η6-Benzene(tricarbonyl)chromium and Cymantrene Assemblies

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η6‑Benzene(tricarbonyl)chromium and Cymantrene Assemblies Supported on an Organostannoxane Platform Subrata Kundu†,‡ and Vadapalli Chandrasekhar*,†,‡ †

Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur-208016, India National Institute of Science Education and Research, Institute of Physics Campus, School of Chemical Sciences, Bhubaneshwar-751005, India

‡

S Supporting Information *

ABSTRACT: A series of η6-benzene(tricarbonyl)chromium and cymantrene-containing [cymantrene = cyclopentadienylmanganese(I) tricarbonyl] assemblies supported on organostannoxane platforms are reported. The reaction of [Cr(η6-C6H5CO2H)(CO)3] (L1H) with n-Bu2SnCl2 in a 1:1 ratio afforded the tetranuclear derivative [{n-Bu2Sn}2(μ3-O)(μ-OMe)(L1)]2 (1) whereas a similar reaction carried out in a 2:1 stoichiometry afforded the mononuclear derivative [n-Bu2Sn(L1)2] (2). The reaction of (t-Bu2SnO)3 with L1H in toluene in a 1:3 ratio afforded the hydroxide-bridged dimer, [t-Bu2Sn(μ-OH)(L1)]2 (3). A 1:2 reaction between [{η6-C6H4(COOH)2-1,3}Cr(CO)3] (L2H2) and Me3SnCl afforded a two-dimensional coordination polymer [{Me3Sn}2(μ4-L2)]n (4). A similar reaction between [{η6-C6H4(COOH)2-1,4}Cr(CO)3] (L3H2) and Me3SnCl in a 1:2 ratio also afforded a two-dimensional coordination polymer [{Me3Sn}2(μ4-L3)]n (5). The reaction of L3H2 with Me3SnCl in the presence of 4,4′-bipyridine afforded a 1D-coordination polymer [(Me3Sn)2(μ-L3)(μ-4,4′-bipy)]n (6). The reaction of L3H2 with (Ph3Sn)2O (in a 1:1 ratio) gave a dimer [(H2O)SnPh3(μ-L3)SnPh3(MeOH)] (7). The 1:1 reaction of [Mn(η5-C5H4COOH)(CO)3] (L4H) with Me2SnCl2 yielded the tetranuclear derivative [{Me2Sn}2(μ3-O)(L4)2]2 (8). A similar reaction of [Mn{η5-C5H4C(O)CH2CH2COOH}(CO)3] (L5H) with Me2SnCl2 in a 1:1 ratio also afforded a tetrameric derivative [{Me2Sn}2(μ3-O)(μ2OMe)(L5)]2 (9). All the compounds were characterized by single crystal X-ray diffraction. Complexes 4 and 5 are planar organometallic 2D-coordination polymers.

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INTRODUCTION

are several reasons for this, including the fact that they serve as air- and moisture-stable building blocks in organometallic chemistry. Cymantrene itself is easy to functionalize and also is nontoxic. It is used as a robust organometallic biomarker for peptides as it has strong C−O stretching vibrations which are not obscured by signals from the peptide.22,23 The CO groups of [(η6-arene)Cr(CO)3] complexes can be easily substituted under UV light.24 In many cases CO substitution reactions are the basis for synthesis of complex molecules and intermolecular CO transfer reactions.25,26 Zheng et al. and Long et al. succeeded in decomposing (η6-C6H6)Cr(CO)3 to (η6-C6H6)Cr(CO) under 266 nm UV irradiation in molecular and MOF systems,

There has been considerable recent interest in dendrimers and polymers containing organometallic motifs.1−4 This is because of their potential applications in different fields such as multielectron reservoirs, catalysis, electron-transfer mediators and ion sensors. In addition, the structural chemistry of such compounds has also attracted interest, particularly in terms of their supramolecular organization in the solid state.5−10 Among the organometallic motifs used for such purposes, metallocenes in general and ferrocene in particular have been widely studied. Investigations on other motifs such as the so-called piano-stool, [(η5-C5H5)M(CO)3; (η6-arene)M(CO)3] are still rare.11−14 Over the past few years, the compounds containing arenetricarbonylchromium complexes [(η6-arene)Cr(CO)3] and cyclopentadienyl-manganese tricarbonyl complexes (η5-C5H5)Mn(CO)3 have been attracting significant attention.15−21 There © XXXX American Chemical Society

Received: July 25, 2015 Revised: September 9, 2015

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DOI: 10.1021/acs.cgd.5b01064 Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Reagents and General Procedure. All the reactions were performed under a dry nitrogen atmosphere by employing standard Schlenk techniques. Solvents were stored over appropriate reagents and distilled under nitrogen prior to use. [n-Bu2SnO]n, Me2SnCl2, Me3SnCl, and Cr(CO)6 were purchased from Aldrich and used as supplied. CpMn(CO)3 was purchased from Alfa Aesar and used as supplied. [t-Bu2SnO]346 was prepared according to literature procedures. [(η6-C6H5CO2H)Cr(CO)3] (L1H),47,48 [{η6-C6H4(COOH)21,3}Cr(CO)3]47,48 (L2H2), [{η6-C6H4(COOH)2-1,4}Cr(CO)3]47,48 (L3H2), [(η5-C5H4COOH)Mn(CO)3]49 (L4H), and [{η5-C5H4C(O)CH2CH2COOH}Mn(CO)3]22 (L5H) were prepared according to literature procedures with slight modification (see Supporting Information). Synthesis of Various Organostannoxanes. The following two general synthetic procedures have been used for the preparation of various organostannoxanes (Schemes 1−4). Method A (from organotin halides): A stoichiometric mixture of the organotin chloride and the protic acid were stirred in the presence of triethylamine (0.2 mL) or NaOH, in methanol at room temperature for 6 h. The resulting solution was concentrated and filtered. Slow evaporation of the solution under dark afforded the corresponding crystalline products. Specific details of each reaction are given below. Method B (from organotin oxides): A stoichiometric mixture of the organotin oxide precursor and the protic acid were taken in toluene (30 mL) and heated under reflux for 6 h. The water formed in the reaction was removed by using a Dean−Stark apparatus. The reaction mixture was evaporated to afford the corresponding products. Slow evaporation from the suitable solution of these products in the dark afforded the corresponding crystalline products. Specific details of each reaction are given below. [{n-Bu2Sn}2(μ3-O)(μ-OMe)(L1)]2 (1). (Method A) n-Bu2SnCl 2 (0.10 g, 0.33 mmol), L1H (0.08 g, 0.33 mmol). Yield: 0.08 g (63%). Mp 168 °C. Anal. (%) Calcd for C54H88Cr2O14Sn4: C, 42.11; H, 5.76. Found: C, 41.97; H, 5.65. 1H NMR [500 MHz, CDCl3, ppm]: δ = 0.84 (s, 24H, n-Bu-CH3), 1.24 (s, 16H, n-Bu-CH2), 1.37 (s, 16H, n-Bu-CH2), 1.67 (s, 16H, n-Bu-CH2), 3.47 (s, 6H, -OCH3); 5.26 (s, 4H, Ar), 5.41 (s, 2H, Ar), 6.00 (s, 4H, Ar); 119Sn NMR (150 MHz): δ = −160 (s), − 167(s) ppm. ESI-MS: m/z (%) 1285.1313 [M − L1]+ (10). IR (KBr, ν/cm−1): 2956(m), 2924 (m), 2855 (m), 1972 (s), 1887 (s), 1608 (m), 1342 (s), 682 (m), 659 (s), 646 (m). Orange crystals of 1 were obtained from slow evaporation of a methanol solution of 1. [n-Bu2Sn(L1)2] (2). (Method A) n-Bu2SnCl2 (0.10 g, 0.33 mmol), L1H (0.17 g, 0.66 mmol). Yield: 0.19 g (77%). Mp 172 °C. Anal. (%) Calcd for C28H28Cr2O10Sn: C, 45.01; H, 3.78. Found: C, 44.84; H, 3.69. 1H NMR [500 MHz, CDCl3, ppm]: δ = 0.90 (s, 6H, n-Bu-CH3), 1.39 (s, 4H, n-Bu-CH2), 1.58 (s, 4H, n-Bu-CH2), 1.73 (s, 4H, n-BuCH2), 5.27 (s, 4H, Ar), 5.56 (s, 2H, Ar), 6.12 (d, 4H, Ar); 119Sn NMR (186 MHz, ppm): δ= −136 (s). ESI-MS: m/z (%) 490.9974 [L1 + n-Bu2Sn]+ (30), 739.0384 [2 − CO + H2O + H]+ (20). IR (KBr, ν/cm−1): 2960 (m, br), 2929 (m, br), 2869 (m), 1981 (s), 1889 (s), 1579 (m), 1392 (s), 1342 (m), 659 (s), 629 (m), 616 (s). Orange crystals of 2 were obtained from slow evaporation of a chloroform solution of 2. [t-Bu2Sn(μ-OH)(L1)]2 (3). (Method B) (t-Bu2SnO)3 (0.10 g, 0.13 mmol), L1H (0.11 g, 0.40 mmol). Yield: 0.18 g (88%). Mp 175 °C. Anal. (%) Calcd for C36H48Cr2O12Sn2: C, 42.63; H, 4.77. Found: C, 42.44; H, 4.68. 1H NMR [500 MHz, CDCl3, ppm]: δ = 1.44 (s, 36H, t-Bu), 5.27 (s, 4H, Ar), 5.48 (s, 2H, Ar), 6.11 (s, 4H, Ar); 119 Sn NMR (150 MHz): δ = −264 ppm (s). ESI-MS: m/z (%) 1005.0879 [M − CO + H2O + H]+ (100). IR (KBr, ν/cm−1): 3082 (m, br), 2968 (m), 2968 (m), 2855 (m), 1972 (s), 1889 (s), 1600 (s), 1371 (s), 1353 (s) 1145 (m), 822 (m), 849 (m), 680(m), 660 (m). Orange crystals of 3 were obtained from slow evaporation of a chloroform solution of 3. [{Me3Sn}2(μ4-L2)]n (4). (Method A) Me3SnCl (0.93 g, 0.46 mmol), L2H2 (0.069 g, 0.23 mmol), NaOH (0.02g, 0.48 mmol). Yield: 0.12 (74%). Mp > 200 °C. Anal. (%) Calcd for C17H22CrO7Sn2: C, 32.53; H, 3.53. Found: C, 32.33; H, 3.49. 1H NMR [500 MHz, CDCl3 + CD3OD, ppm]: δ = 0.43 (s, 18H, Sn−CH3), 5.43 (s, 1H, Ar),

respectively; substitution of the single CO ligand per metal by N2 or H2 was observed in the latter case.27,28 (η6-C6H6)Cr(CO) is a very interesting intermediate because the Cr center possesses two coordination vacancies.29 If the same decomposition reaction can be achieved in dendrimeric assemblies involving (η6-arene)Cr(CO)3, this can allow the creation of multiple chromium sites having two coordination vacancies which would have important implications in the field of catalysis. In view of this we were interested in exploring synthetic strategies that would allow the ready assembly of multi-[(η6-arene)Cr(CO)3] and multi-[(η5-C5H5)Mn(CO)3] compounds. Previously, we have utilized the so-called one-step stannoxane synthetic route30−38 to prepare multiferrocene39−41 and multiruthenocene42 derivatives. The latter was used to prepare the binary oxide, (Ru−Sn)O2, at a relatively low temperature.42 The main advantage of the stannoxane synthetic route is the general robustness of this procedure as indicated by the reasonable predictability of the types of products that can be formed in a given reaction.30,31 Keeping this in mind, we explored the reactions of [(η6-C6H5CO2H)Cr(CO)3] (L1H), [{η6-C6H4(COOH)2-1,3}Cr (CO)3] (L2H2), [{η6-C6H4(COOH)2-1,4}Cr(CO)3] (L3H2) [(η5-C5H4COOH)Mn(CO)3] (L4H), and [{η5-C5H4C(O)CH2CH2COOH}Mn(CO)3] (L5H) with various organotin substrates [n-Bu2SnO]n, Me2SnCl2, (t-Bu2SnO)3, and Me3SnCl. The synthesis and characterization of the various products obtained in these reactions, [{n-Bu2Sn}2(μ3-O)(μOMe)(L1)]2 (1), [n-Bu2Sn(L1)2] (2), [t-Bu2Sn(μ-OH)(L1)]2 (3), [{Me3Sn} 2(μ4 -L2)]n (4), [{Me3 Sn}2 (μ4-L3)]n (5), [(Me3Sn)2(μ-L3)(μ-4,4′-bipy)]n (6), [(H2O)SnPh3(μ-L3)SnPh3(MeOH)] (7), [{Me2Sn}2(μ3-O)(L4)2]2 (8), and [{Me2Sn}2(μ3-O)(μ2-OMe)(L5)]2 (9), are discussed herein. Complexes 4 and 5 are planar organometallic 2D-coordination polymers.

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EXPERIMENTAL SECTION

Instrumentation. Elemental analyses were carried out by using a thermoquest CE instruments model EA/110 CHNS-O elemental analyzer. 1H and 119Sn NMR spectra were recorded on a JEOL JNM Lambda spectrometer operating at 500.0 and 186.0 MHz, respectively. The chemical shifts are referenced with respect to tetramethylsilane (for 1H) and tetramethyltin (for 119Sn). High resolution ESI-MS spectra were recorded on a Micromass Quattro II triple quadrupole mass spectrometer. Methanol was used as the solvent for the ESI-MS studies. Melting points were recorded using a JSGW melting point apparatus and are uncorrected. IR spectra were recorded as KBr pellets on a Bruker Vector 22 FT IR spectrophotometer operating from 400 to 4000 cm−1. Powder X-ray diffraction (PXRD) patterns were recorded with a Bruker D8 advance diffractometer equipped with nickel-filtered Cu Kα radiation. TGA measurements were carried out using a PerkinElmer Pyris6 thermogravimetric analyzer at a heating rate of 10 °C/min under a nitrogen atmosphere. Single Crystal X-ray Crystallography. Suitable crystals for single crystal X-ray diffraction measurements were mounted on a CCD Bruker SMART APEX or D8 QUEST diffractometer. Data were collected at 100(2) K using graphite monochromated Mo Kα radiation. The structures were solved by direct methods and refined (SHELXL 97) by full matrix least-squares procedures on F2.43,44 The hydrogen atoms were included in idealized positions and were refined according to the riding model. Non-hydrogen atoms were refined with anisotropic displacement parameters. The O−H protons were included from the electron density map and refined isotopically. The residual electron densities present near to the tin center ( 2σ(I)] R indices (all data) Largest diff. peak and hole

6495.5(19), 4 1.575 Mg/m3 1.892 mm−1 3088.0 0.15 × 0.13 × 0.11 4.09−25.03° −15 ≤ h ≤ 18, −21 ≤ k ≤ 24, −25 ≤ l ≤ 25 33248 11392 [R(int) = 0.0763] 99.4% Empirical 0.812 and 0.753 11392/61/671 1.042 R1 = 0.0778, wR2 = 0.1695 R1 = 0.1191, wR2 = 0.1920 3.750 and −1.524 e.Å−3

Volume (Å3), Z Density Absorption coefficient F(000) Crystal size (mm3) Theta range for data collection Index ranges

1

C54H88Cr2O14 Sn4 1540.08 100(2) 0.71073 Å Monoclinic P21/c a = 15.186(3) Å, b = 20.183(3) Å, c = 21.725(4) Å, α = 90°, β = 102.707(3)°, γ = 90°

Empirical formula Formula weight Temperature (K) Wavelength Crystal system Space group Unit cell dimensions

Complex 2 C28H28Cr2O10Sn 747.21 100(2) 0.71069 Å Triclinic P1̅ a = 11.267(5) Å, b = 11.793(5) Å, c = 11.808(5) Å, α = 98.599(5)°, β = 108.484(5)°, γ = 93.685(5)° 1460.8(11), 2 1.699 Mg/m3 1.634 mm−1 748 0.16 × 0.14 × 0.12 1.92−25.50° −12 ≤ h ≤ 13, −13 ≤ k ≤ 14, −14 ≤ l ≤ 14 7788 5286 [R(int) = 0.0421] 97.0% Empirical 1.00 and 0.538 5286/0/372 0.981 R1 = 0.0644, wR2 = 0.1476 R1 = 0.0956, wR2 = 0.1663 3.016 and −1.049 e.Å−3

Table 1. Crystal Data Collection and Refinement Parameters for 1−5 3 C36H48Cr2O12Sn2 1014.16 100(2) 0.71069 Å Triclinic P1̅ a = 11.415(5) Å, b = 12.170(5) Å, c = 15.433(5) Å, α = 89.680(5)°, β = 73.644(5)°, γ = 89.977(5)° 2057.2(14), 2 1.637 Mg/m3 1.771 mm−1 1016.0 0.14 × 0.13 × 0.10 4.08−24.71° −13 ≤ h ≤ 13, −12 ≤ k ≤ 14, −17 ≤ l ≤ 18 10017 6774 [R(int) = 0.0278] 96.4% Empirical 0.838 and 0.780 6774/8/489 1.190 R1 = 0.0917, wR2 = 0.1987 R1 = 0.1018, wR2 = 0.2050 3.469 and −2.923 e.Å−3

4 C17H22CrO7Sn2 627.73 100(2) K 0.71073 Å Triclinic P1̅ a = 9.9186(14) Å, b = 10.343(2) Å, c = 12.9428(18) Å, α = 107.696(3)°, β = 91.561(3)°, γ = 118.564(2)° 1087.1(3), 2 1.918 Mg/m3 2.803 mm−1 608 0.15 × 0.14 × 0.13 2.37−26.00° −12 ≤ h ≤ 11, −12 ≤ k ≤ 12, −7 ≤ l ≤ 15 6814 4175 [R(int) = 0.0198] 97.6% Empirical 0.695 and 0.663 4175/0/250 1.186 R1 = 0.0486, wR2 = 0.1202 R1 = 0.0522, wR2 = 0.1219 4.265 and −1.515 e.Å−3

5 C17H22CrO7Sn2 627.73 100(2) K 0.71073 Å Monoclinic I2/a a = 18.317(7) Å, b = 10.150(4) Å, c = 25.277(13) Å, α = 90°, β = 110.942(11)°, γ = 90° 4389(3), 8 1.900 Mg/m3 2.777 mm−1 2432 0.10 × 0.10 × 0.10 2.18−25.49° −21 ≤ h ≤ 20, −12 ≤ k ≤ 12, −30 ≤ l ≤ 21 8058 3891 [R(int) = 0.0793] 95.2% Empirical 0.7687 and 0.7687 3891/0/226 1.047 R1 = 0.0673, wR2 = 0.1640 R1 = 0.1034, wR2 = 0.1853 3.857 and −1.524 e.Å−3

Crystal Growth & Design Article

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DOI: 10.1021/acs.cgd.5b01064 Cryst. Growth Des. XXXX, XXX, XXX−XXX

Reflections collected Independent reflections Completeness to θ = 25.50° Absorption correction Max. and min transmission Data/restraints/parameters Goodness-of-fit on F2 Final R indices [I > 2σ(I)] R indices (all data) Largest diff. peak and hole

Volume (Å3), Z Density (calculated) Absorption coefficient F(000) Crystal size (mm3) θ range for data collection Index ranges

Empirical formula Formula weight Temperature Wavelength Crystal system Space group Unit cell dimensions

Complex 7 C48H40CrO9Sn2 1050.18 100(2) K 0.71073 Å Monoclinic P21/n a = 13.193(5) Å b = 18.567(5) Å c = 18.021(5) Å α = 90° β = 93.435(5)° γ = 90° 4406(2), 4 1.583 Mg/m3 1.422 mm−1 2096 0.17 × 0.15 × 0.13 2.16−25.50° −15 ≤ h ≤ 15, −22 ≤ k ≤ 22, −16 ≤ l ≤ 21 30927 8189 [R(int) = 0.0388] 99.8% Empirical 0.831 and 0.785 8189/12/554 1.038 R1 = 0.0274, wR2 = 0.0595 R1 = 0.0385, wR2 = 0.0633 0.954 and −0.563 e.Å−3

6 C27H30CrN2O7Sn2 783.91 100(2) K 0.71073 Å Monoclinic P21/c a = 13.8560(10) Å b = 10.3151(8) Å c = 20.5239(15) Å α = 90° β = 96.6260(10)° γ = 90° 2913.8(4), 4 1.787 Mg/m3 2.114 mm−1 1544 0.14 × 0.13 × 0.11 2.21−25.50° −16 ≤ h ≤ 12, −12 ≤ k ≤ 11, −24 ≤ l ≤ 23 18670 5398 [R(int) = 0.0259] 99.7% Empirical 0.793 and 0.751 5398/0/358 1.082 R1 = 0.0203, wR2 = 0.0478 R1 = 0.0231, wR2 = 0.0489 0.433 and −0.602 e.Å−3

Table 2. Crystal Data Collection and Refinement Parameters for 6−9 C44H40Mn4O22Sn4 1615.36 100(2) 0.71073 Å Triclinic P1̅ a = 9.836(5) Å b = 10.743(5) Å c = 14.063(5) Å α = 109.941(5)° β = 100.146(5)° γ = 96.279(5)° 1351.8(10), 1 1.984 Mg/m3 2.794 mm−1 780.0 0.14 × 0.13 × 0.11 2.05−25.50° −11 ≤ h ≤ 8, −13 ≤ k ≤ 13, −14 ≤ l ≤ 17 9680 5001 [R(int) = 0.0219] 99.6% Empirical 0.738 and 0.686 5001/0/338 1.091 R1 = 0.0224, wR2 = 0.0525 R1 = 0.0267, wR2 = 0.0540 0.514 and −0.717 e.Å−3

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C34H46Mn2O16Sn4 1295.43 100(2) 0.71069 Å Triclinic P1̅ a = 7.073(5) Å b = 10.244(5) Å c = 16.376(5) Å α = 98.435(5)° β = 91.365(5)° γ = 93.543(5)° 1170.8(11), 1 1.837 Mg/m3 2.684 mm−1 628.0 0.14 × 0.12 × 0.09 2.21−25.50° −8 ≤ h ≤ 8, −12 ≤ k ≤ 12, −19 ≤ l ≤ 19 11339 4367 [R(int) = 0.0324] 99.8% Empirical 0.747 and 0.642 4367/0/258 1.038 R1 = 0.0293, wR2 = 0.0613 R1 = 0.0484, wR2 = 0.0676 0.498 and −0.375 e.Å−3

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Crystal Growth & Design Article

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DOI: 10.1021/acs.cgd.5b01064 Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Scheme 1. Synthesis of 1−3

Scheme 2. Synthesis of 4

6.09 (s, 2H, Ar), 6.60 (s, 1H, Ar). 119Sn NMR (186 MHz, ppm): δ = −143 (s). ESI-MS: m/z (%) 164.97 [CH3Sn]+ (100), 628.8918 [{Me3Sn}2(L4) + H]+ (60), 928.8281 [(CH3)3Sn − L4 − (CH3)3Sn − L4H]− (40), 1090.7663 [(CH3)3Sn − L4 − (CH3)3Sn − L4 − (CH3)3Sn]− (20). IR (KBr, ν/cm−1): 2993 (m), 2919 (m), 1997 (s), 1919 (s), 1589 (s), 1603 (s), 1378 (s), 1352 (m), 785 (s) 710 (m), 661 (s), 612 (s). Orange crystals of 4 were obtained from slow evaporation of a chloroform/MeOH (1:1) solution of 4. [{Me3Sn}2(μ4-L3)]n (5). (Method A) Me3SnCl (0.093 g, 0.46 mmol), L3H2 (0.069 g, 0.23 mmol). Yield: 0.13 (78%). Mp > 200 °C. Anal. (%) Calcd for C17H22CrO7Sn2: C, 32.53; H, 3.53. Found: C, 32.42; H, 3.48. 1H NMR [500 MHz, CDCl3 + CD3OD, ppm]: δ = 0.51 (s, 18H, Sn−CH3), 6.02 (s, 4H, Ar). 119Sn NMR (186 MHz, ppm): δ = 25 (s). ESI-MS: m/z (%) 164.9812 [CH 3 Sn] + (100), 628.8217 [{Me3Sn}2(L4) + H]+ (60). IR (KBr, ν/cm−1): 3003 (m), 2923 (m), 1979 (s), 1913 (s), 1898 (s), 1613 (s), 1366 (s), 1337 (s), 1147 (m), 779 (s) 755 (m), 619 (s). Orange crystals of 5 were obtained from slow evaporation of a chloroform/MeOH (1:1) solution of 5. [(Me3Sn)2(μ-L3)(μ-4,4′-bipy)]n (6). (Method A) Me3SnCl (0.093 g, 0.46 mmol), L3H2 (0.069 g, 0.23 mmol), 4,4′-bipyridine (0.012, 0.23 mmol). Yield: 0.13 (70%). Mp > 200 °C. Anal. (%) Calcd for C27H30CrN2O7Sn2: C, 41.37; H, 3.86; N, 3.57. Found: C, 41.44; H, 3.81; N, 3.52.1H NMR [500 MHz, CDCl3, ppm]: δ = 0.44 (s, 18H, Sn−CH3), 5.90 (s, 4H, Ar), 7.55 (d, 4H, Ar), 8.57 (d, 4H, Ar). ESIMS: m/z (%) 784.9598 [{Me3Sn}2(L3) + 4,4′bipyridine + H]+ (5). IR (KBr, ν/cm−1): 3065 (m), 3037 (m), 2998 (m), 2921(m), 1976 (s), 1912 (s), 1883 (s), 1641 (s), 1600(s), 1358 (s), 1327 (s), 781 (s),

654 (s), 621 (s). Orange crystals of 6 were obtained from slow evaporation of a chloroform/MeOH (1:1) solution of 6. [(H2O)SnPh3(μ-L3)SnPh3(MeOH)] (7). (Method B) (Ph3Sn)2O (0.10 g, 0.14 mmol), L3H2 (0.042 g, 0.14 mmol). Yield: 0.15 g (79%). Mp 155 °C. Anal. (%) Calcd for C48H40CrO9Sn2: C, 54.89; H, 3.84. Found: C, 54.74; H, 3.86. 1H NMR [500 MHz, CDCl3, ppm]: δ = 3.49 (s, 3H, HO−CH3), 6.08 (s, 4H, Ar), 7.48−7.76 (m, 30H, Ph). 119 Sn NMR (150 MHz): δ= −44 (s), −90 (s) ppm. ESI-MS: m/z (%) 913.57 [M − CO − MeOH − Ph]+ (5), 351.01 [Ph3Sn]+ (20). IR (KBr, ν/cm−1): 3553 (m, br), 3169 (m, br), 3068 (m), 1980 (s), 1931 (s), 1903 (s), 1615 (s), 1370 (s) 1339 (s), 733 (m), 698 (m), 614(m). Orange crystals of 7 were obtained from slow evaporation of a chloroform/MeOH (1:1) solution of 7. [{Me2Sn}2(μ3-O)(L4)2]2 (8). (Method A) Me2SnCl2 (0.10 g, 0.46 mmol), L4H (0.12 g, 0.46 mmol). Yield: 0.13g (70%). Mp 185 °C. Anal. (%) Calcd for C44H40Mn4O22Sn4: C, 32.72; H, 2.50. Found: C32.33, H 2.43. 1H NMR [500 MHz, CDCl3, ppm]: δ = 0.87−1.24 (br, 24H, Sn−CH3), 4.77 (s, 8H, Cp), 5.30 (s, 8H, Cp). 119Sn NMR (186 MHz, ppm): δ= −212 (s), −219 (s). ESI-MS: m/z (%) 396.8936 [L4SnMe2]+ (30), 562.8480 [L4Me2SnOMe2Sn]+ (4), 678.8028 [(L4)Me2Sn(OH)Me2Sn+H2O]¯ (10). IR (KBr, ν/cm−1): 3425 (m, br), 2930 (m, br), 2676 (m), 2027 (s), 1942 (s), 1616 (m), 1565 (s), 1479 (m), 1337 (m) 1185 (m), 787 (s), 667 (s), 633 (m). Brown crystals of 8 were obtained from slow evaporation of a chloroform/ MeOH solution of 8. [{Me2Sn}2(μ3-O)(μ2-OMe)(L5)]2 (9). (Method A) Me2SnCl2 (0.10 g, 0.46 mmol), L5H (0.15 g, 0.46 mmol). Yield: 0.09 g (61%). Mp 170 °C. Anal. (%) Calcd for C34H46Mn2O16Sn4: C, 31.52; H, 3.58. E

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Scheme 3. Synthesis of 5-7

Scheme 4. Synthesis of 8 and 9

■

Found: C 31.27, H 3.49. 1H NMR [500 MHz, (CDCl3, ppm]: δ = 0.72 (s, 12H, Sn−CH3), 0.78 (s, 12H, Sn−CH3), 2.50 (s, 4H, -CH2-), 2.83 (s, 4H, -CH2-), 3.47 (s, 6H, -OCH3) 4.84 (s, 4H, Cp), 5.45 (s, 4H, Cp). 119Sn NMR (186 MHz, ppm): δ= −192 (s), −202(s). ESI-MS: m/z (%) 304.9854 [L5+H]+ (35), 452.9209 [L5Me2Sn]+ (30), 652.9307 [L5(Me2Sn)2O+2H2O]+ (20). IR (KBr, ν/cm−1): 3439 (m, br), 3161 (m, br), 2855 (m), 2026 (m), 1938 (m), 1569 (m), 1374 (s), 1296 (m), 1085 (s) 1062 (m), 987 (s), 851(m), 756(m), 711 (m), 662(s). Brown crystals of 9 were obtained from slow evaporation of a chloroform solution of 9.

RESULTS AND DISCUSSION Synthesis. In general, the reactions of organotin precursors such as organotin oxides and chlorides with carboxylic acids are known to afford various types of products whose structure depends on the number and the nature of organic moieties attached to the tin center.30−38 Normally the reaction of monocarboxylic acids with monoorgano- or diorganotin precursors are known to afford mainly discrete molecular complexes, but the same reaction with a trialkylorganotin precursor affords F

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Figure 1. (a) Molecular structure of 1 (some hydrogen atoms have been omitted for clarity). (b,c) Geometry around tin centers. Bond distances(Å): Sn(1)−O(6), 2.027(7); Sn(1)−O(7), 2.193(9); Sn(1)−O(6)*, 2.110(6); Sn(2)−O(1), 2.172(6); Sn(2)−O(6), 2.008(7); Sn(2)−O(7), 2.196(8); Sn(2)−O(2), 2.964(7). Bond angles (deg): Sn(1)−O(6)−Sn(2), 114.59(4); Sn(1)−O(7)−Sn(2), 101.35(4); Sn(1)−O(6)−Sn(1)*, 106.54(3); O(1)−Sn(2)−O(7), 150.90(3); O(6)−Sn(1)−O(6)*, 73.46(3); O(6)−Sn(1)−O(7), 71.86(3); O(6)−Sn(2)−O(7), 72.14(3).

of 9 only two cymantrene groups are attached (Scheme 4). H and 119Sn NMR of 1−9 are consistent with their chemical structures (see Experimental Section and Supporting Information) and are comparable with the literature precedents.30−32 In the IR spectra the strong A1 and E ν-CO stretching frequencies were observed: 1972 and 1887 cm−1 (1), 1981 and 1889 cm−1 (2), 1972 and 1889 cm−1 (3), 1997 and 1919 cm−1 (4), 1979 and 1913 cm−1 (5), 1976 and 1912 cm−1 (6), 1980 and 1931 cm−1 (7), 2027 and 1942 cm−1 (8), and 2026 and 1938 cm−1 (9). As expected complexes 4−7 have slightly higher carbonyl stretching frequencies than those found in complexes 1−3. Complexes 8−9 possess the highest C−O stretching frequencies. The ESI-MS of 1 was observed at 1285.1313 [M − L1]+ which indicates the structural integrity of the tetranuclear core. ESI-MS of 2 and 3 under positive ion ionization modes showed peaks at m/z 739.0384 and 1005.0879, respectively, which correspond to [M − CO + H2O + H]+ fragment (Experimental Section). ESI-MS of 4 under positive ion ionization mode showed a peak at m/z 628.8918 which corresponds to [{Me3Sn}2(L4) + H]+. In the negative ionization mode peaks at m/z 928.8281 and m/z 1090.7663 are observed, which correspond to [(CH3)3Sn−L4−(CH3)3Sn−L4H]− and [(CH3)3Sn−L4−(CH3)3Sn−L4−(CH3)3Sn]−, respectively. The ESI-MS of 5−9 reveal a breakdown of the structural integrity of the compounds (Experimental Section). X-ray Crystallography. The molecular structure of the methoxy-bridged tetrameric organostannoxane ladder 1 is shown in Figure 1a. This reveals that there are two distannoxane motifs (Sn2O2) which are fused to each other to form a ladderlike structure. Apart from the two methoxy bridges (O7 and O7*) in the two stannoxane units, there are two capping (μ3-O) oxygen atoms O6 and O6* which also serve to bridge the stannoxane units. The selected bond parameters corresponding to the tetrameric stannoxane core are summarized in the caption of Figure 1. The molecular structure of 1 shows that the two η6-benzene(tricarbonyl)chromium moieties, related by a center of inversion, are supported by a planar Sn4O2(OMe)2 core (Figure 1a). The η6-benzene(tricarbonyl)chromium carboxylate binds to the terminal tin atoms in an anisobidentate chelating mode as can be seen by the difference in the corresponding Sn− O bond lengths: Sn2−O1, 2.172(6) and Sn2−O2, 2.964(7) Å. The central tin atoms (Sn1 and Sn1*) are five-coordinated (Figure 1b) with a distorted trigonal bipyramidal geometry (τ = 0.56; cf., the τ values for the idealized geometries are τ = 0,

compounds which possess extended polymeric structures due to the bridging action of the carboxylate ligand connecting successive triorganotin units.50−54 On the other hand, recent investigations have revealed that reactions of dicarboxylic acids with triorganotin precursors can lead to the formation of 2Dcoordination polymers. In view of this, it was of interest to examine the reactivity of [Cr(η6-C6H5CO2H)(CO)3] (L1H), [{η 6 -C 6 H 4 (COOH) 2 -1,3}Cr(CO) 3 ] (L2H 2 ), and [{η 6 C6H4(COOH)2-1,4}Cr(CO)3] (L3H2) with selected organotin substrates. The reaction of [Cr(η6-C6H5CO2H) (CO)3] (L1H) with n-Bu2SnCl2 in 1:1 ratio afforded the tetranuclear derivative [{n-Bu2Sn}2(μ3-O)(μ-OMe)(L1)]2 (1) (Scheme 1). Upon increasing the stoichiometric ratio between L1H and n-Bu2SnCl2 (2:1) we obtained a mononuclear derivative [n-Bu2Sn(L1)2] (2) (Scheme 1). The reaction of (t-Bu2SnO)3 with L1H in toluene in a 1:3 ratio afforded the hydroxide-bridged dimer, [t-Bu2Sn(μOH)(L1)]2 (3) (Scheme 1). All the complexes (1−3) contain two η6-benzene(tricarbonyl)chromium groups although the nuclearity of the organostannoxane varies from one to four. The 1:2 reaction between [{η6-C6H4(COOH)2-1,3}Cr(CO)3] (L2H2) and Me3SnCl in the presence of an equivalent amount of NaOH as a HCl scavenger afforded a two-dimensional coordination polymer [{Me3Sn}2(μ4-L2)]n (4) (Scheme 2). A similar reaction between [{η6-C6H4(COOH)2-1,4}Cr(CO)3] (L3H2) and Me3SnCl in a 1:2 ratio in the presence of an excess amount of triethylamine also afforded a two-dimensional coordination polymer [{Me3Sn}2(μ4-L3)]n (5) (Scheme 3). The reaction of L3H2 with Me3SnCl in the presence of 4,4′bipyridine afforded a 1D-coordination polymer [(Me3Sn)2(μL3)(μ-4,4′-bipy)]n (6) (Scheme 3). The reaction of L3H2 with (Ph3Sn)2O (in a 1:1 ratio) was also expected to yield a similar 2D-coordination polymer. However, the polymer formation is terminated due to the coordination action of water and methanol molecules, and a dimer [H2OSnPh3(μ-L3)SnPh3MeOH] (7) is the resulting product (Scheme 3). The 1:1 reaction of L4H, [Mn(η5-C5H4COOH) (CO)3], with Me2SnCl2 yielded the tetranuclear derivative [{Me2Sn}2(μ3-O)(L4)2]2 (8) (Scheme 4). A similar reaction of L5H [Mn{η5-C5H4C(O)CH2CH2COOH}(CO)3] with Me2SnCl2 in a 1:1 ratio also afforded a tetrameric derivative [{Me2Sn}2(μ3-O)(μ2-OMe)(L5)]2 (9) (Scheme 4) but the structure of the latter is slightly different from that of 8. In complex 8, four cymantrene carboxylate groups are appended on a tetranuclear organostannoxane platform, whereas in the case

1

G

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Figure 2. (a) Molecular structure of 2 (some hydrogen atoms have been omitted for clarity). (b) Geometry around tin center. Bond distances (Å): Sn(1)−O(1), 2.133(6); Sn(1)−O(2), 2.592(6); Sn(1)−O(3), 2.114(5); Sn(1)−O(4), 2.700(5); Sn(1)−C(21), 2.100(6); Sn(1)−C(25), 2.112(6). Bond angles (deg): O(1)−Sn(1)−O(3), 80.94(2); C(21)−Sn(1)−C(25), 146.28(3).

Figure 3. (a) Molecular structure of 3 (some hydrogen atoms have been omitted for clarity). (b) Geometry around tin center. Bond distances (Å): Sn(1)−O(2), 2.178(6); Sn(1)−O(3), 2.034(8); Sn(1)−O(3*), 2.202(9); Sn(1)−C(32), 2.220(2); Sn(1)−C(73), 2.156(2); O(1)−H(3H), 1.873. Bond angles (deg): Sn(1)−O(3)−Sn(1*), 109.46(4); O(3)−Sn(1)−O(3*), 70.53(3); O(2)−Sn(1)−O(3), 85.90(3); O(2)−Sn(1)−O(3*), 156.43(3); C(32)−Sn(1)−C(73), 128.78(6); O(1)−H(3H)−O(3), 138.75.

rectangular pyramidal; τ = 1, trigonal-bipyramidal),55 while the terminal tin atoms (Sn2 and Sn2*) in complex 1 are sixcoordinated (Figure 1c). The molecular structure of complex 2 is shown in Figure 2a. Some important bond parameters for this compound are listed in the caption of Figure 2. Complex 2 crystallizes in the triclinic P1̅ space group. The two η6-benzene(tricarbonyl)chromium moieties which are attached to the tin atom through the chelating carboxylate ligands (anisobidentate coordination mode) are on the opposite side of the plane containing the tin and the carboxylate chelate (Figure 2a). The tin atom is sixcoordinate with a 2C, 4O coordination environment with a skewed trapezoidal bipyramid geometry which is the characteristic feature of the mononuclear diorganotin dicarboxylate compounds (Figure 2b).40 The molecular structure of 3 is depicted in Figure 3a and its selected bond parameters are listed in the caption of Figure 3. Complex 3 crystallized as a discrete dimer where the two tin atoms are bridged by two hydroxide ligands to generate a fourmembered Sn2O2 ring. Each of the tins contains a unidentate [(η6-C6H5CO2)Cr(CO)3]− ligand. Both the tin centers are five-coordinate in a distorted rectangular pyramidal geometry (τ = 0.46) (Figure 3b) possessing two t-butyl groups, two hydroxides, and one monodentate carboxylate ligand with slight

variation in their bond lengths and angles. The bridging hydroxide ligands are involved in an intramolecular hydrogen bonding with the CO unit of the carboxylate ligands [O3−H3H···O1, 1.873(3) Å; ∠O1−H3H−O3, 138.75(6)°] (Figure 3a) to generate a six-membered ring on either side of the four-membered Sn2O2 ring. The asymmetric unit of the 2D-polymer 4 is shown in Figure 4a. Selected bond parameters are listed in the caption of Figure 4. Each tin atom has distorted trigonal bipyramidal (3C, 2O) geometry and the tin oxygen distances are Sn(1)−O(1), 2.169(5) Å and Sn(1)−O(3), 2.404(5) Å (Figure 4b). The average Sn−O bond distance is 2.286(5) Å. The average O−Sn−O bond angle is 178.01(5)°. Each carboxylate binds to the tin center in a μ2-η1:η1 bridging mode. Compound 4 is a planar 2D-polymer containing interconnected 24-membered (Sn4O8C12) macrocyclic rings (Figures 5 and 6a). Each macrocyclic ring consists of four triorganotin units and four dicarboxylate ligands (Figure 5). Surprisingly, in spite of its large size each macrocyclic ring is quite planar (Figure 6b). Within each macrocyclic ring three types of intertin distances are found (5.166, 7.674, and 10.493 Å) (Figure 6 a). The η6-benzene(tricarbonyl)chromium moieties of the 2D-sheets are arranged in the same direction within the crystal structure (Figure 6c). Each 2D-sheets are arranged in such a way that the CO groups H

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Figure 4. (a) The structure of the asymmetric unit of 4. (b) Geometry around the tin center (hydrogen atoms have been omitted for clarity). Bond distances (Å): Sn(1)−O(1), 2.169(5); Sn(1)−O(3), 2.404(5); Sn(1)−C(11), 2.111(8); Sn(1)−C(12), 2.122(7); Sn(1)−C(13), 2.138(8). Bond angles (deg): O(1)−Sn(1)−O(3), 178.36(19); C(11)−Sn(1)−C(12), 126.8(3), C(11)−Sn(1)−C(13), 118.0(3); C(12)−Sn(1)−C(13), 114.3(3).

Figure 5. Representation of 4 in two dimensions (hydrogen atoms are removed for clarity).

of the η6-benzene(tricarbonyl)chromium overlap each other (Figure 7). The interplane distance between such successive planar sheets is 7.5 and 4.5 Å (Figure 7). It may be of interest to note that such 2D coordination polymer formation through the interaction of carboxylate groups has been observed by us in [(Me3Sn)2(η5-C5H4COO)2Fe]n.51 The asymmetric unit of the 2D-polymer 5 is given in Figure 8 and its selected bond parameters are listed in the caption of Figure 8. Compound 5 is a planar 2D-polymer containing interconnected 26-membered (Sn4O8C14) macrocyclic rings (Figure 9). Each macrocyclic ring consists of four triorganotin units and two dicarboxylate ligands. Each tin atom is trigonal bipyramidal (3C, 2O) and the tin oxygen distances are Sn(1)−O(2), 2.144(7) Å and Sn(1)−O(3), 2.542(7) Å. The average Sn−O bond distance is 2.343(7) Å. The average O−Sn−O bond angle is 175.15(5)°. Interestingly, as in 4, in the present instance also all the macrocyclic rings are nearly planar. The 2D-polymer contains a criss-cross arrangement of the macrocyclic rings (Figure 9). Within each macrocyclic ring two types of intertin distances are found (9.806 and 5.261 Å) (Figure 9). Similar to 4, here also the 2D-sheets are arranged in such a way that the CO groups of the η6-benzene(tricarbonyl)chromium overlap each other. The interplane distance between such successive planar sheets is 6.71 and 5.03 Å (Figure S1, Supporting Information). The X-ray crystal structure of 6 is given in Figure 10 and its selected bond parameters are listed in the caption of Figure 10.

Figure 6. (a) 2D polymer (4) formed by the connection between successive 24-membered macrocycles. (b) The plane passing through atoms of 24-membered macrocycle. (c) Direction of the Cr(CO)3 groups in the polymer.

This compound is a 1D-coordination polymer. The effect of the 4,4′-bipyridine ligand in altering the polymeric structure of 6 can be clearly seen, here the 4,4′-bipyridine ligand is also involved in a bridging coordination mode and alternates with the dicarboxylate ligand in forming the polymer chain. The triorganotin center (Sn1) is five-coordinated (2C, O, N) in a distorted trigonal bipyramidal geometry where the two oxygen atoms occupy the axial positions (Figure 10). Similar to polymers 4 and 5, in the present instance also the CO groups of the η6-benzene(tricarbonyl)chromium are oriented into the same direction (Figure 10). I

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via a dicarboxylate ligand (L3). The essential difference between the two tin centers is that in one case water is a terminal ligand, whereas in the other case it is methanol. Both tin centers are five-coordinated in distorted trigonal bipyramidal geometry with the oxygen atoms occupying the axial positions. The average Sn−C (2.126 Å for Sn1; 2.131 Å for Sn2) and Sn−O (2.245 Å for Sn1and 2.302 Å for Sn2) bond distances of both the tin centers are also nearly equal. In addition, a weak interaction is present between the CO unit and the tin centers (3.223 Å for Sn1; 3.011 Å for Sn2) (Figure 11). The intermolecular hydrogen bonding interaction between the hydrogen atoms of the coordinated water and methanol molecules with the CO unit of the carboxylate leads to the formation of a 2D-supramolecular structure by repetitive 34-membered supramolecular macrocycle formation and the macrocycles are situated in a criss-cross arrangement with in the 2D-supramolecular framework (Figure 12). The molecular structure of 8 is shown in Figure 13 and its selected bond parameters are summarized in the caption of Figure 13. Compound 8 adopts the familiar ladder framework and has two central (Sn1 and Sn1*) and two terminal (Sn2 and Sn2*) tin atoms. The molecular structure of 8 shows that the four cymantrene moieties present in this compound are supported by a planar Sn4O2 core. All the tin atoms are in a distorted trigonal bipyramidal geometry with five covalent bonds (2C, 3O) (Figure 13b,c). Also, another carboxyl oxygen (O5/O5* to the terminal tin atom Sn2/Sn2*) is involved in a sixth weaker bonding interaction with tin [Sn(2)−O(5), 2.775(2) Å]. The sum of the van der Waals radii of tin and oxygen is 3.7 Å.56 By considering this, terminal tin atoms can be thought of as possessing distorted octahedral geometry. The carboxylate ligands are involved in both anisobidentate chelating [Sn(2)−O(4), 2.184(2) Å; Sn(2)−O(5), 2.775(2) Å] as well as isobidentate bridging [Sn(1)−O(6), 2.243(2) Å; Sn(2)−O(7), 2.247(7) Å] coordination modes. The Sn−O distances in the central Sn2O2 unit of 8 are as follows: Sn(1)− O(8), 2.039(2); Sn(1)−O(8*), 2.158(2); Sn(2)−O(8),

Figure 7. Packing of 4 showing the orientation of CO groups. The interlayer distances are indicated.

Figure 8. Structure of the asymmetric unit of 5 (some hydrogen atoms have been omitted for clarity). Bond distances (Å): Sn(1)−O(2), 2.144(7); Sn(1)−O(3), 2.542(7); Sn(1)−C(2), 2.112(10); Sn(1)− C(1), 2.153(11); Sn(1)−C(12), 2.104(11), Sn(2)−O(4), 2.151(7); Sn(2)−O(1), 2.534(8). Bond angles (deg): O(2)−Sn(1)−O(5), 174.9(3); O(4)−Sn(2)−O(1), 175.4(2); C(2)−Sn(1)−C(1), 114.0(5); C(12)−Sn(1)−C(1), 120.7(5); C(12)−Sn(1)−C(2), 123.1(5).

The molecular structure of 7 is given in Figure 11 and its selected bond parameters are listed in the caption of Figure 11. This reveals that there are two tin centers which are attached

Figure 9. 2D polymeric structure of 5 containing interconnected 26-membered macrocyclic rings (methyl groups and hydrogen atoms are removed for clarity). J

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Figure 10. 1D-polymeric structure of 6 (hydrogen atoms omitted for clarity). Bond distances (Å): Sn(1)−O(1), 2.1479(15); Sn(1)−N(1), 2.5521(18); Sn(1)−C(12), 2.127(2); Sn(1)−C(13), 2.130(2); Sn(1)−C(14), 2.128(2). Bond angles (deg): O(1)−Sn(1)−N(1), 172.78(6); C(12)−Sn(1)−C(14), 118.91(12); C(12)−Sn(1)−C(13), 122.33(11); C(14)−Sn(1)−C(13), 117.95(10).

that the two cymantrene moieties, related by a center of inversion, are supported by a planar Sn4O2(OMe)2 core (Figure 14). The carboxylate ligand (L5H) binds to the terminal tin atoms (Sn2 and Sn2*) in an anisobidentate chelating mode as can be seen by the difference in the corresponding Sn−O bond lengths: Sn(2)−O(3), 2.129(3) Å; Sn(2)−O(4), 2.945(3) Å. The terminal tin atoms (Sn2 and Sn2*) in complex 9 are sixcoordinate while the central tin atoms (Sn1 and Sn1*) are fivecoordinate (Figure 14). The essential difference between the molecular structures of 8 and 9 is that in the former there are four carboxylate ligands. The oxygen atom of a carboxylate ligand (O6 and O7) serves to bridge a pair of tin atoms. In 9 this function is carried out by a μ-OMe ligand. Thermogravimetric Analysis (TGA) Studies. TGA measurements were performed on compounds 1−5 (Figure 15a) and 8 and 9 (Figure 15b). Complexes 1−5 decompose sharply in the temperature range 230−260 °C losing part of the organic substituents. Subsequently, complexes 1−5 further decompose (obsd 11%, calcd 11% (1); obsd 20%, calcd 22% (2); obsd 16%, calcd 16% (3); obsd 17%, calcd 13% (4); obsd 17%, calcd 13% (5); calculated for the asymmetric unit) due to the loss of the CO groups in the temperature range 390−540 °C. A separate decomposition step due to the loss of CO groups of the cymantrene containing complexes (8, 9) was not observed. TGA revealed that all of these compounds have substantial char yields even after heating up to 800 °C. XRD data analysis of the

Figure 11. Molecular structure of 7. (Some hydrogen atoms have been omitted for clarity). Bond distances (Å): Sn(1)−O(1), 2.348(2); Sn(1)−O(2), 2.142(2); Sn(1)−C(13), 2.135(3); Sn(1)−C(1), 2.125(3); Sn(1)−C(7), 2.119(3); Sn(2)−O(5), 2.164(2); Sn(2)− O(6), 2.441(2). Bond angles (deg): O(2)−Sn(1)−O(1), 174.01(9); O(5)−Sn(2)−O(6), 176.18(8).

2.042(2). These are comparable with the literature precedents.38,57,58 The molecular structure of the methoxy-bridged tetrameric organostannoxane ladder 9 is shown in Figure 14 and it has a similar structural motif that is present in 1. Thus, 9 also has two distannoxane motifs (Sn2O2) which are fused to each other to form a ladder-like structure. The selected bond parameters corresponding to the tetrameric stannoxane core are summarized in the caption of Figure 14. The molecular structure of 9 shows

Figure 12. 2D-polymeric supramolecular structure of 7 formed by intermolecular O−H···O interactions. (phenyl and Cr(CO)3 groups are omitted for clarity). Bond distances (Å): H1W···O4, 1.839(3); H1M···O3, 1.933(3). Bond angles (deg): O1−H1W···O4, 169.91(4); O6−H1M···O3, 167.83(2). K

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Figure 13. (a) Molecular structure of 8. (b,c) Geometry around the tin centers. Some hydrogen atoms have been omitted for clarity. Bond distances (Å): Sn(1)−O(6), 2.243(2); Sn(1)−O(8), 2.039(2); Sn(1)−O(8*), 2.158(2); Sn(2)−O(8), 2.042(2); Sn(2)−O(4), 2.184(2); Sn(2)−O(7), 2.247(7); Sn(2)−O(5), 2.775(2). Bond angles (deg): Sn(1)−O(8)−Sn(1*), 103.20(9); Sn(1)−O(8)−Sn(2), 134.73(1); O8(1)−Sn(1)−O(8*), 76.80(8); O(6)−Sn(1)−O(8*), 168.75(3); O(4)−Sn(2)−O(7), 173.60(8); C(12)−Sn(1)−C(13), 142.47(1), C(10)−Sn(2)−C(11), 141.71(1).

Figure 14. Molecular structure of 14. Some hydrogen atoms have been omitted for clarity. Bond distances(Å): Sn(1)−O(1), 2.022(2); Sn(1)− O(1*), 2.114(2); Sn(1)−O(2), 2.143(2); Sn(2)−O(1), 2.009(2); Sn(2)−O(2), 2.225(7); Sn(2)−O(3), 2.129(3); Sn(2)−O(4), 2.945(3). Bond angles (deg): Sn(1)−O(1)−Sn(2), 113.78(1); Sn(1)−O(2)−Sn(2), 101.53(1); Sn(1)−O(1)−Sn(1)*, 106.51(1); O(1)−Sn(1)−O(2), 73.02(9); O(1)−Sn(2)−O(2), 71.64(9); O(1)−Sn(1)−O(1*), 73.49(7); C(13)−Sn(2)−C(14), 132.04(1), C(15)−Sn(1)−C(16), 126.82(2).

Figure 15. TGA curves for 1−5 and 8 and 9.

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residue of complex 3 which was left after heating 800 °C indicates a mixture of CrO2 and SnO2 (Figure S2(a), Supporting Information). The decomposition of complex 8 resulted in the formation of the binary oxide, MnSnO3 (Figure S2(b), Supporting Information). The reference XRD patterns [PCD entry no. 1824248 (SnO2); 1624522 (Cr2O3); 307504 (MnSnO3)] are given in the Supporting Information Figure S3−S5.

CONCLUSIONS An organometallic platform (organostannoxane) was utilized for supporting organometallic piano-ptool [(η6-arene)Cr(CO)3] and [(η5-C5H5)Mn(CO)3] assemblies. Here the complexes were prepared through the one step stannoxane synthetic route. Among the multi [(η6-arene)Cr(CO)3] assemblies (1−7), complexes 4 and 5 are planar 2D-coordination polymers. L

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(17) Murugesapandian, B.; Roesky, P. W. Dalton Trans. 2010, 39, 9598−9603. (18) Day, D. P.; Dann, T.; Hughes, D. L.; Oganesyan, V. S.; Steverding, D.; Wildgoose, G. G. Organometallics 2014, 33, 4687− 4696. (19) Calladine, J. A.; Duckett, S. B.; George, M. W.; Matthews, S. L.; Perutz, R. N.; Torres, O.; Vuong, K. J. Am. Chem. Soc. 2011, 133, 2303−2310. (20) Kee, J. W.; Tan, Y. Y.; Swennenhuis, B. H. G.; Bengali, A. A.; Fan, W.Y. Organometallics 2011, 30, 2154−2159. (21) Ziessel, R.; Suffert, J. J. Chem. Soc., Chem. Commun. 1990, 1105− 1107. (22) N’Dongo, H. W. P.; Neundorf, I.; Merz, K.; Schatzschneider, U. J. Inorg. Biochem. 2008, 102, 2114−2119. (23) Splith, K.; Neundorf, I.; Hu, W.; N’Dongo, H. W. P.; Vasylyeva, V.; Merz, K.; Schatzschneider, U. Dalton Trans. 2010, 39, 2536−2545. (24) Dale, M. J.; Dyson, P. J.; Suman, P.; Zenobi, R. Organometallics 1997, 16, 197−204. (25) Gloriozov, I. P.; Marchal, R.; Saillard, J.-Y.; Oprunenko, Y. F. Eur. J. Inorg. Chem. 2015, 2015, 250−257. (26) Caldirola, P.; Chowdhury, R.; Johansson, A. M.; Hacksell, U. Organometallics 1995, 14, 3897−3900. (27) Zheng, Y.; Wang, W.; Lin, J.; She, Y.; Fu, K. J. Phys. Chem. 1992, 96, 9821−9827. (28) Kaye, S. S.; Long, J. R. J. Am. Chem. Soc. 2008, 130, 806−807. (29) Vitillo, J. G.; Groppo, E.; Bordiga, S.; Chavan, S.; Ricchiardi, G.; Zecchina, A. Inorg. Chem. 2009, 48, 5439−5448. (30) Chandrasekhar, V.; Nagendran, S.; Baskar, V. Coord. Chem. Rev. 2002, 235, 1−52. (31) Chandrasekhar, V.; Gopal, K.; Thilagar, P. Acc. Chem. Res. 2007, 40, 420−34. (32) Davies, A. G.; Gielen, M.; Pannell, K. H.; Tiekink, E. R. T. Tin Chemistry: Fundamental, Frontiers and Applications; Wiley-VCH: Weinheim, 2008. (33) Garcia-Zarracino, R.; Höpfl, H. Angew. Chem., Int. Ed. 2004, 43, 1507−1510. (34) Garcia-Zarracino, R.; Höpfl, H. J. Am. Chem. Soc. 2005, 127, 3120−3130. (35) Chandrasekhar, V.; Day, R. O.; Holmes, R. R. Inorg. Chem. 1985, 24, 1970−1971. (36) Alcock, N. W.; Roej, S. M. J. Chem. Soc., Dalton Trans. 1989, 1589−1598. (37) Zhang, R.; Sun, J.; Ma, C. J. Organomet. Chem. 2005, 690, 4366−4372. (38) Chandrasekhar, V.; Kundu, S.; Kumar, J.; Verma, S.; Gopal, K.; Chaturbedi, A.; Subramaniam, K. Cryst. Growth Des. 2013, 13, 1665− 1675. (39) Chandrasekhar, V.; Nagendran, S.; Bansal, S.; Kozee, M. A.; Powell, D. R. Angew. Chem., Int. Ed. 2000, 39, 1833−1835. (40) Chandrasekhar, V.; Gopal, K.; Nagendran, S.; Singh, P.; Steiner, A.; Zacchini, S.; Bickley, J. F. Chem. - Eur. J. 2005, 11, 5437−5448. (41) Chandrasekhar, V.; Nagendran, S.; Bansal, S.; Cordes, A. W.; Vij, A. Organometallics 2002, 21, 3297−3300. (42) Kundu, S.; Chakraborty, A.; Mondal, K.; Chandrasekhar, V. Cryst. Growth Des. 2014, 14, 861−870. (43) SMART & SAINT Software Reference Manuals, version 6.45; Bruker Analytical X-ray Systems, Inc.: Madison, WI, 2003. (44) Sheldrick, G. M. SADABS: A Software for Empirical Absorption Correction, v 2.05; University of Göttingen: Göttingen, Germany, 2002. (45) Brandenburg, K. Diamond, v 3.1eM; Crystal Impact GbR: Bonn, Germany, 2005. (46) Puff, H.; Schuh, W.; Sievers, R.; Wald, W.; Zimmer, R. J. Organomet. Chem. 1984, 260, 271−275. (47) Atencio, R.; Brammer, L.; Fang, S.; Pigge, F. C. New J. Chem. 1999, 23, 461−463. (48) Brammer, L.; Rivas, J. C. M.; Atencio, R.; Fang, S.; Pigge, F. C. J. Chem. Soc., Dalton Trans. 2000, 3855−3867. (49) Biehl, E. R.; Reeves, P. C. Synthesis 1973, 1973, 360−366.

Interestingly, all the Cr(CO)3 groups of the polymer are situated in the same direction. Complex 5 [{Me2Sn}2(μ3-O){η5C5H5Mn(CO)3}2]2 has been shown to be a convenient singlesource precursor for preparing the binary oxide, MnSnO3. This is the first instance where such a synthetic modulation have been done with respect to η6-benzene(tricarbonyl)chromium and cymantrene. It would be interesting to investigate the catalytic behavior of η6-benzene(tricarbonyl)chromium and cymantrene assemblies on the organostannoxane platform. It appears that the use of stable metallocene ligands and stable organotin nodes may be a profitable area of research particularly for the ready synthesis of heterometallic assemblies.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.5b01064. Synthesis of ligands and some figures (PDF) Crystallographic data (CIF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Phone: (+91) 512-259-7259. Fax: (+91) 521-259-0007/7436. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS S.K. is thankful to the CSIR, New Delhi for the award of a Senior Research Fellowship and NISER Bhubaneswar for postdoctoral fellowship. V.C. is thankful to the Department of Science and Technology, New Delhi for the award of National J. C. Bose Fellowship.

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