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A low-resolution X-ray mol­ecular structure of the title hydrated salt, [Na(C19H21N6O6)]·2H2O, displays scorpionate character and resolves apparent ambiguities between solution and solid-state NMR spectroscopies. The 13C NMR CPMAS spectrum is consistent with this structure showing some splittings, which have been rationalized using GIAO/B3LYP/6-311++G(d,p) theoretical calculations.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113018969/yf3036sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113018969/yf3036Isup2.hkl
Contains datablock I

CCDC reference: 964752

Introduction top

Our inter­est in tris­(pyrazol-1-yl)methanes as neutral analogues of scorpionates (Claramunt et al., 1989, 1995; Ochando et al., 1997) [for a review, see Bigmore et al. (2005)], coupled with the inter­esting dynamic properties of pyrazole-4-carb­oxy­lic acids (Foces-Foces et al., 2001; Infantes et al., 2003; Claramunt et al., 2005), prompted us to attempt the synthesis of a tris­(pyrazol-1-yl)methane bearing carb­oxy­lic acid groups at pyrazolyl position 4 [compound (3) in Scheme 1]. The product proved to be the sodium salt, (4).

Experimental top

Synthesis and crystallization top

A mixture of ethyl 3,5-di­methyl-1H-pyrazole-4-carboxyl­ate, (1) (5.95 mmol), anhydrous potassium carbonate (29.8 mmol) and tetra­butyl­ammonium bromide (0.298 mmol) was dissolved in dry chloro­form (25 ml) and refluxed for 8 h with vigorous magnetic stirring. The hot reaction mixture was filtered and the residue washed with hot chloro­form (3 × 25 ml). All organic layers were collected and the solvent evaporated off to afford an oil, which was further purified by column chromatography on silica gel with chloro­form–ethanol as eluent (99:1 v/v). Removing the column eluent under vacuum afforded tris­[(4-eth­oxy­carbonyl-3,5-di­methyl)­pyrazol-1yl]methane, (2) (yield 157.7 mg, 15.4%; m.p. 433–434 K). Analysis, calculated for C25H34N6O6: C 58.35, H 6.66, N 16.33%; found: C 58.46, H 6.82, N 16.11%. 1H NMR (400 MHz, CDCl3, δ, p.p.m.): 2.34 and 2.37 (pyrazole Me groups), 1.35 and 4.29 (ester, 3J = 7.1 Hz), 8.12 (CH); 13C NMR (400 MHz, CDCl3δ, p.p.m.): 10.9 (5-Me), 14.3 and 14.6 (3-Me and Me of the CO2Et), 60.0 (CH2 of the CO2Et), 80.5 (CH), 112.2 (C4), 146.0 (C5), 151.4 (C3); 15N NMR (400 MHz, CDCl3, δ, p.p.m.): -83.0 (N2), -177.4 (N1). CPMAS (400 MHz instrument), 13C (δ): 11.4 (5-Me), 14.3 (Me of the CO2Et), 15.5 (3-Me), 59.8 (CH2 of the CO2Et), 76.9 (CH), 111.1 (C4), 144.6 (C5), 152.1 and 154.2 (C3); 15N (δ): -83.2 (N2), -176.5 (N1).

Sodium metal (21.7 mmol) was added to dry ethanol (10 ml) and the mixture was gently heated until all the metal had reacted. The solution was allowed to cool to ambient temperature. Compound (2) (0.972 mmol) suspended in water (0.25 ml) was added and the mixture heated for 30 min. The sodium salt precipitated and was isolated by filtration. The crude product was dissolved in water (10 ml). Acetic acid was added to quench excess sodium hydroxide until a white precipitate formed. The reaction mixture was refrigerated and the residue isolated on a filter [paper?]. The product was purified by recrystallization in methanol–water [Solvent ratio?] to yield the title compound, (4) [yield 327 mg, 78%; m.p. 429–430 K (decomposition)]. Analysis, calculated for C19H21N6NaO6.0.5H2O: C 49.46, H 4.81, N 18.21%; found: C 49.24, H 5.26, N 18.01%. 1H NMR (400 MHz, DMSO-d6, δ, p.p.m.): 2.23 (pyrazole Me groups), 8.58 (CH and CO2H); 13C NMR (400 MHz, DMSO-d6, δ, p.p.m.): 10.3 (5-Me), 14.2 (3-Me), 79.5 (CH), 113.2 (C4), 144.8 (C5), 149.7 (C3); 15N NMR (400 MHz, CDCl3, δ, p.p.m.): -82.6 (N2), -175.9 (N1). CPMAS (400 MHz instrument), 13C (δ): 10.4 (5-Me), 13.1 (3-Me), 77.5 (CH), 111.5 and 118.5 (C4), 146.7 (C5), 152.1 (C3), 166.9 (CO2H), 170.7 and 173.6 (CO2-); 15N (δ): -84.6 (N2), -176.5 (N1).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. Despite repeated attempts using different conditions, compound (4), in our hands, consistently deposited as either a microcrystalline powder or very small multiple crystals. The data presented herein (final R = 0.1358, 0.98 Å resolution, 85.3% coverage at 45.95° θ) represent the best results from crystals grown by slow evaporation of a saturated solution in methanol, data crystal size = 0.10 × 0.06 × 0.04 mm. Absolute structure parameter refinement yielded insignificant results because of the absence of sufficiently heavy atoms and the Friedel pairs were merged instead. The three arms of the compound were treated with 1,2 and 1,3 geometric restraints based on noncrystallographic symmetry. The structure was treated with equivalent isotropic atomic displacement parameter rigid-bond restraints. The longer C—O fragment in each carb­oxy­lic acid group was assigned a calculated H atom, except for the carboxyl­ate anion that is coordinated to Na. The O atoms of the slvent water molecules were constrained with equal atomic displacement parameters. The H atoms of the slvent water molecules were located, allowed to converge with damping and finally treated as rigid groups. All other H atoms were treated as idealized contributions, with C—H = 0.98–1.00 Å, and with Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for methyl H. [Please check added text] Structure factors are contained in the SHELXTL program library (Sheldrick, 2008).

Results and discussion top

In principle, tris­pyrazolyl­methanes can exist in four helical conformations, depending on the orientation of the N2 lone pair (up or u: the lone pair pointing towards the CH; down or d: the lone pair opposite to the CH group) (Claramunt et al., 1989, 1995). The most stable conformations for methane-1,1',1''-triyltris(3,5-di­methyl-1H-pyrazole-4-carb­oxy­lic acid), (3), and tris­(3,5-di­methyl-1H-pyrazolyl-1-yl)methane, (5), were calculated at the B3LYP/6-31G* level (Becke, 1993; Hariharan & Pople, 1973) using GAUSSIAN09 (Frisch et al., 2009). The uud structure isomerizes into the udd one by rotation of one of the pyrazole rings. Of the three remaining conformations, the relative energies in kJ mol-1 are [those of (5) in parentheses] udd 0.0 (0.0), ddd 16.5 (20.4) and uuu 24.8 (16.5). For (5), the udd and ddd structures have been solved by crystallography (in the second case, by X-ray powder diffraction) (Declercq & Van Meerssche, 1984; Ochando et al., 1997). Note that the `scorpionate' array ddd is not stable without a cation linked to the three N-atom lone pairs.

To prepare compound (3), we used the sequence reported above (see Scheme 1) starting from ethyl 3,5-di­methyl-1H-pyrazole-4-carboxyl­ate, (1), and going through the triester, (2).

The 1H, 13C and 15N NMR spectra of the product in DMSO-d6 appear to be reasonably consistent with the expected resonances of triacid (3). However, the 13C NMR spectrum in the solid state (Fig. 1) displays additional minor lateral signals apparently accompanying the expected major resonances. Thus, besides the major signal at 111.5 p.p.m. assigned to C4, there is another minor signal at 118.5 p.p.m. (δ = 7.0 p.p.m.). Additionally, instead of only one major signal accompanying the 166.9 p.p.m. signal for the magnetically equivalent carb­oxy­lic acid groups, there are two minor signals at 170.8 and 173.6 p.p.m. (δ = 3.9 and 6.7 p.p.m., respectively).

A perusal of the literature (Kalinowski et al., 1997) suggests that these shifts between the major and minor resonances are similar to the shifts found when comparing carb­oxy­lic acids and their carboxyl­ate salts (Fig. 1). Therefore, the spectroscopy suggests that the product, isolated in 78% yield, exists as a salt. Presumably, the salt resonances are obscured in the solution NMR spectra because of rapid exchange. At least one of the carb­oxy­lic acid groups seems to be in the form of a carboxyl­ate anion and, since only Na+ was used in the synthesis, we suspected that the minor component was the title sodium carboxyl­ate, (4). To determine the molecular structure of the product, an X-ray structure analysis was attempted. Unfortunately the bulk material consistently deposited as a powder. Fortuitously, crystals, barely of X-ray quality, were occasionally obtained in the powdery mixtures. After several attempts we can only obtain at best a 0.98 Å low-resolution diffraction data set, which nonetheless validates our hypothesis consistent with the spectroscopy results. Although it was subsequently found that the salt was easier to purify and manage, no better quality crystals could be obtained.

In contrast with the predicted native udd conformation, the ligand of compound (4) (Fig. 2) adopts a characteristic tridentate ddd scorpionate configuration, suggesting complexation to a metal ion. The low resolution of the data di­cta­tes a conservative inter­pretation. An inspection of close contacts for the pyrazole groups revealed a symmetry-unique atomic peak, assigned as Na, apparently residing in a distorted o­cta­hedral or trigonal anti­prismatic environment that is completed by coordination by two neighboring carbonyl groups and a water molecule (Tables 2 and 3). It must be remembered that the usual coordination of Na+ is 6 (very seldom 8) (Mähler & Persson, 2011; Maria et al., 2009). The average Na—N bond length of 2.62 (2) Å is comparable with those reported previously for tris­pyrazolylborate Na complexes (Chisholm et al., 2006; Dias & Goh, 2004; Dias & Kim, 1996; Dias et al., 1996; Hu et al., 2009; Gardner et al., 2008; King et al., 2009; Reglinski et al., 1999) and tris­pyrazolyl­methane Na complexes (Reger et al. 2001, 2002; Maria et al., 2009). The H atoms of the carb­oxy­lic acid groups were assigned to each O atom having a longer C—O bond as free acids, except for O4, which is bound to Na as part of the carboxyl­ate anion.

The hydrogen-bonding donor assignments for the molecule of (4) appear to be reasonable, with each pointing either to a possible lone pair on a neighboring carb­oxy­lic acid –OH group or to a carbonyl group or to a solvent water molecule. A three-dimensional extended lattice (Fig. 2, left) is generated by the hydrogen-bonding inter­actions of the Na-coordinated aqua ligand O7 to neighboring carb­oxy­lic acid atom O5, and by the coordinated carb­oxy­lic acid groups of O2 and O4 that are coordinated to each other through hydrogen-bearing atom O1, and to O6 through O3. Carb­oxy­lic acid atom O3 is also coordinated to water molecule O8, uncoordinated to Na, which does not appear to extend the network. Note that the crystal structure corresponds to a dihydrate, whereas the analytical result (see Experimental) corresponds to a hemihydrate, this being due to vacuum drying of the sample.

Starting with the X-ray structure, we have optimized compound (4) at the B3LYP/6-311++G(d,p) level (Becke 1993; Ditchfield et al., 1971), and for this structure we have calculated its chemical shifts (with two Na+ atoms, one chelated by the N atoms and one on the CO2- group, i.e. CO2Na), using the GIAO method (Ditchfield, 1974) and transforming the absolute shieldings (σ, p.p.m.) into chemical shifts (δ, p.p.m.) by means of empirical equations (Blanco et al. 2007). The results (see Scheme 2) are reported graphically in Fig. 1. The agreement is good and the observed splittings explained. The further splitting of the carbonyl of the sodium carboxyl­ate (170.8 and 173.6 p.p.m.; Fig. 1) is probably due to solid-state effects, i.e. to different environments of the CO2- group in the crystal structure.

The reason why the saponification of triester (2) does not lead to tri­carb­oxy­lic acid (3) but instead yields (4) is due to the `scorpionate chelating effect', corresponding to the ddd conformation, which stabilizes only one sodium cation due to the tridentate property of scorpionates (Trofimenko, 1999). The compound reported in this paper is a new example of sodium chelation in the series of tris­pyrazolyl­methanes without an external counter-anion.

Conclusion top

Related literature top

For related literature, see: Becke (1993); Bigmore et al. (2005); Blanco et al. (2007); Chisholm et al. (2006); Claramunt et al. (1989, 1995, 2005); Declercq & Van Meerssche (1984); Dias & Goh (2004); Dias & Kim (1996); Dias, Jin, Kim & Lu (1996); Ditchfield (1974); Ditchfield et al. (1971); Foces-Foces, Echevarría, Jagerovic, Alkorta, Elguero, Langer, Klein, Minguet-Bonvehí & Limbach (2001); Frisch (2009); Gardner et al. (2008); Hariharan & Pople (1973); Hu et al. (2009); Infantes et al. (2003); Kalinowski et al. (1997); King et al. (2009); Mähler & Persson (2011); Maria et al. (2009); Ochando et al. (1997); Reger et al. (2001, 2002); Reglinski et al. (1999); Sheldrick (2008); Trofimenko (1999).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
Fig. 1. The CPMAS 13C NMR spectrum [for (4)?]. The values at the bottom are calculated values (see text). Underlined resonances are assigned to the sodium pyrazolate ring.

Fig. 2. (Left) A diagram showing the propagation of intermolecular ionic and hydrogen-bonding interactions [in (4)?]. (Right) A molecular diagram for (I), with the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. An associated hydrogen-bonded solvent water molecule (O8) has been omitted for clarity. H atoms are shown as small spheres of arbitrary radius (left) or omitted (right). [Symmetry codes: x - 1/2, -y + 1/2, -z + 1; (ii) -x + 1/2, -y, z - 1/2; (iii) x + 1/2, -y + 1/2, -z + 1; (iv) -x + 1/2, -y, z + 1/2; (v) -x + 1, -y - 1/2, -z + 3/2; (vi) -x + 1, y + 1/2, -z + 3/2; (vii) x + 1/2, -y - 1/2, -z + 1; (viii) -x + 1, y - 1/2, -z + 1.]
{1-[Bis(4-carboxy-3,5-dimethyl-1H-pyrazol-1-yl)methyl]-3,5-dimethyl-1H-pyrazole-4-carboxylato}sodium dihydrate top
Crystal data top
[Na(C19H21N6O6)]·2H2ODx = 1.285 Mg m3
Mr = 488.44Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, P212121Cell parameters from 839 reflections
a = 9.2589 (9) Åθ = 5.2–32.3°
b = 16.1630 (14) ŵ = 1.00 mm1
c = 16.8728 (17) ÅT = 200 K
V = 2525.0 (4) Å3Block, colourless
Z = 40.10 × 0.06 × 0.03 mm
F(000) = 1024
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1071 independent reflections
Radiation source: fine-focus sealed tube630 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.105
Detector resolution: 8.33 pixels mm-1θmax = 46.0°, θmin = 5.5°
ϕ and ω scansh = 67
Absorption correction: multi-scan
(APEX2; Bruker, 2007)
k = 915
Tmin = 0.906, Tmax = 0.974l = 1414
3877 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)] = 0.136Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.381H-atom parameters constrained
S = 1.45 w = 1/[σ2(Fo2) + (0.2P)2]
where P = (Fo2 + 2Fc2)/3
1071 reflections(Δ/σ)max = 0.002
301 parametersΔρmax = 1.48 e Å3
382 restraintsΔρmin = 0.36 e Å3
Crystal data top
[Na(C19H21N6O6)]·2H2OV = 2525.0 (4) Å3
Mr = 488.44Z = 4
Orthorhombic, P212121Cu Kα radiation
a = 9.2589 (9) ŵ = 1.00 mm1
b = 16.1630 (14) ÅT = 200 K
c = 16.8728 (17) Å0.10 × 0.06 × 0.03 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1071 independent reflections
Absorption correction: multi-scan
(APEX2; Bruker, 2007)
630 reflections with I > 2σ(I)
Tmin = 0.906, Tmax = 0.974Rint = 0.105
3877 measured reflectionsθmax = 46.0°
Refinement top
R[F2 > 2σ(F2)] = 0.136382 restraints
wR(F2) = 0.381H-atom parameters constrained
S = 1.45Δρmax = 1.48 e Å3
1071 reflectionsΔρmin = 0.36 e Å3
301 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.

The selected crystal was mounted using viscous oil onto a plastic mesh and cooled to the data collection temperature. Data were collected on a Bruker AXS APEXII Duo CCD diffractometer with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å ). Unit-cell parameters were obtained from 60 data frames, 0.3° ω, from three different sections of the Ewald sphere. The systematic absences in the diffraction data are uniquely consistent with P212121. The data set was treated with absorption corrections based on redundant multi-scan data (Bruker, 2007). The structure was solved using direct methods and refined with full-matrix least-squares procedures on F2.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.577 (3)0.0362 (15)0.7011 (15)0.050 (5)
H1A0.62950.03890.75280.061*
N10.636 (3)0.0893 (11)0.5694 (10)0.056 (5)
N20.639 (2)0.0999 (10)0.6490 (10)0.053 (5)
C20.722 (4)0.1648 (17)0.4535 (12)0.102 (12)
H2A0.68080.11730.42530.153*
H2B0.82650.16660.44450.153*
H2C0.67790.21590.43370.153*
C30.693 (3)0.1566 (14)0.5391 (12)0.063 (7)
C40.726 (3)0.2116 (13)0.5999 (11)0.060 (7)
C50.684 (3)0.1782 (12)0.6727 (11)0.051 (6)
C60.678 (3)0.2036 (14)0.7556 (11)0.066 (9)
H6A0.71790.25950.76090.099*
H6B0.73470.16510.78790.099*
H6C0.57740.20340.77370.099*
C70.785 (3)0.2976 (14)0.5917 (13)0.054 (7)
O10.829 (2)0.3327 (10)0.6566 (9)0.070 (6)
H1B0.85430.38170.64690.105*
O20.796 (2)0.3324 (10)0.5255 (9)0.060 (6)
N30.342 (2)0.0891 (12)0.6634 (11)0.059 (5)
N40.425 (2)0.0477 (12)0.7171 (11)0.048 (5)
C80.090 (2)0.1293 (17)0.6554 (15)0.073 (9)
H8A0.12320.15000.60380.110*
H8B0.05220.17530.68690.110*
H8C0.01440.08790.64740.110*
C90.213 (3)0.0910 (16)0.6977 (13)0.058 (6)
C100.215 (2)0.0488 (14)0.7693 (13)0.053 (6)
C110.353 (2)0.0173 (15)0.7826 (12)0.048 (6)
C120.426 (3)0.0365 (17)0.8398 (12)0.070 (9)
H12A0.35750.05300.88120.106*
H12B0.50700.00670.86390.106*
H12C0.46220.08590.81270.106*
C130.100 (3)0.0428 (13)0.8315 (14)0.050 (6)
O30.005 (2)0.1019 (10)0.8317 (9)0.062 (6)
O40.0892 (19)0.0189 (10)0.8773 (9)0.056 (5)
N50.507 (2)0.0754 (11)0.6118 (11)0.051 (5)
N60.603 (2)0.0471 (10)0.6667 (10)0.042 (5)
C140.471 (3)0.2006 (14)0.5355 (15)0.074 (9)
H14A0.39670.16650.51010.111*
H14B0.42520.24750.56240.111*
H14C0.53820.22120.49530.111*
C150.551 (3)0.1502 (14)0.5940 (12)0.049 (6)
C160.673 (3)0.1704 (12)0.6379 (14)0.055 (6)
C170.710 (3)0.1039 (13)0.6867 (13)0.053 (6)
C180.827 (2)0.0830 (14)0.7409 (13)0.051 (8)
H18A0.89240.13050.74590.076*
H18B0.78720.06920.79300.076*
H18C0.88060.03550.72010.076*
C190.756 (3)0.2495 (14)0.6387 (19)0.072 (8)
O50.696 (2)0.3115 (10)0.6030 (9)0.062 (6)
O60.881 (2)0.2529 (10)0.6711 (10)0.068 (6)
H6D0.91320.30130.66760.102*
Na10.3874 (13)0.0380 (6)0.5198 (5)0.064 (3)
O70.189 (2)0.0633 (11)0.5142 (11)0.097 (5)
H710.15290.08600.56290.117*
H720.12830.08850.47500.117*
O80.2580 (19)0.0549 (12)0.8863 (10)0.097 (5)
H810.30070.05960.93780.117*
H820.15820.06700.89610.117*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.053 (11)0.054 (8)0.045 (11)0.001 (9)0.004 (10)0.002 (8)
N10.076 (10)0.049 (10)0.043 (8)0.004 (10)0.002 (9)0.005 (8)
N20.069 (12)0.050 (8)0.040 (8)0.002 (10)0.001 (9)0.008 (8)
C20.17 (3)0.08 (2)0.050 (11)0.01 (2)0.06 (2)0.005 (13)
C30.090 (16)0.057 (12)0.041 (9)0.010 (12)0.029 (14)0.008 (9)
C40.067 (18)0.066 (12)0.047 (10)0.022 (12)0.005 (14)0.003 (9)
C50.070 (18)0.047 (11)0.036 (9)0.005 (12)0.004 (14)0.002 (9)
C60.10 (3)0.052 (16)0.041 (10)0.01 (2)0.011 (17)0.004 (11)
C70.041 (18)0.070 (13)0.052 (12)0.022 (13)0.017 (15)0.014 (10)
O10.109 (18)0.055 (11)0.046 (10)0.000 (11)0.003 (12)0.014 (8)
O20.065 (14)0.064 (11)0.053 (10)0.028 (11)0.015 (11)0.011 (8)
N30.066 (12)0.059 (11)0.053 (9)0.011 (10)0.000 (8)0.012 (7)
N40.052 (10)0.043 (12)0.049 (9)0.007 (9)0.001 (9)0.010 (8)
C80.066 (16)0.063 (19)0.09 (2)0.002 (18)0.014 (16)0.034 (16)
C90.046 (13)0.068 (16)0.060 (12)0.005 (13)0.012 (9)0.011 (10)
C100.040 (12)0.049 (14)0.070 (14)0.006 (12)0.002 (9)0.010 (11)
C110.044 (13)0.060 (16)0.039 (13)0.002 (13)0.005 (10)0.000 (10)
C120.09 (2)0.11 (2)0.018 (15)0.035 (18)0.003 (14)0.005 (12)
C130.051 (15)0.042 (13)0.058 (15)0.014 (12)0.006 (12)0.020 (11)
O30.064 (15)0.054 (12)0.069 (13)0.000 (9)0.022 (12)0.020 (10)
O40.057 (14)0.059 (11)0.052 (12)0.010 (10)0.006 (9)0.004 (8)
N50.058 (12)0.055 (8)0.039 (12)0.002 (8)0.005 (9)0.004 (7)
N60.036 (13)0.049 (7)0.041 (12)0.003 (8)0.004 (8)0.005 (7)
C140.07 (2)0.059 (16)0.10 (2)0.025 (18)0.024 (16)0.004 (13)
C150.072 (17)0.059 (10)0.017 (13)0.002 (11)0.004 (10)0.004 (9)
C160.067 (17)0.052 (10)0.045 (15)0.007 (10)0.011 (11)0.003 (10)
C170.072 (17)0.050 (11)0.037 (15)0.004 (11)0.017 (11)0.013 (10)
C180.06 (2)0.049 (16)0.047 (18)0.025 (15)0.010 (13)0.014 (13)
C190.07 (2)0.054 (12)0.09 (2)0.006 (11)0.007 (15)0.003 (14)
O50.071 (15)0.063 (10)0.052 (12)0.013 (11)0.014 (11)0.009 (9)
O60.079 (16)0.052 (11)0.073 (14)0.021 (10)0.010 (12)0.008 (10)
Na10.082 (9)0.054 (6)0.055 (6)0.006 (6)0.016 (6)0.002 (5)
O70.059 (10)0.089 (10)0.143 (13)0.001 (8)0.037 (10)0.009 (10)
O80.059 (10)0.089 (10)0.143 (13)0.001 (8)0.037 (10)0.009 (10)
Geometric parameters (Å, º) top
C1—N41.44 (3)C10—C131.50 (2)
C1—N21.47 (3)C11—C121.46 (2)
C1—N61.48 (3)C12—H12A0.9800
C1—H1A1.0000C12—H12B0.9800
N1—C31.31 (2)C12—H12C0.9800
N1—N21.355 (17)C13—O41.266 (19)
N1—Na12.59 (3)C13—O31.297 (19)
N2—C51.391 (19)O4—Na1ii2.434 (18)
C2—C31.48 (2)N5—C151.31 (2)
C2—H2A0.9800N5—N61.364 (17)
C2—H2B0.9800N5—Na12.644 (19)
C2—H2C0.9800N6—C171.39 (2)
C3—C41.39 (2)C14—C151.48 (2)
C4—C51.40 (2)C14—H14A0.9800
C4—C71.50 (2)C14—H14B0.9800
C5—C61.46 (2)C14—H14C0.9800
C6—H6A0.9800C15—C161.39 (2)
C6—H6B0.9800C16—C171.40 (2)
C6—H6C0.9800C16—C191.49 (2)
C7—O21.254 (19)C17—C181.46 (2)
C7—O11.298 (19)C18—H18A0.9800
O1—H1B0.8400C18—H18B0.9800
O2—Na1i2.385 (18)C18—H18C0.9800
N3—C91.33 (2)C19—O51.29 (2)
N3—N41.363 (17)C19—O61.28 (2)
N3—Na12.59 (2)O6—H6D0.8400
N4—C111.381 (19)Na1—O2iii2.385 (18)
C8—C91.48 (2)Na1—O4iv2.434 (18)
C8—H8A0.9800Na1—O72.46 (2)
C8—H8B0.9800O7—H710.9590
C8—H8C0.9800O7—H720.9579
C9—C101.39 (2)O8—H810.9584
C10—C111.39 (2)O8—H820.9584
N4—C1—N2114 (2)C11—C12—H12B109.5
N4—C1—N6110 (2)H12A—C12—H12B109.5
N2—C1—N6109.9 (19)C11—C12—H12C109.5
N4—C1—H1A107.6H12A—C12—H12C109.5
N2—C1—H1A107.6H12B—C12—H12C109.5
N6—C1—H1A107.6O4—C13—O3122 (2)
C3—N1—N2105.9 (16)O4—C13—C10122.2 (19)
C3—N1—Na1119.8 (19)O3—C13—C10116.0 (18)
N2—N1—Na1112.2 (17)C13—O4—Na1ii134.1 (16)
N1—N2—C5114.0 (15)C15—N5—N6105.2 (16)
N1—N2—C1119.8 (18)C15—N5—Na1129.4 (14)
C5—N2—C1125.6 (18)N6—N5—Na1116.0 (13)
C3—C2—H2A109.5N5—N6—C17114.0 (15)
C3—C2—H2B109.5N5—N6—C1117.7 (19)
H2A—C2—H2B109.5C17—N6—C1128.2 (19)
C3—C2—H2C109.5C15—C14—H14A109.5
H2A—C2—H2C109.5C15—C14—H14B109.5
H2B—C2—H2C109.5H14A—C14—H14B109.5
N1—C3—C4109.4 (17)C15—C14—H14C109.5
N1—C3—C2122 (2)H14A—C14—H14C109.5
C4—C3—C2129 (2)H14B—C14—H14C109.5
C3—C4—C5109.8 (17)N5—C15—C16110.3 (17)
C3—C4—C7127.2 (16)N5—C15—C14120 (2)
C5—C4—C7122.8 (16)C16—C15—C14129 (2)
N2—C5—C4100.5 (16)C15—C16—C17109.4 (17)
N2—C5—C6121.4 (18)C15—C16—C19128.8 (17)
C4—C5—C6138.1 (19)C17—C16—C19121.8 (17)
C5—C6—H6A109.5N6—C17—C16101.1 (16)
C5—C6—H6B109.5N6—C17—C18121.9 (18)
H6A—C6—H6B109.5C16—C17—C18137 (2)
C5—C6—H6C109.5C17—C18—H18A109.5
H6A—C6—H6C109.5C17—C18—H18B109.5
H6B—C6—H6C109.5H18A—C18—H18B109.5
O2—C7—O1122 (2)C17—C18—H18C109.5
O2—C7—C4121.7 (17)H18A—C18—H18C109.5
O1—C7—C4116.2 (17)H18B—C18—H18C109.5
C7—O1—H1B109.5O5—C19—O6124 (2)
C7—O2—Na1i134.9 (14)O5—C19—C16115.8 (19)
C9—N3—N4103.2 (16)O6—C19—C16120.5 (18)
C9—N3—Na1124.0 (17)C19—O6—H6D109.5
N4—N3—Na1111.9 (13)O2iii—Na1—O4iv80.0 (6)
N3—N4—C11115.7 (17)O2iii—Na1—O7107.8 (8)
N3—N4—C1119.2 (19)O4iv—Na1—O786.8 (6)
C11—N4—C1125.1 (19)O2iii—Na1—N387.8 (7)
C9—C8—H8A109.5O4iv—Na1—N3167.9 (7)
C9—C8—H8B109.5O7—Na1—N397.3 (7)
H8A—C8—H8B109.5O2iii—Na1—N198.0 (7)
C9—C8—H8C109.5O4iv—Na1—N1106.3 (7)
H8A—C8—H8C109.5O7—Na1—N1152.8 (8)
H8B—C8—H8C109.5N3—Na1—N174.9 (7)
N3—C9—C10110.8 (18)O2iii—Na1—N5161.0 (7)
N3—C9—C8119.5 (19)O4iv—Na1—N5117.1 (7)
C10—C9—C8130 (2)O7—Na1—N582.7 (7)
C9—C10—C11109.4 (18)N3—Na1—N574.9 (7)
C9—C10—C13129.0 (18)N1—Na1—N570.2 (7)
C11—C10—C13121.2 (17)Na1—O7—H71118.8
N4—C11—C10100.6 (16)Na1—O7—H72138.2
N4—C11—C12121.1 (19)H71—O7—H72103.0
C10—C11—C12138 (2)H81—O8—H82103.0
C11—C12—H12A109.5
Na1—N1—N2—C145 (3)C11—C10—C13—O435 (4)
Na1—N1—N2—C5126 (2)C9—C10—C13—O323 (4)
Na1—N3—N4—C147 (2)C11—C10—C13—O3150 (2)
Na1—N3—N4—C11131.1 (18)O3—C13—O4—Na1ii70 (3)
Na1—N5—N6—C133 (2)C10—C13—O4—Na1ii116 (2)
Na1—N5—N6—C17151.0 (17)C15—N5—N6—C171 (3)
N2—C1—N4—N326 (3)C15—N5—N6—C1178 (2)
N2—C1—N6—N585 (3)N4—C1—N6—C17135 (3)
N4—C1—N2—N189 (3)N2—C1—N6—C1799 (3)
N4—C1—N6—N541 (3)N6—N5—C15—C161 (3)
N6—C1—N2—N135 (3)Na1—N5—C15—C16145.2 (18)
N6—C1—N4—N398 (3)N6—N5—C15—C14180 (2)
C3—N1—N2—C56 (4)Na1—N5—C15—C1436 (4)
C3—N1—N2—C1178 (2)N5—C15—C16—C170 (3)
N4—C1—N2—C581 (3)C14—C15—C16—C17179 (3)
N6—C1—N2—C5155 (2)N5—C15—C16—C19178 (3)
N2—N1—C3—C43 (4)C14—C15—C16—C191 (5)
Na1—N1—C3—C4126 (2)N5—N6—C17—C161 (3)
N2—N1—C3—C2174 (3)C1—N6—C17—C16177 (2)
Na1—N1—C3—C258 (4)N5—N6—C17—C18176 (2)
N1—C3—C4—C52 (4)C1—N6—C17—C188 (4)
C2—C3—C4—C5178 (3)C15—C16—C17—N60 (3)
N1—C3—C4—C7176 (3)C19—C16—C17—N6179 (3)
C2—C3—C4—C78 (6)C15—C16—C17—C18174 (3)
N1—N2—C5—C47 (3)C19—C16—C17—C187 (5)
C1—N2—C5—C4178 (3)C15—C16—C19—O511 (5)
N1—N2—C5—C6173 (3)C17—C16—C19—O5167 (3)
C1—N2—C5—C62 (4)C15—C16—C19—O6167 (3)
C3—C4—C5—N25 (3)C17—C16—C19—O615 (5)
C7—C4—C5—N2180 (3)C9—N3—Na1—O2iii77.5 (19)
C3—C4—C5—C6175 (4)N4—N3—Na1—O2iii157.8 (15)
C7—C4—C5—C60 (6)C9—N3—Na1—O4iv79 (5)
C3—C4—C7—O28 (5)N4—N3—Na1—O4iv156 (4)
C5—C4—C7—O2166 (3)C9—N3—Na1—O730 (2)
C3—C4—C7—O1170 (3)N4—N3—Na1—O794.5 (15)
C5—C4—C7—O117 (5)C9—N3—Na1—N1176.4 (19)
O1—C7—O2—Na1i0 (5)N4—N3—Na1—N159.0 (14)
C4—C7—O2—Na1i177.2 (19)C9—N3—Na1—N5111 (2)
C9—N3—N4—C114 (3)N4—N3—Na1—N514.1 (14)
C9—N3—N4—C1178 (2)C3—N1—Na1—O2iii25.0 (18)
N2—C1—N4—C11156 (2)N2—N1—Na1—O2iii100.1 (15)
N6—C1—N4—C1180 (3)C3—N1—Na1—O4iv56.9 (19)
N4—N3—C9—C102 (3)N2—N1—Na1—O4iv178.0 (13)
Na1—N3—C9—C10126.0 (19)C3—N1—Na1—O7173.2 (17)
N4—N3—C9—C8178 (2)N2—N1—Na1—O762 (2)
Na1—N3—C9—C850 (3)C3—N1—Na1—N3110.6 (19)
N3—C9—C10—C110 (3)N2—N1—Na1—N314.6 (14)
C8—C9—C10—C11175 (3)C3—N1—Na1—N5170.4 (19)
N3—C9—C10—C13173 (3)N2—N1—Na1—N564.5 (14)
C8—C9—C10—C1312 (5)C15—N5—Na1—O2iii169 (3)
N3—N4—C11—C104 (3)N6—N5—Na1—O2iii28 (4)
C1—N4—C11—C10178 (2)C15—N5—Na1—O4iv16 (3)
N3—N4—C11—C12173 (2)N6—N5—Na1—O4iv124.7 (14)
C1—N4—C11—C125 (4)C15—N5—Na1—O766 (2)
C9—C10—C11—N43 (3)N6—N5—Na1—O7152.7 (15)
C13—C10—C11—N4171 (2)C15—N5—Na1—N3166 (2)
C9—C10—C11—C12174 (3)N6—N5—Na1—N353.0 (14)
C13—C10—C11—C1213 (5)C15—N5—Na1—N1115 (2)
C9—C10—C13—O4152 (3)N6—N5—Na1—N126.0 (14)
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x+1/2, y, z+1/2; (iii) x1/2, y+1/2, z+1; (iv) x+1/2, y, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O4v0.841.742.58 (2)177
O6—H6D···O3vi0.841.742.57 (2)174
O7—H72···O5vii0.962.182.83 (2)124
O8—H82···O30.961.952.71 (3)135
Symmetry codes: (v) x+1, y+1/2, z+3/2; (vi) x+1, y1/2, z+3/2; (vii) x1/2, y1/2, z+1.

Experimental details

Crystal data
Chemical formula[Na(C19H21N6O6)]·2H2O
Mr488.44
Crystal system, space groupOrthorhombic, P212121
Temperature (K)200
a, b, c (Å)9.2589 (9), 16.1630 (14), 16.8728 (17)
V3)2525.0 (4)
Z4
Radiation typeCu Kα
µ (mm1)1.00
Crystal size (mm)0.10 × 0.06 × 0.03
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(APEX2; Bruker, 2007)
Tmin, Tmax0.906, 0.974
No. of measured, independent and
observed [I > 2σ(I)] reflections
3877, 1071, 630
Rint0.105
θmax (°)46.0
(sin θ/λ)max1)0.466
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.136, 0.381, 1.45
No. of reflections1071
No. of parameters301
No. of restraints382
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.48, 0.36

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
N1—Na12.59 (3)N5—Na12.644 (19)
O2—Na1i2.385 (18)Na1—O2iii2.385 (18)
N3—Na12.59 (2)Na1—O4iv2.434 (18)
O4—Na1ii2.434 (18)Na1—O72.46 (2)
C3—N1—Na1119.8 (19)O7—Na1—N397.3 (7)
N2—N1—Na1112.2 (17)O2iii—Na1—N198.0 (7)
C7—O2—Na1i134.9 (14)O4iv—Na1—N1106.3 (7)
C9—N3—Na1124.0 (17)O7—Na1—N1152.8 (8)
N4—N3—Na1111.9 (13)N3—Na1—N174.9 (7)
C13—O4—Na1ii134.1 (16)O2iii—Na1—N5161.0 (7)
C15—N5—Na1129.4 (14)O4iv—Na1—N5117.1 (7)
N6—N5—Na1116.0 (13)O7—Na1—N582.7 (7)
O2iii—Na1—O4iv80.0 (6)N3—Na1—N574.9 (7)
O2iii—Na1—O7107.8 (8)N1—Na1—N570.2 (7)
O4iv—Na1—O786.8 (6)Na1—O7—H71118.8
O2iii—Na1—N387.8 (7)Na1—O7—H72138.2
O4iv—Na1—N3167.9 (7)
Na1—N1—N2—C145 (3)N2—C1—N4—N326 (3)
Na1—N1—N2—C5126 (2)N2—C1—N6—N585 (3)
Na1—N3—N4—C147 (2)N4—C1—N2—N189 (3)
Na1—N3—N4—C11131.1 (18)N4—C1—N6—N541 (3)
Na1—N5—N6—C133 (2)N6—C1—N2—N135 (3)
Na1—N5—N6—C17151.0 (17)N6—C1—N4—N398 (3)
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x+1/2, y, z+1/2; (iii) x1/2, y+1/2, z+1; (iv) x+1/2, y, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O4v0.841.742.58 (2)177.1
O6—H6D···O3vi0.841.742.57 (2)173.5
O7—H72···O5vii0.962.182.83 (2)124.3
O8—H82···O30.961.952.71 (3)135.3
Symmetry codes: (v) x+1, y+1/2, z+3/2; (vi) x+1, y1/2, z+3/2; (vii) x1/2, y1/2, z+1.
 

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