Copper(II) complexes with an arylhydrazone of methyl 2-cyanoacetate as effective catalysts in the microwave-assisted oxidation of cyclohexane

Inorganica Chimica Acta 471 (2018) 658–663

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Research paper

Copper(II) complexes with an arylhydrazone of methyl 2-cyanoacetate as effective catalysts in the microwave-assisted oxidation of cyclohexane Raja Jlassi a,b, Ana P.C. Ribeiro a,⇑, Elisabete C.B.A. Alegria a,c,⇑, Houcine Naïli b,⇑, Gonçalo A.O. Tiago a, Tobias Rüffer d, Heinrich Lang d, Fedor I. Zubkov e, Armando J.L. Pombeiro a, Walid Rekik b a

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal Laboratoire de physico-chimie de l’Etat Solide, Département de Chimie, Faculté des Sciences de Sfax, Université de Sfax, BP 1171, 3000 Sfax, Tunisia Chemical Engineering Departament, ISEL-Instituto Superior de Engenharia de Lisboa, Instituto Politecnico de Lisboa, 1959-007 Lisboa, Portugal d Technische Universität Chemnitz, Fakultät für Naturwissenschaften, Institut für Chemie, Anorganische Chemie, D-09107 Chemnitz, Germany e Organic Chemistry Department, RUDN University, 6 Miklukho-Maklaya str., Moscow 117198, Russian Federation b c

a r t i c l e

i n f o

Article history: Received 12 October 2017 Received in revised form 28 November 2017 Accepted 1 December 2017 Available online 5 December 2017 Keywords: COPPER(II) complexes Arylhydrazones of active methylene compounds (AHAMC) Catalytic activity Microwave irradiation Cyclohexane oxidation

a b s t r a c t Reaction of sodium (E/Z)-2-(2-(1-cyano-2-methoxy-2-oxoethylidene)hydrazinyl)benzene-sulfonate (NaHL) with copper(II) nitrate hydrate in the presence of imidazole (im) in methanol affords [CuL(im) (H2O)] (1). Complex 1 is characterized by IR spectroscopy and ESI-MS spectrometry, elemental and single crystal X-ray crystal structural analyses. The coordination environment of the central copper(II) is nearly intermediate between ideal square-based pyramidal and trigonal bipyramidal geometry, three sites being occupied by the L2 ligand, which chelates in the O, N, O fashion, while two other sites are filled with the water and imidazole molecules. Extensive intermolecular hydrogen bonds between the L2 , water and imidazole ligands lead to a 3D supramolecular network. 1 and known Cu(II) complexes [Cu(H2O)2L]
H2O (2), [Cu(H2O)(py)L]
H2O (3) and [Cu3(m3-OH)(NO3)(CH3OH)(m2-X)3(m2-HL)] (4) act as effective catalysts in the oxidation of cyclohexane to cyclohexanol and cyclohexanone, using low power microwave (MW) irradiation, under mild conditions. Without a promoter, the activity of the catalyst reached a turnover number of 1.44  103 and a turnover frequency of 1.98  103 h 1, after 2 h, at 50 °C. Ó 2017 Elsevier B.V. All rights reserved.

1. Introduction Arylhydrazones of active methylene compounds (AHAMC) bear hydrazone, carbonyl and cyano moieties and thus provide a rich organic and coordination chemistry [1,2]. Usually the AHAMC ligands are prepared by the Japp-Klingemann reaction [3]. Nucleophilic additions to cyano group(s) of the obtained hydrazone compounds lead to new AHAMC ligands [4]. AHAMC and their complexes have been found to possess a wide variety of useful properties, such as sensor or analytical reagents, spin-coating films, optical storage media, catalysts, etc [1,5]. The modification of the active methylene fragment or aromatic moiety can be used as a synthetic approach for the regulation of properties of those ligands and their coordination compounds. For instance, introduction of hydrophilic polar groups, such as sulfo or carboxy group(s),

⇑ Corresponding authors at: Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal (E.C.B. A. Alegria). E-mail addresses: [email protected] (A.P.C. Ribeiro), [email protected]. ipl.pt (E.C.B.A. Alegria), [email protected] (H. Naïli). https://doi.org/10.1016/j.ica.2017.12.001 0020-1693/Ó 2017 Elsevier B.V. All rights reserved.

to AHAMC can increase the solubility of the obtained complexes and provide an acidic medium in the peroxidative oxidation of alkanes [6]. Acidic medium can also be created/organized by using an axillary ligand which has an acidic proton, for example, imidazole (im). Their application in the functionalization of inert CAH bonds of hydrocarbons with a metal catalyst and an oxidant is a promising area of catalysis [2f,4a,4b,6]. Alkanes are attractive substrates for added value organic chemicals (alcohols, ketones, aldehydes and carboxylic acids). Unfortunately, their low reactivity constitutes a considerable limitation towards their broad application for direct syntheses of oxygenated products under relatively mild conditions [7]. However, the use of an appropriate metal catalyst, namely a copper complex [8], that promotes the catalytic functionalization of the non-activated CAH bonds of hydrocarbons has been one of the goals of some of us [7,9]. We chose cyclohexane oxidation as the model reaction to test our complexes, which constitutes an important step for Nylon 6 and Nylon 6,6 production, a main industrial process [10]. Thus, in this work we combine the above mentioned approaches towards the following aims: i) to synthesize a new

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copper(II) complex, [CuL(im)(H2O)] (1), derived from sodium (E/Z)2-(2-(1-cyano-2-methoxy-2-oxoethylidene)hydrazinyl) benzenesulfonate (NaHL) and imidazole (im) ligands and ii) to apply 1 and known Cu(II) complexes, [Cu(H2O)2L]
H2O (2), [Cu(H2O)(Py) L]
H2O (3), [Cu3(m3-OH)(NO3)(CH3OH)(m2-X)3(m2-HL)] (4) [4], as catalysts for the peroxidative oxidation of cyclohexane. 2. Results and discussion 2.1. Synthesis and characterization of 1 The synthesis and characterization of sodium (E/Z)-2-(2-(1cyano-2-methoxy-oxoethylidene)hydrazinyl) benzenesulfonate (NaHL) (Scheme 1) was reported earlier by us [4a] and will not be discussed here. Reaction of copper(II) nitrate hydrate with NaHL in the presence of imidazole (im) in a methanol solution leads to the mononuclear compound [CuL(im)(H2O)] (1) (Scheme 1). 1 was characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray diffraction. The IR spectrum of 1 displays bands at 3448 m(O–H), 2222 m(C„N), 1646 m(C@O) and 1579 m(C@N) cm 1 which are significantly shifted in relation to those of the free ligand [3475 m(OH), 2209 m (C„N), 1710 m(C@O), 1628 m(C@O


H), 1596 m(C@N)] [4a]. Elemental analysis and ESI-MS in methanol (peak at m/z 431.7 [Mr+H]+) support the proposed formulation of 1 as a monomer. 2.2. Description of the X-ray crystal structure The asymmetric unit of the title compound (Fig. 1) contains one monomeric unit of the title compound, in which the Cu(II) ion is coordinated by the L2 ligand together with one water molecule and one imidazole ligand. The Cu atom adopts a five-coordinated geometry defined by three oxygen atoms O1, O4 and OW1 belonging to the sulfonate group, ester group and water molecule and two nitrogen atoms N1 in the hydrazo group and N4 of imidazole entity. The geometry around the CuII centre in the monomeric unit can be described as distorted trigonal bipyramidal. Considering that the complex presents a coordination number of 5, the parameter was calculated for the complex to measure the grade of distortion, and its value varies from 0 (in regular square-based pyramidal geometry) to 1 (in regular trigonal bipyramidal geometry) [11]. In the title complex the calculated s value is equal to 0.40. This value is lower than 0.5 and shows that in the title compound the geometry around the copper atom is nearly intermediate between

Scheme 1. Synthesis of 1.

Fig. 1. Asymmetric unit of 1.

the two ideal coordination geometries. The apical positions are occupied by the N donor atoms N1 and N4; the bond lengths are located at 1.976(3) Å and 1.956(3) Å, respectively. The angle of N4–Cu1–N1 is with 179.12(11)° close to 180°. The equatorial positions of the trigonal plane are occupied by the O donor atoms O4, OW1 and O1 (Fig. 2). The bond lengths are Cu1–O1 = 1.991(2), Cu1–O4 = 1.978(2) and Cu1–OW1 = 2.234(2) Å. The copper ion forms two fused six-membered metallacycles, Cu1-O1-S1-C1-C2-N1 and Cu1-O4-C9-C7-N2-N1. Consistent with electron delocalization in these metallacycles are the N1–N2, C7– N2, and C9@O4 bond lengths of 1.295(3), 1.344(4), and 1.241(4) Å (see Table S1), respectively. The crystal structure is stabilized by weak intermolecular hydrogen bonding interactions (Fig. 3; Table S2) between the coordinated water molecule, the imidazol entities and the nitrile or sulfonate bridging group. Within the intermolecular hydrogen bonds; O1W H2


N3ii, N5–H5A


O3iii and O1W–H1


O2i, the donor-acceptor distances are equal to 2.873(1), 3.047(1) and 2.744(1) Å, respectively. 2.3. Catalytic oxidation of cyclohexane The catalytic study focused on the use of cyclohexane as model substrate for the investigation of the catalytic performance of 1 and known Cu(II) complexes, [Cu(H2O)2L]
H2O (2), [Cu(H2O)(py)L]
H2O (3) and [Cu3(m3-OH)(NO3)(CH3OH)(m2-X)3(m2-HL)] (4), derived from the same ligand (Scheme 2) [4a], in oxidation reactions of cycloalkanes using tert-butyl hydroperoxide (TBHP, 70% aq.

Fig. 2. Schematic drawing of coordination geometry of Cu(II) in 1.

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Fig. 3. H-bond interactions in compound 1 which lead to a 3D framework. Ball-andstick model of a selected part of the 3D network formed by 1 in the solid state due to intermolecular hydrogen bonds, indicated by green coloured dashed bonds.

(Fig. 4 for complex 1, Table 1). The oxidation reaction proceeds even if a very small relative amount of catalyst is used leading to rather high TONs up to 1.44  103 (Table 1, entry 12, for complex 1) and TOFs up to 1.98  103h 1 were observed for the lowest amount of catalyst (Table 1, entry 9, complex 1). The effect of the catalyst amount on the overall yield and TON is illustrated in Fig. 4a and b, respectively, for complex 1. An increase of the catalyst amount leads to an enhancement of the product yield but to a decrease of TON. The combination of a considerable good yield (up to 12%, Table 1, entry 1), with TON and TOF values up to 110 and 220, respectively, (Table 1, entry 1), reached in a short reaction time (30 mins) and under mild conditions, is indicative of an remarkable activity of the catalytic system based on complex 1. Cyclohexanol is the main product under our experimental conditions (after treatment of the final reaction mixture with triphenylphosphine) with selectivity values up to ca. 89% (Table 1, entry 9) for complex 1. Although complexes 1 and 4 have similar catalytic activities after 120 min reaction at same conditions (17 and 15%, entries 4 and 25, Table 2, respectively for 1 and 4,), it is noteworthy to mention the existence of 3 metal centers in the latter whereas in the former this activity is ensured only by one copper metal center. These transformations (Scheme 3) are expected to occur mainly via cyclohexyl hydroperoxide (CyOOH), as reported for other copper (II) catalysts [7,8], which, upon addition of PPh3, converts into the CyOH. Hence, the measured alcohol predominates significantly over the ketone (cyclohexanone) for all catalyst concentrations (Fig. 5). It deserves to be highlighted that the levels of activity and ratio towards the formation of cyclohexanol are high. No traces of byproducts were detected by gas chromatography–mass spectrometry (GC-MS) analysis of the final reaction mixtures. In comparison with the industrial process, our yields and selectivities are much higher [10f,12]. Our system also achieves higher yields than those reported Cu(II) complexes with arylhydrazone of acetylacetone, [Cu(H2O){(CH3)2NCHO}(HL)] and [Cu2(CH3OH)2(mHL)2] [6], where a total yield of 14% is reached after 4.5 h of reaction, using hydrogen peroxide as oxidant (H2O2, 50% aq. solution) and performing the reaction at 50 °C. Our yields are comparable to those reported Cu(II) complexes with arylhydrazones of barbituric acid [Cu(H2L1)(H2O)(im)]
3H2O and [Cu(H2L2)(im)2]H2O (im = imidazole; H4L1 = 5-(2-(2-hydroxyphenyl)hydrazono)pyrimidine-2,4,6(1H,3H,5H)-trione; H4L2 = 2(2-(2,4,6-trioxotetra-hydropyrimidin-5(2H)-ylidene) hydrazinyl) benzenesulfonic acid) (yields up to 21% and TON up to 213) in the peroxidative (with H2O2) oxidation of cyclohexane after 6 h reaction at room temperature [13].

Scheme 2. Structures of 2–4.

3. Conclusions solution) as oxidant and acetonitrile (CH3CN) as solvent at 50 °C (Scheme 3). The results are shown in Table 1. The systems based on 1 and 4 exhibit the highest catalytic activity toward the oxidation of cyclohexane to cyclohexanol and cyclohexanone, according to Scheme 3 and Table 2. The influence of the amount of catalyst was studied for 1 in the range of concentrations from 4.0  10 4 to 4.0  10 6 M

Scheme 3. Peroxidative oxidation of cyclohexane catalysed by 1–4.

In this study we have successfully used AHAMC chelating ligands bearing the –SO3H group in ortho-position of the aromatic part and imidazole (im) to synthesize a new mononuclear copper(II) complex, [CuL(im)(H2O)] (1). Both ligands and the coordinated water molecule play a crucial structural role in the organization of the hydrogen bonded assemblies, influencing the overall 3D supramolecular structure and increasing the water solubility of the complex. The catalytic activity of 1 was compared with known copper(II) arylhydrazone complexes 2–4 derived from the same ligand (NaHL). The work has shown that 1 acts as a good catalyst for the oxidation of cyclohexane to cyclohexanol and cyclohexanone, under mild conditions and in the presence of tert-butyl hydroperoxide (TBHP, 70% aq. solution) as oxidant, under low power microwave irradiation. The effects

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R. Jlassi et al. / Inorganica Chimica Acta 471 (2018) 658–663 Table 1 Oxidation of cyclohexane using 1–4 as catalyst precursors.a Entry

Catalyst precursor

Yields, (%)b

Catalyst concentration mol L

1

Total TONd

Total TOFe

Conversionf(%)

Selectivityg(%)

c

Time (min)

CyO

CyOH

Total

1 2 3 4

1

4  10

4

30 60 90 120

1.9 2 2.3 2.7

10.3 12.1 13.7 14.4

12.2 14.1 16 17.1

110 127 126 154

220 127 84 77

14.1 15.1 19.0 22.1

73.3 80.4 72.0 65.2

5 6 7 8

1

4  10

5

30 60 90 120

1.5 1.6 1.8 2.1

4.1 6.3 7.1 9.3

5.6 7.9 8.9 11.4

504 711 801 1.03  103

1.01  103 711 534 513

6.0 8.5 9.9 12.1

68.4 74.2 71.9 76.9

9 10 11 12

1

4  10

6

30 60 90 120

0.1 0.1 0.1 0.1

1.0 1.1 1.3 1.5

1.1 1.2 1.4 1.6

990 1.08  103 1.26  103 1.44  103

1.98  103 1.08  103 840 720

1.1 1.5 1.6 1.7

89.3 75.3 82.8 87.6

13h

1

4  10

4

120

1.6

3.8

5.4

49

24

5.9

64.3

14 15 16 17

2

4  10

4

30 60 90 120

0 0 0 0

0.6 0.6 1.0 3.3

0.6 0.6 1 3.3

5 5 9 30

10 5 6 15

0.7 0.7 1.2 4.2

92.3 88.1 83.3 78.6

18 19 20 21

3

4  10

4

30 60 90 120

0 0 0 0

5.3 6.3 7.5 8.8

5.3 6.3 7.5 8.8

49 40 69 35

99 40 46 17

5.7 6.7 8.0 10.1

93.5 94.0 93.5 87.1

22 23 24 25

4

4  10

4

30 60 90 120

0 0 0 0

11.2 11.4 12.0 15.2

11.2 11.4 12 15.2

10 105 111 141

208 105 74 70

12.0 12.2 13.3 19.2

93.5 93.4 90.2 79.2

26

–

Blank

30

–

–

–

–

–

–

–

a

Reaction conditions, unless stated otherwise: [cyclohexane]0 = 0.36 mol L 1, [TBHP]0 = 1.8 mol L 1, MeCN (up to 5 mL total volume), 50 °C, using 10 W of microwave irradiation b Moles of product/100 mols of C6H12, based on GC analysis, after treatment with PPh3. c Moles of products [cyclohexanol (CyOH) + cyclohexanone (CyO)]/100 mol of cyclohexane, determined by GC after treatment with PPh3. d Total turnover number = moles of products per mol of catalyst. e Turnover frequency (moles of products per mol of catalyst per hour). f Conversion = moles of converted (reacted) substrate per mole of substrate. g Selectivity = moles of cyclohexanol per mole of converted substrate. h For comparative purposes, Cu(NO3)2 was used as the catalyst.

Table 2 Crystallographic data for 1.

4. Experimental

Empirical formula

C13H13CuN5O6S

Formula weight (g/mol) Temperature (K) Crystal system Space group a (Å) b (Å) c (Å) b (°) V (Å3) Z Calculated density k (MoKa) (Å) Measured reflections Independent reflections Reflections [I > 2r (I)] h range for data collection (°) F (0 0 0) Number of parameters R1 [I > 2r (I)] wR2 [I > 2r (I)] GOOF

430.88 100 K Monoclinic P21/c 16.1553(6) 7.1108(3) 14.2457(5) 103.153(4) 1593.57(11) 4 1.796 0.71073 6185 2777 2415 2.928–24.993 876 244 0.0385 0.0905 1.079

of various parameters have been investigated and allowed us to achieve total yields and TONs up to 17% and 1.44  103, respectively.

4.1. Equipment and materials All chemicals were obtained from commercial sources and used as received. NaHL was prepared according to a published procedure [4a]. The infrared spectrum (4000–400 cm 1) was recorded on a Nicolet FTIR Nexus spectrophotometer on KBr pellets. Chromatographic analyses were undertaken by using a FISONS Instruments GC 8000 series gas chromatograph (Fisons Instruments), equipped with an Flame Ionization Detector FID detector, a DB-WAX capillary column (length: 30 m; internal diameter: 0.32 mm) (Agilent Technologies, Santa Clara, CA, USA), and He as the carrier gas, and run by the Jasco-Borwin v.1.50 software (Jasco, Tokyo, Japan). The temperature of injection was 240 °C. The column was initially maintained at 100 °C for 1 min, and heated up to 180 °C with the heating rate of 10 °C/min, and held at this temperature for 1 min. The attribution of the peaks observed in GC was carried out on the basis of calibration curves obtained with known concentrations of pure samples. The catalytic tests were performed under MW irradiation in a focused microwave Anton Paar Monowave 300 reactor (10 W), using a 10 mL capacity reaction tube with a 13 mm internal diameter, fitted with a rotational system and an IR temperature detector.

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(a)

(b)

Fig. 4. Effect of the amount of catalyst and of the reaction time on a) the total yield (cyclohexanol + cyclohexanone) and b) the total turnover number (TON) (cyclohexanol + cyclohexanone) in the oxidation of cyclohexane by TBHP, catalysed by complex 1 in different concentrations. Reaction conditions: [cyclohexane]0 = 0.36 mol L–1, CH3CN up to 5 mL total volume, 50 °C, 10 W, [1]0 = 4  10 4 mol L–1; [1]0 = 4  10 5 mol L–1; [1]0 = 4  10 6 mol L–1.

angles calculated from the final atomic coordinates, as well as hydrogen bonds, are listed in Tables S1 and S2, respectively. The drawings were made with Diamond program [15]. CCDC 1448651 contains the supplementary crystallographic data for this paper. 4.4. Catalytic studies

Fig. 5. Effect of the reaction time on the yields of oxygenated products (cyclohexanol and cyclohexanone) in the oxidation of cyclohexane by TBHP, catalysed by complex 1. Total (Cyclohexanol + Cyclohexanone); Cyclohexanol; Cyclohexanone. Reaction conditions: [cyclohexane]0 = 0.36 mol L–1, CH3CN up to 5 mL total volume, 50 °C, 10 W, [1]0 = 4  10 4 mol L–1.

4.2. Synthesis and characterization of 1 0.305 g (1.0 mmol) of NaHL were dissolved in 15 mL methanol, whereafter 0.233 g (1.0 mmol) of Cu(NO3)2
2.5H2O and 0.068 g (1.0 mmol) imidazole were added. The mixture was stirred for 30 min at 80 °C and left for slow evaporation; green crystals of the product started to appear after ca. 3 days at room temperature. Finally, the crystals were filtered off and dried in air. 1: Yield, 78% (based on Cu). The pale green crystalline compound is soluble in ethanol, methanol, acetonitrile and water. Anal. Calcd for C13H13CuN5O6S (Mr = 430.88): C, 36.24; H, 3.04; N, 16.25. Found: C, 36.13; H, 2.95; N, 16.18. ESI-MS: m/z: 431.7 [Mr+H]+. IR (KBr, selected bands, cm 1): 3448 m(O–H), 2222 m(C@N), 1646 m (C@O), 1579 m(C@N). 4.3. Crystallographic structure determination A suitable crystal of the title compound was immersed in cryooil, mounted in a Nylon loop, and measured at 110 K. All data were collected on an Oxford Gemini S diffractometer. For data collection, cell refinement and data reduction the software CrysAlisPro was used [14a]. All structures were solved by direct methods using SHELXS-2013 and refined by full-matrix least-squares procedures on F2 using SHELXL-2013 [14b]. All non-hydrogen atoms were refined anisotropically. All C- and N-bonded hydrogen atoms were refined using a riding model. The positions of N-bonded hydrogen atoms were taken from difference Fourier maps and refined isotropically. Crystallographic data and structural refinements are summarized in Table 2. Bond distances and

The catalytic tests under MW irradiation (MW) were performed in a focused microwave CEM using a 10 mL capacity glass reactor tube with a 13 mm internal diameter, fitted with a rotational system and an IR temperature detector. The cyclohexane oxidations were carried out using MeCN as solvent (up to 5.0 mL of total volume), and the catalyst precursors 1–4 were introduced into the reaction mixture in the form of a stock solution of acetonitrile (1  10 3 mol L 1). The cyclohexane (1.82 mmol) was then introduced, and the reaction started when 8.8 mmol of tert-butyl hydroperoxide (TBHP, 70% aq. solution) were added in a single portion. The final concentrations of the reactants in the reaction mixture were as follows: catalyst precursor 1 (4  10 6 to 4  10 4 mol L 1), substrate (0.36 mol L 1) and TBHP (1.8 mol L 1). The reaction mixture was stirred for 0.25 to 2 h at 50 °C under MW irradiation (10 W), then 90 lL of cycloheptanone (as internal standard) and 10 mL of diethyl ether (to extract the substrate and the products from the reaction mixture) were added. The resulting mixture was stirred for 15 min and then PPh3 was added to the final organic phase (to reduce the cyclohexyl hydroperoxide, if formed) and the mixture was analyzed according to Shul’pin’s method [16,17]. Blank experiments were performed and confirmed that no cyclohexane oxidation products were obtained in a considerable yield in the absence of the metal catalyst precursor. Acknowledgements This work has been partially supported by the Foundation for Science and Technology (FCT), Portugal (UID/QUI/00100/2013 and also for the PTDC/QEQ-QIN/3967/2014). G.A.O.T. and A.P.C.R. are thankful to the CATSUS doctoral and post-doctoral programs of FCT for their PhD (SFRH/ PD/BD/106015/2014) and post-doc (SFRH/BPD/90883/2012) grants, respectively. The authors acknowledge the IST Node of the Portuguese Network of Mass-spectrometry for the ESI-MS measurements. This work also was supported by the ’’RUDN University Program 5-100’’, Russian Federation. Appendix A. Supplementary data X-ray analysis. Selected bond distances (Å) and angles (°) for 1. Hydrogen-bonding geometry (Å) for 1. Supplementary data associ-

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