research communications
and hydrogen bonding in the water-stabilized proton-transfer salt brucinium 4-aminophenylarsonate tetrahydrate
aScience and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia
*Correspondence e-mail: g.smith@qut.edu.au
In the structure of the brucinium salt of 4-aminophenylarsonic acid (p-arsanilic acid), systematically 2,3-dimethoxy-10-oxostrychnidinium 4-aminophenylarsonate tetrahydrate, (C23H27N2O4)[As(C6H7N)O2(OH)]·4H2O, the brucinium cations form the characteristic undulating and overlapping head-to-tail layered brucine substructures packed along [010]. The arsanilate anions and the water molecules of solvation are accommodated between the layers and are linked to them through a primary cation N—H⋯O(anion) hydrogen bond, as well as through water O—H⋯O hydrogen bonds to brucinium and arsanilate ions as well as bridging water O-atom acceptors, giving an overall three-dimensional network structure.
Keywords: crystal structure; brucinium salts; p-arsanilic acid; water stabilization; hydrogen bonding.
CCDC reference: 1475231
1. Chemical context
The Strychnos alkaloid base brucine, (2,3-dimethoxystrychnidin-10-one; BRU) has been extensively employed as a resolving agent for chiral organic compounds (Wilen, 1972). With chiral acids, the separation is achieved through proton-transfer to N19 of the strychnidine cage (pKa2 = 11.7; O'Neil, 2001), followed by separation of the resultant crystalline salt products by fractional crystallization. Similar effects are achieved with the essentially identical Strychnos alkaloid strychnine but separation efficiency favours brucine. This is probably because of the formation in the crystal of characteristic brucinium host substructures comprising head-to-tail undulating layers of brucine molecules or cations which accommodate selectively the hydrogen-bonded guest molecules in the A characteristic of the is the repeat interval in the layer of ca 12.3 Å along a 21 screw axis in the crystal, which is reflected in the unit-cell dimension, with brucine being predominantly in the monoclinic P21 or the orthorhombic P212121 (Smith, Wermuth & White, 2006; Smith, Wermuth, Young & White, 2006).
This example of molecular recognition was described in the early structure determinations of brucinium benzoyl-D-alaninate (Gould & Walkinshaw, 1984) and in the structures of the pseudopolymorphic brucine solvates, brucine–MeOH (1:1) and brucine–EtOH–water (1/1/2) (Glover et al., 1985). The guest molecules are accommodated interstitially within the layers and are commonly accompanied by compatible molecules, usually generating high-dimensional hydrogen-bonded crystal structures.
Currently, a large number of structures of brucine compounds with chiral organic molecules, including both acids and non-acids are known, but in addition those with achiral compounds also feature. Of interest to us have been the structures of brucinium proton-transfer salts with largely simple organic acids, prepared under aqueous alcoholic conditions, the crystalline products being stabilized by solvent molecules. Water-stabilized achiral carboxylate examples include BRU+ hydrogen fumarate−·1.5H2O (Dijksma, Gould, Parsons & Walkinshaw, 1998), BRU+ dihydrogen citrate−·3H2O (Smith, Wermuth & White, 2005) and BRU+ benzoate−·3H2O (Białońska & Ciunik, 2006b).
Other organic acids besides carboxylates may be included among the set but fewer structural examples are known, e.g. sulfonates (BRU+ toluene-4-sulfonate−·3H2O; Smith, Wermuth, Healy et al., 2005). However, no brucinium arsonate structures are known, so that the reaction of brucine with 4-aminophenylarsonic acid (p-arsanilic acid) in 2-propanol/water was carried out, resulting in the formation of the crystalline hydrated title salt, C23H27N2O4+· C6H7AsNO3−·4H2O, and the structure is reported herein. The acid has biological significance as an anti-helminth in veterinary applications (Thomas, 1905; Steverding, 2010) and as a monohydrated sodium salt (atoxyl) which had early usage as an anti-syphilitic (Ehrlich & Bertheim, 1907; Bosch & Rosich, 2008). Simple p-arsanilate salt structures are not common in the Cambridge Structural Database (Groom et al., 2016), with only the NH4+ and K+ salts (Smith & Wermuth, 2014) and the guanidinium salts (Smith & Wermuth, 2010; Latham et al., 2011) being known.
2. Structural commentary
The p-arsanilate anion A and four water molecules of solvation, (O1W–O4W), all inter-associated through hydrogen bonds (Fig. 1). Protonation has occurred as expected at N19 of the brucine cage, the invoked Peerdeman (1956) for the strychnidinium molecule giving the overall Cahn–Ingold stereochemistry of the cation as C7(R), C8(S), C12(S), C13(R), C14(R), C16(S) and the additional introduced (S) chiral centre at N19.
of the title salt comprises a brucinium cation, a3. Supramolecular features
The brucinium cations form into the previously described undulating sheet–host substructures which are considered to be the reason for the molecular recognition peculiar to brucine (Gould & Walkinshaw, 1984; Gould et al., 1985; Dijksma, Gould, Parsons & Walkinshaw, 1998; Dijksma, Gould, Parsons, Taylor & Walkinshaw, 1998; Oshikawa et al., 2002; Białońska & Ciunik, 2004). In the title salt, these substructures extend along the b-axis direction, with the previously described 21 propagation of the brucinium cations along the ca 12.3 Å axis (Fig. 2). The p-arsanilate anions and the water molecules occupy the interstitial spaces in the structure. The protonated N19 atom of the cation gives a single hydrogen-bonding interaction with a p-arsanilate oxygen acceptor (O12A) while two of the solvent water molecules (O1W and O3W) form hydrogen bonds with the carbonyl O25 atom of the the brucinium cation (Table 1). Within the inter-sheet channels, the p-arsanilate anions are linked head-to-head through an O13A—H⋯O11Aii hydrogen bond while both H atoms of the amine group form hydrogen bonds with water molecules O3W and O4Wi. The water molecules O2W and O4A are further linked to the p-arsanilate O-atom O12A with O2W also linked to O11Aiv. Water molecules O3W and O4Wi give inter-water hydrogen bonds and together with a number of inter-molecular C—H⋯O interactions (Table 1) result in an overall three-dimensional network structure (Fig. 3).
4. Database survey
Interstitial water molecules are present in the structures of the brucine pseudo-polymorphic structures, e.g. the common tetrahydrate form and the 5.2 hydrate (Smith et al., 2006a) and the dihydrate (Smith et al., 2007), as well as the mixed solvates BRU–EtOH–H2O (1/1/2) (Glover et al., 1985) and BRU–i-PrOH–H2O (1/1/2) (Białońska & Ciunik, 2004). A large number of water-stabilized brucinium salts of acids are known: with the inorganic sulfate (BRU)2SO4·7H2O (Białońska & Ciunik, 2005) and most commonly with aromatic carboxylates, e.g. the benzoate (a trihydrate; Białońska & Ciunik, 2006b); the 4-nitrobenzoate (a dihydrate; Białońska & Ciunik, 2007); the 3,5-dinitrobenzoate (a trihydrate; Białońska & Ciunik, 2006a); the 3,5-dinitrosalicylate (a monohydrate; Smith et al., 2006a); the phthalate (a monohydrate; Krishnan, Gayathri, Sivakumar, Gunasekaran & Anbalagen, 2013); the hydrogen isophthalate (a trihydrate; Smith, Wermuth, Young & White, 2006); the hydrogen 3-nitrophthalate (a dihydrate; Smith, Wermuth, Young & Healy, 2005) and the picraminobenzoate (a monohydrate; Smith & Wermuth, 2011).
Aliphatic carboxylate examples are: with hydrogen oxalate (a dihydrate; Krishnan, Gayathri, Sivakumar, Chakkaravathi & Anbalagen, 2013); with hydrogen fumarate (a sesquihydrate; Dijksma, Gould, Parsons & Walkinshaw, 1998); with hydrogen (S)-malate (a pentahydrate; Smith, Wermuth & White, 2006); with dihydrogen citrate (a trihydrate; Smith, Wermuth & White, 2005); with L-glycerate (a 4.75 hydrate; Białońska et al., 2005) and with hydrogen cis-cyclohexane-1,2-dicarboxylate (a dihydrate; Smith et al., 2012). Some sulfonate salts are also known, e.g. with toluene-4-sulfonate (a trihydrate; Smith, Wermuth, Healy et al., 2005); with 3-carboxy-4-hydroxybenzenesulfonate (a pentahydrate; Smith et al., 2006b) and with biphenyl-4,4′-disulfonate (a hexahydrate; Smith et al., 2010).
5. Synthesis and crystallization
The title compound was synthesized by heating together under reflux for 10 min, 1 mmol quantities of brucine tetrahydrate and 4-aminophenylarsonic acid in 50 mL of 80% 2-propanol/water. After concentration to ca 30 mL, partial room-temperature evaporation of the hot-filtered solution gave thin colourless crystal plates of the title compound from which a specimen was cleaved for the X-ray analysis.
6. details
Crystal data, data collection and structure . Hydrogen atoms potentially involved in hydrogen-bonding interactions were located by difference methods but their positional parameters were constrained in the with N—H and O—H = 0.90 Å, and with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O). Other H atoms were included in the at calculated positions [C—H(aromatic) = 0.95 Å and C—H (aliphatic) = 0.97–1.00 Å] and treated as riding with Uiso(H) = 1.2Ueq(C). The determined for the parent strychnidinin-10-one molecule (Peerdeman, 1956) was invoked and was confirmed in the the structure refinement.
details are summarized in Table 2
|
Supporting information
CCDC reference: 1475231
10.1107/S2056989016006691/lh5811sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016006691/lh5811Isup2.hkl
The Strychnos alkaloid base brucine, (2,3-dimethoxystrychnidin-10-one; BRU) has been extensively employed as a resolving agent for chiral organic compounds (Wilen, 1972). With chiral acids, the separation is achieved through proton-transfer to N19 of the strychnidine cage (pKa2 = 11.7; O'Neil, 2001), followed by separation of the resultant crystalline salt products by fractional crystallization. Similar effects are achieved with the essentially identical Strychnos alkaloid but separation efficiency favours brucine. This is probably because of the formation in the crystal of characteristic brucinium host substructures comprising head-to-tail undulating layers of brucine molecules or cations which accommodate selectively the hydrogen-bonded guest molecules in the
A characteristic of the is the repeat interval in the layer of ca 12.3 Å along a 21 screw axis in the crystal, which is reflected in the unit-cell dimension, with brucine being predominantly in the monoclinic P21 or the orthorhombic P212121 (Smith, Wermuth & White, 2006; Smith, Wermuth, Young & White, 2006).This example of molecular recognition was described in the early structure determinations of brucinium benzoyl-D-alaninate (Gould & Walkinshaw, 1984) and in the structures of the pseudopolymorphic brucine solvates, brucine–MeOH (1:1) and brucine–EtOH–water (1/1/2) (Glover et al., 1985). The guest molecules are accommodated interstitially within the layers and are commonly accompanied by compatible
molecules, usually generating high-dimensional hydrogen-bonded crystal structures.Currently, a large number of structures of brucine compounds with chiral organic molecules, including both acids and non-acids are known, but in addition those with achiral compounds also feature. Of interest to us have been the structures of brucinium proton-transfer salts with largely simple organic acids, prepared under aqueous alcoholic conditions, the crystalline products being stabilized by solvent molecules. Water-stabilized achiral carboxylate examples include BRU+ hydrogen fumarate·1.5H2O (Dijksma, Gould, Parsons & Walkinshaw, 1998), BRU+ dihydrogen citrate·3H2O (Smith, Wermuth & White, 2005) and BRU+ benzoate-·3H2O (Bialońska & Ciunik, 2006b).
Other organic acids besides carboxylates may be included among the set but fewer structural examples are known, e.g. sulfonates (BRU+ toluene-4-sulfonate-·3H2O; Smith, Wermuth, Healy et al., 2005). However, no brucinium arsonate structures are known, so that the reaction of brucine with 4-aminophenylarsonic acid (p-arsanilic acid) in 2-propanol/water was carried out, resulting in the formation of the crystalline hydrated title salt, C23H27N2O4+· C6H7AsNO3-·4H2O, and the structure is reported herein. The acid has biological significance as an anti-helminth in veterinary applications (Thomas, 1905; Steverding, 2010) and as a monohydrated sodium salt (atoxyl) which had early usage as an anti-syphilitic (Ehrlich & Bertheim, 1907; Bosch & Rosich, 2008). Simple p-arsanilate salt structures are not common in the Cambridge Structural Database (Groom et al., 2016), with only the NH4+ and K+ salts (Smith & Wermuth, 2014) and the guanidinium salts (Smith & Wermuth, 2010; Latham et al., 2011) being known.
The
of the title salt comprises a brucinium cation, a p-arsanilate anion A and four water molecules of solvation, (O1W–O4W), all inter-associated through hydrogen bonds (Fig. 1). Protonation has occurred as expected at N19 of the brucine cage, the invoked Peerdeman (1956) for the strychnidinium molecule giving the overall Cahn–Ingold stereochemistry of the cation as C7(R), C8(S), C12(S), C13(R), C14(R), C16(S) and the additional introduced (S) chiral centre at N19.The brucinium cations form into the previously described undulating sheet–host substructures which are considered to be the reason for the molecular recognition peculiar to brucine (Gould & Walkinshaw, 1984; Gould et al., 1985; Dijksma, Gould, Parsons & Walkinshaw, 1998; Dijksma, Gould, Parsons, Taylor & Walkinshaw, 1998; Oshikawa et al., 2002; Bialońska & Ciunik, 2004). In the title salt, these substructures extend along the b-axis direction, with the previously described 21 propagation of the brucinium cations along the ca 12.3 Å b axis (Fig. 2). The p-arsanilate anions and the water molecules occupy the interstitial spaces in the structure. The protonated N19 atom of the cation gives a single hydrogen-bonding interaction with a p-arsanilate oxygen acceptor (O12A) while two of the solvent water molecules (O1W and O3W) form hydrogen bonds with the carbonyl O25 atom of the the brucinium cation (Table 1). Within the inter-sheet channels, the p-arsanilate anions are linked head-to-head through an O13A—H···O11Aii hydrogen bond while both H atoms of the amine group form H bonds with water molecules O3W and O4Wi. The water molecules O2W and O4A are further linked to the p-arsanilate O-atom O12A with O2W also linked to O11Aiv. Water molecules O3W and O4Wi give inter-water hydrogen bonds and together with a number of inter-molecular C—H···O interactions (Table 1) result in an overall three-dimensional network structure (Fig. 3).
Interstitial water molecules are present in the structures of the brucine pseudo-polymorphic structures, e.g. the common tetrahydrate form and the 5.2 hydrate (Smith et al., 2006a) and the dihydrate (Smith et al., 2007), as well as the mixed solvates BRU–EtOH–H2O (1/1/2) (Glover et al., 1985) and BRU–i-PrOH–H2O (1/1/2) (Bialońska & Ciunik, 2004). A large number of water-stabilized brucinium salts of acids are known: with the inorganic sulfate (BRU)2SO4·7H2O (Bialońska & Ciunik, 2005) and most commonly with the aromatic carboxylates, e.g. the benzoate (a trihydrate; Bialońska & Ciunik, 2006b); the 4-nitrobenzoate (a dihydrate; Bialońska & Ciunik, 2007); the 3,5-dinitrobenzoate (a trihydrate; Bialońska & Ciunik, 2006a); the 3,5-dinitrosalicylate (a monohydrate; Smith et al., 2006a); the phthalate (a monohydrate; Krishnan, Gayathri, Sivakumar, Gunasekaran & Anbalagen, 2013); the hydrogen isophthalate (a trihydrate; Smith, Wermuth, Young & White, 2006); the hydrogen 3-nitrophthalate (a dihydrate; Smith, Wermuth, Young & Healy, 2005) and the picraminobenzoate (a monohydrate; Smith & Wermuth, 2011).
Aliphatic carboxylate examples are: with hydrogen oxalate (a dihydrate; Krishnan, Gayathri, Sivakumar, Chakkaravathi & Anbalagen, 2013); with hydrogen fumarate (a sesquihydrate; Dijksma, Gould, Parsons & Walkinshaw, 1998); with hydrogen (S)-malate (a pentahydrate; Smith, Wermuth & White, 2006); with dihydrogen citrate (a trihydrate; Smith, Wermuth & White, 2005); with L-glycerate (a 4.75 hydrate; Bialońska et al., 2005) and with hydrogen cis-cyclohexane-1,2-dicarboxylate (a dihydrate; Smith et al., 2012). Some sulfonate salts are also known, e.g. with toluene-4-sulfonate (a trihydrate; Smith, Wermuth, Healy et al., 2005); with 3-carboxy-4-hydroxybenzenesulfonate (a pentahydrate; Smith et al., 2006b) and with biphenyl-4,4'-disulfonate (a hexahydrate; Smith et al., 2010).
The title compound was synthesized by heating together under reflux for 10 min, 1 mmol quantities of brucine tetrahydrate and 4-aminophenylarsonic acid in 50 mL of 80% 2-propanol/water. After concentration to ca 30 mL, partial room-temperature evaporation of the hot-filtered solution gave thin colourless crystal plates of the title compound from which a specimen was cleaved for the X-ray analysis.
Crystal data, data collection and structure
details are summarized in Table 2. Hydrogen atoms potentially involved in hydrogen-bonding interactions were located by difference methods but their positional parameters were constrained in the with N—H and O—H = 0.90 Å, and with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O). Other H atoms were included in the at calculated positions [C—H(aromatic) = 0.95 Å and C—H (aliphatic) = 0.97–1.00 Å] and treated as riding with Uiso(H) = 1.2Ueq(C). The determined for the parent strychnidinin-10-one molecule (Peerdeman, 1956) was invoked and was confirmed in the the structure (Flack, 1983) [absolute structure parameter -0.005 (9) for 3672 Friedel pairs].The Strychnos alkaloid base brucine, (2,3-dimethoxystrychnidin-10-one; BRU) has been extensively employed as a resolving agent for chiral organic compounds (Wilen, 1972). With chiral acids, the separation is achieved through proton-transfer to N19 of the strychnidine cage (pKa2 = 11.7; O'Neil, 2001), followed by separation of the resultant crystalline salt products by fractional crystallization. Similar effects are achieved with the essentially identical Strychnos alkaloid but separation efficiency favours brucine. This is probably because of the formation in the crystal of characteristic brucinium host substructures comprising head-to-tail undulating layers of brucine molecules or cations which accommodate selectively the hydrogen-bonded guest molecules in the
A characteristic of the is the repeat interval in the layer of ca 12.3 Å along a 21 screw axis in the crystal, which is reflected in the unit-cell dimension, with brucine being predominantly in the monoclinic P21 or the orthorhombic P212121 (Smith, Wermuth & White, 2006; Smith, Wermuth, Young & White, 2006).This example of molecular recognition was described in the early structure determinations of brucinium benzoyl-D-alaninate (Gould & Walkinshaw, 1984) and in the structures of the pseudopolymorphic brucine solvates, brucine–MeOH (1:1) and brucine–EtOH–water (1/1/2) (Glover et al., 1985). The guest molecules are accommodated interstitially within the layers and are commonly accompanied by compatible
molecules, usually generating high-dimensional hydrogen-bonded crystal structures.Currently, a large number of structures of brucine compounds with chiral organic molecules, including both acids and non-acids are known, but in addition those with achiral compounds also feature. Of interest to us have been the structures of brucinium proton-transfer salts with largely simple organic acids, prepared under aqueous alcoholic conditions, the crystalline products being stabilized by solvent molecules. Water-stabilized achiral carboxylate examples include BRU+ hydrogen fumarate·1.5H2O (Dijksma, Gould, Parsons & Walkinshaw, 1998), BRU+ dihydrogen citrate·3H2O (Smith, Wermuth & White, 2005) and BRU+ benzoate-·3H2O (Bialońska & Ciunik, 2006b).
Other organic acids besides carboxylates may be included among the set but fewer structural examples are known, e.g. sulfonates (BRU+ toluene-4-sulfonate-·3H2O; Smith, Wermuth, Healy et al., 2005). However, no brucinium arsonate structures are known, so that the reaction of brucine with 4-aminophenylarsonic acid (p-arsanilic acid) in 2-propanol/water was carried out, resulting in the formation of the crystalline hydrated title salt, C23H27N2O4+· C6H7AsNO3-·4H2O, and the structure is reported herein. The acid has biological significance as an anti-helminth in veterinary applications (Thomas, 1905; Steverding, 2010) and as a monohydrated sodium salt (atoxyl) which had early usage as an anti-syphilitic (Ehrlich & Bertheim, 1907; Bosch & Rosich, 2008). Simple p-arsanilate salt structures are not common in the Cambridge Structural Database (Groom et al., 2016), with only the NH4+ and K+ salts (Smith & Wermuth, 2014) and the guanidinium salts (Smith & Wermuth, 2010; Latham et al., 2011) being known.
The
of the title salt comprises a brucinium cation, a p-arsanilate anion A and four water molecules of solvation, (O1W–O4W), all inter-associated through hydrogen bonds (Fig. 1). Protonation has occurred as expected at N19 of the brucine cage, the invoked Peerdeman (1956) for the strychnidinium molecule giving the overall Cahn–Ingold stereochemistry of the cation as C7(R), C8(S), C12(S), C13(R), C14(R), C16(S) and the additional introduced (S) chiral centre at N19.The brucinium cations form into the previously described undulating sheet–host substructures which are considered to be the reason for the molecular recognition peculiar to brucine (Gould & Walkinshaw, 1984; Gould et al., 1985; Dijksma, Gould, Parsons & Walkinshaw, 1998; Dijksma, Gould, Parsons, Taylor & Walkinshaw, 1998; Oshikawa et al., 2002; Bialońska & Ciunik, 2004). In the title salt, these substructures extend along the b-axis direction, with the previously described 21 propagation of the brucinium cations along the ca 12.3 Å b axis (Fig. 2). The p-arsanilate anions and the water molecules occupy the interstitial spaces in the structure. The protonated N19 atom of the cation gives a single hydrogen-bonding interaction with a p-arsanilate oxygen acceptor (O12A) while two of the solvent water molecules (O1W and O3W) form hydrogen bonds with the carbonyl O25 atom of the the brucinium cation (Table 1). Within the inter-sheet channels, the p-arsanilate anions are linked head-to-head through an O13A—H···O11Aii hydrogen bond while both H atoms of the amine group form H bonds with water molecules O3W and O4Wi. The water molecules O2W and O4A are further linked to the p-arsanilate O-atom O12A with O2W also linked to O11Aiv. Water molecules O3W and O4Wi give inter-water hydrogen bonds and together with a number of inter-molecular C—H···O interactions (Table 1) result in an overall three-dimensional network structure (Fig. 3).
Interstitial water molecules are present in the structures of the brucine pseudo-polymorphic structures, e.g. the common tetrahydrate form and the 5.2 hydrate (Smith et al., 2006a) and the dihydrate (Smith et al., 2007), as well as the mixed solvates BRU–EtOH–H2O (1/1/2) (Glover et al., 1985) and BRU–i-PrOH–H2O (1/1/2) (Bialońska & Ciunik, 2004). A large number of water-stabilized brucinium salts of acids are known: with the inorganic sulfate (BRU)2SO4·7H2O (Bialońska & Ciunik, 2005) and most commonly with the aromatic carboxylates, e.g. the benzoate (a trihydrate; Bialońska & Ciunik, 2006b); the 4-nitrobenzoate (a dihydrate; Bialońska & Ciunik, 2007); the 3,5-dinitrobenzoate (a trihydrate; Bialońska & Ciunik, 2006a); the 3,5-dinitrosalicylate (a monohydrate; Smith et al., 2006a); the phthalate (a monohydrate; Krishnan, Gayathri, Sivakumar, Gunasekaran & Anbalagen, 2013); the hydrogen isophthalate (a trihydrate; Smith, Wermuth, Young & White, 2006); the hydrogen 3-nitrophthalate (a dihydrate; Smith, Wermuth, Young & Healy, 2005) and the picraminobenzoate (a monohydrate; Smith & Wermuth, 2011).
Aliphatic carboxylate examples are: with hydrogen oxalate (a dihydrate; Krishnan, Gayathri, Sivakumar, Chakkaravathi & Anbalagen, 2013); with hydrogen fumarate (a sesquihydrate; Dijksma, Gould, Parsons & Walkinshaw, 1998); with hydrogen (S)-malate (a pentahydrate; Smith, Wermuth & White, 2006); with dihydrogen citrate (a trihydrate; Smith, Wermuth & White, 2005); with L-glycerate (a 4.75 hydrate; Bialońska et al., 2005) and with hydrogen cis-cyclohexane-1,2-dicarboxylate (a dihydrate; Smith et al., 2012). Some sulfonate salts are also known, e.g. with toluene-4-sulfonate (a trihydrate; Smith, Wermuth, Healy et al., 2005); with 3-carboxy-4-hydroxybenzenesulfonate (a pentahydrate; Smith et al., 2006b) and with biphenyl-4,4'-disulfonate (a hexahydrate; Smith et al., 2010).
The title compound was synthesized by heating together under reflux for 10 min, 1 mmol quantities of brucine tetrahydrate and 4-aminophenylarsonic acid in 50 mL of 80% 2-propanol/water. After concentration to ca 30 mL, partial room-temperature evaporation of the hot-filtered solution gave thin colourless crystal plates of the title compound from which a specimen was cleaved for the X-ray analysis.
detailsCrystal data, data collection and structure
details are summarized in Table 2. Hydrogen atoms potentially involved in hydrogen-bonding interactions were located by difference methods but their positional parameters were constrained in the with N—H and O—H = 0.90 Å, and with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O). Other H atoms were included in the at calculated positions [C—H(aromatic) = 0.95 Å and C—H (aliphatic) = 0.97–1.00 Å] and treated as riding with Uiso(H) = 1.2Ueq(C). The determined for the parent strychnidinin-10-one molecule (Peerdeman, 1956) was invoked and was confirmed in the the structure (Flack, 1983) [absolute structure parameter -0.005 (9) for 3672 Friedel pairs].Data collection: CrysAlis PRO (Rigaku OD, 2015); cell
CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).Fig. 1. Molecular configuration and atom-numbering scheme for the brucinium cation, p-arsanilate anion A and the four water molecules of solvation in the asymmetric unit of the title salt. Inter-species hydrogen bonds are shown as dashed lines. Non-H atoms are shown as 40% probability displacement ellipsoids. | |
Fig. 2. The undulating brucinium sheet substructures in the unit cell of the title salt, less the inter-sheet anion and water molecules, viewed down a. All H atoms except that of the protonated N19 atom have also been removed. | |
Fig. 3. A perspective view of the packing in the unit cell, viewed along the approximate a-axial direction, showing the associated anions and the water molecules in the interstitial regions of the brucinium layered substructures, with hydrogen-bonding interactions shown as dashed lines. |
(C23H27N2O4)[As(C6H7N)O2(OH)]·4H2O | F(000) = 1432 |
Mr = 683.58 | Dx = 1.506 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 2822 reflections |
a = 7.6553 (3) Å | θ = 3.4–27.9° |
b = 12.3238 (5) Å | µ = 1.19 mm−1 |
c = 31.960 (2) Å | T = 200 K |
V = 3015.2 (3) Å3 | Plate, colourless |
Z = 4 | 0.36 × 0.34 × 0.10 mm |
Oxford Diffraction Gemini-S CCD-detector diffractometer | 6980 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 5901 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
Detector resolution: 16.077 pixels mm-1 | θmax = 29.5°, θmin = 3.1° |
ω scans | h = −10→6 |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015) | k = −16→16 |
Tmin = 0.811, Tmax = 0.980 | l = −43→25 |
11983 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.0414P)2 + 0.2011P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
6980 reflections | Δρmax = 0.55 e Å−3 |
433 parameters | Δρmin = −0.46 e Å−3 |
14 restraints | Absolute structure: Flack (1983), 3672 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.005 (9) |
(C23H27N2O4)[As(C6H7N)O2(OH)]·4H2O | V = 3015.2 (3) Å3 |
Mr = 683.58 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.6553 (3) Å | µ = 1.19 mm−1 |
b = 12.3238 (5) Å | T = 200 K |
c = 31.960 (2) Å | 0.36 × 0.34 × 0.10 mm |
Oxford Diffraction Gemini-S CCD-detector diffractometer | 6980 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015) | 5901 reflections with I > 2σ(I) |
Tmin = 0.811, Tmax = 0.980 | Rint = 0.032 |
11983 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.096 | Δρmax = 0.55 e Å−3 |
S = 1.05 | Δρmin = −0.46 e Å−3 |
6980 reflections | Absolute structure: Flack (1983), 3672 Friedel pairs |
433 parameters | Absolute structure parameter: −0.005 (9) |
14 restraints |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O2 | 0.2664 (3) | 0.56076 (19) | 0.24172 (7) | 0.0288 (8) | |
O3 | 0.2324 (3) | 0.44912 (19) | 0.17363 (7) | 0.0251 (7) | |
O24 | 0.2010 (3) | −0.13571 (17) | 0.32202 (7) | 0.0224 (7) | |
O25 | 0.2193 (4) | 0.0496 (2) | 0.19539 (7) | 0.0336 (9) | |
N9 | 0.1591 (3) | 0.1193 (2) | 0.25929 (8) | 0.0192 (7) | |
N19 | 0.1326 (4) | 0.2044 (2) | 0.39973 (8) | 0.0220 (8) | |
C1 | 0.2107 (4) | 0.4025 (3) | 0.28549 (10) | 0.0220 (10) | |
C2 | 0.2316 (4) | 0.4525 (3) | 0.24709 (10) | 0.0206 (10) | |
C3 | 0.2176 (4) | 0.3914 (3) | 0.21006 (10) | 0.0200 (9) | |
C4 | 0.1912 (4) | 0.2806 (2) | 0.21125 (9) | 0.0192 (9) | |
C5 | 0.1762 (5) | 0.2319 (2) | 0.25023 (10) | 0.0186 (9) | |
C6 | 0.1822 (5) | 0.2909 (3) | 0.28690 (9) | 0.0200 (9) | |
C7 | 0.1402 (4) | 0.2196 (3) | 0.32382 (10) | 0.0194 (9) | |
C8 | 0.1639 (4) | 0.1035 (3) | 0.30544 (9) | 0.0178 (9) | |
C10 | 0.2084 (5) | 0.0380 (3) | 0.23349 (10) | 0.0224 (10) | |
C11 | 0.2482 (5) | −0.0701 (3) | 0.25362 (11) | 0.0244 (11) | |
C12 | 0.3195 (5) | −0.0703 (3) | 0.29876 (10) | 0.0216 (10) | |
C13 | 0.3369 (4) | 0.0468 (3) | 0.31477 (9) | 0.0173 (9) | |
C14 | 0.3946 (4) | 0.0634 (3) | 0.36027 (10) | 0.0208 (10) | |
C15 | 0.4243 (4) | 0.1858 (3) | 0.36540 (11) | 0.0217 (10) | |
C16 | 0.2486 (5) | 0.2415 (3) | 0.36351 (10) | 0.0215 (10) | |
C17 | −0.0479 (4) | 0.2361 (3) | 0.33974 (11) | 0.0236 (11) | |
C18 | −0.0461 (4) | 0.1812 (3) | 0.38190 (10) | 0.0236 (10) | |
C20 | 0.2066 (5) | 0.1088 (3) | 0.42293 (9) | 0.0234 (10) | |
C21 | 0.2646 (4) | 0.0242 (3) | 0.39246 (10) | 0.0221 (10) | |
C22 | 0.2076 (5) | −0.0761 (3) | 0.39424 (10) | 0.0235 (10) | |
C23 | 0.2581 (5) | −0.1618 (3) | 0.36323 (11) | 0.0269 (11) | |
C25 | 0.2845 (6) | 0.6248 (3) | 0.27850 (12) | 0.0400 (14) | |
C26 | 0.2222 (4) | 0.3880 (3) | 0.13581 (10) | 0.0263 (10) | |
As1A | 0.18853 (4) | 0.38087 (2) | 0.50015 (1) | 0.0194 (1) | |
O11A | 0.0706 (3) | 0.2967 (2) | 0.52906 (7) | 0.0288 (8) | |
O12A | 0.1351 (3) | 0.37219 (19) | 0.44956 (7) | 0.0256 (7) | |
O13A | 0.4046 (3) | 0.3544 (2) | 0.50798 (9) | 0.0361 (9) | |
N4A | 0.1284 (6) | 0.8469 (3) | 0.55939 (14) | 0.0526 (15) | |
C1A | 0.1723 (5) | 0.5265 (2) | 0.51885 (9) | 0.0213 (9) | |
C2A | 0.0081 (5) | 0.5733 (3) | 0.52485 (11) | 0.0277 (11) | |
C3A | −0.0043 (6) | 0.6792 (3) | 0.53827 (11) | 0.0320 (12) | |
C4A | 0.1423 (6) | 0.7411 (3) | 0.54628 (12) | 0.0314 (13) | |
C5A | 0.3047 (6) | 0.6939 (3) | 0.53962 (11) | 0.0324 (11) | |
C6A | 0.3193 (5) | 0.5885 (3) | 0.52554 (10) | 0.0271 (10) | |
O1W | 0.4311 (4) | −0.0600 (3) | 0.13578 (10) | 0.0461 (11) | |
O2W | −0.2441 (4) | 0.3881 (3) | 0.43528 (11) | 0.0521 (11) | |
O3W | 0.4514 (4) | 0.8770 (3) | 0.61869 (11) | 0.0587 (12) | |
O4W | 0.2795 (4) | 0.5374 (3) | 0.40023 (10) | 0.0511 (11) | |
H1 | 0.21570 | 0.44380 | 0.31060 | 0.0260* | |
H4 | 0.18370 | 0.23920 | 0.18630 | 0.0230* | |
H8 | 0.06440 | 0.05630 | 0.31430 | 0.0210* | |
H12 | 0.43720 | −0.10550 | 0.29900 | 0.0260* | |
H13 | 0.42710 | 0.08270 | 0.29690 | 0.0210* | |
H14 | 0.50800 | 0.02480 | 0.36480 | 0.0250* | |
H16 | 0.26740 | 0.32150 | 0.36610 | 0.0260* | |
H19 | 0.122 (6) | 0.258 (3) | 0.4190 (11) | 0.0620* | |
H22 | 0.13050 | −0.09540 | 0.41630 | 0.0280* | |
H111 | 0.33410 | −0.10810 | 0.23570 | 0.0290* | |
H112 | 0.13960 | −0.11370 | 0.25330 | 0.0290* | |
H151 | 0.48150 | 0.20080 | 0.39260 | 0.0260* | |
H152 | 0.50090 | 0.21300 | 0.34270 | 0.0260* | |
H171 | −0.07610 | 0.31420 | 0.34240 | 0.0280* | |
H172 | −0.13360 | 0.20150 | 0.32080 | 0.0280* | |
H181 | −0.06470 | 0.10210 | 0.37890 | 0.0280* | |
H182 | −0.13850 | 0.21120 | 0.40020 | 0.0280* | |
H201 | 0.30700 | 0.13230 | 0.44020 | 0.0280* | |
H202 | 0.11670 | 0.07810 | 0.44180 | 0.0280* | |
H231 | 0.38680 | −0.17010 | 0.36320 | 0.0320* | |
H232 | 0.20630 | −0.23190 | 0.37180 | 0.0320* | |
H251 | 0.30870 | 0.70020 | 0.27070 | 0.0600* | |
H252 | 0.38120 | 0.59660 | 0.29540 | 0.0600* | |
H253 | 0.17600 | 0.62160 | 0.29470 | 0.0600* | |
H261 | 0.23380 | 0.43690 | 0.11180 | 0.0390* | |
H262 | 0.10930 | 0.35070 | 0.13440 | 0.0390* | |
H263 | 0.31660 | 0.33430 | 0.13520 | 0.0390* | |
H2A | −0.09470 | 0.53230 | 0.51970 | 0.0330* | |
H3A | −0.11650 | 0.71040 | 0.54210 | 0.0390* | |
H5A | 0.40740 | 0.73490 | 0.54490 | 0.0390* | |
H6A | 0.43160 | 0.55850 | 0.52040 | 0.0330* | |
H13A | 0.445 (6) | 0.298 (3) | 0.4931 (13) | 0.0770* | |
H41A | 0.022 (3) | 0.876 (4) | 0.5617 (15) | 0.0620* | |
H42A | 0.227 (3) | 0.861 (4) | 0.5735 (13) | 0.0620* | |
H11W | 0.360 (5) | −0.029 (4) | 0.1548 (10) | 0.0770* | |
H12W | 0.358 (5) | −0.071 (4) | 0.1141 (10) | 0.0770* | |
H21W | −0.134 (3) | 0.406 (4) | 0.4425 (16) | 0.0770* | |
H22W | −0.273 (7) | 0.328 (2) | 0.4492 (14) | 0.0770* | |
H31W | 0.406 (6) | 0.917 (3) | 0.6400 (11) | 0.0770* | |
H32W | 0.548 (4) | 0.917 (3) | 0.6129 (15) | 0.0770* | |
H41W | 0.378 (4) | 0.512 (4) | 0.3885 (15) | 0.0770* | |
H42W | 0.242 (7) | 0.483 (3) | 0.4163 (13) | 0.0770* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0412 (17) | 0.0165 (12) | 0.0288 (13) | −0.0036 (11) | 0.0025 (12) | −0.0002 (10) |
O3 | 0.0292 (13) | 0.0255 (13) | 0.0207 (12) | −0.0021 (11) | 0.0027 (10) | 0.0008 (10) |
O24 | 0.0244 (12) | 0.0185 (11) | 0.0243 (11) | −0.0011 (11) | −0.0001 (11) | 0.0000 (9) |
O25 | 0.0533 (19) | 0.0281 (14) | 0.0195 (12) | 0.0026 (14) | 0.0064 (13) | −0.0055 (10) |
N9 | 0.0226 (14) | 0.0182 (12) | 0.0168 (12) | 0.0001 (13) | −0.0003 (11) | −0.0035 (11) |
N19 | 0.0261 (15) | 0.0230 (15) | 0.0169 (14) | −0.0009 (12) | 0.0011 (12) | −0.0052 (12) |
C1 | 0.0251 (19) | 0.0207 (17) | 0.0203 (16) | 0.0005 (14) | −0.0011 (15) | −0.0087 (13) |
C2 | 0.0181 (18) | 0.0173 (16) | 0.0263 (18) | 0.0022 (13) | 0.0011 (15) | 0.0004 (14) |
C3 | 0.0169 (17) | 0.0247 (17) | 0.0183 (15) | −0.0004 (15) | 0.0021 (13) | 0.0018 (14) |
C4 | 0.0200 (16) | 0.0229 (16) | 0.0148 (14) | −0.0001 (15) | 0.0007 (15) | −0.0046 (12) |
C5 | 0.0196 (17) | 0.0181 (15) | 0.0181 (15) | 0.0014 (14) | −0.0008 (15) | −0.0012 (12) |
C6 | 0.0196 (16) | 0.0213 (15) | 0.0192 (15) | 0.0022 (15) | 0.0023 (15) | 0.0000 (13) |
C7 | 0.0228 (17) | 0.0176 (16) | 0.0177 (16) | 0.0017 (13) | 0.0007 (14) | −0.0031 (13) |
C8 | 0.0193 (16) | 0.0188 (16) | 0.0153 (14) | −0.0002 (14) | 0.0004 (13) | −0.0039 (12) |
C10 | 0.0214 (18) | 0.0235 (17) | 0.0224 (17) | −0.0025 (16) | 0.0005 (16) | −0.0059 (14) |
C11 | 0.030 (2) | 0.0184 (17) | 0.0248 (18) | 0.0021 (14) | −0.0014 (16) | −0.0066 (14) |
C12 | 0.0204 (17) | 0.0190 (16) | 0.0255 (17) | 0.0035 (16) | 0.0024 (16) | −0.0047 (13) |
C13 | 0.0137 (16) | 0.0175 (15) | 0.0208 (16) | −0.0005 (13) | 0.0031 (13) | −0.0038 (12) |
C14 | 0.0164 (17) | 0.0248 (18) | 0.0211 (17) | 0.0020 (14) | −0.0029 (14) | −0.0028 (14) |
C15 | 0.0210 (18) | 0.0250 (18) | 0.0192 (17) | −0.0039 (15) | −0.0021 (15) | −0.0058 (15) |
C16 | 0.0291 (18) | 0.0173 (16) | 0.0182 (16) | −0.0043 (13) | 0.0024 (15) | −0.0043 (13) |
C17 | 0.0249 (19) | 0.0242 (19) | 0.0216 (17) | 0.0053 (15) | 0.0030 (15) | −0.0054 (14) |
C18 | 0.0186 (17) | 0.0283 (19) | 0.0239 (18) | 0.0018 (15) | 0.0061 (15) | −0.0032 (15) |
C20 | 0.0289 (18) | 0.0239 (17) | 0.0175 (15) | −0.0004 (17) | −0.0029 (15) | 0.0001 (14) |
C21 | 0.0204 (17) | 0.0257 (18) | 0.0201 (16) | 0.0025 (14) | −0.0065 (14) | 0.0003 (14) |
C22 | 0.0229 (18) | 0.0272 (17) | 0.0205 (16) | 0.0019 (15) | −0.0026 (16) | 0.0032 (13) |
C23 | 0.0284 (19) | 0.0210 (17) | 0.0314 (19) | −0.0009 (14) | −0.0039 (16) | 0.0031 (15) |
C25 | 0.062 (3) | 0.0220 (19) | 0.036 (2) | −0.004 (2) | −0.002 (2) | −0.0032 (17) |
C26 | 0.0268 (19) | 0.0317 (19) | 0.0204 (15) | 0.0005 (17) | −0.0019 (14) | 0.0030 (16) |
As1A | 0.0219 (2) | 0.0175 (1) | 0.0187 (1) | −0.0005 (1) | 0.0006 (2) | −0.0038 (2) |
O11A | 0.0363 (15) | 0.0273 (13) | 0.0229 (12) | −0.0063 (12) | 0.0047 (11) | −0.0041 (11) |
O12A | 0.0368 (14) | 0.0204 (12) | 0.0197 (11) | 0.0008 (11) | 0.0016 (10) | −0.0054 (10) |
O13A | 0.0239 (12) | 0.0339 (14) | 0.0505 (19) | 0.0038 (11) | −0.0055 (13) | −0.0178 (13) |
N4A | 0.060 (3) | 0.0279 (19) | 0.070 (3) | 0.0095 (18) | −0.011 (2) | −0.0174 (18) |
C1A | 0.0328 (19) | 0.0171 (15) | 0.0139 (15) | −0.0015 (15) | 0.0001 (16) | −0.0007 (12) |
C2A | 0.0270 (19) | 0.0250 (19) | 0.031 (2) | 0.0009 (15) | 0.0045 (17) | −0.0009 (16) |
C3A | 0.042 (2) | 0.026 (2) | 0.028 (2) | 0.0090 (17) | 0.0073 (18) | 0.0008 (16) |
C4A | 0.048 (3) | 0.0208 (18) | 0.0254 (18) | 0.0027 (17) | −0.0018 (18) | 0.0023 (15) |
C5A | 0.043 (2) | 0.0239 (18) | 0.0303 (19) | −0.0078 (19) | −0.0059 (19) | −0.0012 (15) |
C6A | 0.0313 (19) | 0.0277 (18) | 0.0224 (16) | −0.0030 (17) | −0.0018 (18) | −0.0022 (14) |
O1W | 0.0439 (18) | 0.0500 (19) | 0.0445 (18) | 0.0115 (16) | 0.0045 (15) | −0.0085 (16) |
O2W | 0.0453 (17) | 0.053 (2) | 0.058 (2) | 0.0021 (17) | 0.0002 (16) | 0.0257 (18) |
O3W | 0.059 (2) | 0.059 (2) | 0.058 (2) | −0.0071 (19) | 0.0088 (17) | −0.0055 (18) |
O4W | 0.050 (2) | 0.0452 (19) | 0.058 (2) | 0.0023 (16) | 0.0108 (17) | 0.0184 (16) |
As1A—O12A | 1.671 (2) | C13—C14 | 1.534 (4) |
As1A—O13A | 1.704 (2) | C14—C21 | 1.511 (5) |
As1A—C1A | 1.896 (3) | C14—C15 | 1.534 (5) |
As1A—O11A | 1.657 (2) | C15—C16 | 1.511 (5) |
O2—C2 | 1.371 (4) | C17—C18 | 1.508 (5) |
O2—C25 | 1.423 (4) | C20—C21 | 1.494 (5) |
O3—C26 | 1.426 (4) | C21—C22 | 1.312 (5) |
O3—C3 | 1.369 (4) | C22—C23 | 1.499 (5) |
O24—C23 | 1.425 (4) | C1—H1 | 0.9500 |
O24—C12 | 1.423 (4) | C4—H4 | 0.9500 |
O25—C10 | 1.229 (4) | C8—H8 | 1.0000 |
O13A—H13A | 0.90 (4) | C11—H111 | 0.9900 |
O1W—H12W | 0.90 (3) | C11—H112 | 0.9900 |
O1W—H11W | 0.90 (4) | C12—H12 | 1.0000 |
O2W—H22W | 0.89 (3) | C13—H13 | 1.0000 |
O2W—H21W | 0.90 (3) | C14—H14 | 1.0000 |
O3W—H32W | 0.91 (3) | C15—H152 | 0.9900 |
O3W—H31W | 0.91 (4) | C15—H151 | 0.9900 |
N9—C5 | 1.424 (4) | C16—H16 | 1.0000 |
N9—C10 | 1.351 (4) | C17—H171 | 0.9900 |
N9—C8 | 1.488 (4) | C17—H172 | 0.9900 |
N19—C16 | 1.529 (4) | C18—H182 | 0.9900 |
N19—C18 | 1.509 (4) | C18—H181 | 0.9900 |
N19—C20 | 1.503 (4) | C20—H202 | 0.9900 |
O4W—H42W | 0.89 (4) | C20—H201 | 0.9900 |
O4W—H41W | 0.90 (4) | C22—H22 | 0.9500 |
N19—H19 | 0.91 (4) | C23—H232 | 0.9900 |
N4A—C4A | 1.374 (5) | C23—H231 | 0.9900 |
N4A—H41A | 0.89 (3) | C25—H252 | 0.9800 |
N4A—H42A | 0.90 (3) | C25—H251 | 0.9800 |
C1—C2 | 1.383 (5) | C25—H253 | 0.9800 |
C1—C6 | 1.393 (5) | C26—H262 | 0.9800 |
C2—C3 | 1.407 (5) | C26—H263 | 0.9800 |
C3—C4 | 1.381 (4) | C26—H261 | 0.9800 |
C4—C5 | 1.388 (4) | C1A—C6A | 1.377 (5) |
C5—C6 | 1.380 (4) | C1A—C2A | 1.396 (5) |
C6—C7 | 1.506 (5) | C2A—C3A | 1.377 (5) |
C7—C17 | 1.541 (4) | C3A—C4A | 1.381 (6) |
C7—C16 | 1.540 (5) | C4A—C5A | 1.389 (6) |
C7—C8 | 1.557 (5) | C5A—C6A | 1.379 (5) |
C8—C13 | 1.527 (5) | C2A—H2A | 0.9500 |
C10—C11 | 1.511 (5) | C3A—H3A | 0.9500 |
C11—C12 | 1.543 (5) | C5A—H5A | 0.9500 |
C12—C13 | 1.537 (5) | C6A—H6A | 0.9500 |
O12A—As1A—C1A | 110.46 (12) | N9—C8—H8 | 110.00 |
O13A—As1A—C1A | 101.45 (14) | C7—C8—H8 | 110.00 |
O12A—As1A—O13A | 111.55 (13) | C13—C8—H8 | 110.00 |
O11A—As1A—C1A | 112.41 (13) | C12—C11—H111 | 108.00 |
O11A—As1A—O12A | 111.48 (11) | C10—C11—H111 | 108.00 |
O11A—As1A—O13A | 109.09 (12) | C10—C11—H112 | 108.00 |
C2—O2—C25 | 117.1 (3) | H111—C11—H112 | 107.00 |
C3—O3—C26 | 116.2 (3) | C12—C11—H112 | 108.00 |
C12—O24—C23 | 114.5 (3) | O24—C12—H12 | 109.00 |
As1A—O13A—H13A | 114 (3) | C13—C12—H12 | 109.00 |
H11W—O1W—H12W | 102 (3) | C11—C12—H12 | 109.00 |
H21W—O2W—H22W | 108 (5) | C8—C13—H13 | 107.00 |
H31W—O3W—H32W | 100 (4) | C12—C13—H13 | 107.00 |
C8—N9—C10 | 120.1 (3) | C14—C13—H13 | 106.00 |
C5—N9—C10 | 125.0 (3) | C15—C14—H14 | 109.00 |
C5—N9—C8 | 109.1 (2) | C21—C14—H14 | 109.00 |
C16—N19—C18 | 107.3 (2) | C13—C14—H14 | 109.00 |
C16—N19—C20 | 112.9 (3) | H151—C15—H152 | 109.00 |
C18—N19—C20 | 112.3 (3) | C16—C15—H151 | 110.00 |
H41W—O4W—H42W | 104 (4) | C16—C15—H152 | 110.00 |
C20—N19—H19 | 106 (2) | C14—C15—H151 | 110.00 |
C18—N19—H19 | 108 (3) | C14—C15—H152 | 110.00 |
C16—N19—H19 | 110 (3) | N19—C16—H16 | 108.00 |
H41A—N4A—H42A | 130 (4) | C15—C16—H16 | 108.00 |
C4A—N4A—H42A | 106 (3) | C7—C16—H16 | 109.00 |
C4A—N4A—H41A | 119 (3) | C7—C17—H171 | 111.00 |
C2—C1—C6 | 119.1 (3) | C7—C17—H172 | 111.00 |
O2—C2—C1 | 124.6 (3) | C18—C17—H171 | 111.00 |
O2—C2—C3 | 115.5 (3) | C18—C17—H172 | 111.00 |
C1—C2—C3 | 120.0 (3) | H171—C17—H172 | 109.00 |
O3—C3—C2 | 115.5 (3) | H181—C18—H182 | 109.00 |
O3—C3—C4 | 123.3 (3) | C17—C18—H182 | 111.00 |
C2—C3—C4 | 121.2 (3) | N19—C18—H182 | 111.00 |
C3—C4—C5 | 117.7 (3) | C17—C18—H181 | 111.00 |
C4—C5—C6 | 122.1 (3) | N19—C18—H181 | 111.00 |
N9—C5—C4 | 127.7 (3) | C21—C20—H201 | 110.00 |
N9—C5—C6 | 110.1 (3) | N19—C20—H202 | 110.00 |
C5—C6—C7 | 110.5 (3) | H201—C20—H202 | 108.00 |
C1—C6—C7 | 129.4 (3) | N19—C20—H201 | 110.00 |
C1—C6—C5 | 119.9 (3) | C21—C20—H202 | 110.00 |
C6—C7—C8 | 102.5 (3) | C23—C22—H22 | 118.00 |
C16—C7—C17 | 102.0 (3) | C21—C22—H22 | 118.00 |
C6—C7—C17 | 112.4 (3) | O24—C23—H232 | 109.00 |
C8—C7—C17 | 110.8 (3) | O24—C23—H231 | 109.00 |
C6—C7—C16 | 115.4 (3) | H231—C23—H232 | 108.00 |
C8—C7—C16 | 114.1 (3) | C22—C23—H232 | 109.00 |
C7—C8—C13 | 116.6 (3) | C22—C23—H231 | 109.00 |
N9—C8—C7 | 104.5 (3) | H251—C25—H253 | 109.00 |
N9—C8—C13 | 106.0 (2) | H252—C25—H253 | 110.00 |
O25—C10—C11 | 120.7 (3) | H251—C25—H252 | 109.00 |
O25—C10—N9 | 122.5 (3) | O2—C25—H253 | 109.00 |
N9—C10—C11 | 116.8 (3) | O2—C25—H251 | 110.00 |
C10—C11—C12 | 118.1 (3) | O2—C25—H252 | 109.00 |
O24—C12—C11 | 105.3 (3) | O3—C26—H261 | 110.00 |
O24—C12—C13 | 114.4 (3) | H261—C26—H262 | 109.00 |
C11—C12—C13 | 109.9 (3) | H261—C26—H263 | 109.00 |
C8—C13—C12 | 106.8 (3) | H262—C26—H263 | 109.00 |
C8—C13—C14 | 112.0 (3) | O3—C26—H262 | 110.00 |
C12—C13—C14 | 117.8 (3) | O3—C26—H263 | 109.00 |
C13—C14—C15 | 106.0 (3) | As1A—C1A—C2A | 119.6 (3) |
C15—C14—C21 | 109.8 (3) | C2A—C1A—C6A | 119.0 (3) |
C13—C14—C21 | 114.4 (3) | As1A—C1A—C6A | 121.4 (3) |
C14—C15—C16 | 108.1 (3) | C1A—C2A—C3A | 119.8 (4) |
C7—C16—C15 | 115.7 (3) | C2A—C3A—C4A | 121.7 (4) |
N19—C16—C7 | 105.0 (3) | N4A—C4A—C5A | 120.9 (4) |
N19—C16—C15 | 110.5 (3) | N4A—C4A—C3A | 121.2 (4) |
C7—C17—C18 | 103.1 (3) | C3A—C4A—C5A | 117.9 (4) |
N19—C18—C17 | 105.1 (3) | C4A—C5A—C6A | 121.1 (4) |
N19—C20—C21 | 109.7 (2) | C1A—C6A—C5A | 120.5 (4) |
C14—C21—C20 | 114.6 (3) | C1A—C2A—H2A | 120.00 |
C14—C21—C22 | 123.4 (3) | C3A—C2A—H2A | 120.00 |
C20—C21—C22 | 122.0 (3) | C2A—C3A—H3A | 119.00 |
C21—C22—C23 | 123.3 (3) | C4A—C3A—H3A | 119.00 |
O24—C23—C22 | 111.9 (3) | C6A—C5A—H5A | 119.00 |
C6—C1—H1 | 120.00 | C4A—C5A—H5A | 119.00 |
C2—C1—H1 | 120.00 | C1A—C6A—H6A | 120.00 |
C5—C4—H4 | 121.00 | C5A—C6A—H6A | 120.00 |
C3—C4—H4 | 121.00 | ||
O11A—As1A—C1A—C2A | −51.9 (3) | C17—C7—C8—C13 | −140.8 (3) |
O11A—As1A—C1A—C6A | 130.0 (2) | C6—C7—C16—N19 | 153.5 (3) |
O12A—As1A—C1A—C2A | 73.4 (3) | C8—C7—C16—N19 | −88.2 (3) |
O12A—As1A—C1A—C6A | −104.8 (3) | C8—C7—C16—C15 | 33.9 (4) |
O13A—As1A—C1A—C2A | −168.3 (3) | C17—C7—C16—N19 | 31.3 (3) |
O13A—As1A—C1A—C6A | 13.6 (3) | C17—C7—C16—C15 | 153.4 (3) |
C25—O2—C2—C1 | 1.0 (5) | C6—C7—C17—C18 | −166.0 (3) |
C25—O2—C2—C3 | −178.9 (3) | C8—C7—C17—C18 | 80.1 (3) |
C26—O3—C3—C2 | 178.7 (3) | C6—C7—C16—C15 | −84.4 (4) |
C26—O3—C3—C4 | −1.1 (4) | C6—C7—C8—N9 | −17.5 (3) |
C23—O24—C12—C13 | −69.2 (4) | C6—C7—C8—C13 | 99.1 (3) |
C12—O24—C23—C22 | 87.0 (4) | C16—C7—C8—N9 | −142.9 (3) |
C23—O24—C12—C11 | 170.0 (3) | C16—C7—C8—C13 | −26.3 (4) |
C8—N9—C5—C6 | −3.2 (4) | C17—C7—C8—N9 | 102.6 (3) |
C8—N9—C5—C4 | 174.7 (3) | C16—C7—C17—C18 | −41.8 (3) |
C5—N9—C10—O25 | −24.5 (5) | N9—C8—C13—C12 | −71.7 (3) |
C10—N9—C5—C4 | 22.1 (6) | N9—C8—C13—C14 | 158.0 (3) |
C10—N9—C5—C6 | −155.9 (3) | C7—C8—C13—C14 | 42.2 (4) |
C5—N9—C8—C7 | 13.4 (3) | C7—C8—C13—C12 | 172.5 (3) |
C5—N9—C8—C13 | −110.4 (3) | O25—C10—C11—C12 | 150.9 (4) |
C10—N9—C8—C7 | 167.6 (3) | N9—C10—C11—C12 | −29.9 (5) |
C10—N9—C8—C13 | 43.9 (4) | C10—C11—C12—C13 | −0.2 (4) |
C8—N9—C10—O25 | −174.4 (3) | C10—C11—C12—O24 | 123.5 (3) |
C8—N9—C10—C11 | 6.3 (5) | C11—C12—C13—C8 | 49.1 (3) |
C5—N9—C10—C11 | 156.3 (3) | O24—C12—C13—C8 | −69.1 (3) |
C20—N19—C16—C15 | −10.7 (4) | O24—C12—C13—C14 | 57.9 (4) |
C16—N19—C18—C17 | −16.7 (3) | C11—C12—C13—C14 | 176.1 (3) |
C18—N19—C16—C7 | −9.6 (3) | C12—C13—C14—C15 | 172.5 (3) |
C18—N19—C16—C15 | −134.9 (3) | C8—C13—C14—C15 | −63.1 (3) |
C20—N19—C16—C7 | 114.7 (3) | C8—C13—C14—C21 | 58.1 (4) |
C18—N19—C20—C21 | 74.2 (3) | C12—C13—C14—C21 | −66.4 (4) |
C20—N19—C18—C17 | −141.3 (3) | C15—C14—C21—C22 | 176.6 (3) |
C16—N19—C20—C21 | −47.3 (4) | C21—C14—C15—C16 | −54.5 (3) |
C2—C1—C6—C7 | −174.0 (3) | C13—C14—C15—C16 | 69.6 (3) |
C6—C1—C2—O2 | −177.6 (3) | C15—C14—C21—C20 | −4.2 (4) |
C6—C1—C2—C3 | 2.3 (5) | C13—C14—C21—C20 | −123.2 (3) |
C2—C1—C6—C5 | 0.4 (5) | C13—C14—C21—C22 | 57.6 (5) |
C1—C2—C3—C4 | −3.1 (5) | C14—C15—C16—N19 | 62.7 (3) |
O2—C2—C3—O3 | −3.0 (4) | C14—C15—C16—C7 | −56.4 (4) |
O2—C2—C3—C4 | 176.9 (3) | C7—C17—C18—N19 | 36.4 (3) |
C1—C2—C3—O3 | 177.1 (3) | N19—C20—C21—C14 | 56.0 (4) |
O3—C3—C4—C5 | −179.2 (3) | N19—C20—C21—C22 | −124.8 (4) |
C2—C3—C4—C5 | 1.0 (5) | C20—C21—C22—C23 | 177.7 (3) |
C3—C4—C5—N9 | −176.0 (3) | C14—C21—C22—C23 | −3.2 (5) |
C3—C4—C5—C6 | 1.8 (5) | C21—C22—C23—O24 | −62.7 (5) |
N9—C5—C6—C7 | −9.0 (4) | As1A—C1A—C2A—C3A | −179.7 (3) |
N9—C5—C6—C1 | 175.6 (3) | C6A—C1A—C2A—C3A | −1.6 (5) |
C4—C5—C6—C1 | −2.5 (6) | As1A—C1A—C6A—C5A | −179.2 (3) |
C4—C5—C6—C7 | 172.9 (3) | C2A—C1A—C6A—C5A | 2.7 (5) |
C5—C6—C7—C16 | 141.2 (3) | C1A—C2A—C3A—C4A | −0.4 (5) |
C1—C6—C7—C8 | −168.6 (4) | C2A—C3A—C4A—N4A | 179.6 (4) |
C1—C6—C7—C16 | −44.0 (5) | C2A—C3A—C4A—C5A | 1.2 (5) |
C1—C6—C7—C17 | 72.5 (5) | N4A—C4A—C5A—C6A | −178.5 (4) |
C5—C6—C7—C8 | 16.6 (4) | C3A—C4A—C5A—C6A | −0.1 (5) |
C5—C6—C7—C17 | −102.4 (4) | C4A—C5A—C6A—C1A | −1.8 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N19—H19···O12A | 0.91 (4) | 1.72 (4) | 2.610 (3) | 168 (4) |
N4A—H41A···O4Wi | 0.89 (3) | 2.46 (4) | 3.291 (5) | 155 (4) |
N4A—H42A···O3W | 0.90 (3) | 2.25 (3) | 3.137 (6) | 169 (4) |
O13A—H13A···O11Aii | 0.90 (4) | 1.67 (4) | 2.546 (3) | 165 (4) |
O1W—H11W···O25 | 0.90 (4) | 1.95 (4) | 2.843 (4) | 175 (3) |
O1W—H12W···O2Wiii | 0.90 (3) | 1.87 (4) | 2.760 (5) | 168 (4) |
O2W—H21W···O12A | 0.90 (3) | 2.11 (3) | 2.945 (4) | 153 (4) |
O2W—H22W···O11Aiv | 0.89 (3) | 2.07 (4) | 2.915 (4) | 158 (5) |
O3W—H31W···O25v | 0.91 (4) | 2.06 (4) | 2.922 (4) | 159 (3) |
O3W—H32W···O4Wvi | 0.91 (3) | 1.91 (3) | 2.791 (4) | 164 (3) |
O4W—H41W···O1Wvii | 0.90 (4) | 1.88 (4) | 2.770 (5) | 172 (5) |
O4W—H42W···O12A | 0.89 (4) | 1.91 (4) | 2.802 (4) | 174 (5) |
C4—H4···O25 | 0.95 | 2.37 | 2.900 (4) | 115 |
C6A—H6A···O13A | 0.95 | 2.55 | 3.011 (4) | 110 |
C8—H8···O24 | 1.00 | 2.60 | 3.009 (4) | 104 |
C14—H14···O3viii | 1.00 | 2.52 | 3.363 (4) | 142 |
C15—H151···O11Aii | 0.99 | 2.60 | 3.561 (4) | 165 |
C18—H182···O2W | 0.99 | 2.58 | 3.422 (5) | 143 |
C20—H201···O11Aii | 0.99 | 2.41 | 3.388 (4) | 170 |
C20—H202···O13Aiv | 0.99 | 2.43 | 3.229 (4) | 137 |
Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) x+1/2, −y+1/2, −z+1; (iii) −x, y−1/2, −z+1/2; (iv) x−1/2, −y+1/2, −z+1; (v) −x+1/2, −y+1, z+1/2; (vi) x+1/2, −y+3/2, −z+1; (vii) −x+1, y+1/2, −z+1/2; (viii) −x+1, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N19—H19···O12A | 0.91 (4) | 1.72 (4) | 2.610 (3) | 168 (4) |
N4A—H41A···O4Wi | 0.89 (3) | 2.46 (4) | 3.291 (5) | 155 (4) |
N4A—H42A···O3W | 0.90 (3) | 2.25 (3) | 3.137 (6) | 169 (4) |
O13A—H13A···O11Aii | 0.90 (4) | 1.67 (4) | 2.546 (3) | 165 (4) |
O1W—H11W···O25 | 0.90 (4) | 1.95 (4) | 2.843 (4) | 175 (3) |
O1W—H12W···O2Wiii | 0.90 (3) | 1.87 (4) | 2.760 (5) | 168 (4) |
O2W—H21W···O12A | 0.90 (3) | 2.11 (3) | 2.945 (4) | 153 (4) |
O2W—H22W···O11Aiv | 0.89 (3) | 2.07 (4) | 2.915 (4) | 158 (5) |
O3W—H31W···O25v | 0.91 (4) | 2.06 (4) | 2.922 (4) | 159 (3) |
O3W—H32W···O4Wvi | 0.91 (3) | 1.91 (3) | 2.791 (4) | 164 (3) |
O4W—H41W···O1Wvii | 0.90 (4) | 1.88 (4) | 2.770 (5) | 172 (5) |
O4W—H42W···O12A | 0.89 (4) | 1.91 (4) | 2.802 (4) | 174 (5) |
C14—H14···O3viii | 1.00 | 2.52 | 3.363 (4) | 142 |
C15—H151···O11Aii | 0.99 | 2.60 | 3.561 (4) | 165 |
C18—H182···O2W | 0.99 | 2.58 | 3.422 (5) | 143 |
C20—H201···O11Aii | 0.99 | 2.41 | 3.388 (4) | 170 |
C20—H202···O13Aiv | 0.99 | 2.43 | 3.229 (4) | 137 |
Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) x+1/2, −y+1/2, −z+1; (iii) −x, y−1/2, −z+1/2; (iv) x−1/2, −y+1/2, −z+1; (v) −x+1/2, −y+1, z+1/2; (vi) x+1/2, −y+3/2, −z+1; (vii) −x+1, y+1/2, −z+1/2; (viii) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | (C23H27N2O4)[As(C6H7N)O2(OH)]·4H2O |
Mr | 683.58 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 200 |
a, b, c (Å) | 7.6553 (3), 12.3238 (5), 31.960 (2) |
V (Å3) | 3015.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.19 |
Crystal size (mm) | 0.36 × 0.34 × 0.10 |
Data collection | |
Diffractometer | Oxford Diffraction Gemini-S CCD-detector diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Rigaku OD, 2015) |
Tmin, Tmax | 0.811, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11983, 6980, 5901 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.693 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.096, 1.05 |
No. of reflections | 6980 |
No. of parameters | 433 |
No. of restraints | 14 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.55, −0.46 |
Absolute structure | Flack (1983), 3672 Friedel pairs |
Absolute structure parameter | −0.005 (9) |
Computer programs: CrysAlis PRO (Rigaku OD, 2015), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012), PLATON (Spek, 2009).
Acknowledgements
The authors acknowledge support from the Science and Engineering Faculty, Queensland University of Technology.
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