syn and anti conformations in 2-hy­droxy-5-[(E)-(4-nitro­phen­yl)diazen­yl]benzoic acid and two related salts

The crystal structures of 2-hy­droxy-5-[(E)-(4-nitro­phen­yl)diazen­yl]benzoic acid, C₁₃H₉N₃O₅, (I), ammonium 2-hy­droxy-5-[(E)-phenyl­diazen­yl]benzoate, NH₄⁺·C₁₃H₉N₂O₃⁻, (II), and sodium 2-hy­droxy-5-[(E)-(4-nitro­phen­yl)diazen­yl]benzoate trihydrate, Na⁺·C₁₃H₈N₃O₅⁻·3H₂O, (III), have been determined using single-crystal X-ray diffraction. In (I) and (III), the phenyl­diazenyl and carb­oxy­lic acid/carboxyl­ate groups are in an anti orientation with respect to each other, which is in accord with the results of density functional theory (DFT) calculations, whereas in (II), the anion adopts a syn conformation. In (I), mol­ecules form slanted stacks along the [100] direction. In (II), anions form bilayers parallel to (010), the inner part of the bilayers being formed by the benzene rings, with the –OH and –COO⁻ substituents on the bilayer surface. The NH₄⁺ cations in (II) are located between the bilayers and are engaged in numerous N—H...O hydrogen bonds. In (III), anions form layers parallel to (001). Both Na⁺ cations have a distorted octa­hedral environment, with four octa­hedra edge-shared by bridging water O atoms, forming [Na₄(H₂O)₁₂]⁴⁺ units.

Computing details

For all structures, data collection: X-AREA (Stoe & Cie, 2012); cell refinement: X-AREA (Stoe & Cie, 2012); data reduction: X-RED32 (Stoe & Cie, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

2-Hydroxy-5-[(E)-(4-nitrophenyl)diazenyl]benzoic acid (I)

Crystal data

C13H9N3O5	F(000) = 592.0
Mr = 287.23	Dx = 1.540 Mg m^−3
Monoclinic, P21/c	Melting point: 530 K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54186 Å
a = 4.9319 (5) Å	Cell parameters from 2234 reflections
b = 11.6649 (14) Å	θ = 3.8–56.3°
c = 21.619 (2) Å	µ = 1.04 mm^−1
β = 94.991 (8)°	T = 293 K
V = 1239.0 (2) Å^3	Needle, red–orange
Z = 4	0.12 × 0.04 × 0.03 mm

Data collection

Stoe STADI VARI diffractometer	2334 independent reflections
Radiation source: microfocus sealed tube	1804 reflections with I > 2σ(I)
None monochromator	Rint = 0.074
Detector resolution: 5.81 pixels mm^-1	θmax = 70.0°, θmin = 4.1°
rotation method scans	h = −5→6
Absorption correction: multi-scan (Blessing, 1995)	k = −14→13
Tmin = 0.925, Tmax = 0.979	l = −22→26
14169 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.0832P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
2334 reflections	Δρmax = 0.22 e Å^−3
199 parameters	Δρmin = −0.18 e Å^−3
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0143 (13)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The C-bound H atoms were placed in idealized positions, with constrained distances of 0.93 Å and with U_iso(H) = 1.2U_eq(C). Phenol and carboxylic H atoms were restrained so that to reproduce the C—O—H angle values observed in salicylic acid (neutron structure determination, Bacon et al., 1973): 107° for phenol and 109° for COOH group.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	1.1662 (2)	0.16995 (10)	−0.01162 (5)	0.0516 (3)
H1	1.259 (4)	0.2232 (6)	−0.0226 (7)	0.086 (8)*
O2	1.3733 (2)	0.37681 (10)	−0.00850 (5)	0.0529 (3)
O3	1.2554 (2)	0.50125 (10)	0.06235 (6)	0.0559 (3)
H13	1.370 (3)	0.5406 (7)	0.0471 (7)	0.074 (6)*
O4	−0.3794 (3)	0.26095 (12)	0.40909 (6)	0.0658 (4)
O5	−0.3102 (3)	0.44066 (11)	0.39742 (6)	0.0676 (4)
N1	0.5734 (3)	0.30930 (12)	0.18177 (6)	0.0470 (3)
N2	0.4515 (3)	0.22991 (13)	0.20677 (6)	0.0508 (4)
N3	−0.2672 (3)	0.34058 (12)	0.38566 (6)	0.0488 (3)
C1	1.0527 (3)	0.31879 (13)	0.05999 (6)	0.0395 (3)
C2	1.0260 (3)	0.20830 (13)	0.03457 (6)	0.0413 (4)
C3	0.8421 (3)	0.13098 (14)	0.05774 (7)	0.0482 (4)
H3	0.8203	0.0583	0.0404	0.058*
C4	0.6948 (3)	0.16214 (14)	0.10573 (7)	0.0469 (4)
H4	0.5739	0.1101	0.1209	0.056*
C5	0.7233 (3)	0.27134 (13)	0.13239 (7)	0.0423 (4)
C6	0.8975 (3)	0.34931 (13)	0.10875 (7)	0.0417 (4)
H6	0.9122	0.4228	0.1253	0.050*
C7	0.2843 (3)	0.26631 (14)	0.25364 (7)	0.0458 (4)
C8	0.2244 (3)	0.37942 (15)	0.26665 (7)	0.0510 (4)
H8	0.3036	0.4386	0.2457	0.061*
C9	0.0471 (3)	0.40402 (15)	0.31068 (7)	0.0506 (4)
H9	0.0063	0.4796	0.3200	0.061*
C10	−0.0687 (3)	0.31457 (14)	0.34076 (6)	0.0435 (4)
C11	−0.0092 (3)	0.20176 (15)	0.32949 (8)	0.0522 (4)
H11	−0.0872	0.1431	0.3510	0.063*
C12	0.1689 (4)	0.17777 (15)	0.28548 (8)	0.0534 (4)
H12	0.2119	0.1021	0.2771	0.064*
C13	1.2401 (3)	0.40097 (13)	0.03518 (7)	0.0422 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0522 (7)	0.0533 (7)	0.0528 (6)	−0.0086 (5)	0.0242 (5)	−0.0106 (5)
O2	0.0544 (7)	0.0533 (7)	0.0554 (6)	−0.0111 (5)	0.0299 (5)	−0.0075 (5)
O3	0.0622 (7)	0.0464 (6)	0.0640 (7)	−0.0148 (5)	0.0344 (6)	−0.0092 (5)
O4	0.0675 (8)	0.0678 (8)	0.0679 (8)	−0.0032 (6)	0.0393 (6)	0.0040 (6)
O5	0.0713 (9)	0.0625 (8)	0.0725 (8)	0.0196 (6)	0.0272 (6)	0.0011 (6)
N1	0.0430 (7)	0.0571 (8)	0.0426 (7)	−0.0059 (6)	0.0141 (5)	0.0007 (6)
N2	0.0491 (8)	0.0597 (8)	0.0463 (7)	−0.0077 (6)	0.0197 (6)	0.0011 (6)
N3	0.0450 (7)	0.0584 (8)	0.0446 (7)	0.0076 (6)	0.0132 (5)	0.0027 (6)
C1	0.0354 (7)	0.0450 (8)	0.0391 (7)	−0.0024 (6)	0.0092 (6)	0.0013 (6)
C2	0.0364 (7)	0.0495 (8)	0.0390 (7)	−0.0009 (6)	0.0095 (6)	−0.0021 (6)
C3	0.0496 (9)	0.0461 (8)	0.0506 (9)	−0.0083 (7)	0.0146 (7)	−0.0049 (7)
C4	0.0441 (8)	0.0493 (8)	0.0492 (8)	−0.0098 (7)	0.0145 (7)	0.0029 (7)
C5	0.0383 (8)	0.0508 (8)	0.0390 (7)	−0.0031 (6)	0.0107 (6)	0.0003 (6)
C6	0.0409 (8)	0.0444 (8)	0.0415 (7)	−0.0043 (6)	0.0129 (6)	−0.0026 (6)
C7	0.0429 (8)	0.0561 (9)	0.0399 (7)	−0.0042 (7)	0.0118 (6)	0.0009 (6)
C8	0.0534 (9)	0.0538 (9)	0.0479 (8)	−0.0092 (7)	0.0165 (7)	0.0061 (7)
C9	0.0564 (10)	0.0479 (9)	0.0490 (8)	−0.0008 (7)	0.0135 (7)	0.0017 (7)
C10	0.0412 (8)	0.0537 (9)	0.0369 (7)	0.0014 (7)	0.0112 (6)	0.0025 (6)
C11	0.0561 (10)	0.0508 (9)	0.0534 (9)	−0.0038 (7)	0.0255 (7)	0.0051 (7)
C12	0.0603 (10)	0.0487 (9)	0.0546 (9)	−0.0025 (7)	0.0252 (8)	−0.0009 (7)
C13	0.0391 (8)	0.0459 (8)	0.0433 (8)	−0.0035 (6)	0.0134 (6)	−0.0004 (6)

Geometric parameters (Å, º)

O1—C2	1.3400 (17)	C3—H3	0.9300
O1—H1	0.820 (14)	C4—C5	1.400 (2)
O2—C13	1.2290 (17)	C4—H4	0.9300
O3—C13	1.3081 (19)	C5—C6	1.379 (2)
O3—H13	0.820 (13)	C6—H6	0.9300
O4—N3	1.2142 (18)	C7—C8	1.386 (2)
O5—N3	1.2173 (19)	C7—C12	1.390 (2)
N1—N2	1.2519 (19)	C8—C9	1.378 (2)
N1—C5	1.4213 (19)	C8—H8	0.9300
N2—C7	1.4256 (19)	C9—C10	1.379 (2)
N3—C10	1.4691 (19)	C9—H9	0.9300
C1—C6	1.4014 (19)	C10—C11	1.375 (2)
C1—C2	1.403 (2)	C11—C12	1.378 (2)
C1—C13	1.4653 (19)	C11—H11	0.9300
C2—C3	1.402 (2)	C12—H12	0.9300
C3—C4	1.367 (2)
C2—O1—H1	107.5 (10)	C5—C6—H6	119.7
C13—O3—H13	109.6 (8)	C1—C6—H6	119.7
N2—N1—C5	113.24 (13)	C8—C7—C12	120.18 (14)
N1—N2—C7	114.56 (14)	C8—C7—N2	125.06 (14)
O4—N3—O5	123.55 (13)	C12—C7—N2	114.70 (15)
O4—N3—C10	118.15 (13)	C9—C8—C7	119.86 (15)
O5—N3—C10	118.30 (14)	C9—C8—H8	120.1
C6—C1—C2	119.29 (13)	C7—C8—H8	120.1
C6—C1—C13	120.81 (13)	C8—C9—C10	118.81 (16)
C2—C1—C13	119.89 (12)	C8—C9—H9	120.6
O1—C2—C3	116.31 (13)	C10—C9—H9	120.6
O1—C2—C1	124.17 (13)	C11—C10—C9	122.48 (14)
C3—C2—C1	119.51 (13)	C11—C10—N3	118.66 (14)
C4—C3—C2	120.22 (14)	C9—C10—N3	118.85 (15)
C4—C3—H3	119.9	C10—C11—C12	118.38 (15)
C2—C3—H3	119.9	C10—C11—H11	120.8
C3—C4—C5	120.88 (14)	C12—C11—H11	120.8
C3—C4—H4	119.6	C11—C12—C7	120.26 (16)
C5—C4—H4	119.6	C11—C12—H12	119.9
C6—C5—C4	119.40 (13)	C7—C12—H12	119.9
C6—C5—N1	117.03 (13)	O2—C13—O3	122.43 (13)
C4—C5—N1	123.52 (13)	O2—C13—C1	121.83 (14)
C5—C6—C1	120.64 (14)	O3—C13—C1	115.74 (12)
C5—N1—N2—C7	−175.91 (12)	C12—C7—C8—C9	−0.8 (3)
C6—C1—C2—O1	−179.33 (14)	N2—C7—C8—C9	176.20 (15)
C13—C1—C2—O1	1.1 (2)	C7—C8—C9—C10	−0.4 (3)
C6—C1—C2—C3	0.9 (2)	C8—C9—C10—C11	1.5 (3)
C13—C1—C2—C3	−178.70 (14)	C8—C9—C10—N3	−177.25 (14)
O1—C2—C3—C4	178.64 (14)	O4—N3—C10—C11	−3.1 (2)
C1—C2—C3—C4	−1.6 (2)	O5—N3—C10—C11	176.89 (16)
C2—C3—C4—C5	0.3 (2)	O4—N3—C10—C9	175.76 (15)
C3—C4—C5—C6	1.7 (2)	O5—N3—C10—C9	−4.3 (2)
C3—C4—C5—N1	179.13 (15)	C9—C10—C11—C12	−1.4 (3)
N2—N1—C5—C6	−170.02 (13)	N3—C10—C11—C12	177.42 (15)
N2—N1—C5—C4	12.4 (2)	C10—C11—C12—C7	0.1 (3)
C4—C5—C6—C1	−2.3 (2)	C8—C7—C12—C11	1.0 (3)
N1—C5—C6—C1	−179.96 (13)	N2—C7—C12—C11	−176.32 (16)
C2—C1—C6—C5	1.0 (2)	C6—C1—C13—O2	−178.27 (14)
C13—C1—C6—C5	−179.36 (13)	C2—C1—C13—O2	1.3 (2)
N1—N2—C7—C8	8.5 (2)	C6—C1—C13—O3	1.5 (2)
N1—N2—C7—C12	−174.29 (14)	C2—C1—C13—O3	−178.89 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82 (1)	1.90 (1)	2.6189 (16)	147 (1)
O1—H1···O4^i	0.82 (1)	2.42 (1)	3.0461 (18)	134 (1)
O3—H13···O2^ii	0.82 (1)	1.85 (1)	2.6651 (16)	176 (1)
C4—H4···O5^iii	0.93	2.38	3.202 (2)	147

Symmetry codes: (i) x+2, −y+1/2, z−1/2; (ii) −x+3, −y+1, −z; (iii) −x, y−1/2, −z+1/2.

Ammonium 2-hydroxy-5-[(E)-phenyldiazenyl]benzoate (II)

Crystal data

NH4^+·C13H9N2O3^−	F(000) = 544
Mr = 259.26	Dx = 1.355 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54186 Å
Hall symbol: -P 2yn	Cell parameters from 3698 reflections
a = 6.0471 (1) Å	θ = 5.1–72.1°
b = 34.371 (1) Å	µ = 0.82 mm^−1
c = 6.2824 (2) Å	T = 293 K
β = 103.278 (2)°	Irregular block, dark yellow
V = 1270.85 (6) Å^3	0.08 × 0.05 × 0.05 mm
Z = 4

Data collection

Stoe STADI VARI diffractometer	2352 independent reflections
Radiation source: microfocus sealed tube	1561 reflections with I > 2σ(I)
None monochromator	Rint = 0.052
Detector resolution: 5.81 pixels mm^-1	θmax = 69.0°, θmin = 5.2°
rotation method scans	h = −7→6
Absorption correction: multi-scan (Blessing, 1995)	k = −41→41
Tmin = 0.945, Tmax = 0.960	l = −7→7
15094 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.141	w = 1/[σ^2(Fo^2) + (0.063P)^2 + 0.38P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2352 reflections	Δρmax = 0.14 e Å^−3
189 parameters	Δρmin = −0.16 e Å^−3
12 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0052 (7)

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'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 s.u.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The C-bound H atoms were placed in idealized positions, with constrained distances of 0.93 Å and with U_iso(H) = 1.2U_eq(C). Phenol H atoms were restrained so that to reproduce the C—O—H angle value of 107° observed in salicylic acid (neutron structure determination, Bacon et al., 1973). All N—H distances and tetrahedral environment of the N atom were also restrained.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.2531 (3)	0.05503 (5)	0.8971 (3)	0.0534 (5)
H1	0.370 (3)	0.0422 (7)	0.930 (3)	0.087 (12)*
O2	0.6199 (3)	0.02302 (5)	0.8656 (3)	0.0539 (5)
O3	0.7530 (3)	0.03045 (5)	0.5682 (3)	0.0534 (5)
N1	0.2848 (4)	0.14683 (5)	0.1780 (4)	0.0512 (5)
N2	0.4682 (4)	0.14854 (6)	0.1187 (4)	0.0508 (5)
C1	0.4416 (4)	0.06971 (6)	0.6068 (4)	0.0403 (5)
C2	0.2647 (4)	0.07579 (6)	0.7175 (4)	0.0432 (5)
C3	0.0987 (4)	0.10345 (7)	0.6398 (4)	0.0499 (6)
H3	−0.0193	0.1071	0.7101	0.060*
C4	0.1077 (4)	0.12544 (7)	0.4601 (4)	0.0509 (6)
H4	−0.0066	0.1434	0.4072	0.061*
C5	0.2866 (4)	0.12113 (6)	0.3555 (4)	0.0456 (6)
C6	0.4488 (4)	0.09291 (6)	0.4288 (4)	0.0425 (5)
H6	0.5656	0.0894	0.3567	0.051*
C7	0.4620 (4)	0.17474 (7)	−0.0590 (4)	0.0495 (6)
C8	0.2868 (5)	0.20058 (7)	−0.1365 (5)	0.0634 (8)
H8	0.1650	0.2022	−0.0696	0.076*
C9	0.2935 (6)	0.22386 (8)	−0.3135 (6)	0.0771 (10)
H9	0.1763	0.2414	−0.3648	0.093*
C10	0.4716 (6)	0.22141 (8)	−0.4152 (5)	0.0723 (9)
H10	0.4726	0.2367	−0.5373	0.087*
C11	0.6476 (6)	0.19641 (9)	−0.3356 (5)	0.0703 (8)
H11	0.7696	0.1950	−0.4025	0.084*
C12	0.6445 (5)	0.17321 (8)	−0.1560 (5)	0.0619 (7)
H12	0.7655	0.1566	−0.1009	0.074*
C13	0.6177 (4)	0.03893 (6)	0.6836 (4)	0.0421 (5)
N3	−0.0209 (3)	0.03147 (5)	1.2283 (3)	0.0487 (5)
H21	−0.087 (3)	0.0405 (6)	1.331 (2)	0.073*
H22	−0.127 (3)	0.0243 (6)	1.111 (2)	0.073*
H23	0.066 (3)	0.0499 (4)	1.191 (3)	0.073*
H24	0.065 (3)	0.0110 (4)	1.281 (3)	0.073*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0507 (11)	0.0624 (11)	0.0521 (11)	0.0042 (8)	0.0223 (9)	0.0090 (8)
O2	0.0459 (10)	0.0673 (11)	0.0499 (10)	0.0061 (8)	0.0140 (9)	0.0170 (8)
O3	0.0461 (9)	0.0588 (10)	0.0618 (11)	0.0132 (7)	0.0258 (9)	0.0138 (8)
N1	0.0489 (11)	0.0437 (10)	0.0638 (14)	0.0045 (8)	0.0186 (11)	0.0046 (9)
N2	0.0469 (11)	0.0476 (11)	0.0605 (14)	0.0030 (8)	0.0174 (11)	0.0067 (9)
C1	0.0376 (12)	0.0407 (11)	0.0444 (13)	−0.0014 (8)	0.0129 (11)	−0.0016 (9)
C2	0.0442 (12)	0.0410 (12)	0.0481 (14)	−0.0040 (9)	0.0184 (12)	−0.0008 (10)
C3	0.0446 (13)	0.0515 (13)	0.0590 (16)	0.0055 (10)	0.0231 (12)	−0.0027 (11)
C4	0.0459 (13)	0.0425 (12)	0.0680 (17)	0.0072 (10)	0.0206 (13)	0.0005 (11)
C5	0.0460 (13)	0.0398 (11)	0.0521 (15)	0.0018 (9)	0.0136 (12)	0.0034 (10)
C6	0.0384 (12)	0.0443 (12)	0.0468 (13)	−0.0002 (9)	0.0141 (11)	−0.0011 (10)
C7	0.0488 (14)	0.0438 (12)	0.0585 (16)	−0.0022 (10)	0.0178 (13)	0.0029 (11)
C8	0.0599 (16)	0.0523 (15)	0.083 (2)	0.0089 (12)	0.0273 (16)	0.0201 (14)
C9	0.076 (2)	0.0567 (17)	0.103 (3)	0.0123 (14)	0.031 (2)	0.0335 (16)
C10	0.084 (2)	0.0585 (17)	0.078 (2)	−0.0127 (15)	0.0248 (19)	0.0154 (14)
C11	0.0701 (19)	0.0738 (19)	0.076 (2)	−0.0055 (15)	0.0348 (18)	0.0052 (16)
C12	0.0557 (16)	0.0593 (16)	0.077 (2)	0.0044 (12)	0.0273 (16)	0.0078 (13)
C13	0.0355 (11)	0.0444 (12)	0.0463 (13)	−0.0028 (9)	0.0092 (11)	0.0027 (10)
N3	0.0473 (11)	0.0484 (11)	0.0536 (13)	0.0040 (8)	0.0182 (10)	0.0039 (9)

Geometric parameters (Å, º)

O1—C2	1.350 (3)	C6—H6	0.9300
O1—H1	0.82 (2)	C7—C12	1.379 (3)
O2—C13	1.265 (3)	C7—C8	1.383 (4)
O3—C13	1.246 (3)	C8—C9	1.378 (4)
N1—N2	1.249 (3)	C8—H8	0.9300
N1—C5	1.421 (3)	C9—C10	1.375 (4)
N2—C7	1.428 (3)	C9—H9	0.9300
C1—C6	1.382 (3)	C10—C11	1.370 (4)
C1—C2	1.419 (3)	C10—H10	0.9300
C1—C13	1.500 (3)	C11—C12	1.385 (4)
C2—C3	1.387 (3)	C11—H11	0.9300
C3—C4	1.370 (3)	C12—H12	0.9300
C3—H3	0.9300	N3—H21	0.89 (2)
C4—C5	1.397 (3)	N3—H22	0.89 (2)
C4—H4	0.9300	N3—H23	0.89 (2)
C5—C6	1.381 (3)	N3—H24	0.89 (2)
C2—O1—H1	106.6 (14)	C9—C8—C7	119.7 (3)
N2—N1—C5	114.6 (2)	C9—C8—H8	120.2
N1—N2—C7	113.4 (2)	C7—C8—H8	120.2
C6—C1—C2	118.6 (2)	C10—C9—C8	120.7 (3)
C6—C1—C13	121.01 (19)	C10—C9—H9	119.7
C2—C1—C13	120.4 (2)	C8—C9—H9	119.7
O1—C2—C3	119.0 (2)	C11—C10—C9	119.6 (3)
O1—C2—C1	121.4 (2)	C11—C10—H10	120.2
C3—C2—C1	119.6 (2)	C9—C10—H10	120.2
C4—C3—C2	120.4 (2)	C10—C11—C12	120.2 (3)
C4—C3—H3	119.8	C10—C11—H11	119.9
C2—C3—H3	119.8	C12—C11—H11	119.9
C3—C4—C5	120.7 (2)	C7—C12—C11	120.0 (3)
C3—C4—H4	119.6	C7—C12—H12	120.0
C5—C4—H4	119.6	C11—C12—H12	120.0
C6—C5—C4	119.0 (2)	O3—C13—O2	123.6 (2)
C6—C5—N1	125.1 (2)	O3—C13—C1	119.4 (2)
C4—C5—N1	115.9 (2)	O2—C13—C1	117.1 (2)
C5—C6—C1	121.5 (2)	H21—N3—H22	110 (2)
C5—C6—H6	119.2	H21—N3—H23	110 (2)
C1—C6—H6	119.2	H22—N3—H23	109 (2)
C12—C7—C8	119.7 (2)	H21—N3—H24	109 (2)
C12—C7—N2	116.2 (2)	H22—N3—H24	110 (2)
C8—C7—N2	124.1 (2)	H23—N3—H24	109 (2)
C5—N1—N2—C7	−179.7 (2)	C13—C1—C6—C5	179.5 (2)
C6—C1—C2—O1	−177.6 (2)	N1—N2—C7—C12	−169.5 (2)
C13—C1—C2—O1	1.9 (3)	N1—N2—C7—C8	10.1 (4)
C6—C1—C2—C3	2.8 (3)	C12—C7—C8—C9	1.6 (4)
C13—C1—C2—C3	−177.8 (2)	N2—C7—C8—C9	−178.0 (3)
O1—C2—C3—C4	178.9 (2)	C7—C8—C9—C10	0.6 (5)
C1—C2—C3—C4	−1.4 (4)	C8—C9—C10—C11	−2.0 (5)
C2—C3—C4—C5	−1.6 (4)	C9—C10—C11—C12	1.1 (5)
C3—C4—C5—C6	3.3 (4)	C8—C7—C12—C11	−2.5 (4)
C3—C4—C5—N1	−176.8 (2)	N2—C7—C12—C11	177.2 (3)
N2—N1—C5—C6	−15.3 (3)	C10—C11—C12—C7	1.1 (5)
N2—N1—C5—C4	164.9 (2)	C6—C1—C13—O3	−10.1 (3)
C4—C5—C6—C1	−1.9 (4)	C2—C1—C13—O3	170.4 (2)
N1—C5—C6—C1	178.2 (2)	C6—C1—C13—O2	169.6 (2)
C2—C1—C6—C5	−1.1 (3)	C2—C1—C13—O2	−9.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82 (2)	1.78 (2)	2.524 (3)	151 (2)
N3—H21···O3^i	0.89 (2)	1.99 (2)	2.788 (3)	150 (2)
N3—H22···O2^ii	0.89 (2)	1.91 (2)	2.779 (3)	164 (2)
N3—H23···O1	0.89 (2)	2.38 (2)	3.052 (3)	132 (2)
N3—H24···O3^iii	0.89 (2)	1.91 (2)	2.799 (3)	172 (2)

Symmetry codes: (i) x−1, y, z+1; (ii) x−1, y, z; (iii) −x+1, −y, −z+2.

Sodium 2-hydroxy-5-[(E)-(4-nitrophenyl)diazenyl]benzoate trihydrate (III)

Crystal data

Na^+·C13H8N3O5^−·3H2O	Z = 4
Mr = 363.26	F(000) = 752
Triclinic, P1	Dx = 1.572 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2123 (5) Å	Cell parameters from 5966 reflections
b = 13.0205 (8) Å	θ = 2.4–30.4°
c = 17.0317 (11) Å	µ = 0.16 mm^−1
α = 77.185 (6)°	T = 293 K
β = 80.933 (5)°	Irregular block, dark yellow
γ = 83.401 (5)°	0.50 × 0.45 × 0.40 mm
V = 1534.76 (17) Å^3

Data collection

Stoe STADI VARI diffractometer	5936 independent reflections
Radiation source: fine-focus sealed tube	3776 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 5.81 pixels mm^-1	θmax = 26.0°, θmin = 2.7°
rotation method scans	h = −4→8
Absorption correction: multi-scan (Blessing, 1995)	k = −15→16
Tmin = 0.926, Tmax = 0.952	l = −19→20
6773 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 0.92	w = 1/[σ^2(Fo^2) + (0.0662P)^2] where P = (Fo^2 + 2Fc^2)/3
5936 reflections	(Δ/σ)max < 0.001
493 parameters	Δρmax = 0.21 e Å^−3
22 restraints	Δρmin = −0.26 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The C-bound H atoms were placed in idealized positions, with constrained distances of 0.93 Å and with U_iso(H) = 1.2U_eq(C). Phenol H atoms were restrained so that to reproduce the C—O—H angle value of 107° observed in salicylic acid (neutron structure determination, Bacon et al., 1973). For all water molecules, the O—H distances and H—O—H angles of 106° were restrained.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Na1	0.29209 (14)	0.54778 (7)	0.04310 (5)	0.0411 (2)
Na2	0.12688 (15)	0.81138 (8)	−0.01809 (6)	0.0489 (3)
O20	−0.0003 (2)	0.63987 (14)	0.01501 (10)	0.0413 (4)
H21	−0.085 (2)	0.651 (2)	0.0511 (11)	0.062*
H22	−0.055 (3)	0.630 (2)	−0.0212 (11)	0.062*
O30	0.5998 (3)	0.48619 (14)	0.09144 (10)	0.0447 (4)
H31	0.597 (4)	0.4339 (14)	0.1286 (12)	0.067*
H32	0.681 (3)	0.5201 (19)	0.0997 (17)	0.067*
O40	0.4292 (3)	0.71079 (14)	−0.00868 (10)	0.0424 (4)
H41	0.478 (3)	0.742 (2)	0.0187 (13)	0.064*
H42	0.503 (3)	0.713 (2)	−0.0508 (9)	0.064*
O50	0.0461 (4)	0.90808 (16)	0.08695 (13)	0.0630 (6)
H51	0.106 (5)	0.9606 (18)	0.072 (2)	0.095*
H52	0.086 (5)	0.876 (2)	0.1289 (13)	0.095*
O60	−0.1860 (3)	0.88960 (16)	−0.05485 (12)	0.0536 (5)
H61	−0.257 (4)	0.870 (3)	−0.0806 (15)	0.080*
H62	−0.210 (5)	0.856 (2)	−0.0083 (7)	0.080*
O70	0.2955 (5)	0.9520 (2)	−0.0899 (2)	0.1026 (10)
H71	0.236 (7)	1.010 (2)	−0.100 (3)	0.154*
H72	0.360 (7)	0.946 (4)	−0.1331 (16)	0.154*
O1	−0.0793 (3)	0.46163 (13)	0.22701 (10)	0.0473 (4)
H1	−0.018 (3)	0.4605 (14)	0.1823 (4)	0.057*
O2	0.1590 (3)	0.39434 (13)	0.11992 (9)	0.0436 (4)
O3	0.3135 (3)	0.23308 (14)	0.15024 (10)	0.0458 (4)
O4	0.1739 (3)	−0.22444 (16)	0.84208 (10)	0.0604 (6)
O5	0.3900 (3)	−0.29157 (14)	0.76258 (11)	0.0505 (5)
N1	0.1704 (3)	0.12249 (15)	0.45539 (11)	0.0371 (4)
N2	0.1011 (3)	0.12523 (16)	0.52805 (11)	0.0404 (5)
N3	0.2706 (3)	−0.21953 (15)	0.77658 (11)	0.0365 (4)
C1	0.1194 (3)	0.30052 (17)	0.25700 (12)	0.0311 (5)
C2	−0.0165 (3)	0.37726 (17)	0.28110 (14)	0.0362 (5)
C3	−0.0952 (4)	0.36977 (18)	0.36155 (14)	0.0380 (5)
H3	−0.1871	0.4210	0.3761	0.046*
C4	−0.0366 (4)	0.28584 (18)	0.42029 (14)	0.0386 (5)
H4	−0.0902	0.2800	0.4743	0.046*
C5	0.1029 (3)	0.21024 (17)	0.39831 (13)	0.0337 (5)
C6	0.1779 (3)	0.21715 (17)	0.31709 (13)	0.0326 (5)
H6	0.2685	0.1653	0.3027	0.039*
C7	0.1589 (3)	0.03711 (17)	0.58710 (13)	0.0342 (5)
C8	0.2876 (4)	−0.04755 (19)	0.57064 (14)	0.0391 (5)
H8	0.3462	−0.0474	0.5179	0.047*
C9	0.3263 (3)	−0.13020 (18)	0.63268 (13)	0.0364 (5)
H9	0.4103	−0.1870	0.6224	0.044*
C10	0.2389 (3)	−0.12844 (18)	0.71104 (13)	0.0367 (5)
C11	0.1150 (4)	−0.0458 (2)	0.72882 (14)	0.0453 (6)
H11	0.0575	−0.0465	0.7818	0.054*
C12	0.0773 (4)	0.0385 (2)	0.66638 (15)	0.0510 (7)
H12	−0.0029	0.0963	0.6775	0.061*
C13	0.2054 (3)	0.30891 (18)	0.16969 (13)	0.0356 (5)
O1A	0.6032 (3)	0.07174 (15)	0.80581 (11)	0.0539 (5)
H1A	0.560 (4)	0.0856 (15)	0.85009 (16)	0.065*
O2A	0.4361 (3)	0.18204 (14)	0.90509 (10)	0.0493 (5)
O3A	0.2881 (3)	0.33815 (14)	0.86157 (10)	0.0470 (4)
O4A	0.2033 (3)	0.66000 (15)	0.15994 (10)	0.0525 (5)
O5A	0.0646 (3)	0.75726 (14)	0.24188 (11)	0.0526 (5)
N1A	0.3363 (3)	0.38085 (16)	0.55961 (11)	0.0384 (5)
N2A	0.3935 (3)	0.36973 (16)	0.48885 (11)	0.0423 (5)
N3A	0.1545 (3)	0.67607 (16)	0.22755 (12)	0.0399 (5)
C1A	0.4205 (3)	0.23760 (17)	0.76376 (13)	0.0322 (5)
C2A	0.5323 (4)	0.14575 (18)	0.74698 (14)	0.0380 (5)
C3A	0.5708 (4)	0.1304 (2)	0.66745 (16)	0.0482 (6)
H3A	0.6399	0.0691	0.6567	0.058*
C4A	0.5078 (4)	0.2049 (2)	0.60525 (15)	0.0461 (6)
H4A	0.5349	0.1939	0.5524	0.055*
C5A	0.4012 (3)	0.29899 (17)	0.62036 (13)	0.0342 (5)
C6A	0.3575 (3)	0.31237 (18)	0.70010 (14)	0.0367 (5)
H6A	0.2846	0.3727	0.7109	0.044*
C7A	0.3266 (3)	0.45134 (18)	0.42707 (13)	0.0362 (5)
C8A	0.2047 (4)	0.53881 (19)	0.44037 (13)	0.0408 (6)
H8A	0.1622	0.5473	0.4932	0.049*
C9A	0.1465 (4)	0.61303 (19)	0.37529 (14)	0.0395 (5)
H9A	0.0645	0.6714	0.3835	0.047*
C10A	0.2138 (3)	0.59775 (17)	0.29782 (12)	0.0322 (5)
C11A	0.3370 (3)	0.51270 (18)	0.28285 (13)	0.0370 (5)
H11A	0.3811	0.5049	0.2300	0.044*
C12A	0.3923 (4)	0.43972 (19)	0.34866 (14)	0.0395 (5)
H12A	0.4752	0.3818	0.3401	0.047*
C13A	0.3759 (4)	0.2550 (2)	0.84887 (14)	0.0389 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0435 (6)	0.0394 (5)	0.0368 (5)	−0.0051 (4)	−0.0020 (4)	−0.0016 (4)
Na2	0.0520 (6)	0.0389 (5)	0.0562 (6)	−0.0043 (4)	−0.0044 (5)	−0.0123 (5)
O20	0.0436 (10)	0.0475 (10)	0.0345 (9)	−0.0057 (8)	−0.0055 (7)	−0.0112 (8)
O30	0.0524 (11)	0.0462 (10)	0.0351 (9)	−0.0039 (8)	−0.0060 (8)	−0.0076 (7)
O40	0.0480 (11)	0.0491 (10)	0.0319 (9)	−0.0103 (8)	−0.0040 (7)	−0.0103 (8)
O50	0.0938 (17)	0.0480 (12)	0.0484 (12)	−0.0096 (11)	−0.0190 (11)	−0.0041 (9)
O60	0.0611 (13)	0.0582 (12)	0.0440 (10)	−0.0114 (10)	−0.0044 (9)	−0.0149 (9)
O70	0.113 (3)	0.0613 (16)	0.129 (3)	−0.0298 (15)	−0.006 (2)	−0.0059 (16)
O1	0.0568 (12)	0.0376 (9)	0.0408 (10)	0.0063 (8)	−0.0115 (8)	0.0046 (8)
O2	0.0574 (11)	0.0397 (9)	0.0317 (8)	−0.0162 (8)	−0.0054 (8)	0.0024 (7)
O3	0.0586 (12)	0.0470 (10)	0.0308 (8)	−0.0037 (9)	0.0024 (8)	−0.0124 (7)
O4	0.0763 (14)	0.0646 (12)	0.0291 (9)	0.0013 (11)	0.0036 (9)	0.0025 (8)
O5	0.0551 (12)	0.0411 (10)	0.0476 (10)	0.0069 (9)	−0.0087 (9)	0.0028 (8)
N1	0.0443 (12)	0.0340 (10)	0.0290 (10)	−0.0009 (9)	−0.0054 (8)	0.0008 (8)
N2	0.0534 (13)	0.0403 (11)	0.0261 (10)	0.0012 (9)	−0.0065 (9)	−0.0058 (8)
N3	0.0437 (12)	0.0383 (11)	0.0278 (10)	−0.0095 (9)	−0.0046 (8)	−0.0044 (8)
C1	0.0388 (13)	0.0301 (11)	0.0258 (10)	−0.0107 (9)	−0.0052 (9)	−0.0045 (8)
C2	0.0424 (14)	0.0290 (11)	0.0361 (12)	−0.0047 (10)	−0.0103 (10)	0.0000 (9)
C3	0.0485 (14)	0.0289 (11)	0.0349 (12)	0.0060 (10)	−0.0053 (10)	−0.0078 (9)
C4	0.0464 (14)	0.0375 (12)	0.0304 (11)	0.0016 (11)	−0.0019 (10)	−0.0083 (10)
C5	0.0408 (13)	0.0325 (11)	0.0265 (11)	−0.0012 (10)	−0.0064 (9)	−0.0027 (9)
C6	0.0338 (12)	0.0282 (11)	0.0348 (12)	−0.0004 (9)	−0.0042 (9)	−0.0060 (9)
C7	0.0435 (14)	0.0301 (11)	0.0291 (11)	−0.0028 (10)	−0.0089 (10)	−0.0041 (9)
C8	0.0458 (14)	0.0408 (13)	0.0277 (11)	−0.0023 (11)	0.0039 (10)	−0.0078 (10)
C9	0.0402 (13)	0.0353 (12)	0.0312 (11)	−0.0010 (10)	−0.0002 (10)	−0.0061 (9)
C10	0.0415 (14)	0.0398 (13)	0.0273 (11)	−0.0045 (10)	−0.0028 (10)	−0.0046 (9)
C11	0.0633 (18)	0.0424 (13)	0.0237 (11)	0.0081 (12)	−0.0012 (11)	−0.0027 (10)
C12	0.0685 (19)	0.0462 (15)	0.0318 (12)	0.0155 (13)	−0.0023 (12)	−0.0075 (11)
C13	0.0405 (13)	0.0365 (12)	0.0308 (11)	−0.0100 (10)	−0.0085 (10)	−0.0028 (10)
O1A	0.0668 (13)	0.0477 (11)	0.0422 (10)	0.0057 (9)	−0.0099 (9)	−0.0023 (8)
O2A	0.0659 (13)	0.0486 (10)	0.0308 (9)	−0.0013 (9)	−0.0116 (8)	−0.0009 (8)
O3A	0.0658 (12)	0.0454 (10)	0.0319 (9)	0.0063 (9)	−0.0066 (8)	−0.0181 (7)
O4A	0.0711 (13)	0.0586 (11)	0.0258 (9)	0.0027 (10)	−0.0067 (8)	−0.0084 (8)
O5A	0.0676 (13)	0.0427 (10)	0.0413 (10)	0.0097 (9)	−0.0057 (9)	−0.0044 (8)
N1A	0.0431 (12)	0.0428 (11)	0.0300 (10)	−0.0050 (9)	−0.0059 (8)	−0.0078 (8)
N2A	0.0502 (13)	0.0460 (12)	0.0293 (10)	−0.0023 (10)	−0.0035 (9)	−0.0068 (9)
N3A	0.0435 (12)	0.0418 (11)	0.0331 (11)	−0.0092 (9)	−0.0029 (9)	−0.0038 (9)
C1A	0.0330 (12)	0.0345 (12)	0.0292 (11)	−0.0069 (9)	−0.0046 (9)	−0.0044 (9)
C2A	0.0457 (14)	0.0320 (12)	0.0326 (12)	−0.0037 (10)	−0.0079 (10)	0.0029 (9)
C3A	0.0531 (16)	0.0401 (14)	0.0476 (15)	0.0024 (12)	0.0014 (12)	−0.0102 (11)
C4A	0.0563 (17)	0.0477 (14)	0.0334 (13)	0.0055 (12)	−0.0080 (11)	−0.0100 (11)
C5A	0.0396 (13)	0.0348 (12)	0.0295 (11)	−0.0038 (10)	−0.0078 (9)	−0.0071 (9)
C6A	0.0389 (13)	0.0331 (12)	0.0377 (12)	−0.0026 (10)	−0.0011 (10)	−0.0099 (10)
C7A	0.0408 (13)	0.0354 (12)	0.0315 (11)	−0.0058 (10)	−0.0024 (10)	−0.0054 (9)
C8A	0.0554 (16)	0.0429 (13)	0.0241 (11)	0.0016 (11)	−0.0054 (10)	−0.0101 (10)
C9A	0.0441 (14)	0.0389 (13)	0.0351 (12)	−0.0019 (11)	−0.0047 (10)	−0.0081 (10)
C10A	0.0371 (13)	0.0345 (11)	0.0240 (10)	−0.0071 (9)	−0.0063 (9)	−0.0006 (9)
C11A	0.0415 (13)	0.0424 (13)	0.0280 (11)	−0.0034 (10)	−0.0020 (10)	−0.0111 (10)
C12A	0.0472 (15)	0.0414 (13)	0.0316 (12)	−0.0040 (11)	−0.0001 (10)	−0.0148 (10)
C13A	0.0424 (14)	0.0471 (14)	0.0273 (11)	−0.0149 (11)	−0.0052 (10)	−0.0016 (10)

Geometric parameters (Å, º)

Na1—O2	2.3474 (18)	C3—H3	0.9300
Na1—O20	2.366 (2)	C4—C5	1.392 (3)
Na1—O40	2.3743 (19)	C4—H4	0.9300
Na1—O30^i	2.4211 (19)	C5—C6	1.391 (3)
Na1—O30	2.474 (2)	C6—H6	0.9300
Na1—O4A	2.679 (2)	C7—C12	1.388 (3)
Na1—Na1^i	3.3560 (19)	C7—C8	1.406 (3)
Na1—Na2	3.4857 (14)	C8—C9	1.368 (3)
Na2—O70	2.319 (3)	C8—H8	0.9300
Na2—O50	2.372 (2)	C9—C10	1.387 (3)
Na2—O40	2.420 (2)	C9—H9	0.9300
Na2—O20	2.428 (2)	C10—C11	1.374 (3)
Na2—O60	2.481 (3)	C11—C12	1.384 (3)
Na2—O4^ii	2.491 (2)	C11—H11	0.9300
Na2—H21	2.67 (3)	C12—H12	0.9300
Na2—H62	2.42 (3)	O1A—C2A	1.347 (3)
O20—H21	0.821 (3)	O1A—H1A	0.8200 (10)
O20—H22	0.820 (3)	O2A—C13A	1.281 (3)
O30—Na1^i	2.4212 (19)	O3A—C13A	1.234 (3)
O30—H31	0.820 (3)	O4A—N3A	1.207 (2)
O30—H32	0.820 (3)	O5A—N3A	1.226 (3)
O40—H41	0.820 (3)	N1A—N2A	1.245 (3)
O40—H42	0.820 (3)	N1A—C5A	1.405 (3)
O50—H51	0.821 (3)	N2A—C7A	1.420 (3)
O50—H52	0.821 (3)	N3A—C10A	1.475 (3)
O60—H61	0.821 (3)	C1A—C6A	1.384 (3)
O60—H62	0.820 (3)	C1A—C2A	1.421 (3)
O70—H71	0.821 (3)	C1A—C13A	1.496 (3)
O70—H72	0.821 (3)	C2A—C3A	1.393 (4)
O1—C2	1.352 (3)	C3A—C4A	1.365 (4)
O1—H1	0.8201 (10)	C3A—H3A	0.9300
O2—C13	1.286 (3)	C4A—C5A	1.421 (3)
O3—C13	1.257 (3)	C4A—H4A	0.9300
O4—N3	1.212 (3)	C5A—C6A	1.390 (3)
O4—Na2^iii	2.491 (2)	C6A—H6A	0.9300
O5—N3	1.236 (3)	C7A—C12A	1.380 (3)
N1—N2	1.266 (3)	C7A—C8A	1.394 (3)
N1—C5	1.420 (3)	C8A—C9A	1.384 (3)
N2—C7	1.419 (3)	C8A—H8A	0.9300
N3—C10	1.462 (3)	C9A—C10A	1.382 (3)
C1—C6	1.394 (3)	C9A—H9A	0.9300
C1—C2	1.399 (3)	C10A—C11A	1.381 (3)
C1—C13	1.503 (3)	C11A—C12A	1.379 (3)
C2—C3	1.385 (3)	C11A—H11A	0.9300
C3—C4	1.384 (3)	C12A—H12A	0.9300
O2—Na1—O20	94.62 (7)	C13—O2—Na1	139.59 (16)
O2—Na1—O40	168.45 (7)	N3—O4—Na2^iii	149.03 (19)
O20—Na1—O40	87.33 (7)	N2—N1—C5	112.87 (19)
O2—Na1—O30^i	106.34 (7)	N1—N2—C7	114.96 (19)
O20—Na1—O30^i	97.26 (7)	O4—N3—O5	121.8 (2)
O40—Na1—O30^i	84.66 (7)	O4—N3—C10	119.2 (2)
O2—Na1—O30	91.35 (7)	O5—N3—C10	118.96 (18)
O20—Na1—O30	165.76 (7)	C6—C1—C2	117.82 (19)
O40—Na1—O30	84.32 (7)	C6—C1—C13	120.6 (2)
O30^i—Na1—O30	93.44 (6)	C2—C1—C13	121.53 (19)
O2—Na1—O4A	95.53 (7)	O1—C2—C3	116.7 (2)
O20—Na1—O4A	76.60 (6)	O1—C2—C1	121.8 (2)
O40—Na1—O4A	73.82 (6)	C3—C2—C1	121.5 (2)
O30^i—Na1—O4A	157.77 (7)	C4—C3—C2	119.8 (2)
O30—Na1—O4A	89.97 (7)	C4—C3—H3	120.1
O2—Na1—Na1^i	102.72 (6)	C2—C3—H3	120.1
O20—Na1—Na1^i	143.67 (6)	C3—C4—C5	119.8 (2)
O40—Na1—Na1^i	81.95 (6)	C3—C4—H4	120.1
O30^i—Na1—Na1^i	47.38 (5)	C5—C4—H4	120.1
O30—Na1—Na1^i	46.07 (5)	C6—C5—C4	119.9 (2)
O4A—Na1—Na1^i	131.87 (7)	C6—C5—N1	117.2 (2)
O2—Na1—Na2	135.26 (6)	C4—C5—N1	122.8 (2)
O20—Na1—Na2	44.06 (5)	C5—C6—C1	121.0 (2)
O40—Na1—Na2	43.88 (5)	C5—C6—H6	119.5
O30^i—Na1—Na2	97.02 (5)	C1—C6—H6	119.5
O30—Na1—Na2	125.25 (6)	C12—C7—C8	120.0 (2)
O4A—Na1—Na2	63.55 (5)	C12—C7—N2	114.8 (2)
Na1^i—Na1—Na2	120.90 (4)	C8—C7—N2	125.2 (2)
O70—Na2—O50	86.84 (11)	C9—C8—C7	119.6 (2)
O70—Na2—O40	86.28 (11)	C9—C8—H8	120.2
O50—Na2—O40	111.51 (8)	C7—C8—H8	120.2
O70—Na2—O20	159.68 (11)	C8—C9—C10	119.3 (2)
O50—Na2—O20	113.44 (8)	C8—C9—H9	120.3
O40—Na2—O20	84.92 (7)	C10—C9—H9	120.3
O70—Na2—O60	96.60 (11)	C11—C10—C9	122.2 (2)
O50—Na2—O60	82.84 (8)	C11—C10—N3	118.3 (2)
O40—Na2—O60	165.54 (8)	C9—C10—N3	119.5 (2)
O20—Na2—O60	87.70 (7)	C10—C11—C12	118.7 (2)
O70—Na2—O4^ii	78.88 (11)	C10—C11—H11	120.7
O50—Na2—O4^ii	158.56 (8)	C12—C11—H11	120.7
O40—Na2—O4^ii	83.66 (7)	C11—C12—C7	120.2 (2)
O20—Na2—O4^ii	81.96 (7)	C11—C12—H12	119.9
O60—Na2—O4^ii	83.01 (7)	C7—C12—H12	119.9
O70—Na2—Na1	128.35 (10)	O3—C13—O2	124.9 (2)
O50—Na2—Na1	115.65 (6)	O3—C13—C1	118.8 (2)
O40—Na2—Na1	42.85 (5)	O2—C13—C1	116.3 (2)
O20—Na2—Na1	42.65 (5)	C2A—O1A—H1A	108.9 (14)
O60—Na2—Na1	130.21 (6)	N3A—O4A—Na1	157.52 (16)
O4^ii—Na2—Na1	85.78 (6)	N2A—N1A—C5A	114.6 (2)
O70—Na2—H21	174.1 (5)	N1A—N2A—C7A	115.0 (2)
O50—Na2—H21	96.7 (3)	O4A—N3A—O5A	123.8 (2)
O40—Na2—H21	96.7 (5)	O4A—N3A—C10A	119.3 (2)
O20—Na2—H21	17.7 (3)	O5A—N3A—C10A	116.80 (19)
O60—Na2—H21	79.3 (5)	C6A—C1A—C2A	119.2 (2)
O4^ii—Na2—H21	96.4 (3)	C6A—C1A—C13A	120.2 (2)
Na1—Na2—H21	54.0 (5)	C2A—C1A—C13A	120.5 (2)
O70—Na2—H62	112.2 (5)	O1A—C2A—C3A	118.2 (2)
O50—Na2—H62	73.5 (7)	O1A—C2A—C1A	122.1 (2)
O40—Na2—H62	161.3 (6)	C3A—C2A—C1A	119.7 (2)
O20—Na2—H62	76.8 (6)	C4A—C3A—C2A	120.4 (2)
O60—Na2—H62	19.22 (10)	C4A—C3A—H3A	119.8
O4^ii—Na2—H62	97.0 (5)	C2A—C3A—H3A	119.8
Na1—Na2—H62	118.5 (6)	C3A—C4A—C5A	120.8 (2)
H21—Na2—H62	64.7 (7)	C3A—C4A—H4A	119.6
Na1—O20—Na2	93.28 (7)	C5A—C4A—H4A	119.6
Na1—O20—H21	122.3 (19)	C6A—C5A—N1A	117.0 (2)
Na2—O20—H21	98 (2)	C6A—C5A—C4A	118.7 (2)
Na1—O20—H22	122.5 (19)	N1A—C5A—C4A	124.3 (2)
Na2—O20—H22	112 (2)	C1A—C6A—C5A	121.2 (2)
H21—O20—H22	105 (2)	C1A—C6A—H6A	119.4
Na1^i—O30—Na1	86.56 (6)	C5A—C6A—H6A	119.4
Na1^i—O30—H31	116 (2)	C12A—C7A—C8A	119.8 (2)
Na1—O30—H31	114 (2)	C12A—C7A—N2A	114.9 (2)
Na1^i—O30—H32	104 (2)	C8A—C7A—N2A	125.2 (2)
Na1—O30—H32	130 (2)	C9A—C8A—C7A	120.3 (2)
H31—O30—H32	105 (3)	C9A—C8A—H8A	119.9
Na1—O40—Na2	93.27 (7)	C7A—C8A—H8A	119.9
Na1—O40—H41	124 (2)	C10A—C9A—C8A	118.0 (2)
Na2—O40—H41	102 (2)	C10A—C9A—H9A	121.0
Na1—O40—H42	115 (2)	C8A—C9A—H9A	121.0
Na2—O40—H42	117 (2)	C9A—C10A—C11A	122.9 (2)
H41—O40—H42	105 (3)	C9A—C10A—N3A	119.0 (2)
Na2—O50—H51	106 (3)	C11A—C10A—N3A	118.11 (19)
Na2—O50—H52	111 (3)	C12A—C11A—C10A	118.0 (2)
H51—O50—H52	105 (3)	C12A—C11A—H11A	121.0
Na2—O60—H61	130 (3)	C10A—C11A—H11A	121.0
Na2—O60—H62	76 (2)	C11A—C12A—C7A	121.0 (2)
H61—O60—H62	105 (3)	C11A—C12A—H12A	119.5
Na2—O70—H71	117 (4)	C7A—C12A—H12A	119.5
Na2—O70—H72	118 (4)	O3A—C13A—O2A	123.4 (2)
H71—O70—H72	105 (5)	O3A—C13A—C1A	119.5 (2)
C2—O1—H1	108.3 (13)	O2A—C13A—C1A	117.1 (2)
O2—Na1—Na2—O70	176.45 (14)	C6—C1—C2—C3	−1.8 (3)
O20—Na1—Na2—O70	−154.96 (15)	C13—C1—C2—C3	−179.7 (2)
O40—Na1—Na2—O70	12.97 (14)	O1—C2—C3—C4	−179.6 (2)
O30^i—Na1—Na2—O70	−61.76 (14)	C1—C2—C3—C4	1.3 (4)
O30—Na1—Na2—O70	37.51 (15)	C2—C3—C4—C5	0.8 (4)
O4A—Na1—Na2—O70	106.88 (14)	C3—C4—C5—C6	−2.3 (4)
Na1^i—Na1—Na2—O70	−17.94 (15)	C3—C4—C5—N1	179.6 (2)
O2—Na1—Na2—O50	68.87 (11)	N2—N1—C5—C6	176.9 (2)
O20—Na1—Na2—O50	97.46 (10)	N2—N1—C5—C4	−5.0 (3)
O40—Na1—Na2—O50	−94.61 (10)	C4—C5—C6—C1	1.7 (4)
O30^i—Na1—Na2—O50	−169.34 (9)	N1—C5—C6—C1	179.9 (2)
O30—Na1—Na2—O50	−70.07 (10)	C2—C1—C6—C5	0.3 (3)
O4A—Na1—Na2—O50	−0.69 (9)	C13—C1—C6—C5	178.2 (2)
Na1^i—Na1—Na2—O50	−125.52 (9)	N1—N2—C7—C12	−177.8 (2)
O2—Na1—Na2—O40	163.48 (10)	N1—N2—C7—C8	2.1 (4)
O20—Na1—Na2—O40	−167.93 (9)	C12—C7—C8—C9	2.5 (4)
O30^i—Na1—Na2—O40	−74.73 (8)	N2—C7—C8—C9	−177.4 (2)
O30—Na1—Na2—O40	24.54 (8)	C7—C8—C9—C10	−0.6 (4)
O4A—Na1—Na2—O40	93.92 (8)	C8—C9—C10—C11	−0.4 (4)
Na1^i—Na1—Na2—O40	−30.91 (7)	C8—C9—C10—N3	176.2 (2)
O2—Na1—Na2—O20	−28.60 (10)	O4—N3—C10—C11	7.3 (3)
O40—Na1—Na2—O20	167.93 (9)	O5—N3—C10—C11	−175.7 (2)
O30^i—Na1—Na2—O20	93.20 (8)	O4—N3—C10—C9	−169.4 (2)
O30—Na1—Na2—O20	−167.53 (9)	O5—N3—C10—C9	7.6 (3)
O4A—Na1—Na2—O20	−98.16 (8)	C9—C10—C11—C12	−0.4 (4)
Na1^i—Na1—Na2—O20	137.02 (8)	N3—C10—C11—C12	−177.0 (3)
O2—Na1—Na2—O60	−34.14 (12)	C10—C11—C12—C7	2.2 (4)
O20—Na1—Na2—O60	−5.54 (9)	C8—C7—C12—C11	−3.3 (4)
O40—Na1—Na2—O60	162.38 (10)	N2—C7—C12—C11	176.6 (3)
O30^i—Na1—Na2—O60	87.65 (9)	Na1—O2—C13—O3	−71.7 (3)
O30—Na1—Na2—O60	−173.08 (9)	Na1—O2—C13—C1	109.3 (2)
O4A—Na1—Na2—O60	−103.70 (9)	C6—C1—C13—O3	8.7 (3)
Na1^i—Na1—Na2—O60	131.48 (8)	C2—C1—C13—O3	−173.5 (2)
O2—Na1—Na2—O4^ii	−111.30 (10)	C6—C1—C13—O2	−172.3 (2)
O20—Na1—Na2—O4^ii	−82.71 (8)	C2—C1—C13—O2	5.6 (3)
O40—Na1—Na2—O4^ii	85.22 (8)	O2—Na1—O4A—N3A	15.2 (5)
O30^i—Na1—Na2—O4^ii	10.49 (8)	O20—Na1—O4A—N3A	108.6 (5)
O30—Na1—Na2—O4^ii	109.76 (8)	O40—Na1—O4A—N3A	−160.3 (5)
O4A—Na1—Na2—O4^ii	179.14 (8)	O30^i—Na1—O4A—N3A	−175.2 (4)
Na1^i—Na1—Na2—O4^ii	54.31 (8)	O30—Na1—O4A—N3A	−76.2 (5)
O2—Na1—O20—Na2	160.25 (7)	Na1^i—Na1—O4A—N3A	−97.4 (5)
O40—Na1—O20—Na2	−8.34 (6)	Na2—Na1—O4A—N3A	153.7 (5)
O30^i—Na1—O20—Na2	−92.61 (7)	C5A—N1A—N2A—C7A	179.2 (2)
O30—Na1—O20—Na2	45.8 (3)	Na1—O4A—N3A—O5A	−148.3 (3)
O4A—Na1—O20—Na2	65.65 (6)	Na1—O4A—N3A—C10A	35.5 (6)
Na1^i—Na1—O20—Na2	−80.88 (12)	C6A—C1A—C2A—O1A	177.8 (2)
O70—Na2—O20—Na1	72.9 (3)	C13A—C1A—C2A—O1A	−0.5 (4)
O50—Na2—O20—Na1	−103.05 (9)	C6A—C1A—C2A—C3A	−2.4 (4)
O40—Na2—O20—Na1	8.21 (6)	C13A—C1A—C2A—C3A	179.4 (2)
O60—Na2—O20—Na1	175.77 (7)	O1A—C2A—C3A—C4A	−177.7 (3)
O4^ii—Na2—O20—Na1	92.50 (7)	C1A—C2A—C3A—C4A	2.5 (4)
O2—Na1—O30—Na1^i	106.46 (7)	C2A—C3A—C4A—C5A	−0.3 (4)
O20—Na1—O30—Na1^i	−138.7 (3)	N2A—N1A—C5A—C6A	173.7 (2)
O40—Na1—O30—Na1^i	−84.28 (6)	N2A—N1A—C5A—C4A	−6.1 (3)
O30^i—Na1—O30—Na1^i	0.0	C3A—C4A—C5A—C6A	−1.9 (4)
O4A—Na1—O30—Na1^i	−158.02 (7)	C3A—C4A—C5A—N1A	177.9 (3)
Na2—Na1—O30—Na1^i	−101.09 (7)	C2A—C1A—C6A—C5A	0.2 (4)
O2—Na1—O40—Na2	−91.7 (4)	C13A—C1A—C6A—C5A	178.4 (2)
O20—Na1—O40—Na2	8.37 (6)	N1A—C5A—C6A—C1A	−177.9 (2)
O30^i—Na1—O40—Na2	105.92 (7)	C4A—C5A—C6A—C1A	1.9 (4)
O30—Na1—O40—Na2	−160.07 (7)	N1A—N2A—C7A—C12A	179.1 (2)
O4A—Na1—O40—Na2	−68.45 (7)	N1A—N2A—C7A—C8A	−0.6 (4)
Na1^i—Na1—O40—Na2	153.57 (6)	C12A—C7A—C8A—C9A	1.2 (4)
O70—Na2—O40—Na1	−169.84 (11)	N2A—C7A—C8A—C9A	−179.1 (2)
O50—Na2—O40—Na1	105.03 (8)	C7A—C8A—C9A—C10A	−0.4 (4)
O20—Na2—O40—Na1	−8.18 (6)	C8A—C9A—C10A—C11A	−0.6 (4)
O60—Na2—O40—Na1	−67.7 (3)	C8A—C9A—C10A—N3A	−179.7 (2)
O4^ii—Na2—O40—Na1	−90.63 (7)	O4A—N3A—C10A—C9A	−175.5 (2)
O20—Na1—O2—C13	−165.9 (2)	O5A—N3A—C10A—C9A	8.1 (3)
O40—Na1—O2—C13	−66.6 (5)	O4A—N3A—C10A—C11A	5.3 (3)
O30^i—Na1—O2—C13	95.1 (2)	O5A—N3A—C10A—C11A	−171.1 (2)
O30—Na1—O2—C13	1.2 (2)	C9A—C10A—C11A—C12A	0.8 (4)
O4A—Na1—O2—C13	−88.9 (2)	N3A—C10A—C11A—C12A	179.9 (2)
Na1^i—Na1—O2—C13	46.2 (2)	C10A—C11A—C12A—C7A	0.0 (4)
Na2—Na1—O2—C13	−146.4 (2)	C8A—C7A—C12A—C11A	−1.0 (4)
C5—N1—N2—C7	177.7 (2)	N2A—C7A—C12A—C11A	179.3 (2)
Na2^iii—O4—N3—O5	90.3 (4)	C6A—C1A—C13A—O3A	−2.5 (4)
Na2^iii—O4—N3—C10	−92.8 (3)	C2A—C1A—C13A—O3A	175.7 (2)
C6—C1—C2—O1	179.0 (2)	C6A—C1A—C13A—O2A	179.0 (2)
C13—C1—C2—O1	1.1 (3)	C2A—C1A—C13A—O2A	−2.8 (3)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z−1; (iii) x, y−1, z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82 (1)	1.80 (2)	2.534 (3)	149 (2)
O1A—H1A···O2A	0.82 (1)	1.80 (2)	2.532 (3)	147 (2)
O20—H21···O3A^iv	0.82 (2)	1.93 (2)	2.750 (2)	174 (3)
O20—H22···O2^v	0.82 (2)	2.04 (2)	2.862 (2)	173 (2)
O30—H31···O5^vi	0.82 (2)	2.32 (2)	3.135 (3)	175 (2)
O30—H32···O3A^vii	0.82 (2)	2.14 (3)	2.823 (3)	141 (2)
O40—H41···O2A^vii	0.82 (2)	2.00 (2)	2.819 (3)	172 (2)
O40—H42···O3^i	0.82 (2)	2.02 (2)	2.813 (3)	161 (3)
O50—H51···O60^viii	0.82 (3)	2.04 (2)	2.838 (3)	163 (3)
O50—H52···O5A	0.82 (3)	2.18 (2)	2.931 (3)	152 (3)
O60—H61···O3^v	0.82 (3)	2.09 (3)	2.828 (3)	150 (3)
O60—H62···O2A^iv	0.82 (2)	2.21 (3)	2.917 (3)	145 (3)
O70—H71···O50^viii	0.82 (4)	2.19 (5)	2.892 (4)	144 (4)
O70—H72···O1A^ii	0.82 (3)	2.48 (5)	2.972 (4)	119 (4)
C12—H12···O5A^iv	0.93	2.55	3.358 (3)	146
C12A—H12A···O5^vi	0.93	2.34	3.125 (3)	141

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z−1; (iv) −x, −y+1, −z+1; (v) −x, −y+1, −z; (vi) −x+1, −y, −z+1; (vii) −x+1, −y+1, −z+1; (viii) −x, −y+2, −z.