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ISSN: 2056-9890
Volume 72| Part 2| February 2016| Pages 229-232

Crystal structure of zwitterionic 2-[bis­­(2-meth­­oxy­phen­yl)phosphanium­yl]-4-methyl­benzene­sulfonate monohydrate di­chloro­methane monosolvate

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aDepartment of Chemistry, the University of Chicago, 5735 South Ellis ave, Chicago, IL 60637, USA
*Correspondence e-mail: rfjordan@uchicago.edu

Edited by V. V. Chernyshev, Moscow State University, Russia (Received 22 December 2015; accepted 13 January 2016; online 27 January 2016)

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 zwitterions 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.

1. Chemical context

Phosphane ligands (Allen, 2014[Allen, D. W. (2014). Organophosphorous Chemistry, Vol. 43, pp. 1-51. London: Royal Society of Chemistry.]) are ubiquitous in coordination and organometallic chemistry and have been used to synthesize a wide variety of metal complexes and catalysts (Hartwig, 2010[Hartwig, J. F. (2010). In Organotransition Metal Chemistry, from Bonding to Catalysis. New York: University Science Books.]). 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[Cai, Z., Shen, Z., Zhou, X. & Jordan, R. F. (2012). ACS Catal. 2, 1187-1195.]; Contrella & Jordan, 2014[Contrella, N. D. & Jordan, R. F. (2014). Organometallics, 33, 7199-7208.]; Zhou et al., 2014[Zhou, X., Lau, K.-C., Petro, B. J. & Jordan, R. F. (2014). Organometallics, 33, 7209-7214.]), copolymerization of ethyl­ene and polar monomers (Drent et al., 2002a[Drent, E., van Dijk, R., van Ginkel, R., van Oort, B. & Pugh, R. I. (2002a). Chem. Commun. pp. 744-745.]; Nakamura et al., 2013[Nakamura, A., Anselment, T. M. J., Claverie, J., Goodall, B., Jordan, R. F., Mecking, S., Rieger, B., Sen, A., van Leeuwen, P. W. N. M. & Nozaki, K. (2013). Acc. Chem. Res. 46, 1438-1449.]), non-alternating copolymerization of ethyl­ene and CO (Drent et al., 2002b[Drent, E., van Dijk, R., van Ginkel, R., van Oort, B. & Pugh, R. I. (2002b). Chem. Commun. pp. 964-965.]), and alternating copolymerization of CO with polar monomers (Nakamura et al., 2011[Nakamura, A., Munakata, K., Ito, S., Kochi, T., Chung, L. W., Morokuma, K. & Nozaki, K. (2011). J. Am. Chem. Soc. 133, 6761-6779.], 2012[Nakamura, A., Kageyama, T., Goto, H., Carrow, B. P., Ito, S. & Nozaki, K. (2012). J. Am. Chem. Soc. 134, 12366-12369.]). 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.

[Scheme 1]

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[Vela, J., Lief, G. R., Shen, Z. & Jordan, R. F. (2007). Organometallics, 26, 6624-6635.]). Here we report the crystal structure of 1·H2O·CH2Cl2, (I)[link].

[Scheme 2]

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[link]). 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[Feng, G., Conley, M. P. & Jordan, R. F. (2014). Organometallics, 33, 4486-4496.]). Tris(ortho-substituted ar­yl)phosphanes normally exhibit exo3 conformations (Howell et al., 1999[Howell, J. A. S., Fey, N., Lovatt, J. D., Yates, P. C., McArdle, P., Cunningham, D., Sadeh, E., Gottlieb, H. E., Goldschmidt, Z., Hursthouse, M. B. & Light, M. E. J. (1999). J. Chem. Soc. Dalton Trans. pp. 3015-3028.]) 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.

[Figure 1]
Figure 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.

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[Perdew, J. P., Burke, K. & Ernzerhof, M. (1996). Phys. Rev. Lett. 77, 3865-3868.], 1997[Perdew, J. P., Burke, K. & Ernzerhof, M. (1997). Phys. Rev. Lett. 78, 1396.]) 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[link]).

[Figure 2]
Figure 2
HOMO (−0.2289 Hartrees, left) and LUMO (−0.0483 Hartrees, right) orbitals of 1.

4. Supra­molecular features

Two O atoms of the SO3 group are hydrogen bonded with the co-crystallized water mol­ecule, forming inversion dimers (Fig. 3[link]). The Owater—H⋯Osulfonate contacts are 1.96 (3) and 1.98 (3) Å (Table 1[link]). These dimers are further linked by CAryl—H⋯Osulfonate hydrogen bonds into infinite chains running along the [100] direction (Fig. 4[link]). 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[Feng, G., Conley, M. P. & Jordan, R. F. (2014). Organometallics, 33, 4486-4496.]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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.
[Figure 3]
Figure 3
Dimer formation through Owater—H⋯Osulfonate hydrogen bonds (dashed lines).
[Figure 4]
Figure 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.

5. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.36, last update May 2015; Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) revealed structural reports for two analogues of 1 that contain 4-chloro-substituted meth­oxy­phenyl (CSD refcode ODUNOS; Wucher et al., 2013[Wucher, P., Goldbach, S. & Mecking, S. (2013). Organometallics, 32, 4516-4522.]) or 2,6-di­meth­oxy­phenyl substituents at phospho­rous (CSD refcode: LEXLEG; Liu et al., 2007[Liu, S., Borkar, D., Newsham, D., Yennawar, H. & Sen, A. (2007). Organometallics, 26, 210-216.]). These compounds also crystallized as zwitterions 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[Bettucci, L., Bianchini, C., Meli, A. & Oberhauser, W. (2008). J. Mol. Catal. A Chem. 291, 57-65.]). 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[Vela, J., Lief, G. R., Shen, Z. & Jordan, R. F. (2007). Organometallics, 26, 6624-6635.]) 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 diffraction analysis were obtained by layering Et2O on a CH2Cl2 solution of 1 at 277 K.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. Carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and were included in the refinement 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.

Table 2
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)
V3) 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[Bruker (2014). SAINT, APEX2 and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
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−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 and SAINT (Bruker, 2014[Bruker (2014). SAINT, APEX2 and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXT (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), SHELXL2014 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]), OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]), Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Chemical context top

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), copolymerization of ethyl­ene and polar monomers (Drent et al., 2002a; Nakamura et al., 2013), non-alternating copolymerization of ethyl­ene and CO (Drent et al., 2002b), and alternating copolymerization 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 crystal structure of 1·H2O·CH2Cl2, (I).

Structural commentary top

Crystals of 1·H2O·CH2Cl2 (I) suitable for X-ray diffraction analysis 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.

DFT calculations top

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).

Supra­molecular features top

Two O atoms of the SO3 group are hydrogen-bonded with the co-crystallized water molecule, forming inversion dimers (Fig. 3). The OwaterH···Osulfonate contacts are 1.96 (3) and 1.98 (3) Å (Table 1). These dimers are further linked by CArylH···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).

Database survey top

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 zwitterions 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.

Synthesis and crystallization top

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 diffraction analysis were obtained by layering Et2O on a wet CH2Cl2 solution of 1 at 277 K.

Refinement top

Crystal data, data collection and structure refinement 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 refinement 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.

Structure description top

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), copolymerization of ethyl­ene and polar monomers (Drent et al., 2002a; Nakamura et al., 2013), non-alternating copolymerization of ethyl­ene and CO (Drent et al., 2002b), and alternating copolymerization 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 crystal structure of 1·H2O·CH2Cl2, (I).

Crystals of 1·H2O·CH2Cl2 (I) suitable for X-ray diffraction analysis 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 OwaterH···Osulfonate contacts are 1.96 (3) and 1.98 (3) Å (Table 1). These dimers are further linked by CArylH···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 zwitterions 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.

Synthesis and crystallization top

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 diffraction analysis were obtained by layering Et2O on a wet CH2Cl2 solution of 1 at 277 K.

Refinement details top

Crystal data, data collection and structure refinement 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 refinement 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.

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: 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).

Figures top
[Figure 1] 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.
[Figure 2] Fig. 2. HOMO (−0.2289 Hartrees, left) and LUMO (−0.0483 Hartrees, right) orbitals of 1.
[Figure 3] Fig. 3. Dimer formation through OwaterH···Osulfonate hydrogen bonds (dashed lines).
[Figure 4] 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.
2-[Bis(2-methoxyphenyl)phosphaniumyl]-4-methylbenzenesulfonate monohydrate dichloromethane monosolvate top
Crystal data top
C21H21O5PS·CH2Cl2·H2OF(000) = 1080
Mr = 519.35Dx = 1.455 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.6437 (6) ÅCell parameters from 9610 reflections
b = 15.9441 (11) Åθ = 2.2–26.4°
c = 15.9641 (11) ŵ = 0.47 mm1
β = 105.051 (2)°T = 100 K
V = 2370.4 (3) Å3Block, colorless
Z = 40.32 × 0.18 × 0.12 mm
Data collection top
Bruker D8 Venture PHOTON 100 CMOS
diffractometer
4888 independent reflections
Radiation source: INCOATEC ImuS micro-focus source4349 reflections with I > 2σ(I)
Mirrors monochromatorRint = 0.030
Detector resolution: 10.4167 pixels mm-1θmax = 26.5°, θmin = 2.2°
ω and phi scansh = 1212
Absorption correction: multi-scan
(SADABS; Bruker, 2014)
k = 1919
Tmin = 0.693, Tmax = 0.745l = 2019
53574 measured reflections
Refinement top
Refinement on F2Primary atom site location: dual
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: mixed
wR(F2) = 0.106H 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 parametersΔρmax = 0.48 e Å3
0 restraintsΔρmin = 0.66 e Å3
Crystal data top
C21H21O5PS·CH2Cl2·H2OV = 2370.4 (3) Å3
Mr = 519.35Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.6437 (6) ŵ = 0.47 mm1
b = 15.9441 (11) ÅT = 100 K
c = 15.9641 (11) Å0.32 × 0.18 × 0.12 mm
β = 105.051 (2)°
Data collection top
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 = 0.745Rint = 0.030
53574 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.48 e Å3
4888 reflectionsΔρmin = 0.66 e Å3
304 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.63863 (5)0.30456 (3)0.33309 (3)0.01288 (12)
H1P0.592 (2)0.2397 (14)0.2950 (14)0.018 (5)*
S10.43769 (5)0.17697 (3)0.41453 (3)0.01702 (12)
O10.50338 (15)0.10620 (9)0.38266 (10)0.0261 (3)
O20.34252 (15)0.15453 (10)0.46751 (10)0.0269 (3)
O30.37411 (14)0.23600 (9)0.34604 (9)0.0210 (3)
O40.86431 (15)0.19197 (8)0.35798 (9)0.0210 (3)
O50.51406 (15)0.34403 (9)0.15930 (8)0.0206 (3)
C10.77958 (19)0.33171 (11)0.50245 (12)0.0155 (4)
H10.83720.36780.47810.019*
C20.66711 (19)0.28789 (11)0.44773 (11)0.0139 (3)
C30.58188 (19)0.23434 (11)0.48294 (12)0.0155 (4)
C40.6117 (2)0.22566 (12)0.57215 (12)0.0188 (4)
H40.55520.18900.59660.023*
C50.7235 (2)0.27025 (12)0.62605 (12)0.0187 (4)
H50.74170.26420.68710.022*
C60.8093 (2)0.32358 (12)0.59237 (12)0.0170 (4)
C70.9324 (2)0.37081 (13)0.65044 (13)0.0227 (4)
H7A0.92200.37080.70990.034*
H7B0.93230.42870.62990.034*
H7C1.02310.34370.64930.034*
C80.51505 (19)0.38810 (11)0.29746 (12)0.0159 (4)
C90.4711 (2)0.44064 (12)0.35526 (13)0.0202 (4)
H90.50890.43360.41600.024*
C100.3720 (2)0.50321 (13)0.32356 (14)0.0239 (4)
H100.34260.54020.36240.029*
C110.3158 (2)0.51167 (13)0.23483 (15)0.0246 (4)
H110.24610.55400.21360.030*
C120.3583 (2)0.46027 (12)0.17634 (13)0.0209 (4)
H120.31850.46700.11570.025*
C130.46023 (19)0.39848 (12)0.20784 (12)0.0173 (4)
C140.4860 (2)0.36077 (14)0.06819 (13)0.0261 (4)
H14A0.38270.35610.04130.039*
H14B0.53780.32010.04160.039*
H14C0.51840.41760.05950.039*
C150.80656 (19)0.32846 (12)0.31142 (11)0.0152 (4)
C160.8366 (2)0.40458 (12)0.27736 (12)0.0192 (4)
H160.76720.44820.26650.023*
C170.9686 (2)0.41647 (13)0.25930 (13)0.0224 (4)
H170.98940.46780.23490.027*
C181.0697 (2)0.35248 (13)0.27735 (13)0.0226 (4)
H181.16120.36150.26700.027*
C191.0407 (2)0.27600 (13)0.30998 (13)0.0208 (4)
H191.11060.23260.32080.025*
C200.9083 (2)0.26368 (12)0.32663 (12)0.0173 (4)
C210.9467 (2)0.11736 (13)0.35617 (14)0.0258 (4)
H21A0.95090.10620.29650.039*
H21B0.90120.06990.37750.039*
H21C1.04420.12510.39320.039*
C220.2653 (5)0.3457 (2)0.5203 (2)0.0676 (11)
H22A0.20560.30470.48010.081*
H22B0.35690.35180.50380.081*
Cl10.30192 (7)0.30568 (5)0.62409 (4)0.04587 (19)
Cl20.17791 (9)0.44136 (4)0.50619 (5)0.0517 (2)
O60.73753 (17)0.00322 (11)0.45863 (11)0.0308 (4)
H1O0.656 (4)0.027 (2)0.436 (2)0.049 (8)*
H2O0.701 (3)0.053 (2)0.4720 (19)0.043 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0121 (2)0.0138 (2)0.0124 (2)0.00178 (16)0.00263 (17)0.00083 (16)
S10.0143 (2)0.0180 (2)0.0173 (2)0.00200 (17)0.00148 (17)0.00157 (17)
O10.0245 (7)0.0214 (7)0.0283 (8)0.0011 (6)0.0007 (6)0.0049 (6)
O20.0227 (7)0.0324 (8)0.0255 (8)0.0092 (6)0.0062 (6)0.0041 (6)
O30.0141 (6)0.0255 (7)0.0207 (7)0.0009 (5)0.0003 (5)0.0048 (6)
O40.0217 (7)0.0174 (7)0.0268 (7)0.0068 (5)0.0115 (6)0.0045 (5)
O50.0244 (7)0.0213 (7)0.0148 (7)0.0010 (6)0.0027 (5)0.0006 (5)
C10.0151 (8)0.0143 (8)0.0173 (9)0.0025 (7)0.0044 (7)0.0010 (7)
C20.0147 (8)0.0138 (8)0.0134 (8)0.0043 (7)0.0043 (7)0.0012 (7)
C30.0137 (8)0.0159 (9)0.0162 (9)0.0026 (7)0.0025 (7)0.0006 (7)
C40.0182 (9)0.0209 (9)0.0179 (9)0.0014 (7)0.0058 (7)0.0035 (7)
C50.0213 (9)0.0210 (9)0.0139 (9)0.0045 (7)0.0047 (7)0.0015 (7)
C60.0160 (9)0.0168 (9)0.0173 (9)0.0047 (7)0.0026 (7)0.0020 (7)
C70.0234 (10)0.0239 (10)0.0186 (9)0.0010 (8)0.0017 (8)0.0030 (8)
C80.0123 (8)0.0153 (9)0.0198 (9)0.0020 (7)0.0038 (7)0.0036 (7)
C90.0198 (9)0.0202 (10)0.0211 (9)0.0029 (7)0.0063 (8)0.0025 (7)
C100.0229 (10)0.0199 (10)0.0323 (11)0.0051 (8)0.0131 (9)0.0028 (8)
C110.0159 (9)0.0206 (10)0.0381 (12)0.0039 (7)0.0080 (8)0.0117 (9)
C120.0162 (9)0.0209 (9)0.0229 (10)0.0024 (7)0.0002 (7)0.0093 (8)
C130.0133 (8)0.0172 (9)0.0211 (9)0.0029 (7)0.0039 (7)0.0027 (7)
C140.0339 (11)0.0273 (11)0.0166 (9)0.0028 (9)0.0055 (8)0.0023 (8)
C150.0136 (8)0.0191 (9)0.0131 (8)0.0004 (7)0.0037 (7)0.0023 (7)
C160.0199 (9)0.0189 (9)0.0183 (9)0.0006 (7)0.0040 (7)0.0011 (7)
C170.0247 (10)0.0223 (10)0.0213 (10)0.0082 (8)0.0077 (8)0.0020 (8)
C180.0170 (9)0.0303 (11)0.0221 (10)0.0056 (8)0.0083 (8)0.0079 (8)
C190.0158 (9)0.0272 (10)0.0196 (9)0.0025 (8)0.0049 (7)0.0045 (8)
C200.0183 (9)0.0196 (9)0.0140 (8)0.0001 (7)0.0042 (7)0.0015 (7)
C210.0311 (11)0.0198 (10)0.0289 (11)0.0109 (8)0.0117 (9)0.0024 (8)
C220.126 (3)0.0495 (18)0.0368 (15)0.043 (2)0.0374 (19)0.0161 (13)
Cl10.0453 (4)0.0621 (4)0.0305 (3)0.0225 (3)0.0103 (3)0.0118 (3)
Cl20.0798 (5)0.0347 (3)0.0452 (4)0.0190 (3)0.0245 (4)0.0098 (3)
O60.0241 (8)0.0272 (8)0.0389 (9)0.0020 (7)0.0040 (7)0.0056 (7)
Geometric parameters (Å, º) top
P1—C81.7794 (18)C10—C111.386 (3)
P1—C151.7828 (18)C10—H100.9500
P1—C21.7984 (18)C11—C121.382 (3)
P1—H1P1.22 (2)C11—H110.9500
S1—O21.4453 (15)C12—C131.390 (3)
S1—O11.4495 (15)C12—H120.9500
S1—O31.4521 (14)C14—H14A0.9800
S1—C31.7816 (19)C14—H14B0.9800
O4—C201.359 (2)C14—H14C0.9800
O4—C211.435 (2)C15—C161.391 (3)
O5—C131.354 (2)C15—C201.402 (3)
O5—C141.434 (2)C16—C171.389 (3)
C1—C21.391 (3)C16—H160.9500
C1—C61.395 (3)C17—C181.389 (3)
C1—H10.9500C17—H170.9500
C2—C31.400 (3)C18—C191.383 (3)
C3—C41.385 (3)C18—H180.9500
C4—C51.388 (3)C19—C201.384 (3)
C4—H40.9500C19—H190.9500
C5—C61.388 (3)C21—H21A0.9800
C5—H50.9500C21—H21B0.9800
C6—C71.505 (3)C21—H21C0.9800
C7—H7A0.9800C22—Cl11.725 (3)
C7—H7B0.9800C22—Cl21.728 (3)
C7—H7C0.9800C22—H22A0.9900
C8—C91.391 (3)C22—H22B0.9900
C8—C131.400 (3)O6—H1O0.91 (3)
C9—C101.384 (3)O6—H2O0.92 (3)
C9—H90.9500
C8—P1—C15110.16 (9)C12—C11—C10121.81 (18)
C8—P1—C2110.40 (8)C12—C11—H11119.1
C15—P1—C2108.82 (8)C10—C11—H11119.1
C8—P1—H1P110.0 (10)C11—C12—C13118.80 (18)
C15—P1—H1P108.8 (10)C11—C12—H12120.6
C2—P1—H1P108.6 (10)C13—C12—H12120.6
O2—S1—O1114.48 (9)O5—C13—C12125.99 (18)
O2—S1—O3113.14 (9)O5—C13—C8114.20 (16)
O1—S1—O3112.20 (9)C12—C13—C8119.81 (18)
O2—S1—C3106.35 (9)O5—C14—H14A109.5
O1—S1—C3105.80 (8)O5—C14—H14B109.5
O3—S1—C3103.80 (8)H14A—C14—H14B109.5
C20—O4—C21117.55 (15)O5—C14—H14C109.5
C13—O5—C14117.51 (15)H14A—C14—H14C109.5
C2—C1—C6121.17 (17)H14B—C14—H14C109.5
C2—C1—H1119.4C16—C15—C20120.20 (17)
C6—C1—H1119.4C16—C15—P1123.67 (14)
C1—C2—C3119.83 (17)C20—C15—P1116.05 (14)
C1—C2—P1116.93 (14)C17—C16—C15119.71 (18)
C3—C2—P1123.24 (14)C17—C16—H16120.1
C4—C3—C2119.16 (17)C15—C16—H16120.1
C4—C3—S1119.96 (14)C16—C17—C18119.23 (19)
C2—C3—S1120.87 (14)C16—C17—H17120.4
C3—C4—C5120.43 (18)C18—C17—H17120.4
C3—C4—H4119.8C19—C18—C17121.78 (18)
C5—C4—H4119.8C19—C18—H18119.1
C6—C5—C4121.25 (17)C17—C18—H18119.1
C6—C5—H5119.4C18—C19—C20118.94 (18)
C4—C5—H5119.4C18—C19—H19120.5
C5—C6—C1118.16 (17)C20—C19—H19120.5
C5—C6—C7121.47 (17)O4—C20—C19125.57 (18)
C1—C6—C7120.37 (17)O4—C20—C15114.34 (16)
C6—C7—H7A109.5C19—C20—C15120.09 (18)
C6—C7—H7B109.5O4—C21—H21A109.5
H7A—C7—H7B109.5O4—C21—H21B109.5
C6—C7—H7C109.5H21A—C21—H21B109.5
H7A—C7—H7C109.5O4—C21—H21C109.5
H7B—C7—H7C109.5H21A—C21—H21C109.5
C9—C8—C13120.48 (17)H21B—C21—H21C109.5
C9—C8—P1122.19 (15)Cl1—C22—Cl2115.01 (17)
C13—C8—P1117.32 (14)Cl1—C22—H22A108.5
C10—C9—C8119.47 (19)Cl2—C22—H22A108.5
C10—C9—H9120.3Cl1—C22—H22B108.5
C8—C9—H9120.3Cl2—C22—H22B108.5
C9—C10—C11119.59 (19)H22A—C22—H22B107.5
C9—C10—H10120.2H1O—O6—H2O102 (3)
C11—C10—H10120.2
C6—C1—C2—C30.2 (3)C8—C9—C10—C111.2 (3)
C6—C1—C2—P1179.37 (14)C9—C10—C11—C121.4 (3)
C8—P1—C2—C191.04 (15)C10—C11—C12—C130.0 (3)
C15—P1—C2—C129.98 (16)C14—O5—C13—C1212.9 (3)
C8—P1—C2—C388.50 (16)C14—O5—C13—C8167.84 (16)
C15—P1—C2—C3150.48 (15)C11—C12—C13—O5179.18 (17)
C1—C2—C3—C40.3 (3)C11—C12—C13—C81.6 (3)
P1—C2—C3—C4179.79 (14)C9—C8—C13—O5178.92 (16)
C1—C2—C3—S1179.67 (13)P1—C8—C13—O52.3 (2)
P1—C2—C3—S10.8 (2)C9—C8—C13—C121.7 (3)
O2—S1—C3—C421.46 (18)P1—C8—C13—C12177.04 (14)
O1—S1—C3—C4100.67 (16)C8—P1—C15—C164.33 (19)
O3—S1—C3—C4141.04 (15)C2—P1—C15—C16116.84 (16)
O2—S1—C3—C2159.14 (15)C8—P1—C15—C20172.54 (14)
O1—S1—C3—C278.73 (16)C2—P1—C15—C2066.29 (16)
O3—S1—C3—C239.55 (17)C20—C15—C16—C170.7 (3)
C2—C3—C4—C50.8 (3)P1—C15—C16—C17177.42 (15)
S1—C3—C4—C5179.82 (14)C15—C16—C17—C181.3 (3)
C3—C4—C5—C60.8 (3)C16—C17—C18—C192.3 (3)
C4—C5—C6—C10.4 (3)C17—C18—C19—C201.3 (3)
C4—C5—C6—C7178.82 (18)C21—O4—C20—C1914.4 (3)
C2—C1—C6—C50.1 (3)C21—O4—C20—C15165.79 (17)
C2—C1—C6—C7179.34 (17)C18—C19—C20—O4179.46 (18)
C15—P1—C8—C9109.47 (16)C18—C19—C20—C150.8 (3)
C2—P1—C8—C910.75 (19)C16—C15—C20—O4178.46 (16)
C15—P1—C8—C1371.78 (16)P1—C15—C20—O41.5 (2)
C2—P1—C8—C13168.00 (14)C16—C15—C20—C191.7 (3)
C13—C8—C9—C100.3 (3)P1—C15—C20—C19178.73 (14)
P1—C8—C9—C10178.39 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O6—H1O···O10.91 (3)1.96 (3)2.862 (2)170 (3)
O6—H2O···O2i0.92 (3)1.98 (3)2.877 (2)164 (3)
C19—H19···O3ii0.952.473.180 (2)132
Symmetry codes: (i) x+1, y, z+1; (ii) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O6—H1O···O10.91 (3)1.96 (3)2.862 (2)170 (3)
O6—H2O···O2i0.92 (3)1.98 (3)2.877 (2)164 (3)
C19—H19···O3ii0.952.473.180 (2)131.7
Symmetry codes: (i) x+1, y, z+1; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC21H21O5PS·CH2Cl2·H2O
Mr519.35
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)9.6437 (6), 15.9441 (11), 15.9641 (11)
β (°) 105.051 (2)
V3)2370.4 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.47
Crystal size (mm)0.32 × 0.18 × 0.12
Data collection
DiffractometerBruker D8 Venture PHOTON 100 CMOS
Absorption correctionMulti-scan
(SADABS; Bruker, 2014)
Tmin, Tmax0.693, 0.745
No. of measured, independent and
observed [I > 2σ(I)] reflections
53574, 4888, 4349
Rint0.030
(sin θ/λ)max1)0.627
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.106, 1.05
No. of reflections4888
No. of parameters304
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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).

References

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Volume 72| Part 2| February 2016| Pages 229-232
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