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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 10| October 2014| Pages 228-230
doi:10.1107/S1600536814020625

Crystal structure of 7-phenyl-7-(2,4,5-tri­methyl-3,6-dioxo­cyclo­hexa-1,4-dien-1-yl)hepta­noate 1,3-dihy­dr­oxy-2-(hy­dr­oxy­meth­yl)propan-2-aminium monohydrate: a new solid form of seratrodast

Benyong Loua*

aDepartment of Chemistry and Chemical Engineering, Minjiang University, Fuzhou, 350108, People's Republic of China
*Correspondence e-mail: lby@mju.edu.cn

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 5 September 2014; accepted 14 September 2014; online 20 September 2014)

In the title hydrated salt, C4H12NO3+·C22H25O4−·H2O, seratrodast [systematic name: 7-phenyl-7-(2,4,5-trimethyl-3,6-dioxo­cyclo­hexa-1,4-dien-1-yl)hepta­noic acid] crystallized with trometamol [systematic name: 2-amino-2-(hydroxyméth­yl)propane-1,3-diol] to form a monohydrated salt form of seratrodast. The carb­oxy­lic acid group of seratrodast has transferred its proton to the amino N atom of trometamol. In the crystal, the trometamol cations are linked to the water mol­ecules and to each other by N—H⋯O and O—H⋯O hydrogen bonds forming sheets parallel to (100). The seratrodast anions are linked to both sides of these sheets by O—H⋯O and C—H⋯O hydrogen bonds, forming a three-layer two-dimensional structure. After forming the title salt, the solubility of seratrodast was found to be greatly improved.

CCDC reference: 975488

1. Chemical context

Seratrodast is the first thromboxane A2 receptor antagonist to have been developed as an anti-asthmatic drug (Samara, 1996[Samara, E. E. (1996). Cardiovasc. Drug. Rev. 14, 272-285.]). This drug mol­ecule with a carb­oxy­lic group is practically insoluble in water. Its new solid forms have been scarcely exploited and only a polymorphic transition was ever investigated (Urakami & Beezer, 2003[Urakami, K. & Beezer, A. E. (2003). Int. J. Pharm. 257, 265-271.]). Tris(hy­droxy­meth­yl)amino methane, commonly called trometamol, is often used as a buffer in biochemical studies. It has been successfully exploited for improving properties of APIs such as ketoprofen (Zippel & Wagenitz, 2006[Zippel, H. & Wagenitz, A. (2006). Clin. Drug Investig. 26, 517-528.]). In this study, trometamol was employed to co-crystallize with seratrodast to give rise to a hydrated salt. To the best of our knowledge, the title salt is the first multi-component crystalline form of seratrodast to be reported.

[Scheme 1]

2. Structural commentary

The mol­ecular structure of the title salt is illustrated in Fig. 1[link]. It was clear from a difference Fourier map that the carb­oxy­lic group of seratrodast had transferred its proton to the amino N atom of trometamol. The bond distances C1—O1 and C1—O2 of the carboxyl­ate group of the seratrodast anion are 1.258 (4) and 1.232 (4) Å, respectively. The phenyl ring is normal to the dioxo­cyclo­hexa­diene ring, with a dihedral angle of 89.95 (19)°, and the alkyl chain has an extended conformation.

[Figure 1]
Figure 1
A view of the mol­ecular structure of the title salt, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines (see Table 1[link] for details).

3. Supra­molecular features

In the crystal, the trometamol cations are linked to the water mol­ecules and to each other by N—H⋯O and O—H⋯O hydrogen bonds, forming sheets parallel to (100); see Table 1[link] and Fig. 2[link]. The seratrodast anions are linked to both sides of these sheets by O—H⋯O and C—H⋯O hydrogen bonds, forming a three-layer two-dimensional structure (Fig. 3[link] and Table 1[link]). Further details of the hydrogen bonding are given below and in Table 1[link]. The carboxyl­ate anion inter­acts with one hydroxyl group of trometamol through strong hydrogen bonding [O6⋯O1 = 2.662 (3) Å]. There also exist hydrogen-bonding inter­actions between carboxyl­ate anion and water mol­ecule [O8⋯O2 = 2.617 (3) Å, O8⋯O1i = 2.667 (3) Å]. The protonated trometamol cation inter­acts with each other through three kinds of hydrogen-bonding inter­actions. An R22(11) heterosynthon is formed through hydrogen-bonding inter­actions between the hydroxyl groups [O5⋯O7iii = 2.714 (3) Å] and between the hydroxyl group and the amino group [N1⋯O6iii = 2.779 (3) Å]. Along the c axis, the R22(11) heterosynthon gives rise to a hydrogen-bonded chain of trometamol cations, which is further linked into a two-dimensional structure by hydrogen-bonding inter­actions between the amino and the hydroxyl groups [N1⋯O5ii = 2.935 (3) Å]. There also exist hydrogen-bonding inter­actions between water and trometamol [N1⋯O8i = 2.800 (4) Å; O7⋯O8iii = 2.686 (3) Å]. The various hydrogen-bonding inter­actions result in a two-dimensional layer structure in which the seratrodast anions are spread around two sides of the layer in an orderly manner (Table 1[link] and Fig. 3[link]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1C⋯O8i 0.99 1.85 2.800 (4) 160
N1—H1B⋯O5ii 0.91 2.04 2.935 (3) 166
N1—H1A⋯O6iii 0.97 1.88 2.779 (3) 153
O5—H5⋯O7iii 0.97 1.76 2.714 (3) 170
O6—H6⋯O1 0.91 1.81 2.662 (3) 154
O7—H7A⋯O8iii 0.92 1.77 2.686 (3) 173
O8—H8B⋯O2 0.92 1.76 2.617 (3) 1523
O8—H8A⋯O1iv 0.91 1.76 2.667 (3) 173
C24—H24A⋯O1 0.99 2.55 3.410 (4) 146
C25—H25A⋯O2iii 0.99 2.44 3.326 (4) 149
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iii) [x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]; (iv) [x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}].
[Figure 2]
Figure 2
A view along the a axis of the two-dimensional hydrogen-bonded structure of the trometamol cations and the water mol­ecules (hydrogen bonds are shown as dashed lines; see Table 1[link] for details).
[Figure 3]
Figure 3
A view along the c axis of the crystal packing of the title compound (hydrogen bonds are shown as dashed lines; see Table 1[link] for details). H atoms not involved in hydrogen bonding have been omitted for clarity

4. Database survey

To the best of our knowledge, the title salt is the first multi-component crystalline form of seratrodast to be reported.

5. Synthesis and crystallization

Seratrodast (354 mg, 1 mmol) and trometamol (121 mg, 1 mmol) were dissolved in methanol (15 ml). The resulting solution was kept in air and after several days yellow block-like crystals of the title salt were obtained.

6. Solubility Studies

Excess amounts of seratrodast and the title salt were suspended in 10 ml of water in screw-capped glass vials, respectively. These vials were kept at 310 K and were stirred at 100 r.p.m. using a magnetic stirrer. After 72 h, the suspensions were filtered through a 0.2 µm syringe filter. The filtered aliquots were sufficiently diluted, and the absorbances were measured at 268 nm in triplicate. Finally, the concentration of seratrodast after 72 h in each sample was determined from the previously made standard graph. A standard graph was made by measuring the absorbance of varied concentrations of seratrodast (2–16 mg/L) in water/methanol (9:1) solution using a UV-2500 spectrophotometer at 268 nm. The calibrated plot showed a good correlation coefficient (y = 0.04997x + 0.00459, R2 = 0.9991). After forming the title salt, the solubility of seratrodast was found to be greatly improved.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. The C-bound H atoms were positioned geometrically and refined as riding atoms: C—H = 0.95–1.00 Å with Uiso(H) = 1.2Ueq(C). The OH and NH3+ H atoms were located in difference Fourier maps and refined as riding atoms with Uiso(H) = 1.2Ueq(O,N).

Table 2
Experimental details

Crystal data
Chemical formula C4H12NO3+·C22H25O4−·H2O
Mr 493.58
Crystal system, space group Monoclinic, P21/c
Temperature (K) 293
a, b, c (Å) 23.506 (9), 9.665 (4), 11.344 (5)
β (°) 94.223 (7)
V (Å3) 2570.0 (17)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.09
Crystal size (mm) 0.20 × 0.20 × 0.20
 
Data collection
Diffractometer Rigaku Mercury CCD
Absorption correction Multi-scan (CrystalClear; Rigaku, 2000[Rigaku (2000). CrystalClear. Rigaku Corporation, Tokyo, Japan.])
Tmin, Tmax 0.549, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 20028, 5762, 3564
Rint 0.062
(sin θ/λ)max (Å−1) 0.649
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.074, 0.288, 1.10
No. of reflections 5762
No. of parameters 319
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.55, −0.42
Computer programs: CrystalClear (Rigaku, 2000[Rigaku (2000). CrystalClear. Rigaku Corporation, Tokyo, Japan.]), SHELXS97 and SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]), PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information

CCDC reference: 975488

Crystal structure: contains datablocks I, lou. DOI: 10.1107/S1600536814020625/su2780sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814020625/su2780Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814020625/su2780Isup3.cml

checkCIF report


Chemical context top

Seratrodast is the first thromboxane A2 receptor antagonist to have been developed as an anti-asthmatic drug (Samara, 1996). This drug molecule with a carb­oxy­lic group is practically insoluble in water. Its new solid forms have been scarcely exploited and only a polymorphic transition was ever investigated (Urakami & Beezer, 2003). Tris(hy­droxy­methyl)­amino methane, commonly called trometamol, is often used as a buffer in biochemical studies. It has been successfully exploited for improving properties of APIs such as ketoprofen (Zippel & Wagenitz, 2006). In this study, trometamol was employed to co-crystallize with seratrodast to give rise to a new crystalline form. To the best of our knowledge, the title salt is the first multi-component crystalline form of seratrodast to be reported.

Structural commentary top

The molecular structure of the title salt is illustrated in Fig. 1. It was clear from a difference Fourier map that the carb­oxy­lic group of seratrodast had transferred its proton to the amino N atom of trometamol. The bond distances C1—O1 and C1—O2 of the carboxyl­ate group of the seratrodast anion are 1.258 (4) and 1.232 (4) Å, respectively. The phenyl ring is normal to the dioxo­cyclo­hexadiene ring, with a dihedral angle of 89.95 (19)°, and the alkyl chain has an extended conformation.

Supra­molecular features top

In the crystal, the trometamol cations are linked to the water molecules and to each other by N—H···O and O—H···O hydrogen bonds, forming sheets parallel to (100); see Table 1 and Fig 2. The seratrodast anions are linked to both sides of these sheets by O—H···O and C—H···O hydrogen bonds, forming a three-layer two-dimensional structure (Fig. 3 and Table 1). Further details of the hydrogen bonding are given below and in Table 1. The carboxyl­ate anion inter­acts with one hydroxyl group of trometamol through strong hydrogen bonding [O6···O1 = 2.662 (3) Å]. There also exist hydrogen-bonding inter­actions between carboxyl­ate anion and water molecule [O8···O2 = 2.617 (3) Å, O8···O1i = 2.667 (3) Å]. The protonated trometamol cation inter­acts with each other through three kinds of hydrogen-bonding inter­actions. An R22(11) heterosynthon is formed through hydrogen-bonding inter­actions between the hydroxyl groups [O5···O7iii = 2.714 (3) Å] and between the hydroxyl group and the amino group [N1···O6iii = 2.779 (3) Å]. Along the c axis, the R22(11) heterosynthon gives rise to a hydrogen-bonded chain of trometamol cations, which is further linked into a two-dimensional structure by hydrogen-bonding inter­actions between the amino and the hydroxyl groups [N1···O5ii = 2.935 (3) Å]. There also exist hydrogen-bonding inter­actions between water and trometamol [N1···O8i = 2.800 (4) Å; O7···O8iii = 2.686 (3) Å]. The various hydrogen-bonding inter­actions result in a two-dimensional layer structure in which the seratrodast anions are spread around two sides of the layer in an orderly manner (Table 1 and Fig. 3).

Database survey top

To the best of our knowledge, the title salt is the first multi-component crystalline form of seratrodast to be reported.

Synthesis and crystallization top

Seratrodast (354 mg, 1 mmol) and trometamol (121 mg, 1 mmol) were dissolved in methanol (15 ml). The resulting solution was kept in air and after several days yellow block-like crystals of the title salt were obtained.

Solubility Studies top

Excess amounts of seratrodast and the title salt were suspended in 10 ml of water in screw-capped glass vials, respectively. These vials were kept at 310 K and were stirred at 100 r.p.m. using a magnetic stirrer. After 72 h, the suspensions were filtered through a 0.2 µm syringe filter. The filtered aliquots were sufficiently diluted, and the absorbances were measured at 268 nm in triplicate. Finally, the concentration of seratrodast after 72 h in each sample was determined from the previously made standard graph. A standard graph was made by measuring the absorbance of varied concentrations of seratrodast (2–16 mg/L) in water/methanol (9:1) solution using a UV-2500 spectrophotometer at 268 nm. The calibrated plot showed a good correlation coefficient (y = 0.04997x + 0.00459, R2 = 0.9991). After forming the title salt, the solubility of seratrodast was found to be greatly improved.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound H atoms were positioned geometrically and refined as riding atoms: C—H = 0.95–1.00 Å with Uiso(H) = 1.2Ueq(C). The OH and NH3+ H atoms were located in difference Fourier maps and refined as riding atoms with Uiso(H) = 1.2Ueq(O,N).

Related literature top

For related literature, see: Samara (1996); Urakami & Beezer (2003); Zippel & Wagenitz (2006).

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of the title salt, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines (see Table 1 for details).
[Figure 2] Fig. 2. A view along the a axis of the two-dimensional hydrogen-bonded structure of the trometamol cations and the water molecules (hydrogen bonds are shown as dashed lines; see Table 1 for details).
[Figure 3] Fig. 3. A view along the c axis of the crystal packing of the title compound (hydrogen bonds are shown as dashed lines; see Table 1 for details). H atoms not involved in hydrogen bonding have been omitted for clarity
7-Phenyl-7-(2,4,5-trimethyl-3,6-dioxocyclohexa-1,4-dien-1-yl)heptanoate 1,3-dihydroxy-2-(hydroxymethyl)propan-2-aminium monohydrate top
Crystal data top
C4H12NO3+·C22H25O4−·H2OF(000) = 1064
Mr = 493.58Dx = 1.276 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6295 reflections
a = 23.506 (9) Åθ = 2.1–27.5°
b = 9.665 (4) ŵ = 0.09 mm−1
c = 11.344 (5) ÅT = 293 K
β = 94.223 (7)°Prism, yellow
V = 2570.0 (17) Å30.20 × 0.20 × 0.20 mm
Z = 4
Data collection top
Rigaku Mercury CCD
diffractometer		5762 independent reflections
Radiation source: fine-focus sealed tube3564 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.062
Detector resolution: 28.5714 pixels mm-1θmax = 27.5°, θmin = 2.6°
CCD_Profile_fitting scansh = −30→30
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2000)		k = −12→12
Tmin = 0.549, Tmax = 1.000l = −12→14
20028 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)] = 0.074Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.288H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.1567P)2]
where P = (Fo2 + 2Fc2)/3
5762 reflections(Δ/σ)max < 0.001
319 parametersΔρmax = 0.55 e Å−3
0 restraintsΔρmin = −0.42 e Å−3
Crystal data top
C4H12NO3+·C22H25O4−·H2OV = 2570.0 (17) Å3
Mr = 493.58Z = 4
Monoclinic, P21/cMo Kα radiation
a = 23.506 (9) ŵ = 0.09 mm−1
b = 9.665 (4) ÅT = 293 K
c = 11.344 (5) Å0.20 × 0.20 × 0.20 mm
β = 94.223 (7)°
Data collection top
Rigaku Mercury CCD
diffractometer		5762 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2000)		3564 reflections with I > 2σ(I)
Tmin = 0.549, Tmax = 1.000Rint = 0.062
20028 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0740 restraints
wR(F2) = 0.288H-atom parameters constrained
S = 1.10Δρmax = 0.55 e Å−3
5762 reflectionsΔρmin = −0.42 e Å−3
319 parameters
Special details top

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

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*/Ueq
O10.38025 (10)0.4145 (2)0.4397 (2)0.0447 (6)
O20.38047 (12)0.4204 (3)0.6328 (2)0.0537 (7)
O30.09684 (12)0.0531 (3)0.8988 (3)0.0749 (9)
O40.25430 (13)−0.0713 (4)1.2339 (3)0.0789 (10)
O50.44774 (10)0.5677 (2)0.17616 (18)0.0408 (6)
O60.44283 (9)0.6368 (2)0.49902 (17)0.0389 (6)
O70.42596 (11)0.9565 (2)0.43874 (19)0.0482 (6)
O80.42283 (9)0.2989 (2)0.8260 (2)0.0440 (6)
H8B0.40790.31360.74980.053*
H1C0.50770.78210.19920.053*
H7A0.42221.03800.39690.053*
H1B0.49620.91710.26500.053*
H1A0.45900.86840.16370.053*
H8A0.40590.22520.85990.053*
H50.43890.57030.09170.053*
H60.42740.56230.45920.053*
N10.47892 (10)0.8382 (3)0.2369 (2)0.0333 (6)
C10.36324 (13)0.3727 (3)0.5360 (3)0.0339 (7)
C20.31629 (15)0.2633 (4)0.5285 (3)0.0469 (8)
H2A0.28010.30870.50010.056*
H2B0.32540.19440.46810.056*
C30.30659 (14)0.1871 (4)0.6411 (3)0.0470 (8)
H3A0.30180.25540.70470.056*
H3B0.34080.13090.66440.056*
C40.25457 (15)0.0926 (4)0.6304 (3)0.0465 (8)
H4A0.22040.14950.60800.056*
H4B0.25920.02590.56560.056*
C50.24405 (15)0.0123 (4)0.7421 (3)0.0502 (9)
H5A0.2750−0.05600.75800.060*
H5B0.24480.07690.80990.060*
C60.18728 (15)−0.0623 (4)0.7312 (3)0.0475 (9)
H6A0.15670.00780.71840.057*
H6B0.1861−0.12120.65970.057*
C70.17374 (14)−0.1507 (4)0.8334 (3)0.0452 (8)
H70.2046−0.22220.83970.054*
C80.11810 (13)−0.2336 (4)0.8148 (3)0.0412 (8)
C90.08118 (15)−0.2237 (4)0.7166 (4)0.0566 (10)
H90.0876−0.15620.65810.068*
C100.03397 (16)−0.3118 (5)0.7012 (5)0.0725 (13)
H100.0092−0.30510.63140.087*
C130.10716 (18)−0.3320 (5)0.8987 (4)0.0670 (12)
H130.1327−0.34260.96700.080*
C120.0590 (2)−0.4157 (5)0.8836 (5)0.0860 (16)
H120.0512−0.48000.94370.103*
C110.02316 (17)−0.4075 (5)0.7856 (5)0.0689 (12)
H11−0.0090−0.46710.77520.083*
C140.17815 (13)−0.0778 (3)0.9519 (3)0.0397 (8)
C150.13375 (14)0.0248 (4)0.9771 (3)0.0463 (9)
C160.13441 (16)0.0942 (4)1.0924 (4)0.0531 (9)
C190.22057 (13)−0.1042 (4)1.0361 (3)0.0426 (8)
C180.21906 (15)−0.0386 (4)1.1559 (3)0.0494 (9)
C170.17570 (17)0.0652 (4)1.1788 (4)0.0555 (10)
C200.27017 (17)−0.1961 (4)1.0232 (4)0.0655 (11)
H20A0.2645−0.24810.94910.098*
H20B0.2740−0.26071.08980.098*
H20C0.3049−0.14011.02200.098*
C210.0871 (2)0.1955 (6)1.1065 (5)0.0896 (16)
H21A0.09280.24081.18380.134*
H21B0.05050.14661.10110.134*
H21C0.08710.26531.04390.134*
C220.1798 (2)0.1297 (6)1.2988 (4)0.0891 (17)
H22A0.21940.15561.32070.134*
H22B0.16690.06341.35650.134*
H22C0.15560.21251.29790.134*
C230.47623 (12)0.6918 (3)0.4125 (2)0.0319 (6)
H23A0.49920.61680.38010.038*
H23B0.50290.76120.44940.038*
C240.40803 (12)0.6541 (3)0.2309 (3)0.0346 (7)
H24A0.38330.59650.27810.042*
H24B0.38340.70230.16930.042*
C250.39738 (13)0.8612 (3)0.3592 (3)0.0392 (7)
H25A0.37730.91240.29300.047*
H25B0.36860.80930.40080.047*
C260.43939 (11)0.7603 (3)0.3108 (2)0.0296 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0627 (15)0.0412 (12)0.0308 (13)−0.0161 (10)0.0075 (10)0.0027 (10)
O20.0810 (18)0.0487 (14)0.0311 (13)−0.0191 (12)0.0032 (12)−0.0005 (11)
O30.0648 (18)0.090 (2)0.067 (2)0.0198 (16)−0.0195 (15)0.0060 (17)
O40.0712 (19)0.099 (3)0.062 (2)−0.0058 (17)−0.0235 (15)0.0159 (18)
O50.0564 (13)0.0365 (11)0.0280 (12)0.0050 (10)−0.0064 (10)−0.0036 (9)
O60.0626 (14)0.0380 (12)0.0156 (10)−0.0120 (10)−0.0012 (9)0.0025 (9)
O70.0854 (18)0.0351 (12)0.0226 (12)0.0038 (11)−0.0057 (11)0.0000 (9)
O80.0505 (13)0.0447 (13)0.0368 (13)−0.0080 (10)0.0037 (10)−0.0006 (10)
N10.0433 (14)0.0333 (12)0.0227 (13)−0.0094 (10)−0.0014 (10)0.0024 (10)
C10.0450 (17)0.0294 (14)0.0279 (17)0.0010 (12)0.0072 (13)0.0024 (12)
C20.052 (2)0.053 (2)0.0360 (19)−0.0131 (16)0.0066 (15)0.0017 (16)
C30.0459 (18)0.052 (2)0.044 (2)−0.0116 (15)0.0043 (15)0.0099 (16)
C40.0498 (19)0.052 (2)0.038 (2)−0.0124 (15)0.0065 (15)0.0046 (16)
C50.053 (2)0.057 (2)0.040 (2)−0.0163 (16)0.0010 (16)0.0065 (17)
C60.052 (2)0.056 (2)0.0357 (19)−0.0158 (16)0.0109 (15)−0.0008 (16)
C70.0446 (18)0.053 (2)0.0377 (19)−0.0103 (15)0.0033 (14)−0.0009 (16)
C80.0364 (16)0.0511 (19)0.0372 (18)−0.0077 (14)0.0110 (13)−0.0085 (15)
C90.045 (2)0.066 (2)0.059 (2)−0.0098 (17)0.0019 (17)−0.006 (2)
C100.043 (2)0.083 (3)0.089 (3)−0.010 (2)−0.015 (2)−0.017 (3)
C130.061 (2)0.081 (3)0.059 (3)−0.031 (2)0.0041 (19)0.004 (2)
C120.067 (3)0.073 (3)0.119 (5)−0.032 (2)0.011 (3)0.008 (3)
C110.044 (2)0.064 (3)0.099 (4)−0.0171 (19)0.003 (2)−0.012 (3)
C140.0358 (16)0.0472 (18)0.0365 (18)−0.0106 (13)0.0043 (13)0.0026 (15)
C150.0420 (18)0.053 (2)0.043 (2)−0.0035 (15)−0.0028 (15)0.0080 (16)
C160.056 (2)0.048 (2)0.057 (2)−0.0016 (16)0.0137 (18)−0.0014 (18)
C190.0399 (17)0.0440 (17)0.044 (2)−0.0069 (13)0.0005 (14)0.0041 (15)
C180.0477 (19)0.055 (2)0.044 (2)−0.0183 (16)−0.0044 (16)0.0112 (17)
C170.064 (2)0.054 (2)0.049 (2)−0.0185 (18)0.0087 (18)−0.0054 (18)
C200.053 (2)0.060 (2)0.082 (3)0.0060 (18)−0.003 (2)0.009 (2)
C210.087 (3)0.082 (4)0.101 (4)0.029 (3)0.021 (3)−0.009 (3)
C220.120 (4)0.092 (4)0.058 (3)−0.029 (3)0.025 (3)−0.026 (3)
C230.0401 (15)0.0323 (14)0.0224 (15)−0.0022 (12)−0.0033 (12)0.0006 (12)
C240.0361 (15)0.0371 (15)0.0297 (16)−0.0072 (12)−0.0043 (12)0.0038 (13)
C250.0427 (17)0.0362 (16)0.0385 (18)0.0011 (13)0.0009 (13)0.0006 (14)
C260.0362 (15)0.0316 (14)0.0210 (14)−0.0061 (11)0.0009 (11)0.0043 (12)
Geometric parameters (Å, º) top
O1—C11.258 (4)C9—C101.400 (5)
O2—C11.232 (4)C9—H90.9500
O3—C151.226 (4)C10—C111.369 (7)
O4—C181.209 (4)C10—H100.9500
O5—C241.428 (4)C13—C121.392 (5)
O5—H50.9657C13—H130.9500
O6—C231.406 (4)C12—C111.347 (7)
O6—H60.9109C12—H120.9500
O7—C251.423 (4)C11—H110.9500
O7—H7A0.9202C14—C191.353 (4)
O8—H8B0.9191C14—C151.483 (5)
O8—H8A0.9142C15—C161.469 (5)
N1—C261.499 (4)C16—C171.357 (6)
N1—H1C0.9892C16—C211.499 (6)
N1—H1B0.9100C19—C201.482 (5)
N1—H1A0.9682C19—C181.502 (5)
C1—C21.526 (4)C18—C171.467 (6)
C2—C31.507 (5)C17—C221.493 (6)
C2—H2A0.9900C20—H20A0.9800
C2—H2B0.9900C20—H20B0.9800
C3—C41.523 (4)C20—H20C0.9800
C3—H3A0.9900C21—H21A0.9800
C3—H3B0.9900C21—H21B0.9800
C4—C51.522 (5)C21—H21C0.9800
C4—H4A0.9900C22—H22A0.9800
C4—H4B0.9900C22—H22B0.9800
C5—C61.514 (5)C22—H22C0.9800
C5—H5A0.9900C23—C261.540 (4)
C5—H5B0.9900C23—H23A0.9900
C6—C71.493 (5)C23—H23B0.9900
C6—H6A0.9900C24—C261.524 (4)
C6—H6B0.9900C24—H24A0.9900
C7—C141.515 (5)C24—H24B0.9900
C7—C81.535 (4)C25—C261.519 (4)
C7—H71.0000C25—H25A0.9900
C8—C91.364 (5)C25—H25B0.9900
C8—C131.383 (5)
C24—O5—H5108.4C12—C11—C10118.7 (4)
C23—O6—H6100.0C12—C11—H11120.6
C25—O7—H7A101.8C10—C11—H11120.6
H8B—O8—H8A111.6C19—C14—C15118.8 (3)
C26—N1—H1C116.1C19—C14—C7122.5 (3)
C26—N1—H1B120.2C15—C14—C7118.7 (3)
H1C—N1—H1B108.0O3—C15—C16120.2 (4)
C26—N1—H1A110.6O3—C15—C14118.7 (3)
H1C—N1—H1A95.6C16—C15—C14121.1 (3)
H1B—N1—H1A102.8C17—C16—C15120.6 (4)
O2—C1—O1123.3 (3)C17—C16—C21123.7 (4)
O2—C1—C2119.9 (3)C15—C16—C21115.7 (4)
O1—C1—C2116.7 (3)C14—C19—C20126.0 (3)
C3—C2—C1116.4 (3)C14—C19—C18119.6 (3)
C3—C2—H2A108.2C20—C19—C18114.4 (3)
C1—C2—H2A108.2O4—C18—C17119.8 (4)
C3—C2—H2B108.2O4—C18—C19119.4 (4)
C1—C2—H2B108.2C17—C18—C19120.8 (3)
H2A—C2—H2B107.3C16—C17—C18118.8 (4)
C2—C3—C4113.3 (3)C16—C17—C22124.5 (4)
C2—C3—H3A108.9C18—C17—C22116.7 (4)
C4—C3—H3A108.9C19—C20—H20A109.5
C2—C3—H3B108.9C19—C20—H20B109.5
C4—C3—H3B108.9H20A—C20—H20B109.5
H3A—C3—H3B107.7C19—C20—H20C109.5
C5—C4—C3114.7 (3)H20A—C20—H20C109.5
C5—C4—H4A108.6H20B—C20—H20C109.5
C3—C4—H4A108.6C16—C21—H21A109.5
C5—C4—H4B108.6C16—C21—H21B109.5
C3—C4—H4B108.6H21A—C21—H21B109.5
H4A—C4—H4B107.6C16—C21—H21C109.5
C6—C5—C4111.8 (3)H21A—C21—H21C109.5
C6—C5—H5A109.3H21B—C21—H21C109.5
C4—C5—H5A109.3C17—C22—H22A109.5
C6—C5—H5B109.3C17—C22—H22B109.5
C4—C5—H5B109.3H22A—C22—H22B109.5
H5A—C5—H5B107.9C17—C22—H22C109.5
C7—C6—C5116.5 (3)H22A—C22—H22C109.5
C7—C6—H6A108.2H22B—C22—H22C109.5
C5—C6—H6A108.2O6—C23—C26111.9 (2)
C7—C6—H6B108.2O6—C23—H23A109.2
C5—C6—H6B108.2C26—C23—H23A109.2
H6A—C6—H6B107.3O6—C23—H23B109.2
C6—C7—C14114.7 (3)C26—C23—H23B109.2
C6—C7—C8114.9 (3)H23A—C23—H23B107.9
C14—C7—C8111.5 (3)O5—C24—C26110.5 (2)
C6—C7—H7104.8O5—C24—H24A109.6
C14—C7—H7104.8C26—C24—H24A109.6
C8—C7—H7104.8O5—C24—H24B109.6
C9—C8—C13118.1 (3)C26—C24—H24B109.6
C9—C8—C7124.0 (3)H24A—C24—H24B108.1
C13—C8—C7117.7 (3)O7—C25—C26110.8 (2)
C8—C9—C10120.7 (4)O7—C25—H25A109.5
C8—C9—H9119.7C26—C25—H25A109.5
C10—C9—H9119.7O7—C25—H25B109.5
C11—C10—C9120.7 (4)C26—C25—H25B109.5
C13—C10—H10119.7H25A—C25—H25B108.1
C9—C10—H10119.7N1—C26—C25109.1 (2)
C8—C13—C12120.4 (4)N1—C26—C24107.3 (2)
C8—C13—H13119.8C25—C26—C24110.4 (2)
C12—C13—H13119.8N1—C26—C23107.3 (2)
C11—C12—C13121.4 (5)C25—C26—C23110.5 (2)
C11—C12—H12119.3C24—C26—C23112.1 (2)
C13—C12—H12119.3
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O8i0.991.852.800 (4)160
N1—H1B···O5ii0.912.042.935 (3)166
N1—H1A···O6iii0.971.882.779 (3)153
O5—H5···O7iii0.971.762.714 (3)170
O6—H6···O10.911.812.662 (3)154
O7—H7A···O8iii0.921.772.686 (3)173
O8—H8B···O20.921.762.617 (3)1523
O8—H8A···O1iv0.911.762.667 (3)173
C24—H24A···O10.992.553.410 (4)146
C25—H25A···O2iii0.992.443.326 (4)149
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+1/2; (iii) x, −y+3/2, z−1/2; (iv) x, −y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O8i0.991.852.800 (4)160
N1—H1B···O5ii0.912.042.935 (3)166
N1—H1A···O6iii0.971.882.779 (3)153
O5—H5···O7iii0.971.762.714 (3)170
O6—H6···O10.911.812.662 (3)154
O7—H7A···O8iii0.921.772.686 (3)173
O8—H8B···O20.921.762.617 (3)1523
O8—H8A···O1iv0.911.762.667 (3)173
C24—H24A···O10.992.553.410 (4)146
C25—H25A···O2iii0.992.443.326 (4)149
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+1/2; (iii) x, −y+3/2, z−1/2; (iv) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC4H12NO3+·C22H25O4−·H2O
Mr493.58
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)23.506 (9), 9.665 (4), 11.344 (5)
β (°) 94.223 (7)
V (Å3)2570.0 (17)
Z4
Radiation typeMo Kα
µ (mm−1)0.09
Crystal size (mm)0.20 × 0.20 × 0.20
Data collection
DiffractometerRigaku Mercury CCD
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2000)
Tmin, Tmax0.549, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections		20028, 5762, 3564
Rint0.062
(sin θ/λ)max (Å−1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.074, 0.288, 1.10
No. of reflections5762
No. of parameters319
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.55, −0.42

Computer programs: CrystalClear (Rigaku, 2000), SHELXS97 (Sheldrick, 2008), Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

 

Acknowledgements

The author is grateful to the Natural Science Foundation of Fujian Province (2012D107) and Research Project for Young and Middle-aged Faculty of Fujian Province (JA14250) for financial support. The experimental contributions of collaborators S. Cai and Z. Feng are greatly appreciated.

References

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 First citationRigaku (2000). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
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 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationUrakami, K. & Beezer, A. E. (2003). Int. J. Pharm. 257, 265–271.  Web of Science CrossRef PubMed CAS Google Scholar
 First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationZippel, H. & Wagenitz, A. (2006). Clin. Drug Investig. 26, 517–528.  Web of Science CrossRef PubMed CAS Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 10| October 2014| Pages 228-230
doi:10.1107/S1600536814020625
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