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The crystal structures of two dyestuffs, Na+·C11H8N3O2-·H2O, (I), and NH4+·C10H5N2O5-, (II), were determined from X-ray powder diffraction data. In both structures, translationally related anions form stacks, and cations fill interstack channels. A comparison of the diffuse reflectance spectra of crystalline (I) and (II) with the absorption spectra of their aqueous solutions demonstrates that the geometry of their anions does not change significantly upon transfer from the crystalline to the solution state.
Supporting information
CCDC references: 163900; 163901
For both compounds, data collection: home-written program; cell refinement: LSPAID (Visser, 1986); program(s) used to solve structure: MRIA (Zlokazov & Chernyshev, 1992); program(s) used to refine structure: MRIA; molecular graphics: PLUTON (Spek, 1992); software used to prepare material for publication: PARST (Nardelli, 1983).
(I) sodium 4-(2-pyridinylazo)-1,3-benzenediolate monohydrate
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Crystal data top
Na(C11H8N3O2)·H2O | Z = 4 |
Mr = 255.21 | F(000) = 528 |
Monoclinic, P21/c | Dx = 1.553 Mg m−3 |
a = 16.703 (3) Å | Cu Kα radiation, λ = 1.5418 Å |
b = 3.634 (1) Å | T = 295 K |
c = 20.248 (3) Å | Particle morphology: plates |
β = 117.38 (1)° | orange |
V = 1091.4 (5) Å3 | flat_sheet, 25 × 25 mm |
Data collection top
DRON-3M diffractometer (Burevestnik, Russia) | Data collection mode: reflection |
Radiation source: X-ray sealed tube | Scan method: step |
Ni filtered monochromator | 2θmin = 5.4°, 2θmax = 69.4°, 2θstep = 0.02° |
Specimen mounting: pressed as a thin layer in the specimen holder | |
Refinement top
Refinement on Inet | 104 parameters |
Least-squares matrix: full with fixed elements per cycle | 10 restraints |
Rp = 0.038 | 0 constraints |
Rwp = 0.050 | H-atom parameters not refined |
Rexp = 0.023 | Weighting scheme based on measured s.u.'s |
3231 data points | (Δ/σ)max = 0.045 |
Excluded region(s): 69.42 - 70.00 | Background function: Chebyshev polynomial up to the 5th order |
Profile function: split-type pseudo-Voigt | Preferred orientation correction: March-Dollase (Dollase, 1986) along [010], G1 = 0.865(1) |
Special details top
Experimental. specimen was rotated in its plane |
Refinement. Hydrogen atoms were constrained at calculated positions, and planarity of
pyridine and resorcinol rings was restrained. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Na | 0.5465 (3) | 0.4571 (16) | 0.4216 (3) | 0.030 (2)* | |
O1 | 0.5688 (4) | 0.491 (2) | 0.1151 (3) | 0.037 (2)* | |
O2 | 0.6156 (5) | −0.086 (2) | 0.5105 (4) | 0.049 (3)* | |
O3 | 0.6297 (4) | 0.293 (2) | 0.3663 (4) | 0.037 (2)* | |
N1 | 0.8041 (6) | −0.026 (3) | 0.3980 (4) | 0.037 (2)* | |
N2 | 0.7808 (5) | 0.015 (2) | 0.4499 (4) | 0.037 (2)* | |
N8 | 0.8107 (5) | −0.170 (1) | 0.5631 (5) | 0.041 (2)* | |
C1 | 0.6184 (5) | 0.372 (3) | 0.1784 (4) | 0.024 (2)* | |
C2 | 0.5986 (5) | 0.392 (2) | 0.2400 (4) | 0.024 (2)* | |
C3 | 0.6565 (5) | 0.256 (3) | 0.3101 (4) | 0.024 (2)* | |
C4 | 0.7464 (5) | 0.106 (2) | 0.3293 (4) | 0.024 (2)* | |
C5 | 0.7669 (5) | 0.105 (3) | 0.2684 (4) | 0.024 (2)* | |
C6 | 0.7068 (5) | 0.221 (2) | 0.1967 (4) | 0.024 (2)* | |
C7 | 0.8398 (6) | −0.149 (2) | 0.5127 (4) | 0.041 (2)* | |
C9 | 0.8672 (6) | −0.287 (2) | 0.6336 (5) | 0.041 (2)* | |
C10 | 0.9575 (6) | −0.400 (2) | 0.6573 (4) | 0.041 (2)* | |
C11 | 0.9839 (6) | −0.360 (3) | 0.6047 (5) | 0.041 (2)* | |
C12 | 0.9302 (5) | −0.220 (2) | 0.5343 (4) | 0.041 (2)* | |
H3 | 0.6862 | 0.1840 | 0.4123 | 0.051* | |
H17 | 0.5349 | 0.5146 | 0.2316 | 0.051* | |
H18 | 0.7260 | 0.2099 | 0.1525 | 0.051* | |
H19 | 0.8321 | −0.0187 | 0.2766 | 0.051* | |
H20 | 0.8350 | −0.3304 | 0.6687 | 0.051* | |
H21 | 0.9948 | −0.5114 | 0.7136 | 0.051* | |
H22 | 1.0558 | −0.4295 | 0.6181 | 0.051* | |
H23 | 0.9574 | −0.1865 | 0.4954 | 0.051* | |
Geometric parameters (Å, º) top
Na—O2 | 2.561 (13) | C1—C6 | 1.454 (12) |
Na—O3 | 2.231 (11) | C2—C3 | 1.390 (9) |
Na—O2i | 2.328 (13) | C2—H17 | 1.094 |
Na—O1ii | 2.411 (11) | C3—C4 | 1.471 (12) |
Na—O1iii | 2.590 (12) | C4—C5 | 1.423 (14) |
O2—N8 | 2.942 (15) | C5—C6 | 1.397 (9) |
O2—O1iv | 2.596 (14) | C5—H19 | 1.117 |
O1—C1 | 1.240 (9) | C6—H18 | 1.081 |
O3—C3 | 1.407 (13) | C7—C12 | 1.391 (13) |
O3—H3 | 1.053 | C9—C10 | 1.417 (13) |
N1—N2 | 1.287 (14) | C9—H20 | 1.081 |
N1—C4 | 1.365 (10) | C10—C11 | 1.336 (16) |
N2—C7 | 1.338 (9) | C10—H21 | 1.095 |
N8—C7 | 1.317 (16) | C11—C12 | 1.384 (11) |
N8—C9 | 1.368 (11) | C11—H22 | 1.131 |
C1—C2 | 1.432 (14) | C12—H23 | 1.083 |
| | | |
Na—O2—N8 | 114 (1) | N1—C4—C5 | 122.9 (7) |
Na—O2—Nav | 96.0 (8) | C4—C5—H19 | 119 |
Na—O2—O1iv | 105 (1) | C4—C5—C6 | 123.7 (7) |
N8—O2—Nav | 106 (1) | C6—C5—H19 | 117 |
N8—O2—O1iv | 115 (1) | C1—C6—C5 | 122.6 (7) |
Nav—O2—O1iv | 120 (1) | C5—C6—H18 | 120 |
C3—O3—H3 | 101 | C1—C6—H18 | 117 |
N2—N1—C4 | 117.0 (7) | N2—C7—N8 | 112.9 (7) |
N1—N2—H3 | 106 | N8—C7—C12 | 118.6 (9) |
N1—N2—C7 | 111.0 (7) | N2—C7—C12 | 126.9 (8) |
C7—N8—C9 | 120.3 (8) | N8—C9—H20 | 115 |
O1—C1—C6 | 120.8 (8) | N8—C9—C10 | 124.0 (8) |
O1—C1—C2 | 124.8 (7) | C10—C9—H20 | 121 |
C2—C1—C6 | 114.2 (8) | C9—C10—H21 | 118 |
C1—C2—H17 | 119 | C9—C10—C11 | 112.9 (10) |
C1—C2—C3 | 122.8 (7) | C11—C10—H21 | 129 |
C3—C2—H17 | 118 | C10—C11—H22 | 119 |
O3—C3—C2 | 117.5 (7) | C10—C11—C12 | 124.5 (8) |
C2—C3—C4 | 123.1 (7) | C12—C11—H22 | 116 |
O3—C3—C4 | 119.2 (8) | C7—C12—C11 | 119.2 (8) |
N1—C4—C3 | 123.8 (8) | C11—C12—H23 | 120 |
C3—C4—C5 | 113.3 (8) | C7—C12—H23 | 120 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+1/2, z+1/2; (v) x, y−1, z. |
(II) ammonium 2,4-dinitro-1-naphthalenolate
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Crystal data top
NH4+·C10H5N2O5− | Z = 4 |
Mr = 251.20 | F(000) = 520 |
Monoclinic, P21/c | Dx = 1.574 Mg m−3 |
a = 3.924 (1) Å | Cu Kα radiation, λ = 1.5418 Å |
b = 20.314 (4) Å | T = 295 K |
c = 13.336 (3) Å | Particle morphology: plates |
β = 94.31 (1)° | orange-red |
V = 1060 (1) Å3 | flat_sheet, 25 × 25 mm |
Data collection top
DRON-3M diffractometer (Burevestnik, Russia) | Data collection mode: reflection |
Radiation source: X-ray sealed tube | Scan method: step |
Ni filtered monochromator | 2θmin = 7.0°, 2θmax = 57.0°, 2θstep = 0.02° |
Specimen mounting: pressed as a thin layer in the specimen holder | |
Refinement top
Refinement on Inet | 106 parameters |
Least-squares matrix: full with fixed elements per cycle | 12 restraints |
Rp = 0.023 | 0 constraints |
Rwp = 0.030 | H-atom parameters not refined |
Rexp = 0.015 | Weighting scheme based on measured s.u.'s |
2726 data points | (Δ/σ)max = 0.04 |
Excluded region(s): 5.5 - 6.98, 57.02 - 60.0 | Background function: Chebyshev polynomial up to the 5th order |
Profile function: split-type pseudo-Voigt | Preferred orientation correction: March-Dollase (Dollase, 1986) along [100], G1 = 1.338(1) |
Special details top
Experimental. specimen was rotated in its plane |
Refinement. Hydrogen atoms were constrained at calculated positions, and planarity of phenyl
ring and naphthalene residue was restrained. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.049 (4) | 0.0265 (3) | 0.2437 (5) | 0.064 (3)* | |
O21 | 0.420 (3) | 0.1504 (3) | 0.0309 (5) | 0.092 (2)* | |
O22 | 0.179 (3) | 0.0589 (3) | 0.0503 (6) | 0.092 (2)* | |
O41 | −0.129 (4) | 0.3244 (3) | 0.3512 (5) | 0.092 (2)* | |
O42 | 0.195 (3) | 0.3263 (4) | 0.2255 (5) | 0.092 (2)* | |
N1 | 0.466 (4) | 0.4475 (4) | 0.3438 (7) | 0.087 (5)* | |
N2 | 0.269 (2) | 0.1127 (4) | 0.0847 (5) | 0.064 (3)* | |
N4 | 0.032 (3) | 0.2985 (4) | 0.2905 (6) | 0.064 (3)* | |
C1 | 0.046 (2) | 0.0875 (4) | 0.2534 (6) | 0.046 (2)* | |
C2 | 0.156 (3) | 0.1321 (4) | 0.1790 (5) | 0.046 (2)* | |
C3 | 0.133 (3) | 0.1991 (4) | 0.1964 (6) | 0.046 (2)* | |
C4 | 0.029 (3) | 0.2250 (3) | 0.2861 (6) | 0.046 (2)* | |
C5 | −0.208 (2) | 0.2048 (3) | 0.4530 (6) | 0.046 (2)* | |
C6 | −0.308 (3) | 0.1611 (4) | 0.5264 (6) | 0.046 (2)* | |
C7 | −0.301 (3) | 0.0953 (4) | 0.5029 (6) | 0.046 (2)* | |
C8 | −0.181 (2) | 0.0687 (3) | 0.4189 (6) | 0.046 (2)* | |
C9 | −0.067 (3) | 0.1149 (4) | 0.3463 (5) | 0.046 (2)* | |
C10 | −0.086 (4) | 0.1817 (4) | 0.3635 (6) | 0.046 (2)* | |
H3 | 0.2168 | 0.2328 | 0.1375 | 0.076* | |
H5 | −0.2154 | 0.2587 | 0.4669 | 0.076* | |
H6 | −0.4052 | 0.1806 | 0.5938 | 0.076* | |
H7 | −0.3798 | 0.0586 | 0.5624 | 0.076* | |
H8 | −0.1628 | 0.0170 | 0.4031 | 0.076* | |
H11 | 0.6091 | 0.4445 | 0.2879 | 0.095* | |
H12 | 0.2522 | 0.4234 | 0.3352 | 0.095* | |
H13 | 0.4004 | 0.4978 | 0.3502 | 0.095* | |
H14 | 0.5937 | 0.4358 | 0.4099 | 0.095* | |
Geometric parameters (Å, º) top
N1—O41 | 3.43 (1) | C5—C10 | 1.400 (13) |
N1—O42 | 3.07 (1) | C5—H5 | 1.111 |
N1—O1i | 2.77 (1) | C6—C7 | 1.372 (12) |
N1—O1ii | 2.81 (1) | C6—H6 | 1.078 |
N1—O22ii | 2.96 (1) | C7—C8 | 1.361 (12) |
N1—O41iii | 2.96 (1) | C7—H7 | 1.149 |
N1—O22iv | 3.06 (1) | C8—C9 | 1.444 (11) |
N1—O21iv | 3.21 (1) | C8—H8 | 1.073 |
C1—C2 | 1.434 (12) | C9—C10 | 1.378 (12) |
C1—C9 | 1.457 (11) | N1—H11 | 0.970 |
C1—O1 | 1.246 (10) | N1—H12 | 0.971 |
C2—C3 | 1.385 (12) | N1—H13 | 1.058 |
C2—N2 | 1.420 (11) | N1—H14 | 1.009 |
C3—C4 | 1.396 (12) | N2—O21 | 1.230 (11) |
C3—H3 | 1.109 | N2—O22 | 1.228 (10) |
C4—C10 | 1.454 (13) | N4—O41 | 1.188 (14) |
C4—N4 | 1.494 (10) | N4—O42 | 1.250 (13) |
C5—C6 | 1.401 (12) | | |
| | | |
C9—C1—O1 | 118.3 (7) | C7—C8—H8 | 126 |
C2—C1—O1 | 123.4 (8) | C7—C8—C9 | 115.9 (7) |
C2—C1—C9 | 118.2 (7) | C9—C8—H8 | 118 |
C1—C2—N2 | 124.6 (7) | C1—C9—C8 | 116.7 (7) |
C1—C2—C3 | 118.6 (7) | C8—C9—C10 | 120.3 (7) |
C3—C2—N2 | 116.7 (7) | C1—C9—C10 | 122.8 (7) |
C2—C3—H3 | 117 | C5—C10—C9 | 119.9 (7) |
C2—C3—C4 | 122.8 (7) | C4—C10—C9 | 116.9 (7) |
C4—C3—H3 | 120 | C4—C10—C5 | 123.1 (8) |
C3—C4—N4 | 114.1 (6) | H13—N1—H14 | 106 |
C3—C4—C10 | 120.4 (8) | H12—N1—H14 | 110 |
C10—C4—N4 | 125.4 (6) | H12—N1—H13 | 107 |
C10—C5—H5 | 119 | H11—N1—H14 | 112 |
C6—C5—H5 | 120 | H11—N1—H13 | 106 |
C6—C5—C10 | 121.0 (8) | H11—N1—H12 | 114 |
C5—C6—H6 | 119 | C2—N2—O22 | 118.5 (7) |
C5—C6—C7 | 116.5 (7) | C2—N2—O21 | 122.7 (7) |
C7—C6—H6 | 124 | O21—N2—O22 | 118.3 (8) |
C6—C7—H7 | 118 | C4—N4—O42 | 115.3 (8) |
C6—C7—C8 | 126.2 (8) | C4—N4—O41 | 117.8 (7) |
C8—C7—H7 | 116 | O41—N4—O42 | 126.7 (9) |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x+1, y, z; (iv) x, −y+1/2, z+1/2. |
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