research communications
μ-1,4-dicarboxybutane-1,4-dicarboxylato)bis[bis(triphenylphosphane)silver(I)] dichloromethane trisolvate
of (aTechnische Universität Chemnitz, Fakultät für Naturwissenschaften, Institut für Chemie, Anorganische Chemie, D-09107 Chemnitz
*Correspondence e-mail: heinrich.lang@chemie.tu-chemnitz.de
The molecular structure of the tetrakis(triphenylphosphanyl)disilver salt of butane-1,1,4,4-tetracarboxylic acid, [Ag2(C8H8O8)(C18H15P)4]·3CH2Cl2, crystallizes with one and a half molecules of dichloromethane in the The coordination complex exhibits an inversion centre through the central CH2—CH2 bond. The AgI atom has a distorted trigonal–planar P2O coordination environment. The packing is characterized by intermolecular T-shaped π–π interactions between the phenyl rings of the PPh3 substituents in neighbouring molecules, forming a ladder-type parallel to [010]. These ladders are arranged in layers parallel to (101). Intramolecular hydrogen bonds between the OH group and one O atom of the Ag-bonded carboxylate group results in an asymmetric bidendate coordination of the carboxylate moiety to the AgI ion.
Keywords: crystal structure; silver; triphenylphosphane; tetracarboxylic acid; hydrogen bond; bridges.
CCDC reference: 1447419
1. Chemical context
Silver precursors [e.g. silver(I) carboxylates and silver(I) β-diketonates] exhibit a wide range of applications, for instance the formation of thin, metallic layers by means of CVD (Chemical Vapour Deposition) or CCVD (Combustion Chemical Vapour Deposition) (Struppert et al., 2010; Jakob et al., 2006; Schmidt et al., 2005; Lang & Buschbeck, 2009; Lang, 2011; Lang & Dietrich, 2013; Chi & Lu, 2001), spin coating (Jakob et al., 2010) or inkjet printing (Jahn et al., 2010a,b; Gäbler et al., 2016). The respective silver layers show closed and homogeneous silver films and therefore possess a good conductivity. In addition, silver carboxylates such as [AgO2CR]n (n is the degree of aggregation) allow for the formation and stabilization of silver nanoparticles, which can, for example, be used for catalytic processes (Steffan et al., 2009). They are also used in biological studies (Fourie et al., 2012; Langner et al., 2012).
A further application of silver carboxylate precursors includes their use for joining of bulk copper to produce metallic interconnects, for example in microelectronic applications (Oestreicher et al., 2012, 2013).
We anticipate that a metal oxide layer will need to be removed during such a silver-facilitated copper-joining process. Leaving some of the carboxyl groups of the silver precursor uncoordinated is expected to assist in this process. In the case of sparingly soluble silver carboxylates, the solubility in common organic solvents can be increased through addition of was prepared by the reaction of the disilver salt of butane-1,1,4,4-tetracarboxyl acid (BTCA) with triphenylphosphane.
such as triphenyl phosphane. In this context, the title compound (I)2. Structural commentary
The title compound (I) crystallizes in the triclinic P. The contains a half molecule of butane-1,4-dicarboxy-1,4-dicarboxylate bonded to a bis(triphenylphosphanyl)silver moiety and 1.5 molecules of dichloromethane. The inversion centre to build up the whole disilver complex is located in the middle of the C4—C4′ bond (Fig. 1; (A): –x, –y + 1, –z + 2). The three molecules of dichloromethane are also located on or nearby inversion centres (Fig. 1; C2S, (B): –x + 1, –y + 1, –z; C1S, C1SB, –x + 1, –y, –z; see Refinement section for details).
The anionic C8H8O8 moiety contains an intramolecular hydrogen bond between the O3 atom of the HO2C-carboxy group and the O2 atom that is in interaction with Ag1 (Fig. 1, Table 1), resulting in a boat-type conformation including the C1, C2 and C3 atoms, due to a torsion of the C1—O2 and C3—O3 bonds by 6.3 (2)°. Within the H-bearing carboxylato substituent a distinction between the C,O single [1.321 (3) Å] and double [1.205 (3) Å] bonds can be observed. The C1 labeled carboxylato group exhibits an unsymmetrically bidendate binding to Ag1. Therefore, O1 is, with 2.3305 (17) Å, σ-bonded, whereas O2 exhibits a weaker interaction with an increased O2⋯Ag1 distance of 2.6872 (19) Å, probably due to the involvement in the hydrogen bond.
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The Ag1 atom exhibits a somewhat distorted trigonal–planar P2O coordination environment, whereby the two enclose an increased P—Ag—P angle of 128.56 (2)°, in contrast to the O1—Ag1—P angles of 117.69 (5) (P1) and 113.27 (5)° (P2). The weak interaction to the O2 atom occurs below this AgP2 plane with an interaction to the CO2 group of 67.38 (17)° with, however, two nearly equal C1—O1/O2 bond lengths of 1.251 (3) (O1) and 1.261 (3) Å (O2). Both reveal an eclipsed conformation regarding the phenyl rings of 2.09 (10)°.
3. Supramolecular features
The packing of (I) consists of a layer-type structure parallel to (101), which is supported by weak T-shaped π–π interactions (Sinnokrot et al., 2002) between the C5–C10 and the C35–C40 labeled phenyl rings with centroid–centroid distances of 4.8497 (16) Å [α = 77.40 (13)°] at both sides of the molecules, forming a ladder-type arrangement parallel to [010] (Fig. 2). These ladders are packed along (101) through the phenyl rings, however, without showing any further π–π or C—H interactions.
One dichloromethane is stabilized by a non-classical hydrogen-bridge bond from C1S, as the hydrogen-bond donor, to the hydroxyl O3 atom (Table 1), which also acts as hydrogen-bridge bond donor in an intramolecular classical bridge bond (see Structural commentary).
Further intermolecular interactions involving hydrogen bonds or O⋯Ag interactions are not observed.
4. Database survey
In the CSD database (Groom & Allen, 2014; Version 5.36), only two acyclic silver tetracarboxylates with six-membered carbon backbones are reported. These are butane-1,2,3,4-tetracarboxylato silver compounds containing further nitrogen and oxygen donor ligands, coordinating the silver ions either in a tetrahedral or a T-shaped trigonal fashion (Sun et al., 2010). Three aliphatic cyclohexane silver complexes with four to six carboxylate groups are also known. Within those, the silver ions are also coordinated by additional ligands such as ammonia and water and possess distorted tetrahedral coordination or Y-shaped coordination environments (Wang et al., 2006, 2009). For six-membered unbranched acyclic silver dicarboxylates derived from adipic acid, more crystal structures are reported compared to the respective tetracarboxylato derivatives. Several coordination geometries for the silver atoms are reported such as T-shaped (Wu et al., 1995), tetrahedral (Li et al., 2011) or trigonal–planar environments (Liu et al., 2009) containing nitrogen, oxygen or sulfur donor ligands. To the best of our knowledge, the title compound (I) is the only example of a silver tetracarboxylate consisting of a six-membered carbon backbone and containing a silver–phosphorus bond. In contrast to the title compound, which exists as a monomer presumably due to the steric shielding by triphenyl phosphane, all of the above-mentioned complexes exist as polymeric networks, formed by bridging through the different donor atoms of the ligands. For example, by using silver dicarboxylates frequently the formation of dimeric sub-units can take place, which in turn results in the construction of polymeric systems (Wu et al., 1995). Structures containing water molecules coordinating to the AgI ions result in the formation of a further polymeric hydrogen bridge-bond network, also including carboxylato moieties (Wang et al., 2006, 2009).
5. Synthesis and crystallization
Synthesis of butane-1,4-dicarboxyl-1,4-dicarboxylatodisilver(I):
Potassium tert-butanolate (192 mg, 1.71 mmol) was added to a solution of butane-1,1,4,4-tetracarboxyl acid (200 mg, 0.854 mmol) in 5 mL of tetrahydrofuran. After stirring overnight at ambient temperature, the reaction mixture was filtered off and the residue was washed trice with tetrahydrofuran (10 mL each) and dried under vacuum (yield 243 mg). Subsequently, the obtained colorless solid (243 mg, 0.783 mmol) was dissolved in water (15 mL) and added dropwise to a solution of silver nitrate (267 mg, 1.57 mmol) in water (8 mL). After 12 h of stirring the colorless precipitate was filtered off and washed twice with water (10 mL each) and dried in a desiccator. The desired colorless butane-1,4-dicarboxyl-1,4-dicarboxylatodisilver(I) was obtained in a yield of 71%, based on butane-1,1,4,4-tetracarboxyl acid (271 mg, 0.608 mmol). Analysis calculated for C8H8Ag2O8 (447.88): C, 21.45; H, 1.80. Found: C, 21.49; H, 1.68. IR (KBr, cm−1): ν = 2977 (m), 2903 (m), 2461 (m), 1660 (s), 1549 (vs), 1380 (s), 1257 (s), 1069 (s), 955 (m), 711 (m).
Synthesis of (μ-1,4-dicarboxybutane-1,4-dicarboxylato)bis[bis(triphenylphosphane)silver(I)]:
To a suspension of butane-1,4-dicarboxyl-1,4-dicarboxylatodisilver(I) (100 mg, 0.223 mmol) in 10 mL of tetrahydrofuran, PPh3 (234 mg, 0.892 mmol) was added in a single portion at ambient temperature. After 12 h of stirring the reaction mixture was filtered through a pad of celite. After removal of all volatiles under reduced pressure, the title compound (I) was obtained as a colorless solid (275 mg, 0.184 mmol, 83% based on butane-1,4-dicarboxyl-1,4-dicarboxylatodisilver(I). Slow diffusion of pentane into a dichloromethane solution containing (I) at ambient temperature afforded colourless crystals of (I). M.p. 398 K (decomp.). 1H NMR (500 MHz, CDCl3, 298 K, p.p.m.): δ = 7.39–7.29 (m, 60H, C6H5), 2.93 (m, 2H, CH), 2.04 (m, 4H, CH2). 13C{1H} NMR (126 MHz, CDCl3, 298 K, p.p.m.): δ = 175.9 (s, C=O), 134.0 (d, 2JPC = 16.1 Hz, o-C6H5), 131.7 (d, 1JPC = 29.3 Hz, Ci-C6H5), 130.6 (s, p-C6H5), 129.1 (d, 3JPC = 9.3 Hz, m-C6H5), 50.8 (s, CH), 29.6 (s, CH2). 31P{1H} NMR (203 MHz, CDCl3, 298 K, p.p.m.): δ = 10.3 (s). IR (KBr, cm−1): ν = 3108 (w), 2993 (w), 1751 (s), 1494 (vs), 1106 (s), 752 (vs), 701 (vs).
6. Refinement
Crystal data, data collection and structure . C-bonded hydrogen atoms were placed in calculated positions and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C) and a C—H distance of 0.93 Å for aromatic (AFIX 43), 0.98 Å for methine (AFIX 13) and 0.97 Å for methylene H atoms (AFIX 23). The same applies for the O-bonded H atom; however, the torsion angle was derived from electron density (AFIX 147). The structure contains three molecules of dichloromethane as the solvent. Both crystallographically independent molecules consist of two moieties each. One molecule was refined as disordered over two positions (C1S; C1SB) with occupancies of 92.7 (2) and 7.3 (3)%, respectively. The less prevalent moiety of C1SB is located close to a crystallographic inversion centre and symmetry-related pairs are mutually exclusive. The second disordered molecule is located directly atop of another inversion centre with an occupancy of 0.5 (Fig. 1), with the inversion centre located near the C2S and Cl1B atoms. The less-occupied methylene chloride molecule was restrained to have a geometry similar to that of its major moiety counterpart by using the SAME command. Uij components of ADPs for C1S C1SB Cl1B and Cl2B were restrained to be similar if closer than 1.7 Å (SIMU restraint, McArdle, 1995; Sheldrick, 2008).
details are summarized in Table 2Supporting information
CCDC reference: 1447419
10.1107/S2056989016000797/zl2653sup1.cif
contains datablocks I, 1R. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016000797/zl2653Isup2.hkl
Silver precursors [e.g. silver(I) carboxylates and silver(I) β-diketonates] exhibit a wide range of applications, for instance the formation of thin, metallic layers by means of CVD (Chemical Vapour Deposition) or CCVD (Combustion Chemical Vapour Deposition) (Struppert et al., 2010; Jakob et al., 2006; Schmidt et al., 2005; Lang & Buschbeck, 2009; Lang, 2011; Lang & Dietrich, 2013; Chi & Lu, 2001), spin coating (Jakob et al., 2010) or inkjet printing (Jahn et al., 2010a,b; Gäbler et al., 2016). The respective silver layers show closed and homogeneous silver films and therefore possess a good conductivity. In addition, silver carboxylates such as [AgO2CR]n (n is the degree of aggregation) allow for the formation and stabilization of silver nanoparticles, which can, for example, be used for catalytic processes (Steffan et al., 2009). They are also used in biological studies (Fourie et al., 2012; Langner et al., 2012).
A further application of silver carboxylate precursors includes their use for joining of bulk copper to produce metallic interconnects, for example in microelectronic applications (Oestreicher et al., 2012, 2013).
We anticipate that a metal oxide layer will need to be removed during such a silver-facilitated copper-joining process. Leaving some of the carboxyl groups of the silver precursor uncoordinated is expected to assist in this process. In the case of sparingly soluble silver carboxylates, the solubility in common organic solvents can be increased through addition of
such as e.g. triphenyl phosphane. In this context, the title compound (I) was prepared by reaction of the disilver salt of butane-1,1,4,4-tetracarboxyl acid (BTCA) with triphenylphosphane.The title compound (I) crystallizes in the triclinic 1. The contains a half molecule of butane-1,4-dicarboxy-1,4-dicarboxylate bonded to a bis(triphenylphosphanyl)silver moiety and 1.5 molecules of dichloromethane. The inversion centre to build up the whole disilver complex is located in the middle of the C4—C4' bond (Fig. 1; (A): –x, –y + 1, –z + 2). The three molecules of dichloromethane are also located on or nearby inversion centres (Fig. 1; C2S, (B): –x + 1, –y + 1, –z; C1S, C1SB, –x + 1, –y, –z; see section for details).
PThe butane tetracarboxylic moiety contains an intramolecular hydrogen bond between the O3 atom of the HO2C-carboxy group and the O2 atom that is in interaction with Ag1 (Fig. 1, Table 1), resulting in a boat-type conformation including the C1, C2 and C3 atoms, due to a σ-bonded, whereas O2 exhibits a weaker interaction with an increased O2···Ag1 distance of 2.6872 (19) Å, probably due to the involvement in the hydrogen bond.
torsion of the C1—O2 and C3—O3 bonds by 6.3 (2)°. Within the H-bearing carboxylato substituent a distinction between the C,O single [1.321 (3) Å] and double [1.205 (3) Å] bonds can be observed. The C1 labeled carboxylato group exhibits an unsymmetrically bidendate binding to Ag1. Therefore, O1 is, with 2.3305 (17) Å,The Ag1 atom exhibits a somewhat distorted trigonal–planar coordination environment, whereby the two
enclose an increased P—Ag—P angle of 128.56 (2)°, in contrast to the O1—Ag1—P angles of 117.69 (5) (P1) and 113.27 (5)° (P2). The weak interaction to the O2 atom occurs below this AgP2 plane with an interaction to the CO2 group of 67.38 (17)° with, however, two nearly equal C1—O1/O2 bond lengths of 1.251 (3) (O1) and 1.261 (3) Å (O2). Both reveal an eclipsed conformation regarding the phenyl rings of 2.09 (10)°.The packing of (I) consists of a layer-type structure parallel to (101), which is supported by weak T-shaped π–π interactions (Sinnokrot et al., 2002) between the C5–C10 and the C35–C40 labeled phenyl rings with centroid–centroid distances of 4.8497 (16) Å [α = 77.40 (13)°] at both sides of the molecules, forming a ladder-type arrangement parallel to [010], the b axis (Fig. 2). These ladders are packed along (101) through the phenyl rings, however, without showing any further π–π or C—H interactions.
One dichloromethane is stabilized by a non-classical hydrogen-bridge bond from C1S, as the hydrogen-bond donor, to the hydroxyl O3 atom (Table 1), which also acts as hydrogen-bridge bond donor in an intramolecular classical bridge bond (see Structural commentary).
Further intermolecular interactions involving hydrogen bonds or O···Ag interactions are not observed.
In the CSD database (Groom & Allen, 2014; Version 5.36), only two acyclic silver tetracarboxylates with six-membered carbon backbones are reported. These are butane-1,2,3,4-tetracarboxylato silver compounds containing further nitrogen and oxygen donor ligands, coordinating the silver ions either in a tetrahedral or a T-shaped trigonal fashion (Sun et al., 2010). Three aliphatic cyclohexane silver complexes with four to six carboxylate groups are also known. Within those, the silver ions are also coordinated by additional ligands such as ammonia and water and possess distorted tetrahedral coordination or Y-shaped geometries (Wang et al., 2006, 2009). For six-membered unbranched acyclic silver dicarboxylates derived from adipic acid, more crystal structures are reported compared to the respective tetracarboxylato derivatives. Several coordination geometries for the silver atoms are reported such as T-shaped (Wu et al., 1995), tetrahedral (Li et al., 2011) or trigonal–planar environments (Liu et al., 2009) containing nitrogen, oxygen or sulfur donor ligands. To the best of our knowledge, the title compound (I) is the only example of a silver tetracarboxylate consisting of a six-membered carbon backbone and containing a silver–phosphorus bond. In contrast to the title compound, which exists as a monomer presumably due to the steric shielding by triphenyl phosphane, all of the above-mentioned complexes exist as polymeric networks, formed by bridging through the different donor atoms of the ligands. For example, by using silver dicarboxylates frequently the formation of dimeric sub-units can take place, which in turn results in the construction of polymeric systems (Wu et al., 1995). Structures containing water molecules coordinating to the Ag ions results in the formation of a further polymeric hydrogen bridge-bond network, also including carboxylato moieties (Wang et al., 2006, 2009).
\ Synthesis of butane-1,4-dicarboxyl-1,4-dicarboxylatodisilver(I):
Potassium tert-butanolate (192 mg, 1.71 mmol) was added to a solution of butane-1,1,4,4-tetracarboxyl acid (200 mg, 0.854 mmol) in 5 ml of tetrahydrofuran. After stirring overnight at ambient temperature, the reaction mixture was filtered off and the residue was washed trice with tetrahydrofuran (10 ml each) and dried under vacuum (yield 243 mg). Subsequently, the obtained colorless solid (243 mg, 0.783 mmol) was dissolved in water (15 ml) and added dropwise to a solution of silver nitrate (267 mg, 1.57 mmol) in water (8 ml). After 12 h of stirring the colorless precipitate was filtered off and washed twice with water (10 ml each) and dried in a desiccator. The desired colorless butane-1,4-dicarboxyl-1,4-dicarboxylatodisilver(I) was obtained in a yield of 71%, based on butane-1,1,4,4-tetracarboxyl acid (271 mg, 0.608 mmol). Analysis calculated for C8H8Ag2O8 (447.88): C, 21.45; H, 1.80. Found: C, 21.49; H, 1.68. IR (KBr, cm−1): ν = 2977 (m), 2903 (m), 2461 (m), 1660 (s), 1549 (vs), 1380 (s), 1257 (s), 1069 (s), 955 (m), 711 (m).
Synthesis of butane-1,4-dicarboxy-1,4-dicarboxylato-tetrakis(triphenylphosphine-\ κP)disilver(I):
To a suspension of butane-1,4-dicarboxyl-1,4-dicarboxylatodisilver(I) (100 mg, 0.223 mmol) in 10 ml of tetrahydrofuran, PPh3 (234 mg, 0.892 mmol) was added in a single portion at ambient temperature. After 12 h of stirring the reaction mixture was filtered through a pad of celite. After removal of all volatiles under reduced pressure, the title compound (I) was obtained as a colorless solid (275 mg, 0.184 mmol, 83% based on butane-1,4-dicarboxyl-1,4-dicarboxylatodisilver(I). Slow diffusion of pentane into a dichloromethane solution containing (I) at ambient temperature afforded colourless crystals of (I). M.p. 398 K (decomp.). 1H NMR (500 MHz, CDCl3, 298 K, p.p.m.): δ = 7.39–7.29 (m, 60H, C6H5), 2.93 (m, 2H, CH), 2.04 (m, 4H, CH2). 13C{1H} NMR (126 MHz, CDCl3, 298 K, p.p.m.): δ = 175.9 (s, C=O), 134.0 (d, 2JPC = 16.1 Hz, o-C6H5), 131.7 (d, 1JPC = 29.3 Hz, Ci-C6H5), 130.6 (s, p-C6H5), 129.1 (d, 3JPC = 9.3 Hz, m-C6H5), 50.8 (s, CH), 29.6 (s, CH2). 31P{1H} NMR (203 MHz, CDCl3, 298 K, p.p.m.): δ = 10.3 (s). IR (KBr, cm−1): ν = 3108 (w), 2993 (w), 1751 (s), 1494 (vs), 1106 (s), 752 (vs), 701 (vs).
Crystal data, data collection and structure
details are summarized in Table 2. C-bonded hydrogen atoms were placed in calculated positions and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C) and a C—H distance of 0.93 Å for aromatic (AFIX 43), 0.98 Å for methine (AFIX 13) and 0.97 Å for methylene H atoms (AFIX 23). The same applies for the O-bonded H atom; however, the torsion angle was derived from electron density (AFIX 147). The structure contains three molecules of dichloromethane as the packing solvent. Both crystallographically independent molecules consist of two moieties each. One molecule was refined as disordered over two positions (C1S; C1SB) with occupancies of 92.7 (2) and 7.3 (3)%, respectively. The less prevalent moiety of C1SB is located close to a crystallographic inversion centre and symmetry-related pairs are mutually exclusive. The second disordered molecule is located directly atop of another inversion centre with an occupancy of 0.5 (Fig. 1), with the inversion centre located near the C2S and Cl1B atoms. The less-occupied methylene chloride molecule was restrained to have a geometry similar to that of its major moiety counterpart by using the SAME command. Uij components of ADPs for C1S C1SB Cl1B and Cl2B were restrained to be similar if closer than 1.7 Å (SIMU restraint, McArdle, 1995; Sheldrick, 2008).Silver precursors [e.g. silver(I) carboxylates and silver(I) β-diketonates] exhibit a wide range of applications, for instance the formation of thin, metallic layers by means of CVD (Chemical Vapour Deposition) or CCVD (Combustion Chemical Vapour Deposition) (Struppert et al., 2010; Jakob et al., 2006; Schmidt et al., 2005; Lang & Buschbeck, 2009; Lang, 2011; Lang & Dietrich, 2013; Chi & Lu, 2001), spin coating (Jakob et al., 2010) or inkjet printing (Jahn et al., 2010a,b; Gäbler et al., 2016). The respective silver layers show closed and homogeneous silver films and therefore possess a good conductivity. In addition, silver carboxylates such as [AgO2CR]n (n is the degree of aggregation) allow for the formation and stabilization of silver nanoparticles, which can, for example, be used for catalytic processes (Steffan et al., 2009). They are also used in biological studies (Fourie et al., 2012; Langner et al., 2012).
A further application of silver carboxylate precursors includes their use for joining of bulk copper to produce metallic interconnects, for example in microelectronic applications (Oestreicher et al., 2012, 2013).
We anticipate that a metal oxide layer will need to be removed during such a silver-facilitated copper-joining process. Leaving some of the carboxyl groups of the silver precursor uncoordinated is expected to assist in this process. In the case of sparingly soluble silver carboxylates, the solubility in common organic solvents can be increased through addition of
such as e.g. triphenyl phosphane. In this context, the title compound (I) was prepared by reaction of the disilver salt of butane-1,1,4,4-tetracarboxyl acid (BTCA) with triphenylphosphane.The title compound (I) crystallizes in the triclinic 1. The contains a half molecule of butane-1,4-dicarboxy-1,4-dicarboxylate bonded to a bis(triphenylphosphanyl)silver moiety and 1.5 molecules of dichloromethane. The inversion centre to build up the whole disilver complex is located in the middle of the C4—C4' bond (Fig. 1; (A): –x, –y + 1, –z + 2). The three molecules of dichloromethane are also located on or nearby inversion centres (Fig. 1; C2S, (B): –x + 1, –y + 1, –z; C1S, C1SB, –x + 1, –y, –z; see section for details).
PThe butane tetracarboxylic moiety contains an intramolecular hydrogen bond between the O3 atom of the HO2C-carboxy group and the O2 atom that is in interaction with Ag1 (Fig. 1, Table 1), resulting in a boat-type conformation including the C1, C2 and C3 atoms, due to a σ-bonded, whereas O2 exhibits a weaker interaction with an increased O2···Ag1 distance of 2.6872 (19) Å, probably due to the involvement in the hydrogen bond.
torsion of the C1—O2 and C3—O3 bonds by 6.3 (2)°. Within the H-bearing carboxylato substituent a distinction between the C,O single [1.321 (3) Å] and double [1.205 (3) Å] bonds can be observed. The C1 labeled carboxylato group exhibits an unsymmetrically bidendate binding to Ag1. Therefore, O1 is, with 2.3305 (17) Å,The Ag1 atom exhibits a somewhat distorted trigonal–planar coordination environment, whereby the two
enclose an increased P—Ag—P angle of 128.56 (2)°, in contrast to the O1—Ag1—P angles of 117.69 (5) (P1) and 113.27 (5)° (P2). The weak interaction to the O2 atom occurs below this AgP2 plane with an interaction to the CO2 group of 67.38 (17)° with, however, two nearly equal C1—O1/O2 bond lengths of 1.251 (3) (O1) and 1.261 (3) Å (O2). Both reveal an eclipsed conformation regarding the phenyl rings of 2.09 (10)°.The packing of (I) consists of a layer-type structure parallel to (101), which is supported by weak T-shaped π–π interactions (Sinnokrot et al., 2002) between the C5–C10 and the C35–C40 labeled phenyl rings with centroid–centroid distances of 4.8497 (16) Å [α = 77.40 (13)°] at both sides of the molecules, forming a ladder-type arrangement parallel to [010], the b axis (Fig. 2). These ladders are packed along (101) through the phenyl rings, however, without showing any further π–π or C—H interactions.
One dichloromethane is stabilized by a non-classical hydrogen-bridge bond from C1S, as the hydrogen-bond donor, to the hydroxyl O3 atom (Table 1), which also acts as hydrogen-bridge bond donor in an intramolecular classical bridge bond (see Structural commentary).
Further intermolecular interactions involving hydrogen bonds or O···Ag interactions are not observed.
In the CSD database (Groom & Allen, 2014; Version 5.36), only two acyclic silver tetracarboxylates with six-membered carbon backbones are reported. These are butane-1,2,3,4-tetracarboxylato silver compounds containing further nitrogen and oxygen donor ligands, coordinating the silver ions either in a tetrahedral or a T-shaped trigonal fashion (Sun et al., 2010). Three aliphatic cyclohexane silver complexes with four to six carboxylate groups are also known. Within those, the silver ions are also coordinated by additional ligands such as ammonia and water and possess distorted tetrahedral coordination or Y-shaped geometries (Wang et al., 2006, 2009). For six-membered unbranched acyclic silver dicarboxylates derived from adipic acid, more crystal structures are reported compared to the respective tetracarboxylato derivatives. Several coordination geometries for the silver atoms are reported such as T-shaped (Wu et al., 1995), tetrahedral (Li et al., 2011) or trigonal–planar environments (Liu et al., 2009) containing nitrogen, oxygen or sulfur donor ligands. To the best of our knowledge, the title compound (I) is the only example of a silver tetracarboxylate consisting of a six-membered carbon backbone and containing a silver–phosphorus bond. In contrast to the title compound, which exists as a monomer presumably due to the steric shielding by triphenyl phosphane, all of the above-mentioned complexes exist as polymeric networks, formed by bridging through the different donor atoms of the ligands. For example, by using silver dicarboxylates frequently the formation of dimeric sub-units can take place, which in turn results in the construction of polymeric systems (Wu et al., 1995). Structures containing water molecules coordinating to the Ag ions results in the formation of a further polymeric hydrogen bridge-bond network, also including carboxylato moieties (Wang et al., 2006, 2009).
\ Synthesis of butane-1,4-dicarboxyl-1,4-dicarboxylatodisilver(I):
Potassium tert-butanolate (192 mg, 1.71 mmol) was added to a solution of butane-1,1,4,4-tetracarboxyl acid (200 mg, 0.854 mmol) in 5 ml of tetrahydrofuran. After stirring overnight at ambient temperature, the reaction mixture was filtered off and the residue was washed trice with tetrahydrofuran (10 ml each) and dried under vacuum (yield 243 mg). Subsequently, the obtained colorless solid (243 mg, 0.783 mmol) was dissolved in water (15 ml) and added dropwise to a solution of silver nitrate (267 mg, 1.57 mmol) in water (8 ml). After 12 h of stirring the colorless precipitate was filtered off and washed twice with water (10 ml each) and dried in a desiccator. The desired colorless butane-1,4-dicarboxyl-1,4-dicarboxylatodisilver(I) was obtained in a yield of 71%, based on butane-1,1,4,4-tetracarboxyl acid (271 mg, 0.608 mmol). Analysis calculated for C8H8Ag2O8 (447.88): C, 21.45; H, 1.80. Found: C, 21.49; H, 1.68. IR (KBr, cm−1): ν = 2977 (m), 2903 (m), 2461 (m), 1660 (s), 1549 (vs), 1380 (s), 1257 (s), 1069 (s), 955 (m), 711 (m).
Synthesis of butane-1,4-dicarboxy-1,4-dicarboxylato-tetrakis(triphenylphosphine-\ κP)disilver(I):
To a suspension of butane-1,4-dicarboxyl-1,4-dicarboxylatodisilver(I) (100 mg, 0.223 mmol) in 10 ml of tetrahydrofuran, PPh3 (234 mg, 0.892 mmol) was added in a single portion at ambient temperature. After 12 h of stirring the reaction mixture was filtered through a pad of celite. After removal of all volatiles under reduced pressure, the title compound (I) was obtained as a colorless solid (275 mg, 0.184 mmol, 83% based on butane-1,4-dicarboxyl-1,4-dicarboxylatodisilver(I). Slow diffusion of pentane into a dichloromethane solution containing (I) at ambient temperature afforded colourless crystals of (I). M.p. 398 K (decomp.). 1H NMR (500 MHz, CDCl3, 298 K, p.p.m.): δ = 7.39–7.29 (m, 60H, C6H5), 2.93 (m, 2H, CH), 2.04 (m, 4H, CH2). 13C{1H} NMR (126 MHz, CDCl3, 298 K, p.p.m.): δ = 175.9 (s, C=O), 134.0 (d, 2JPC = 16.1 Hz, o-C6H5), 131.7 (d, 1JPC = 29.3 Hz, Ci-C6H5), 130.6 (s, p-C6H5), 129.1 (d, 3JPC = 9.3 Hz, m-C6H5), 50.8 (s, CH), 29.6 (s, CH2). 31P{1H} NMR (203 MHz, CDCl3, 298 K, p.p.m.): δ = 10.3 (s). IR (KBr, cm−1): ν = 3108 (w), 2993 (w), 1751 (s), 1494 (vs), 1106 (s), 752 (vs), 701 (vs).
detailsCrystal data, data collection and structure
details are summarized in Table 2. C-bonded hydrogen atoms were placed in calculated positions and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C) and a C—H distance of 0.93 Å for aromatic (AFIX 43), 0.98 Å for methine (AFIX 13) and 0.97 Å for methylene H atoms (AFIX 23). The same applies for the O-bonded H atom; however, the torsion angle was derived from electron density (AFIX 147). The structure contains three molecules of dichloromethane as the packing solvent. Both crystallographically independent molecules consist of two moieties each. One molecule was refined as disordered over two positions (C1S; C1SB) with occupancies of 92.7 (2) and 7.3 (3)%, respectively. The less prevalent moiety of C1SB is located close to a crystallographic inversion centre and symmetry-related pairs are mutually exclusive. The second disordered molecule is located directly atop of another inversion centre with an occupancy of 0.5 (Fig. 1), with the inversion centre located near the C2S and Cl1B atoms. The less-occupied methylene chloride molecule was restrained to have a geometry similar to that of its major moiety counterpart by using the SAME command. Uij components of ADPs for C1S C1SB Cl1B and Cl2B were restrained to be similar if closer than 1.7 Å (SIMU restraint, McArdle, 1995; Sheldrick, 2008).Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell
CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS2013 (Sheldrick, 200); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level, including the intramolecular hydrogen bonds. All non-O-bonded H atoms and the labels of the o-, m- and p-phenyl C atoms have been omitted for clarity. [Symmetry codes: (A) −x, −y + 1, −z + 2; (B) −x + 1, −y + 1, −z; (C) −x + 1, −y, −z.] | |
Fig. 2. Intermolecular T-shaped π–π interactions (blue) between the centroids (D) of the C5–C10 and C35–C40 labeled phenyl rings in the crystal structure of (I). All H atoms and solvent molecules have been omitted for clarity. D—D = 4.8497 (16) Å; α = 77.40 (13) °. [Symmetry codes: (') −x, −y + 1, −z + 2; (A) x, 1/2 − y, z − 1/2; (B) x, y, x − 1.] |
[Ag2(C8H8O8)(C18H15P)4]·3CH2Cl2 | Z = 1 |
Mr = 1751.74 | F(000) = 892 |
Triclinic, P1 | Dx = 1.517 Mg m−3 |
a = 10.0279 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.9540 (4) Å | Cell parameters from 12088 reflections |
c = 16.8190 (5) Å | θ = 3.4–28.8° |
α = 112.306 (3)° | µ = 0.86 mm−1 |
β = 96.080 (3)° | T = 110 K |
γ = 103.601 (3)° | Block, colorless |
V = 1917.80 (11) Å3 | 0.3 × 0.3 × 0.2 mm |
Oxford Gemini S diffractometer | Rint = 0.024 |
ω scans | θmax = 28.9°, θmin = 2.9° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | h = −13→12 |
Tmin = 0.889, Tmax = 1.000 | k = −17→17 |
21441 measured reflections | l = −22→20 |
8700 independent reflections | 2 standard reflections every 50 reflections |
7959 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.032P)2 + 2.6912P] where P = (Fo2 + 2Fc2)/3 |
8700 reflections | (Δ/σ)max = 0.001 |
507 parameters | Δρmax = 2.28 e Å−3 |
27 restraints | Δρmin = −0.61 e Å−3 |
[Ag2(C8H8O8)(C18H15P)4]·3CH2Cl2 | γ = 103.601 (3)° |
Mr = 1751.74 | V = 1917.80 (11) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.0279 (3) Å | Mo Kα radiation |
b = 12.9540 (4) Å | µ = 0.86 mm−1 |
c = 16.8190 (5) Å | T = 110 K |
α = 112.306 (3)° | 0.3 × 0.3 × 0.2 mm |
β = 96.080 (3)° |
Oxford Gemini S diffractometer | 7959 reflections with I > 2σ(I) |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | Rint = 0.024 |
Tmin = 0.889, Tmax = 1.000 | 2 standard reflections every 50 reflections |
21441 measured reflections | intensity decay: none |
8700 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | 27 restraints |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.06 | Δρmax = 2.28 e Å−3 |
8700 reflections | Δρmin = −0.61 e Å−3 |
507 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.1098 (3) | 0.4419 (2) | 0.82508 (15) | 0.0190 (5) | |
C2 | 0.0325 (2) | 0.5106 (2) | 0.88968 (15) | 0.0174 (4) | |
H2 | −0.0699 | 0.4812 | 0.8615 | 0.021* | |
C3 | 0.0822 (3) | 0.6429 (2) | 0.91901 (16) | 0.0247 (5) | |
C4 | 0.0521 (3) | 0.4833 (2) | 0.97147 (15) | 0.0189 (5) | |
H4A | 0.0402 | 0.3987 | 0.9518 | 0.023* | |
H4B | 0.1489 | 0.5265 | 1.0070 | 0.023* | |
C5 | 0.2398 (2) | −0.00432 (19) | 0.61984 (14) | 0.0158 (4) | |
C6 | 0.1010 (3) | −0.0530 (2) | 0.57113 (16) | 0.0204 (5) | |
H6 | 0.0276 | −0.0297 | 0.5975 | 0.024* | |
C7 | 0.0703 (3) | −0.1351 (2) | 0.48448 (16) | 0.0232 (5) | |
H7 | −0.0241 | −0.1678 | 0.4518 | 0.028* | |
C8 | 0.1774 (3) | −0.1698 (2) | 0.44511 (16) | 0.0243 (5) | |
H8 | 0.1562 | −0.2258 | 0.3857 | 0.029* | |
C9 | 0.3145 (3) | −0.1225 (2) | 0.49301 (16) | 0.0231 (5) | |
H9 | 0.3875 | −0.1461 | 0.4663 | 0.028* | |
C10 | 0.3465 (3) | −0.0403 (2) | 0.58043 (16) | 0.0193 (5) | |
H10 | 0.4409 | −0.0088 | 0.6131 | 0.023* | |
C11 | 0.4578 (2) | 0.1469 (2) | 0.77394 (15) | 0.0173 (4) | |
C12 | 0.5538 (3) | 0.2188 (2) | 0.74783 (17) | 0.0230 (5) | |
H12 | 0.5203 | 0.2509 | 0.7103 | 0.028* | |
C13 | 0.6972 (3) | 0.2435 (2) | 0.77632 (17) | 0.0256 (5) | |
H13 | 0.7616 | 0.2911 | 0.7575 | 0.031* | |
C14 | 0.7467 (3) | 0.1989 (2) | 0.83205 (18) | 0.0280 (6) | |
H14 | 0.8450 | 0.2153 | 0.8512 | 0.034* | |
C15 | 0.6527 (3) | 0.1299 (3) | 0.86010 (19) | 0.0314 (6) | |
H15 | 0.6869 | 0.1010 | 0.8997 | 0.038* | |
C16 | 0.5089 (3) | 0.1029 (2) | 0.83059 (17) | 0.0251 (5) | |
H16 | 0.4451 | 0.0544 | 0.8491 | 0.030* | |
C17 | 0.1720 (2) | 0.0459 (2) | 0.78922 (15) | 0.0172 (4) | |
C18 | 0.1697 (3) | −0.0662 (2) | 0.78067 (16) | 0.0222 (5) | |
H18 | 0.2230 | −0.1071 | 0.7440 | 0.027* | |
C19 | 0.0898 (3) | −0.1177 (2) | 0.82571 (17) | 0.0269 (5) | |
H19 | 0.0880 | −0.1940 | 0.8196 | 0.032* | |
C20 | 0.0124 (3) | −0.0581 (2) | 0.87957 (17) | 0.0266 (5) | |
H20 | −0.0423 | −0.0938 | 0.9103 | 0.032* | |
C21 | 0.0144 (3) | 0.0534 (2) | 0.88891 (17) | 0.0256 (5) | |
H21 | −0.0382 | 0.0942 | 0.9263 | 0.031* | |
C22 | 0.0939 (3) | 0.1055 (2) | 0.84336 (16) | 0.0215 (5) | |
H22 | 0.0948 | 0.1816 | 0.8493 | 0.026* | |
C23 | 0.2912 (2) | 0.2770 (2) | 0.50087 (15) | 0.0162 (4) | |
C24 | 0.2945 (3) | 0.1622 (2) | 0.47850 (16) | 0.0207 (5) | |
H24 | 0.3061 | 0.1354 | 0.5234 | 0.025* | |
C25 | 0.2812 (3) | 0.0869 (2) | 0.39126 (17) | 0.0239 (5) | |
H25 | 0.2846 | 0.0094 | 0.3768 | 0.029* | |
C26 | 0.2629 (3) | 0.1250 (2) | 0.32544 (17) | 0.0259 (5) | |
H26 | 0.2542 | 0.0739 | 0.2658 | 0.031* | |
C27 | 0.2574 (3) | 0.2385 (2) | 0.34706 (17) | 0.0276 (6) | |
H27 | 0.2436 | 0.2644 | 0.3019 | 0.033* | |
C28 | 0.2719 (3) | 0.3141 (2) | 0.43393 (16) | 0.0220 (5) | |
H28 | 0.2686 | 0.3917 | 0.4480 | 0.026* | |
C29 | 0.5028 (2) | 0.4324 (2) | 0.65811 (15) | 0.0175 (4) | |
C30 | 0.5974 (3) | 0.4021 (2) | 0.60549 (16) | 0.0212 (5) | |
H30 | 0.5636 | 0.3484 | 0.5454 | 0.025* | |
C31 | 0.7417 (3) | 0.4499 (2) | 0.64032 (18) | 0.0245 (5) | |
H31 | 0.8060 | 0.4283 | 0.6041 | 0.029* | |
C32 | 0.7910 (3) | 0.5285 (2) | 0.72730 (18) | 0.0269 (5) | |
H32 | 0.8893 | 0.5623 | 0.7507 | 0.032* | |
C33 | 0.6974 (3) | 0.5585 (2) | 0.78088 (17) | 0.0285 (6) | |
H33 | 0.7319 | 0.6123 | 0.8409 | 0.034* | |
C34 | 0.5535 (3) | 0.5101 (2) | 0.74688 (16) | 0.0240 (5) | |
H34 | 0.4896 | 0.5297 | 0.7838 | 0.029* | |
C35 | 0.2611 (2) | 0.4971 (2) | 0.61527 (14) | 0.0171 (4) | |
C36 | 0.1241 (3) | 0.4982 (2) | 0.61812 (18) | 0.0252 (5) | |
H36 | 0.0602 | 0.4370 | 0.6253 | 0.030* | |
C37 | 0.0796 (3) | 0.5889 (2) | 0.6105 (2) | 0.0303 (6) | |
H37 | −0.0151 | 0.5885 | 0.6114 | 0.036* | |
C38 | 0.1724 (3) | 0.6791 (2) | 0.60168 (16) | 0.0253 (5) | |
H38 | 0.1413 | 0.7401 | 0.5955 | 0.030* | |
C39 | 0.3101 (3) | 0.6805 (2) | 0.60184 (17) | 0.0248 (5) | |
H39 | 0.3749 | 0.7438 | 0.5977 | 0.030* | |
C40 | 0.3546 (3) | 0.5896 (2) | 0.60809 (17) | 0.0223 (5) | |
H40 | 0.4495 | 0.5906 | 0.6075 | 0.027* | |
P1 | 0.27220 (6) | 0.11490 (5) | 0.72910 (4) | 0.01518 (12) | |
P2 | 0.31285 (6) | 0.37213 (5) | 0.61693 (4) | 0.01519 (12) | |
Ag1 | 0.22109 (2) | 0.27730 (2) | 0.70903 (2) | 0.01622 (6) | |
O1 | 0.04100 (19) | 0.34138 (15) | 0.76927 (11) | 0.0239 (4) | |
O2 | 0.23936 (19) | 0.48772 (17) | 0.83418 (12) | 0.0301 (4) | |
O3 | 0.2146 (2) | 0.68777 (18) | 0.91847 (15) | 0.0409 (5) | |
H3 | 0.2542 | 0.6350 | 0.9052 | 0.061* | |
O4 | 0.0070 (2) | 0.70357 (16) | 0.94320 (13) | 0.0333 (4) | |
C1S | 0.4951 (4) | 0.1726 (4) | 0.0721 (3) | 0.0525 (11) | 0.928 (2) |
H1S1 | 0.5689 | 0.1417 | 0.0457 | 0.063* | 0.928 (2) |
H1S2 | 0.4983 | 0.2447 | 0.0638 | 0.063* | 0.928 (2) |
Cl1 | 0.33022 (9) | 0.06889 (12) | 0.01685 (7) | 0.0647 (4) | 0.928 (2) |
Cl2 | 0.53101 (12) | 0.20717 (8) | 0.18454 (6) | 0.0474 (3) | 0.928 (2) |
C1SB | 0.525 (5) | 0.125 (3) | 0.069 (3) | 0.069 (7) | 0.072 (2) |
H1S3 | 0.6161 | 0.1301 | 0.1016 | 0.083* | 0.072 (2) |
H1S4 | 0.5460 | 0.1770 | 0.0381 | 0.083* | 0.072 (2) |
Cl1B | 0.451 (2) | −0.0184 (18) | −0.0110 (13) | 0.088 (6) | 0.072 (2) |
Cl2B | 0.429 (3) | 0.183 (2) | 0.1455 (16) | 0.112 (7) | 0.072 (2) |
C2S | 0.5061 (9) | 0.4570 (8) | −0.0394 (6) | 0.060 (2) | 0.5 |
H2S1 | 0.4788 | 0.4427 | −0.1019 | 0.072* | 0.5 |
H2S2 | 0.5940 | 0.4361 | −0.0319 | 0.072* | 0.5 |
Cl3 | 0.3762 (2) | 0.3690 (2) | −0.01470 (16) | 0.0548 (5) | 0.5 |
Cl4 | 0.5373 (5) | 0.6054 (2) | 0.0271 (3) | 0.1237 (17) | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0254 (12) | 0.0211 (12) | 0.0169 (11) | 0.0116 (9) | 0.0102 (9) | 0.0105 (9) |
C2 | 0.0230 (11) | 0.0167 (11) | 0.0149 (10) | 0.0077 (9) | 0.0082 (9) | 0.0070 (9) |
C3 | 0.0380 (14) | 0.0213 (13) | 0.0158 (11) | 0.0076 (11) | 0.0087 (10) | 0.0087 (10) |
C4 | 0.0236 (11) | 0.0206 (12) | 0.0174 (11) | 0.0112 (9) | 0.0094 (9) | 0.0092 (9) |
C5 | 0.0237 (11) | 0.0118 (10) | 0.0156 (10) | 0.0066 (9) | 0.0074 (9) | 0.0080 (8) |
C6 | 0.0230 (12) | 0.0206 (12) | 0.0214 (11) | 0.0085 (9) | 0.0081 (9) | 0.0109 (10) |
C7 | 0.0250 (12) | 0.0215 (12) | 0.0210 (12) | 0.0037 (10) | 0.0011 (9) | 0.0097 (10) |
C8 | 0.0388 (14) | 0.0169 (12) | 0.0179 (11) | 0.0099 (10) | 0.0077 (10) | 0.0067 (9) |
C9 | 0.0336 (13) | 0.0204 (12) | 0.0227 (12) | 0.0149 (10) | 0.0149 (10) | 0.0105 (10) |
C10 | 0.0239 (12) | 0.0166 (11) | 0.0216 (11) | 0.0089 (9) | 0.0086 (9) | 0.0098 (9) |
C11 | 0.0211 (11) | 0.0149 (11) | 0.0165 (10) | 0.0072 (9) | 0.0057 (9) | 0.0056 (9) |
C12 | 0.0258 (12) | 0.0201 (12) | 0.0247 (12) | 0.0061 (10) | 0.0051 (10) | 0.0117 (10) |
C13 | 0.0241 (12) | 0.0200 (12) | 0.0304 (13) | 0.0032 (10) | 0.0086 (10) | 0.0092 (10) |
C14 | 0.0210 (12) | 0.0267 (14) | 0.0312 (14) | 0.0076 (10) | 0.0020 (10) | 0.0074 (11) |
C15 | 0.0312 (14) | 0.0380 (16) | 0.0314 (14) | 0.0139 (12) | 0.0034 (11) | 0.0200 (13) |
C16 | 0.0264 (13) | 0.0275 (13) | 0.0270 (13) | 0.0088 (10) | 0.0069 (10) | 0.0164 (11) |
C17 | 0.0218 (11) | 0.0156 (11) | 0.0163 (10) | 0.0055 (9) | 0.0061 (9) | 0.0084 (9) |
C18 | 0.0327 (13) | 0.0187 (12) | 0.0195 (11) | 0.0104 (10) | 0.0103 (10) | 0.0096 (9) |
C19 | 0.0390 (15) | 0.0187 (12) | 0.0241 (12) | 0.0046 (11) | 0.0091 (11) | 0.0120 (10) |
C20 | 0.0293 (13) | 0.0307 (14) | 0.0224 (12) | 0.0039 (11) | 0.0087 (10) | 0.0160 (11) |
C21 | 0.0269 (13) | 0.0335 (14) | 0.0223 (12) | 0.0117 (11) | 0.0117 (10) | 0.0148 (11) |
C22 | 0.0258 (12) | 0.0214 (12) | 0.0227 (12) | 0.0116 (10) | 0.0094 (10) | 0.0110 (10) |
C23 | 0.0171 (10) | 0.0168 (11) | 0.0170 (10) | 0.0056 (8) | 0.0077 (8) | 0.0080 (9) |
C24 | 0.0273 (12) | 0.0197 (12) | 0.0211 (11) | 0.0100 (10) | 0.0094 (9) | 0.0120 (10) |
C25 | 0.0299 (13) | 0.0182 (12) | 0.0257 (12) | 0.0095 (10) | 0.0107 (10) | 0.0087 (10) |
C26 | 0.0306 (13) | 0.0236 (13) | 0.0195 (12) | 0.0069 (10) | 0.0071 (10) | 0.0052 (10) |
C27 | 0.0398 (15) | 0.0277 (14) | 0.0190 (12) | 0.0108 (11) | 0.0060 (11) | 0.0134 (10) |
C28 | 0.0286 (13) | 0.0197 (12) | 0.0216 (12) | 0.0094 (10) | 0.0064 (10) | 0.0112 (10) |
C29 | 0.0198 (11) | 0.0173 (11) | 0.0217 (11) | 0.0075 (9) | 0.0062 (9) | 0.0131 (9) |
C30 | 0.0235 (12) | 0.0199 (12) | 0.0240 (12) | 0.0098 (10) | 0.0081 (10) | 0.0106 (10) |
C31 | 0.0212 (12) | 0.0256 (13) | 0.0338 (14) | 0.0100 (10) | 0.0094 (10) | 0.0173 (11) |
C32 | 0.0223 (12) | 0.0292 (14) | 0.0342 (14) | 0.0052 (10) | 0.0022 (10) | 0.0209 (12) |
C33 | 0.0331 (14) | 0.0281 (14) | 0.0207 (12) | 0.0033 (11) | 0.0002 (10) | 0.0116 (11) |
C34 | 0.0286 (13) | 0.0253 (13) | 0.0215 (12) | 0.0087 (10) | 0.0088 (10) | 0.0121 (10) |
C35 | 0.0247 (12) | 0.0156 (11) | 0.0150 (10) | 0.0091 (9) | 0.0077 (9) | 0.0080 (9) |
C36 | 0.0249 (12) | 0.0216 (13) | 0.0360 (14) | 0.0094 (10) | 0.0107 (11) | 0.0167 (11) |
C37 | 0.0270 (13) | 0.0295 (14) | 0.0432 (16) | 0.0162 (11) | 0.0109 (12) | 0.0190 (12) |
C38 | 0.0389 (14) | 0.0198 (12) | 0.0222 (12) | 0.0156 (11) | 0.0084 (11) | 0.0096 (10) |
C39 | 0.0366 (14) | 0.0165 (12) | 0.0266 (13) | 0.0087 (10) | 0.0117 (11) | 0.0127 (10) |
C40 | 0.0264 (12) | 0.0196 (12) | 0.0271 (12) | 0.0095 (10) | 0.0121 (10) | 0.0132 (10) |
P1 | 0.0194 (3) | 0.0141 (3) | 0.0162 (3) | 0.0073 (2) | 0.0073 (2) | 0.0084 (2) |
P2 | 0.0195 (3) | 0.0148 (3) | 0.0162 (3) | 0.0079 (2) | 0.0082 (2) | 0.0089 (2) |
Ag1 | 0.02215 (9) | 0.01473 (9) | 0.01672 (9) | 0.00874 (7) | 0.00930 (6) | 0.00856 (7) |
O1 | 0.0280 (9) | 0.0196 (9) | 0.0237 (9) | 0.0090 (7) | 0.0139 (7) | 0.0053 (7) |
O2 | 0.0226 (9) | 0.0352 (11) | 0.0260 (9) | 0.0061 (8) | 0.0114 (7) | 0.0060 (8) |
O3 | 0.0440 (12) | 0.0228 (10) | 0.0449 (12) | −0.0002 (9) | 0.0212 (10) | 0.0058 (9) |
O4 | 0.0535 (13) | 0.0207 (10) | 0.0303 (10) | 0.0192 (9) | 0.0126 (9) | 0.0100 (8) |
C1S | 0.040 (2) | 0.069 (3) | 0.046 (2) | −0.0016 (19) | 0.0037 (16) | 0.034 (2) |
Cl1 | 0.0314 (5) | 0.1057 (9) | 0.0486 (6) | −0.0137 (5) | −0.0060 (4) | 0.0476 (6) |
Cl2 | 0.0634 (6) | 0.0420 (5) | 0.0313 (4) | 0.0193 (4) | 0.0035 (4) | 0.0091 (4) |
C1SB | 0.063 (9) | 0.077 (9) | 0.062 (9) | 0.007 (9) | 0.008 (8) | 0.033 (9) |
Cl1B | 0.124 (15) | 0.080 (11) | 0.075 (10) | 0.032 (12) | 0.019 (11) | 0.047 (9) |
Cl2B | 0.101 (11) | 0.108 (11) | 0.106 (11) | 0.021 (10) | 0.014 (10) | 0.029 (10) |
C2S | 0.044 (4) | 0.063 (6) | 0.082 (6) | 0.011 (4) | 0.023 (4) | 0.041 (5) |
Cl3 | 0.0507 (11) | 0.0616 (14) | 0.0619 (12) | 0.0195 (10) | 0.0221 (10) | 0.0321 (11) |
Cl4 | 0.165 (4) | 0.0433 (15) | 0.109 (3) | −0.009 (2) | −0.068 (3) | 0.0238 (16) |
C1—O1 | 1.251 (3) | C24—C25 | 1.390 (3) |
C1—O2 | 1.261 (3) | C24—H24 | 0.9500 |
C1—C2 | 1.531 (3) | C25—C26 | 1.385 (4) |
C2—C3 | 1.527 (3) | C25—H25 | 0.9500 |
C2—C4 | 1.550 (3) | C26—C27 | 1.390 (4) |
C2—H2 | 1.0000 | C26—H26 | 0.9500 |
C3—O4 | 1.205 (3) | C27—C28 | 1.385 (4) |
C3—O3 | 1.321 (3) | C27—H27 | 0.9500 |
C4—C4i | 1.520 (4) | C28—H28 | 0.9500 |
C4—H4A | 0.9900 | C29—C30 | 1.388 (3) |
C4—H4B | 0.9900 | C29—C34 | 1.399 (3) |
C5—C10 | 1.397 (3) | C29—P2 | 1.825 (2) |
C5—C6 | 1.400 (3) | C30—C31 | 1.395 (3) |
C5—P1 | 1.831 (2) | C30—H30 | 0.9500 |
C6—C7 | 1.387 (3) | C31—C32 | 1.379 (4) |
C6—H6 | 0.9500 | C31—H31 | 0.9500 |
C7—C8 | 1.395 (4) | C32—C33 | 1.389 (4) |
C7—H7 | 0.9500 | C32—H32 | 0.9500 |
C8—C9 | 1.382 (4) | C33—C34 | 1.389 (4) |
C8—H8 | 0.9500 | C33—H33 | 0.9500 |
C9—C10 | 1.396 (3) | C34—H34 | 0.9500 |
C9—H9 | 0.9500 | C35—C36 | 1.384 (3) |
C10—H10 | 0.9500 | C35—C40 | 1.391 (3) |
C11—C16 | 1.393 (3) | C35—P2 | 1.821 (2) |
C11—C12 | 1.402 (3) | C36—C37 | 1.394 (4) |
C11—P1 | 1.819 (2) | C36—H36 | 0.9500 |
C12—C13 | 1.386 (4) | C37—C38 | 1.380 (4) |
C12—H12 | 0.9500 | C37—H37 | 0.9500 |
C13—C14 | 1.381 (4) | C38—C39 | 1.376 (4) |
C13—H13 | 0.9500 | C38—H38 | 0.9500 |
C14—C15 | 1.389 (4) | C39—C40 | 1.389 (3) |
C14—H14 | 0.9500 | C39—H39 | 0.9500 |
C15—C16 | 1.389 (4) | C40—H40 | 0.9500 |
C15—H15 | 0.9500 | P1—Ag1 | 2.4109 (6) |
C16—H16 | 0.9500 | P2—Ag1 | 2.4433 (6) |
C17—C22 | 1.393 (3) | Ag1—O1 | 2.3305 (17) |
C17—C18 | 1.398 (3) | O3—H3 | 0.8400 |
C17—P1 | 1.819 (2) | C1S—Cl2 | 1.744 (4) |
C18—C19 | 1.387 (3) | C1S—Cl1 | 1.756 (4) |
C18—H18 | 0.9500 | C1S—H1S1 | 0.9900 |
C19—C20 | 1.385 (4) | C1S—H1S2 | 0.9900 |
C19—H19 | 0.9500 | C1SB—Cl2B | 1.73 (2) |
C20—C21 | 1.387 (4) | C1SB—Cl1B | 1.75 (2) |
C20—H20 | 0.9500 | C1SB—H1S3 | 0.9900 |
C21—C22 | 1.395 (3) | C1SB—H1S4 | 0.9900 |
C21—H21 | 0.9500 | C2S—Cl3 | 1.716 (8) |
C22—H22 | 0.9500 | C2S—Cl4 | 1.748 (10) |
C23—C28 | 1.395 (3) | C2S—H2S1 | 0.9900 |
C23—C24 | 1.398 (3) | C2S—H2S2 | 0.9900 |
C23—P2 | 1.826 (2) | ||
O1—C1—O2 | 124.4 (2) | C25—C26—C27 | 119.7 (2) |
O1—C1—C2 | 117.4 (2) | C25—C26—H26 | 120.2 |
O2—C1—C2 | 118.1 (2) | C27—C26—H26 | 120.2 |
C3—C2—C1 | 115.15 (19) | C28—C27—C26 | 120.5 (2) |
C3—C2—C4 | 109.22 (19) | C28—C27—H27 | 119.7 |
C1—C2—C4 | 106.96 (18) | C26—C27—H27 | 119.7 |
C3—C2—H2 | 108.4 | C27—C28—C23 | 120.3 (2) |
C1—C2—H2 | 108.4 | C27—C28—H28 | 119.8 |
C4—C2—H2 | 108.4 | C23—C28—H28 | 119.8 |
O4—C3—O3 | 121.6 (2) | C30—C29—C34 | 119.4 (2) |
O4—C3—C2 | 122.5 (2) | C30—C29—P2 | 122.57 (19) |
O3—C3—C2 | 115.8 (2) | C34—C29—P2 | 118.00 (18) |
C4i—C4—C2 | 112.2 (2) | C29—C30—C31 | 120.4 (2) |
C4i—C4—H4A | 109.2 | C29—C30—H30 | 119.8 |
C2—C4—H4A | 109.2 | C31—C30—H30 | 119.8 |
C4i—C4—H4B | 109.2 | C32—C31—C30 | 119.9 (2) |
C2—C4—H4B | 109.2 | C32—C31—H31 | 120.0 |
H4A—C4—H4B | 107.9 | C30—C31—H31 | 120.0 |
C10—C5—C6 | 119.2 (2) | C31—C32—C33 | 120.2 (2) |
C10—C5—P1 | 123.58 (18) | C31—C32—H32 | 119.9 |
C6—C5—P1 | 116.88 (17) | C33—C32—H32 | 119.9 |
C7—C6—C5 | 120.2 (2) | C32—C33—C34 | 120.1 (2) |
C7—C6—H6 | 119.9 | C32—C33—H33 | 119.9 |
C5—C6—H6 | 119.9 | C34—C33—H33 | 119.9 |
C6—C7—C8 | 120.3 (2) | C33—C34—C29 | 119.9 (2) |
C6—C7—H7 | 119.8 | C33—C34—H34 | 120.0 |
C8—C7—H7 | 119.8 | C29—C34—H34 | 120.0 |
C9—C8—C7 | 119.7 (2) | C36—C35—C40 | 119.1 (2) |
C9—C8—H8 | 120.2 | C36—C35—P2 | 119.20 (18) |
C7—C8—H8 | 120.2 | C40—C35—P2 | 121.65 (18) |
C8—C9—C10 | 120.5 (2) | C35—C36—C37 | 120.1 (2) |
C8—C9—H9 | 119.8 | C35—C36—H36 | 119.9 |
C10—C9—H9 | 119.8 | C37—C36—H36 | 119.9 |
C9—C10—C5 | 120.0 (2) | C38—C37—C36 | 120.3 (2) |
C9—C10—H10 | 120.0 | C38—C37—H37 | 119.8 |
C5—C10—H10 | 120.0 | C36—C37—H37 | 119.8 |
C16—C11—C12 | 118.9 (2) | C39—C38—C37 | 119.8 (2) |
C16—C11—P1 | 124.05 (18) | C39—C38—H38 | 120.1 |
C12—C11—P1 | 117.01 (18) | C37—C38—H38 | 120.1 |
C13—C12—C11 | 120.5 (2) | C38—C39—C40 | 120.2 (2) |
C13—C12—H12 | 119.8 | C38—C39—H39 | 119.9 |
C11—C12—H12 | 119.8 | C40—C39—H39 | 119.9 |
C14—C13—C12 | 120.1 (2) | C39—C40—C35 | 120.4 (2) |
C14—C13—H13 | 119.9 | C39—C40—H40 | 119.8 |
C12—C13—H13 | 119.9 | C35—C40—H40 | 119.8 |
C13—C14—C15 | 119.9 (2) | C11—P1—C17 | 107.82 (11) |
C13—C14—H14 | 120.0 | C11—P1—C5 | 103.98 (11) |
C15—C14—H14 | 120.0 | C17—P1—C5 | 103.48 (10) |
C14—C15—C16 | 120.4 (2) | C11—P1—Ag1 | 112.08 (8) |
C14—C15—H15 | 119.8 | C17—P1—Ag1 | 120.40 (8) |
C16—C15—H15 | 119.8 | C5—P1—Ag1 | 107.53 (7) |
C15—C16—C11 | 120.2 (2) | C35—P2—C29 | 102.98 (11) |
C15—C16—H16 | 119.9 | C35—P2—C23 | 104.23 (10) |
C11—C16—H16 | 119.9 | C29—P2—C23 | 104.33 (11) |
C22—C17—C18 | 119.6 (2) | C35—P2—Ag1 | 120.17 (7) |
C22—C17—P1 | 119.02 (17) | C29—P2—Ag1 | 106.98 (7) |
C18—C17—P1 | 121.32 (18) | C23—P2—Ag1 | 116.33 (7) |
C19—C18—C17 | 120.1 (2) | O1—Ag1—P1 | 117.69 (5) |
C19—C18—H18 | 120.0 | O1—Ag1—P2 | 113.27 (5) |
C17—C18—H18 | 120.0 | P1—Ag1—P2 | 128.56 (2) |
C20—C19—C18 | 120.1 (2) | C1—O1—Ag1 | 100.12 (14) |
C20—C19—H19 | 120.0 | C3—O3—H3 | 109.5 |
C18—C19—H19 | 120.0 | Cl2—C1S—Cl1 | 112.6 (2) |
C19—C20—C21 | 120.3 (2) | Cl2—C1S—H1S1 | 109.1 |
C19—C20—H20 | 119.8 | Cl1—C1S—H1S1 | 109.1 |
C21—C20—H20 | 119.8 | Cl2—C1S—H1S2 | 109.1 |
C20—C21—C22 | 119.9 (2) | Cl1—C1S—H1S2 | 109.1 |
C20—C21—H21 | 120.0 | H1S1—C1S—H1S2 | 107.8 |
C22—C21—H21 | 120.0 | Cl2B—C1SB—Cl1B | 118 (2) |
C17—C22—C21 | 119.9 (2) | Cl2B—C1SB—H1S3 | 107.8 |
C17—C22—H22 | 120.0 | Cl1B—C1SB—H1S3 | 107.8 |
C21—C22—H22 | 120.0 | Cl2B—C1SB—H1S4 | 107.8 |
C28—C23—C24 | 118.8 (2) | Cl1B—C1SB—H1S4 | 107.8 |
C28—C23—P2 | 122.78 (18) | H1S3—C1SB—H1S4 | 107.1 |
C24—C23—P2 | 118.41 (17) | Cl3—C2S—Cl4 | 112.3 (5) |
C25—C24—C23 | 120.7 (2) | Cl3—C2S—H2S1 | 109.1 |
C25—C24—H24 | 119.7 | Cl4—C2S—H2S1 | 109.1 |
C23—C24—H24 | 119.7 | Cl3—C2S—H2S2 | 109.1 |
C26—C25—C24 | 120.0 (2) | Cl4—C2S—H2S2 | 109.1 |
C26—C25—H25 | 120.0 | H2S1—C2S—H2S2 | 107.9 |
C24—C25—H25 | 120.0 | ||
O1—C1—C2—C3 | −147.4 (2) | C30—C29—C34—C33 | 1.8 (4) |
O2—C1—C2—C3 | 35.8 (3) | P2—C29—C34—C33 | −179.70 (19) |
O1—C1—C2—C4 | 91.0 (2) | C40—C35—C36—C37 | 2.4 (4) |
O2—C1—C2—C4 | −85.7 (3) | P2—C35—C36—C37 | −175.4 (2) |
C1—C2—C3—O4 | 153.9 (2) | C35—C36—C37—C38 | −1.2 (4) |
C4—C2—C3—O4 | −85.8 (3) | C36—C37—C38—C39 | −1.1 (4) |
C1—C2—C3—O3 | −27.7 (3) | C37—C38—C39—C40 | 2.0 (4) |
C4—C2—C3—O3 | 92.6 (2) | C38—C39—C40—C35 | −0.8 (4) |
C3—C2—C4—C4i | 71.3 (3) | C36—C35—C40—C39 | −1.5 (4) |
C1—C2—C4—C4i | −163.5 (2) | P2—C35—C40—C39 | 176.25 (19) |
C10—C5—C6—C7 | −0.6 (3) | C16—C11—P1—C17 | 12.2 (2) |
P1—C5—C6—C7 | 173.30 (18) | C12—C11—P1—C17 | −168.95 (18) |
C5—C6—C7—C8 | 0.0 (4) | C16—C11—P1—C5 | −97.2 (2) |
C6—C7—C8—C9 | 0.3 (4) | C12—C11—P1—C5 | 81.6 (2) |
C7—C8—C9—C10 | 0.0 (4) | C16—C11—P1—Ag1 | 146.97 (19) |
C8—C9—C10—C5 | −0.7 (3) | C12—C11—P1—Ag1 | −34.2 (2) |
C6—C5—C10—C9 | 1.0 (3) | C22—C17—P1—C11 | 112.8 (2) |
P1—C5—C10—C9 | −172.51 (18) | C18—C17—P1—C11 | −68.5 (2) |
C16—C11—C12—C13 | 1.5 (4) | C22—C17—P1—C5 | −137.45 (19) |
P1—C11—C12—C13 | −177.4 (2) | C18—C17—P1—C5 | 41.2 (2) |
C11—C12—C13—C14 | −1.1 (4) | C22—C17—P1—Ag1 | −17.5 (2) |
C12—C13—C14—C15 | −0.5 (4) | C18—C17—P1—Ag1 | 161.23 (17) |
C13—C14—C15—C16 | 1.7 (4) | C10—C5—P1—C11 | −10.3 (2) |
C14—C15—C16—C11 | −1.3 (4) | C6—C5—P1—C11 | 176.06 (17) |
C12—C11—C16—C15 | −0.3 (4) | C10—C5—P1—C17 | −122.87 (19) |
P1—C11—C16—C15 | 178.5 (2) | C6—C5—P1—C17 | 63.48 (19) |
C22—C17—C18—C19 | 0.2 (4) | C10—C5—P1—Ag1 | 108.71 (18) |
P1—C17—C18—C19 | −178.5 (2) | C6—C5—P1—Ag1 | −64.94 (18) |
C17—C18—C19—C20 | −0.3 (4) | C36—C35—P2—C29 | −157.1 (2) |
C18—C19—C20—C21 | −0.1 (4) | C40—C35—P2—C29 | 25.2 (2) |
C19—C20—C21—C22 | 0.5 (4) | C36—C35—P2—C23 | 94.2 (2) |
C18—C17—C22—C21 | 0.2 (4) | C40—C35—P2—C23 | −83.5 (2) |
P1—C17—C22—C21 | 178.93 (19) | C36—C35—P2—Ag1 | −38.4 (2) |
C20—C21—C22—C17 | −0.5 (4) | C40—C35—P2—Ag1 | 143.93 (17) |
C28—C23—C24—C25 | 1.0 (4) | C30—C29—P2—C35 | −110.1 (2) |
P2—C23—C24—C25 | −178.78 (19) | C34—C29—P2—C35 | 71.4 (2) |
C23—C24—C25—C26 | −0.6 (4) | C30—C29—P2—C23 | −1.5 (2) |
C24—C25—C26—C27 | −0.3 (4) | C34—C29—P2—C23 | −179.95 (18) |
C25—C26—C27—C28 | 0.9 (4) | C30—C29—P2—Ag1 | 122.33 (18) |
C26—C27—C28—C23 | −0.5 (4) | C34—C29—P2—Ag1 | −56.13 (19) |
C24—C23—C28—C27 | −0.5 (4) | C28—C23—P2—C35 | 13.2 (2) |
P2—C23—C28—C27 | 179.3 (2) | C24—C23—P2—C35 | −167.02 (19) |
C34—C29—C30—C31 | −1.0 (3) | C28—C23—P2—C29 | −94.5 (2) |
P2—C29—C30—C31 | −179.43 (18) | C24—C23—P2—C29 | 85.3 (2) |
C29—C30—C31—C32 | −0.5 (4) | C28—C23—P2—Ag1 | 147.93 (18) |
C30—C31—C32—C33 | 1.3 (4) | C24—C23—P2—Ag1 | −32.3 (2) |
C31—C32—C33—C34 | −0.5 (4) | O2—C1—O1—Ag1 | 4.6 (3) |
C32—C33—C34—C29 | −1.1 (4) | C2—C1—O1—Ag1 | −171.92 (16) |
Symmetry code: (i) −x, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.84 | 1.79 | 2.525 (3) | 146 |
C1S—H1S1···O3ii | 0.99 | 2.53 | 2.997 (4) | 108 |
C1SB—H1S4···O3ii | 0.99 | 2.46 | 3.04 (4) | 117 |
Symmetry code: (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.84 | 1.79 | 2.525 (3) | 145.8 |
C1S—H1S1···O3i | 0.99 | 2.53 | 2.997 (4) | 108.4 |
C1SB—H1S4···O3i | 0.99 | 2.46 | 3.04 (4) | 117.0 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ag2(C8H8O8)(C18H15P)4]·3CH2Cl2 |
Mr | 1751.74 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 110 |
a, b, c (Å) | 10.0279 (3), 12.9540 (4), 16.8190 (5) |
α, β, γ (°) | 112.306 (3), 96.080 (3), 103.601 (3) |
V (Å3) | 1917.80 (11) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.86 |
Crystal size (mm) | 0.3 × 0.3 × 0.2 |
Data collection | |
Diffractometer | Oxford Gemini S |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.889, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21441, 8700, 7959 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.680 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.083, 1.06 |
No. of reflections | 8700 |
No. of parameters | 507 |
No. of restraints | 27 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.28, −0.61 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS2013 (Sheldrick, 200), SHELXL2014 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012) and SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).
Acknowledgements
MK thanks the Fonds der Chemischen Industrie for a PhD Chemiefonds fellowship. This work was performed within the Federal Cluster of Excellence EXC 1075 MERGE Technologies for Multifunctional Lightweight Structures and supported by the German Research Foundation (DFG). Financial support is gratefully acknowledged.
References
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