research communications
of zwitterionic 2-[bis(2-methoxyphenyl)phosphaniumyl]-4-methylbenzenesulfonate monohydrate dichloromethane monosolvate
aDepartment of Chemistry, the University of Chicago, 5735 South Ellis ave, Chicago, IL 60637, USA
*Correspondence e-mail: rfjordan@uchicago.edu
In the title compound, C21H21O5PS·H2O·CH2Cl2, the phosphonium–sulfonate zwitterion has the acidic H atom located on the P atom rather than the sulfonate group. The S—O bond lengths [1.4453 (15)–1.4521 (14) Å] are essentially equal. In the crystal, the water molecules bridge two via Owater—H⋯Osulfonate hydrogen bonds into a centrosymmetric dimer. The dimers are further linked by weak CAryl—H⋯Osulfonate hydrogen bonds into chains extending along [100]. The PH+ group is not involved in intermolecular interactions.
Keywords: crystal structure; sulfonic acid; zwitterion; hydrogen bonding.
CCDC reference: 1447138
1. Chemical context
Phosphane ligands (Allen, 2014) are ubiquitous in coordination and organometallic chemistry and have been used to synthesize a wide variety of metal complexes and catalysts (Hartwig, 2010). Incorporation of additional potential donor groups within the phosphane structure provides added versatility to such ligands. For example, ortho-phosphanyl-benzenesulfonate (PO) ligands, such as 2-[bis(2-methoxyphenyl)phosphanyl]benzenesulfonate, bind to PdII in a κ2P,O mode to form (PO)PdR species that are active for the polymerization of ethylene (Cai et al., 2012; Contrella & Jordan, 2014; Zhou et al., 2014), of ethylene and polar monomers (Drent et al., 2002a; Nakamura et al., 2013), non-alternating of ethylene and CO (Drent et al., 2002b), and of CO with polar monomers (Nakamura et al., 2011, 2012). Phosphanyl-arenesulfonate ligands derived from para-toluenesulfonic acid are useful because the extra methyl group provides a convenient NMR handle for characterizing complexes and monitoring reactions.
The zwitterion 2-[bis(2-methoxyphenyl)phosphaniumyl]-4-methylbenzenesulfonate (1, Scheme 1) was synthesized by sequential reaction of PCl3 with dilithiated p-toluenesulfonate and 1-lithio-2-methoxybenzene, followed by acidification of HCl (Scheme 2) (Vela et al., 2007). Here we report the of 1·H2O·CH2Cl2, (I).
2. Structural commentary
Compound 1 crystallizes as the phosphonium–sulfonate zwitterion in which the acidic H atom is located on the P atom rather than the sulfonate group (Fig. 1). The S—O bond distances fall within the narrow range of 1.4453 (15) to 1.4521 (14) Å, and the P—C distances lie within the range of 1.7794 (18) to 1.7984 (18) Å. The P—H atom was located in a difference Fourier map and refined without additional restraints. The P—H bond length is 1.22 (2) Å. Compound 1 adopts an exo3 conformation, i.e. the ortho methoxy and sulfonate groups point toward the PH+ group (Feng et al., 2014). Tris(ortho-substituted aryl)phosphanes normally exhibit exo3 conformations (Howell et al., 1999) because the ortho substituents cause less steric congestion when they point toward the P lone pair (exo) rather than toward the other aryl rings (endo). Addition of an H+ at phosphorous should not add significant steric congestion and therefore it is not surprising that 1 also adopts the exo3 conformation. The Omethoxy⋯P distances, 2.7691 (14) and 2.7940 (14) Å, are shorter than the sum of the O and P van der Waals radii (3.35 Å). The O3⋯H1(P1) distance is 2.44 (2) Å.
3. DFT calculations
The relative stability of the observed exo3 conformation versus alternative exo2 and exo1 conformations was investigated by DFT calculations using the hybrid exchange-correlation functional PBE0 (Perdew et al., 1996, 1997) and the 6-311G(d,p) basis set for all atoms. The optimized structure is the exo3 conformer, in which the methoxy and sulfonate groups point toward the PH+ group. Geometry optimizations were also carried out on two conformers in which the SO3 group was kept exo but one (exo2) or two (exo1) methoxy groups were rotated away from the PH+ group. The exo2 and exo1 conformers were calculated to be 1.2 and 2.5 kcal mol−1 less stable than the exo3 isomer, respectively. The HOMO of the exo3 conformer is comprised of p orbitals of the sulfonate O atoms, while the LUMO is delocalized over the phenyl rings and P—Caromatic bonds (Fig. 2).
4. Supramolecular features
Two O atoms of the SO3− group are hydrogen bonded with the co-crystallized water molecule, forming inversion dimers (Fig. 3). The Owater—H⋯Osulfonate contacts are 1.96 (3) and 1.98 (3) Å (Table 1). These dimers are further linked by CAryl—H⋯Osulfonate hydrogen bonds into infinite chains running along the [100] direction (Fig. 4). A similar CAr–SO3−⋯H2O⋯CAr–SO3−⋯H2O⋯ hydrogen-bonding motif was observed in [Na(18-crown-6)(H2O)][2-{(o-CF3-Ph)2P}-4-Me-benzenesulfonate] (Feng et al., 2014).
5. Database survey
A search of the Cambridge Structural Database (CSD, Version 5.36, last update May 2015; Groom & Allen, 2014) revealed structural reports for two analogues of 1 that contain 4-chloro-substituted methoxyphenyl (CSD refcode ODUNOS; Wucher et al., 2013) or 2,6-dimethoxyphenyl substituents at phosphorous (CSD refcode: LEXLEG; Liu et al., 2007). These compounds also crystallized as in which the acidic proton is located on the P atom and feature close Omethoxy⋯P contacts (2.764 to 2.927 Å). The structure of the triethylammonium salt of 2-[bis(2-methoxyphenyl)phosphanyl]benzenesulfonate has also been reported (CSD refcode HAGKEH; Bettucci et al., 2008). In this case, the acidic H atom is located at triethylamine rather than on the P atom and the Omethoxy⋯P distances are 2.877 and 2.903 Å.
6. Synthesis and crystallization
Compound 1 was synthesized by a modification of a previously reported procedure (Vela et al., 2007) comprising sequential reaction of PCl3 with dilithiated p-toluenesulfonate and 1-lithio-2-methoxybenzene, followed by acidification of HCl, to afford 1 in 70–75% yield on a 3–4 g scale (Scheme 2). The product was purified by recrystallization (CH2Cl2/Et2O, volume ratio 1/3, layering at 273K). Crystals of 1·H2O·CH2Cl2 (I) suitable for the X-ray were obtained by layering Et2O on a CH2Cl2 solution of 1 at 277 K.
7. Refinement
Crystal data, data collection and structure . Carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and were included in the in the riding-model approximation, with Uiso(H) set to 1.2–1.5Ueq(C). The P- and O-bound H atoms were located in a difference Fourier map and refined isotropically.
details are summarized in Table 2Supporting information
CCDC reference: 1447138
10.1107/S2056989016000669/cv5502sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016000669/cv5502Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989016000669/cv5502Isup3.cml
Phosphine ligands (Allen, 2014) are ubiquitous in coordination and organometallic chemistry and have been used to synthesize a wide variety of metal complexes and catalysts (Hartwig, 2010). Incorporation of additional potential donor groups within the phosphine structure provides added versatility to such ligands. For example, ortho-phosphino-benzenesulfonate (PO) ligands, such as 2-(bis{2-methoxyphenyl}-phosphino)benzenesulfonate, bind to PdII in a κ2-P,O mode to form (PO)PdR species that are active for the polymerization of ethylene (Cai et al., 2012; Contrella & Jordan, 2014; Zhou et al., 2014), of ethylene and polar monomers (Drent et al., 2002a; Nakamura et al., 2013), non-alternating of ethylene and CO (Drent et al., 2002b), and of CO with polar monomers (Nakamura et al., 2011, 2012). Phosphino-arenesulfonate ligands derived from para-toluenesulfonic acid are useful because the extra methyl group provides a convenient NMR handle for characterizing complexes and monitoring reactions. The zwitterion 2-(bis{2-methoxyphenyl}{hydrido}phosphonium)-4-methylbenzenesulfonate (1, Scheme 1) was synthesized by sequential reaction of PCl3 with dilithiated p-toluenesulfonate and 1-lithio-2-methoxybenzene, followed by acidification of HCl (Scheme 2) (Vela et al., 2007). Here we report the of 1·H2O·CH2Cl2, (I).
Crystals of 1·H2O·CH2Cl2 (I) suitable for X-ray
were obtained by layering Et2O on a wet CH2Cl2 solution of 1 at 277 K. 1 crystallizes as the phosphonium sulfonate zwitterion in which the acidic hydrogen atom is located on the phosphorous atom rather than the sulfonate group (Fig. 1). The SO bond distances fall within the narrow range of 1.4453 (15) to 1.4521 (14) Å, and the P—C distances lie within the range of 1.7794 (18) to 1.7984 (18) Å. The P—H atom was located in a difference Fourier map and refined without additional restraints. The P—H bond length is 1.22 (2) Å. Compound 1 adopts an exo3 conformation, i.e. the ortho methoxy and sulfonate groups point toward the PH+ group (Feng et al., 2014). Tris(ortho-substituted aryl)phosphines normally exhibit exo3 conformations (Howell et al., 1999) because the ortho substituents cause less steric congestion when they point toward the P lone pair (exo) rather than toward the other aryl rings (endo). Addition of an H+ at phosphorous should not add significant steric congestion and therefore it is not surprising that 1 also adopts the exo3 conformation. The Omethoxy···P distances, 2.7691 (14) and 2.7940 (14) Å, are shorter than the sum of the O and P van der Waals radii (3.35 Å). The O3···H1(P1) distance is 2.44 (2) Å.The relative stability of the observed exo3 conformation versus alternative exo2 and exo1 conformations was investigated by DFT calculations using the hybrid exchange-correlation functional PBE0 (Perdew et al., 1996, 1997) and the 6–311 G(d,p) basis set for all atoms. The optimized structure is the exo3 conformer, in which the methoxy and sulfonate groups point toward the PH+ group. Geometry optimizations were also carried out on two conformers in which the SO3 group was kept exo but one (exo2) or two (exo1) methoxy groups were rotated away from the PH+ group. The exo2 and exo1 conformers were calculated to be 1.2 and 2.5 kcal mol−1 less stable than the exo3 isomer, respectively. The HOMO of the exo3 conformer is comprised of p orbitals of the sulfonate oxygen atoms, while the LUMO is delocalized over the phenyl rings and P—Caromatic bonds (Fig. 2).
Two O atoms of the SO3− group are hydrogen-bonded with the co-crystallized water molecule, forming inversion dimers (Fig. 3). The Owater—H···Osulfonate contacts are 1.96 (3) and 1.98 (3) Å (Table 1). These dimers are further linked by CAryl—H···Osulfonate hydrogen bonds into infinite chains running along [100] direction (Figure 4). A similar CAr—SO3−···H2O···CAr—SO3−···H2O··· hydrogen bonding motif was observed in [Na(18-crown-6)(H2O)][2-{(o-CF3—Ph)2P}-4-Me-benzenesulfonate] (Feng et al., 2014).
A search of the Cambridge Structural Database (CSD, Version 5.36, last update May 2015; Groom & Allen, 2014) revealed structural reports for two analogues of 1 that contain 4-chloro-substituted methoxyphenyl (CSD refcode ODUNOS; Wucher et al., 2013) or 2,6-dimethoxyphenyl substituents at phosphorous (CSD refcode: LEXLEG; Liu et al., 2007). These compounds also crystallized as
in which the acidic proton is located on the phosphorous atom and feature close Omethoxy···P contacts (2.764 to 2.927 Å). The structure of the triethylammonium salt of 2-(bis{2-methoxyphenyl}phosphino)benzenesulfonate has also been reported (CSD refcode HAGKEH; Bettucci et al., 2008). In this case, the acidic hydrogen is located at triethylamine rather than on the phosphorous atom and the Omethoxy···P distances are 2.877 and 2.903 Å.Compound 1 was synthesized by a modification of a previously reported procedure (Vela et al., 2007) comprising sequential reaction of PCl3 with dilithiated p-toluenesulfonate and 1-lithio-2-methoxybenzene, followed by acidification of HCl, to afford 1 in 70–75% yield on a 3–4 g scale (Scheme 2). The product was purified by recrystallization (CH2Cl2/Et2O, volume ratio 1/3, layering at 273 K). Crystals of 1·H2O·CH2Cl2 (I) suitable for the X-ray
were obtained by layering Et2O on a wet CH2Cl2 solution of 1 at 277 K.Crystal data, data collection and structure
details are summarized in Table 2. Carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and were included in the in the riding-model approximation, with Uiso(H) set to 1.2–1.5Ueq(C). The P– and O-bound H atoms were located in a difference Fourier map and refined isotropically.Phosphine ligands (Allen, 2014) are ubiquitous in coordination and organometallic chemistry and have been used to synthesize a wide variety of metal complexes and catalysts (Hartwig, 2010). Incorporation of additional potential donor groups within the phosphine structure provides added versatility to such ligands. For example, ortho-phosphino-benzenesulfonate (PO) ligands, such as 2-(bis{2-methoxyphenyl}-phosphino)benzenesulfonate, bind to PdII in a κ2-P,O mode to form (PO)PdR species that are active for the polymerization of ethylene (Cai et al., 2012; Contrella & Jordan, 2014; Zhou et al., 2014), of ethylene and polar monomers (Drent et al., 2002a; Nakamura et al., 2013), non-alternating of ethylene and CO (Drent et al., 2002b), and of CO with polar monomers (Nakamura et al., 2011, 2012). Phosphino-arenesulfonate ligands derived from para-toluenesulfonic acid are useful because the extra methyl group provides a convenient NMR handle for characterizing complexes and monitoring reactions. The zwitterion 2-(bis{2-methoxyphenyl}{hydrido}phosphonium)-4-methylbenzenesulfonate (1, Scheme 1) was synthesized by sequential reaction of PCl3 with dilithiated p-toluenesulfonate and 1-lithio-2-methoxybenzene, followed by acidification of HCl (Scheme 2) (Vela et al., 2007). Here we report the of 1·H2O·CH2Cl2, (I).
Crystals of 1·H2O·CH2Cl2 (I) suitable for X-ray
were obtained by layering Et2O on a wet CH2Cl2 solution of 1 at 277 K. 1 crystallizes as the phosphonium sulfonate zwitterion in which the acidic hydrogen atom is located on the phosphorous atom rather than the sulfonate group (Fig. 1). The SO bond distances fall within the narrow range of 1.4453 (15) to 1.4521 (14) Å, and the P—C distances lie within the range of 1.7794 (18) to 1.7984 (18) Å. The P—H atom was located in a difference Fourier map and refined without additional restraints. The P—H bond length is 1.22 (2) Å. Compound 1 adopts an exo3 conformation, i.e. the ortho methoxy and sulfonate groups point toward the PH+ group (Feng et al., 2014). Tris(ortho-substituted aryl)phosphines normally exhibit exo3 conformations (Howell et al., 1999) because the ortho substituents cause less steric congestion when they point toward the P lone pair (exo) rather than toward the other aryl rings (endo). Addition of an H+ at phosphorous should not add significant steric congestion and therefore it is not surprising that 1 also adopts the exo3 conformation. The Omethoxy···P distances, 2.7691 (14) and 2.7940 (14) Å, are shorter than the sum of the O and P van der Waals radii (3.35 Å). The O3···H1(P1) distance is 2.44 (2) Å.The relative stability of the observed exo3 conformation versus alternative exo2 and exo1 conformations was investigated by DFT calculations using the hybrid exchange-correlation functional PBE0 (Perdew et al., 1996, 1997) and the 6–311 G(d,p) basis set for all atoms. The optimized structure is the exo3 conformer, in which the methoxy and sulfonate groups point toward the PH+ group. Geometry optimizations were also carried out on two conformers in which the SO3 group was kept exo but one (exo2) or two (exo1) methoxy groups were rotated away from the PH+ group. The exo2 and exo1 conformers were calculated to be 1.2 and 2.5 kcal mol−1 less stable than the exo3 isomer, respectively. The HOMO of the exo3 conformer is comprised of p orbitals of the sulfonate oxygen atoms, while the LUMO is delocalized over the phenyl rings and P—Caromatic bonds (Fig. 2).
Two O atoms of the SO3− group are hydrogen-bonded with the co-crystallized water molecule, forming inversion dimers (Fig. 3). The Owater—H···Osulfonate contacts are 1.96 (3) and 1.98 (3) Å (Table 1). These dimers are further linked by CAryl—H···Osulfonate hydrogen bonds into infinite chains running along [100] direction (Figure 4). A similar CAr—SO3−···H2O···CAr—SO3−···H2O··· hydrogen bonding motif was observed in [Na(18-crown-6)(H2O)][2-{(o-CF3—Ph)2P}-4-Me-benzenesulfonate] (Feng et al., 2014).
A search of the Cambridge Structural Database (CSD, Version 5.36, last update May 2015; Groom & Allen, 2014) revealed structural reports for two analogues of 1 that contain 4-chloro-substituted methoxyphenyl (CSD refcode ODUNOS; Wucher et al., 2013) or 2,6-dimethoxyphenyl substituents at phosphorous (CSD refcode: LEXLEG; Liu et al., 2007). These compounds also crystallized as
in which the acidic proton is located on the phosphorous atom and feature close Omethoxy···P contacts (2.764 to 2.927 Å). The structure of the triethylammonium salt of 2-(bis{2-methoxyphenyl}phosphino)benzenesulfonate has also been reported (CSD refcode HAGKEH; Bettucci et al., 2008). In this case, the acidic hydrogen is located at triethylamine rather than on the phosphorous atom and the Omethoxy···P distances are 2.877 and 2.903 Å.Compound 1 was synthesized by a modification of a previously reported procedure (Vela et al., 2007) comprising sequential reaction of PCl3 with dilithiated p-toluenesulfonate and 1-lithio-2-methoxybenzene, followed by acidification of HCl, to afford 1 in 70–75% yield on a 3–4 g scale (Scheme 2). The product was purified by recrystallization (CH2Cl2/Et2O, volume ratio 1/3, layering at 273 K). Crystals of 1·H2O·CH2Cl2 (I) suitable for the X-ray
were obtained by layering Et2O on a wet CH2Cl2 solution of 1 at 277 K. detailsCrystal data, data collection and structure
details are summarized in Table 2. Carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and were included in the in the riding-model approximation, with Uiso(H) set to 1.2–1.5Ueq(C). The P– and O-bound H atoms were located in a difference Fourier map and refined isotropically.Data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The dashed line denotes a hydrogen bond. | |
Fig. 2. HOMO (−0.2289 Hartrees, left) and LUMO (−0.0483 Hartrees, right) orbitals of 1. | |
Fig. 3. Dimer formation through Owater—H···Osulfonate hydrogen bonds (dashed lines). | |
Fig. 4. A fragment of the crystal packing of the title compound with intermolecular hydrogen bonds shown as dashed light-blue lines. Color scheme: C grey, H white, O red, P orange, S yellow. |
C21H21O5PS·CH2Cl2·H2O | F(000) = 1080 |
Mr = 519.35 | Dx = 1.455 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.6437 (6) Å | Cell parameters from 9610 reflections |
b = 15.9441 (11) Å | θ = 2.2–26.4° |
c = 15.9641 (11) Å | µ = 0.47 mm−1 |
β = 105.051 (2)° | T = 100 K |
V = 2370.4 (3) Å3 | Block, colorless |
Z = 4 | 0.32 × 0.18 × 0.12 mm |
Bruker D8 Venture PHOTON 100 CMOS diffractometer | 4888 independent reflections |
Radiation source: INCOATEC ImuS micro-focus source | 4349 reflections with I > 2σ(I) |
Mirrors monochromator | Rint = 0.030 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 26.5°, θmin = 2.2° |
ω and phi scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | k = −19→19 |
Tmin = 0.693, Tmax = 0.745 | l = −20→19 |
53574 measured reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: mixed |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0536P)2 + 2.7024P] where P = (Fo2 + 2Fc2)/3 |
4888 reflections | (Δ/σ)max = 0.001 |
304 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.66 e Å−3 |
C21H21O5PS·CH2Cl2·H2O | V = 2370.4 (3) Å3 |
Mr = 519.35 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.6437 (6) Å | µ = 0.47 mm−1 |
b = 15.9441 (11) Å | T = 100 K |
c = 15.9641 (11) Å | 0.32 × 0.18 × 0.12 mm |
β = 105.051 (2)° |
Bruker D8 Venture PHOTON 100 CMOS diffractometer | 4888 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | 4349 reflections with I > 2σ(I) |
Tmin = 0.693, Tmax = 0.745 | Rint = 0.030 |
53574 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.48 e Å−3 |
4888 reflections | Δρmin = −0.66 e Å−3 |
304 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 | ||
P1 | 0.63863 (5) | 0.30456 (3) | 0.33309 (3) | 0.01288 (12) | |
H1P | 0.592 (2) | 0.2397 (14) | 0.2950 (14) | 0.018 (5)* | |
S1 | 0.43769 (5) | 0.17697 (3) | 0.41453 (3) | 0.01702 (12) | |
O1 | 0.50338 (15) | 0.10620 (9) | 0.38266 (10) | 0.0261 (3) | |
O2 | 0.34252 (15) | 0.15453 (10) | 0.46751 (10) | 0.0269 (3) | |
O3 | 0.37411 (14) | 0.23600 (9) | 0.34604 (9) | 0.0210 (3) | |
O4 | 0.86431 (15) | 0.19197 (8) | 0.35798 (9) | 0.0210 (3) | |
O5 | 0.51406 (15) | 0.34403 (9) | 0.15930 (8) | 0.0206 (3) | |
C1 | 0.77958 (19) | 0.33171 (11) | 0.50245 (12) | 0.0155 (4) | |
H1 | 0.8372 | 0.3678 | 0.4781 | 0.019* | |
C2 | 0.66711 (19) | 0.28789 (11) | 0.44773 (11) | 0.0139 (3) | |
C3 | 0.58188 (19) | 0.23434 (11) | 0.48294 (12) | 0.0155 (4) | |
C4 | 0.6117 (2) | 0.22566 (12) | 0.57215 (12) | 0.0188 (4) | |
H4 | 0.5552 | 0.1890 | 0.5966 | 0.023* | |
C5 | 0.7235 (2) | 0.27025 (12) | 0.62605 (12) | 0.0187 (4) | |
H5 | 0.7417 | 0.2642 | 0.6871 | 0.022* | |
C6 | 0.8093 (2) | 0.32358 (12) | 0.59237 (12) | 0.0170 (4) | |
C7 | 0.9324 (2) | 0.37081 (13) | 0.65044 (13) | 0.0227 (4) | |
H7A | 0.9220 | 0.3708 | 0.7099 | 0.034* | |
H7B | 0.9323 | 0.4287 | 0.6299 | 0.034* | |
H7C | 1.0231 | 0.3437 | 0.6493 | 0.034* | |
C8 | 0.51505 (19) | 0.38810 (11) | 0.29746 (12) | 0.0159 (4) | |
C9 | 0.4711 (2) | 0.44064 (12) | 0.35526 (13) | 0.0202 (4) | |
H9 | 0.5089 | 0.4336 | 0.4160 | 0.024* | |
C10 | 0.3720 (2) | 0.50321 (13) | 0.32356 (14) | 0.0239 (4) | |
H10 | 0.3426 | 0.5402 | 0.3624 | 0.029* | |
C11 | 0.3158 (2) | 0.51167 (13) | 0.23483 (15) | 0.0246 (4) | |
H11 | 0.2461 | 0.5540 | 0.2136 | 0.030* | |
C12 | 0.3583 (2) | 0.46027 (12) | 0.17634 (13) | 0.0209 (4) | |
H12 | 0.3185 | 0.4670 | 0.1157 | 0.025* | |
C13 | 0.46023 (19) | 0.39848 (12) | 0.20784 (12) | 0.0173 (4) | |
C14 | 0.4860 (2) | 0.36077 (14) | 0.06819 (13) | 0.0261 (4) | |
H14A | 0.3827 | 0.3561 | 0.0413 | 0.039* | |
H14B | 0.5378 | 0.3201 | 0.0416 | 0.039* | |
H14C | 0.5184 | 0.4176 | 0.0595 | 0.039* | |
C15 | 0.80656 (19) | 0.32846 (12) | 0.31142 (11) | 0.0152 (4) | |
C16 | 0.8366 (2) | 0.40458 (12) | 0.27736 (12) | 0.0192 (4) | |
H16 | 0.7672 | 0.4482 | 0.2665 | 0.023* | |
C17 | 0.9686 (2) | 0.41647 (13) | 0.25930 (13) | 0.0224 (4) | |
H17 | 0.9894 | 0.4678 | 0.2349 | 0.027* | |
C18 | 1.0697 (2) | 0.35248 (13) | 0.27735 (13) | 0.0226 (4) | |
H18 | 1.1612 | 0.3615 | 0.2670 | 0.027* | |
C19 | 1.0407 (2) | 0.27600 (13) | 0.30998 (13) | 0.0208 (4) | |
H19 | 1.1106 | 0.2326 | 0.3208 | 0.025* | |
C20 | 0.9083 (2) | 0.26368 (12) | 0.32663 (12) | 0.0173 (4) | |
C21 | 0.9467 (2) | 0.11736 (13) | 0.35617 (14) | 0.0258 (4) | |
H21A | 0.9509 | 0.1062 | 0.2965 | 0.039* | |
H21B | 0.9012 | 0.0699 | 0.3775 | 0.039* | |
H21C | 1.0442 | 0.1251 | 0.3932 | 0.039* | |
C22 | 0.2653 (5) | 0.3457 (2) | 0.5203 (2) | 0.0676 (11) | |
H22A | 0.2056 | 0.3047 | 0.4801 | 0.081* | |
H22B | 0.3569 | 0.3518 | 0.5038 | 0.081* | |
Cl1 | 0.30192 (7) | 0.30568 (5) | 0.62409 (4) | 0.04587 (19) | |
Cl2 | 0.17791 (9) | 0.44136 (4) | 0.50619 (5) | 0.0517 (2) | |
O6 | 0.73753 (17) | −0.00322 (11) | 0.45863 (11) | 0.0308 (4) | |
H1O | 0.656 (4) | 0.027 (2) | 0.436 (2) | 0.049 (8)* | |
H2O | 0.701 (3) | −0.053 (2) | 0.4720 (19) | 0.043 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0121 (2) | 0.0138 (2) | 0.0124 (2) | 0.00178 (16) | 0.00263 (17) | 0.00083 (16) |
S1 | 0.0143 (2) | 0.0180 (2) | 0.0173 (2) | −0.00200 (17) | 0.00148 (17) | 0.00157 (17) |
O1 | 0.0245 (7) | 0.0214 (7) | 0.0283 (8) | 0.0011 (6) | −0.0007 (6) | −0.0049 (6) |
O2 | 0.0227 (7) | 0.0324 (8) | 0.0255 (8) | −0.0092 (6) | 0.0062 (6) | 0.0041 (6) |
O3 | 0.0141 (6) | 0.0255 (7) | 0.0207 (7) | −0.0009 (5) | −0.0003 (5) | 0.0048 (6) |
O4 | 0.0217 (7) | 0.0174 (7) | 0.0268 (7) | 0.0068 (5) | 0.0115 (6) | 0.0045 (5) |
O5 | 0.0244 (7) | 0.0213 (7) | 0.0148 (7) | 0.0010 (6) | 0.0027 (5) | 0.0006 (5) |
C1 | 0.0151 (8) | 0.0143 (8) | 0.0173 (9) | 0.0025 (7) | 0.0044 (7) | −0.0010 (7) |
C2 | 0.0147 (8) | 0.0138 (8) | 0.0134 (8) | 0.0043 (7) | 0.0043 (7) | 0.0012 (7) |
C3 | 0.0137 (8) | 0.0159 (9) | 0.0162 (9) | 0.0026 (7) | 0.0025 (7) | 0.0006 (7) |
C4 | 0.0182 (9) | 0.0209 (9) | 0.0179 (9) | 0.0014 (7) | 0.0058 (7) | 0.0035 (7) |
C5 | 0.0213 (9) | 0.0210 (9) | 0.0139 (9) | 0.0045 (7) | 0.0047 (7) | 0.0015 (7) |
C6 | 0.0160 (9) | 0.0168 (9) | 0.0173 (9) | 0.0047 (7) | 0.0026 (7) | −0.0020 (7) |
C7 | 0.0234 (10) | 0.0239 (10) | 0.0186 (9) | −0.0010 (8) | 0.0017 (8) | −0.0030 (8) |
C8 | 0.0123 (8) | 0.0153 (9) | 0.0198 (9) | 0.0020 (7) | 0.0038 (7) | 0.0036 (7) |
C9 | 0.0198 (9) | 0.0202 (10) | 0.0211 (9) | 0.0029 (7) | 0.0063 (8) | 0.0025 (7) |
C10 | 0.0229 (10) | 0.0199 (10) | 0.0323 (11) | 0.0051 (8) | 0.0131 (9) | 0.0028 (8) |
C11 | 0.0159 (9) | 0.0206 (10) | 0.0381 (12) | 0.0039 (7) | 0.0080 (8) | 0.0117 (9) |
C12 | 0.0162 (9) | 0.0209 (9) | 0.0229 (10) | −0.0024 (7) | 0.0002 (7) | 0.0093 (8) |
C13 | 0.0133 (8) | 0.0172 (9) | 0.0211 (9) | −0.0029 (7) | 0.0039 (7) | 0.0027 (7) |
C14 | 0.0339 (11) | 0.0273 (11) | 0.0166 (9) | −0.0028 (9) | 0.0055 (8) | 0.0023 (8) |
C15 | 0.0136 (8) | 0.0191 (9) | 0.0131 (8) | −0.0004 (7) | 0.0037 (7) | −0.0023 (7) |
C16 | 0.0199 (9) | 0.0189 (9) | 0.0183 (9) | −0.0006 (7) | 0.0040 (7) | −0.0011 (7) |
C17 | 0.0247 (10) | 0.0223 (10) | 0.0213 (10) | −0.0082 (8) | 0.0077 (8) | −0.0020 (8) |
C18 | 0.0170 (9) | 0.0303 (11) | 0.0221 (10) | −0.0056 (8) | 0.0083 (8) | −0.0079 (8) |
C19 | 0.0158 (9) | 0.0272 (10) | 0.0196 (9) | 0.0025 (8) | 0.0049 (7) | −0.0045 (8) |
C20 | 0.0183 (9) | 0.0196 (9) | 0.0140 (8) | −0.0001 (7) | 0.0042 (7) | −0.0015 (7) |
C21 | 0.0311 (11) | 0.0198 (10) | 0.0289 (11) | 0.0109 (8) | 0.0117 (9) | 0.0024 (8) |
C22 | 0.126 (3) | 0.0495 (18) | 0.0368 (15) | 0.043 (2) | 0.0374 (19) | 0.0161 (13) |
Cl1 | 0.0453 (4) | 0.0621 (4) | 0.0305 (3) | 0.0225 (3) | 0.0103 (3) | 0.0118 (3) |
Cl2 | 0.0798 (5) | 0.0347 (3) | 0.0452 (4) | 0.0190 (3) | 0.0245 (4) | 0.0098 (3) |
O6 | 0.0241 (8) | 0.0272 (8) | 0.0389 (9) | −0.0020 (7) | 0.0040 (7) | 0.0056 (7) |
P1—C8 | 1.7794 (18) | C10—C11 | 1.386 (3) |
P1—C15 | 1.7828 (18) | C10—H10 | 0.9500 |
P1—C2 | 1.7984 (18) | C11—C12 | 1.382 (3) |
P1—H1P | 1.22 (2) | C11—H11 | 0.9500 |
S1—O2 | 1.4453 (15) | C12—C13 | 1.390 (3) |
S1—O1 | 1.4495 (15) | C12—H12 | 0.9500 |
S1—O3 | 1.4521 (14) | C14—H14A | 0.9800 |
S1—C3 | 1.7816 (19) | C14—H14B | 0.9800 |
O4—C20 | 1.359 (2) | C14—H14C | 0.9800 |
O4—C21 | 1.435 (2) | C15—C16 | 1.391 (3) |
O5—C13 | 1.354 (2) | C15—C20 | 1.402 (3) |
O5—C14 | 1.434 (2) | C16—C17 | 1.389 (3) |
C1—C2 | 1.391 (3) | C16—H16 | 0.9500 |
C1—C6 | 1.395 (3) | C17—C18 | 1.389 (3) |
C1—H1 | 0.9500 | C17—H17 | 0.9500 |
C2—C3 | 1.400 (3) | C18—C19 | 1.383 (3) |
C3—C4 | 1.385 (3) | C18—H18 | 0.9500 |
C4—C5 | 1.388 (3) | C19—C20 | 1.384 (3) |
C4—H4 | 0.9500 | C19—H19 | 0.9500 |
C5—C6 | 1.388 (3) | C21—H21A | 0.9800 |
C5—H5 | 0.9500 | C21—H21B | 0.9800 |
C6—C7 | 1.505 (3) | C21—H21C | 0.9800 |
C7—H7A | 0.9800 | C22—Cl1 | 1.725 (3) |
C7—H7B | 0.9800 | C22—Cl2 | 1.728 (3) |
C7—H7C | 0.9800 | C22—H22A | 0.9900 |
C8—C9 | 1.391 (3) | C22—H22B | 0.9900 |
C8—C13 | 1.400 (3) | O6—H1O | 0.91 (3) |
C9—C10 | 1.384 (3) | O6—H2O | 0.92 (3) |
C9—H9 | 0.9500 | ||
C8—P1—C15 | 110.16 (9) | C12—C11—C10 | 121.81 (18) |
C8—P1—C2 | 110.40 (8) | C12—C11—H11 | 119.1 |
C15—P1—C2 | 108.82 (8) | C10—C11—H11 | 119.1 |
C8—P1—H1P | 110.0 (10) | C11—C12—C13 | 118.80 (18) |
C15—P1—H1P | 108.8 (10) | C11—C12—H12 | 120.6 |
C2—P1—H1P | 108.6 (10) | C13—C12—H12 | 120.6 |
O2—S1—O1 | 114.48 (9) | O5—C13—C12 | 125.99 (18) |
O2—S1—O3 | 113.14 (9) | O5—C13—C8 | 114.20 (16) |
O1—S1—O3 | 112.20 (9) | C12—C13—C8 | 119.81 (18) |
O2—S1—C3 | 106.35 (9) | O5—C14—H14A | 109.5 |
O1—S1—C3 | 105.80 (8) | O5—C14—H14B | 109.5 |
O3—S1—C3 | 103.80 (8) | H14A—C14—H14B | 109.5 |
C20—O4—C21 | 117.55 (15) | O5—C14—H14C | 109.5 |
C13—O5—C14 | 117.51 (15) | H14A—C14—H14C | 109.5 |
C2—C1—C6 | 121.17 (17) | H14B—C14—H14C | 109.5 |
C2—C1—H1 | 119.4 | C16—C15—C20 | 120.20 (17) |
C6—C1—H1 | 119.4 | C16—C15—P1 | 123.67 (14) |
C1—C2—C3 | 119.83 (17) | C20—C15—P1 | 116.05 (14) |
C1—C2—P1 | 116.93 (14) | C17—C16—C15 | 119.71 (18) |
C3—C2—P1 | 123.24 (14) | C17—C16—H16 | 120.1 |
C4—C3—C2 | 119.16 (17) | C15—C16—H16 | 120.1 |
C4—C3—S1 | 119.96 (14) | C16—C17—C18 | 119.23 (19) |
C2—C3—S1 | 120.87 (14) | C16—C17—H17 | 120.4 |
C3—C4—C5 | 120.43 (18) | C18—C17—H17 | 120.4 |
C3—C4—H4 | 119.8 | C19—C18—C17 | 121.78 (18) |
C5—C4—H4 | 119.8 | C19—C18—H18 | 119.1 |
C6—C5—C4 | 121.25 (17) | C17—C18—H18 | 119.1 |
C6—C5—H5 | 119.4 | C18—C19—C20 | 118.94 (18) |
C4—C5—H5 | 119.4 | C18—C19—H19 | 120.5 |
C5—C6—C1 | 118.16 (17) | C20—C19—H19 | 120.5 |
C5—C6—C7 | 121.47 (17) | O4—C20—C19 | 125.57 (18) |
C1—C6—C7 | 120.37 (17) | O4—C20—C15 | 114.34 (16) |
C6—C7—H7A | 109.5 | C19—C20—C15 | 120.09 (18) |
C6—C7—H7B | 109.5 | O4—C21—H21A | 109.5 |
H7A—C7—H7B | 109.5 | O4—C21—H21B | 109.5 |
C6—C7—H7C | 109.5 | H21A—C21—H21B | 109.5 |
H7A—C7—H7C | 109.5 | O4—C21—H21C | 109.5 |
H7B—C7—H7C | 109.5 | H21A—C21—H21C | 109.5 |
C9—C8—C13 | 120.48 (17) | H21B—C21—H21C | 109.5 |
C9—C8—P1 | 122.19 (15) | Cl1—C22—Cl2 | 115.01 (17) |
C13—C8—P1 | 117.32 (14) | Cl1—C22—H22A | 108.5 |
C10—C9—C8 | 119.47 (19) | Cl2—C22—H22A | 108.5 |
C10—C9—H9 | 120.3 | Cl1—C22—H22B | 108.5 |
C8—C9—H9 | 120.3 | Cl2—C22—H22B | 108.5 |
C9—C10—C11 | 119.59 (19) | H22A—C22—H22B | 107.5 |
C9—C10—H10 | 120.2 | H1O—O6—H2O | 102 (3) |
C11—C10—H10 | 120.2 | ||
C6—C1—C2—C3 | −0.2 (3) | C8—C9—C10—C11 | 1.2 (3) |
C6—C1—C2—P1 | 179.37 (14) | C9—C10—C11—C12 | −1.4 (3) |
C8—P1—C2—C1 | −91.04 (15) | C10—C11—C12—C13 | 0.0 (3) |
C15—P1—C2—C1 | 29.98 (16) | C14—O5—C13—C12 | 12.9 (3) |
C8—P1—C2—C3 | 88.50 (16) | C14—O5—C13—C8 | −167.84 (16) |
C15—P1—C2—C3 | −150.48 (15) | C11—C12—C13—O5 | −179.18 (17) |
C1—C2—C3—C4 | −0.3 (3) | C11—C12—C13—C8 | 1.6 (3) |
P1—C2—C3—C4 | −179.79 (14) | C9—C8—C13—O5 | 178.92 (16) |
C1—C2—C3—S1 | −179.67 (13) | P1—C8—C13—O5 | −2.3 (2) |
P1—C2—C3—S1 | 0.8 (2) | C9—C8—C13—C12 | −1.7 (3) |
O2—S1—C3—C4 | 21.46 (18) | P1—C8—C13—C12 | 177.04 (14) |
O1—S1—C3—C4 | −100.67 (16) | C8—P1—C15—C16 | 4.33 (19) |
O3—S1—C3—C4 | 141.04 (15) | C2—P1—C15—C16 | −116.84 (16) |
O2—S1—C3—C2 | −159.14 (15) | C8—P1—C15—C20 | −172.54 (14) |
O1—S1—C3—C2 | 78.73 (16) | C2—P1—C15—C20 | 66.29 (16) |
O3—S1—C3—C2 | −39.55 (17) | C20—C15—C16—C17 | −0.7 (3) |
C2—C3—C4—C5 | 0.8 (3) | P1—C15—C16—C17 | −177.42 (15) |
S1—C3—C4—C5 | −179.82 (14) | C15—C16—C17—C18 | −1.3 (3) |
C3—C4—C5—C6 | −0.8 (3) | C16—C17—C18—C19 | 2.3 (3) |
C4—C5—C6—C1 | 0.4 (3) | C17—C18—C19—C20 | −1.3 (3) |
C4—C5—C6—C7 | −178.82 (18) | C21—O4—C20—C19 | −14.4 (3) |
C2—C1—C6—C5 | 0.1 (3) | C21—O4—C20—C15 | 165.79 (17) |
C2—C1—C6—C7 | 179.34 (17) | C18—C19—C20—O4 | 179.46 (18) |
C15—P1—C8—C9 | −109.47 (16) | C18—C19—C20—C15 | −0.8 (3) |
C2—P1—C8—C9 | 10.75 (19) | C16—C15—C20—O4 | −178.46 (16) |
C15—P1—C8—C13 | 71.78 (16) | P1—C15—C20—O4 | −1.5 (2) |
C2—P1—C8—C13 | −168.00 (14) | C16—C15—C20—C19 | 1.7 (3) |
C13—C8—C9—C10 | 0.3 (3) | P1—C15—C20—C19 | 178.73 (14) |
P1—C8—C9—C10 | −178.39 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H1O···O1 | 0.91 (3) | 1.96 (3) | 2.862 (2) | 170 (3) |
O6—H2O···O2i | 0.92 (3) | 1.98 (3) | 2.877 (2) | 164 (3) |
C19—H19···O3ii | 0.95 | 2.47 | 3.180 (2) | 132 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H1O···O1 | 0.91 (3) | 1.96 (3) | 2.862 (2) | 170 (3) |
O6—H2O···O2i | 0.92 (3) | 1.98 (3) | 2.877 (2) | 164 (3) |
C19—H19···O3ii | 0.95 | 2.47 | 3.180 (2) | 131.7 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C21H21O5PS·CH2Cl2·H2O |
Mr | 519.35 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 9.6437 (6), 15.9441 (11), 15.9641 (11) |
β (°) | 105.051 (2) |
V (Å3) | 2370.4 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.47 |
Crystal size (mm) | 0.32 × 0.18 × 0.12 |
Data collection | |
Diffractometer | Bruker D8 Venture PHOTON 100 CMOS |
Absorption correction | Multi-scan (SADABS; Bruker, 2014) |
Tmin, Tmax | 0.693, 0.745 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 53574, 4888, 4349 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.627 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.106, 1.05 |
No. of reflections | 4888 |
No. of parameters | 304 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.48, −0.66 |
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008), publCIF (Westrip, 2010).
Acknowledgements
This work was supported by the National Science Foundation (grants CHE-0911180 and CHE-1048528). Calculations were carried out with the GAMESS-US computational package provided by the University of Chicago Research Computing Center (Midway high-performance computing cluster).
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