12)	C15—C16—C17	116.7 (2)
O3—S1—C23	108.45 (14)	C18—C17—C22	118.0 (3)
O2—S1—C23	108.75 (15)	C18—C17—C16	121.4 (2)
O1—S1—C23	101.19 (13)	C22—C17—C16	120.6 (2)
S1—O1—Sn1	132.25 (11)	C17—C18—C19	121.0 (3)
C1—N1—C4	108.6 (2)	C17—C18—H18A	119.5
C1—N1—Sn1	125.42 (17)	C19—C18—H18A	119.5
C4—N1—Sn1	125.57 (16)	C20—C19—C18	120.3 (3)
C12—N2—C15	108.3 (2)	C20—C19—H19A	119.8
C12—N2—Sn1	125.80 (16)	C18—C19—H19A	119.8
C15—N2—Sn1	125.87 (16)	C19—C20—C21	119.1 (3)
N1—C1—C16ⁱ	126.7 (2)	C19—C20—H20A	120.4
N1—C1—C2	107.4 (2)	C21—C20—H20A	120.4
C16ⁱ—C1—C2	125.9 (2)	C20—C21—C22	121.0 (3)
C3—C2—C1	108.1 (2)	C20—C21—H21A	119.5
C3—C2—H2A	125.9	C22—C21—H21A	119.5
C1—C2—H2A	125.9	C17—C22—C21	120.5 (3)
C2—C3—C4	108.2 (2)	C17—C22—H22A	119.8
C2—C3—H3A	125.9	C21—C22—H22A	119.8
C4—C3—H3A	125.9	S1—C23—H23A	109.5
N1—C4—C5	126.3 (2)	S1—C23—H23B	109.5
N1—C4—C3	107.7 (2)	H23A—C23—H23B	109.5
C5—C4—C3	125.9 (2)	S1—C23—H23C	109.5
C4—C5—C12	126.2 (2)	H23A—C23—H23C	109.5
C4—C5—C6	116.8 (2)	H23B—C23—H23C	109.5
C12—C5—C6	117.0 (2)	Cl1—C24—Cl2	112.9 (2)
C11—C6—C7	118.9 (3)	Cl1—C24—Cl3	110.4 (2)
C11—C6—C5	119.5 (2)	Cl2—C24—Cl3	109.52 (19)
C7—C6—C5	121.6 (2)	Cl1—C24—H24A	107.9
C8—C7—C6	120.3 (3)	Cl2—C24—H24A	107.9
C8—C7—H7A	119.8	Cl3—C24—H24A	107.9
C6—C7—H7A	119.8	Cl5—C25—Cl4	136.0 (7)
C9—C8—C7	120.4 (3)	Cl5—C25—Cl4ⁱⁱ	107.4 (6)
C9—C8—H8A	119.8	Cl4—C25—Cl4ⁱⁱ	107.5 (4)
C7—C8—H8A	119.8	Cl5—C25—H25	99.8
C8—C9—C10	120.2 (3)	Cl4—C25—H25	99.8
C8—C9—H9A	119.9	Cl4ⁱⁱ—C25—H25	99.8
C10—C9—H9A	119.9	C25—Cl4—C25ⁱⁱ	30.5 (5)
C9—C10—C11	120.0 (3)	Cl5ⁱⁱ—Cl5—C25	84.5 (4)
C9—C10—H10A	120.0	Cl5ⁱⁱ—Cl5—C25ⁱⁱ	60.8 (4)
C11—C10—H10A	120.0	C25—Cl5—C25ⁱⁱ	32.7 (6)

O3—S1—O1—Sn1	−60.68 (19)	C6—C7—C8—C9	1.5 (4)
O2—S1—O1—Sn1	68.94 (18)	C7—C8—C9—C10	−1.2 (5)
C23—S1—O1—Sn1	−175.95 (16)	C8—C9—C10—C11	0.2 (5)
N1—Sn1—O1—S1	172.62 (16)	C7—C6—C11—C10	0.0 (4)
N1ⁱ—Sn1—O1—S1	−7.38 (16)	C5—C6—C11—C10	179.2 (3)
N2ⁱ—Sn1—O1—S1	82.59 (16)	C9—C10—C11—C6	0.4 (5)
N2—Sn1—O1—S1	−97.41 (16)	C15—N2—C12—C5	178.9 (2)
N2ⁱ—Sn1—N1—C1	−2.8 (2)	Sn1—N2—C12—C5	−0.5 (4)
N2—Sn1—N1—C1	177.2 (2)	C15—N2—C12—C13	−1.0 (3)
O1—Sn1—N1—C1	−92.3 (2)	Sn1—N2—C12—C13	179.53 (17)
O1ⁱ—Sn1—N1—C1	87.7 (2)	C4—C5—C12—N2	3.9 (4)
N2ⁱ—Sn1—N1—C4	−174.7 (2)	C6—C5—C12—N2	−173.0 (2)
N2—Sn1—N1—C4	5.3 (2)	C4—C5—C12—C13	−176.2 (3)
O1—Sn1—N1—C4	95.8 (2)	C6—C5—C12—C13	6.9 (4)
O1ⁱ—Sn1—N1—C4	−84.2 (2)	N2—C12—C13—C14	0.3 (3)
N1—Sn1—N2—C12	−3.1 (2)	C5—C12—C13—C14	−179.6 (3)
N1ⁱ—Sn1—N2—C12	176.9 (2)	C12—C13—C14—C15	0.5 (3)
O1—Sn1—N2—C12	−90.9 (2)	C12—N2—C15—C16	−177.5 (2)
O1ⁱ—Sn1—N2—C12	89.1 (2)	Sn1—N2—C15—C16	2.0 (4)
N1—Sn1—N2—C15	177.5 (2)	C12—N2—C15—C14	1.3 (3)
N1ⁱ—Sn1—N2—C15	−2.5 (2)	Sn1—N2—C15—C14	−179.23 (16)
O1—Sn1—N2—C15	89.8 (2)	C13—C14—C15—N2	−1.1 (3)
O1ⁱ—Sn1—N2—C15	−90.2 (2)	C13—C14—C15—C16	177.6 (3)
C4—N1—C1—C16ⁱ	175.8 (3)	N2—C15—C16—C1ⁱ	−0.9 (4)
Sn1—N1—C1—C16ⁱ	2.8 (4)	C14—C15—C16—C1ⁱ	−179.4 (3)
C4—N1—C1—C2	−1.6 (3)	N2—C15—C16—C17	−179.5 (2)
Sn1—N1—C1—C2	−174.65 (17)	C14—C15—C16—C17	1.9 (4)
N1—C1—C2—C3	1.8 (3)	C1ⁱ—C16—C17—C18	89.4 (4)
C16ⁱ—C1—C2—C3	−175.7 (3)	C15—C16—C17—C18	−91.8 (4)
C1—C2—C3—C4	−1.2 (3)	C1ⁱ—C16—C17—C22	−88.7 (4)
C1—N1—C4—C5	−177.3 (2)	C15—C16—C17—C22	90.1 (3)
Sn1—N1—C4—C5	−4.2 (4)	C22—C17—C18—C19	−0.7 (6)
C1—N1—C4—C3	0.9 (3)	C16—C17—C18—C19	−178.9 (4)
Sn1—N1—C4—C3	173.93 (17)	C17—C18—C19—C20	0.8 (7)
C2—C3—C4—N1	0.2 (3)	C18—C19—C20—C21	−0.6 (7)
C2—C3—C4—C5	178.4 (3)	C19—C20—C21—C22	0.3 (7)
N1—C4—C5—C12	−1.2 (4)	C18—C17—C22—C21	0.4 (6)
C3—C4—C5—C12	−179.1 (3)	C16—C17—C22—C21	178.6 (4)
N1—C4—C5—C6	175.6 (2)	C20—C21—C22—C17	−0.2 (7)
C3—C4—C5—C6	−2.2 (4)	Cl5—C25—Cl4—C25ⁱⁱ	80.4 (10)
C4—C5—C6—C11	−101.8 (3)	Cl4ⁱⁱ—C25—Cl4—C25ⁱⁱ	−60.6 (7)
C12—C5—C6—C11	75.3 (3)	Cl4—C25—Cl5—Cl5ⁱⁱ	−39.6 (13)
C4—C5—C6—C7	77.4 (3)	Cl4ⁱⁱ—C25—Cl5—Cl5ⁱⁱ	101.5 (9)
C12—C5—C6—C7	−105.5 (3)	Cl4—C25—Cl5—C25ⁱⁱ	−80.3 (14)
C11—C6—C7—C8	−0.9 (4)	Cl4ⁱⁱ—C25—Cl5—C25ⁱⁱ	60.8 (10)
C5—C6—C7—C8	179.9 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O2ⁱⁱ	0.95	2.55	3.280 (4)	134
C24—H24A···O2ⁱⁱⁱ	1.00	2.35	3.191 (4)	141

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

Experimental details

Crystal data
Chemical formula	[Sn(C₄₄H₂₈N₄)(CH₃O₃S)₂]·3CHCl₃
M_r	1279.69
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	25.379 (2), 11.6269 (9), 20.860 (3)
β (°)	120.934 (1)
V (Å³)	5279.9 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.07
Crystal size (mm)	0.26 × 0.19 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.765, 0.848
No. of measured, independent and observed [I > 2σ(I)] reflections	22613, 5192, 4525
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.088, 1.04
No. of reflections	5192
No. of parameters	331
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0404P)² + 12.8121P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.91, −0.86

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O2ⁱ	0.95	2.55	3.280 (4)	133.5
C24—H24A···O2ⁱⁱ	1.00	2.35	3.191 (4)	140.8

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

Acknowledgements

This work was supported by Kumoh National Institute of Technology.

References

Arnold, D. P. & Blok, J. (2004). Coord. Chem. Rev. 248, 299–319. Web of Science CrossRef CAS Google Scholar
Bruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kim, H. J., Jeon, W. S., Lim, J. H., Hong, C. S. & Kim, H.-J. (2007). Polyhedron, 26, 2517–2522. Web of Science CSD CrossRef CAS Google Scholar
Kim, H.-J., Jo, H. J., Kim, J., Kim, S.-Y., Kim, D. & Kim, K. (2005). CrystEngComm, 7, 417–420. Web of Science CSD CrossRef CAS Google Scholar
Kim, S. H., Kim, H., Kim, K. & Kim, H.-J. (2009). J. Porphyrins Phthalocyanines, 13, 805–810. Web of Science CSD CrossRef CAS Google Scholar
Kim, H. J., Park, K.-M., Ahn, T. K., Kim, S. K., Kim, K. S., Kim, D. & Kim, H.-J. (2004). Chem. Commun. pp. 2594–2595. Web of Science CSD CrossRef Google Scholar
Liu, I.-C., Lin, C.-C., Chen, J.-H. & Wang, S.-S. (1996). Polyhedron, 15, 459–463. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Smith, G., Arnold, D. P., Kennard, C. H. L. & Mak, T. C. W. (1991). Polyhedron, 10, 509–516. CSD CrossRef CAS Web of Science Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.