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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 67| Part 8| August 2011| Pages o334-o336
doi:10.1107/S010827011102782X

2,3-Dimeth­­oxy-10-oxostrychnidinium 2-(2,4,6-tri­nitro­anilino)benzoate monohydrate: a 1:1 proton-transfer salt of brucine with o-picramino­benzoic acid

CROSSMARK_Color_square_no_text.svg
Graham Smitha* and Urs D. Wermutha

aFaculty of Science and Technology, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia
*Correspondence e-mail: g.smith@qut.edu.au

(Received 23 June 2011; accepted 11 July 2011; online 28 July 2011)

In the structure of the title 1:1 proton-transfer compound of brucine with 2-(2,4,6-trinitro­anilino)benzoic acid, C23H27N2O4+·C13H7N4O8−·H2O, the brucinium cations form classic undulating ribbon substructures through overlapping head-to-tail inter­actions, while the anions and the three related partial solvent water mol­ecules (having occupancies of 0.73, 0.17 and 0.10) occupy the inter­stitial regions of the structure. The cations are linked to the anions directly through N—H⋯OCOO− hydrogen bonds and indirectly by the three water mol­ecules, which form similar conjoint cyclic bridging units [graph set R24(8)] through O—H⋯OC=O and O—H⋯OCOO− hydrogen bonds, giving a two-dimensional layered structure. Within the anion, intra­molecular N—H⋯OCOO− and N—H⋯Onitro hydrogen bonds result in the benzoate and picrate rings being rotated slightly out of coplanarity [inter-ring dihedral angle = 32.50 (14)°]. This work provides another example of the mol­ecular selectivity of brucine in forming stable crystal structures, and also represents the first reported structure of any form of the guest compound 2-(2,4,6-tri­nitro­anil­ino)benzoic acid.

Comment

Although brucine has been used largely for the resolution of certain chiral compounds (Wilen, 1972[Wilen, S. H. (1972). Tables of Resolving Agents and Optical Resolutions, edited by E. L. Eliel, pp. 68-75. London: University of Notre Dame Press.]), it has proven utility in the formation of crystalline adducts and salts with achiral carb­oxy­lic acids. In particular, the benzoic acid analogues have provided a number of brucinium salt structures, many of which are solvated, e.g. benzoic acid (a trihydrate) (Białońska & Ciunik, 2006b[Białońska, A. & Ciunik, Z. (2006b). Acta Cryst. E62, o5817-o5819.]), 3-nitro­benzoic acid (methanol monosolvate) (Oshikawa et al., 2002[Oshikawa, T., Pochamroen, S., Takai, N., Ide, N., Takemoto, T. & Yamashita, M. (2002). Heterocycl. Commun. 8, 271-274.]), 4-nitro­benzoic acid (isomorphous dihydrate and methanol monosolvate) (Białońska & Ciunik, 2007[Białońska, A. & Ciunik, Z. (2007). Acta Cryst. C63, o120-o122.]), 4-hy­droxy­benzoic acid (isopropyl alcohol monosolvate) (Sada et al., 1998[Sada, K., Yoshikawa, K. & Miyata, M. (1998). Chem. Commun. pp. 1763-1764.]), 3,5-dinitro­benzoic acid (trihydrate, methanol monosolvate and disolvate) (Białońska & Ciunik, 2006a[Białońska, A. & Ciunik, Z. (2006a). Acta Cryst. C62, o450-o453.]) and the anhydrous example with 5-nitro­salicylic acid (Smith, Wermuth, Healy & White, 2006[Smith, G., Wermuth, U. D., Healy, P. C. & White, J. M. (2006). Aust. J. Chem. 59, 320-328.]). Three 1:1 salts are also known, viz. with 5-nitro­phthalic acid (a dihydrate) (Smith et al., 2005[Smith, G., Wermuth, U. D., Young, D. J. & Healy, P. C. (2005). Acta Cryst. E61, o2008-o2011.]), isophthalic acid (a trihydrate) (Smith, Wermuth, Young & White, 2006[Smith, G., Wermuth, U. D., Young, D. J. & White, J. M. (2006). Acta Cryst. E62, o1553-o1555.]) and 4,5-dichloro­phthalic acid (anhydrous) (Smith et al., 2007a[Smith, G., Wermuth, U. D. & White, J. M. (2007a). Acta Cryst. E63, o4276-o4277.]). However, with these acids, formation is certainly a hit-or-miss process, the selectivity being dependent upon guest mol­ecule compatibility with the inter­stitial cavities in the brucinium cation substructures which are present in a large number of brucine adduct and brucinium proton-transfer compounds (Gould & Walkinshaw, 1984[Gould, R. O. & Walkinshaw, M. D. (1984). J. Am. Chem. Soc. 106, 7840-7842.]; Dijksma et al., 1998[Dijksma, F. J. J., Gould, R. O., Parsons, S., Taylor, P. & Walkinshaw, M. D. (1998). Chem. Commun. pp. 745-746.]; Oshikawa et al., 2002[Oshikawa, T., Pochamroen, S., Takai, N., Ide, N., Takemoto, T. & Yamashita, M. (2002). Heterocycl. Commun. 8, 271-274.]; Białońska & Ciunik, 2004[Białońska, A. & Ciunik, Z. (2004). CrystEngComm, 6, 276-279.]; Smith, Wermuth, Healy & White, 2006[Smith, G., Wermuth, U. D., Healy, P. C. & White, J. M. (2006). Aust. J. Chem. 59, 320-328.]). In these substructures, the brucine species form undulating ribbons comprising overlapping head-to-tail mol­ecules, this host structure then accomodating the compatible guest mol­ecule or mol­ecules and inter­acting with them through hydrogen-bonding associations. This phenomenon accounts for the presence in many of the structures of various polar solvent mol­ecules. It has also been noted that the two-mol­ecule brucine repeat period will be ca 12.5 Å (the cell dimension) in the direction of a 21 screw axis, of which there is a high incidence among the small number of space groups into which brucine and its compounds and adducts fall (Smith, Wermuth, Healy & White, 2006[Smith, G., Wermuth, U. D., Healy, P. C. & White, J. M. (2006). Aust. J. Chem. 59, 320-328.]).

The isomeric picramino­benzoic acids [2-, 3- and 4-(2,4,6-trinitro­anilino)benzoic acid] were first synthesized by the reaction of the corresponding monoamino­benzoic acid with picryl chloride in 1911 (Crocker & Matthews, 1911[Crocker, J. C. & Matthews, F. (1911). J. Chem. Soc. Trans. 99, 301-313.]). We have synthesized these three compounds using picryl­sulfonic acid rather than picryl chloride, reporting the crystal structure of the para isomer (Smith et al., 2007b[Smith, G., Wermuth, U. D. & White, J. M. (2007b). Acta Cryst. E63, o4803.]). However, the uncompromising crystal morphology of the ortho and meta isomers precluded the structure determinations of these. The 1:1 stoichiometric reaction of 2-(2,4,6-trinitro­anilino)benzoic acid with brucine in aqueous ethanol gave good crystals of the orange–red hydrated title salt, (I)[link], and the structure is reported here. No suitable crystals resulted from the reactions of brucine with the meta and para isomers.

[Scheme 1]

In (I)[link], protonation has occurred, as expected, at N19 of the brucine cage (Fig. 1[link]), the absolute configuration of the seven chiral centres of the brucinium cation being invoked (Peerdeman, 1956[Peerdeman, A. F. (1956). Acta Cryst. 9, 824.]). These cations form the previously described undulating ribbon host substructures, which have a dimeric repeat period in (I)[link] of 12.4407 (3) Å along the direction of propagation [a 21 screw axis, the a cell dimension] (Fig. 2[link]). This value for the dimeric repeat in (I)[link] is consistent with those for similarly structured brucine compounds (Gould & Walkinshaw, 1984[Gould, R. O. & Walkinshaw, M. D. (1984). J. Am. Chem. Soc. 106, 7840-7842.]; Smith, Wermuth, Healy & White, 2006[Smith, G., Wermuth, U. D., Healy, P. C. & White, J. M. (2006). Aust. J. Chem. 59, 320-328.]). There is a mol­ecule offset of ca 120° in the repeat unit of (I)[link].

The monoanion and the three associated partial solvent water mol­ecules [O1W (site-occupancy factor = 0.73), O2W (site-occupancy factor = 0.17) and O3W (site-occupancy factor = 0.10)] occupy the inter­stitial volumes between the brucine substructures and are hydrogen bonded to them. The brucinium cations form an N+—H⋯O hydrogen bond with a carboxylate O-atom acceptor of the anion, while the water linkages are unusual, the three partial mol­ecules forming a set of similar conjoint cyclic associations [graph set R42(8); see Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) for graph-set notation] involving two O-atom acceptor atoms (brucinium carbonyl atom O25 and carboxylate atom O3A of the anion) (Table 1[link]) (see Fig. 2[link]), giving a two-dimensional structure which forms layers down the c cell direction (Fig. 3[link]). Within the anion, intra­molecular N—H⋯OCOO− and O—H⋯Onitro hydrogen bonds result in moderate rotation of the benzoate and picrate ring systems out of coplanarity [inter-ring dihedral angle = 32.50 (14)°]. The ortho-carboxylate group of the benzoate ring is rotated slightly out of the plane of the benzene ring [C1A—C2A—C22A—O3A = 159.4 (3)°], while the two ortho-related nitro groups are similarly non-coplanar with the picrate ring [C11A—C21A—N21A—O22A = 151.7 (3)° and C11A—C61A—N61A—O61A = −165.2 (3)°]. The less sterically compromised para-nitro group is essentially coplanar with the picrate ring [C31A—C41A—N41A—O42A = −177.8 (3)°]. One of the O atoms of the ortho-related nitro group at C21A is involved, not unexpectedly, in some short intra­molecular nonbonded inter­actions [O21A⋯C1A = 2.852 (4) Å and O21A⋯N1A = 2.892 (4) Å].

The structure presented here provides another example of the mol­ecular selectivity of brucine in forming stable complexes and is also the first reported structure of any form of the guest compound 2-(2,4,6-trinitro­anilino)benzoic acid.

[Figure 1]
Figure 1
The mol­ecular configuration and atom-numbering scheme for the brucinium cation, the o-picramino­benzoate anion and the partial solvent water mol­ecules (O1W–O3W) in (I)[link]. Displacement ellipsoids are drawn at the 50% probability level. Inter-species hydrogen bonds are shown as dashed lines.
[Figure 2]
Figure 2
The cation–anion–water hydrogen-bonding environment in (I)[link], showing the head-to-tail overlap of the brucinium cations which are part of the substructure extending along a. Hydrogen bonds are shown as dashed lines and non-associative H atoms have been omitted. [For symmetry code (i), see Table 1[link].]
[Figure 3]
Figure 3
The layered structure of (I)[link] in the unit cell, viewed down the a cell direction.

Experimental

Compound (I)[link] was synthesized by heating together brucine tetra­hydrate (1 mmol) and 2-(2,4,6-trinitro­anilino)benzoic acid (o-picramino­benzoic acid) (1 mmol) in ethanol–water (1:1 v/v, 50 ml) under reflux for 10 min. After concentration to ca 30 ml, partial room-temperature evaporation from the hot-filtered solution gave short orange–red prisms of (I)[link] (m.p. 475 K).

Crystal data

  • C23H27N2O4+·C13H7N4O8−·H2O

  • Mr = 760.71

  • Orthorhombic, P 21 21 21

  • a = 12.4407 (3) Å

  • b = 19.1542 (5) Å

  • c = 14.6744 (4) Å

  • V = 3496.79 (16) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.11 mm−1

  • T = 173 K

  • 0.35 × 0.15 × 0.12 mm
Data collection

  • Oxford Gemini-S CCD area-detector diffractometer

  • Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]) Tmin = 0.911, Tmax = 0.980

  • 12634 measured reflections

  • 4487 independent reflections

  • 3291 reflections with I > 2σ(I)

  • Rint = 0.031
Refinement

  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.109

  • S = 0.96

  • 4487 reflections

  • 506 parameters

  • H-atom parameters constrained

  • Δρmax = 0.58 e Å−3

  • Δρmin = −0.20 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N19—H19⋯O2A 0.91 1.94 2.708 (4) 141
N1A—H1A⋯O2A 0.90 1.90 2.662 (3) 141
N1A—H1A⋯O62A 0.90 2.10 2.653 (4) 118
O1W—H11W⋯O3A 0.89 1.80 2.695 (4) 177
O1W—H12W⋯O25i 0.90 2.19 3.091 (4) 178
O2W—H21W⋯O3A 0.91 2.17 3.079 (14) 179
O2W—H22W⋯O25i 0.91 2.11 3.020 (14) 179
O3W—H31W⋯O3A 0.90 2.17 3.08 (2) 179
O3W—H32W⋯O25i 0.91 1.73 2.65 (2) 179
Symmetry code: (i) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z].

A nonstandard orthorhombic axial setting was chosen for a better comparison with previous similar brucine structures. C-bound H atoms were included at calculated positions, with C—H = 0.93 (aromatic and sp2) or 0.96–0.98 Å (aliphatic), and treated as riding, with Uiso(H) = 1.2Ueq(C). The H atom of the brucinium N+—H group was located in a difference Fourier synthesis and its positional and isotropic displacement parameters were allowed to ride in the refinement [Uiso(H) = 1.2Ueq(N)]. The occupancies of the three partial solvent water mol­ecules were determined as 0.73 (O1W), 0.17 (O2W) and 0.10 (O3W) from peak heights, and the O atoms of the two minor-occupancy components were refined isotropically. All three partial water mol­ecules were found to be associated with the same two O-atom acceptors, and the H atoms on these were derived geometrically and also allowed to ride in the refinement [Uiso(H) = 1.2Ueq(O)]. The known absolute configuration of the parent strychnidin-10-one mol­ecule (Peerdeman, 1956[Peerdeman, A. F. (1956). Acta Cryst. 9, 824.]) was invoked and Friedel pairs were averaged for data used in the final cycles of refinement.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) within WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S010827011102782X/fg3225sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S010827011102782X/fg3225Isup2.hkl


Comment top

Although brucine has been used largely for the resolution of certain chiral compounds (Wilen, 1972), it has proven utility in the formation of crystalline adducts and salts with achiral carboxylic acids. In particular, the benzoic acid analogues have provided a number of brucinium salt structures, many of which are solvated, e.g. benzoic acid (a trihydrate) (Białońska & Ciunik, 2006b), 3-nitrobenzoic acid (methanol monosolvate) (Oshikawa et al., 2002), 4-nitrobenzoic acid (isomorphous dihydrate and methanol monosolvate) (Białońska & Ciunik, 2007), 4-hydroxybenzoic acid (isopropyl alcohol monosolvate) (Sada et al., 1998), 3,5-dinitrobenzoic acid (trihydrate, methanol monosolvate and disolvate) (Białońska & Ciunik, 2007) and the anhydrous example with 5-nitrosalicylic acid (Smith, Wermuth, Healy & White, 2006). Three 1:1 salts are also known: with 5-nitrophthalic acid (a dihydrate) (Smith et al., 2005), isophthalic acid (a trihydrate) (Smith, Wermuth, Young & White, 2006) and 4,5-dichlorophthalic acid (anhydrous) (Smith et al., 2007a). However with these acids, formation is certainly a hit-or-miss process, the selectivity being dependent upon guest molecule compatibility with the interstitial cavities in the brucinium cation substructures which are present in a large number of brucine adduct and brucinium proton-transfer compounds (Gould & Walkinshaw, 1984; Dijksma et al., 1998; Oshikawa et al., 2002; Białońska & Ciunik, 2004; Smith, Wermuth, Healy & White, 2006). In these substructures, the brucine species form undulating ribbons comprising overlapping head-to-tail molecules, this host structure then accomodating the compatible guest molecule or molecules and interacting with them through hydrogen-bonding associations. This phenomenon accounts for the presence in many of the structures of various polar solvent molecules. It has also been noted that the two-molecule brucine repeat period will be ca 12.5 Å (the cell dimension) in the direction of a 21 screw axis, of which there is a high incidence among the small number of space groups into which brucine and its compounds and adducts fall (Smith, Wermuth, Healy & White, 2006).

The isomeric picraminobenzoic acids [2-, 3- and 4-(2,4,6-trinitroanilino)benzoic acid] were first synthesized by the reaction of the corresponding monoaminobenzoic acid with picryl chloride in 1911 (Crocker & Matthews, 1911). We have synthesized these three compounds using picrylsulfonic acid rather than picryl chloride, reporting the crystal structure of the para-isomer (Smith et al., 2007b). However, the uncompromising crystal morphology of the ortho- and meta-isomers precluded the structure determinations of these. The 1:1 stoichiometric reaction of 2-(2,4,6-trinitroanilino)benzoic acid with brucine in aqueous ethanol gave good crystals of the orange–red hydrated title salt, (I), and the structure is reported here. No suitable crystals resulted from the reactions of brucine with the meta- and para-isomers.

In (I), protonation has occurred, as expected, at N19 of the brucine cage (Fig. 1), the absolute configuration of the seven chiral centres of the brucinium cation being invoked (Peerdeman, 1956). These cations form the previously described undulating ribbon host substructures, which have a dimeric repeat period in (I) of 12.4407 (3) Å along the direction of propagation [a 21 screw axis, the a cell dimension] (Fig. 2). This value for the dimeric repeat in (I) is consistent with those for similarly structured brucine compounds (Gould & Walkinshaw, 1984; Smith, Wermuth, Healy & White, 2006). There is a molecule offset of ca 120° in the repeat unit of (I).

The monoanion and the three associated partial solvent water molecules [O1W (site occupancy factor 0.73), O2W (site occupancy factor 0.17) and O3W (site occupancy factor 0.10)] occupy the interstitial volumes between the brucine substructures and are hydrogen-bonded to them. The brucinium cations form an N+—H···O hydrogen bond with a carboxyl O acceptor of the anion, while the water linkages are unusual, the three partial molecules forming a set of similar conjoint cyclic associations [graph set R24(8); see Bernstein et al. (1995) for graph-set notation] involving two O acceptor atoms (brucinium carbonyl atom O25 and carboxyl atom O3A of the anion) (Table 1) (see Fig. 2), giving a two-dimensional structure which forms layers down the c cell direction (Fig. 3). Within the anion, intramolecular N—H···Ocarboxyl and O—H···Onitro hydrogen bonds result in moderate rotation of the benzoate and picrate ring systems out of coplanarity [inter-ring dihedral angle = 32.50 (14)°]. The ortho-carboxyl group of the benzoate ring is rotated slightly out of the plane of the benzene ring [torsion angle C1A—C2A—C22A—O3A = 159.4 (3)°], while the two ortho-related nitro groups are similarly non-coplanar with the picrate ring [torsion angles C11A—C21A—N21A—O22A = 151.7 (3)° and C11A—C61A—N61A—O61A = -165.2 (3)°]. The less sterically compromised para-nitro group is essentially coplanar with the picrate ring [torsion angle C31A—C41A—N41A—O42A = -177.8 (3)°]. One of the O atoms of the ortho-related nitro group at C21A is involved, not unexpectedly, in some short intramolecular non-bonded interactions [O21A···C1A = 2.852 (4) Å and O21A···N1A = 2.892 (4) Å].

The structure presented here provides another example of the molecular selectivity of brucine in forming stable complexes and is also the first reported structure of any form of the guest compound 2-(2,4,6-trinitroanilino)benzoic acid.

Related literature top

For related literature, see: Bernstein et al. (1995); Białońska & Ciunik (2004, 2006b, 2007); Crocker & Matthews (1911); Dijksma et al. (1998); Gould & Walkinshaw (1984); Oshikawa et al. (2002); Peerdeman (1956); Sada et al. (1998); Smith et al. (2005, 2007a, 2007b); Smith, Wermuth, Healy & White (2006); Smith, Wermuth, Young & White (2006); Wilen (1972).

Experimental top

Compound (I) was synthesized by heating together brucine tetrahydrate (1 mmol) and 2-(2,4,6-trinitroanilino)benzoic acid (o-picraminobenzoic acid) (1 mmol) in 50% ethanol–water (50 ml) under reflux for 10 min. After concentration to ca 30 ml, partial room-temperature evaporation of the hot-filtered solution gave short orange–red prisms of (I) (m.p. 475 K).

Refinement top

C-bound H atoms were included at calculated positions, with C—H = 0.93 (aromatic) or 0.96–0.98 Å (aliphatic), and treated as riding, with Uiso(H) = 1.2Ueq(C). The H atom of the brucinium N+—H group was located in a difference Fourier synthesis and its positional and isotropic displacement parameters were allowed to ride in the refinement. The occupancy of the three partial solvent water molecules were determined as 0.73 (O1W), 0.17 (O2W) and 0.10 (O3W) from peak heights, and the O atoms of the two minor-occupancy components were refined isotropically. All three partial water molecules were found to be associated with the same two O-atom acceptors, and the H atoms on these were derived geometrically and also allowed to ride in the refinement. The known absolute configuration of the parent strychnidin-10-one molecule (Peerdeman, 1956) was invoked and Friedel pairs were averaged for data used in the final cycles of refinement.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular configuration and atom-numbering scheme for the brucinium cation, the o-picraminobenzoate anion and the partial solvent water molecules [O1W–O3W] in (I). Displacement ellipsoids are drawn at the 50% probability level. Inter-species hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. The cation–anion–water hydrogen-bonding environment in (I), showing the head-to-tail overlap of the brucinium cations which are part of the substructure extending along a. Hydrogen bonds are shown as dashed lines and non-associative H atoms have been omitted. [For symmetry code (i), see Table 1.]
[Figure 3] Fig. 3. A view of the layered structure of (I) in the unit cell, viewed down the a cell direction.
2,3-Dimethoxy-10-oxostrychnidinium 2-(2,4,6-trinitroanilino)benzoate monohydrate top
Crystal data top
C23H27N2O4+·C13H7N4O8−·H2ODx = 1.445 Mg m−3
Mr = 760.71Melting point: 474 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 5473 reflections
a = 12.4407 (3) Åθ = 3.2–28.7°
b = 19.1542 (5) ŵ = 0.11 mm−1
c = 14.6744 (4) ÅT = 173 K
V = 3496.79 (16) Å3Prism, orange–red
Z = 40.35 × 0.15 × 0.12 mm
F(000) = 1592
Data collection top
Oxford Gemini-S CCD area-detector
diffractometer		4487 independent reflections
Radiation source: Enhance(Mo) X-ray source3291 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 16.077 pixels mm-1θmax = 28.7°, θmin = 3.2°
ω scansh = −15→16
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)		k = −15→24
Tmin = 0.911, Tmax = 0.980l = −10→19
12634 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H-atom parameters constrained
S = 0.96 w = 1/[σ2(Fo2) + (0.067P)2]
where P = (Fo2 + 2Fc2)/3
4487 reflections(Δ/σ)max < 0.001
506 parametersΔρmax = 0.58 e Å−3
0 restraintsΔρmin = −0.20 e Å−3
Crystal data top
C23H27N2O4+·C13H7N4O8−·H2OV = 3496.79 (16) Å3
Mr = 760.71Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 12.4407 (3) ŵ = 0.11 mm−1
b = 19.1542 (5) ÅT = 173 K
c = 14.6744 (4) Å0.35 × 0.15 × 0.12 mm
Data collection top
Oxford Gemini-S CCD area-detector
diffractometer		4487 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)		3291 reflections with I > 2σ(I)
Tmin = 0.911, Tmax = 0.980Rint = 0.031
12634 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.109H-atom parameters constrained
S = 0.96Δρmax = 0.58 e Å−3
4487 reflectionsΔρmin = −0.20 e Å−3
506 parameters
Special details top

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 e.s.d.'s 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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O20.43311 (17)0.76601 (11)0.13182 (15)0.0281 (7)
O30.54210 (18)0.88045 (11)0.13700 (17)0.0322 (7)
O241.13073 (17)0.63667 (11)0.10356 (18)0.0326 (7)
O250.94682 (19)0.84959 (10)0.11056 (17)0.0331 (7)
N90.8737 (2)0.74233 (13)0.08799 (18)0.0224 (7)
N190.7968 (2)0.50747 (13)0.06583 (18)0.0241 (8)
C10.5940 (2)0.69516 (15)0.1099 (2)0.0215 (8)
C20.5424 (2)0.75837 (16)0.1225 (2)0.0241 (9)
C30.6016 (3)0.82112 (15)0.1245 (2)0.0243 (9)
C40.7128 (2)0.82058 (16)0.1131 (2)0.0233 (9)
C50.7633 (2)0.75610 (16)0.0998 (2)0.0213 (8)
C60.7057 (2)0.69462 (15)0.0984 (2)0.0215 (8)
C70.7773 (2)0.63375 (15)0.0744 (2)0.0206 (8)
C80.8914 (2)0.66543 (14)0.0880 (2)0.0208 (8)
C100.9571 (3)0.78597 (15)0.1077 (2)0.0244 (9)
C111.0656 (2)0.75091 (16)0.1238 (2)0.0245 (9)
C121.0667 (2)0.67642 (16)0.1652 (2)0.0253 (9)
C130.9507 (2)0.64873 (15)0.1765 (2)0.0207 (8)
C140.9343 (2)0.57309 (16)0.2070 (2)0.0243 (9)
C150.8125 (2)0.56377 (17)0.2203 (2)0.0254 (9)
C160.7572 (2)0.56638 (15)0.1289 (2)0.0218 (9)
C170.7629 (2)0.60873 (16)−0.0243 (2)0.0239 (9)
C180.8216 (3)0.53983 (16)−0.0256 (2)0.0268 (10)
C200.8909 (2)0.46751 (15)0.1057 (2)0.0272 (9)
C210.9743 (2)0.51825 (16)0.1389 (2)0.0271 (9)
C221.0754 (3)0.51547 (17)0.1088 (3)0.0347 (10)
C231.1585 (3)0.56752 (18)0.1356 (3)0.0408 (13)
C250.3698 (3)0.70430 (17)0.1254 (3)0.0310 (10)
C260.5997 (3)0.94476 (17)0.1464 (3)0.0405 (13)
O2A0.70810 (19)0.38946 (13)−0.00247 (18)0.0394 (8)
O3A0.5401 (2)0.42006 (14)−0.03672 (19)0.0514 (9)
O21A0.7589 (2)0.15589 (15)0.00324 (19)0.0447 (9)
O22A0.7869 (2)0.07097 (13)−0.0925 (2)0.0585 (12)
O41A1.1443 (2)0.06880 (13)−0.2137 (2)0.0496 (10)
O42A1.23433 (19)0.16523 (14)−0.22799 (19)0.0414 (9)
O61A1.0688 (2)0.38010 (13)−0.1700 (2)0.0620 (10)
O62A0.9226 (2)0.39008 (13)−0.0948 (2)0.0534 (9)
N1A0.7865 (2)0.28354 (13)−0.09923 (18)0.0257 (8)
N21A0.8024 (2)0.13002 (15)−0.0637 (2)0.0377 (10)
N41A1.1537 (2)0.13260 (16)−0.2063 (2)0.0354 (10)
N61A0.9899 (2)0.35466 (15)−0.1339 (2)0.0329 (9)
C1A0.6792 (2)0.26329 (16)−0.1132 (2)0.0234 (9)
C2A0.5974 (3)0.30770 (16)−0.0813 (2)0.0254 (9)
C3A0.4906 (3)0.2865 (2)−0.0945 (2)0.0342 (11)
C4A0.4641 (3)0.22466 (19)−0.1356 (2)0.0343 (11)
C5A0.5454 (3)0.18486 (18)−0.1736 (2)0.0318 (10)
C6A0.6513 (3)0.20464 (17)−0.1650 (2)0.0265 (9)
C11A0.8777 (2)0.24640 (16)−0.1138 (2)0.0238 (9)
C21A0.8847 (3)0.17189 (16)−0.1116 (2)0.0280 (9)
C22A0.6174 (3)0.37806 (17)−0.0369 (2)0.0304 (10)
C31A0.9717 (3)0.13470 (17)−0.1424 (2)0.0298 (10)
C41A1.0618 (3)0.17046 (17)−0.1701 (2)0.0271 (9)
C51A1.0671 (2)0.24219 (17)−0.1630 (2)0.0258 (9)
C61A0.9782 (3)0.27870 (16)−0.1351 (2)0.0242 (9)
O1W0.5011 (3)0.54468 (17)0.0418 (3)0.0557 (13)0.730
O2W0.3660 (11)0.5033 (7)−0.1388 (9)0.034 (3)*0.170
O3W0.5694 (16)0.5455 (10)−0.1653 (14)0.023 (5)*0.100
H10.555100.653700.109000.0260*
H40.752200.861800.114200.0280*
H80.936900.652800.036000.0250*
H121.102000.677700.224900.0300*
H130.917300.677800.223600.0250*
H140.970500.566000.265500.0290*
H160.679700.561000.138200.0260*
H190.741700.476900.058000.0290*
H221.094700.479600.069400.0420*
H1111.107200.780900.163700.0290*
H1121.103000.749000.065900.0290*
H1510.798200.519300.249500.0310*
H1520.784900.600600.259200.0310*
H1710.687500.60270−0.039100.0290*
H1720.794700.64140−0.067000.0290*
H1810.898300.54680−0.032900.0320*
H1820.795800.51050−0.074800.0320*
H2010.866500.438600.155900.0330*
H2020.921800.437200.059600.0330*
H2311.165200.568200.201500.0490*
H2321.227400.553900.110300.0490*
H2510.295400.715900.133700.0460*
H2520.391700.671900.171600.0460*
H2530.379600.683600.066400.0460*
H2610.550200.981700.160100.0610*
H2620.636600.955000.090600.0610*
H2630.651000.940600.195000.0610*
H1A0.792800.32320−0.066300.0310*
H3A0.435600.31560−0.074600.0410*
H4A0.393000.20970−0.137900.0410*
H5A0.528400.14430−0.205300.0380*
H6A0.704800.17880−0.193800.0320*
H31A0.969800.08620−0.144600.0360*
H51A1.130500.26560−0.177000.0310*
H11W0.513400.502800.017300.0670*0.730
H12W0.484400.57580−0.001700.0670*0.730
H21W0.417300.47820−0.109600.0410*0.170
H22W0.391300.54720−0.130600.0410*0.170
H31W0.560500.50890−0.127200.0280*0.100
H32W0.527500.58190−0.146200.0280*0.100
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O20.0174 (10)0.0278 (11)0.0391 (13)0.0034 (10)−0.0001 (10)−0.0026 (10)
O30.0271 (12)0.0209 (11)0.0487 (14)0.0075 (10)−0.0011 (12)−0.0025 (10)
O240.0199 (11)0.0239 (11)0.0540 (15)0.0016 (10)0.0092 (11)−0.0065 (11)
O250.0291 (12)0.0191 (11)0.0511 (15)−0.0045 (10)−0.0016 (12)−0.0002 (11)
N90.0199 (12)0.0175 (12)0.0298 (14)0.0015 (11)0.0000 (11)0.0006 (11)
N190.0187 (12)0.0170 (12)0.0367 (15)−0.0013 (11)−0.0005 (12)−0.0020 (11)
C10.0177 (14)0.0199 (14)0.0270 (16)0.0002 (12)−0.0015 (13)−0.0028 (13)
C20.0192 (15)0.0289 (16)0.0243 (15)0.0028 (14)−0.0011 (13)0.0010 (14)
C30.0278 (16)0.0197 (14)0.0255 (16)0.0061 (14)−0.0031 (14)−0.0025 (13)
C40.0242 (15)0.0172 (14)0.0286 (16)−0.0008 (13)−0.0027 (14)−0.0002 (14)
C50.0208 (14)0.0217 (15)0.0215 (15)−0.0006 (13)0.0012 (13)−0.0009 (13)
C60.0217 (14)0.0199 (15)0.0229 (15)0.0020 (13)−0.0020 (13)−0.0003 (12)
C70.0132 (13)0.0206 (14)0.0279 (16)0.0028 (12)0.0007 (12)−0.0011 (13)
C80.0175 (14)0.0160 (14)0.0289 (16)−0.0014 (12)0.0019 (13)−0.0022 (12)
C100.0231 (15)0.0216 (15)0.0286 (16)−0.0012 (13)0.0018 (14)−0.0002 (13)
C110.0171 (14)0.0253 (15)0.0311 (16)−0.0058 (14)−0.0002 (13)0.0003 (14)
C120.0207 (15)0.0226 (15)0.0327 (17)−0.0006 (14)−0.0008 (14)−0.0016 (14)
C130.0168 (13)0.0186 (14)0.0268 (16)−0.0009 (13)0.0031 (13)−0.0009 (13)
C140.0198 (15)0.0229 (15)0.0303 (17)−0.0005 (14)−0.0033 (14)0.0013 (14)
C150.0248 (16)0.0203 (15)0.0312 (17)−0.0018 (14)0.0036 (14)0.0034 (13)
C160.0149 (14)0.0175 (13)0.0331 (17)−0.0012 (12)0.0035 (13)0.0001 (13)
C170.0187 (15)0.0225 (15)0.0306 (17)−0.0006 (14)0.0014 (14)−0.0017 (13)
C180.0260 (17)0.0245 (16)0.0299 (17)−0.0007 (14)−0.0009 (15)−0.0060 (14)
C200.0216 (15)0.0180 (14)0.0421 (19)0.0046 (13)−0.0010 (15)−0.0021 (14)
C210.0191 (15)0.0186 (14)0.0435 (19)0.0009 (13)−0.0025 (15)0.0026 (14)
C220.0260 (17)0.0220 (16)0.056 (2)0.0031 (15)−0.0015 (17)−0.0049 (17)
C230.0188 (16)0.0277 (18)0.076 (3)0.0019 (15)−0.0003 (18)−0.0028 (19)
C250.0187 (15)0.0330 (17)0.0412 (19)−0.0026 (15)0.0013 (15)0.0022 (16)
C260.039 (2)0.0245 (17)0.058 (3)0.0078 (17)−0.0003 (19)−0.0052 (17)
O2A0.0327 (13)0.0292 (13)0.0563 (16)−0.0073 (12)0.0093 (12)−0.0160 (12)
O3A0.0586 (18)0.0367 (14)0.0589 (17)0.0214 (15)−0.0006 (15)−0.0066 (13)
O21A0.0278 (13)0.0555 (17)0.0509 (17)−0.0069 (13)0.0052 (13)0.0146 (14)
O22A0.0366 (15)0.0239 (13)0.115 (3)−0.0121 (12)−0.0065 (17)0.0028 (16)
O41A0.0449 (16)0.0317 (14)0.0723 (19)0.0150 (14)−0.0061 (15)−0.0092 (14)
O42A0.0224 (12)0.0469 (16)0.0548 (17)0.0028 (13)0.0010 (12)−0.0015 (13)
O61A0.0559 (17)0.0311 (14)0.099 (2)−0.0140 (15)0.0387 (18)−0.0075 (15)
O62A0.0416 (15)0.0297 (12)0.089 (2)−0.0063 (13)0.0291 (16)−0.0214 (15)
N1A0.0248 (14)0.0205 (12)0.0319 (15)−0.0011 (11)−0.0007 (12)−0.0065 (12)
N21A0.0224 (14)0.0297 (16)0.061 (2)−0.0069 (13)−0.0120 (16)0.0142 (15)
N41A0.0307 (16)0.0359 (17)0.0397 (17)0.0109 (15)−0.0111 (14)−0.0030 (14)
N61A0.0324 (15)0.0260 (14)0.0403 (17)−0.0071 (13)0.0088 (14)−0.0052 (13)
C1A0.0197 (15)0.0251 (15)0.0253 (16)−0.0014 (13)0.0010 (13)0.0025 (14)
C2A0.0261 (16)0.0276 (16)0.0224 (15)0.0017 (14)0.0002 (13)0.0030 (13)
C3A0.0287 (18)0.045 (2)0.0288 (17)0.0058 (17)0.0007 (15)0.0028 (17)
C4A0.0234 (17)0.047 (2)0.0325 (18)−0.0084 (17)−0.0025 (15)0.0010 (17)
C5A0.0347 (18)0.0299 (17)0.0309 (17)−0.0057 (16)−0.0106 (16)0.0001 (15)
C6A0.0248 (16)0.0248 (16)0.0299 (16)0.0027 (14)−0.0049 (14)0.0001 (14)
C11A0.0222 (15)0.0255 (15)0.0238 (16)−0.0033 (14)−0.0003 (14)−0.0011 (13)
C21A0.0225 (15)0.0253 (16)0.0361 (18)−0.0069 (14)−0.0050 (15)0.0013 (15)
C22A0.0376 (19)0.0263 (17)0.0272 (17)0.0023 (17)0.0121 (16)0.0028 (14)
C31A0.0279 (16)0.0201 (15)0.0414 (19)0.0027 (15)−0.0116 (15)−0.0017 (14)
C41A0.0246 (16)0.0268 (16)0.0299 (17)0.0043 (15)−0.0059 (15)−0.0010 (14)
C51A0.0202 (15)0.0310 (17)0.0262 (16)−0.0030 (15)−0.0003 (14)0.0006 (14)
C61A0.0259 (16)0.0214 (15)0.0254 (15)−0.0022 (14)−0.0024 (14)−0.0030 (13)
O1W0.046 (2)0.0161 (16)0.105 (3)0.0007 (16)−0.013 (2)−0.0253 (19)
Geometric parameters (Å, º) top
O2—C21.374 (3)C15—C161.508 (4)
O2—C251.424 (4)C17—C181.508 (4)
O3—C31.369 (4)C20—C211.503 (4)
O3—C261.432 (4)C21—C221.334 (5)
O24—C121.426 (4)C22—C231.489 (5)
O24—C231.447 (4)C1—H10.9300
O25—C101.226 (3)C4—H40.9300
O2A—C22A1.256 (4)C8—H80.9800
O3A—C22A1.254 (4)C11—H1120.9700
O21A—N21A1.226 (4)C11—H1110.9700
O22A—N21A1.223 (4)C12—H120.9800
O41A—N41A1.232 (4)C13—H130.9800
O42A—N41A1.224 (4)C14—H140.9800
O61A—N61A1.217 (4)C15—H1520.9700
O62A—N61A1.221 (4)C15—H1510.9700
O1W—H11W0.8900C16—H160.9800
O1W—H12W0.9000C17—H1720.9700
O2W—H22W0.9100C17—H1710.9700
O2W—H21W0.9100C18—H1810.9700
O3W—H31W0.9000C18—H1820.9700
O3W—H32W0.9100C20—H2020.9700
N9—C51.409 (4)C20—H2010.9700
N9—C81.489 (4)C22—H220.9300
N9—C101.363 (4)C23—H2320.9700
N19—C181.510 (4)C23—H2310.9700
N19—C201.516 (4)C25—H2510.9600
N19—C161.540 (4)C25—H2520.9600
N19—H190.9100C25—H2530.9600
N1A—C1A1.405 (4)C26—H2630.9600
N1A—C11A1.356 (4)C26—H2610.9600
N21A—C21A1.478 (4)C26—H2620.9600
N41A—C41A1.454 (4)C1A—C2A1.407 (4)
N61A—C61A1.462 (4)C1A—C6A1.400 (4)
N1A—H1A0.9000C2A—C3A1.403 (5)
C1—C21.383 (4)C2A—C22A1.518 (4)
C1—C61.400 (4)C3A—C4A1.370 (5)
C2—C31.410 (4)C4A—C5A1.384 (5)
C3—C41.394 (4)C5A—C6A1.377 (5)
C4—C51.399 (4)C11A—C21A1.430 (4)
C5—C61.379 (4)C11A—C61A1.430 (4)
C6—C71.509 (4)C21A—C31A1.372 (5)
C7—C161.539 (4)C31A—C41A1.375 (5)
C7—C81.557 (4)C41A—C51A1.380 (5)
C7—C171.536 (4)C51A—C61A1.371 (4)
C8—C131.528 (4)C3A—H3A0.9300
C10—C111.526 (4)C4A—H4A0.9300
C11—C121.551 (4)C5A—H5A0.9300
C12—C131.546 (4)C6A—H6A0.9300
C13—C141.530 (4)C31A—H31A0.9300
C14—C211.533 (4)C51A—H51A0.9300
C14—C151.538 (4)
C2—O2—C25116.9 (2)C13—C12—H12109.00
C3—O3—C26117.2 (3)C12—C13—H13106.00
C12—O24—C23114.6 (3)C14—C13—H13106.00
H11W—O1W—H12W110.00C8—C13—H13106.00
H21W—O2W—H22W101.00C15—C14—H14109.00
H31W—O3W—H32W109.00C21—C14—H14109.00
C8—N9—C10119.6 (2)C13—C14—H14109.00
C5—N9—C10126.9 (3)C14—C15—H151110.00
C5—N9—C8109.2 (2)H151—C15—H152108.00
C16—N19—C18107.4 (2)C16—C15—H152110.00
C16—N19—C20112.6 (2)C14—C15—H152110.00
C18—N19—C20113.1 (2)C16—C15—H151110.00
C18—N19—H19108.00C15—C16—H16109.00
C20—N19—H19108.00C7—C16—H16109.00
C16—N19—H19108.00N19—C16—H16109.00
C1A—N1A—C11A128.8 (3)C7—C17—H171111.00
O22A—N21A—C21A116.5 (3)H171—C17—H172109.00
O21A—N21A—C21A117.9 (3)C7—C17—H172111.00
O21A—N21A—O22A125.5 (3)C18—C17—H171111.00
O41A—N41A—C41A116.9 (3)C18—C17—H172111.00
O42A—N41A—C41A119.0 (3)N19—C18—H181111.00
O41A—N41A—O42A124.1 (3)C17—C18—H182111.00
O61A—N61A—O62A122.4 (3)C17—C18—H181111.00
O62A—N61A—C61A119.4 (3)N19—C18—H182111.00
O61A—N61A—C61A118.3 (3)H181—C18—H182109.00
C1A—N1A—H1A113.00H201—C20—H202108.00
C11A—N1A—H1A117.00C21—C20—H201110.00
C2—C1—C6118.9 (3)C21—C20—H202110.00
O2—C2—C1124.5 (3)N19—C20—H202110.00
O2—C2—C3115.1 (3)N19—C20—H201110.00
C1—C2—C3120.4 (3)C23—C22—H22119.00
O3—C3—C4124.0 (3)C21—C22—H22119.00
O3—C3—C2115.4 (3)H231—C23—H232108.00
C2—C3—C4120.7 (3)C22—C23—H232109.00
C3—C4—C5118.0 (3)O24—C23—H231109.00
N9—C5—C4128.3 (3)O24—C23—H232109.00
N9—C5—C6110.2 (2)C22—C23—H231109.00
C4—C5—C6121.5 (2)H251—C25—H252110.00
C5—C6—C7110.9 (2)O2—C25—H251109.00
C1—C6—C5120.5 (3)H252—C25—H253110.00
C1—C6—C7128.3 (3)O2—C25—H253109.00
C6—C7—C17113.1 (2)O2—C25—H252109.00
C8—C7—C17110.4 (2)H251—C25—H253109.00
C6—C7—C16115.5 (2)H261—C26—H262110.00
C6—C7—C8102.0 (2)H262—C26—H263109.00
C8—C7—C16114.1 (2)H261—C26—H263109.00
C16—C7—C17102.1 (2)O3—C26—H263109.00
N9—C8—C13106.2 (2)O3—C26—H262109.00
N9—C8—C7104.5 (2)O3—C26—H261109.00
C7—C8—C13117.9 (2)C2A—C1A—C6A119.1 (3)
O25—C10—C11121.6 (3)N1A—C1A—C2A118.2 (3)
O25—C10—N9122.5 (3)N1A—C1A—C6A122.4 (3)
N9—C10—C11115.9 (2)C1A—C2A—C22A124.2 (3)
C10—C11—C12118.3 (2)C3A—C2A—C22A118.1 (3)
O24—C12—C11104.3 (2)C1A—C2A—C3A117.7 (3)
C11—C12—C13110.5 (2)C2A—C3A—C4A122.6 (3)
O24—C12—C13114.0 (2)C3A—C4A—C5A118.6 (3)
C12—C13—C14118.7 (2)C4A—C5A—C6A120.7 (3)
C8—C13—C12106.7 (2)C1A—C6A—C5A120.5 (3)
C8—C13—C14112.5 (2)N1A—C11A—C61A122.6 (3)
C15—C14—C21108.8 (2)N1A—C11A—C21A124.8 (3)
C13—C14—C21114.5 (2)C21A—C11A—C61A112.6 (3)
C13—C14—C15106.2 (2)C11A—C21A—C31A124.0 (3)
C14—C15—C16109.4 (2)N21A—C21A—C11A120.7 (3)
C7—C16—C15114.6 (2)N21A—C21A—C31A114.9 (3)
N19—C16—C15111.4 (2)O2A—C22A—C2A118.3 (3)
N19—C16—C7104.5 (2)O3A—C22A—C2A116.4 (3)
C7—C17—C18103.2 (2)O2A—C22A—O3A125.2 (3)
N19—C18—C17104.4 (2)C21A—C31A—C41A118.8 (3)
N19—C20—C21109.4 (2)N41A—C41A—C31A120.0 (3)
C14—C21—C22123.3 (3)C31A—C41A—C51A120.9 (3)
C20—C21—C22121.2 (3)N41A—C41A—C51A119.1 (3)
C14—C21—C20115.5 (2)C41A—C51A—C61A119.5 (3)
C21—C22—C23122.7 (3)N61A—C61A—C11A121.0 (3)
O24—C23—C22111.2 (3)N61A—C61A—C51A115.5 (3)
C2—C1—H1121.00C11A—C61A—C51A123.4 (3)
C6—C1—H1121.00C4A—C3A—H3A119.00
C3—C4—H4121.00C2A—C3A—H3A119.00
C5—C4—H4121.00C3A—C4A—H4A121.00
N9—C8—H8109.00C5A—C4A—H4A121.00
C13—C8—H8109.00C4A—C5A—H5A120.00
C7—C8—H8109.00C6A—C5A—H5A120.00
C12—C11—H111108.00C5A—C6A—H6A120.00
C10—C11—H111108.00C1A—C6A—H6A120.00
H111—C11—H112107.00C21A—C31A—H31A121.00
C10—C11—H112108.00C41A—C31A—H31A121.00
C12—C11—H112108.00C41A—C51A—H51A120.00
C11—C12—H12109.00C61A—C51A—H51A120.00
O24—C12—H12109.00
C25—O2—C2—C1−1.8 (4)C6—C7—C8—N9−17.5 (3)
C25—O2—C2—C3176.8 (3)C8—C7—C16—N19−88.0 (3)
C26—O3—C3—C2175.4 (3)C8—C7—C16—C1534.2 (3)
C26—O3—C3—C4−5.4 (4)C17—C7—C16—N1931.2 (2)
C23—O24—C12—C11170.2 (2)C17—C7—C16—C15153.3 (2)
C23—O24—C12—C13−69.2 (3)C6—C7—C17—C18−167.8 (2)
C12—O24—C23—C2289.1 (4)C8—C7—C17—C1878.7 (3)
C8—N9—C5—C4172.9 (3)C6—C7—C16—C15−83.6 (3)
C8—N9—C5—C6−6.0 (3)C16—C7—C17—C18−43.0 (3)
C10—N9—C5—C416.5 (5)N9—C8—C13—C12−72.2 (3)
C10—N9—C5—C6−162.4 (3)N9—C8—C13—C14155.9 (2)
C5—N9—C8—C715.1 (3)C7—C8—C13—C12171.1 (2)
C5—N9—C8—C13−110.2 (2)C7—C8—C13—C1439.3 (3)
C10—N9—C8—C7173.5 (3)O25—C10—C11—C12150.7 (3)
C10—N9—C8—C1348.2 (3)N9—C10—C11—C12−30.8 (4)
C5—N9—C10—O25−24.3 (5)C10—C11—C12—O24127.0 (3)
C5—N9—C10—C11157.2 (3)C10—C11—C12—C134.1 (4)
C8—N9—C10—O25−178.5 (3)O24—C12—C13—C8−71.7 (3)
C8—N9—C10—C113.0 (4)O24—C12—C13—C1456.6 (3)
C18—N19—C16—C7−8.4 (3)C11—C12—C13—C845.4 (3)
C18—N19—C16—C15−132.6 (3)C11—C12—C13—C14173.7 (2)
C20—N19—C16—C7116.8 (2)C8—C13—C14—C15−59.5 (3)
C20—N19—C16—C15−7.5 (3)C8—C13—C14—C2160.6 (3)
C16—N19—C18—C17−18.3 (3)C12—C13—C14—C21−65.0 (3)
C20—N19—C18—C17−143.2 (2)C12—C13—C14—C15174.9 (2)
C16—N19—C20—C21−48.6 (3)C21—C14—C15—C16−54.7 (3)
C18—N19—C20—C2173.4 (3)C13—C14—C21—C20−121.7 (3)
C1A—N1A—C11A—C61A152.2 (3)C13—C14—C21—C2257.1 (4)
C11A—N1A—C1A—C2A171.4 (3)C15—C14—C21—C20−3.0 (3)
C11A—N1A—C1A—C6A−15.0 (5)C15—C14—C21—C22175.7 (3)
C1A—N1A—C11A—C21A−26.5 (5)C13—C14—C15—C1669.1 (3)
O21A—N21A—C21A—C11A−31.2 (4)C14—C15—C16—N1960.9 (3)
O21A—N21A—C21A—C31A141.2 (3)C14—C15—C16—C7−57.4 (3)
O22A—N21A—C21A—C11A151.7 (3)C7—C17—C18—N1938.0 (3)
O22A—N21A—C21A—C31A−35.8 (4)N19—C20—C21—C1455.1 (3)
O42A—N41A—C41A—C51A1.4 (4)N19—C20—C21—C22−123.8 (3)
O41A—N41A—C41A—C31A2.7 (4)C20—C21—C22—C23176.0 (3)
O41A—N41A—C41A—C51A−178.1 (3)C14—C21—C22—C23−2.7 (6)
O42A—N41A—C41A—C31A−177.8 (3)C21—C22—C23—O24−63.6 (5)
O61A—N61A—C61A—C51A11.1 (4)N1A—C1A—C2A—C3A−179.1 (3)
O62A—N61A—C61A—C11A17.0 (4)N1A—C1A—C2A—C22A3.3 (4)
O61A—N61A—C61A—C11A−165.2 (3)C6A—C1A—C2A—C3A7.0 (4)
O62A—N61A—C61A—C51A−166.8 (3)C6A—C1A—C2A—C22A−170.6 (3)
C6—C1—C2—O2178.0 (3)N1A—C1A—C6A—C5A177.1 (3)
C2—C1—C6—C50.1 (4)C2A—C1A—C6A—C5A−9.4 (5)
C2—C1—C6—C7−173.2 (3)C1A—C2A—C3A—C4A0.9 (5)
C6—C1—C2—C3−0.6 (4)C22A—C2A—C3A—C4A178.6 (3)
C1—C2—C3—O3179.7 (3)C1A—C2A—C22A—O2A−21.5 (5)
O2—C2—C3—O31.1 (4)C1A—C2A—C22A—O3A159.4 (3)
O2—C2—C3—C4−178.1 (3)C3A—C2A—C22A—O2A160.9 (3)
C1—C2—C3—C40.5 (4)C3A—C2A—C22A—O3A−18.2 (4)
C2—C3—C4—C5−0.1 (4)C2A—C3A—C4A—C5A−6.6 (5)
O3—C3—C4—C5−179.2 (3)C3A—C4A—C5A—C6A4.3 (5)
C3—C4—C5—N9−179.1 (3)C4A—C5A—C6A—C1A3.7 (5)
C3—C4—C5—C6−0.4 (4)N1A—C11A—C21A—N21A−20.7 (5)
N9—C5—C6—C7−6.3 (3)N1A—C11A—C21A—C31A167.6 (3)
N9—C5—C6—C1179.3 (3)C61A—C11A—C21A—N21A160.5 (3)
C4—C5—C6—C10.3 (5)C61A—C11A—C21A—C31A−11.2 (4)
C4—C5—C6—C7174.8 (3)N1A—C11A—C61A—N61A5.8 (4)
C5—C6—C7—C16139.3 (3)N1A—C11A—C61A—C51A−170.1 (3)
C1—C6—C7—C8−171.1 (3)C21A—C11A—C61A—N61A−175.3 (3)
C1—C6—C7—C16−46.8 (4)C21A—C11A—C61A—C51A8.7 (4)
C1—C6—C7—C1770.3 (4)N21A—C21A—C31A—C41A−166.4 (3)
C5—C6—C7—C17−103.5 (3)C11A—C21A—C31A—C41A5.8 (5)
C5—C6—C7—C815.0 (3)C21A—C31A—C41A—N41A−177.7 (3)
C6—C7—C8—C13100.1 (3)C21A—C31A—C41A—C51A3.2 (5)
C16—C7—C8—N9−142.7 (2)N41A—C41A—C51A—C61A175.4 (3)
C16—C7—C8—C13−25.2 (3)C31A—C41A—C51A—C61A−5.5 (5)
C17—C7—C8—N9103.0 (3)C41A—C51A—C61A—N61A−177.2 (3)
C17—C7—C8—C13−139.5 (3)C41A—C51A—C61A—C11A−1.0 (5)
C6—C7—C16—N19154.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N19—H19···O2A0.911.942.708 (4)141
N1A—H1A···O2A0.901.902.662 (3)141
N1A—H1A···O62A0.902.102.653 (4)118
O1W—H11W···O3A0.891.802.695 (4)177
O1W—H12W···O25i0.902.193.091 (4)178
O2W—H21W···O3A0.912.173.079 (14)179
O2W—H22W···O25i0.912.113.020 (14)179
O3W—H31W···O3A0.902.173.08 (2)179
O3W—H32W···O25i0.911.732.65 (2)179
C1—H1···O1W0.932.413.263 (4)153
C4A—H4A···O42Aii0.932.533.364 (4)150
C20—H202···O62A0.972.443.319 (4)150
Symmetry codes: (i) x−1/2, −y+3/2, −z; (ii) x−1, y, z.

Experimental details

Crystal data
Chemical formulaC23H27N2O4+·C13H7N4O8−·H2O
Mr760.71
Crystal system, space groupOrthorhombic, P212121
Temperature (K)173
a, b, c (Å)12.4407 (3), 19.1542 (5), 14.6744 (4)
V (Å3)3496.79 (16)
Z4
Radiation typeMo Kα
µ (mm−1)0.11
Crystal size (mm)0.35 × 0.15 × 0.12
Data collection
DiffractometerOxford Gemini-S CCD area-detector
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
Tmin, Tmax0.911, 0.980
No. of measured, independent and
observed [I > 2σ(I)] reflections		12634, 4487, 3291
Rint0.031
(sin θ/λ)max (Å−1)0.676
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.109, 0.96
No. of reflections4487
No. of parameters506
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.58, −0.20

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N19—H19···O2A0.911.942.708 (4)141
N1A—H1A···O2A0.901.902.662 (3)141
N1A—H1A···O62A0.902.102.653 (4)118
O1W—H11W···O3A0.891.802.695 (4)177
O1W—H12W···O25i0.902.193.091 (4)178
O2W—H21W···O3A0.912.173.079 (14)179
O2W—H22W···O25i0.912.113.020 (14)179
O3W—H31W···O3A0.902.173.08 (2)179
O3W—H32W···O25i0.911.732.65 (2)179
Symmetry code: (i) x−1/2, −y+3/2, −z.
 

Acknowledgements

The authors acknowledge financial support from the Australian Research Grants Committee and from the Faculty of Science and Technology, Queensland University of Technology.

References

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ISSN: 2053-2296
Volume 67| Part 8| August 2011| Pages o334-o336
doi:10.1107/S010827011102782X
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