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The structures of two 1:1 proton-transfer red–black dye compounds formed by reaction of aniline yellow [4-(phenyldiazenyl)aniline] with 5-sulfosalicylic acid and benzenesulfonic acid, and a 1:2 nontransfer adduct compound with 3,5-dinitrobenzoic acid have been determined at either 130 or 200 K. The compounds are 2-(4-aminophenyl)-1-phenylhydrazin-1-ium 3-carboxy-4-hydroxybenzenesulfonate methanol solvate, C
12H
12N
3+·C
7H
5O
6S
−·CH
3OH, (I), 2-(4-aminophenyl)-1-phenylhydrazin-1-ium 4-(phenyldiazenyl)anilinium bis(benzenesulfonate), 2C
12H
12N
3+·2C
6H
5O
3S
−, (II), and 4-(phenyldiazenyl)aniline–3,5-dinitrobenzoic acid (1/2), C
12H
11N
3·2C
7H
4N
2O
6, (III). In compound (I), the diazenyl rather than the aniline group of aniline yellow is protonated, and this group subsequently takes part in a primary hydrogen-bonding interaction with a sulfonate O-atom acceptor, producing overall a three-dimensional framework structure. A feature of the hydrogen bonding in (I) is a peripheral edge-on cation–anion association also involving aromatic C—H
O hydrogen bonds, giving a conjoint
R12(6)
R12(7)
R21(4) motif. In the dichroic crystals of (II), one of the two aniline yellow species in the asymmetric unit is diazenyl-group protonated, while in the other the aniline group is protonated. Both of these groups form hydrogen bonds with sulfonate O-atom acceptors and these, together with other associations, give a one-dimensional chain structure. In compound (III), rather than proton transfer, there is preferential formation of a classic
R22(8) cyclic head-to-head hydrogen-bonded carboxylic acid homodimer between the two 3,5-dinitrobenzoic acid molecules, which, in association with the aniline yellow molecule that is disordered across a crystallographic inversion centre, results in an overall two-dimensional ribbon structure. This work has shown the correlation between structure and observed colour in crystalline aniline yellow compounds, illustrated graphically in the dichroic benzenesulfonate compound.
Supporting information
CCDC references: 755999; 756000; 756001
Compounds (I)–(III) were synthesized by heating together for 10 min under
reflux 4-(phenylazo)aniline (1 mmol) and, respectively,
3-carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic acid),
benzenesulfonic acid or 3,5-dinitrobenzoic acid (1 mmol), in either methanol
(50 ml) [for (I)] or 1:1 ethanol–water (50 ml) [for (II) and (III)]. Both (I)
(m.p. 435–437 K) and (II) (m.p. >538 K ) were obtained as red–black needle
prisms, with (II) exhibiting red to red–black dichroism, and (III) (m.p. 433 K) as red needles, after partial room-temperature evaporation of solvent.
H atoms potentially involved in hydrogen-bonding interactions were located by
difference methods and their positional and isotropic displacement parameters
were refined. Other H atoms were included at calculated positions, with C—H
= 0.93 Å, and treated as riding, with Uiso(H) = 1.2Ueq(C).
The sulfonate group of the D benzenesulfonate anion in (II) is
rotationally disordered, with refined occupancies of the major and minor
component O atoms of 0.80 (1) for O11D/O12D/O13D and
0.20 (1) for O14D/O15D/O16D. The occupancies of these
atoms were subsequently fixed at these values and the atoms of the minor
component were refined isotropically.
Data collection: SMART (Bruker, 2000) for (I); CrysAlis PRO (Oxford Diffraction, 2009) for (II), (III). Cell refinement: SMART (Bruker, 2000) for (I); CrysAlis PRO (Oxford Diffraction, 2009) for (II), (III). Data reduction: SAINT (Bruker, 1999) for (I); CrysAlis PRO (Oxford Diffraction, 2009) for (II), (III). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I); SIR92 (Altomare et al., 1994) for (II); SHELXS97 (Sheldrick, 2008) within WinGX (Farrugia, 1999) for (III). Program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) for (I); SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999) for (II), (III). For all compounds, molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).
(I) 2-(4-aminophenyl)-1-phenylhydrazin-1-ium
3-carboxy-4-hydroxybenzenesulfonate methanol solvate
top
Crystal data top
C12H12N3+·C7H5O6S−·CH4O | F(000) = 936 |
Mr = 447.46 | Dx = 1.437 Mg m−3 |
Monoclinic, P21/c | Melting point = 485–488 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 8.7174 (7) Å | Cell parameters from 3449 reflections |
b = 20.1160 (16) Å | θ = 2.4–27.1° |
c = 11.8827 (9) Å | µ = 0.21 mm−1 |
β = 97.145 (2)° | T = 130 K |
V = 2067.6 (3) Å3 | Prism, red-black |
Z = 4 | 0.45 × 0.25 × 0.20 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3640 independent reflections |
Radiation source: sealed tube | 3102 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.91, Tmax = 0.96 | k = −21→23 |
10840 measured reflections | l = −14→8 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0552P)2 + 0.4842P] where P = (Fo2 + 2Fc2)/3 |
3640 reflections | (Δ/σ)max < 0.001 |
305 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
Crystal data top
C12H12N3+·C7H5O6S−·CH4O | V = 2067.6 (3) Å3 |
Mr = 447.46 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.7174 (7) Å | µ = 0.21 mm−1 |
b = 20.1160 (16) Å | T = 130 K |
c = 11.8827 (9) Å | 0.45 × 0.25 × 0.20 mm |
β = 97.145 (2)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3640 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3102 reflections with I > 2σ(I) |
Tmin = 0.91, Tmax = 0.96 | Rint = 0.028 |
10840 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.101 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.37 e Å−3 |
3640 reflections | Δρmin = −0.33 e Å−3 |
305 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.78242 (17) | 0.46205 (8) | 1.01332 (12) | 0.0246 (5) | |
N4 | 1.1149 (2) | 0.36212 (10) | 0.69069 (15) | 0.0304 (6) | |
N11 | 0.72559 (17) | 0.52174 (8) | 1.01081 (13) | 0.0233 (5) | |
C1 | 0.8681 (2) | 0.44231 (9) | 0.93342 (15) | 0.0238 (6) | |
C2 | 0.9185 (2) | 0.37486 (9) | 0.94103 (16) | 0.0279 (6) | |
C3 | 0.9995 (2) | 0.34780 (9) | 0.86188 (16) | 0.0283 (6) | |
C4 | 1.0383 (2) | 0.38742 (9) | 0.76953 (15) | 0.0249 (6) | |
C5 | 0.9929 (2) | 0.45582 (9) | 0.76398 (15) | 0.0252 (6) | |
C6 | 0.9100 (2) | 0.48194 (9) | 0.84200 (15) | 0.0239 (6) | |
C11 | 0.6330 (2) | 0.54270 (9) | 1.09300 (15) | 0.0233 (5) | |
C21 | 0.5890 (2) | 0.49893 (10) | 1.17349 (15) | 0.0285 (6) | |
C31 | 0.4954 (2) | 0.52202 (10) | 1.25116 (16) | 0.0322 (6) | |
C41 | 0.4486 (2) | 0.58784 (10) | 1.25095 (16) | 0.0318 (6) | |
C51 | 0.4936 (2) | 0.63108 (10) | 1.17027 (16) | 0.0301 (6) | |
C61 | 0.5847 (2) | 0.60885 (9) | 1.09048 (15) | 0.0272 (6) | |
S5A | 0.77589 (5) | 0.66095 (2) | 0.75604 (4) | 0.0213 (1) | |
O2A | 0.28226 (17) | 0.73177 (8) | 0.38947 (12) | 0.0365 (5) | |
O51A | 0.70411 (14) | 0.62667 (6) | 0.84291 (10) | 0.0271 (4) | |
O52A | 0.88066 (14) | 0.61723 (6) | 0.70188 (10) | 0.0256 (4) | |
O53A | 0.85243 (15) | 0.72214 (7) | 0.79400 (11) | 0.0322 (4) | |
O71A | 0.17089 (16) | 0.64824 (7) | 0.69100 (11) | 0.0320 (5) | |
O72A | 0.08191 (15) | 0.69695 (7) | 0.52619 (11) | 0.0329 (4) | |
C1A | 0.3538 (2) | 0.68866 (9) | 0.57885 (15) | 0.0231 (5) | |
C2A | 0.3909 (2) | 0.71480 (9) | 0.47587 (15) | 0.0268 (6) | |
C3A | 0.5464 (2) | 0.72337 (10) | 0.45986 (16) | 0.0283 (6) | |
C4A | 0.6626 (2) | 0.70695 (9) | 0.54426 (15) | 0.0261 (6) | |
C5A | 0.6252 (2) | 0.68110 (9) | 0.64739 (14) | 0.0215 (5) | |
C6A | 0.4731 (2) | 0.67221 (9) | 0.66416 (15) | 0.0223 (5) | |
C7A | 0.1901 (2) | 0.67887 (9) | 0.59552 (16) | 0.0261 (6) | |
O1B | 0.8397 (2) | 0.55217 (8) | 0.49274 (14) | 0.0501 (6) | |
C1B | 0.7595 (3) | 0.49165 (13) | 0.49324 (19) | 0.0521 (9) | |
H41 | 0.38620 | 0.60320 | 1.30570 | 0.0380* | |
H2 | 0.89500 | 0.34830 | 1.00270 | 0.0340* | |
H3 | 1.03040 | 0.30250 | 0.86790 | 0.0340* | |
H5 | 1.02140 | 0.48320 | 0.70480 | 0.0300* | |
H6 | 0.87910 | 0.52720 | 0.83610 | 0.0290* | |
H11 | 0.738 (2) | 0.5498 (10) | 0.9590 (17) | 0.026 (5)* | |
H21 | 0.62240 | 0.45390 | 1.17530 | 0.0340* | |
H31 | 0.46270 | 0.49220 | 1.30550 | 0.0390* | |
H43 | 1.135 (2) | 0.3197 (12) | 0.6923 (17) | 0.037 (6)* | |
H42 | 1.135 (3) | 0.3862 (12) | 0.633 (2) | 0.046 (7)* | |
H51 | 0.46180 | 0.67630 | 1.16980 | 0.0360* | |
H61 | 0.61400 | 0.63840 | 1.03450 | 0.0330* | |
H2A | 0.192 (3) | 0.7255 (13) | 0.417 (2) | 0.057 (8)* | |
H3A | 0.57150 | 0.74070 | 0.39010 | 0.0340* | |
H4A | 0.76770 | 0.71300 | 0.53300 | 0.0310* | |
H6A | 0.44900 | 0.65480 | 0.73420 | 0.0270* | |
H71A | 0.070 (3) | 0.6443 (12) | 0.698 (2) | 0.050 (7)* | |
H1B | 0.846 (3) | 0.5699 (13) | 0.553 (2) | 0.054 (8)* | |
H11B | 0.75490 | 0.47070 | 0.41840 | 0.0780* | |
H12B | 0.81330 | 0.46210 | 0.55070 | 0.0780* | |
H13B | 0.65430 | 0.49990 | 0.51090 | 0.0780* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0252 (8) | 0.0244 (9) | 0.0233 (8) | −0.0001 (7) | −0.0004 (6) | 0.0011 (6) |
N4 | 0.0387 (10) | 0.0250 (10) | 0.0277 (10) | 0.0064 (8) | 0.0046 (8) | −0.0015 (8) |
N11 | 0.0255 (8) | 0.0223 (9) | 0.0220 (8) | 0.0000 (7) | 0.0031 (6) | 0.0030 (7) |
C1 | 0.0235 (9) | 0.0238 (10) | 0.0232 (10) | −0.0001 (8) | −0.0005 (7) | −0.0004 (7) |
C2 | 0.0312 (10) | 0.0254 (11) | 0.0265 (10) | −0.0007 (8) | 0.0011 (8) | 0.0048 (8) |
C3 | 0.0330 (11) | 0.0193 (10) | 0.0317 (10) | 0.0028 (8) | 0.0008 (8) | 0.0007 (8) |
C4 | 0.0249 (9) | 0.0246 (10) | 0.0235 (10) | −0.0006 (8) | −0.0033 (8) | −0.0025 (7) |
C5 | 0.0272 (10) | 0.0236 (10) | 0.0241 (10) | −0.0014 (8) | 0.0005 (8) | 0.0025 (8) |
C6 | 0.0248 (9) | 0.0204 (10) | 0.0257 (10) | 0.0017 (8) | −0.0001 (7) | 0.0011 (7) |
C11 | 0.0206 (9) | 0.0269 (10) | 0.0216 (9) | −0.0016 (8) | −0.0006 (7) | −0.0024 (7) |
C21 | 0.0318 (10) | 0.0260 (11) | 0.0274 (10) | −0.0020 (8) | 0.0026 (8) | 0.0007 (8) |
C31 | 0.0357 (11) | 0.0353 (12) | 0.0264 (10) | −0.0046 (9) | 0.0065 (8) | 0.0033 (8) |
C41 | 0.0294 (10) | 0.0400 (12) | 0.0264 (10) | −0.0014 (9) | 0.0054 (8) | −0.0060 (9) |
C51 | 0.0307 (11) | 0.0284 (11) | 0.0311 (11) | 0.0021 (8) | 0.0037 (8) | −0.0037 (8) |
C61 | 0.0290 (10) | 0.0264 (10) | 0.0264 (10) | −0.0017 (8) | 0.0044 (8) | 0.0024 (8) |
S5A | 0.0215 (2) | 0.0203 (3) | 0.0226 (2) | −0.0005 (2) | 0.0052 (2) | 0.0011 (2) |
O2A | 0.0328 (8) | 0.0484 (10) | 0.0272 (8) | 0.0024 (7) | −0.0002 (6) | 0.0072 (6) |
O51A | 0.0273 (7) | 0.0296 (8) | 0.0257 (7) | 0.0041 (6) | 0.0080 (5) | 0.0065 (5) |
O52A | 0.0226 (7) | 0.0272 (7) | 0.0279 (7) | 0.0013 (5) | 0.0065 (5) | 0.0013 (5) |
O53A | 0.0352 (8) | 0.0248 (7) | 0.0352 (8) | −0.0054 (6) | −0.0012 (6) | −0.0008 (6) |
O71A | 0.0206 (7) | 0.0443 (9) | 0.0321 (8) | −0.0013 (6) | 0.0069 (6) | 0.0053 (6) |
O72A | 0.0253 (7) | 0.0384 (8) | 0.0340 (8) | 0.0019 (6) | 0.0001 (6) | −0.0001 (6) |
C1A | 0.0255 (10) | 0.0198 (9) | 0.0246 (9) | −0.0003 (8) | 0.0055 (7) | −0.0023 (7) |
C2A | 0.0306 (10) | 0.0243 (10) | 0.0251 (10) | 0.0013 (8) | 0.0019 (8) | −0.0004 (8) |
C3A | 0.0345 (11) | 0.0286 (11) | 0.0229 (10) | −0.0009 (8) | 0.0076 (8) | 0.0039 (8) |
C4A | 0.0258 (10) | 0.0245 (10) | 0.0294 (10) | −0.0009 (8) | 0.0094 (8) | 0.0003 (8) |
C5A | 0.0244 (9) | 0.0182 (9) | 0.0227 (9) | 0.0014 (7) | 0.0057 (7) | −0.0001 (7) |
C6A | 0.0263 (10) | 0.0195 (9) | 0.0221 (9) | 0.0002 (7) | 0.0065 (7) | 0.0005 (7) |
C7A | 0.0277 (10) | 0.0220 (10) | 0.0283 (10) | 0.0006 (8) | 0.0024 (8) | −0.0052 (8) |
O1B | 0.0865 (14) | 0.0374 (9) | 0.0287 (9) | 0.0017 (9) | 0.0158 (8) | −0.0042 (7) |
C1B | 0.0475 (14) | 0.0724 (18) | 0.0350 (13) | −0.0121 (13) | 0.0000 (11) | 0.0041 (12) |
Geometric parameters (Å, º) top
S5A—C5A | 1.7706 (18) | C21—C31 | 1.386 (3) |
S5A—O53A | 1.4453 (14) | C31—C41 | 1.385 (3) |
S5A—O51A | 1.4468 (13) | C41—C51 | 1.387 (3) |
S5A—O52A | 1.4724 (13) | C51—C61 | 1.385 (3) |
O2A—C2A | 1.351 (2) | C2—H2 | 0.9500 |
O71A—C7A | 1.320 (2) | C3—H3 | 0.9500 |
O72A—C7A | 1.228 (2) | C5—H5 | 0.9500 |
O2A—H2A | 0.90 (3) | C6—H6 | 0.9500 |
O71A—H71A | 0.90 (3) | C21—H21 | 0.9500 |
O1B—C1B | 1.404 (3) | C31—H31 | 0.9500 |
O1B—H1B | 0.80 (2) | C41—H41 | 0.9500 |
N1—C1 | 1.339 (2) | C51—H51 | 0.9500 |
N1—N11 | 1.298 (2) | C61—H61 | 0.9500 |
N4—C4 | 1.318 (3) | C1A—C2A | 1.406 (3) |
N11—C11 | 1.407 (2) | C1A—C7A | 1.478 (2) |
N4—H42 | 0.88 (2) | C1A—C6A | 1.399 (3) |
N4—H43 | 0.87 (2) | C2A—C3A | 1.403 (2) |
N11—H11 | 0.85 (2) | C3A—C4A | 1.374 (3) |
C1—C6 | 1.431 (3) | C4A—C5A | 1.406 (2) |
C1—C2 | 1.426 (3) | C5A—C6A | 1.377 (2) |
C2—C3 | 1.358 (3) | C3A—H3A | 0.9500 |
C3—C4 | 1.430 (3) | C4A—H4A | 0.9500 |
C4—C5 | 1.431 (3) | C6A—H6A | 0.9500 |
C5—C6 | 1.351 (3) | C1B—H11B | 0.9800 |
C11—C21 | 1.389 (3) | C1B—H12B | 0.9800 |
C11—C61 | 1.395 (3) | C1B—H13B | 0.9800 |
| | | |
O52A—S5A—O53A | 110.96 (8) | C5—C6—H6 | 120.00 |
O52A—S5A—C5A | 105.21 (8) | C1—C6—H6 | 120.00 |
O53A—S5A—C5A | 107.73 (8) | C31—C21—H21 | 121.00 |
O51A—S5A—O53A | 114.02 (8) | C11—C21—H21 | 121.00 |
O51A—S5A—C5A | 106.37 (8) | C41—C31—H31 | 119.00 |
O51A—S5A—O52A | 111.96 (7) | C21—C31—H31 | 119.00 |
C2A—O2A—H2A | 104.5 (16) | C31—C41—H41 | 120.00 |
C7A—O71A—H71A | 110.6 (15) | C51—C41—H41 | 120.00 |
C1B—O1B—H1B | 111.3 (18) | C41—C51—H51 | 120.00 |
N11—N1—C1 | 120.20 (15) | C61—C51—H51 | 120.00 |
N1—N11—C11 | 120.77 (15) | C51—C61—H61 | 120.00 |
H43—N4—H42 | 120 (2) | C11—C61—H61 | 120.00 |
C4—N4—H43 | 118.8 (13) | C2A—C1A—C7A | 119.79 (16) |
C4—N4—H42 | 120.8 (16) | C6A—C1A—C7A | 120.97 (16) |
C11—N11—H11 | 116.0 (13) | C2A—C1A—C6A | 119.24 (16) |
N1—N11—H11 | 123.2 (13) | O2A—C2A—C3A | 117.63 (16) |
C2—C1—C6 | 118.21 (16) | C1A—C2A—C3A | 119.66 (16) |
N1—C1—C6 | 126.20 (17) | O2A—C2A—C1A | 122.71 (16) |
N1—C1—C2 | 115.59 (16) | C2A—C3A—C4A | 120.57 (17) |
C1—C2—C3 | 121.35 (17) | C3A—C4A—C5A | 119.68 (16) |
C2—C3—C4 | 120.06 (17) | C4A—C5A—C6A | 120.40 (16) |
C3—C4—C5 | 118.73 (16) | S5A—C5A—C4A | 119.25 (13) |
N4—C4—C3 | 121.27 (17) | S5A—C5A—C6A | 120.35 (13) |
N4—C4—C5 | 120.00 (17) | C1A—C6A—C5A | 120.47 (16) |
C4—C5—C6 | 120.73 (16) | O71A—C7A—O72A | 123.10 (16) |
C1—C6—C5 | 120.88 (17) | O71A—C7A—C1A | 113.91 (16) |
N11—C11—C21 | 121.30 (16) | O72A—C7A—C1A | 122.99 (17) |
C21—C11—C61 | 120.74 (17) | C4A—C3A—H3A | 120.00 |
N11—C11—C61 | 117.95 (16) | C2A—C3A—H3A | 120.00 |
C11—C21—C31 | 118.82 (18) | C3A—C4A—H4A | 120.00 |
C21—C31—C41 | 121.12 (18) | C5A—C4A—H4A | 120.00 |
C31—C41—C51 | 119.48 (17) | C1A—C6A—H6A | 120.00 |
C41—C51—C61 | 120.43 (18) | C5A—C6A—H6A | 120.00 |
C11—C61—C51 | 119.39 (17) | O1B—C1B—H11B | 109.00 |
C1—C2—H2 | 119.00 | O1B—C1B—H12B | 109.00 |
C3—C2—H2 | 119.00 | O1B—C1B—H13B | 109.00 |
C4—C3—H3 | 120.00 | H11B—C1B—H12B | 109.00 |
C2—C3—H3 | 120.00 | H11B—C1B—H13B | 109.00 |
C4—C5—H5 | 120.00 | H12B—C1B—H13B | 109.00 |
C6—C5—H5 | 120.00 | | |
| | | |
O51A—S5A—C5A—C4A | −171.49 (14) | C61—C11—C21—C31 | 0.3 (3) |
O52A—S5A—C5A—C4A | −52.56 (16) | N11—C11—C61—C51 | −179.93 (17) |
O53A—S5A—C5A—C4A | 65.87 (16) | C11—C21—C31—C41 | −1.4 (3) |
O51A—S5A—C5A—C6A | 9.19 (17) | C21—C31—C41—C51 | 1.3 (3) |
O52A—S5A—C5A—C6A | 128.12 (15) | C31—C41—C51—C61 | −0.1 (3) |
O53A—S5A—C5A—C6A | −113.45 (16) | C41—C51—C61—C11 | −1.0 (3) |
N11—N1—C1—C6 | 1.7 (3) | C2A—C1A—C7A—O71A | 173.86 (16) |
C1—N1—N11—C11 | 178.80 (16) | C2A—C1A—C7A—O72A | −5.4 (3) |
N11—N1—C1—C2 | −177.08 (16) | C6A—C1A—C7A—O71A | −6.1 (3) |
N1—N11—C11—C21 | −5.3 (3) | C6A—C1A—C7A—O72A | 174.71 (18) |
N1—N11—C11—C61 | 175.47 (16) | C7A—C1A—C2A—O2A | 0.0 (3) |
C6—C1—C2—C3 | −2.3 (3) | C7A—C1A—C2A—C3A | −179.32 (17) |
N1—C1—C2—C3 | 176.64 (17) | C2A—C1A—C6A—C5A | −0.4 (3) |
N1—C1—C6—C5 | −177.72 (17) | C7A—C1A—C6A—C5A | 179.54 (17) |
C2—C1—C6—C5 | 1.1 (3) | C6A—C1A—C2A—O2A | 179.89 (17) |
C1—C2—C3—C4 | 1.1 (3) | C6A—C1A—C2A—C3A | 0.6 (3) |
C2—C3—C4—C5 | 1.2 (3) | O2A—C2A—C3A—C4A | −179.86 (18) |
C2—C3—C4—N4 | −179.02 (18) | C1A—C2A—C3A—C4A | −0.5 (3) |
N4—C4—C5—C6 | 177.82 (18) | C2A—C3A—C4A—C5A | 0.2 (3) |
C3—C4—C5—C6 | −2.4 (3) | C3A—C4A—C5A—C6A | 0.0 (3) |
C4—C5—C6—C1 | 1.3 (3) | C3A—C4A—C5A—S5A | −179.34 (15) |
N11—C11—C21—C31 | −178.85 (16) | S5A—C5A—C6A—C1A | 179.41 (14) |
C21—C11—C61—C51 | 0.9 (3) | C4A—C5A—C6A—C1A | 0.1 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2A—H2A···O72A | 0.90 (3) | 1.80 (3) | 2.624 (2) | 151 (2) |
O71A—H71A···O52Ai | 0.90 (3) | 1.74 (3) | 2.6246 (19) | 166 (2) |
O1B—H1B···O52A | 0.80 (2) | 2.00 (2) | 2.792 (2) | 175 (2) |
N11—H11···O51A | 0.85 (2) | 2.07 (2) | 2.895 (2) | 163.1 (17) |
N4—H43···O53Aii | 0.87 (2) | 1.97 (2) | 2.834 (2) | 170.5 (17) |
N4—H42···O1Biii | 0.88 (2) | 1.98 (2) | 2.845 (2) | 173 (2) |
C6—H6···O51A | 0.95 | 2.52 | 3.421 (2) | 158 |
C6—H6···O52A | 0.95 | 2.41 | 3.184 (2) | 138 |
C6A—H6A···O51A | 0.95 | 2.49 | 2.888 (2) | 105 |
C61—H61···O51A | 0.95 | 2.51 | 3.260 (2) | 136 |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, y−1/2, −z+3/2; (iii) −x+2, −y+1, −z+1. |
(II) 2-(4-aminophenyl)-1-phenylhydrazin-1-ium (4-phenyldiazenyl)anilinium
bis(benzenesulfonate)
top
Crystal data top
2C12H12N3+·2C6H5O3S− | Z = 2 |
Mr = 710.82 | F(000) = 744 |
Triclinic, P1 | Dx = 1.363 Mg m−3 |
Hall symbol: -P 1 | Melting point > 533 K |
a = 5.7601 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.0794 (8) Å | Cell parameters from 9206 reflections |
c = 23.6556 (15) Å | θ = 3.1–28.8° |
α = 77.937 (5)° | µ = 0.21 mm−1 |
β = 83.985 (5)° | T = 200 K |
γ = 86.971 (5)° | Flat prism, red-black |
V = 1732.4 (2) Å3 | 0.40 × 0.20 × 0.12 mm |
Data collection top
Oxford Gemini-S CCD area-detector diffractometer | 7187 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 5717 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ω scans | θmax = 26.5°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→7 |
Tmin = 0.870, Tmax = 0.980 | k = −16→16 |
22657 measured reflections | l = −29→29 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0526P)2 + 0.1286P] where P = (Fo2 + 2Fc2)/3 |
7187 reflections | (Δ/σ)max = 0.002 |
487 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
Crystal data top
2C12H12N3+·2C6H5O3S− | γ = 86.971 (5)° |
Mr = 710.82 | V = 1732.4 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.7601 (4) Å | Mo Kα radiation |
b = 13.0794 (8) Å | µ = 0.21 mm−1 |
c = 23.6556 (15) Å | T = 200 K |
α = 77.937 (5)° | 0.40 × 0.20 × 0.12 mm |
β = 83.985 (5)° | |
Data collection top
Oxford Gemini-S CCD area-detector diffractometer | 7187 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5717 reflections with I > 2σ(I) |
Tmin = 0.870, Tmax = 0.980 | Rint = 0.028 |
22657 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.28 e Å−3 |
7187 reflections | Δρmin = −0.33 e Å−3 |
487 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
N1A | 0.5326 (2) | 0.15945 (10) | 0.55716 (5) | 0.0249 (4) | |
N4A | −0.2488 (2) | 0.41954 (11) | 0.52166 (7) | 0.0302 (4) | |
N11A | 0.6418 (2) | 0.14091 (10) | 0.60432 (6) | 0.0252 (4) | |
C1A | 0.3444 (3) | 0.22648 (12) | 0.55278 (6) | 0.0234 (4) | |
C2A | 0.2423 (3) | 0.28433 (12) | 0.59501 (7) | 0.0276 (5) | |
C3A | 0.0487 (3) | 0.34701 (13) | 0.58471 (7) | 0.0288 (5) | |
C4A | −0.0586 (3) | 0.35780 (11) | 0.53126 (7) | 0.0237 (4) | |
C5A | 0.0447 (3) | 0.30193 (13) | 0.48861 (7) | 0.0284 (5) | |
C6A | 0.2387 (3) | 0.23909 (13) | 0.49927 (7) | 0.0279 (5) | |
C11A | 0.8343 (3) | 0.06750 (12) | 0.61005 (6) | 0.0246 (4) | |
C21A | 0.9775 (3) | 0.06756 (12) | 0.65455 (7) | 0.0270 (5) | |
C31A | 1.1706 (3) | −0.00158 (13) | 0.66037 (7) | 0.0315 (5) | |
C41A | 1.2221 (3) | −0.06907 (13) | 0.62224 (7) | 0.0330 (5) | |
C51A | 1.0777 (3) | −0.06926 (13) | 0.57850 (8) | 0.0351 (6) | |
C61A | 0.8820 (3) | −0.00135 (13) | 0.57228 (7) | 0.0308 (5) | |
N1B | 0.9485 (2) | 0.62632 (11) | 0.92492 (6) | 0.0315 (4) | |
N4B | 0.8937 (3) | 0.38824 (12) | 0.75157 (7) | 0.0297 (5) | |
N11B | 1.1276 (2) | 0.61019 (11) | 0.95245 (6) | 0.0313 (4) | |
C1B | 0.9441 (3) | 0.56207 (12) | 0.88232 (7) | 0.0256 (5) | |
C2B | 0.7475 (3) | 0.57629 (13) | 0.85084 (7) | 0.0305 (5) | |
C3B | 0.7279 (3) | 0.51812 (13) | 0.80848 (7) | 0.0283 (5) | |
C4B | 0.9062 (3) | 0.44658 (12) | 0.79819 (6) | 0.0234 (4) | |
C5B | 1.1024 (3) | 0.43097 (13) | 0.82944 (7) | 0.0294 (5) | |
C6B | 1.1205 (3) | 0.48867 (13) | 0.87155 (7) | 0.0295 (5) | |
C11B | 1.1364 (3) | 0.67357 (13) | 0.99493 (7) | 0.0291 (5) | |
C21B | 0.9626 (3) | 0.74718 (15) | 1.00706 (8) | 0.0376 (6) | |
C31B | 0.9901 (4) | 0.80453 (17) | 1.04875 (9) | 0.0484 (7) | |
C41B | 1.1895 (3) | 0.78828 (16) | 1.07946 (8) | 0.0458 (7) | |
C51B | 1.3604 (3) | 0.71506 (16) | 1.06759 (8) | 0.0411 (6) | |
C61B | 1.3348 (3) | 0.65765 (15) | 1.02560 (7) | 0.0364 (6) | |
S1D | 0.37349 (7) | 0.53551 (3) | 0.64795 (2) | 0.0253 (1) | |
O11D | 0.4719 (4) | 0.5609 (2) | 0.58754 (10) | 0.0322 (7) | 0.80 (1) |
O12D | 0.4817 (4) | 0.44266 (13) | 0.68188 (9) | 0.0437 (7) | 0.80 (1) |
O13D | 0.1139 (3) | 0.53091 (17) | 0.65288 (9) | 0.0292 (6) | 0.80 (1) |
C1D | 0.4297 (3) | 0.64119 (12) | 0.68114 (6) | 0.0229 (4) | |
C2D | 0.6437 (3) | 0.69011 (13) | 0.66785 (7) | 0.0299 (5) | |
C3D | 0.6903 (3) | 0.76852 (14) | 0.69672 (8) | 0.0396 (6) | |
C4D | 0.5269 (3) | 0.79604 (14) | 0.73903 (8) | 0.0421 (6) | |
C5D | 0.3164 (3) | 0.74701 (14) | 0.75231 (8) | 0.0391 (6) | |
C6D | 0.2653 (3) | 0.66965 (12) | 0.72327 (7) | 0.0285 (5) | |
O16D | 0.5670 (17) | 0.4570 (8) | 0.6626 (4) | 0.056 (3)* | 0.20 (1) |
O14D | 0.415 (2) | 0.5810 (10) | 0.5842 (6) | 0.047 (4)* | 0.20 (1) |
O15D | 0.1543 (19) | 0.5028 (8) | 0.6657 (5) | 0.048 (3)* | 0.20 (1) |
S1C | 0.42375 (7) | 0.18835 (3) | 0.76892 (2) | 0.0247 (1) | |
O11C | 0.5634 (2) | 0.18672 (10) | 0.71390 (5) | 0.0423 (4) | |
O12C | 0.50971 (19) | 0.26263 (9) | 0.79942 (5) | 0.0312 (3) | |
O13C | 0.1729 (2) | 0.20097 (9) | 0.76321 (6) | 0.0413 (4) | |
C1C | 0.4682 (3) | 0.06238 (12) | 0.81416 (7) | 0.0278 (5) | |
C2C | 0.6882 (3) | 0.01280 (14) | 0.81285 (8) | 0.0372 (6) | |
C3C | 0.7235 (4) | −0.08399 (15) | 0.84969 (9) | 0.0468 (7) | |
C4C | 0.5430 (4) | −0.13037 (16) | 0.88718 (9) | 0.0539 (8) | |
C5C | 0.3268 (4) | −0.08039 (19) | 0.88912 (10) | 0.0663 (9) | |
C6C | 0.2877 (3) | 0.01656 (17) | 0.85245 (9) | 0.0486 (7) | |
H43A | −0.313 (3) | 0.4262 (14) | 0.4872 (9) | 0.041 (5)* | |
H2A | 0.30910 | 0.27890 | 0.62970 | 0.0330* | |
H3A | −0.01570 | 0.38360 | 0.61270 | 0.0340* | |
H5A | −0.02020 | 0.30840 | 0.45360 | 0.0340* | |
H6A | 0.30440 | 0.20340 | 0.47110 | 0.0340* | |
H11A | 0.595 (3) | 0.1643 (15) | 0.6357 (8) | 0.042 (5)* | |
H21A | 0.94410 | 0.11320 | 0.67990 | 0.0320* | |
H31A | 1.26550 | −0.00250 | 0.69000 | 0.0380* | |
H41A | 1.35260 | −0.11410 | 0.62590 | 0.0400* | |
H42A | −0.298 (3) | 0.4526 (16) | 0.5477 (9) | 0.047 (6)* | |
H51A | 1.11180 | −0.11490 | 0.55320 | 0.0420* | |
H61A | 0.78500 | −0.00210 | 0.54330 | 0.0370* | |
H44B | 0.946 (4) | 0.4341 (18) | 0.7143 (10) | 0.062 (7)* | |
H2B | 0.63000 | 0.62460 | 0.85820 | 0.0370* | |
H3B | 0.59780 | 0.52710 | 0.78750 | 0.0340* | |
H5B | 1.21950 | 0.38240 | 0.82200 | 0.0350* | |
H6B | 1.24990 | 0.47870 | 0.89270 | 0.0350* | |
H21B | 0.82950 | 0.75740 | 0.98720 | 0.0450* | |
H31B | 0.87610 | 0.85410 | 1.05650 | 0.0580* | |
H41B | 1.20660 | 0.82660 | 1.10770 | 0.0550* | |
H42B | 0.759 (5) | 0.3715 (19) | 0.7518 (10) | 0.068 (8)* | |
H43B | 0.998 (4) | 0.3254 (18) | 0.7557 (9) | 0.055 (6)* | |
H51B | 1.49260 | 0.70440 | 1.08780 | 0.0490* | |
H61B | 1.44980 | 0.60850 | 1.01780 | 0.0440* | |
H3D | 0.83130 | 0.80250 | 0.68760 | 0.0480* | |
H6D | 0.12240 | 0.63720 | 0.73190 | 0.0340* | |
H4D | 0.55990 | 0.84770 | 0.75840 | 0.0500* | |
H5D | 0.20800 | 0.76550 | 0.78070 | 0.0470* | |
H2D | 0.75400 | 0.67070 | 0.64010 | 0.0360* | |
H2C | 0.81110 | 0.04400 | 0.78760 | 0.0450* | |
H3C | 0.87030 | −0.11720 | 0.84880 | 0.0560* | |
H4C | 0.56670 | −0.19530 | 0.91120 | 0.0650* | |
H5C | 0.20540 | −0.11130 | 0.91500 | 0.0800* | |
H6C | 0.14100 | 0.04980 | 0.85390 | 0.0580* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1A | 0.0252 (6) | 0.0261 (7) | 0.0231 (7) | −0.0006 (5) | −0.0037 (5) | −0.0040 (5) |
N4A | 0.0290 (7) | 0.0313 (8) | 0.0323 (8) | 0.0053 (6) | −0.0065 (6) | −0.0111 (7) |
N11A | 0.0253 (7) | 0.0289 (7) | 0.0222 (7) | 0.0021 (5) | −0.0032 (5) | −0.0075 (6) |
C1A | 0.0237 (7) | 0.0225 (8) | 0.0241 (8) | −0.0021 (6) | −0.0023 (6) | −0.0047 (6) |
C2A | 0.0326 (8) | 0.0290 (8) | 0.0242 (8) | 0.0006 (7) | −0.0094 (6) | −0.0093 (7) |
C3A | 0.0332 (9) | 0.0285 (8) | 0.0282 (9) | 0.0022 (7) | −0.0037 (7) | −0.0145 (7) |
C4A | 0.0243 (8) | 0.0198 (7) | 0.0270 (8) | −0.0034 (6) | −0.0022 (6) | −0.0040 (6) |
C5A | 0.0300 (8) | 0.0345 (9) | 0.0222 (8) | 0.0027 (7) | −0.0072 (6) | −0.0081 (7) |
C6A | 0.0320 (8) | 0.0313 (9) | 0.0226 (8) | 0.0019 (7) | −0.0027 (6) | −0.0110 (7) |
C11A | 0.0236 (7) | 0.0247 (8) | 0.0240 (8) | −0.0006 (6) | −0.0008 (6) | −0.0021 (6) |
C21A | 0.0286 (8) | 0.0272 (8) | 0.0258 (8) | −0.0012 (6) | −0.0028 (6) | −0.0065 (6) |
C31A | 0.0288 (8) | 0.0334 (9) | 0.0312 (9) | −0.0018 (7) | −0.0076 (7) | −0.0016 (7) |
C41A | 0.0296 (8) | 0.0283 (9) | 0.0379 (10) | 0.0057 (7) | −0.0029 (7) | −0.0016 (7) |
C51A | 0.0417 (10) | 0.0304 (9) | 0.0341 (10) | 0.0068 (8) | −0.0031 (7) | −0.0107 (7) |
C61A | 0.0362 (9) | 0.0316 (9) | 0.0260 (8) | 0.0024 (7) | −0.0077 (7) | −0.0075 (7) |
N1B | 0.0330 (7) | 0.0345 (8) | 0.0290 (7) | 0.0029 (6) | −0.0074 (6) | −0.0099 (6) |
N4B | 0.0278 (8) | 0.0295 (8) | 0.0350 (9) | 0.0001 (6) | −0.0065 (6) | −0.0125 (6) |
N11B | 0.0312 (7) | 0.0365 (8) | 0.0274 (7) | −0.0009 (6) | −0.0063 (6) | −0.0079 (6) |
C1B | 0.0276 (8) | 0.0255 (8) | 0.0243 (8) | 0.0000 (6) | −0.0035 (6) | −0.0059 (6) |
C2B | 0.0280 (8) | 0.0317 (9) | 0.0328 (9) | 0.0095 (7) | −0.0070 (7) | −0.0093 (7) |
C3B | 0.0252 (8) | 0.0326 (9) | 0.0280 (8) | 0.0039 (7) | −0.0090 (6) | −0.0065 (7) |
C4B | 0.0252 (8) | 0.0218 (7) | 0.0232 (8) | −0.0034 (6) | −0.0021 (6) | −0.0039 (6) |
C5B | 0.0241 (8) | 0.0291 (9) | 0.0357 (9) | 0.0052 (7) | −0.0050 (7) | −0.0089 (7) |
C6B | 0.0242 (8) | 0.0339 (9) | 0.0325 (9) | 0.0035 (7) | −0.0096 (7) | −0.0091 (7) |
C11B | 0.0324 (8) | 0.0319 (9) | 0.0227 (8) | −0.0046 (7) | −0.0027 (6) | −0.0041 (7) |
C21B | 0.0374 (10) | 0.0461 (11) | 0.0325 (10) | 0.0035 (8) | −0.0108 (7) | −0.0130 (8) |
C31B | 0.0515 (12) | 0.0532 (12) | 0.0472 (12) | 0.0124 (10) | −0.0117 (9) | −0.0254 (10) |
C41B | 0.0544 (12) | 0.0530 (12) | 0.0365 (11) | −0.0029 (10) | −0.0105 (9) | −0.0210 (9) |
C51B | 0.0385 (10) | 0.0562 (12) | 0.0318 (10) | −0.0040 (9) | −0.0114 (8) | −0.0117 (9) |
C61B | 0.0328 (9) | 0.0431 (10) | 0.0349 (10) | 0.0010 (8) | −0.0069 (7) | −0.0105 (8) |
S1D | 0.0300 (2) | 0.0225 (2) | 0.0249 (2) | 0.0015 (2) | −0.0078 (2) | −0.0064 (2) |
O11D | 0.0311 (12) | 0.0422 (13) | 0.0263 (10) | 0.0013 (11) | −0.0014 (9) | −0.0154 (8) |
O12D | 0.0653 (14) | 0.0198 (8) | 0.0498 (13) | 0.0073 (9) | −0.0322 (11) | −0.0047 (8) |
O13D | 0.0259 (9) | 0.0322 (10) | 0.0324 (10) | −0.0068 (8) | −0.0049 (8) | −0.0108 (9) |
C1D | 0.0258 (8) | 0.0209 (7) | 0.0226 (8) | 0.0013 (6) | −0.0079 (6) | −0.0035 (6) |
C2D | 0.0248 (8) | 0.0298 (9) | 0.0335 (9) | 0.0012 (7) | −0.0058 (7) | −0.0016 (7) |
C3D | 0.0340 (9) | 0.0309 (9) | 0.0546 (12) | −0.0089 (8) | −0.0225 (8) | 0.0007 (8) |
C4D | 0.0598 (12) | 0.0262 (9) | 0.0470 (11) | 0.0017 (8) | −0.0279 (10) | −0.0126 (8) |
C5D | 0.0521 (11) | 0.0341 (10) | 0.0332 (10) | 0.0084 (8) | −0.0072 (8) | −0.0123 (8) |
C6D | 0.0295 (8) | 0.0267 (8) | 0.0290 (9) | 0.0017 (7) | −0.0035 (7) | −0.0056 (7) |
S1C | 0.0268 (2) | 0.0245 (2) | 0.0253 (2) | 0.0042 (2) | −0.0072 (2) | −0.0099 (2) |
O11C | 0.0589 (8) | 0.0420 (7) | 0.0242 (6) | 0.0176 (6) | −0.0033 (6) | −0.0077 (5) |
O12C | 0.0342 (6) | 0.0294 (6) | 0.0340 (6) | −0.0025 (5) | −0.0068 (5) | −0.0134 (5) |
O13C | 0.0299 (6) | 0.0324 (7) | 0.0663 (9) | 0.0056 (5) | −0.0199 (6) | −0.0148 (6) |
C1C | 0.0335 (9) | 0.0269 (8) | 0.0265 (8) | −0.0008 (7) | −0.0098 (7) | −0.0099 (7) |
C2C | 0.0380 (10) | 0.0350 (10) | 0.0385 (10) | 0.0059 (8) | −0.0091 (8) | −0.0063 (8) |
C3C | 0.0536 (12) | 0.0386 (11) | 0.0504 (12) | 0.0100 (9) | −0.0228 (10) | −0.0083 (9) |
C4C | 0.0698 (15) | 0.0381 (11) | 0.0524 (13) | −0.0080 (10) | −0.0304 (11) | 0.0077 (9) |
C5C | 0.0620 (15) | 0.0632 (15) | 0.0608 (15) | −0.0211 (12) | −0.0038 (11) | 0.0203 (12) |
C6C | 0.0381 (10) | 0.0516 (12) | 0.0507 (12) | −0.0024 (9) | −0.0025 (9) | 0.0012 (10) |
Geometric parameters (Å, º) top
S1D—O16D | 1.493 (10) | C61A—H61A | 0.9300 |
S1D—O15D | 1.351 (11) | C1B—C2B | 1.403 (2) |
S1D—O13D | 1.4910 (18) | C1B—C6B | 1.401 (2) |
S1D—O11D | 1.458 (2) | C2B—C3B | 1.395 (2) |
S1D—O12D | 1.458 (2) | C3B—C4B | 1.390 (2) |
S1D—C1D | 1.7849 (16) | C4B—C5B | 1.398 (2) |
S1D—O14D | 1.500 (14) | C5B—C6B | 1.385 (2) |
S1C—C1C | 1.7892 (17) | C11B—C61B | 1.400 (2) |
S1C—O13C | 1.4628 (12) | C11B—C21B | 1.402 (3) |
S1C—O11C | 1.4601 (12) | C21B—C31B | 1.384 (3) |
S1C—O12C | 1.4589 (12) | C31B—C41B | 1.406 (3) |
N1A—N11A | 1.3103 (18) | C41B—C51B | 1.386 (3) |
N1A—C1A | 1.356 (2) | C51B—C61B | 1.388 (3) |
N4A—C4A | 1.336 (2) | C2B—H2B | 0.9300 |
N11A—C11A | 1.426 (2) | C3B—H3B | 0.9300 |
N4A—H43A | 0.92 (2) | C5B—H5B | 0.9300 |
N4A—H42A | 0.84 (2) | C6B—H6B | 0.9300 |
N11A—H11A | 0.873 (19) | C21B—H21B | 0.9300 |
N1B—C1B | 1.444 (2) | C31B—H31B | 0.9300 |
N1B—N11B | 1.2623 (17) | C41B—H41B | 0.9300 |
N4B—C4B | 1.476 (2) | C51B—H51B | 0.9300 |
N11B—C11B | 1.436 (2) | C61B—H61B | 0.9300 |
N4B—H44B | 0.99 (2) | C1D—C6D | 1.396 (2) |
N4B—H43B | 0.99 (2) | C1D—C2D | 1.395 (2) |
N4B—H42B | 0.82 (3) | C2D—C3D | 1.397 (3) |
C1A—C2A | 1.436 (2) | C3D—C4D | 1.391 (3) |
C1A—C6A | 1.437 (2) | C4D—C5D | 1.378 (3) |
C2A—C3A | 1.361 (2) | C5D—C6D | 1.395 (2) |
C3A—C4A | 1.442 (2) | C2D—H2D | 0.9300 |
C4A—C5A | 1.429 (2) | C3D—H3D | 0.9300 |
C5A—C6A | 1.365 (2) | C4D—H4D | 0.9300 |
C11A—C21A | 1.404 (2) | C5D—H5D | 0.9300 |
C11A—C61A | 1.394 (2) | C6D—H6D | 0.9300 |
C21A—C31A | 1.396 (2) | C1C—C2C | 1.393 (2) |
C31A—C41A | 1.389 (2) | C1C—C6C | 1.379 (3) |
C41A—C51A | 1.394 (2) | C2C—C3C | 1.397 (3) |
C51A—C61A | 1.398 (2) | C3C—C4C | 1.373 (3) |
C2A—H2A | 0.9300 | C4C—C5C | 1.377 (3) |
C3A—H3A | 0.9300 | C5C—C6C | 1.401 (3) |
C5A—H5A | 0.9300 | C2C—H2C | 0.9300 |
C6A—H6A | 0.9300 | C3C—H3C | 0.9300 |
C21A—H21A | 0.9300 | C4C—H4C | 0.9300 |
C31A—H31A | 0.9300 | C5C—H5C | 0.9300 |
C41A—H41A | 0.9300 | C6C—H6C | 0.9300 |
C51A—H51A | 0.9300 | | |
| | | |
O15D—S1D—C1D | 109.6 (5) | N1B—C1B—C6B | 124.10 (15) |
O16D—S1D—C1D | 105.0 (4) | C1B—C2B—C3B | 120.18 (16) |
O14D—S1D—O15D | 114.4 (7) | C2B—C3B—C4B | 118.79 (15) |
O14D—S1D—O16D | 106.8 (6) | N4B—C4B—C3B | 119.45 (15) |
O15D—S1D—O16D | 116.4 (6) | N4B—C4B—C5B | 118.77 (15) |
O12D—S1D—O13D | 112.43 (12) | C3B—C4B—C5B | 121.73 (15) |
O12D—S1D—C1D | 105.85 (10) | C4B—C5B—C6B | 119.21 (16) |
O13D—S1D—C1D | 104.83 (10) | C1B—C6B—C5B | 120.13 (16) |
O14D—S1D—C1D | 103.5 (5) | C21B—C11B—C61B | 119.80 (16) |
O11D—S1D—O12D | 113.57 (13) | N11B—C11B—C61B | 115.63 (15) |
O11D—S1D—O13D | 111.75 (12) | N11B—C11B—C21B | 124.57 (15) |
O11D—S1D—C1D | 107.73 (12) | C11B—C21B—C31B | 119.65 (17) |
O11C—S1C—C1C | 106.08 (8) | C21B—C31B—C41B | 120.4 (2) |
O12C—S1C—O13C | 113.22 (7) | C31B—C41B—C51B | 119.84 (18) |
O12C—S1C—C1C | 105.28 (7) | C41B—C51B—C61B | 120.15 (17) |
O11C—S1C—O12C | 111.91 (7) | C11B—C61B—C51B | 120.19 (17) |
O13C—S1C—C1C | 106.44 (8) | C3B—C2B—H2B | 120.00 |
O11C—S1C—O13C | 113.16 (8) | C1B—C2B—H2B | 120.00 |
N11A—N1A—C1A | 120.09 (12) | C2B—C3B—H3B | 121.00 |
N1A—N11A—C11A | 120.31 (13) | C4B—C3B—H3B | 121.00 |
C4A—N4A—H43A | 119.4 (12) | C6B—C5B—H5B | 120.00 |
H42A—N4A—H43A | 124.0 (17) | C4B—C5B—H5B | 120.00 |
C4A—N4A—H42A | 116.5 (13) | C5B—C6B—H6B | 120.00 |
N1A—N11A—H11A | 124.6 (12) | C1B—C6B—H6B | 120.00 |
C11A—N11A—H11A | 114.6 (12) | C31B—C21B—H21B | 120.00 |
N11B—N1B—C1B | 113.66 (13) | C11B—C21B—H21B | 120.00 |
N1B—N11B—C11B | 114.68 (14) | C41B—C31B—H31B | 120.00 |
H42B—N4B—H43B | 110 (2) | C21B—C31B—H31B | 120.00 |
C4B—N4B—H44B | 108.1 (14) | C51B—C41B—H41B | 120.00 |
H42B—N4B—H44B | 111 (2) | C31B—C41B—H41B | 120.00 |
H43B—N4B—H44B | 106.8 (18) | C41B—C51B—H51B | 120.00 |
C4B—N4B—H43B | 112.6 (13) | C61B—C51B—H51B | 120.00 |
C4B—N4B—H42B | 108.8 (17) | C11B—C61B—H61B | 120.00 |
N1A—C1A—C2A | 127.53 (14) | C51B—C61B—H61B | 120.00 |
N1A—C1A—C6A | 114.66 (13) | C2D—C1D—C6D | 120.27 (15) |
C2A—C1A—C6A | 117.81 (15) | S1D—C1D—C2D | 119.94 (12) |
C1A—C2A—C3A | 120.56 (15) | S1D—C1D—C6D | 119.65 (13) |
C2A—C3A—C4A | 121.23 (15) | C1D—C2D—C3D | 119.24 (15) |
N4A—C4A—C3A | 120.68 (15) | C2D—C3D—C4D | 120.33 (16) |
C3A—C4A—C5A | 118.48 (15) | C3D—C4D—C5D | 120.24 (17) |
N4A—C4A—C5A | 120.84 (15) | C4D—C5D—C6D | 120.24 (17) |
C4A—C5A—C6A | 119.97 (15) | C1D—C6D—C5D | 119.68 (16) |
C1A—C6A—C5A | 121.93 (15) | C1D—C2D—H2D | 120.00 |
N11A—C11A—C61A | 121.38 (14) | C3D—C2D—H2D | 120.00 |
C21A—C11A—C61A | 120.70 (15) | C2D—C3D—H3D | 120.00 |
N11A—C11A—C21A | 117.92 (14) | C4D—C3D—H3D | 120.00 |
C11A—C21A—C31A | 119.27 (15) | C5D—C4D—H4D | 120.00 |
C21A—C31A—C41A | 120.44 (15) | C3D—C4D—H4D | 120.00 |
C31A—C41A—C51A | 119.89 (16) | C4D—C5D—H5D | 120.00 |
C41A—C51A—C61A | 120.58 (16) | C6D—C5D—H5D | 120.00 |
C11A—C61A—C51A | 119.11 (16) | C5D—C6D—H6D | 120.00 |
C3A—C2A—H2A | 120.00 | C1D—C6D—H6D | 120.00 |
C1A—C2A—H2A | 120.00 | S1C—C1C—C2C | 120.03 (13) |
C2A—C3A—H3A | 119.00 | S1C—C1C—C6C | 120.02 (14) |
C4A—C3A—H3A | 119.00 | C2C—C1C—C6C | 119.86 (16) |
C6A—C5A—H5A | 120.00 | C1C—C2C—C3C | 119.72 (17) |
C4A—C5A—H5A | 120.00 | C2C—C3C—C4C | 120.4 (2) |
C5A—C6A—H6A | 119.00 | C3C—C4C—C5C | 119.8 (2) |
C1A—C6A—H6A | 119.00 | C4C—C5C—C6C | 120.7 (2) |
C31A—C21A—H21A | 120.00 | C1C—C6C—C5C | 119.53 (18) |
C11A—C21A—H21A | 120.00 | C1C—C2C—H2C | 120.00 |
C41A—C31A—H31A | 120.00 | C3C—C2C—H2C | 120.00 |
C21A—C31A—H31A | 120.00 | C2C—C3C—H3C | 120.00 |
C51A—C41A—H41A | 120.00 | C4C—C3C—H3C | 120.00 |
C31A—C41A—H41A | 120.00 | C3C—C4C—H4C | 120.00 |
C61A—C51A—H51A | 120.00 | C5C—C4C—H4C | 120.00 |
C41A—C51A—H51A | 120.00 | C4C—C5C—H5C | 120.00 |
C11A—C61A—H61A | 120.00 | C6C—C5C—H5C | 120.00 |
C51A—C61A—H61A | 120.00 | C1C—C6C—H6C | 120.00 |
C2B—C1B—C6B | 119.95 (15) | C5C—C6C—H6C | 120.00 |
N1B—C1B—C2B | 115.95 (14) | | |
| | | |
O11D—S1D—C1D—C2D | −39.56 (17) | C21A—C31A—C41A—C51A | −1.2 (3) |
O12D—S1D—C1D—C2D | 82.26 (16) | C31A—C41A—C51A—C61A | 0.6 (3) |
O13D—S1D—C1D—C2D | −158.70 (15) | C41A—C51A—C61A—C11A | 0.7 (3) |
O11D—S1D—C1D—C6D | 144.84 (15) | C6B—C1B—C2B—C3B | −0.5 (2) |
O12D—S1D—C1D—C6D | −93.35 (16) | N1B—C1B—C2B—C3B | 179.68 (15) |
O13D—S1D—C1D—C6D | 25.69 (16) | N1B—C1B—C6B—C5B | −179.48 (15) |
O12C—S1C—C1C—C6C | 96.33 (16) | C2B—C1B—C6B—C5B | 0.7 (2) |
O11C—S1C—C1C—C2C | 38.32 (16) | C1B—C2B—C3B—C4B | −0.1 (2) |
O11C—S1C—C1C—C6C | −144.90 (15) | C2B—C3B—C4B—C5B | 0.6 (2) |
O13C—S1C—C1C—C6C | −24.11 (17) | C2B—C3B—C4B—N4B | −176.99 (15) |
O13C—S1C—C1C—C2C | 159.10 (14) | C3B—C4B—C5B—C6B | −0.4 (2) |
O12C—S1C—C1C—C2C | −80.46 (15) | N4B—C4B—C5B—C6B | 177.22 (15) |
N11A—N1A—C1A—C2A | 0.5 (2) | C4B—C5B—C6B—C1B | −0.3 (2) |
C1A—N1A—N11A—C11A | 177.61 (14) | C61B—C11B—C21B—C31B | 0.9 (3) |
N11A—N1A—C1A—C6A | −179.27 (14) | N11B—C11B—C21B—C31B | −179.59 (17) |
N1A—N11A—C11A—C21A | 165.81 (14) | C21B—C11B—C61B—C51B | −0.5 (3) |
N1A—N11A—C11A—C61A | −13.2 (2) | N11B—C11B—C61B—C51B | 179.93 (16) |
N11B—N1B—C1B—C2B | 179.45 (14) | C11B—C21B—C31B—C41B | −0.9 (3) |
C1B—N1B—N11B—C11B | 179.74 (13) | C21B—C31B—C41B—C51B | 0.5 (3) |
N11B—N1B—C1B—C6B | −0.4 (2) | C31B—C41B—C51B—C61B | −0.2 (3) |
N1B—N11B—C11B—C21B | 1.0 (2) | C41B—C51B—C61B—C11B | 0.1 (3) |
N1B—N11B—C11B—C61B | −179.41 (15) | S1D—C1D—C2D—C3D | −176.26 (13) |
C6A—C1A—C2A—C3A | 1.4 (2) | C2D—C1D—C6D—C5D | −0.3 (2) |
N1A—C1A—C6A—C5A | 178.49 (15) | C6D—C1D—C2D—C3D | −0.7 (2) |
C2A—C1A—C6A—C5A | −1.3 (2) | S1D—C1D—C6D—C5D | 175.27 (13) |
N1A—C1A—C2A—C3A | −178.40 (16) | C1D—C2D—C3D—C4D | 1.2 (3) |
C1A—C2A—C3A—C4A | −0.4 (3) | C2D—C3D—C4D—C5D | −0.8 (3) |
C2A—C3A—C4A—C5A | −0.8 (2) | C3D—C4D—C5D—C6D | −0.2 (3) |
C2A—C3A—C4A—N4A | 179.95 (18) | C4D—C5D—C6D—C1D | 0.8 (3) |
N4A—C4A—C5A—C6A | −179.87 (16) | S1C—C1C—C2C—C3C | 177.88 (15) |
C3A—C4A—C5A—C6A | 0.8 (2) | C6C—C1C—C2C—C3C | 1.1 (3) |
C4A—C5A—C6A—C1A | 0.2 (3) | S1C—C1C—C6C—C5C | −177.74 (16) |
N11A—C11A—C61A—C51A | 177.76 (15) | C2C—C1C—C6C—C5C | −1.0 (3) |
C21A—C11A—C61A—C51A | −1.3 (2) | C1C—C2C—C3C—C4C | −0.1 (3) |
C61A—C11A—C21A—C31A | 0.6 (2) | C2C—C3C—C4C—C5C | −1.0 (3) |
N11A—C11A—C21A—C31A | −178.43 (14) | C3C—C4C—C5C—C6C | 1.2 (3) |
C11A—C21A—C31A—C41A | 0.6 (2) | C4C—C5C—C6C—C1C | −0.2 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11A—H11A···O11C | 0.873 (19) | 1.921 (19) | 2.7672 (18) | 162.9 (17) |
N4A—H42A···O11Di | 0.84 (2) | 2.18 (2) | 2.967 (3) | 155.7 (18) |
N4A—H43A···O11Dii | 0.92 (2) | 2.05 (2) | 2.962 (3) | 177.2 (18) |
N4B—H42B···O12C | 0.82 (3) | 2.14 (3) | 2.820 (2) | 141 (2) |
N4B—H42B···O12D | 0.82 (3) | 2.43 (3) | 3.001 (3) | 128 (2) |
N4B—H43B···O13Ciii | 0.99 (2) | 1.85 (2) | 2.838 (2) | 175 (2) |
N4B—H44B···O13Diii | 0.99 (2) | 1.93 (2) | 2.890 (3) | 165 (2) |
C3A—H3A···O13D | 0.93 | 2.50 | 3.220 (3) | 135 |
C5B—H5B···O12Ciii | 0.93 | 2.33 | 3.258 (2) | 178 |
C6C—H6C···O13C | 0.93 | 2.59 | 2.951 (3) | 103 |
C6D—H6D···O13D | 0.93 | 2.56 | 2.926 (3) | 104 |
C21A—H21A···O11C | 0.93 | 2.47 | 3.148 (2) | 130 |
Symmetry codes: (i) x−1, y, z; (ii) −x, −y+1, −z+1; (iii) x+1, y, z. |
(III) 4-(phenyldiazenyl)aniline–3,5-dinitrobenzoic acid (1/2)
top
Crystal data top
C12H11N3·2C7H4N2O6 | Z = 1 |
Mr = 621.48 | F(000) = 320 |
Triclinic, P1 | Dx = 1.489 Mg m−3 |
Hall symbol: -P 1 | Melting point: 453 K |
a = 8.2048 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.8859 (7) Å | Cell parameters from 4012 reflections |
c = 11.5802 (9) Å | θ = 2.9–28.8° |
α = 112.292 (8)° | µ = 0.12 mm−1 |
β = 92.560 (7)° | T = 200 K |
γ = 114.072 (8)° | Prism, red |
V = 693.09 (13) Å3 | 0.30 × 0.30 × 0.15 mm |
Data collection top
Oxford Gemini-S CCD area-detector diffractometer | 2440 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 1989 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ω scans | θmax = 25.0°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.930, Tmax = 0.980 | k = −10→10 |
8021 measured reflections | l = −13→13 |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0446P)2 + 0.0825P] where P = (Fo2 + 2Fc2)/3 |
2440 reflections | (Δ/σ)max < 0.001 |
220 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.14 e Å−3 |
Crystal data top
C12H11N3·2C7H4N2O6 | γ = 114.072 (8)° |
Mr = 621.48 | V = 693.09 (13) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.2048 (7) Å | Mo Kα radiation |
b = 8.8859 (7) Å | µ = 0.12 mm−1 |
c = 11.5802 (9) Å | T = 200 K |
α = 112.292 (8)° | 0.30 × 0.30 × 0.15 mm |
β = 92.560 (7)° | |
Data collection top
Oxford Gemini-S CCD area-detector diffractometer | 2440 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1989 reflections with I > 2σ(I) |
Tmin = 0.930, Tmax = 0.980 | Rint = 0.018 |
8021 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.15 e Å−3 |
2440 reflections | Δρmin = −0.14 e Å−3 |
220 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All su's are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
N1A | 0.55044 (15) | 2.00276 (15) | 0.46048 (10) | 0.0365 (3) | |
N4A | 0.5346 (4) | 1.3392 (4) | 0.1456 (3) | 0.0522 (10) | 0.500 |
C1A | 0.54603 (17) | 1.83104 (18) | 0.38400 (13) | 0.0344 (4) | |
C2A | 0.46975 (18) | 1.67703 (18) | 0.40837 (13) | 0.0381 (5) | |
C3A | 0.46505 (19) | 1.51471 (19) | 0.32679 (14) | 0.0424 (5) | |
C4A | 0.53747 (19) | 1.5009 (2) | 0.21861 (15) | 0.0438 (5) | |
C5A | 0.6170 (2) | 1.6555 (2) | 0.19546 (14) | 0.0454 (5) | |
C6A | 0.62273 (18) | 1.81963 (19) | 0.27822 (14) | 0.0408 (5) | |
O11 | −0.06079 (15) | 0.12182 (14) | 0.14147 (10) | 0.0468 (4) | |
O12 | 0.08141 (14) | 0.20224 (12) | −0.00162 (9) | 0.0411 (3) | |
O31 | 0.32547 (15) | 0.84705 (14) | 0.07643 (10) | 0.0491 (4) | |
O32 | 0.29333 (17) | 1.04248 (14) | 0.24268 (11) | 0.0621 (4) | |
O51 | −0.04017 (17) | 0.84183 (14) | 0.53163 (11) | 0.0621 (4) | |
O52 | −0.16179 (15) | 0.55597 (15) | 0.49171 (10) | 0.0521 (4) | |
N3 | 0.26847 (16) | 0.88755 (15) | 0.17407 (11) | 0.0389 (4) | |
N5 | −0.07430 (16) | 0.68298 (16) | 0.46627 (11) | 0.0379 (4) | |
C1 | 0.04311 (17) | 0.42637 (16) | 0.17231 (11) | 0.0302 (4) | |
C2 | 0.14076 (17) | 0.56494 (17) | 0.13703 (12) | 0.0303 (4) | |
C3 | 0.16234 (17) | 0.73976 (16) | 0.21019 (12) | 0.0302 (4) | |
C4 | 0.09292 (17) | 0.78354 (17) | 0.31756 (12) | 0.0314 (4) | |
C5 | −0.00239 (17) | 0.64194 (17) | 0.34949 (12) | 0.0309 (4) | |
C6 | −0.03051 (17) | 0.46434 (17) | 0.27937 (12) | 0.0311 (4) | |
C11 | 0.02321 (18) | 0.23897 (18) | 0.09566 (13) | 0.0333 (4) | |
H2A | 0.42170 | 1.68440 | 0.48040 | 0.0460* | |
H3A | 0.41310 | 1.41310 | 0.34390 | 0.0510* | |
H4A | 0.53290 | 1.39060 | 0.16290 | 0.0530* | 0.500 |
H5A | 0.66650 | 1.64850 | 0.12400 | 0.0540* | |
H6A | 0.67820 | 1.92250 | 0.26290 | 0.0490* | |
H41A | 0.572 (5) | 1.324 (5) | 0.078 (4) | 0.074 (13)* | 0.500 |
H42A | 0.481 (5) | 1.264 (5) | 0.163 (4) | 0.067 (14)* | 0.500 |
H2 | 0.19080 | 0.54090 | 0.06570 | 0.0360* | |
H4 | 0.10930 | 0.90170 | 0.36580 | 0.0380* | |
H6 | −0.09720 | 0.37240 | 0.30340 | 0.0370* | |
H11 | −0.074 (3) | 0.010 (3) | 0.0908 (18) | 0.078 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1A | 0.0334 (6) | 0.0353 (6) | 0.0360 (6) | 0.0127 (5) | 0.0070 (5) | 0.0143 (5) |
N4A | 0.0599 (19) | 0.0429 (16) | 0.0554 (19) | 0.0276 (15) | 0.0310 (15) | 0.0168 (14) |
C1A | 0.0275 (7) | 0.0333 (7) | 0.0361 (7) | 0.0108 (6) | 0.0041 (6) | 0.0129 (6) |
C2A | 0.0361 (8) | 0.0383 (8) | 0.0378 (8) | 0.0148 (6) | 0.0072 (6) | 0.0172 (6) |
C3A | 0.0391 (8) | 0.0365 (8) | 0.0511 (9) | 0.0164 (6) | 0.0083 (7) | 0.0199 (7) |
C4A | 0.0354 (8) | 0.0400 (8) | 0.0497 (9) | 0.0198 (7) | 0.0064 (7) | 0.0111 (7) |
C5A | 0.0385 (8) | 0.0523 (9) | 0.0445 (9) | 0.0221 (7) | 0.0173 (7) | 0.0182 (7) |
C6A | 0.0340 (8) | 0.0404 (8) | 0.0475 (8) | 0.0145 (6) | 0.0128 (6) | 0.0212 (7) |
O11 | 0.0738 (8) | 0.0320 (6) | 0.0451 (6) | 0.0293 (5) | 0.0295 (5) | 0.0200 (5) |
O12 | 0.0556 (6) | 0.0322 (5) | 0.0386 (6) | 0.0231 (5) | 0.0214 (5) | 0.0143 (4) |
O31 | 0.0592 (7) | 0.0489 (6) | 0.0487 (6) | 0.0256 (5) | 0.0272 (5) | 0.0282 (5) |
O32 | 0.0910 (9) | 0.0269 (6) | 0.0610 (7) | 0.0211 (6) | 0.0299 (7) | 0.0171 (5) |
O51 | 0.0869 (9) | 0.0423 (6) | 0.0535 (7) | 0.0327 (6) | 0.0378 (6) | 0.0119 (5) |
O52 | 0.0644 (7) | 0.0532 (7) | 0.0528 (7) | 0.0296 (6) | 0.0337 (6) | 0.0318 (6) |
N3 | 0.0436 (7) | 0.0331 (7) | 0.0395 (7) | 0.0154 (5) | 0.0120 (6) | 0.0174 (5) |
N5 | 0.0406 (7) | 0.0419 (7) | 0.0344 (6) | 0.0226 (6) | 0.0138 (5) | 0.0153 (6) |
C1 | 0.0325 (7) | 0.0293 (7) | 0.0276 (7) | 0.0151 (6) | 0.0044 (5) | 0.0106 (5) |
C2 | 0.0329 (7) | 0.0331 (7) | 0.0249 (6) | 0.0168 (6) | 0.0072 (5) | 0.0108 (5) |
C3 | 0.0299 (7) | 0.0283 (7) | 0.0300 (7) | 0.0120 (6) | 0.0045 (5) | 0.0121 (5) |
C4 | 0.0321 (7) | 0.0274 (6) | 0.0304 (7) | 0.0145 (6) | 0.0038 (5) | 0.0078 (5) |
C5 | 0.0308 (7) | 0.0334 (7) | 0.0272 (7) | 0.0163 (6) | 0.0067 (5) | 0.0104 (5) |
C6 | 0.0317 (7) | 0.0314 (7) | 0.0313 (7) | 0.0144 (6) | 0.0070 (5) | 0.0148 (6) |
C11 | 0.0385 (8) | 0.0305 (7) | 0.0317 (7) | 0.0172 (6) | 0.0080 (6) | 0.0130 (6) |
Geometric parameters (Å, º) top
O11—C11 | 1.306 (2) | C4A—C5A | 1.396 (3) |
O12—C11 | 1.2247 (18) | C5A—C6A | 1.388 (2) |
O31—N3 | 1.2258 (17) | C2A—H2A | 0.9300 |
O32—N3 | 1.2226 (18) | C3A—H3A | 0.9300 |
O51—N5 | 1.2214 (18) | C4A—H4A | 0.9300 |
O52—N5 | 1.2190 (19) | C5A—H5A | 0.9300 |
O11—H11 | 0.90 (2) | C6A—H6A | 0.9300 |
N1A—C1A | 1.429 (2) | C1—C6 | 1.3898 (19) |
N1A—N1Ai | 1.2625 (17) | C1—C11 | 1.494 (2) |
N4A—C4A | 1.352 (4) | C1—C2 | 1.390 (2) |
N4A—H41A | 0.84 (4) | C2—C3 | 1.388 (2) |
N4A—H42A | 0.74 (5) | C3—C4 | 1.3780 (19) |
N3—C3 | 1.475 (2) | C4—C5 | 1.381 (2) |
N5—C5 | 1.4774 (18) | C5—C6 | 1.385 (2) |
C1A—C2A | 1.398 (2) | C2—H2 | 0.9300 |
C1A—C6A | 1.391 (2) | C4—H4 | 0.9300 |
C2A—C3A | 1.376 (2) | C6—H6 | 0.9300 |
C3A—C4A | 1.395 (2) | | |
| | | |
C11—O11—H11 | 111.2 (15) | C3A—C4A—H4A | 121.00 |
N1Ai—N1A—C1A | 114.21 (13) | C5A—C4A—H4A | 121.00 |
H41A—N4A—H42A | 124 (5) | C4A—C5A—H5A | 120.00 |
C4A—N4A—H41A | 120 (3) | C6A—C5A—H5A | 120.00 |
H4A—N4A—H42A | 120.00 | C1A—C6A—H6A | 120.00 |
C4A—N4A—H42A | 114 (3) | C5A—C6A—H6A | 120.00 |
H4A—N4A—H41A | 113.00 | C2—C1—C11 | 119.02 (12) |
O32—N3—C3 | 118.15 (12) | C6—C1—C11 | 121.01 (13) |
O31—N3—C3 | 117.83 (12) | C2—C1—C6 | 119.95 (13) |
O31—N3—O32 | 124.02 (14) | C1—C2—C3 | 118.83 (12) |
O51—N5—O52 | 124.44 (13) | N3—C3—C2 | 118.87 (12) |
O52—N5—C5 | 117.62 (13) | C2—C3—C4 | 123.08 (13) |
O51—N5—C5 | 117.94 (13) | N3—C3—C4 | 118.03 (12) |
C2A—C1A—C6A | 119.01 (14) | C3—C4—C5 | 116.16 (13) |
N1A—C1A—C6A | 116.52 (14) | N5—C5—C6 | 118.26 (13) |
N1A—C1A—C2A | 124.48 (13) | C4—C5—C6 | 123.42 (13) |
C1A—C2A—C3A | 120.63 (14) | N5—C5—C4 | 118.30 (13) |
C2A—C3A—C4A | 120.66 (16) | C1—C6—C5 | 118.56 (13) |
N4A—C4A—C3A | 117.4 (2) | O11—C11—C1 | 114.17 (12) |
N4A—C4A—C5A | 123.7 (2) | O12—C11—C1 | 121.55 (14) |
C3A—C4A—C5A | 118.81 (15) | O11—C11—O12 | 124.28 (14) |
C4A—C5A—C6A | 120.53 (15) | C1—C2—H2 | 121.00 |
C1A—C6A—C5A | 120.32 (15) | C3—C2—H2 | 121.00 |
C3A—C2A—H2A | 120.00 | C3—C4—H4 | 122.00 |
C1A—C2A—H2A | 120.00 | C5—C4—H4 | 122.00 |
C4A—C3A—H3A | 120.00 | C1—C6—H6 | 121.00 |
C2A—C3A—H3A | 120.00 | C5—C6—H6 | 121.00 |
| | | |
N1Ai—N1A—C1A—C2A | −12.6 (2) | N4A—C4A—C5A—C6A | −176.8 (2) |
N1Ai—N1A—C1A—C6A | 167.00 (13) | C4A—C5A—C6A—C1A | −1.2 (2) |
C1A—N1A—N1Ai—C1Ai | −180.00 (12) | C6—C1—C2—C3 | −0.1 (2) |
O31—N3—C3—C2 | 3.6 (2) | C11—C1—C2—C3 | −178.60 (13) |
O31—N3—C3—C4 | −177.94 (14) | C2—C1—C6—C5 | −0.7 (2) |
O32—N3—C3—C2 | −176.79 (14) | C11—C1—C6—C5 | 177.76 (13) |
O32—N3—C3—C4 | 1.6 (2) | C2—C1—C11—O11 | 175.89 (13) |
O52—N5—C5—C4 | 178.35 (14) | C2—C1—C11—O12 | −4.4 (2) |
O52—N5—C5—C6 | −3.1 (2) | C6—C1—C11—O11 | −2.6 (2) |
O51—N5—C5—C6 | 175.97 (14) | C6—C1—C11—O12 | 177.18 (14) |
O51—N5—C5—C4 | −2.6 (2) | C1—C2—C3—N3 | 179.03 (13) |
N1A—C1A—C2A—C3A | 177.48 (14) | C1—C2—C3—C4 | 0.7 (2) |
C6A—C1A—C2A—C3A | −2.1 (2) | N3—C3—C4—C5 | −178.73 (13) |
C2A—C1A—C6A—C5A | 2.5 (2) | C2—C3—C4—C5 | −0.4 (2) |
N1A—C1A—C6A—C5A | −177.13 (14) | C3—C4—C5—N5 | 177.99 (13) |
C1A—C2A—C3A—C4A | 0.5 (2) | C3—C4—C5—C6 | −0.5 (2) |
C2A—C3A—C4A—N4A | 177.5 (2) | N5—C5—C6—C1 | −177.47 (13) |
C2A—C3A—C4A—C5A | 0.8 (2) | C4—C5—C6—C1 | 1.0 (2) |
C3A—C4A—C5A—C6A | −0.4 (2) | | |
Symmetry code: (i) −x+1, −y+4, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11···O12ii | 0.90 (2) | 1.75 (2) | 2.6426 (16) | 175 (2) |
N4A—H41A···O31iii | 0.84 (4) | 2.31 (4) | 3.042 (4) | 147 (4) |
N4A—H42A···O32 | 0.74 (5) | 2.48 (4) | 3.213 (4) | 173 (4) |
C2A—H2A···O52iv | 0.93 | 2.47 | 3.134 (2) | 129 |
C4—H4···O51iv | 0.93 | 2.45 | 3.339 (2) | 161 |
Symmetry codes: (ii) −x, −y, −z; (iii) −x+1, −y+2, −z; (iv) −x, −y+2, −z+1. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C12H12N3+·C7H5O6S−·CH4O | 2C12H12N3+·2C6H5O3S− | C12H11N3·2C7H4N2O6 |
Mr | 447.46 | 710.82 | 621.48 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 130 | 200 | 200 |
a, b, c (Å) | 8.7174 (7), 20.1160 (16), 11.8827 (9) | 5.7601 (4), 13.0794 (8), 23.6556 (15) | 8.2048 (7), 8.8859 (7), 11.5802 (9) |
α, β, γ (°) | 90, 97.145 (2), 90 | 77.937 (5), 83.985 (5), 86.971 (5) | 112.292 (8), 92.560 (7), 114.072 (8) |
V (Å3) | 2067.6 (3) | 1732.4 (2) | 693.09 (13) |
Z | 4 | 2 | 1 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.21 | 0.21 | 0.12 |
Crystal size (mm) | 0.45 × 0.25 × 0.20 | 0.40 × 0.20 × 0.12 | 0.30 × 0.30 × 0.15 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Oxford Gemini-S CCD area-detector diffractometer | Oxford Gemini-S CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.91, 0.96 | 0.870, 0.980 | 0.930, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10840, 3640, 3102 | 22657, 7187, 5717 | 8021, 2440, 1989 |
Rint | 0.028 | 0.028 | 0.018 |
(sin θ/λ)max (Å−1) | 0.595 | 0.628 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.101, 1.05 | 0.036, 0.094, 1.06 | 0.030, 0.085, 1.07 |
No. of reflections | 3640 | 7187 | 2440 |
No. of parameters | 305 | 487 | 220 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.37, −0.33 | 0.28, −0.33 | 0.15, −0.14 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2A—H2A···O72A | 0.90 (3) | 1.80 (3) | 2.624 (2) | 151 (2) |
O71A—H71A···O52Ai | 0.90 (3) | 1.74 (3) | 2.6246 (19) | 166 (2) |
O1B—H1B···O52A | 0.80 (2) | 2.00 (2) | 2.792 (2) | 175 (2) |
N11—H11···O51A | 0.85 (2) | 2.07 (2) | 2.895 (2) | 163.1 (17) |
N4—H43···O53Aii | 0.87 (2) | 1.97 (2) | 2.834 (2) | 170.5 (17) |
N4—H42···O1Biii | 0.88 (2) | 1.98 (2) | 2.845 (2) | 173 (2) |
C6—H6···O51A | 0.95 | 2.52 | 3.421 (2) | 158 |
C6—H6···O52A | 0.95 | 2.41 | 3.184 (2) | 138 |
C6A—H6A···O51A | 0.95 | 2.49 | 2.888 (2) | 105 |
C61—H61···O51A | 0.95 | 2.51 | 3.260 (2) | 136 |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, y−1/2, −z+3/2; (iii) −x+2, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11A—H11A···O11C | 0.873 (19) | 1.921 (19) | 2.7672 (18) | 162.9 (17) |
N4A—H42A···O11Di | 0.84 (2) | 2.18 (2) | 2.967 (3) | 155.7 (18) |
N4A—H43A···O11Dii | 0.92 (2) | 2.05 (2) | 2.962 (3) | 177.2 (18) |
N4B—H42B···O12C | 0.82 (3) | 2.14 (3) | 2.820 (2) | 141 (2) |
N4B—H42B···O12D | 0.82 (3) | 2.43 (3) | 3.001 (3) | 128 (2) |
N4B—H43B···O13Ciii | 0.99 (2) | 1.85 (2) | 2.838 (2) | 175 (2) |
N4B—H44B···O13Diii | 0.99 (2) | 1.93 (2) | 2.890 (3) | 165 (2) |
Symmetry codes: (i) x−1, y, z; (ii) −x, −y+1, −z+1; (iii) x+1, y, z. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11···O12i | 0.90 (2) | 1.75 (2) | 2.6426 (16) | 175 (2) |
N4A—H41A···O31ii | 0.84 (4) | 2.31 (4) | 3.042 (4) | 147 (4) |
N4A—H42A···O32 | 0.74 (5) | 2.48 (4) | 3.213 (4) | 173 (4) |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y+2, −z. |
Selected bond distances (Å) in the PAZAN species in (I),
(II) (A and B) and (III) compared with those in the
hydrochloride (PAZAN.HCl), and the 1:1 PAZAN compounds with the three
nitrophthalalic acids, PAZAN.3-NPA (with 3-nitrophthalic acid),
PAZAN.4-NPA (with 4-nitrophthalic acid) and PAZAN.5-NIPA (with
5-nitroisophthalic acid) topBond | (I)a | (IIA)a | (IIB)a | (III)a |
N1–N11 | 1.339 (2) | 1.3103 (14) | 1.2623 (17) | 1.2625 (17) |
N1–C1 | 1.339 (3) | 1.356 (2) | 1.442 (2) | 1.429 (2) |
N11–C11 | 1.407 (2) | 1.426 (2) | 1.436 (2) | 1.429 (2) |
N4–C4 | 1.318 (3) | 1.366 (2) | 1.476 (2) | 1.352 (4) |
C1–C2 | 1.426 (3) | 1.436 (2) | 1.403 (2) | 1.398 (2) |
C1–C6 | 1.431 (3) | 1.437 (2) | 1.401 (2) | 1.391 (2) |
C2–C3 | 1.358 (3) | 1.361 (2) | 1.395 (2) | 1.376 (2) |
C5–C6 | 1.351 (3) | 1.365 (2) | 1.385 (2) | 1.388 (2) |
C3–C4 | 1.430 (3) | 1.442 (2) | 1.390 (2) | 1.395 (2) |
C4–C5 | 1.431 (3) | 1.429 (2) | 1.398 (2) | 1.396 (3) |
Bond | PAZAN.HClb | PAZAN.3-NPAc | PAZAN.4-NPAc | PAZAN.5-NIPAc |
N1—N11 | 1.291 (3) | 1.234 (4) | 1.224 (4) | 1.262 (6) |
N1—C1 | 1.324 (3) | 1.442 (5) | 1.462 (4) | 1.415 (6) |
N11—C11 | 1.417 (3) | 1.445 (5) | 1.461 (4) | 1.428 (7) |
N4—C4 | 1.324 (3) | 1.463 (2) | 1.463 (4) | 1.455 (6) |
C1—C2 | 1.428 (3) | 1.412 (6) | 1.398 (4) | 1.387 (6) |
C1—C6 | 1.419 (3) | 1.384 (7) | 1.379 (4) | 1.395 (6) |
C2—C3 | 1.349 (3) | 1.420 (5) | 1.393 (4) | 1.374 (7) |
C5—C6 | 1.357 (3) | 1.369 (4) | 1.380 (4) | 1.382 (7) |
C3—C4 | 1.425 (3) | 1.375 (2) | 1.384 (4) | 1.391 (6) |
C4—C5 | 1.421 (3) | 1.383 (2) | 1.382 (4) | 1.380 (7) |
a this work; b Mahmoudkhani & Langer, 2001a; c Smith
et al. (2008). |
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Aniline yellow [4-(phenylazo)aniline, p-aminoazobenzene, PAZAN] is a diazo-dye precursor (O'Neil, 2001) and in the structures of its proton-transfer compounds with organic acids [oxalic acid (Mahmoudkhani & Langer, 2001b), phenylphosphonic acid (two concomitant polymorphs) (Mahmoudkhani & Langer, 2002a), 1,4-butanebisphosphonic acid (Mahmoudkhani & Langer, 2002b) and the isomeric 3- and 4-nitrophthalic and 5-nitroisophthalic acids (Smith et al., 2008], as might intuitively be expected, the aniline functional group is protonated. However, in the purple–black hydrochloride (Yatsenko et al., 2000; Mahmoudkhani & Langer, 2001a) and the hydrochloride of the analogous 4-(phenylazo)-1,3-diaminobenzene (Moreiras et al., 1981) the azo group is protonated. Also, with phosphoric acid (Halasz et al., 2007), the orange monohydrogen phosphate is an anilinium salt while the purple dihydrogen phosphate salt is azo-group protonated. The dye methyl red [4-(N,N'-dimethylanilino)azobenzene-2-carboxylic acid] also gives azo-protonated salts and adducts with 2,5-dihydroxybenzoic acid (Benedict et al., 2006) and the MALDI host 2,6-dihydroxybenzoic acid (Cohen et al., 2007). It is of interest also that the azo dyes 4-[4-(N,N'-dimethylamino)phenylazo ] benzenesulfonic acid (Burke et al., 2004) and 4-[4-(N,N'-diethylamino)phenylazo ] benzenesulfonic (Burke et al., 2006) exist as sulfonate–azo-group zwitterions.
This study was therefore aimed at characterizing crystalline products from the reaction of aniline yellow with strong organic acids, to enable the identification of the nature of the interaction involved, i.e. proton transfer versus non-transfer, and its correlation with qualitative recognition through the observed colour of the crystals. Our general observation regarding the reaction of PAZAN with carboxylic acids has been that proton-transfer compounds are rarely formed (Smith et al., 2008). This is in evidence in the general paucity of reported structures of PAZAN–aminium salts in the literature. We now have obtained suitable crystalline salts of aniline yellow with the strong organic acids, 5-sulfosalicylic acid (5-SSA), benzenesulfonic acid (BSA) and 3,5-dinitrobenzoic acid (3,5-DNBA) which, unlike [those of] the aminium salts, are intense red–black or deep red in colour, crystallizing from solutions with a significantly different colour. The structures of the two red–black compounds, the methanol solvate 4-(phenylazonium)aniline–3-carboxy-4-hydroxybenzenesulfonate–methanol (1/1/1), C12H12N3+. C7H5O6S-. CH3OH, (I), and anhydrous 4-(phenylazonium)aniline 4-(phenylazo)anilinium bis(benzenesulfonate), 2(C12H12N3+). 2(C6H5O3S-), (II), and the red crystal of the adduct compound 4-(phenylazo)aniline–3,5-dinitrobenzoic acid (1/2), C12H11N3. 2(C7H4N2O6), (III), are reported here.
With both compounds (I) and (II), proton transfer has occurred while with (III) there is no transfer. However, the differences even between the structures of (I) and (II) are significant so the discussion considers each structure individually. In (I), the 1:1 methanol solvate compound of PAZAN with 5-SSA, the azo group rather than the amino group is protonated and gives a direct N11–H···O51Asulfonate hydrogen bond while a sulfonate O acts as an acceptor in an interaction with the methanol hydroxyl group (O1B···O52A) (Fig. 1). Other lateral cation aromatic C–H···Osulfonate hydrogen-bonding associations (Table 1) close conjoint cyclic ring systems [graph sets R12(6), R12(7) and R21(4) (Etter et al., 1990)], also shown in Fig. 1. The 5-sulfosalicylate anions form infinite head-to-tail homomolecular hydrogen-bonded chain structures through carboxylic acid proton donors and sulfonate-O acceptors, extending along the a cell direction (Fig. 4). The result is a three-dimensional framework structure.
In the dichroic proton-transfer compound (II) with BSA, the unusual feature is the presence of both azo- and amine-protonated PAZAN species (A and B, respectively) in the structure. The asymmetric unit in the triclinic unit cell comprises both of these cationic species as well as two benzenesulfonate anions (C and D), the D molecule having rotational disorder (80/20%) in the sulfonate group (Fig. 2). The azo-group proton on N11A interacts directly with a sulfonate O (O11C) while all three anilinium protons on N4B similarly form hydrogen bonds with both C- and D-anion sulfonate-O acceptors (Table 2). These and other N—H···O interactions result in one-dimensional chain structures (Fig. 5). Within these chain structures the A- and B-cation species are oriented approximately mutually perpendicularly in the unit cell, corresponding to the observed ca 90° red-to-black dichroism in the crystal. It should also be noted that there are solvent-accessible voids (41 Å3) in the structure of (II) (PLATON; Spek, 2009), centred at (1/2, 0, 0) with the closest atom C5C [3.28 (1) Å].
The formation of the 1:2 adduct molecule (III) rather than a proton-transfer compound from the 1:1 reaction of aniline yellow with 3,5-dinitrobenzoic acid is unexpected, considering the relative strength of the acid (pKa = 2.82). However, 3,5-DNBA has been recognized as a useful adduct-forming synthon for crystal engineering (Etter & Frankenbach, 1989), with a number of 1:1 non-transfer adducts being reported, including one with the azo dye methyl red (Aakeröy et al., 2004). However, most compounds involve proton transfer, with a number having an additional adduct molecule of 3,5-DNBA in the structure, although 1:2 adducts are not unknown, e.g. phenoxyacetic acid-(3,5-DNBA)-H2O (1/2/1) (Lynch et al., 1991). However, in compound (III) the two molecules preferentially form an uncommon hydrogen-bonded homodimer adduct. The asymmetric unit of (III) (Fig. 3) comprises a 3,5-DNBA molecule and half of an inversion-related aniline yellow molecule. The single para-related amine substituent group as well as the para-related proton of the second ring are disordered over two 50%-occupancy sites. The two 3,5-DNBA molecules form classic cyclic hydrogen-bonded homodimers through cyclic carboxylic acid associations [graph set R22(8)] which lie across crystallographic inversion centres in the unit cell (Fig. 6). This dimer is similar to those found in the structures of polymorphs of the parent acid (Colapietro et al., 1983; Domenicano et al., 1990; Prince et al., 1991). The two amine protons of the PAZAN molecule give weak lateral hydrogen-bonding associations with two 3,5-DNBA nitro-O acceptors (O31, O32) (Fig. 3), completing a centrosymmetric cyclic R44(12) four-molecule unit which is then extended into a two-dimensional sheet structure lying in the [-2 1 - 2] plane in the cell. Within this layered structure the aromatic ring of 3,5-DNBA and one of the aniline yellow rings give partial overlap with weak π–π interactions [minimum ring centroid separation for ring C1–C6 to ring C1A–C6A, 3.7061 (19) Å].
With the cation species in (I) and (II), as well as the PAZAN molecule in (III), the two phenyl rings are essentially coplanar, as has been found in other compounds of aniline yellow (Mahmoudkhani & Langer, 2001a,b, 2002a,b; Smith et al., 2008). The torsion angles C2/6–C1–N1–N11 and C21–C11–N11–N1 are -177.08 (16) and 175.47 (16)°, respectively, for (I), 179.27 (14) and 165.81 (14)°, respectively, for (IIA), 179.45 (14) and -179.41 (15)°, respectively, for (IIB), and 167.00 (13)° for (III) [which of the two torsion angles does this value relate to?].
The anion in (I) has conformational features similar to those found in other proton-transfer compounds of 5-sulfosalicylic acid (Smith et al., 2005a,b,c, 2006). These include the presence of the intramolecular hydroxyl–carboxyl hydrogen bond [O···O, 2.634 (2) Å] which results in the essential coplanarity of the carboxylic acid group and the benzene ring [torsion angle C2A–C1A– C71A–O71A, -173.86 (16)°]. Also, the common C6–H···Osulfonate interaction [C···O 2.888 (2) Å] is present. In (III) the 3,5-DNBA molecule is essentially planar [torsion angles C2–C1–C11–012 175.88 (13)°, C2–C3–N3–O32 -176.79 (14)°, C4–C5–N5–O52 178.35 (14)°].
It has been shown in the structures of compounds (I) and (II) that the protonated PAZAN cation species act as acid–base indicators, undergoing a colour change from red [the anilinium ('benzenoid') form] to red–black (the 'quinoid' form) in much the same manner as the analogous azo-dye indicator methyl red (yellow to red). Compound (II) has fortuitously captured the dichroic red to red–black equilibrium state with the presence of both hybrid colour forms, the ca 90° colour dichroism being consistent with the orientation of the two protonated forms in the crystal. These forms are readily identified crystallographically, not only with the proton location and the associated hydrogen bonding, but also convincingly in the comparative bond distances and angles in the aniline moiety and the azo-group extension (Table 4). In (I) and molecule A in (II), these are consistent with the presence of the localized single–double bond 'quinoid' system in the aniline molecular moiety, as is also found in the hydrochloride (Mahmoudkhani & Langer, 2001a). The red anilinium-protonated examples [molecule B in (II) and the three isomeric PAZAN hydrogen nitrophthalates (Smith et al., 2008)] are considered 'normal' for aminium-protonated compounds.