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The crystal structures of sodium 4-({4-[N,N-bis(2-hydroxy­ethyl)­amino]­phenyl}diazenyl)­benzoate 3.5-hydrate, Na+·C17H18N3O4-·3.5H2O, (I), and potassium 4-({4-[N,N-bis(2-hydroxy­ethyl)­amino]­phenyl}diazenyl)­benzoate dihydrate, K+·C17H18N3O4-·2H2O, (II), are described. The results indicate an octahedral coordination around sodium in (I) and a trigonal prismatic coordination around potassium in (II). In both cases, coordination around the metal cation is achieved through O atoms of the water mol­ecules and hydroxy groups of the chromophore. The organic conjugated part of the chromophore is approximately planar in (I), while a dihedral angle of 30.7 (2)° between the planes of the phenyl rings is observed in (II).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101004231/na1508sup1.cif
Contains datablocks global, II, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101004231/na1508Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101004231/na1508IIsup3.hkl
Contains datablock II

CCDC references: 153701; 153702

Comment top

Organic π-electron conjugated systems containing electron donor–acceptor groups (chromophores) have received renewed interest in recent times. Owing to their large hyperpolarizabilities, they may be used to obtain materials able to display second order non-linear optical (NLO) properties (Dalton et al., 1999).

A large number of chemical variables may be considered in the synthesis of push–pull chromophores, such as the length of the conjugated system, its chemical nature (i.e. aromatic or polyenic), the presence of heteroatoms or heterocycles, and the strength of the donor–acceptor groups. All these variables affect to a various extent the electronic properties of chromophores and, therefore, also their intrinsic NLO activity (i.e. β values) (Marder et al., 1993; Kanis et al., 1994; Morley, 1995).

Among chemical variables, the presence of metallic centres in the chromophores may also be considered (Whittall et al., 1998). In this respect, a first possibility is to introduce covalently bonded metallic centres along the conjugated bridge, allowing conjugation through a possible dπ–pπ contribution to the covalent bond between the metallic centre and the organic pπ-conjugated system. Some interesting results have also been obtained with organometallic moieties covalently bonded to a conjugated organic system, acting generally as electron donor (Houlton et al., 1993; Coe et al., 1999) or, more rarely, as acceptor groups (Bandy et al., 1992; Lambert et al., 1999). Another possibility not yet considered is to use metallic centres ionically bonded to a negatively charged organic conjugated system, thus working as electron-withdrawing groups through the ionic bond. The rather high polarizability of organic conjugated systems and the strength of the ionic bond could make this approach interesting, taking into account also the possibility of changing the metallic cation, thus modulating the strength of the ionic interaction and varying the coordination geometry. On these grounds, we have undertaken a systematic study of a series of metal carboxylates containing the aminophenylazo chromophore group, whose good NLO activity is well known (Xie et al., 1993). The structures of sodium 4-({4-[N,N-bis(2-hydroxyethyl)amino]phenyl}diazenyl)benzoate 3.5-hydrate, (I), and potassium 4-({4-[N,N-bis(2-hydroxyethyl)amino]phenyl}diazenyl)benzoate dihydrate, (II), are reported here.

Both compounds crystallize in the hydrated form. The water content (thermogravimetry) indicates the presence of 3.5 water molecules for the unit formula in (I) and two in (II). The asymmetric unit of (II) contains two independent molecules. The coordination around each Na+ cation is substantially octahedral and is achieved through O atoms of the water molecules and hydroxyl groups. A bridging water molecule is coordinated to both Na+ cations of the two independent molecules, whose octahedra, therefore, share a vertex. The structure of the organic conjugated part is almost identical in the two independent molecules, showing, in particular, a planar conformation. Coordination around the K+ cations in (II) is trigonal prismatic, which is a rarer finding among six-coordinated atoms, and, as for (I), is achieved through O atoms of the water molecules and hydroxy groups. The conformation of the organic conjugated part is not planar in (II), a dihedral angle of 30.7 (2)° being observed between the planes of the phenyl rings, a result of a torsion around the N3—C11 bond. The geometry around the amino N atom is planar (sp2 hybridization) in both structures, thus favouring electron donation toward the adjacent phenyl ring. Analysis of the bond distances in the phenyl rings shows some distorsions that, in the case of the first phenyl ring (C5–C10), which is close to the amino donor group, point toward a quinoid pattern, and are comparable with similar distortions found in the crystal structure of some NLO active compounds (Centore & Garzillo, 1997; Centore et al., 1997).

The crystal packing is of the layered type (Figs. 3 and 4), with the inorganic part of the structure lying on the (001) planes and the organic part placed between them. Carboxylate anions (COO-) are located just outside the coordination spheres of the Na+ and K+ cations, giving an ionic bond; they are also involved, as acceptors, in hydrogen bonding with the water molecules coordinated to metal cations. The inorganic part is arranged in rows running along b (Fig. 5). In the case of (I), the rows are formed by NaO6 octahedra sharing alternatively one vertex and one edge (sharing of edges being across inversion centres) and in (II) by screw related edge-sharing KO6 trigonal prisms. The rows are held together along a by a complex hydrogen-bonding pattern between carboxylate and hydroxy groups of the molecules and water molecules coordinated to the metal ions.

The lateral packing of organic moieties is dominated, in both structures, by face-to-edge interactions between phenyl rings (T contacts), with molecular dipoles arranged in an antiparallel manner. For (I), this is simply a consequence of the centrosymmetric nature of the space group (actually the orientation of dipoles is antiparallel in the two molecules of the asymmetric unit), for (II), it comes from the dipole of the independent molecule being perpendicular to the direction of the screw axes.

Related literature top

For related literature, see: Bandy et al. (1992); Centore & Garzillo (1997); Centore, Panunzi & Tuzi (1997); Coe et al. (1999); Dalton et al. (1999); Houlton et al. (1993); Kanis et al. (1994); Lambert et al. (1999); Marder et al. (1993); Morley (1995); Whittall et al. (1998); Xie et al. (1993).

Experimental top

The synthesis of 4-({4-[N,N-bis(2-hydroxyethyl)amino]phenyl}diazenyl)benzoic acid was performed according to the well known diazotization-coupling procedure starting from N,N-bis(2-hydroxyethyl)aniline and 4-aminobenzoic acid. Carboxylate salts were prepared by reaction of the acid with the corresponding alkali metal hydroxides. As an example, for (II), 0.370 g (1.123 mmol) of the acid were heated in 20 ml of 95% ethanol. To the boiling suspension, a water solution of potassium hydroxide (0.5 g in 10 ml) was added up to alkaline pH (13–14). The solution was boiled until the total volume reduced to about 10 ml. On cooling, orange crystals of the potassium salt were obtained. Yield 0.383 g (0.949 mmol) (84.5% for the dihydrate salt). Analysis calculated for (I) (C17H18N3NaO4·3.5H2O): C 58.12, H 5.16, N 11.96, H2O 15.2%; found: C 57.81, H 5.17, N 11.65, H2O 15.7%. λmax (nm), ε (104 M-1 dm3): 278 (1), 461 (3) in water; 271 (1), 418 (3) in ethanol. Analysis calculated for (II) (C17H18KN3O4·2H2O): C 55.57, H 4.94, N 11.44, H2O 8.9%; found: C 55.42, H 4.86, N 11.57, H2O 9.05%. λmax (nm), ε (104 M-1 dm3): 278 (1), 458 (3) in water; 271 (1), 418 (3) in ethanol. Crystals of (I) and (II) suitable for single-crystal X-ray diffraction analysis were obtained by slow evaporation of methanol/water solutions.

Refinement top

All H atoms were stereochemically positioned, but those of the water molecules and the hydroxy groups were located by difference Fourier map. For all H atoms, refinement was by the riding model, with Uiso equal to Ueq of the carrier atom.

Computing details top

For both compounds, data collection: MACH3 Software (Nonius, 1996); cell refinement: CELLDIM (Nonius, 1996); data reduction: XCAD4-PC (Harms, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1999) and PLATON92 (Spek, 1992).

Figures top
[Figure 1] Fig. 1. Molecular drawing of the crystallographically independent unit of (I) shown with 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. Molecular drawing of (II) shown with 50% probability displacement ellipsoids.
[Figure 3] Fig. 3. The crystal packing of (I) (H atoms have been omitted for clarity).
[Figure 4] Fig. 4. The crystal packing of (II) (H atoms have been omitted for clarity).
[Figure 5] Fig. 5. Rows of coordination polyhedra for (a) (I) and (b) (II). Only metal and O atoms are shown.
(I) Sodium 4-({4-[N,N-bis(2-hydroxyethyl)amino]phenyl}diazenyl)benzoate 3.5-hydrate top
Crystal data top
Na+·C17H18N3O4·3.5H2OZ = 4
Mr = 414.39F(000) = 876
Triclinic, P1Dx = 1.372 Mg m3
a = 9.023 (3) ÅMo Kα radiation, λ = 0.71069 Å
b = 11.818 (3) ÅCell parameters from 24 reflections
c = 19.400 (5) Åθ = 7.1–9.9°
α = 99.31 (4)°µ = 0.13 mm1
β = 99.41 (4)°T = 293 K
γ = 93.36 (2)°Plate, orange
V = 2006.3 (10) Å30.6 × 0.4 × 0.1 mm
Data collection top
Nonius MACH3
diffractometer
Rint = 0.043
Radiation source: fine-focus sealed tubeθmax = 24.9°, θmin = 1.1°
Graphite monochromatorh = 1010
ω/θ scansk = 1413
7259 measured reflectionsl = 023
7030 independent reflections2 standard reflections every 120 min
4387 reflections with I > 2σ(I) intensity decay: 6%
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)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.209H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.1333P)2]
where P = (Fo2 + 2Fc2)/3
7030 reflections(Δ/σ)max = 0.008
514 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.54 e Å3
Crystal data top
Na+·C17H18N3O4·3.5H2Oγ = 93.36 (2)°
Mr = 414.39V = 2006.3 (10) Å3
Triclinic, P1Z = 4
a = 9.023 (3) ÅMo Kα radiation
b = 11.818 (3) ŵ = 0.13 mm1
c = 19.400 (5) ÅT = 293 K
α = 99.31 (4)°0.6 × 0.4 × 0.1 mm
β = 99.41 (4)°
Data collection top
Nonius MACH3
diffractometer
Rint = 0.043
7259 measured reflections2 standard reflections every 120 min
7030 independent reflections intensity decay: 6%
4387 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0690 restraints
wR(F2) = 0.209H-atom parameters constrained
S = 1.00Δρmax = 0.38 e Å3
7030 reflectionsΔρmin = 0.54 e Å3
514 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. Hydrogen atoms of water molecules and hydroxy groups were located by difference Fourier synthesis and refined by the riding model, with Uiso equal to Ueq of the carrier atom.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Na10.31425 (15)0.93508 (12)0.00863 (7)0.0399 (4)
Na20.31211 (15)0.54319 (12)0.02193 (7)0.0414 (4)
OW0.4395 (3)0.7413 (2)0.00645 (14)0.0462 (7)
H1WW0.49670.75000.03950.046*
H2WW0.46030.74390.05020.046*
O1WA0.0862 (3)0.8443 (2)0.06666 (14)0.0484 (7)
HA110.08270.87490.10650.048*
HA210.10150.77440.06780.048*
O2WA0.5508 (3)1.0210 (2)0.08154 (12)0.0392 (6)
HA120.58240.98250.12160.039*
HA220.51971.07810.10240.039*
O3WA0.2089 (3)1.1190 (3)0.03208 (17)0.0684 (9)
HA130.26981.16440.06900.068*
HA230.12121.12950.03090.068*
O1WB0.4968 (3)0.5291 (2)0.08580 (13)0.0420 (6)
HB110.47790.48250.12220.042*
HB210.48470.59850.10890.042*
O2WB0.1273 (3)0.6269 (2)0.04455 (14)0.0503 (7)
HB120.13680.58450.08340.050*
HB220.16200.70320.06450.050*
O3WB0.1867 (4)0.3617 (4)0.0247 (3)0.128 (2)
HB130.16830.38380.06590.128*
HB230.18000.29520.00900.128*
O1A0.0890 (3)1.0637 (3)0.19002 (14)0.0544 (7)
HO1A0.16981.02560.17480.054*
O2A0.2572 (3)0.8485 (2)0.10858 (12)0.0417 (6)
HO2A0.34790.82030.13070.042*
O3A0.5448 (3)0.7676 (2)0.86538 (13)0.0430 (6)
O4A0.5983 (3)0.5956 (2)0.81752 (14)0.0482 (7)
N1A0.2211 (3)1.0501 (3)0.27302 (15)0.0359 (7)
N2A0.3314 (4)0.8893 (3)0.53123 (16)0.0444 (8)
N3A0.4020 (4)0.8026 (3)0.53558 (16)0.0430 (8)
C1A0.0324 (4)1.1233 (3)0.2591 (2)0.0424 (9)
H1A10.05581.07700.29350.042*
H1A20.07991.19470.26730.042*
C2A0.1358 (4)1.1492 (3)0.26837 (19)0.0363 (8)
H2A10.15841.18340.22870.036*
H2A20.16891.20570.31120.036*
C3A0.1842 (4)0.8988 (3)0.16505 (19)0.0398 (9)
H3A10.16430.84160.19370.040*
H3A20.08850.92400.14530.040*
C4A0.2816 (4)1.0001 (3)0.21100 (18)0.0363 (8)
H4A10.38040.97560.22670.036*
H4A20.29461.05910.18250.036*
C5A0.2482 (4)1.0072 (3)0.33512 (18)0.0345 (8)
C6A0.1954 (4)1.0587 (3)0.39622 (19)0.0418 (9)
H6A0.13931.12200.39430.042*
C7A0.2255 (5)1.0169 (3)0.4584 (2)0.0445 (9)
H7A0.18941.05290.49780.045*
C8A0.3079 (4)0.9229 (3)0.46448 (19)0.0384 (8)
C9A0.3612 (4)0.8715 (3)0.4044 (2)0.0432 (9)
H9A0.41810.80870.40690.043*
C10A0.3313 (4)0.9118 (3)0.34198 (19)0.0409 (9)
H10A0.36720.87490.30270.041*
C11A0.4287 (4)0.7757 (3)0.60524 (18)0.0359 (8)
C12A0.3822 (4)0.8405 (3)0.66379 (19)0.0404 (9)
H12A0.32610.90280.65790.040*
C13A0.4197 (4)0.8117 (3)0.72976 (19)0.0355 (8)
H13A0.38840.85520.76830.035*
C14A0.5037 (4)0.7186 (3)0.74023 (18)0.0322 (8)
C15A0.5438 (4)0.6524 (3)0.68086 (19)0.0387 (8)
H15A0.59560.58770.68600.039*
C16A0.5073 (5)0.6820 (3)0.6147 (2)0.0447 (9)
H16A0.53640.63760.57580.045*
C17A0.5521 (4)0.6923 (3)0.81244 (18)0.0318 (8)
O1B0.1504 (3)0.4932 (2)0.15853 (14)0.0455 (7)
HO1B0.23210.54170.16340.045*
O2B0.1301 (3)0.6041 (2)0.11419 (13)0.0436 (6)
HO2B0.03380.57970.13170.044*
O3B0.4896 (3)0.7565 (2)0.84210 (15)0.0514 (7)
O4B0.3192 (4)0.9054 (3)0.81746 (17)0.0693 (10)
N1B0.0430 (3)0.4580 (3)0.27054 (15)0.0371 (7)
N2B0.2023 (4)0.6048 (3)0.52141 (17)0.0486 (8)
N3B0.1385 (4)0.6920 (3)0.53646 (17)0.0476 (8)
C1B0.1853 (4)0.4065 (3)0.2211 (2)0.0422 (9)
H1B10.24680.43680.25860.042*
H1B20.24240.34070.21120.042*
C2B0.0415 (4)0.3692 (3)0.2451 (2)0.0418 (9)
H2B10.02260.34540.20580.042*
H2B20.06680.30280.28280.042*
C3B0.1762 (5)0.6198 (3)0.17862 (19)0.0456 (10)
H3B10.27410.66330.16780.046*
H3B20.10530.66490.20310.046*
C4B0.1862 (4)0.5087 (3)0.22749 (19)0.0397 (9)
H4B10.25620.52270.25880.040*
H4B20.22730.45350.19920.040*
C5B0.0122 (4)0.4935 (3)0.33279 (19)0.0377 (8)
C6B0.1438 (4)0.4389 (3)0.3777 (2)0.0441 (9)
H6B0.19300.37540.36580.044*
C7B0.2005 (5)0.4775 (4)0.4383 (2)0.0477 (10)
H7B0.28690.43880.46730.048*
C8B0.1329 (5)0.5729 (3)0.45788 (19)0.0433 (9)
C9B0.0017 (4)0.6251 (3)0.4156 (2)0.0433 (9)
H9B0.05240.68660.42890.043*
C10B0.0594 (4)0.5868 (3)0.35506 (19)0.0397 (9)
H10B0.14880.62340.32760.040*
C11B0.2084 (4)0.7191 (3)0.60297 (19)0.0419 (9)
C12B0.3425 (5)0.6663 (4)0.6436 (2)0.0493 (10)
H12B0.39650.61000.62710.049*
C13B0.3971 (4)0.6963 (3)0.7084 (2)0.0438 (9)
H13B0.48590.65850.73570.044*
C14B0.3197 (4)0.7830 (3)0.73297 (19)0.0363 (8)
C15B0.1860 (4)0.8363 (3)0.6905 (2)0.0432 (9)
H15B0.13290.89440.70600.043*
C16B0.1317 (5)0.8058 (3)0.6274 (2)0.0472 (10)
H16B0.04240.84300.60030.047*
C17B0.3783 (4)0.8162 (3)0.8023 (2)0.0414 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Na10.0333 (7)0.0458 (8)0.0411 (8)0.0039 (6)0.0128 (6)0.0052 (6)
Na20.0332 (8)0.0487 (9)0.0453 (8)0.0011 (6)0.0152 (6)0.0092 (7)
OW0.0455 (16)0.0506 (16)0.0453 (15)0.0017 (12)0.0157 (12)0.0110 (12)
O1WA0.0451 (16)0.0466 (15)0.0527 (16)0.0016 (13)0.0137 (13)0.0022 (13)
O2WA0.0396 (14)0.0449 (15)0.0345 (13)0.0008 (11)0.0107 (11)0.0078 (11)
O3WA0.0399 (17)0.075 (2)0.083 (2)0.0083 (15)0.0114 (15)0.0086 (18)
O1WB0.0456 (15)0.0426 (14)0.0419 (14)0.0026 (12)0.0195 (12)0.0075 (11)
O2WB0.0520 (17)0.0526 (16)0.0484 (16)0.0071 (13)0.0217 (13)0.0061 (13)
O3WB0.060 (2)0.088 (3)0.247 (6)0.011 (2)0.011 (3)0.085 (4)
O1A0.0367 (15)0.0706 (19)0.0508 (17)0.0122 (14)0.0039 (13)0.0053 (14)
O2A0.0399 (14)0.0464 (15)0.0391 (14)0.0060 (12)0.0132 (11)0.0011 (12)
O3A0.0499 (16)0.0430 (15)0.0381 (14)0.0026 (12)0.0137 (12)0.0071 (12)
O4A0.0528 (17)0.0501 (16)0.0517 (16)0.0173 (13)0.0218 (13)0.0213 (13)
N1A0.0334 (16)0.0425 (17)0.0335 (16)0.0028 (13)0.0112 (13)0.0061 (13)
N2A0.0491 (19)0.0470 (19)0.0398 (18)0.0075 (16)0.0125 (15)0.0101 (15)
N3A0.0455 (19)0.0481 (19)0.0370 (17)0.0054 (16)0.0103 (14)0.0089 (14)
C1A0.041 (2)0.042 (2)0.047 (2)0.0051 (17)0.0138 (17)0.0097 (17)
C2A0.037 (2)0.0365 (19)0.0363 (19)0.0013 (16)0.0076 (16)0.0084 (15)
C3A0.035 (2)0.043 (2)0.044 (2)0.0013 (16)0.0187 (16)0.0042 (17)
C4A0.0349 (19)0.041 (2)0.0344 (19)0.0033 (16)0.0129 (15)0.0070 (16)
C5A0.0322 (18)0.0377 (19)0.0335 (19)0.0001 (15)0.0098 (15)0.0030 (15)
C6A0.049 (2)0.039 (2)0.041 (2)0.0132 (17)0.0163 (17)0.0045 (16)
C7A0.054 (2)0.048 (2)0.035 (2)0.0075 (19)0.0187 (18)0.0035 (17)
C8A0.039 (2)0.042 (2)0.035 (2)0.0024 (17)0.0086 (16)0.0085 (16)
C9A0.043 (2)0.045 (2)0.045 (2)0.0118 (17)0.0139 (18)0.0076 (17)
C10A0.047 (2)0.047 (2)0.0329 (19)0.0118 (18)0.0173 (17)0.0042 (16)
C11A0.0326 (19)0.039 (2)0.037 (2)0.0012 (15)0.0102 (15)0.0056 (16)
C12A0.040 (2)0.038 (2)0.047 (2)0.0073 (16)0.0152 (17)0.0082 (17)
C13A0.0329 (19)0.039 (2)0.038 (2)0.0042 (16)0.0171 (15)0.0067 (16)
C14A0.0271 (17)0.0326 (18)0.0380 (19)0.0045 (14)0.0116 (15)0.0064 (15)
C15A0.041 (2)0.0332 (19)0.044 (2)0.0088 (16)0.0139 (17)0.0048 (16)
C16A0.051 (2)0.046 (2)0.039 (2)0.0081 (19)0.0172 (18)0.0026 (17)
C17A0.0218 (16)0.0333 (19)0.043 (2)0.0025 (14)0.0126 (15)0.0101 (16)
O1B0.0314 (14)0.0526 (16)0.0562 (16)0.0048 (12)0.0192 (12)0.0085 (13)
O2B0.0363 (14)0.0578 (16)0.0370 (14)0.0055 (12)0.0120 (11)0.0068 (12)
O3B0.0463 (16)0.0387 (15)0.0611 (18)0.0017 (13)0.0080 (14)0.0048 (13)
O4B0.066 (2)0.067 (2)0.072 (2)0.0225 (17)0.0117 (17)0.0360 (17)
N1B0.0307 (15)0.0439 (17)0.0391 (17)0.0010 (13)0.0137 (13)0.0084 (14)
N2B0.052 (2)0.051 (2)0.0453 (19)0.0027 (17)0.0183 (16)0.0042 (16)
N3B0.054 (2)0.0456 (19)0.0455 (19)0.0040 (16)0.0178 (16)0.0055 (15)
C1B0.033 (2)0.044 (2)0.053 (2)0.0011 (16)0.0157 (17)0.0131 (18)
C2B0.048 (2)0.0330 (19)0.049 (2)0.0057 (17)0.0173 (18)0.0118 (17)
C3B0.050 (2)0.049 (2)0.039 (2)0.0083 (18)0.0159 (18)0.0069 (17)
C4B0.0307 (19)0.052 (2)0.039 (2)0.0050 (16)0.0119 (16)0.0106 (17)
C5B0.041 (2)0.0342 (19)0.041 (2)0.0045 (16)0.0209 (17)0.0024 (16)
C6B0.046 (2)0.041 (2)0.045 (2)0.0057 (18)0.0092 (18)0.0073 (17)
C7B0.045 (2)0.050 (2)0.044 (2)0.0056 (19)0.0051 (18)0.0014 (18)
C8B0.053 (2)0.047 (2)0.032 (2)0.0087 (19)0.0150 (18)0.0031 (16)
C9B0.050 (2)0.040 (2)0.044 (2)0.0018 (18)0.0226 (19)0.0064 (17)
C10B0.042 (2)0.040 (2)0.037 (2)0.0007 (17)0.0140 (16)0.0006 (16)
C11B0.049 (2)0.042 (2)0.037 (2)0.0099 (18)0.0136 (18)0.0036 (16)
C12B0.051 (2)0.050 (2)0.054 (3)0.0015 (19)0.025 (2)0.015 (2)
C13B0.033 (2)0.046 (2)0.054 (2)0.0008 (17)0.0117 (18)0.0089 (18)
C14B0.0338 (19)0.0325 (18)0.044 (2)0.0086 (15)0.0120 (16)0.0051 (16)
C15B0.040 (2)0.039 (2)0.049 (2)0.0043 (17)0.0038 (18)0.0083 (17)
C16B0.045 (2)0.045 (2)0.048 (2)0.0046 (18)0.0037 (19)0.0035 (18)
C17B0.039 (2)0.035 (2)0.051 (2)0.0074 (17)0.0077 (18)0.0091 (17)
Geometric parameters (Å, º) top
Na1—O2WAi2.394 (3)C9A—C10A1.364 (5)
Na1—O1WA2.402 (3)C11A—C16A1.371 (5)
Na1—O2WA2.425 (3)C11A—C12A1.401 (5)
Na1—O3WA2.429 (3)C12A—C13A1.371 (5)
Na1—O2A2.445 (3)C13A—C14A1.396 (5)
Na1—OW2.608 (3)C14A—C15A1.395 (5)
Na1—Na1i3.692 (3)C14A—C17A1.485 (5)
Na2—O3WB2.354 (4)C15A—C16A1.378 (5)
Na2—O1WBii2.402 (3)O1B—C1B1.434 (5)
Na2—O2WB2.431 (3)O2B—C3B1.416 (4)
Na2—O2B2.452 (3)O3B—C17B1.260 (5)
Na2—O1WB2.486 (3)O4B—C17B1.252 (5)
Na2—OW2.498 (3)N1B—C5B1.369 (5)
Na2—Na2ii3.606 (3)N1B—C4B1.456 (5)
O2WA—Na1i2.394 (3)N1B—C2B1.458 (5)
O1WB—Na2ii2.402 (3)N2B—N3B1.249 (5)
O1A—C1A1.408 (5)N2B—C8B1.407 (5)
O2A—C3A1.435 (4)N3B—C11B1.434 (5)
O3A—C17A1.259 (4)C1B—C2B1.514 (5)
O4A—C17A1.252 (4)C3B—C4B1.507 (5)
N1A—C5A1.373 (4)C5B—C6B1.405 (5)
N1A—C2A1.445 (4)C5B—C10B1.408 (5)
N1A—C4A1.455 (4)C6B—C7B1.363 (6)
N2A—N3A1.245 (4)C7B—C8B1.386 (6)
N2A—C8A1.402 (5)C8B—C9B1.397 (6)
N3A—C11A1.424 (5)C9B—C10B1.362 (5)
C1A—C2A1.505 (5)C11B—C12B1.384 (6)
C3A—C4A1.508 (5)C11B—C16B1.391 (6)
C5A—C10A1.402 (5)C12B—C13B1.381 (6)
C5A—C6A1.410 (5)C13B—C14B1.396 (5)
C6A—C7A1.369 (5)C14B—C15B1.396 (5)
C7A—C8A1.382 (5)C14B—C17B1.486 (5)
C8A—C9A1.396 (5)C15B—C16B1.355 (5)
O2WAi—Na1—O1WA98.47 (10)N1A—C5A—C6A121.3 (3)
O2WAi—Na1—O2WA79.97 (10)C10A—C5A—C6A116.3 (3)
O1WA—Na1—O2WA177.45 (10)C7A—C6A—C5A121.0 (3)
O2WAi—Na1—O3WA97.28 (11)C6A—C7A—C8A122.2 (3)
O1WA—Na1—O3WA93.13 (11)C7A—C8A—C9A117.3 (3)
O2WA—Na1—O3WA89.07 (11)C7A—C8A—N2A116.4 (3)
O2WAi—Na1—O2A158.56 (11)C9A—C8A—N2A126.3 (3)
O1WA—Na1—O2A92.02 (10)C10A—C9A—C8A121.1 (3)
O2WA—Na1—O2A88.82 (10)C9A—C10A—C5A122.1 (3)
O3WA—Na1—O2A100.78 (11)C16A—C11A—C12A119.1 (3)
O2WAi—Na1—OW84.61 (10)C16A—C11A—N3A117.0 (3)
O1WA—Na1—OW90.62 (10)C12A—C11A—N3A123.9 (3)
O2WA—Na1—OW87.23 (10)C13A—C12A—C11A119.9 (3)
O3WA—Na1—OW175.50 (12)C12A—C13A—C14A121.4 (3)
O2A—Na1—OW76.59 (10)C15A—C14A—C13A117.9 (3)
O2WAi—Na1—Na1i40.29 (7)C15A—C14A—C17A121.0 (3)
O1WA—Na1—Na1i138.73 (9)C13A—C14A—C17A121.1 (3)
O2WA—Na1—Na1i39.67 (6)C16A—C15A—C14A120.7 (3)
O3WA—Na1—Na1i94.10 (10)C11A—C16A—C15A121.0 (3)
O2A—Na1—Na1i126.15 (10)O4A—C17A—O3A123.2 (3)
OW—Na1—Na1i84.68 (8)O4A—C17A—C14A118.0 (3)
O3WB—Na2—O1WBii95.50 (15)O3A—C17A—C14A118.8 (3)
O3WB—Na2—O2WB87.68 (15)C3B—O2B—Na2118.8 (2)
O1WBii—Na2—O2WB176.74 (11)C5B—N1B—C4B121.2 (3)
O3WB—Na2—O2B97.04 (14)C5B—N1B—C2B120.7 (3)
O1WBii—Na2—O2B102.91 (10)C4B—N1B—C2B118.2 (3)
O2WB—Na2—O2B77.37 (10)N3B—N2B—C8B114.3 (4)
O3WB—Na2—O1WB93.13 (15)N2B—N3B—C11B112.8 (3)
O1WBii—Na2—O1WB84.91 (10)O1B—C1B—C2B110.2 (3)
O2WB—Na2—O1WB94.20 (10)N1B—C2B—C1B114.1 (3)
O2B—Na2—O1WB166.46 (11)O2B—C3B—C4B113.7 (3)
O3WB—Na2—OW174.15 (17)N1B—C4B—C3B114.4 (3)
O1WBii—Na2—OW89.15 (10)N1B—C5B—C6B121.7 (3)
O2WB—Na2—OW87.63 (10)N1B—C5B—C10B121.8 (3)
O2B—Na2—OW85.33 (10)C6B—C5B—C10B116.5 (3)
O1WB—Na2—OW83.73 (10)C7B—C6B—C5B121.1 (4)
O3WB—Na2—Na2ii95.83 (12)C6B—C7B—C8B121.7 (4)
O1WBii—Na2—Na2ii43.35 (7)C7B—C8B—C9B117.9 (4)
O2WB—Na2—Na2ii135.67 (10)C7B—C8B—N2B116.5 (4)
O2B—Na2—Na2ii144.97 (9)C9B—C8B—N2B125.5 (4)
O1WB—Na2—Na2ii41.55 (7)C10B—C9B—C8B120.6 (4)
OW—Na2—Na2ii85.12 (8)C9B—C10B—C5B122.0 (4)
Na2—OW—Na1127.10 (11)C12B—C11B—C16B118.8 (4)
Na1i—O2WA—Na1100.03 (10)C12B—C11B—N3B125.5 (4)
Na2ii—O1WB—Na295.09 (10)C16B—C11B—N3B115.7 (4)
C3A—O2A—Na1127.4 (2)C13B—C12B—C11B120.8 (4)
C5A—N1A—C2A120.6 (3)C12B—C13B—C14B120.4 (4)
C5A—N1A—C4A121.2 (3)C13B—C14B—C15B117.8 (3)
C2A—N1A—C4A118.2 (3)C13B—C14B—C17B120.7 (3)
N3A—N2A—C8A115.8 (3)C15B—C14B—C17B121.5 (3)
N2A—N3A—C11A113.4 (3)C16B—C15B—C14B121.7 (4)
O1A—C1A—C2A110.0 (3)C15B—C16B—C11B120.5 (4)
N1A—C2A—C1A114.5 (3)O4B—C17B—O3B122.6 (4)
O2A—C3A—C4A110.7 (3)O4B—C17B—C14B118.5 (3)
N1A—C4A—C3A114.1 (3)O3B—C17B—C14B118.8 (3)
N1A—C5A—C10A122.4 (3)
O1WBii—Na2—OW—Na1152.36 (14)C17A—C14A—C15A—C16A175.6 (3)
O2WB—Na2—OW—Na128.18 (15)C12A—C11A—C16A—C15A1.5 (6)
O2B—Na2—OW—Na149.33 (15)N3A—C11A—C16A—C15A177.2 (3)
O1WB—Na2—OW—Na1122.67 (15)C14A—C15A—C16A—C11A1.1 (6)
Na2ii—Na2—OW—Na1164.41 (13)C15A—C14A—C17A—O4A16.3 (5)
O2WAi—Na1—OW—Na2131.31 (15)C13A—C14A—C17A—O4A165.1 (3)
O1WA—Na1—OW—Na232.86 (15)C15A—C14A—C17A—O3A163.7 (3)
O2WA—Na1—OW—Na2148.52 (14)C13A—C14A—C17A—O3A14.8 (5)
O2A—Na1—OW—Na259.07 (15)O3WB—Na2—O2B—C3B114.4 (3)
Na1i—Na1—OW—Na2171.79 (13)O1WBii—Na2—O2B—C3B17.1 (3)
O3WA—Na1—O2WA—Na1i97.56 (12)O2WB—Na2—O2B—C3B159.6 (3)
O2A—Na1—O2WA—Na1i161.64 (11)O1WB—Na2—O2B—C3B107.2 (4)
OW—Na1—O2WA—Na1i85.01 (10)OW—Na2—O2B—C3B71.0 (2)
O3WB—Na2—O1WB—Na2ii95.25 (16)Na2ii—Na2—O2B—C3B3.6 (3)
O2WB—Na2—O1WB—Na2ii176.85 (11)C8B—N2B—N3B—C11B177.5 (3)
O2B—Na2—O1WB—Na2ii126.0 (4)C5B—N1B—C2B—C1B69.0 (4)
OW—Na2—O1WB—Na2ii89.71 (10)C4B—N1B—C2B—C1B110.1 (4)
O2WAi—Na1—O2A—C3A145.5 (3)O1B—C1B—C2B—N1B67.1 (4)
O1WA—Na1—O2A—C3A95.0 (3)Na2—O2B—C3B—C4B75.5 (4)
O2WA—Na1—O2A—C3A87.4 (3)C5B—N1B—C4B—C3B83.4 (4)
O3WA—Na1—O2A—C3A1.4 (3)C2B—N1B—C4B—C3B95.8 (4)
OW—Na1—O2A—C3A174.9 (3)O2B—C3B—C4B—N1B82.6 (4)
Na1i—Na1—O2A—C3A101.9 (3)C4B—N1B—C5B—C6B174.7 (3)
C8A—N2A—N3A—C11A177.2 (3)C2B—N1B—C5B—C6B6.2 (5)
C5A—N1A—C2A—C1A78.8 (4)C4B—N1B—C5B—C10B5.6 (5)
C4A—N1A—C2A—C1A103.3 (4)C2B—N1B—C5B—C10B173.6 (3)
O1A—C1A—C2A—N1A72.3 (4)N1B—C5B—C6B—C7B177.7 (3)
Na1—O2A—C3A—C4A66.7 (4)C10B—C5B—C6B—C7B2.0 (5)
C5A—N1A—C4A—C3A85.9 (4)C5B—C6B—C7B—C8B1.1 (6)
C2A—N1A—C4A—C3A96.3 (4)C6B—C7B—C8B—C9B3.8 (6)
O2A—C3A—C4A—N1A175.2 (3)C6B—C7B—C8B—N2B179.6 (4)
C2A—N1A—C5A—C10A179.5 (3)N3B—N2B—C8B—C7B179.2 (3)
C4A—N1A—C5A—C10A1.8 (5)N3B—N2B—C8B—C9B4.6 (5)
C2A—N1A—C5A—C6A0.6 (5)C7B—C8B—C9B—C10B3.5 (5)
C4A—N1A—C5A—C6A177.1 (3)N2B—C8B—C9B—C10B179.7 (3)
N1A—C5A—C6A—C7A178.6 (4)C8B—C9B—C10B—C5B0.5 (5)
C10A—C5A—C6A—C7A0.3 (5)N1B—C5B—C10B—C9B177.5 (3)
C5A—C6A—C7A—C8A0.2 (6)C6B—C5B—C10B—C9B2.3 (5)
C6A—C7A—C8A—C9A0.4 (6)N2B—N3B—C11B—C12B7.8 (5)
C6A—C7A—C8A—N2A179.6 (4)N2B—N3B—C11B—C16B171.9 (3)
N3A—N2A—C8A—C7A178.1 (3)C16B—C11B—C12B—C13B2.0 (6)
N3A—N2A—C8A—C9A2.8 (6)N3B—C11B—C12B—C13B177.6 (3)
C7A—C8A—C9A—C10A0.8 (6)C11B—C12B—C13B—C14B1.8 (6)
N2A—C8A—C9A—C10A179.9 (4)C12B—C13B—C14B—C15B0.7 (5)
C8A—C9A—C10A—C5A1.0 (6)C12B—C13B—C14B—C17B179.6 (3)
N1A—C5A—C10A—C9A178.2 (4)C13B—C14B—C15B—C16B0.1 (5)
C6A—C5A—C10A—C9A0.7 (6)C17B—C14B—C15B—C16B179.6 (3)
N2A—N3A—C11A—C16A179.4 (3)C14B—C15B—C16B—C11B0.1 (6)
N2A—N3A—C11A—C12A0.7 (5)C12B—C11B—C16B—C15B1.2 (6)
C16A—C11A—C12A—C13A2.0 (5)N3B—C11B—C16B—C15B178.5 (3)
N3A—C11A—C12A—C13A176.6 (3)C13B—C14B—C17B—O4B169.1 (4)
C11A—C12A—C13A—C14A0.0 (5)C15B—C14B—C17B—O4B11.2 (5)
C12A—C13A—C14A—C15A2.5 (5)C13B—C14B—C17B—O3B7.8 (5)
C12A—C13A—C14A—C17A176.1 (3)C15B—C14B—C17B—O3B171.9 (3)
C13A—C14A—C15A—C16A3.0 (5)
Symmetry codes: (i) x+1, y+2, z; (ii) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
OW—H1WW···O3Biii0.942.273.121 (4)150
OW—H2WW···O3Aiv0.901.972.858 (4)168
O1WA—HA11···O1Av0.901.892.787 (4)176
O1WA—HA21···O2B0.842.122.910 (4)157
O2WA—HA12···O4Biii0.971.772.717 (4)165
O2WA—HA22···O3Avi0.821.982.785 (4)167
O3WA—HA13···O3Avi0.901.972.835 (4)160
O3WA—HA23···O1WAv0.802.122.890 (4)160
O2WB—HB12···O1Bvii0.971.842.801 (4)178
O2WB—HB22···O2A0.941.882.809 (4)172
O1WB—HB11···O4Aviii0.991.802.775 (4)168
O1WB—HB21···O3Biii0.891.942.808 (4)166
O1A—HO1A···O4Bix0.821.942.682 (4)150
O2A—HO2A···O3Biii0.961.732.689 (4)171
O1B—HO1B···O4Ax0.961.702.642 (4)165
O2B—HO2B···O1B0.891.852.720 (4)164
Symmetry codes: (iii) x+1, y, z+1; (iv) x, y, z1; (v) x, y+2, z; (vi) x+1, y+2, z+1; (vii) x, y+1, z; (viii) x+1, y+1, z+1; (ix) x, y, z+1; (x) x1, y, z1.
(II) Potassium 4-(4-bis(hydroxyethyl)amino-phenylazo)benzoate dihydrate top
Crystal data top
K+·C17H18N3O4·2H2OF(000) = 424
Mr = 403.48Dx = 1.446 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71069 Å
a = 8.238 (8) ÅCell parameters from 24 reflections
b = 7.498 (6) Åθ = 7.3–8.6°
c = 15.016 (8) ŵ = 0.33 mm1
β = 92.81 (5)°T = 293 K
V = 926.4 (13) Å3Plate, orange
Z = 20.3 × 0.3 × 0.1 mm
Data collection top
Nonius MACH3
diffractometer
Rint = 0.035
Radiation source: fine-focus sealed tubeθmax = 24.9°, θmin = 1.4°
Graphite monochromatorh = 99
ω/θ scansk = 08
1927 measured reflectionsl = 017
1757 independent reflections2 standard reflections every 120 min
1427 reflections with I > 2σ(I) intensity decay: 0.1%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.104 w = 1/[σ2(Fo2) + (0.0477P)2 + 0.3483P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
1757 reflectionsΔρmax = 0.23 e Å3
244 parametersΔρmin = 0.21 e Å3
1 restraintAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.03 (9)
Crystal data top
K+·C17H18N3O4·2H2OV = 926.4 (13) Å3
Mr = 403.48Z = 2
Monoclinic, P21Mo Kα radiation
a = 8.238 (8) ŵ = 0.33 mm1
b = 7.498 (6) ÅT = 293 K
c = 15.016 (8) Å0.3 × 0.3 × 0.1 mm
β = 92.81 (5)°
Data collection top
Nonius MACH3
diffractometer
Rint = 0.035
1927 measured reflections2 standard reflections every 120 min
1757 independent reflections intensity decay: 0.1%
1427 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.104Δρmax = 0.23 e Å3
S = 1.03Δρmin = 0.21 e Å3
1757 reflectionsAbsolute structure: Flack (1983)
244 parametersAbsolute structure parameter: 0.03 (9)
1 restraint
Special details top

Experimental. Single crystals were obtained by slow evaporation from methanol/water slution.

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. Hydrogen atoms of water molecules and hydroxy groups were located by difference Fourier synthesis and refined by the riding model with Uiso equal to Ueq of the carrier atom.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
K10.96028 (11)0.27467 (19)0.09027 (7)0.0464 (3)
N11.4270 (4)0.1932 (6)0.3088 (2)0.0302 (9)
N21.8681 (4)0.1598 (5)0.6035 (2)0.0307 (9)
N31.9994 (4)0.2415 (6)0.5956 (2)0.0366 (10)
O11.6378 (3)0.3076 (5)0.10467 (18)0.0407 (9)
HO11.57420.29120.05520.041*
O21.0809 (4)0.3217 (5)0.2787 (2)0.0462 (9)
HO21.10470.45560.30210.046*
O32.4117 (4)0.2497 (6)0.96932 (19)0.0447 (9)
O42.6068 (3)0.2448 (6)0.8718 (2)0.0441 (9)
O1W1.1946 (4)0.0187 (6)0.0535 (2)0.0480 (10)
H1O11.25790.07580.07870.048*
H2O11.26940.05370.01490.048*
O2W1.1908 (4)0.5088 (6)0.0322 (3)0.0521 (11)
H1O21.24960.59160.06780.052*
H2O21.27950.43020.03000.052*
C11.5814 (5)0.1951 (7)0.1714 (3)0.0336 (11)
H1A1.67290.15210.20850.034*
H1B1.52700.09280.14400.034*
C21.4634 (5)0.2948 (7)0.2292 (2)0.0300 (10)
H2A1.51040.40880.24700.030*
H2B1.36320.31790.19450.030*
C31.1328 (5)0.1797 (7)0.3363 (3)0.0394 (12)
H3A1.04450.09520.34120.039*
H3B1.15960.22700.39530.039*
C41.2778 (5)0.0852 (7)0.3029 (3)0.0306 (10)
H4A1.29590.02340.33710.031*
H4B1.25500.05130.24120.031*
C51.5337 (5)0.1858 (6)0.3808 (3)0.0276 (10)
C61.5021 (5)0.0901 (7)0.4586 (3)0.0290 (10)
H61.40390.02970.46200.029*
C71.6132 (5)0.0840 (7)0.5296 (3)0.0307 (10)
H71.58970.01850.57990.031*
C81.7598 (5)0.1738 (7)0.5276 (3)0.0287 (10)
C91.7902 (4)0.2756 (8)0.4525 (2)0.0295 (9)
H91.88600.34100.45120.029*
C101.6831 (4)0.2809 (7)0.3816 (2)0.0280 (9)
H101.70760.34830.33200.028*
C112.1066 (5)0.2367 (6)0.6732 (3)0.0309 (11)
C122.0551 (5)0.2224 (6)0.7597 (3)0.0342 (11)
H121.94500.21240.77000.034*
C132.1686 (5)0.2231 (7)0.8297 (3)0.0374 (12)
H132.13500.21270.88770.037*
C142.3353 (5)0.2394 (6)0.8149 (3)0.0299 (10)
C152.3820 (5)0.2553 (7)0.7284 (3)0.0341 (10)
H152.49190.26360.71760.034*
C162.2696 (5)0.2590 (8)0.6583 (3)0.0348 (10)
H162.30290.27650.60060.035*
C172.4600 (5)0.2432 (7)0.8909 (3)0.0345 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
K10.0303 (5)0.0551 (7)0.0538 (6)0.0007 (6)0.0018 (4)0.0001 (7)
N10.0241 (18)0.042 (2)0.0241 (18)0.0056 (18)0.0012 (15)0.0032 (17)
N20.031 (2)0.035 (2)0.0249 (19)0.0005 (19)0.0044 (15)0.0026 (17)
N30.0334 (19)0.044 (3)0.0313 (18)0.003 (2)0.0068 (15)0.004 (2)
O10.0361 (16)0.061 (3)0.0248 (15)0.0094 (18)0.0006 (12)0.0023 (17)
O20.0409 (18)0.042 (2)0.055 (2)0.0068 (17)0.0029 (16)0.0009 (19)
O30.0447 (17)0.057 (3)0.0314 (16)0.003 (2)0.0088 (13)0.0013 (19)
O40.0307 (16)0.054 (2)0.0463 (17)0.0002 (19)0.0099 (14)0.0013 (19)
O1W0.033 (2)0.061 (3)0.051 (2)0.0126 (19)0.0052 (16)0.0064 (19)
O2W0.029 (2)0.057 (3)0.069 (3)0.0082 (19)0.0089 (17)0.003 (2)
C10.039 (2)0.035 (3)0.026 (2)0.000 (2)0.0010 (19)0.000 (2)
C20.032 (2)0.033 (3)0.0250 (19)0.004 (2)0.0005 (16)0.006 (2)
C30.030 (2)0.048 (3)0.040 (3)0.005 (2)0.006 (2)0.001 (3)
C40.030 (2)0.031 (3)0.030 (2)0.002 (2)0.0010 (18)0.000 (2)
C50.027 (2)0.029 (2)0.027 (2)0.002 (2)0.0048 (18)0.004 (2)
C60.023 (2)0.033 (3)0.032 (2)0.006 (2)0.0031 (18)0.002 (2)
C70.032 (2)0.034 (3)0.026 (2)0.002 (2)0.0025 (18)0.006 (2)
C80.025 (2)0.037 (3)0.024 (2)0.002 (2)0.0016 (17)0.000 (2)
C90.0225 (18)0.036 (2)0.030 (2)0.001 (2)0.0028 (16)0.005 (2)
C100.0272 (19)0.033 (2)0.0240 (19)0.001 (2)0.0049 (16)0.004 (2)
C110.034 (2)0.033 (3)0.025 (2)0.002 (2)0.0068 (17)0.005 (2)
C120.028 (2)0.037 (3)0.037 (2)0.002 (2)0.0034 (18)0.001 (2)
C130.034 (2)0.051 (4)0.027 (2)0.002 (2)0.0009 (18)0.002 (2)
C140.035 (2)0.022 (2)0.032 (2)0.000 (2)0.0064 (18)0.001 (2)
C150.031 (2)0.037 (3)0.035 (2)0.003 (2)0.0013 (17)0.004 (2)
C160.041 (2)0.038 (3)0.026 (2)0.005 (3)0.0032 (17)0.003 (3)
C170.038 (2)0.028 (3)0.036 (2)0.003 (2)0.0082 (19)0.001 (2)
Geometric parameters (Å, º) top
K1—O1i2.687 (4)O4—C171.256 (5)
K1—O2W2.759 (4)O1W—K1ii3.060 (4)
K1—O1W2.796 (4)O2W—K1iii2.946 (5)
K1—O2Wii2.946 (5)C1—C21.530 (6)
K1—O22.974 (4)C1—K1iv3.458 (5)
K1—O1Wiii3.060 (4)C3—C41.497 (6)
K1—C1i3.458 (5)C5—C61.407 (6)
K1—K1ii4.691 (3)C5—C101.421 (6)
K1—K1iii4.691 (3)C6—C71.372 (6)
N1—C51.361 (5)C7—C81.384 (6)
N1—C21.460 (5)C8—C91.395 (6)
N1—C41.471 (6)C9—C101.350 (5)
N2—N31.254 (5)C11—C161.383 (6)
N2—C81.416 (5)C11—C121.390 (6)
N3—C111.428 (5)C12—C131.372 (6)
O1—C11.407 (6)C13—C141.407 (6)
O1—K1iv2.687 (4)C14—C151.377 (6)
O2—C31.424 (6)C14—C171.498 (6)
O3—C171.262 (5)C15—C161.368 (6)
O1i—K1—O2W131.71 (13)C5—N1—C4122.1 (4)
O1i—K1—O1W140.70 (13)C2—N1—C4116.2 (3)
O2W—K1—O1W83.21 (13)N3—N2—C8113.5 (4)
O1i—K1—O2Wii73.95 (12)N2—N3—C11114.3 (4)
O2W—K1—O2Wii120.63 (7)C1—O1—K1iv111.4 (3)
O1W—K1—O2Wii71.75 (12)C3—O2—K1124.5 (3)
O1i—K1—O2101.42 (10)K1—O1W—K1ii106.36 (13)
O2W—K1—O291.27 (12)K1—O2W—K1iii110.59 (13)
O1W—K1—O293.88 (11)O1—C1—C2110.7 (4)
O2Wii—K1—O2141.76 (12)O1—C1—K1iv46.35 (19)
O1i—K1—O1Wiii67.79 (11)C2—C1—K1iv136.5 (3)
O2W—K1—O1Wiii70.50 (12)N1—C2—C1111.8 (4)
O1W—K1—O1Wiii122.62 (7)O2—C3—C4111.8 (4)
O2Wii—K1—O1Wiii79.37 (12)N1—C4—C3113.4 (4)
O2—K1—O1Wiii135.12 (12)N1—C5—C6122.8 (4)
O1i—K1—C1i22.26 (11)N1—C5—C10120.7 (4)
O2W—K1—C1i150.27 (13)C6—C5—C10116.4 (4)
O1W—K1—C1i126.52 (14)C7—C6—C5121.2 (4)
O2Wii—K1—C1i75.07 (12)C6—C7—C8121.1 (4)
O2—K1—C1i87.16 (11)C7—C8—C9118.4 (4)
O1Wiii—K1—C1i89.96 (12)C7—C8—N2117.5 (4)
O1i—K1—K1ii106.64 (9)C9—C8—N2124.1 (4)
O2W—K1—K1ii102.03 (11)C10—C9—C8121.2 (4)
O1W—K1—K1ii38.76 (9)C9—C10—C5121.6 (4)
O2Wii—K1—K1ii33.40 (8)C16—C11—C12120.3 (4)
O2—K1—K1ii126.52 (8)C16—C11—N3115.5 (4)
O1Wiii—K1—K1ii97.79 (10)C12—C11—N3124.0 (4)
C1i—K1—K1ii102.69 (9)C13—C12—C11119.2 (4)
O1i—K1—K1iii98.01 (9)C12—C13—C14120.9 (4)
O2W—K1—K1iii36.01 (9)C15—C14—C13118.4 (4)
O1W—K1—K1iii108.48 (11)C15—C14—C17120.2 (4)
O2Wii—K1—K1iii104.27 (10)C13—C14—C17121.3 (4)
O2—K1—K1iii113.93 (9)C16—C15—C14121.2 (4)
O1Wiii—K1—K1iii34.89 (8)C15—C16—C11119.9 (4)
C1i—K1—K1iii119.70 (9)O4—C17—O3124.3 (4)
K1ii—K1—K1iii106.10 (7)O4—C17—C14117.2 (4)
C5—N1—C2121.4 (3)O3—C17—C14118.4 (4)
C8—N2—N3—C11176.9 (4)C2—N1—C5—C6179.6 (4)
O1i—K1—O2—C3102.6 (3)C4—N1—C5—C66.9 (7)
O2W—K1—O2—C3124.3 (3)C2—N1—C5—C101.5 (6)
O1W—K1—O2—C341.0 (3)C4—N1—C5—C10174.9 (4)
O2Wii—K1—O2—C324.1 (4)N1—C5—C6—C7179.3 (4)
O1Wiii—K1—O2—C3172.5 (3)C10—C5—C6—C72.5 (7)
C1i—K1—O2—C385.4 (3)C5—C6—C7—C80.8 (7)
K1ii—K1—O2—C318.3 (3)C6—C7—C8—C91.9 (7)
K1iii—K1—O2—C3153.2 (3)C6—C7—C8—N2179.7 (4)
O1i—K1—O1W—K1ii36.9 (2)N3—N2—C8—C7178.5 (4)
O2W—K1—O1W—K1ii118.92 (15)N3—N2—C8—C93.2 (6)
O2Wii—K1—O1W—K1ii6.50 (13)C7—C8—C9—C102.9 (7)
O2—K1—O1W—K1ii150.26 (12)N2—C8—C9—C10178.8 (5)
O1Wiii—K1—O1W—K1ii57.3 (2)C8—C9—C10—C51.1 (8)
C1i—K1—O1W—K1ii60.93 (17)N1—C5—C10—C9179.8 (5)
K1iii—K1—O1W—K1ii92.91 (12)C6—C5—C10—C91.6 (7)
O1i—K1—O2W—K1iii24.7 (2)N2—N3—C11—C16155.2 (5)
O1W—K1—O2W—K1iii134.98 (16)N2—N3—C11—C1228.8 (7)
O2Wii—K1—O2W—K1iii70.9 (2)C16—C11—C12—C132.7 (7)
O2—K1—O2W—K1iii131.27 (14)N3—C11—C12—C13178.5 (5)
O1Wiii—K1—O2W—K1iii6.81 (13)C11—C12—C13—C140.5 (8)
C1i—K1—O2W—K1iii44.8 (3)C12—C13—C14—C150.2 (8)
K1ii—K1—O2W—K1iii100.91 (13)C12—C13—C14—C17179.0 (5)
K1iv—O1—C1—C2135.4 (3)C13—C14—C15—C161.3 (8)
C5—N1—C2—C177.9 (5)C17—C14—C15—C16177.5 (5)
C4—N1—C2—C195.9 (4)C14—C15—C16—C113.6 (8)
O1—C1—C2—N1169.1 (3)C12—C11—C16—C154.3 (8)
K1iv—C1—C2—N1121.5 (4)N3—C11—C16—C15179.6 (5)
K1—O2—C3—C462.8 (5)C15—C14—C17—O46.4 (7)
C5—N1—C4—C392.7 (5)C13—C14—C17—O4174.9 (5)
C2—N1—C4—C393.5 (5)C15—C14—C17—O3171.7 (5)
O2—C3—C4—N169.6 (5)C13—C14—C17—O37.1 (7)
Symmetry codes: (i) x1, y, z; (ii) x+2, y1/2, z; (iii) x+2, y+1/2, z; (iv) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—HO1···O3v0.901.842.724 (4)169
O1W—H2O1···O3v0.902.022.831 (6)148
O1W—H1O1···O4vi0.951.882.824 (6)177
O2W—H2O2···O3v0.941.992.855 (6)152
O2W—H1O2···O4vii0.941.852.785 (5)171
O2—HO2···N2viii1.082.093.108 (6)156
Symmetry codes: (v) x1, y, z1; (vi) x+4, y1/2, z+1; (vii) x+4, y+1/2, z+1; (viii) x+3, y+1/2, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaNa+·C17H18N3O4·3.5H2OK+·C17H18N3O4·2H2O
Mr414.39403.48
Crystal system, space groupTriclinic, P1Monoclinic, P21
Temperature (K)293293
a, b, c (Å)9.023 (3), 11.818 (3), 19.400 (5)8.238 (8), 7.498 (6), 15.016 (8)
α, β, γ (°)99.31 (4), 99.41 (4), 93.36 (2)90, 92.81 (5), 90
V3)2006.3 (10)926.4 (13)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.130.33
Crystal size (mm)0.6 × 0.4 × 0.10.3 × 0.3 × 0.1
Data collection
DiffractometerNonius MACH3
diffractometer
Nonius MACH3
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
7259, 7030, 4387 1927, 1757, 1427
Rint0.0430.035
(sin θ/λ)max1)0.5930.592
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.069, 0.209, 1.00 0.039, 0.104, 1.03
No. of reflections70301757
No. of parameters514244
No. of restraints01
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.38, 0.540.23, 0.21
Absolute structure?Flack (1983)
Absolute structure parameter?0.03 (9)

Computer programs: MACH3 Software (Nonius, 1996), CELLDIM (Nonius, 1996), XCAD4-PC (Harms, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1999) and PLATON92 (Spek, 1992).

Selected geometric parameters (Å, º) for (I) top
Na1—O2WAi2.394 (3)C5A—C10A1.402 (5)
Na1—O1WA2.402 (3)C5A—C6A1.410 (5)
Na1—O2WA2.425 (3)C6A—C7A1.369 (5)
Na1—O3WA2.429 (3)C7A—C8A1.382 (5)
Na1—O2A2.445 (3)C8A—C9A1.396 (5)
Na1—OW2.608 (3)C9A—C10A1.364 (5)
Na2—O3WB2.354 (4)O3B—C17B1.260 (5)
Na2—O1WBii2.402 (3)O4B—C17B1.252 (5)
Na2—O2WB2.431 (3)N1B—C5B1.369 (5)
Na2—O2B2.452 (3)N2B—N3B1.249 (5)
Na2—O1WB2.486 (3)N2B—C8B1.407 (5)
Na2—OW2.498 (3)N3B—C11B1.434 (5)
O3A—C17A1.259 (4)C5B—C6B1.405 (5)
O4A—C17A1.252 (4)C5B—C10B1.408 (5)
N1A—C5A1.373 (4)C6B—C7B1.363 (6)
N2A—N3A1.245 (4)C7B—C8B1.386 (6)
N2A—C8A1.402 (5)C8B—C9B1.397 (6)
N3A—C11A1.424 (5)C9B—C10B1.362 (5)
O2WA—Na1—O2A88.82 (10)O3WB—Na2—O2B97.04 (14)
O3WA—Na1—O2A100.78 (11)O2WB—Na2—O2B77.37 (10)
O3WA—Na1—OW175.50 (12)O3WB—Na2—OW174.15 (17)
C8A—N2A—N3A—C11A177.2 (3)C8B—N2B—N3B—C11B177.5 (3)
C2A—N1A—C5A—C6A0.6 (5)C2B—N1B—C5B—C6B6.2 (5)
N3A—N2A—C8A—C7A178.1 (3)N3B—N2B—C8B—C7B179.2 (3)
N2A—N3A—C11A—C16A179.4 (3)N2B—N3B—C11B—C16B171.9 (3)
Symmetry codes: (i) x+1, y+2, z; (ii) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
OW—H1WW···O3Biii0.942.273.121 (4)150
OW—H2WW···O3Aiv0.901.972.858 (4)168
O1WA—HA11···O1Av0.901.892.787 (4)176
O1WA—HA21···O2B0.842.122.910 (4)157
O2WA—HA12···O4Biii0.971.772.717 (4)165
O2WA—HA22···O3Avi0.821.982.785 (4)167
O3WA—HA13···O3Avi0.901.972.835 (4)160
O3WA—HA23···O1WAv0.802.122.890 (4)160
O2WB—HB12···O1Bvii0.971.842.801 (4)178
O2WB—HB22···O2A0.941.882.809 (4)172
O1WB—HB11···O4Aviii0.991.802.775 (4)168
O1WB—HB21···O3Biii0.891.942.808 (4)166
O1A—HO1A···O4Bix0.821.942.682 (4)150
O2A—HO2A···O3Biii0.961.732.689 (4)171
O1B—HO1B···O4Ax0.961.702.642 (4)165
O2B—HO2B···O1B0.891.852.720 (4)164
Symmetry codes: (iii) x+1, y, z+1; (iv) x, y, z1; (v) x, y+2, z; (vi) x+1, y+2, z+1; (vii) x, y+1, z; (viii) x+1, y+1, z+1; (ix) x, y, z+1; (x) x1, y, z1.
Selected geometric parameters (Å, º) for (II) top
K1—O1i2.687 (4)N3—C111.428 (5)
K1—O2W2.759 (4)O3—C171.262 (5)
K1—O1W2.796 (4)O4—C171.256 (5)
K1—O2Wii2.946 (5)C5—C61.407 (6)
K1—O22.974 (4)C5—C101.421 (6)
K1—O1Wiii3.060 (4)C6—C71.372 (6)
N1—C51.361 (5)C7—C81.384 (6)
N2—N31.254 (5)C8—C91.395 (6)
N2—C81.416 (5)C9—C101.350 (5)
O1i—K1—O2101.42 (10)O1W—K1—O293.88 (11)
O2W—K1—O291.27 (12)
C8—N2—N3—C11176.9 (4)N3—N2—C8—C7178.5 (4)
C2—N1—C5—C6179.6 (4)N2—N3—C11—C16155.2 (5)
Symmetry codes: (i) x1, y, z; (ii) x+2, y1/2, z; (iii) x+2, y+1/2, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1—HO1···O3iv0.901.842.724 (4)169
O1W—H2O1···O3iv0.902.022.831 (6)148
O1W—H1O1···O4v0.951.882.824 (6)177
O2W—H2O2···O3iv0.941.992.855 (6)152
O2W—H1O2···O4vi0.941.852.785 (5)171
O2—HO2···N2vii1.082.093.108 (6)156
Symmetry codes: (iv) x1, y, z1; (v) x+4, y1/2, z+1; (vi) x+4, y+1/2, z+1; (vii) x+3, y+1/2, z+1.
 

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