Sodium 4-(2-pyridinyl­diazenyl)­resorcinolate monohydrate and ammonium 2,4-di­nitro-1-naphthalenolate from powder diffraction data

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.

Computing details

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

Crystal data

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) Å^3	flat_sheet, 25 × 25 mm

Data collection

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

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

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 (Ų)

	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)

Na—O2	2.561 (13)	C1—C6	1.454 (12)
Na—O3	2.231 (11)	C2—C3	1.390 (9)
Na—O2^i	2.328 (13)	C2—H17	1.094
Na—O1^ii	2.411 (11)	C3—C4	1.471 (12)
Na—O1^iii	2.590 (12)	C4—C5	1.423 (14)
O2—N8	2.942 (15)	C5—C6	1.397 (9)
O2—O1^iv	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—Na^v	96.0 (8)	C4—C5—H19	119
Na—O2—O1^iv	105 (1)	C4—C5—C6	123.7 (7)
N8—O2—Na^v	106 (1)	C6—C5—H19	117
N8—O2—O1^iv	115 (1)	C1—C6—C5	122.6 (7)
Na^v—O2—O1^iv	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

Crystal data

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) Å^3	flat_sheet, 25 × 25 mm

Data collection

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

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

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 (Ų)

	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)

N1—O41	3.43 (1)	C5—C10	1.400 (13)
N1—O42	3.07 (1)	C5—H5	1.111
N1—O1^i	2.77 (1)	C6—C7	1.372 (12)
N1—O1^ii	2.81 (1)	C6—H6	1.078
N1—O22^ii	2.96 (1)	C7—C8	1.361 (12)
N1—O41^iii	2.96 (1)	C7—H7	1.149
N1—O22^iv	3.06 (1)	C8—C9	1.444 (11)
N1—O21^iv	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.