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
CCDC references: 153701; 153702
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.
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.
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).
(I) Sodium
4-({4-[
N,
N-bis(2-hydroxyethyl)amino]phenyl}diazenyl)benzoate
3.5-hydrate
top
Crystal data top
Na+·C17H18N3O4−·3.5H2O | Z = 4 |
Mr = 414.39 | F(000) = 876 |
Triclinic, P1 | Dx = 1.372 Mg m−3 |
a = 9.023 (3) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 11.818 (3) Å | Cell parameters from 24 reflections |
c = 19.400 (5) Å | θ = 7.1–9.9° |
α = 99.31 (4)° | µ = 0.13 mm−1 |
β = 99.41 (4)° | T = 293 K |
γ = 93.36 (2)° | Plate, orange |
V = 2006.3 (10) Å3 | 0.6 × 0.4 × 0.1 mm |
Data collection top
Nonius MACH3 diffractometer | Rint = 0.043 |
Radiation source: fine-focus sealed tube | θmax = 24.9°, θmin = 1.1° |
Graphite monochromator | h = −10→10 |
ω/θ scans | k = −14→13 |
7259 measured reflections | l = 0→23 |
7030 independent reflections | 2 standard reflections every 120 min |
4387 reflections with I > 2σ(I) | intensity decay: 6% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.209 | H-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 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
Crystal data top
Na+·C17H18N3O4−·3.5H2O | γ = 93.36 (2)° |
Mr = 414.39 | V = 2006.3 (10) Å3 |
Triclinic, P1 | Z = 4 |
a = 9.023 (3) Å | Mo Kα radiation |
b = 11.818 (3) Å | µ = 0.13 mm−1 |
c = 19.400 (5) Å | T = 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 reflections | 2 standard reflections every 120 min |
7030 independent reflections | intensity decay: 6% |
4387 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.209 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.38 e Å−3 |
7030 reflections | Δρmin = −0.54 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Na1 | 0.31425 (15) | 0.93508 (12) | 0.00863 (7) | 0.0399 (4) | |
Na2 | 0.31211 (15) | 0.54319 (12) | −0.02193 (7) | 0.0414 (4) | |
OW | 0.4395 (3) | 0.7413 (2) | −0.00645 (14) | 0.0462 (7) | |
H1WW | 0.4967 | 0.7500 | 0.0395 | 0.046* | |
H2WW | 0.4603 | 0.7439 | −0.0502 | 0.046* | |
O1WA | 0.0862 (3) | 0.8443 (2) | −0.06666 (14) | 0.0484 (7) | |
HA11 | 0.0827 | 0.8749 | −0.1065 | 0.048* | |
HA21 | 0.1015 | 0.7744 | −0.0678 | 0.048* | |
O2WA | 0.5508 (3) | 1.0210 (2) | 0.08154 (12) | 0.0392 (6) | |
HA12 | 0.5824 | 0.9825 | 0.1216 | 0.039* | |
HA22 | 0.5197 | 1.0781 | 0.1024 | 0.039* | |
O3WA | 0.2089 (3) | 1.1190 (3) | 0.03208 (17) | 0.0684 (9) | |
HA13 | 0.2698 | 1.1644 | 0.0690 | 0.068* | |
HA23 | 0.1212 | 1.1295 | 0.0309 | 0.068* | |
O1WB | 0.4968 (3) | 0.5291 (2) | 0.08580 (13) | 0.0420 (6) | |
HB11 | 0.4779 | 0.4825 | 0.1222 | 0.042* | |
HB21 | 0.4847 | 0.5985 | 0.1089 | 0.042* | |
O2WB | 0.1273 (3) | 0.6269 (2) | 0.04455 (14) | 0.0503 (7) | |
HB12 | 0.1368 | 0.5845 | 0.0834 | 0.050* | |
HB22 | 0.1620 | 0.7032 | 0.0645 | 0.050* | |
O3WB | 0.1867 (4) | 0.3617 (4) | −0.0247 (3) | 0.128 (2) | |
HB13 | 0.1683 | 0.3838 | −0.0659 | 0.128* | |
HB23 | 0.1800 | 0.2952 | −0.0090 | 0.128* | |
O1A | −0.0890 (3) | 1.0637 (3) | 0.19002 (14) | 0.0544 (7) | |
HO1A | −0.1698 | 1.0256 | 0.1748 | 0.054* | |
O2A | 0.2572 (3) | 0.8485 (2) | 0.10858 (12) | 0.0417 (6) | |
HO2A | 0.3479 | 0.8203 | 0.1307 | 0.042* | |
O3A | 0.5448 (3) | 0.7676 (2) | 0.86538 (13) | 0.0430 (6) | |
O4A | 0.5983 (3) | 0.5956 (2) | 0.81752 (14) | 0.0482 (7) | |
N1A | 0.2211 (3) | 1.0501 (3) | 0.27302 (15) | 0.0359 (7) | |
N2A | 0.3314 (4) | 0.8893 (3) | 0.53123 (16) | 0.0444 (8) | |
N3A | 0.4020 (4) | 0.8026 (3) | 0.53558 (16) | 0.0430 (8) | |
C1A | −0.0324 (4) | 1.1233 (3) | 0.2591 (2) | 0.0424 (9) | |
H1A1 | −0.0558 | 1.0770 | 0.2935 | 0.042* | |
H1A2 | −0.0799 | 1.1947 | 0.2673 | 0.042* | |
C2A | 0.1358 (4) | 1.1492 (3) | 0.26837 (19) | 0.0363 (8) | |
H2A1 | 0.1584 | 1.1834 | 0.2287 | 0.036* | |
H2A2 | 0.1689 | 1.2057 | 0.3112 | 0.036* | |
C3A | 0.1842 (4) | 0.8988 (3) | 0.16505 (19) | 0.0398 (9) | |
H3A1 | 0.1643 | 0.8416 | 0.1937 | 0.040* | |
H3A2 | 0.0885 | 0.9240 | 0.1453 | 0.040* | |
C4A | 0.2816 (4) | 1.0001 (3) | 0.21100 (18) | 0.0363 (8) | |
H4A1 | 0.3804 | 0.9756 | 0.2267 | 0.036* | |
H4A2 | 0.2946 | 1.0591 | 0.1825 | 0.036* | |
C5A | 0.2482 (4) | 1.0072 (3) | 0.33512 (18) | 0.0345 (8) | |
C6A | 0.1954 (4) | 1.0587 (3) | 0.39622 (19) | 0.0418 (9) | |
H6A | 0.1393 | 1.1220 | 0.3943 | 0.042* | |
C7A | 0.2255 (5) | 1.0169 (3) | 0.4584 (2) | 0.0445 (9) | |
H7A | 0.1894 | 1.0529 | 0.4978 | 0.045* | |
C8A | 0.3079 (4) | 0.9229 (3) | 0.46448 (19) | 0.0384 (8) | |
C9A | 0.3612 (4) | 0.8715 (3) | 0.4044 (2) | 0.0432 (9) | |
H9A | 0.4181 | 0.8087 | 0.4069 | 0.043* | |
C10A | 0.3313 (4) | 0.9118 (3) | 0.34198 (19) | 0.0409 (9) | |
H10A | 0.3672 | 0.8749 | 0.3027 | 0.041* | |
C11A | 0.4287 (4) | 0.7757 (3) | 0.60524 (18) | 0.0359 (8) | |
C12A | 0.3822 (4) | 0.8405 (3) | 0.66379 (19) | 0.0404 (9) | |
H12A | 0.3261 | 0.9028 | 0.6579 | 0.040* | |
C13A | 0.4197 (4) | 0.8117 (3) | 0.72976 (19) | 0.0355 (8) | |
H13A | 0.3884 | 0.8552 | 0.7683 | 0.035* | |
C14A | 0.5037 (4) | 0.7186 (3) | 0.74023 (18) | 0.0322 (8) | |
C15A | 0.5438 (4) | 0.6524 (3) | 0.68086 (19) | 0.0387 (8) | |
H15A | 0.5956 | 0.5877 | 0.6860 | 0.039* | |
C16A | 0.5073 (5) | 0.6820 (3) | 0.6147 (2) | 0.0447 (9) | |
H16A | 0.5364 | 0.6376 | 0.5758 | 0.045* | |
C17A | 0.5521 (4) | 0.6923 (3) | 0.81244 (18) | 0.0318 (8) | |
O1B | −0.1504 (3) | 0.4932 (2) | −0.15853 (14) | 0.0455 (7) | |
HO1B | −0.2321 | 0.5417 | −0.1634 | 0.045* | |
O2B | 0.1301 (3) | 0.6041 (2) | −0.11419 (13) | 0.0436 (6) | |
HO2B | 0.0338 | 0.5797 | −0.1317 | 0.044* | |
O3B | −0.4896 (3) | 0.7565 (2) | −0.84210 (15) | 0.0514 (7) | |
O4B | −0.3192 (4) | 0.9054 (3) | −0.81746 (17) | 0.0693 (10) | |
N1B | 0.0430 (3) | 0.4580 (3) | −0.27054 (15) | 0.0371 (7) | |
N2B | −0.2023 (4) | 0.6048 (3) | −0.52141 (17) | 0.0486 (8) | |
N3B | −0.1385 (4) | 0.6920 (3) | −0.53646 (17) | 0.0476 (8) | |
C1B | −0.1853 (4) | 0.4065 (3) | −0.2211 (2) | 0.0422 (9) | |
H1B1 | −0.2468 | 0.4368 | −0.2586 | 0.042* | |
H1B2 | −0.2424 | 0.3407 | −0.2112 | 0.042* | |
C2B | −0.0415 (4) | 0.3692 (3) | −0.2451 (2) | 0.0418 (9) | |
H2B1 | 0.0226 | 0.3454 | −0.2058 | 0.042* | |
H2B2 | −0.0668 | 0.3028 | −0.2828 | 0.042* | |
C3B | 0.1762 (5) | 0.6198 (3) | −0.17862 (19) | 0.0456 (10) | |
H3B1 | 0.2741 | 0.6633 | −0.1678 | 0.046* | |
H3B2 | 0.1053 | 0.6649 | −0.2031 | 0.046* | |
C4B | 0.1862 (4) | 0.5087 (3) | −0.22749 (19) | 0.0397 (9) | |
H4B1 | 0.2562 | 0.5227 | −0.2588 | 0.040* | |
H4B2 | 0.2273 | 0.4535 | −0.1992 | 0.040* | |
C5B | −0.0122 (4) | 0.4935 (3) | −0.33279 (19) | 0.0377 (8) | |
C6B | −0.1438 (4) | 0.4389 (3) | −0.3777 (2) | 0.0441 (9) | |
H6B | −0.1930 | 0.3754 | −0.3658 | 0.044* | |
C7B | −0.2005 (5) | 0.4775 (4) | −0.4383 (2) | 0.0477 (10) | |
H7B | −0.2869 | 0.4388 | −0.4673 | 0.048* | |
C8B | −0.1329 (5) | 0.5729 (3) | −0.45788 (19) | 0.0433 (9) | |
C9B | 0.0017 (4) | 0.6251 (3) | −0.4156 (2) | 0.0433 (9) | |
H9B | 0.0524 | 0.6866 | −0.4289 | 0.043* | |
C10B | 0.0594 (4) | 0.5868 (3) | −0.35506 (19) | 0.0397 (9) | |
H10B | 0.1488 | 0.6234 | −0.3276 | 0.040* | |
C11B | −0.2084 (4) | 0.7191 (3) | −0.60297 (19) | 0.0419 (9) | |
C12B | −0.3425 (5) | 0.6663 (4) | −0.6436 (2) | 0.0493 (10) | |
H12B | −0.3965 | 0.6100 | −0.6271 | 0.049* | |
C13B | −0.3971 (4) | 0.6963 (3) | −0.7084 (2) | 0.0438 (9) | |
H13B | −0.4859 | 0.6585 | −0.7357 | 0.044* | |
C14B | −0.3197 (4) | 0.7830 (3) | −0.73297 (19) | 0.0363 (8) | |
C15B | −0.1860 (4) | 0.8363 (3) | −0.6905 (2) | 0.0432 (9) | |
H15B | −0.1329 | 0.8944 | −0.7060 | 0.043* | |
C16B | −0.1317 (5) | 0.8058 (3) | −0.6274 (2) | 0.0472 (10) | |
H16B | −0.0424 | 0.8430 | −0.6003 | 0.047* | |
C17B | −0.3783 (4) | 0.8162 (3) | −0.8023 (2) | 0.0414 (9) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Na1 | 0.0333 (7) | 0.0458 (8) | 0.0411 (8) | −0.0039 (6) | 0.0128 (6) | 0.0052 (6) |
Na2 | 0.0332 (8) | 0.0487 (9) | 0.0453 (8) | 0.0011 (6) | 0.0152 (6) | 0.0092 (7) |
OW | 0.0455 (16) | 0.0506 (16) | 0.0453 (15) | −0.0017 (12) | 0.0157 (12) | 0.0110 (12) |
O1WA | 0.0451 (16) | 0.0466 (15) | 0.0527 (16) | 0.0016 (13) | 0.0137 (13) | 0.0022 (13) |
O2WA | 0.0396 (14) | 0.0449 (15) | 0.0345 (13) | 0.0008 (11) | 0.0107 (11) | 0.0078 (11) |
O3WA | 0.0399 (17) | 0.075 (2) | 0.083 (2) | 0.0083 (15) | 0.0114 (15) | −0.0086 (18) |
O1WB | 0.0456 (15) | 0.0426 (14) | 0.0419 (14) | 0.0026 (12) | 0.0195 (12) | 0.0075 (11) |
O2WB | 0.0520 (17) | 0.0526 (16) | 0.0484 (16) | −0.0071 (13) | 0.0217 (13) | 0.0061 (13) |
O3WB | 0.060 (2) | 0.088 (3) | 0.247 (6) | −0.011 (2) | 0.011 (3) | 0.085 (4) |
O1A | 0.0367 (15) | 0.0706 (19) | 0.0508 (17) | −0.0122 (14) | 0.0039 (13) | 0.0053 (14) |
O2A | 0.0399 (14) | 0.0464 (15) | 0.0391 (14) | 0.0060 (12) | 0.0132 (11) | 0.0011 (12) |
O3A | 0.0499 (16) | 0.0430 (15) | 0.0381 (14) | 0.0026 (12) | 0.0137 (12) | 0.0071 (12) |
O4A | 0.0528 (17) | 0.0501 (16) | 0.0517 (16) | 0.0173 (13) | 0.0218 (13) | 0.0213 (13) |
N1A | 0.0334 (16) | 0.0425 (17) | 0.0335 (16) | 0.0028 (13) | 0.0112 (13) | 0.0061 (13) |
N2A | 0.0491 (19) | 0.0470 (19) | 0.0398 (18) | 0.0075 (16) | 0.0125 (15) | 0.0101 (15) |
N3A | 0.0455 (19) | 0.0481 (19) | 0.0370 (17) | 0.0054 (16) | 0.0103 (14) | 0.0089 (14) |
C1A | 0.041 (2) | 0.042 (2) | 0.047 (2) | 0.0051 (17) | 0.0138 (17) | 0.0097 (17) |
C2A | 0.037 (2) | 0.0365 (19) | 0.0363 (19) | 0.0013 (16) | 0.0076 (16) | 0.0084 (15) |
C3A | 0.035 (2) | 0.043 (2) | 0.044 (2) | 0.0013 (16) | 0.0187 (16) | 0.0042 (17) |
C4A | 0.0349 (19) | 0.041 (2) | 0.0344 (19) | −0.0033 (16) | 0.0129 (15) | 0.0070 (16) |
C5A | 0.0322 (18) | 0.0377 (19) | 0.0335 (19) | −0.0001 (15) | 0.0098 (15) | 0.0030 (15) |
C6A | 0.049 (2) | 0.039 (2) | 0.041 (2) | 0.0132 (17) | 0.0163 (17) | 0.0045 (16) |
C7A | 0.054 (2) | 0.048 (2) | 0.035 (2) | 0.0075 (19) | 0.0187 (18) | 0.0035 (17) |
C8A | 0.039 (2) | 0.042 (2) | 0.035 (2) | 0.0024 (17) | 0.0086 (16) | 0.0085 (16) |
C9A | 0.043 (2) | 0.045 (2) | 0.045 (2) | 0.0118 (17) | 0.0139 (18) | 0.0076 (17) |
C10A | 0.047 (2) | 0.047 (2) | 0.0329 (19) | 0.0118 (18) | 0.0173 (17) | 0.0042 (16) |
C11A | 0.0326 (19) | 0.039 (2) | 0.037 (2) | −0.0012 (15) | 0.0102 (15) | 0.0056 (16) |
C12A | 0.040 (2) | 0.038 (2) | 0.047 (2) | 0.0073 (16) | 0.0152 (17) | 0.0082 (17) |
C13A | 0.0329 (19) | 0.039 (2) | 0.038 (2) | 0.0042 (16) | 0.0171 (15) | 0.0067 (16) |
C14A | 0.0271 (17) | 0.0326 (18) | 0.0380 (19) | −0.0045 (14) | 0.0116 (15) | 0.0064 (15) |
C15A | 0.041 (2) | 0.0332 (19) | 0.044 (2) | 0.0088 (16) | 0.0139 (17) | 0.0048 (16) |
C16A | 0.051 (2) | 0.046 (2) | 0.039 (2) | 0.0081 (19) | 0.0172 (18) | 0.0026 (17) |
C17A | 0.0218 (16) | 0.0333 (19) | 0.043 (2) | −0.0025 (14) | 0.0126 (15) | 0.0101 (16) |
O1B | 0.0314 (14) | 0.0526 (16) | 0.0562 (16) | 0.0048 (12) | 0.0192 (12) | 0.0085 (13) |
O2B | 0.0363 (14) | 0.0578 (16) | 0.0370 (14) | −0.0055 (12) | 0.0120 (11) | 0.0068 (12) |
O3B | 0.0463 (16) | 0.0387 (15) | 0.0611 (18) | −0.0017 (13) | −0.0080 (14) | 0.0048 (13) |
O4B | 0.066 (2) | 0.067 (2) | 0.072 (2) | −0.0225 (17) | −0.0117 (17) | 0.0360 (17) |
N1B | 0.0307 (15) | 0.0439 (17) | 0.0391 (17) | −0.0010 (13) | 0.0137 (13) | 0.0084 (14) |
N2B | 0.052 (2) | 0.051 (2) | 0.0453 (19) | 0.0027 (17) | 0.0183 (16) | 0.0042 (16) |
N3B | 0.054 (2) | 0.0456 (19) | 0.0455 (19) | 0.0040 (16) | 0.0178 (16) | 0.0055 (15) |
C1B | 0.033 (2) | 0.044 (2) | 0.053 (2) | −0.0011 (16) | 0.0157 (17) | 0.0131 (18) |
C2B | 0.048 (2) | 0.0330 (19) | 0.049 (2) | 0.0057 (17) | 0.0173 (18) | 0.0118 (17) |
C3B | 0.050 (2) | 0.049 (2) | 0.039 (2) | −0.0083 (18) | 0.0159 (18) | 0.0069 (17) |
C4B | 0.0307 (19) | 0.052 (2) | 0.039 (2) | 0.0050 (16) | 0.0119 (16) | 0.0106 (17) |
C5B | 0.041 (2) | 0.0342 (19) | 0.041 (2) | 0.0045 (16) | 0.0209 (17) | 0.0024 (16) |
C6B | 0.046 (2) | 0.041 (2) | 0.045 (2) | −0.0057 (18) | 0.0092 (18) | 0.0073 (17) |
C7B | 0.045 (2) | 0.050 (2) | 0.044 (2) | −0.0056 (19) | 0.0051 (18) | 0.0014 (18) |
C8B | 0.053 (2) | 0.047 (2) | 0.032 (2) | 0.0087 (19) | 0.0150 (18) | 0.0031 (16) |
C9B | 0.050 (2) | 0.040 (2) | 0.044 (2) | 0.0018 (18) | 0.0226 (19) | 0.0064 (17) |
C10B | 0.042 (2) | 0.040 (2) | 0.037 (2) | −0.0007 (17) | 0.0140 (16) | 0.0006 (16) |
C11B | 0.049 (2) | 0.042 (2) | 0.037 (2) | 0.0099 (18) | 0.0136 (18) | 0.0036 (16) |
C12B | 0.051 (2) | 0.050 (2) | 0.054 (3) | 0.0015 (19) | 0.025 (2) | 0.015 (2) |
C13B | 0.033 (2) | 0.046 (2) | 0.054 (2) | −0.0008 (17) | 0.0117 (18) | 0.0089 (18) |
C14B | 0.0338 (19) | 0.0325 (18) | 0.044 (2) | 0.0086 (15) | 0.0120 (16) | 0.0051 (16) |
C15B | 0.040 (2) | 0.039 (2) | 0.049 (2) | −0.0043 (17) | 0.0038 (18) | 0.0083 (17) |
C16B | 0.045 (2) | 0.045 (2) | 0.048 (2) | −0.0046 (18) | 0.0037 (19) | 0.0035 (18) |
C17B | 0.039 (2) | 0.035 (2) | 0.051 (2) | 0.0074 (17) | 0.0077 (18) | 0.0091 (17) |
Geometric parameters (Å, º) top
Na1—O2WAi | 2.394 (3) | C9A—C10A | 1.364 (5) |
Na1—O1WA | 2.402 (3) | C11A—C16A | 1.371 (5) |
Na1—O2WA | 2.425 (3) | C11A—C12A | 1.401 (5) |
Na1—O3WA | 2.429 (3) | C12A—C13A | 1.371 (5) |
Na1—O2A | 2.445 (3) | C13A—C14A | 1.396 (5) |
Na1—OW | 2.608 (3) | C14A—C15A | 1.395 (5) |
Na1—Na1i | 3.692 (3) | C14A—C17A | 1.485 (5) |
Na2—O3WB | 2.354 (4) | C15A—C16A | 1.378 (5) |
Na2—O1WBii | 2.402 (3) | O1B—C1B | 1.434 (5) |
Na2—O2WB | 2.431 (3) | O2B—C3B | 1.416 (4) |
Na2—O2B | 2.452 (3) | O3B—C17B | 1.260 (5) |
Na2—O1WB | 2.486 (3) | O4B—C17B | 1.252 (5) |
Na2—OW | 2.498 (3) | N1B—C5B | 1.369 (5) |
Na2—Na2ii | 3.606 (3) | N1B—C4B | 1.456 (5) |
O2WA—Na1i | 2.394 (3) | N1B—C2B | 1.458 (5) |
O1WB—Na2ii | 2.402 (3) | N2B—N3B | 1.249 (5) |
O1A—C1A | 1.408 (5) | N2B—C8B | 1.407 (5) |
O2A—C3A | 1.435 (4) | N3B—C11B | 1.434 (5) |
O3A—C17A | 1.259 (4) | C1B—C2B | 1.514 (5) |
O4A—C17A | 1.252 (4) | C3B—C4B | 1.507 (5) |
N1A—C5A | 1.373 (4) | C5B—C6B | 1.405 (5) |
N1A—C2A | 1.445 (4) | C5B—C10B | 1.408 (5) |
N1A—C4A | 1.455 (4) | C6B—C7B | 1.363 (6) |
N2A—N3A | 1.245 (4) | C7B—C8B | 1.386 (6) |
N2A—C8A | 1.402 (5) | C8B—C9B | 1.397 (6) |
N3A—C11A | 1.424 (5) | C9B—C10B | 1.362 (5) |
C1A—C2A | 1.505 (5) | C11B—C12B | 1.384 (6) |
C3A—C4A | 1.508 (5) | C11B—C16B | 1.391 (6) |
C5A—C10A | 1.402 (5) | C12B—C13B | 1.381 (6) |
C5A—C6A | 1.410 (5) | C13B—C14B | 1.396 (5) |
C6A—C7A | 1.369 (5) | C14B—C15B | 1.396 (5) |
C7A—C8A | 1.382 (5) | C14B—C17B | 1.486 (5) |
C8A—C9A | 1.396 (5) | C15B—C16B | 1.355 (5) |
| | | |
O2WAi—Na1—O1WA | 98.47 (10) | N1A—C5A—C6A | 121.3 (3) |
O2WAi—Na1—O2WA | 79.97 (10) | C10A—C5A—C6A | 116.3 (3) |
O1WA—Na1—O2WA | 177.45 (10) | C7A—C6A—C5A | 121.0 (3) |
O2WAi—Na1—O3WA | 97.28 (11) | C6A—C7A—C8A | 122.2 (3) |
O1WA—Na1—O3WA | 93.13 (11) | C7A—C8A—C9A | 117.3 (3) |
O2WA—Na1—O3WA | 89.07 (11) | C7A—C8A—N2A | 116.4 (3) |
O2WAi—Na1—O2A | 158.56 (11) | C9A—C8A—N2A | 126.3 (3) |
O1WA—Na1—O2A | 92.02 (10) | C10A—C9A—C8A | 121.1 (3) |
O2WA—Na1—O2A | 88.82 (10) | C9A—C10A—C5A | 122.1 (3) |
O3WA—Na1—O2A | 100.78 (11) | C16A—C11A—C12A | 119.1 (3) |
O2WAi—Na1—OW | 84.61 (10) | C16A—C11A—N3A | 117.0 (3) |
O1WA—Na1—OW | 90.62 (10) | C12A—C11A—N3A | 123.9 (3) |
O2WA—Na1—OW | 87.23 (10) | C13A—C12A—C11A | 119.9 (3) |
O3WA—Na1—OW | 175.50 (12) | C12A—C13A—C14A | 121.4 (3) |
O2A—Na1—OW | 76.59 (10) | C15A—C14A—C13A | 117.9 (3) |
O2WAi—Na1—Na1i | 40.29 (7) | C15A—C14A—C17A | 121.0 (3) |
O1WA—Na1—Na1i | 138.73 (9) | C13A—C14A—C17A | 121.1 (3) |
O2WA—Na1—Na1i | 39.67 (6) | C16A—C15A—C14A | 120.7 (3) |
O3WA—Na1—Na1i | 94.10 (10) | C11A—C16A—C15A | 121.0 (3) |
O2A—Na1—Na1i | 126.15 (10) | O4A—C17A—O3A | 123.2 (3) |
OW—Na1—Na1i | 84.68 (8) | O4A—C17A—C14A | 118.0 (3) |
O3WB—Na2—O1WBii | 95.50 (15) | O3A—C17A—C14A | 118.8 (3) |
O3WB—Na2—O2WB | 87.68 (15) | C3B—O2B—Na2 | 118.8 (2) |
O1WBii—Na2—O2WB | 176.74 (11) | C5B—N1B—C4B | 121.2 (3) |
O3WB—Na2—O2B | 97.04 (14) | C5B—N1B—C2B | 120.7 (3) |
O1WBii—Na2—O2B | 102.91 (10) | C4B—N1B—C2B | 118.2 (3) |
O2WB—Na2—O2B | 77.37 (10) | N3B—N2B—C8B | 114.3 (4) |
O3WB—Na2—O1WB | 93.13 (15) | N2B—N3B—C11B | 112.8 (3) |
O1WBii—Na2—O1WB | 84.91 (10) | O1B—C1B—C2B | 110.2 (3) |
O2WB—Na2—O1WB | 94.20 (10) | N1B—C2B—C1B | 114.1 (3) |
O2B—Na2—O1WB | 166.46 (11) | O2B—C3B—C4B | 113.7 (3) |
O3WB—Na2—OW | 174.15 (17) | N1B—C4B—C3B | 114.4 (3) |
O1WBii—Na2—OW | 89.15 (10) | N1B—C5B—C6B | 121.7 (3) |
O2WB—Na2—OW | 87.63 (10) | N1B—C5B—C10B | 121.8 (3) |
O2B—Na2—OW | 85.33 (10) | C6B—C5B—C10B | 116.5 (3) |
O1WB—Na2—OW | 83.73 (10) | C7B—C6B—C5B | 121.1 (4) |
O3WB—Na2—Na2ii | 95.83 (12) | C6B—C7B—C8B | 121.7 (4) |
O1WBii—Na2—Na2ii | 43.35 (7) | C7B—C8B—C9B | 117.9 (4) |
O2WB—Na2—Na2ii | 135.67 (10) | C7B—C8B—N2B | 116.5 (4) |
O2B—Na2—Na2ii | 144.97 (9) | C9B—C8B—N2B | 125.5 (4) |
O1WB—Na2—Na2ii | 41.55 (7) | C10B—C9B—C8B | 120.6 (4) |
OW—Na2—Na2ii | 85.12 (8) | C9B—C10B—C5B | 122.0 (4) |
Na2—OW—Na1 | 127.10 (11) | C12B—C11B—C16B | 118.8 (4) |
Na1i—O2WA—Na1 | 100.03 (10) | C12B—C11B—N3B | 125.5 (4) |
Na2ii—O1WB—Na2 | 95.09 (10) | C16B—C11B—N3B | 115.7 (4) |
C3A—O2A—Na1 | 127.4 (2) | C13B—C12B—C11B | 120.8 (4) |
C5A—N1A—C2A | 120.6 (3) | C12B—C13B—C14B | 120.4 (4) |
C5A—N1A—C4A | 121.2 (3) | C13B—C14B—C15B | 117.8 (3) |
C2A—N1A—C4A | 118.2 (3) | C13B—C14B—C17B | 120.7 (3) |
N3A—N2A—C8A | 115.8 (3) | C15B—C14B—C17B | 121.5 (3) |
N2A—N3A—C11A | 113.4 (3) | C16B—C15B—C14B | 121.7 (4) |
O1A—C1A—C2A | 110.0 (3) | C15B—C16B—C11B | 120.5 (4) |
N1A—C2A—C1A | 114.5 (3) | O4B—C17B—O3B | 122.6 (4) |
O2A—C3A—C4A | 110.7 (3) | O4B—C17B—C14B | 118.5 (3) |
N1A—C4A—C3A | 114.1 (3) | O3B—C17B—C14B | 118.8 (3) |
N1A—C5A—C10A | 122.4 (3) | | |
| | | |
O1WBii—Na2—OW—Na1 | 152.36 (14) | C17A—C14A—C15A—C16A | −175.6 (3) |
O2WB—Na2—OW—Na1 | −28.18 (15) | C12A—C11A—C16A—C15A | −1.5 (6) |
O2B—Na2—OW—Na1 | 49.33 (15) | N3A—C11A—C16A—C15A | 177.2 (3) |
O1WB—Na2—OW—Na1 | −122.67 (15) | C14A—C15A—C16A—C11A | −1.1 (6) |
Na2ii—Na2—OW—Na1 | −164.41 (13) | C15A—C14A—C17A—O4A | −16.3 (5) |
O2WAi—Na1—OW—Na2 | −131.31 (15) | C13A—C14A—C17A—O4A | 165.1 (3) |
O1WA—Na1—OW—Na2 | −32.86 (15) | C15A—C14A—C17A—O3A | 163.7 (3) |
O2WA—Na1—OW—Na2 | 148.52 (14) | C13A—C14A—C17A—O3A | −14.8 (5) |
O2A—Na1—OW—Na2 | 59.07 (15) | O3WB—Na2—O2B—C3B | −114.4 (3) |
Na1i—Na1—OW—Na2 | −171.79 (13) | O1WBii—Na2—O2B—C3B | −17.1 (3) |
O3WA—Na1—O2WA—Na1i | −97.56 (12) | O2WB—Na2—O2B—C3B | 159.6 (3) |
O2A—Na1—O2WA—Na1i | 161.64 (11) | O1WB—Na2—O2B—C3B | 107.2 (4) |
OW—Na1—O2WA—Na1i | 85.01 (10) | OW—Na2—O2B—C3B | 71.0 (2) |
O3WB—Na2—O1WB—Na2ii | 95.25 (16) | Na2ii—Na2—O2B—C3B | −3.6 (3) |
O2WB—Na2—O1WB—Na2ii | −176.85 (11) | C8B—N2B—N3B—C11B | 177.5 (3) |
O2B—Na2—O1WB—Na2ii | −126.0 (4) | C5B—N1B—C2B—C1B | −69.0 (4) |
OW—Na2—O1WB—Na2ii | −89.71 (10) | C4B—N1B—C2B—C1B | 110.1 (4) |
O2WAi—Na1—O2A—C3A | 145.5 (3) | O1B—C1B—C2B—N1B | −67.1 (4) |
O1WA—Na1—O2A—C3A | −95.0 (3) | Na2—O2B—C3B—C4B | 75.5 (4) |
O2WA—Na1—O2A—C3A | 87.4 (3) | C5B—N1B—C4B—C3B | 83.4 (4) |
O3WA—Na1—O2A—C3A | −1.4 (3) | C2B—N1B—C4B—C3B | −95.8 (4) |
OW—Na1—O2A—C3A | 174.9 (3) | O2B—C3B—C4B—N1B | 82.6 (4) |
Na1i—Na1—O2A—C3A | 101.9 (3) | C4B—N1B—C5B—C6B | 174.7 (3) |
C8A—N2A—N3A—C11A | 177.2 (3) | C2B—N1B—C5B—C6B | −6.2 (5) |
C5A—N1A—C2A—C1A | −78.8 (4) | C4B—N1B—C5B—C10B | −5.6 (5) |
C4A—N1A—C2A—C1A | 103.3 (4) | C2B—N1B—C5B—C10B | 173.6 (3) |
O1A—C1A—C2A—N1A | −72.3 (4) | N1B—C5B—C6B—C7B | 177.7 (3) |
Na1—O2A—C3A—C4A | −66.7 (4) | C10B—C5B—C6B—C7B | −2.0 (5) |
C5A—N1A—C4A—C3A | 85.9 (4) | C5B—C6B—C7B—C8B | −1.1 (6) |
C2A—N1A—C4A—C3A | −96.3 (4) | C6B—C7B—C8B—C9B | 3.8 (6) |
O2A—C3A—C4A—N1A | −175.2 (3) | C6B—C7B—C8B—N2B | −179.6 (4) |
C2A—N1A—C5A—C10A | −179.5 (3) | N3B—N2B—C8B—C7B | 179.2 (3) |
C4A—N1A—C5A—C10A | −1.8 (5) | N3B—N2B—C8B—C9B | −4.6 (5) |
C2A—N1A—C5A—C6A | −0.6 (5) | C7B—C8B—C9B—C10B | −3.5 (5) |
C4A—N1A—C5A—C6A | 177.1 (3) | N2B—C8B—C9B—C10B | −179.7 (3) |
N1A—C5A—C6A—C7A | −178.6 (4) | C8B—C9B—C10B—C5B | 0.5 (5) |
C10A—C5A—C6A—C7A | 0.3 (5) | N1B—C5B—C10B—C9B | −177.5 (3) |
C5A—C6A—C7A—C8A | −0.2 (6) | C6B—C5B—C10B—C9B | 2.3 (5) |
C6A—C7A—C8A—C9A | 0.4 (6) | N2B—N3B—C11B—C12B | 7.8 (5) |
C6A—C7A—C8A—N2A | 179.6 (4) | N2B—N3B—C11B—C16B | −171.9 (3) |
N3A—N2A—C8A—C7A | 178.1 (3) | C16B—C11B—C12B—C13B | 2.0 (6) |
N3A—N2A—C8A—C9A | −2.8 (6) | N3B—C11B—C12B—C13B | −177.6 (3) |
C7A—C8A—C9A—C10A | −0.8 (6) | C11B—C12B—C13B—C14B | −1.8 (6) |
N2A—C8A—C9A—C10A | −179.9 (4) | C12B—C13B—C14B—C15B | 0.7 (5) |
C8A—C9A—C10A—C5A | 1.0 (6) | C12B—C13B—C14B—C17B | −179.6 (3) |
N1A—C5A—C10A—C9A | 178.2 (4) | C13B—C14B—C15B—C16B | 0.1 (5) |
C6A—C5A—C10A—C9A | −0.7 (6) | C17B—C14B—C15B—C16B | −179.6 (3) |
N2A—N3A—C11A—C16A | −179.4 (3) | C14B—C15B—C16B—C11B | 0.1 (6) |
N2A—N3A—C11A—C12A | −0.7 (5) | C12B—C11B—C16B—C15B | −1.2 (6) |
C16A—C11A—C12A—C13A | 2.0 (5) | N3B—C11B—C16B—C15B | 178.5 (3) |
N3A—C11A—C12A—C13A | −176.6 (3) | C13B—C14B—C17B—O4B | 169.1 (4) |
C11A—C12A—C13A—C14A | 0.0 (5) | C15B—C14B—C17B—O4B | −11.2 (5) |
C12A—C13A—C14A—C15A | −2.5 (5) | C13B—C14B—C17B—O3B | −7.8 (5) |
C12A—C13A—C14A—C17A | 176.1 (3) | C15B—C14B—C17B—O3B | 171.9 (3) |
C13A—C14A—C15A—C16A | 3.0 (5) | | |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
OW—H1WW···O3Biii | 0.94 | 2.27 | 3.121 (4) | 150 |
OW—H2WW···O3Aiv | 0.90 | 1.97 | 2.858 (4) | 168 |
O1WA—HA11···O1Av | 0.90 | 1.89 | 2.787 (4) | 176 |
O1WA—HA21···O2B | 0.84 | 2.12 | 2.910 (4) | 157 |
O2WA—HA12···O4Biii | 0.97 | 1.77 | 2.717 (4) | 165 |
O2WA—HA22···O3Avi | 0.82 | 1.98 | 2.785 (4) | 167 |
O3WA—HA13···O3Avi | 0.90 | 1.97 | 2.835 (4) | 160 |
O3WA—HA23···O1WAv | 0.80 | 2.12 | 2.890 (4) | 160 |
O2WB—HB12···O1Bvii | 0.97 | 1.84 | 2.801 (4) | 178 |
O2WB—HB22···O2A | 0.94 | 1.88 | 2.809 (4) | 172 |
O1WB—HB11···O4Aviii | 0.99 | 1.80 | 2.775 (4) | 168 |
O1WB—HB21···O3Biii | 0.89 | 1.94 | 2.808 (4) | 166 |
O1A—HO1A···O4Bix | 0.82 | 1.94 | 2.682 (4) | 150 |
O2A—HO2A···O3Biii | 0.96 | 1.73 | 2.689 (4) | 171 |
O1B—HO1B···O4Ax | 0.96 | 1.70 | 2.642 (4) | 165 |
O2B—HO2B···O1B | 0.89 | 1.85 | 2.720 (4) | 164 |
Symmetry codes: (iii) x+1, y, z+1; (iv) x, y, z−1; (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) x−1, y, z−1. |
(II) Potassium 4-(4-bis(hydroxyethyl)amino-phenylazo)benzoate dihydrate
top
Crystal data top
K+·C17H18N3O4−·2H2O | F(000) = 424 |
Mr = 403.48 | Dx = 1.446 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71069 Å |
a = 8.238 (8) Å | Cell parameters from 24 reflections |
b = 7.498 (6) Å | θ = 7.3–8.6° |
c = 15.016 (8) Å | µ = 0.33 mm−1 |
β = 92.81 (5)° | T = 293 K |
V = 926.4 (13) Å3 | Plate, orange |
Z = 2 | 0.3 × 0.3 × 0.1 mm |
Data collection top
Nonius MACH3 diffractometer | Rint = 0.035 |
Radiation source: fine-focus sealed tube | θmax = 24.9°, θmin = 1.4° |
Graphite monochromator | h = −9→9 |
ω/θ scans | k = 0→8 |
1927 measured reflections | l = 0→17 |
1757 independent reflections | 2 standard reflections every 120 min |
1427 reflections with I > 2σ(I) | intensity decay: 0.1% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H-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 reflections | Δρmax = 0.23 e Å−3 |
244 parameters | Δρmin = −0.21 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (9) |
Crystal data top
K+·C17H18N3O4−·2H2O | V = 926.4 (13) Å3 |
Mr = 403.48 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.238 (8) Å | µ = 0.33 mm−1 |
b = 7.498 (6) Å | T = 293 K |
c = 15.016 (8) Å | 0.3 × 0.3 × 0.1 mm |
β = 92.81 (5)° | |
Data collection top
Nonius MACH3 diffractometer | Rint = 0.035 |
1927 measured reflections | 2 standard reflections every 120 min |
1757 independent reflections | intensity decay: 0.1% |
1427 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.104 | Δρmax = 0.23 e Å−3 |
S = 1.03 | Δρmin = −0.21 e Å−3 |
1757 reflections | Absolute structure: Flack (1983) |
244 parameters | Absolute 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 | x | y | z | Uiso*/Ueq | |
K1 | 0.96028 (11) | 0.27467 (19) | 0.09027 (7) | 0.0464 (3) | |
N1 | 1.4270 (4) | 0.1932 (6) | 0.3088 (2) | 0.0302 (9) | |
N2 | 1.8681 (4) | 0.1598 (5) | 0.6035 (2) | 0.0307 (9) | |
N3 | 1.9994 (4) | 0.2415 (6) | 0.5956 (2) | 0.0366 (10) | |
O1 | 1.6378 (3) | 0.3076 (5) | 0.10467 (18) | 0.0407 (9) | |
HO1 | 1.5742 | 0.2912 | 0.0552 | 0.041* | |
O2 | 1.0809 (4) | 0.3217 (5) | 0.2787 (2) | 0.0462 (9) | |
HO2 | 1.1047 | 0.4556 | 0.3021 | 0.046* | |
O3 | 2.4117 (4) | 0.2497 (6) | 0.96932 (19) | 0.0447 (9) | |
O4 | 2.6068 (3) | 0.2448 (6) | 0.8718 (2) | 0.0441 (9) | |
O1W | 1.1946 (4) | 0.0187 (6) | 0.0535 (2) | 0.0480 (10) | |
H1O1 | 1.2579 | −0.0758 | 0.0787 | 0.048* | |
H2O1 | 1.2694 | 0.0537 | 0.0149 | 0.048* | |
O2W | 1.1908 (4) | 0.5088 (6) | 0.0322 (3) | 0.0521 (11) | |
H1O2 | 1.2496 | 0.5916 | 0.0678 | 0.052* | |
H2O2 | 1.2795 | 0.4302 | 0.0300 | 0.052* | |
C1 | 1.5814 (5) | 0.1951 (7) | 0.1714 (3) | 0.0336 (11) | |
H1A | 1.6729 | 0.1521 | 0.2085 | 0.034* | |
H1B | 1.5270 | 0.0928 | 0.1440 | 0.034* | |
C2 | 1.4634 (5) | 0.2948 (7) | 0.2292 (2) | 0.0300 (10) | |
H2A | 1.5104 | 0.4088 | 0.2470 | 0.030* | |
H2B | 1.3632 | 0.3179 | 0.1945 | 0.030* | |
C3 | 1.1328 (5) | 0.1797 (7) | 0.3363 (3) | 0.0394 (12) | |
H3A | 1.0445 | 0.0952 | 0.3412 | 0.039* | |
H3B | 1.1596 | 0.2270 | 0.3953 | 0.039* | |
C4 | 1.2778 (5) | 0.0852 (7) | 0.3029 (3) | 0.0306 (10) | |
H4A | 1.2959 | −0.0234 | 0.3371 | 0.031* | |
H4B | 1.2550 | 0.0513 | 0.2412 | 0.031* | |
C5 | 1.5337 (5) | 0.1858 (6) | 0.3808 (3) | 0.0276 (10) | |
C6 | 1.5021 (5) | 0.0901 (7) | 0.4586 (3) | 0.0290 (10) | |
H6 | 1.4039 | 0.0297 | 0.4620 | 0.029* | |
C7 | 1.6132 (5) | 0.0840 (7) | 0.5296 (3) | 0.0307 (10) | |
H7 | 1.5897 | 0.0185 | 0.5799 | 0.031* | |
C8 | 1.7598 (5) | 0.1738 (7) | 0.5276 (3) | 0.0287 (10) | |
C9 | 1.7902 (4) | 0.2756 (8) | 0.4525 (2) | 0.0295 (9) | |
H9 | 1.8860 | 0.3410 | 0.4512 | 0.029* | |
C10 | 1.6831 (4) | 0.2809 (7) | 0.3816 (2) | 0.0280 (9) | |
H10 | 1.7076 | 0.3483 | 0.3320 | 0.028* | |
C11 | 2.1066 (5) | 0.2367 (6) | 0.6732 (3) | 0.0309 (11) | |
C12 | 2.0551 (5) | 0.2224 (6) | 0.7597 (3) | 0.0342 (11) | |
H12 | 1.9450 | 0.2124 | 0.7700 | 0.034* | |
C13 | 2.1686 (5) | 0.2231 (7) | 0.8297 (3) | 0.0374 (12) | |
H13 | 2.1350 | 0.2127 | 0.8877 | 0.037* | |
C14 | 2.3353 (5) | 0.2394 (6) | 0.8149 (3) | 0.0299 (10) | |
C15 | 2.3820 (5) | 0.2553 (7) | 0.7284 (3) | 0.0341 (10) | |
H15 | 2.4919 | 0.2636 | 0.7176 | 0.034* | |
C16 | 2.2696 (5) | 0.2590 (8) | 0.6583 (3) | 0.0348 (10) | |
H16 | 2.3029 | 0.2765 | 0.6006 | 0.035* | |
C17 | 2.4600 (5) | 0.2432 (7) | 0.8909 (3) | 0.0345 (11) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
K1 | 0.0303 (5) | 0.0551 (7) | 0.0538 (6) | 0.0007 (6) | 0.0018 (4) | 0.0001 (7) |
N1 | 0.0241 (18) | 0.042 (2) | 0.0241 (18) | −0.0056 (18) | −0.0012 (15) | 0.0032 (17) |
N2 | 0.031 (2) | 0.035 (2) | 0.0249 (19) | 0.0005 (19) | −0.0044 (15) | −0.0026 (17) |
N3 | 0.0334 (19) | 0.044 (3) | 0.0313 (18) | −0.003 (2) | −0.0068 (15) | 0.004 (2) |
O1 | 0.0361 (16) | 0.061 (3) | 0.0248 (15) | −0.0094 (18) | −0.0006 (12) | 0.0023 (17) |
O2 | 0.0409 (18) | 0.042 (2) | 0.055 (2) | 0.0068 (17) | −0.0029 (16) | 0.0009 (19) |
O3 | 0.0447 (17) | 0.057 (3) | 0.0314 (16) | −0.003 (2) | −0.0088 (13) | 0.0013 (19) |
O4 | 0.0307 (16) | 0.054 (2) | 0.0463 (17) | −0.0002 (19) | −0.0099 (14) | 0.0013 (19) |
O1W | 0.033 (2) | 0.061 (3) | 0.051 (2) | 0.0126 (19) | 0.0052 (16) | 0.0064 (19) |
O2W | 0.029 (2) | 0.057 (3) | 0.069 (3) | −0.0082 (19) | −0.0089 (17) | −0.003 (2) |
C1 | 0.039 (2) | 0.035 (3) | 0.026 (2) | 0.000 (2) | −0.0010 (19) | 0.000 (2) |
C2 | 0.032 (2) | 0.033 (3) | 0.0250 (19) | −0.004 (2) | 0.0005 (16) | 0.006 (2) |
C3 | 0.030 (2) | 0.048 (3) | 0.040 (3) | −0.005 (2) | 0.006 (2) | 0.001 (3) |
C4 | 0.030 (2) | 0.031 (3) | 0.030 (2) | −0.002 (2) | −0.0010 (18) | 0.000 (2) |
C5 | 0.027 (2) | 0.029 (2) | 0.027 (2) | −0.002 (2) | 0.0048 (18) | −0.004 (2) |
C6 | 0.023 (2) | 0.033 (3) | 0.032 (2) | −0.006 (2) | 0.0031 (18) | 0.002 (2) |
C7 | 0.032 (2) | 0.034 (3) | 0.026 (2) | −0.002 (2) | −0.0025 (18) | 0.006 (2) |
C8 | 0.025 (2) | 0.037 (3) | 0.024 (2) | 0.002 (2) | −0.0016 (17) | 0.000 (2) |
C9 | 0.0225 (18) | 0.036 (2) | 0.030 (2) | −0.001 (2) | 0.0028 (16) | −0.005 (2) |
C10 | 0.0272 (19) | 0.033 (2) | 0.0240 (19) | −0.001 (2) | 0.0049 (16) | 0.004 (2) |
C11 | 0.034 (2) | 0.033 (3) | 0.025 (2) | −0.002 (2) | −0.0068 (17) | −0.005 (2) |
C12 | 0.028 (2) | 0.037 (3) | 0.037 (2) | −0.002 (2) | −0.0034 (18) | −0.001 (2) |
C13 | 0.034 (2) | 0.051 (4) | 0.027 (2) | −0.002 (2) | −0.0009 (18) | −0.002 (2) |
C14 | 0.035 (2) | 0.022 (2) | 0.032 (2) | 0.000 (2) | −0.0064 (18) | 0.001 (2) |
C15 | 0.031 (2) | 0.037 (3) | 0.035 (2) | −0.003 (2) | 0.0013 (17) | 0.004 (2) |
C16 | 0.041 (2) | 0.038 (3) | 0.026 (2) | −0.005 (3) | 0.0032 (17) | −0.003 (3) |
C17 | 0.038 (2) | 0.028 (3) | 0.036 (2) | −0.003 (2) | −0.0082 (19) | 0.001 (2) |
Geometric parameters (Å, º) top
K1—O1i | 2.687 (4) | O4—C17 | 1.256 (5) |
K1—O2W | 2.759 (4) | O1W—K1ii | 3.060 (4) |
K1—O1W | 2.796 (4) | O2W—K1iii | 2.946 (5) |
K1—O2Wii | 2.946 (5) | C1—C2 | 1.530 (6) |
K1—O2 | 2.974 (4) | C1—K1iv | 3.458 (5) |
K1—O1Wiii | 3.060 (4) | C3—C4 | 1.497 (6) |
K1—C1i | 3.458 (5) | C5—C6 | 1.407 (6) |
K1—K1ii | 4.691 (3) | C5—C10 | 1.421 (6) |
K1—K1iii | 4.691 (3) | C6—C7 | 1.372 (6) |
N1—C5 | 1.361 (5) | C7—C8 | 1.384 (6) |
N1—C2 | 1.460 (5) | C8—C9 | 1.395 (6) |
N1—C4 | 1.471 (6) | C9—C10 | 1.350 (5) |
N2—N3 | 1.254 (5) | C11—C16 | 1.383 (6) |
N2—C8 | 1.416 (5) | C11—C12 | 1.390 (6) |
N3—C11 | 1.428 (5) | C12—C13 | 1.372 (6) |
O1—C1 | 1.407 (6) | C13—C14 | 1.407 (6) |
O1—K1iv | 2.687 (4) | C14—C15 | 1.377 (6) |
O2—C3 | 1.424 (6) | C14—C17 | 1.498 (6) |
O3—C17 | 1.262 (5) | C15—C16 | 1.368 (6) |
| | | |
O1i—K1—O2W | 131.71 (13) | C5—N1—C4 | 122.1 (4) |
O1i—K1—O1W | 140.70 (13) | C2—N1—C4 | 116.2 (3) |
O2W—K1—O1W | 83.21 (13) | N3—N2—C8 | 113.5 (4) |
O1i—K1—O2Wii | 73.95 (12) | N2—N3—C11 | 114.3 (4) |
O2W—K1—O2Wii | 120.63 (7) | C1—O1—K1iv | 111.4 (3) |
O1W—K1—O2Wii | 71.75 (12) | C3—O2—K1 | 124.5 (3) |
O1i—K1—O2 | 101.42 (10) | K1—O1W—K1ii | 106.36 (13) |
O2W—K1—O2 | 91.27 (12) | K1—O2W—K1iii | 110.59 (13) |
O1W—K1—O2 | 93.88 (11) | O1—C1—C2 | 110.7 (4) |
O2Wii—K1—O2 | 141.76 (12) | O1—C1—K1iv | 46.35 (19) |
O1i—K1—O1Wiii | 67.79 (11) | C2—C1—K1iv | 136.5 (3) |
O2W—K1—O1Wiii | 70.50 (12) | N1—C2—C1 | 111.8 (4) |
O1W—K1—O1Wiii | 122.62 (7) | O2—C3—C4 | 111.8 (4) |
O2Wii—K1—O1Wiii | 79.37 (12) | N1—C4—C3 | 113.4 (4) |
O2—K1—O1Wiii | 135.12 (12) | N1—C5—C6 | 122.8 (4) |
O1i—K1—C1i | 22.26 (11) | N1—C5—C10 | 120.7 (4) |
O2W—K1—C1i | 150.27 (13) | C6—C5—C10 | 116.4 (4) |
O1W—K1—C1i | 126.52 (14) | C7—C6—C5 | 121.2 (4) |
O2Wii—K1—C1i | 75.07 (12) | C6—C7—C8 | 121.1 (4) |
O2—K1—C1i | 87.16 (11) | C7—C8—C9 | 118.4 (4) |
O1Wiii—K1—C1i | 89.96 (12) | C7—C8—N2 | 117.5 (4) |
O1i—K1—K1ii | 106.64 (9) | C9—C8—N2 | 124.1 (4) |
O2W—K1—K1ii | 102.03 (11) | C10—C9—C8 | 121.2 (4) |
O1W—K1—K1ii | 38.76 (9) | C9—C10—C5 | 121.6 (4) |
O2Wii—K1—K1ii | 33.40 (8) | C16—C11—C12 | 120.3 (4) |
O2—K1—K1ii | 126.52 (8) | C16—C11—N3 | 115.5 (4) |
O1Wiii—K1—K1ii | 97.79 (10) | C12—C11—N3 | 124.0 (4) |
C1i—K1—K1ii | 102.69 (9) | C13—C12—C11 | 119.2 (4) |
O1i—K1—K1iii | 98.01 (9) | C12—C13—C14 | 120.9 (4) |
O2W—K1—K1iii | 36.01 (9) | C15—C14—C13 | 118.4 (4) |
O1W—K1—K1iii | 108.48 (11) | C15—C14—C17 | 120.2 (4) |
O2Wii—K1—K1iii | 104.27 (10) | C13—C14—C17 | 121.3 (4) |
O2—K1—K1iii | 113.93 (9) | C16—C15—C14 | 121.2 (4) |
O1Wiii—K1—K1iii | 34.89 (8) | C15—C16—C11 | 119.9 (4) |
C1i—K1—K1iii | 119.70 (9) | O4—C17—O3 | 124.3 (4) |
K1ii—K1—K1iii | 106.10 (7) | O4—C17—C14 | 117.2 (4) |
C5—N1—C2 | 121.4 (3) | O3—C17—C14 | 118.4 (4) |
| | | |
C8—N2—N3—C11 | 176.9 (4) | C2—N1—C5—C6 | 179.6 (4) |
O1i—K1—O2—C3 | 102.6 (3) | C4—N1—C5—C6 | −6.9 (7) |
O2W—K1—O2—C3 | −124.3 (3) | C2—N1—C5—C10 | 1.5 (6) |
O1W—K1—O2—C3 | −41.0 (3) | C4—N1—C5—C10 | 174.9 (4) |
O2Wii—K1—O2—C3 | 24.1 (4) | N1—C5—C6—C7 | 179.3 (4) |
O1Wiii—K1—O2—C3 | 172.5 (3) | C10—C5—C6—C7 | −2.5 (7) |
C1i—K1—O2—C3 | 85.4 (3) | C5—C6—C7—C8 | 0.8 (7) |
K1ii—K1—O2—C3 | −18.3 (3) | C6—C7—C8—C9 | 1.9 (7) |
K1iii—K1—O2—C3 | −153.2 (3) | C6—C7—C8—N2 | −179.7 (4) |
O1i—K1—O1W—K1ii | 36.9 (2) | N3—N2—C8—C7 | 178.5 (4) |
O2W—K1—O1W—K1ii | −118.92 (15) | N3—N2—C8—C9 | −3.2 (6) |
O2Wii—K1—O1W—K1ii | 6.50 (13) | C7—C8—C9—C10 | −2.9 (7) |
O2—K1—O1W—K1ii | 150.26 (12) | N2—C8—C9—C10 | 178.8 (5) |
O1Wiii—K1—O1W—K1ii | −57.3 (2) | C8—C9—C10—C5 | 1.1 (8) |
C1i—K1—O1W—K1ii | 60.93 (17) | N1—C5—C10—C9 | 179.8 (5) |
K1iii—K1—O1W—K1ii | −92.91 (12) | C6—C5—C10—C9 | 1.6 (7) |
O1i—K1—O2W—K1iii | −24.7 (2) | N2—N3—C11—C16 | 155.2 (5) |
O1W—K1—O2W—K1iii | 134.98 (16) | N2—N3—C11—C12 | −28.8 (7) |
O2Wii—K1—O2W—K1iii | 70.9 (2) | C16—C11—C12—C13 | −2.7 (7) |
O2—K1—O2W—K1iii | −131.27 (14) | N3—C11—C12—C13 | −178.5 (5) |
O1Wiii—K1—O2W—K1iii | 6.81 (13) | C11—C12—C13—C14 | 0.5 (8) |
C1i—K1—O2W—K1iii | −44.8 (3) | C12—C13—C14—C15 | 0.2 (8) |
K1ii—K1—O2W—K1iii | 100.91 (13) | C12—C13—C14—C17 | 179.0 (5) |
K1iv—O1—C1—C2 | 135.4 (3) | C13—C14—C15—C16 | 1.3 (8) |
C5—N1—C2—C1 | 77.9 (5) | C17—C14—C15—C16 | −177.5 (5) |
C4—N1—C2—C1 | −95.9 (4) | C14—C15—C16—C11 | −3.6 (8) |
O1—C1—C2—N1 | −169.1 (3) | C12—C11—C16—C15 | 4.3 (8) |
K1iv—C1—C2—N1 | −121.5 (4) | N3—C11—C16—C15 | −179.6 (5) |
K1—O2—C3—C4 | 62.8 (5) | C15—C14—C17—O4 | −6.4 (7) |
C5—N1—C4—C3 | 92.7 (5) | C13—C14—C17—O4 | 174.9 (5) |
C2—N1—C4—C3 | −93.5 (5) | C15—C14—C17—O3 | 171.7 (5) |
O2—C3—C4—N1 | 69.6 (5) | C13—C14—C17—O3 | −7.1 (7) |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, y−1/2, −z; (iii) −x+2, y+1/2, −z; (iv) x+1, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—HO1···O3v | 0.90 | 1.84 | 2.724 (4) | 169 |
O1W—H2O1···O3v | 0.90 | 2.02 | 2.831 (6) | 148 |
O1W—H1O1···O4vi | 0.95 | 1.88 | 2.824 (6) | 177 |
O2W—H2O2···O3v | 0.94 | 1.99 | 2.855 (6) | 152 |
O2W—H1O2···O4vii | 0.94 | 1.85 | 2.785 (5) | 171 |
O2—HO2···N2viii | 1.08 | 2.09 | 3.108 (6) | 156 |
Symmetry codes: (v) x−1, y, z−1; (vi) −x+4, y−1/2, −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 formula | Na+·C17H18N3O4−·3.5H2O | K+·C17H18N3O4−·2H2O |
Mr | 414.39 | 403.48 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21 |
Temperature (K) | 293 | 293 |
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 |
V (Å3) | 2006.3 (10) | 926.4 (13) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.13 | 0.33 |
Crystal size (mm) | 0.6 × 0.4 × 0.1 | 0.3 × 0.3 × 0.1 |
|
Data collection |
Diffractometer | Nonius MACH3 diffractometer | Nonius MACH3 diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7259, 7030, 4387 | 1927, 1757, 1427 |
Rint | 0.043 | 0.035 |
(sin θ/λ)max (Å−1) | 0.593 | 0.592 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.209, 1.00 | 0.039, 0.104, 1.03 |
No. of reflections | 7030 | 1757 |
No. of parameters | 514 | 244 |
No. of restraints | 0 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.54 | 0.23, −0.21 |
Absolute structure | ? | Flack (1983) |
Absolute structure parameter | ? | −0.03 (9) |
Selected geometric parameters (Å, º) for (I) topNa1—O2WAi | 2.394 (3) | C5A—C10A | 1.402 (5) |
Na1—O1WA | 2.402 (3) | C5A—C6A | 1.410 (5) |
Na1—O2WA | 2.425 (3) | C6A—C7A | 1.369 (5) |
Na1—O3WA | 2.429 (3) | C7A—C8A | 1.382 (5) |
Na1—O2A | 2.445 (3) | C8A—C9A | 1.396 (5) |
Na1—OW | 2.608 (3) | C9A—C10A | 1.364 (5) |
Na2—O3WB | 2.354 (4) | O3B—C17B | 1.260 (5) |
Na2—O1WBii | 2.402 (3) | O4B—C17B | 1.252 (5) |
Na2—O2WB | 2.431 (3) | N1B—C5B | 1.369 (5) |
Na2—O2B | 2.452 (3) | N2B—N3B | 1.249 (5) |
Na2—O1WB | 2.486 (3) | N2B—C8B | 1.407 (5) |
Na2—OW | 2.498 (3) | N3B—C11B | 1.434 (5) |
O3A—C17A | 1.259 (4) | C5B—C6B | 1.405 (5) |
O4A—C17A | 1.252 (4) | C5B—C10B | 1.408 (5) |
N1A—C5A | 1.373 (4) | C6B—C7B | 1.363 (6) |
N2A—N3A | 1.245 (4) | C7B—C8B | 1.386 (6) |
N2A—C8A | 1.402 (5) | C8B—C9B | 1.397 (6) |
N3A—C11A | 1.424 (5) | C9B—C10B | 1.362 (5) |
| | | |
O2WA—Na1—O2A | 88.82 (10) | O3WB—Na2—O2B | 97.04 (14) |
O3WA—Na1—O2A | 100.78 (11) | O2WB—Na2—O2B | 77.37 (10) |
O3WA—Na1—OW | 175.50 (12) | O3WB—Na2—OW | 174.15 (17) |
| | | |
C8A—N2A—N3A—C11A | 177.2 (3) | C8B—N2B—N3B—C11B | 177.5 (3) |
C2A—N1A—C5A—C6A | −0.6 (5) | C2B—N1B—C5B—C6B | −6.2 (5) |
N3A—N2A—C8A—C7A | 178.1 (3) | N3B—N2B—C8B—C7B | 179.2 (3) |
N2A—N3A—C11A—C16A | −179.4 (3) | N2B—N3B—C11B—C16B | −171.9 (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···A | D—H | H···A | D···A | D—H···A |
OW—H1WW···O3Biii | 0.94 | 2.27 | 3.121 (4) | 150 |
OW—H2WW···O3Aiv | 0.90 | 1.97 | 2.858 (4) | 168 |
O1WA—HA11···O1Av | 0.90 | 1.89 | 2.787 (4) | 176 |
O1WA—HA21···O2B | 0.84 | 2.12 | 2.910 (4) | 157 |
O2WA—HA12···O4Biii | 0.97 | 1.77 | 2.717 (4) | 165 |
O2WA—HA22···O3Avi | 0.82 | 1.98 | 2.785 (4) | 167 |
O3WA—HA13···O3Avi | 0.90 | 1.97 | 2.835 (4) | 160 |
O3WA—HA23···O1WAv | 0.80 | 2.12 | 2.890 (4) | 160 |
O2WB—HB12···O1Bvii | 0.97 | 1.84 | 2.801 (4) | 178 |
O2WB—HB22···O2A | 0.94 | 1.88 | 2.809 (4) | 172 |
O1WB—HB11···O4Aviii | 0.99 | 1.80 | 2.775 (4) | 168 |
O1WB—HB21···O3Biii | 0.89 | 1.94 | 2.808 (4) | 166 |
O1A—HO1A···O4Bix | 0.82 | 1.94 | 2.682 (4) | 150 |
O2A—HO2A···O3Biii | 0.96 | 1.73 | 2.689 (4) | 171 |
O1B—HO1B···O4Ax | 0.96 | 1.70 | 2.642 (4) | 165 |
O2B—HO2B···O1B | 0.89 | 1.85 | 2.720 (4) | 164 |
Symmetry codes: (iii) x+1, y, z+1; (iv) x, y, z−1; (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) x−1, y, z−1. |
Selected geometric parameters (Å, º) for (II) topK1—O1i | 2.687 (4) | N3—C11 | 1.428 (5) |
K1—O2W | 2.759 (4) | O3—C17 | 1.262 (5) |
K1—O1W | 2.796 (4) | O4—C17 | 1.256 (5) |
K1—O2Wii | 2.946 (5) | C5—C6 | 1.407 (6) |
K1—O2 | 2.974 (4) | C5—C10 | 1.421 (6) |
K1—O1Wiii | 3.060 (4) | C6—C7 | 1.372 (6) |
N1—C5 | 1.361 (5) | C7—C8 | 1.384 (6) |
N2—N3 | 1.254 (5) | C8—C9 | 1.395 (6) |
N2—C8 | 1.416 (5) | C9—C10 | 1.350 (5) |
| | | |
O1i—K1—O2 | 101.42 (10) | O1W—K1—O2 | 93.88 (11) |
O2W—K1—O2 | 91.27 (12) | | |
| | | |
C8—N2—N3—C11 | 176.9 (4) | N3—N2—C8—C7 | 178.5 (4) |
C2—N1—C5—C6 | 179.6 (4) | N2—N3—C11—C16 | 155.2 (5) |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, y−1/2, −z; (iii) −x+2, y+1/2, −z. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—HO1···O3iv | 0.90 | 1.84 | 2.724 (4) | 169 |
O1W—H2O1···O3iv | 0.90 | 2.02 | 2.831 (6) | 148 |
O1W—H1O1···O4v | 0.95 | 1.88 | 2.824 (6) | 177 |
O2W—H2O2···O3iv | 0.94 | 1.99 | 2.855 (6) | 152 |
O2W—H1O2···O4vi | 0.94 | 1.85 | 2.785 (5) | 171 |
O2—HO2···N2vii | 1.08 | 2.09 | 3.108 (6) | 156 |
Symmetry codes: (iv) x−1, y, z−1; (v) −x+4, y−1/2, −z+1; (vi) −x+4, y+1/2, −z+1; (vii) −x+3, y+1/2, −z+1. |
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.