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Syntheses and X-ray structural investigations have been carried out for (E)-(4-hydroxy­phenyl)(4-nitro­phenyl)­diazene, C12H9N3O3, (Ia), (E)-(4-methoxy­phenyl)(4-nitro­phenyl)­diazene, C13H11N3O3, (IIIa), and (E)-[4-(6-bromo­hexyl­oxy)­phenyl](4-cyano­phenyl)­diazene, C19H20BrN3O, (IIIc). In all of these compounds, the mol­ecules are almost planar and the azo­benzene core has a trans geometry. Compound (Ia) contains four and compound (IIIc) contains two independent mol­ecules in the asymmetric unit, both in space group P\overline 1 (No. 2). In compound (Ia), the independent mol­ecules are almost identical, whereas in crystal (IIIc), the two independent mol­ecules differ significantly due to different conformations of the alkyl tails. In the crystals of (Ia) and (IIIa), the mol­ecules are arranged in almost planar sheets. In the crystal of (IIIc), the mol­ecules are packed with a marked separation of the azo­benzene cores and alkyl tails, which is common for the solid crystalline precursors of mesogens.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010201627X/gg1133sup1.cif
Contains datablocks Ia, IIIa, IIIc, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010201627X/gg1133Iasup2.hkl
Contains datablock Ia

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010201627X/gg1133IIIasup3.hkl
Contains datablock IIIa

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010201627X/gg1133IIIcsup4.hkl
Contains datablock IIIc

CCDC references: 197344; 197345; 197346

Comment top

Optically active azobenzene polymers are very important functional materials because of their photoresponsive properties. The pendant azobenzene moieties in these materials behave as both photoresponsive chromophores and mesogens (Rochon et al., 1995; Kim et al., 1995; Labarthet et al., 1999). Recently, the formation of holographic gratings with polymeric azobenzene liquid crystals (LC) containing only azobenzene moieties, where each moiety is mesogenic and photoresponsive, was reported (Yamamoto et al., 2000, 2001). The formation of optically active gratings by such polymers is related to the trans-cis isomerization of the chromophores, which leads to a nematic-isotropic phase transition, and thence to a real-time holographic grating (Hasegawa at al., 1999).

The present investigation is a continuation of a project that includes the synthesis, structural study and property evaluation of organic compounds for potential optical applications (Antipin et al., 1997, 1998, 2001; Nesterov et al., 1998; Timofeeva et al., 2000). Recently, we began the synthesis of new photorefractive LC polymers containing mesogenic polar azobenzene pendants. Despite the fact that the structures of many substituted azobenzenes are known, several basic compounds and LC azobenzene pendants have not been studied before now. Our goal was to investigate the influence of the substituent on the azobenzene core and to correlate the structure of the alkyl-tail pendant compound with its probable mesogenic activity.

In this paper, we present the results of the syntheses and structural investigations of three azobenzene derivatives, (E)-(4-hydroxyphenyl)(4-nitrophenyl)diazene, (Ia), (E)-(4-methoxyphenyl)(4-nitrophenyl)diazene, (IIIa), and (E)-[4-(6-bromohexyloxy)phenyl](4-cyanophenyl)diazene, (IIIc), and a description of the mesogenic properties of (IIIc). The synthetic route for the compounds investigated here and their general molecular structures are shown in the Scheme below. We were unable to crystallize compound (Ib) for X-ray analysis. Crystals of (IIIb) were of poor quality, so the data from the X-ray analysis of (IIIb) are not presented here. \sch

The X-ray analysis revealed that two of the crystals studied comprise more than one symmetrically independent molecule. Crystals of (Ia) contain four molecules in the asymmetric unit (A, B, C and D), and crystals of (IIIc) contain two molecules (A and B). The atom-labelling scheme for these molecules includes the letter corresponding to the independent molecule.

In all of the crystals, the azobenzene fragments have the trans conformation. The geometric parameters of the azobenzene cores in all three compounds (Tables 1, 3 and 5) do not differ from standard values (Allen et al., 1987), and they are very close to the literature data for other azobenzene derivatives (Howard et al., 1994; Zhang et al., 1997, 1998). In all three compounds, the azobenzene cores are almost planar. The dihedral angles between the two phenyl rings are 6.9, 2.5, 4.1 and 1.8° for (Ia) (molecules A—D, respectively), 3.5° for (IIIa), and 1.0 and 1.4° for molecules A and B, respectively, of (IIIc); torsion angle data are given in Tables 1, 3 and 5. The structures of molecules A—D in (Ia) are almost identical, and are presented in Fig. 1. The molecular structure of (IIIa) is shown in Fig. 2.

In crystal (IIIc), molecules A and B (Fig. 3) have different conformations of the Br-substituted alkyl tails (see torsion angles in Table 5). In both molecules, the tails do not have the standard all-trans conformation. In molecule A, two atoms of the alkyl tail (C14 and C15) lie in the plane of the azobenzene core, while in molecule B, three C atoms of the tail (C14—C16) belong to the planar fragment (Fig. 3). The angles between the rest of the C atoms of the tail and the planar core are 103.1 and 91.8° in molecules A and B, respectively. These observations demonstrate the flexibility of alkyl tails, not only in LC phases (Zorky et al., 1989), but also in their solid-state precursors.

Analysis of the bond lengths in the benzene rings of molecules (Ia), (IIIa) and (IIIc) did not demonstrate the quinoid character of bond distribution that is often observed in donor-acceptor substituted conjugated polar molecules.

In the crystal structure of (Ia), the planar molecules form molecular sheets parallel to the unit-cell diagonal plane (110). Within these sheets, molecules A and B and molecules B and C are connected into infinite hydrogen-bonded chains (Table 2). In the crystal structure of (IIIa), the molecules also form sheets that are parallel to the (210) diagonal plane, where molecules are held together by weak C—H···O hydrogen bonds (Table 4). A similar type of hydrogen bond was found in 4'-(dimethylamino)-2-nitroazobenzene (Zhang et al., 1998). Superposition of these sheets leads to the formation of centrosymmetric molecular stacks parallel to the b axis. Within these stacks, the molecules have a head-to-tail orientation and interplanar separations of 3.52 and 3.48 Å.

The molecules in (IIIc) also have a head-to-tail orientation, and form separate stacks of molecules A and B along the a axis, with an interplanar separation of about 3.45 Å in both stacks. A fragment of the molecular packing in the crystal of (IIIc) (Fig. 4) shows a marked separation of the azobenzene cores and alkyl tails, which is quite common for the crystal structures of LC precursors.

The short length of the alkyl tails suggests that (IIIc) may form a nematic phase on heating. This suggestion was confirmed by the results of a differential scanning calorimetry (DSC) analysis, which showed that (IIIc) melts at 374.1 K, with the formation of a nematic phase, and isotropization occurs at 376.4 K. The existence of a nematic mesophase in a narrow temperature interval was supported by observations of a texture change in (IIIc) on heating. We believe that, in this case, the nematic-isotropic transition might be related only to changes of tail conformation, without a change of conformation of the azobenzene core.

Parts of the text have been extensively reworded. Please check carefully to make sure the sense has not been altered.

Experimental top

Compounds (Ia) and (Ib) were synthesized according to the method of Ringsdorf & Schmidt (1984). Product (Ia) was recrystallized from methanol (m.p. 486 K; yield 92%). Compounds (IIIa)-(IIIc) were obtained using the following general procedure. Mixtures of (Ia) or (Ib) (10 mmol), K2CO3 (10 mmol), absolute acetone (30 ml), CH3I [10 mmol, (IIa)], 1,4-dibromobutane [Amount?, (IIb)] or 1,6-dibromohexane [Amount?, (IIc)], and a trace amount of KI were refluxed for 1–3 d. The precipitates (KI or KBr) were filtered off and the filtrates were evaporated. CHCl3 was added and extracted three times with water, and evaporated. The products were recrystallized from acetone. For (IIIa), m.p. 421 K, yield 1.85 g, 72%; for (IIIb), m.p. 403 K, yield 2.05 g, 57%; for (IIIc), m.p. 376 K, yield 2.42 g, 73%. All crystals for X-ray analysis were obtained by slow isothermal evaporation from ethanol solutions.

Refinement top

H atoms were treated as riding, with O—H distances of 0.84 Å and C—H distances in the range 0.93–0.99 Å. Is this added text OK?

Computing details top

Data collection: SMART (Bruker, 1998) for (Ia), (IIIc); CAD-4 Software (Enraf-Nonius, 1989) for (IIIa). Cell refinement: SMART for (Ia), (IIIc); CAD-4 Software for (IIIa). Data reduction: SAINT (Bruker, 1998) for (Ia), (IIIc); SHELXTL-Plus (Sheldrick, 1994) for (IIIa). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: SHELXTL-Plus (Sheldrick, 1994) for (Ia), (IIIc); SHELXTL-Plus for (IIIa). Software used to prepare material for publication: SHELXTL-Plus for (Ia), (IIIc); SHELXL97 for (IIIa).

Figures top
[Figure 1] Fig. 1. Views of molecules A—D of (Ia), showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A view of the molecule of (IIIa), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 3] Fig. 3. Views of molecules A and B of (IIIc), showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 4] Fig. 4. The molecular packing in the crystal of (IIIc).
(Ia) (E)-(4-hydroxyphenyl)(4-nitrophenyl)diazene top
Crystal data top
C12H9N3O3Z = 8
Mr = 243.22F(000) = 1008
Triclinic, P1Dx = 1.505 Mg m3
Hall symbol: -P1Melting point: 486 K
a = 7.290 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.648 (6) ÅCell parameters from 320 reflections
c = 28.353 (16) Åθ = 4–24°
α = 93.685 (10)°µ = 0.11 mm1
β = 94.922 (11)°T = 110 K
γ = 100.811 (10)°Plate, yellow
V = 2147 (2) Å30.50 × 0.40 × 0.15 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
6579 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.031
Graphite monochromatorθmax = 30.1°, θmin = 2.0°
ϕ and ω scansh = 1010
24813 measured reflectionsk = 1414
12208 independent reflectionsl = 3938
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143H-atom parameters constrained
S = 0.89 w = 1/[σ2(Fo2) + (0.075P)2]
where P = (Fo2 + 2Fc2)/3
12208 reflections(Δ/σ)max < 0.001
649 parametersΔρmax = 0.47 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
C12H9N3O3γ = 100.811 (10)°
Mr = 243.22V = 2147 (2) Å3
Triclinic, P1Z = 8
a = 7.290 (4) ÅMo Kα radiation
b = 10.648 (6) ŵ = 0.11 mm1
c = 28.353 (16) ÅT = 110 K
α = 93.685 (10)°0.50 × 0.40 × 0.15 mm
β = 94.922 (11)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
6579 reflections with I > 2σ(I)
24813 measured reflectionsRint = 0.031
12208 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.143H-atom parameters constrained
S = 0.89Δρmax = 0.47 e Å3
12208 reflectionsΔρmin = 0.27 e Å3
649 parameters
Special details top

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. All H atoms were placed in geometrically calculated positions and refined using a riding model.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1A0.0637 (2)0.49990 (12)0.23558 (4)0.0399 (4)
H1A0.03050.45790.21850.060*
O2A0.0480 (2)0.23444 (12)0.65306 (5)0.0371 (3)
O3A0.2984 (2)0.37848 (14)0.67052 (5)0.0424 (4)
N1A0.1713 (2)0.31876 (14)0.64195 (5)0.0288 (3)
N2A0.1735 (2)0.44213 (13)0.45204 (5)0.0240 (3)
N3A0.0589 (2)0.36998 (13)0.42149 (5)0.0245 (3)
C1A0.1656 (2)0.34923 (15)0.59218 (6)0.0228 (4)
C2A0.0250 (2)0.27990 (15)0.55950 (6)0.0246 (4)
H2A0.06770.21390.56900.029*
C3A0.0230 (2)0.30914 (16)0.51268 (6)0.0245 (4)
H3A0.07210.26310.48960.029*
C4A0.1604 (2)0.40613 (15)0.49923 (6)0.0217 (4)
C5A0.2970 (2)0.47610 (16)0.53331 (6)0.0247 (4)
H5A0.38770.54440.52430.030*
C6A0.3012 (2)0.44666 (16)0.57998 (6)0.0257 (4)
H6A0.39560.49270.60320.031*
C7A0.0682 (2)0.40578 (16)0.37445 (6)0.0222 (4)
C8A0.0566 (2)0.32882 (16)0.33966 (6)0.0255 (4)
H8A0.13900.25550.34820.031*
C9A0.0620 (3)0.35770 (17)0.29293 (6)0.0273 (4)
H9A0.14790.30480.26940.033*
C10A0.0591 (3)0.46460 (17)0.28055 (6)0.0272 (4)
C11A0.1864 (3)0.54063 (17)0.31486 (6)0.0298 (4)
H11A0.27100.61250.30600.036*
C12A0.1909 (3)0.51272 (16)0.36155 (6)0.0262 (4)
H12A0.27710.56580.38500.031*
O1B0.09328 (19)0.13282 (12)0.74147 (4)0.0350 (3)
H1B0.11180.19380.72400.052*
O2B0.83062 (18)0.42569 (11)1.15294 (4)0.0314 (3)
O3B0.7259 (2)0.23105 (12)1.16776 (4)0.0379 (3)
N1B0.7416 (2)0.31699 (13)1.14099 (5)0.0246 (3)
N2B0.40260 (19)0.19248 (13)0.95398 (5)0.0235 (3)
N3B0.42434 (19)0.27785 (13)0.92494 (5)0.0231 (3)
C1B0.6539 (2)0.28942 (15)1.09206 (6)0.0202 (3)
C2B0.6722 (2)0.38609 (15)1.06129 (6)0.0224 (4)
H2B0.73920.47011.07160.027*
C3B0.5903 (2)0.35657 (15)1.01511 (6)0.0222 (4)
H3B0.60230.42060.99310.027*
C4B0.4901 (2)0.23332 (15)1.00069 (6)0.0201 (3)
C5B0.4724 (2)0.13947 (15)1.03265 (6)0.0229 (4)
H5B0.40220.05601.02290.027*
C6B0.5564 (2)0.16702 (15)1.07855 (6)0.0231 (4)
H6B0.54710.10271.10040.028*
C7B0.3386 (2)0.23651 (15)0.87840 (6)0.0214 (3)
C8B0.3606 (2)0.32641 (16)0.84480 (6)0.0239 (4)
H8B0.43130.41020.85370.029*
C9B0.2808 (2)0.29516 (16)0.79858 (6)0.0260 (4)
H9B0.29570.35710.77580.031*
C10B0.1785 (2)0.17226 (16)0.78575 (6)0.0253 (4)
C11B0.1595 (2)0.08048 (16)0.81882 (6)0.0257 (4)
H11B0.09260.00420.80950.031*
C12B0.2372 (2)0.11226 (16)0.86492 (6)0.0235 (4)
H12B0.22220.05010.88760.028*
O1C0.68874 (18)0.99896 (12)0.34847 (4)0.0330 (3)
H1C0.61050.95330.32780.049*
O2C0.53167 (19)0.65258 (13)0.75292 (5)0.0404 (4)
O3C0.78189 (19)0.79158 (12)0.77738 (4)0.0351 (3)
N1C0.6586 (2)0.73978 (14)0.74582 (5)0.0275 (3)
N2C0.7027 (2)0.90688 (13)0.56232 (5)0.0226 (3)
N3C0.5955 (2)0.84019 (13)0.52913 (5)0.0226 (3)
C1C0.6661 (2)0.78405 (16)0.69812 (6)0.0230 (4)
C2C0.5330 (2)0.72046 (15)0.66252 (6)0.0230 (4)
H2C0.43910.65080.66910.028*
C3C0.5396 (2)0.76056 (16)0.61732 (6)0.0240 (4)
H3C0.44860.71900.59240.029*
C4C0.6794 (2)0.86190 (15)0.60802 (6)0.0213 (3)
C5C0.8083 (2)0.92530 (16)0.64476 (6)0.0247 (4)
H5C0.90140.99590.63850.030*
C6C0.8025 (2)0.88667 (16)0.69025 (6)0.0260 (4)
H6C0.89040.92980.71550.031*
C7C0.6225 (2)0.88454 (15)0.48366 (6)0.0213 (3)
C8C0.5019 (2)0.81909 (16)0.44566 (6)0.0243 (4)
H8C0.40710.74860.45100.029*
C9C0.5188 (2)0.85594 (16)0.39991 (6)0.0259 (4)
H9C0.43460.81170.37420.031*
C10C0.6593 (3)0.95760 (16)0.39189 (6)0.0250 (4)
C11C0.7805 (2)1.02350 (16)0.43001 (6)0.0252 (4)
H11C0.87621.09340.42460.030*
C12C0.7622 (2)0.98780 (16)0.47530 (6)0.0247 (4)
H12C0.84471.03350.50110.030*
O1D0.27924 (18)0.62093 (12)0.14721 (4)0.0319 (3)
H1D0.25640.67430.16750.048*
O2D0.52516 (18)1.02984 (12)0.24777 (4)0.0327 (3)
O3D0.4248 (2)0.84703 (13)0.27445 (4)0.0374 (3)
N1D0.4331 (2)0.92001 (14)0.24240 (5)0.0267 (3)
N2D0.06133 (19)0.73462 (13)0.06276 (5)0.0214 (3)
N3D0.07701 (19)0.81176 (13)0.03072 (5)0.0212 (3)
C1D0.3314 (2)0.87379 (16)0.19604 (6)0.0218 (4)
C2D0.3369 (2)0.95936 (16)0.16096 (6)0.0233 (4)
H2D0.40081.04590.16740.028*
C3D0.2473 (2)0.91523 (15)0.11663 (6)0.0224 (4)
H3D0.24910.97160.09200.027*
C4D0.1539 (2)0.78815 (15)0.10784 (6)0.0203 (3)
C5D0.1480 (2)0.70543 (15)0.14368 (6)0.0232 (4)
H5D0.08210.61930.13760.028*
C6D0.2385 (2)0.74848 (16)0.18852 (6)0.0245 (4)
H6D0.23620.69260.21340.029*
C7D0.0135 (2)0.75893 (15)0.01440 (6)0.0204 (3)
C8D0.0038 (2)0.84056 (15)0.05084 (6)0.0225 (4)
H8D0.06120.92690.04480.027*
C9D0.0889 (2)0.79619 (16)0.09601 (6)0.0233 (4)
H9D0.08020.85160.12100.028*
C10D0.1868 (2)0.67081 (16)0.10459 (6)0.0233 (4)
C11D0.1945 (2)0.58811 (16)0.06830 (6)0.0239 (4)
H11D0.25900.50160.07440.029*
C12D0.1088 (2)0.63200 (15)0.02368 (6)0.0226 (4)
H12D0.11440.57560.00100.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0514 (9)0.0385 (8)0.0216 (7)0.0093 (6)0.0081 (6)0.0098 (6)
O2A0.0529 (9)0.0296 (7)0.0277 (7)0.0018 (6)0.0056 (6)0.0096 (5)
O3A0.0502 (9)0.0481 (9)0.0235 (7)0.0005 (7)0.0067 (6)0.0050 (6)
N1A0.0396 (9)0.0252 (8)0.0231 (8)0.0090 (7)0.0028 (7)0.0052 (6)
N2A0.0289 (8)0.0247 (7)0.0191 (7)0.0057 (6)0.0033 (6)0.0046 (6)
N3A0.0285 (8)0.0244 (7)0.0216 (8)0.0061 (6)0.0037 (6)0.0043 (6)
C1A0.0309 (9)0.0226 (8)0.0170 (8)0.0101 (7)0.0029 (7)0.0032 (6)
C2A0.0284 (9)0.0214 (8)0.0239 (9)0.0032 (7)0.0028 (7)0.0062 (7)
C3A0.0307 (10)0.0232 (8)0.0183 (8)0.0041 (7)0.0008 (7)0.0007 (6)
C4A0.0289 (9)0.0198 (8)0.0185 (8)0.0080 (7)0.0045 (7)0.0040 (6)
C5A0.0253 (9)0.0230 (8)0.0252 (9)0.0019 (7)0.0037 (7)0.0039 (7)
C6A0.0300 (10)0.0246 (9)0.0215 (9)0.0046 (7)0.0005 (7)0.0001 (7)
C7A0.0253 (9)0.0240 (8)0.0190 (8)0.0074 (7)0.0038 (7)0.0037 (6)
C8A0.0263 (9)0.0261 (9)0.0244 (9)0.0036 (7)0.0032 (7)0.0071 (7)
C9A0.0294 (10)0.0289 (9)0.0222 (9)0.0042 (7)0.0015 (8)0.0023 (7)
C10A0.0334 (10)0.0294 (9)0.0201 (9)0.0078 (8)0.0017 (8)0.0079 (7)
C11A0.0360 (11)0.0252 (9)0.0269 (10)0.0011 (8)0.0033 (8)0.0065 (7)
C12A0.0324 (10)0.0245 (9)0.0212 (9)0.0048 (7)0.0009 (8)0.0029 (7)
O1B0.0466 (8)0.0331 (7)0.0204 (7)0.0016 (6)0.0058 (6)0.0049 (5)
O2B0.0383 (8)0.0249 (6)0.0254 (7)0.0036 (5)0.0050 (6)0.0001 (5)
O3B0.0535 (9)0.0314 (7)0.0231 (7)0.0046 (6)0.0050 (6)0.0099 (5)
N1B0.0242 (8)0.0280 (8)0.0202 (7)0.0024 (6)0.0001 (6)0.0032 (6)
N2B0.0219 (7)0.0272 (8)0.0202 (7)0.0027 (6)0.0003 (6)0.0005 (6)
N3B0.0225 (7)0.0254 (7)0.0206 (7)0.0033 (6)0.0006 (6)0.0021 (6)
C1B0.0195 (8)0.0238 (8)0.0170 (8)0.0035 (6)0.0010 (6)0.0013 (6)
C2B0.0224 (9)0.0215 (8)0.0214 (9)0.0001 (6)0.0013 (7)0.0000 (6)
C3B0.0243 (9)0.0212 (8)0.0210 (8)0.0027 (7)0.0025 (7)0.0048 (6)
C4B0.0174 (8)0.0241 (8)0.0186 (8)0.0040 (6)0.0015 (6)0.0003 (6)
C5B0.0216 (9)0.0214 (8)0.0234 (9)0.0002 (6)0.0002 (7)0.0005 (6)
C6B0.0247 (9)0.0234 (8)0.0213 (9)0.0028 (7)0.0034 (7)0.0058 (6)
C7B0.0212 (8)0.0254 (8)0.0169 (8)0.0041 (6)0.0003 (7)0.0013 (6)
C8B0.0247 (9)0.0227 (8)0.0232 (9)0.0027 (7)0.0006 (7)0.0027 (7)
C9B0.0288 (10)0.0279 (9)0.0218 (9)0.0055 (7)0.0016 (7)0.0076 (7)
C10B0.0248 (9)0.0307 (9)0.0204 (9)0.0069 (7)0.0003 (7)0.0004 (7)
C11B0.0248 (9)0.0270 (9)0.0233 (9)0.0019 (7)0.0000 (7)0.0001 (7)
C12B0.0244 (9)0.0250 (8)0.0201 (9)0.0025 (7)0.0007 (7)0.0043 (7)
O1C0.0415 (8)0.0352 (7)0.0198 (6)0.0019 (6)0.0000 (6)0.0044 (5)
O2C0.0429 (8)0.0451 (8)0.0289 (7)0.0069 (7)0.0026 (6)0.0162 (6)
O3C0.0439 (8)0.0386 (8)0.0194 (7)0.0024 (6)0.0044 (6)0.0033 (5)
N1C0.0355 (9)0.0301 (8)0.0178 (7)0.0088 (7)0.0004 (6)0.0038 (6)
N2C0.0282 (8)0.0226 (7)0.0175 (7)0.0057 (6)0.0016 (6)0.0044 (5)
N3C0.0273 (8)0.0224 (7)0.0189 (7)0.0065 (6)0.0014 (6)0.0033 (5)
C1C0.0285 (9)0.0259 (9)0.0158 (8)0.0078 (7)0.0017 (7)0.0043 (6)
C2C0.0256 (9)0.0219 (8)0.0206 (9)0.0015 (7)0.0012 (7)0.0048 (6)
C3C0.0267 (9)0.0247 (8)0.0184 (8)0.0013 (7)0.0019 (7)0.0020 (6)
C4C0.0267 (9)0.0206 (8)0.0182 (8)0.0080 (7)0.0022 (7)0.0035 (6)
C5C0.0263 (9)0.0220 (8)0.0240 (9)0.0002 (7)0.0010 (7)0.0036 (7)
C6C0.0289 (10)0.0257 (9)0.0208 (9)0.0018 (7)0.0008 (7)0.0015 (7)
C7C0.0262 (9)0.0226 (8)0.0161 (8)0.0082 (7)0.0005 (7)0.0014 (6)
C8C0.0266 (9)0.0226 (8)0.0229 (9)0.0046 (7)0.0007 (7)0.0016 (7)
C9C0.0301 (10)0.0255 (9)0.0206 (9)0.0055 (7)0.0042 (7)0.0004 (7)
C10C0.0320 (10)0.0281 (9)0.0175 (8)0.0117 (7)0.0022 (7)0.0040 (7)
C11C0.0278 (9)0.0244 (9)0.0230 (9)0.0029 (7)0.0038 (7)0.0045 (7)
C12C0.0292 (9)0.0240 (9)0.0205 (9)0.0051 (7)0.0004 (7)0.0023 (7)
O1D0.0405 (8)0.0319 (7)0.0187 (6)0.0022 (6)0.0038 (6)0.0035 (5)
O2D0.0359 (7)0.0304 (7)0.0271 (7)0.0002 (6)0.0044 (6)0.0045 (5)
O3D0.0469 (8)0.0423 (8)0.0198 (7)0.0017 (6)0.0033 (6)0.0073 (6)
N1D0.0269 (8)0.0326 (8)0.0203 (8)0.0062 (6)0.0006 (6)0.0014 (6)
N2D0.0220 (7)0.0229 (7)0.0179 (7)0.0018 (6)0.0007 (6)0.0027 (5)
N3D0.0208 (7)0.0231 (7)0.0187 (7)0.0024 (5)0.0008 (6)0.0028 (5)
C1D0.0210 (8)0.0275 (9)0.0162 (8)0.0047 (7)0.0012 (7)0.0000 (6)
C2D0.0245 (9)0.0221 (8)0.0218 (9)0.0018 (7)0.0003 (7)0.0016 (6)
C3D0.0259 (9)0.0214 (8)0.0188 (8)0.0015 (7)0.0003 (7)0.0041 (6)
C4D0.0184 (8)0.0230 (8)0.0188 (8)0.0028 (6)0.0011 (6)0.0015 (6)
C5D0.0251 (9)0.0202 (8)0.0231 (9)0.0011 (6)0.0018 (7)0.0032 (6)
C6D0.0280 (9)0.0250 (9)0.0213 (9)0.0052 (7)0.0040 (7)0.0068 (7)
C7D0.0181 (8)0.0237 (8)0.0191 (8)0.0039 (6)0.0007 (6)0.0021 (6)
C8D0.0239 (9)0.0201 (8)0.0236 (9)0.0033 (6)0.0025 (7)0.0047 (6)
C9D0.0257 (9)0.0247 (8)0.0204 (9)0.0053 (7)0.0025 (7)0.0074 (7)
C10D0.0226 (9)0.0288 (9)0.0186 (8)0.0058 (7)0.0007 (7)0.0015 (7)
C11D0.0256 (9)0.0218 (8)0.0219 (9)0.0004 (7)0.0002 (7)0.0015 (6)
C12D0.0241 (9)0.0230 (8)0.0199 (9)0.0020 (7)0.0018 (7)0.0052 (6)
Geometric parameters (Å, º) top
O1A—C10A1.354 (2)O1C—C10C1.355 (2)
O1A—H1A0.8400O1C—H1C0.8400
O2A—N1A1.223 (2)O2C—N1C1.222 (2)
O3A—N1A1.2258 (19)O3C—N1C1.2351 (18)
N1A—C1A1.467 (2)N1C—C1C1.463 (2)
N2A—N3A1.2601 (19)N2C—N3C1.2571 (19)
N2A—C4A1.421 (2)N2C—C4C1.423 (2)
N3A—C7A1.414 (2)N3C—C7C1.418 (2)
C1A—C6A1.376 (2)C1C—C6C1.376 (2)
C1A—C2A1.385 (2)C1C—C2C1.385 (2)
C2A—C3A1.383 (2)C2C—C3C1.379 (2)
C2A—H2A0.9500C2C—H2C0.9500
C3A—C4A1.394 (2)C3C—C4C1.394 (2)
C3A—H3A0.9500C3C—H3C0.9500
C4A—C5A1.394 (2)C4C—C5C1.388 (2)
C5A—C6A1.378 (2)C5C—C6C1.380 (2)
C5A—H5A0.9500C5C—H5C0.9500
C6A—H6A0.9500C6C—H6C0.9500
C7A—C8A1.391 (2)C7C—C8C1.390 (2)
C7A—C12A1.399 (2)C7C—C12C1.399 (2)
C8A—C9A1.378 (2)C8C—C9C1.388 (2)
C8A—H8A0.9500C8C—H8C0.9500
C9A—C10A1.388 (2)C9C—C10C1.388 (3)
C9A—H9A0.9500C9C—H9C0.9500
C10A—C11A1.387 (2)C10C—C11C1.396 (2)
C11A—C12A1.374 (3)C11C—C12C1.373 (2)
C11A—H11A0.9500C11C—H11C0.9500
C12A—H12A0.9500C12C—H12C0.9500
O1B—C10B1.356 (2)O1D—C10D1.357 (2)
O1B—H1B0.8400O1D—H1D0.8400
O2B—N1B1.2271 (18)O2D—N1D1.2274 (19)
O3B—N1B1.2212 (18)O3D—N1D1.2311 (19)
N1B—C1B1.465 (2)N1D—C1D1.460 (2)
N2B—N3B1.263 (2)N2D—N3D1.2616 (19)
N2B—C4B1.424 (2)N2D—C4D1.424 (2)
N3B—C7B1.416 (2)N3D—C7D1.418 (2)
C1B—C6B1.376 (2)C1D—C6D1.373 (2)
C1B—C2B1.386 (2)C1D—C2D1.389 (2)
C2B—C3B1.383 (2)C2D—C3D1.377 (2)
C2B—H2B0.9500C2D—H2D0.9500
C3B—C4B1.394 (2)C3D—C4D1.392 (2)
C3B—H3B0.9500C3D—H3D0.9500
C4B—C5B1.387 (2)C4D—C5D1.385 (2)
C5B—C6B1.379 (2)C5D—C6D1.389 (2)
C5B—H5B0.9500C5D—H5D0.9500
C6B—H6B0.9500C6D—H6D0.9500
C7B—C8B1.391 (2)C7D—C8D1.390 (2)
C7B—C12B1.401 (2)C7D—C12D1.396 (2)
C8B—C9B1.381 (2)C8D—C9D1.387 (2)
C8B—H8B0.9500C8D—H8D0.9500
C9B—C10B1.388 (2)C9D—C10D1.386 (2)
C9B—H9B0.9500C9D—H9D0.9500
C10B—C11B1.394 (2)C10D—C11D1.395 (2)
C11B—C12B1.374 (2)C11D—C12D1.374 (2)
C11B—H11B0.9500C11D—H11D0.9500
C12B—H12B0.9500C12D—H12D0.9500
C10A—O1A—H1A109.5C10C—O1C—H1C109.5
O2A—N1A—O3A122.86 (15)O2C—N1C—O3C122.45 (15)
O2A—N1A—C1A118.17 (15)O2C—N1C—C1C118.94 (14)
O3A—N1A—C1A118.97 (15)O3C—N1C—C1C118.60 (15)
N3A—N2A—C4A113.87 (14)N3C—N2C—C4C114.31 (14)
N2A—N3A—C7A114.54 (14)N2C—N3C—C7C113.77 (14)
C6A—C1A—C2A122.65 (16)C6C—C1C—C2C122.56 (15)
C6A—C1A—N1A118.13 (15)C6C—C1C—N1C119.49 (15)
C2A—C1A—N1A119.22 (16)C2C—C1C—N1C117.95 (15)
C3A—C2A—C1A118.39 (16)C3C—C2C—C1C118.51 (16)
C3A—C2A—H2A120.8C3C—C2C—H2C120.7
C1A—C2A—H2A120.8C1C—C2C—H2C120.7
C2A—C3A—C4A120.11 (16)C2C—C3C—C4C120.16 (15)
C2A—C3A—H3A119.9C2C—C3C—H3C119.9
C4A—C3A—H3A119.9C4C—C3C—H3C119.9
C3A—C4A—C5A119.91 (16)C5C—C4C—C3C119.81 (15)
C3A—C4A—N2A124.68 (15)C5C—C4C—N2C115.78 (15)
C5A—C4A—N2A115.41 (15)C3C—C4C—N2C124.40 (15)
C6A—C5A—C4A120.31 (16)C6C—C5C—C4C120.58 (16)
C6A—C5A—H5A119.8C6C—C5C—H5C119.7
C4A—C5A—H5A119.8C4C—C5C—H5C119.7
C1A—C6A—C5A118.59 (16)C1C—C6C—C5C118.33 (15)
C1A—C6A—H6A120.7C1C—C6C—H6C120.8
C5A—C6A—H6A120.7C5C—C6C—H6C120.8
C8A—C7A—C12A119.36 (16)C8C—C7C—C12C119.27 (16)
C8A—C7A—N3A116.34 (15)C8C—C7C—N3C116.71 (15)
C12A—C7A—N3A124.29 (15)C12C—C7C—N3C124.02 (15)
C9A—C8A—C7A120.75 (16)C9C—C8C—C7C120.48 (16)
C9A—C8A—H8A119.6C9C—C8C—H8C119.8
C7A—C8A—H8A119.6C7C—C8C—H8C119.8
C8A—C9A—C10A119.47 (16)C8C—C9C—C10C119.81 (16)
C8A—C9A—H9A120.3C8C—C9C—H9C120.1
C10A—C9A—H9A120.3C10C—C9C—H9C120.1
O1A—C10A—C11A116.36 (16)O1C—C10C—C9C124.03 (16)
O1A—C10A—C9A123.43 (16)O1C—C10C—C11C116.20 (16)
C11A—C10A—C9A120.20 (16)C9C—C10C—C11C119.77 (16)
C12A—C11A—C10A120.45 (17)C12C—C11C—C10C120.31 (16)
C12A—C11A—H11A119.8C12C—C11C—H11C119.8
C10A—C11A—H11A119.8C10C—C11C—H11C119.8
C11A—C12A—C7A119.76 (16)C11C—C12C—C7C120.34 (16)
C11A—C12A—H12A120.1C11C—C12C—H12C119.8
C7A—C12A—H12A120.1C7C—C12C—H12C119.8
C10B—O1B—H1B109.5C10D—O1D—H1D109.5
O3B—N1B—O2B122.98 (15)O2D—N1D—O3D122.52 (15)
O3B—N1B—C1B118.97 (14)O2D—N1D—C1D118.65 (14)
O2B—N1B—C1B118.04 (14)O3D—N1D—C1D118.82 (15)
N3B—N2B—C4B114.43 (14)N3D—N2D—C4D113.83 (13)
N2B—N3B—C7B114.25 (14)N2D—N3D—C7D114.22 (14)
C6B—C1B—C2B122.66 (15)C6D—C1D—C2D122.86 (15)
C6B—C1B—N1B117.94 (14)C6D—C1D—N1D119.32 (15)
C2B—C1B—N1B119.40 (14)C2D—C1D—N1D117.81 (15)
C3B—C2B—C1B118.04 (15)C3D—C2D—C1D118.17 (15)
C3B—C2B—H2B121.0C3D—C2D—H2D120.9
C1B—C2B—H2B121.0C1D—C2D—H2D120.9
C2B—C3B—C4B120.28 (15)C2D—C3D—C4D120.19 (15)
C2B—C3B—H3B119.9C2D—C3D—H3D119.9
C4B—C3B—H3B119.9C4D—C3D—H3D119.9
C5B—C4B—C3B120.08 (15)C5D—C4D—C3D120.44 (15)
C5B—C4B—N2B115.11 (14)C5D—C4D—N2D116.00 (14)
C3B—C4B—N2B124.80 (15)C3D—C4D—N2D123.55 (14)
C6B—C5B—C4B120.20 (15)C4D—C5D—C6D119.99 (15)
C6B—C5B—H5B119.9C4D—C5D—H5D120.0
C4B—C5B—H5B119.9C6D—C5D—H5D120.0
C1B—C6B—C5B118.72 (15)C1D—C6D—C5D118.33 (15)
C1B—C6B—H6B120.6C1D—C6D—H6D120.8
C5B—C6B—H6B120.6C5D—C6D—H6D120.8
C8B—C7B—C12B119.54 (15)C8D—C7D—C12D119.50 (15)
C8B—C7B—N3B116.60 (15)C8D—C7D—N3D116.65 (15)
C12B—C7B—N3B123.86 (15)C12D—C7D—N3D123.85 (14)
C9B—C8B—C7B120.73 (16)C9D—C8D—C7D120.17 (15)
C9B—C8B—H8B119.6C9D—C8D—H8D119.9
C7B—C8B—H8B119.6C7D—C8D—H8D119.9
C8B—C9B—C10B119.26 (16)C10D—C9D—C8D119.86 (15)
C8B—C9B—H9B120.4C10D—C9D—H9D120.1
C10B—C9B—H9B120.4C8D—C9D—H9D120.1
O1B—C10B—C9B123.66 (16)O1D—C10D—C9D123.71 (15)
O1B—C10B—C11B115.84 (15)O1D—C10D—C11D116.16 (15)
C9B—C10B—C11B120.51 (16)C9D—C10D—C11D120.12 (15)
C12B—C11B—C10B120.10 (16)C12D—C11D—C10D119.87 (15)
C12B—C11B—H11B120.0C12D—C11D—H11D120.1
C10B—C11B—H11B120.0C10D—C11D—H11D120.1
C11B—C12B—C7B119.84 (15)C11D—C12D—C7D120.45 (15)
C11B—C12B—H12B120.1C11D—C12D—H12D119.8
C7B—C12B—H12B120.1C7D—C12D—H12D119.8
C4A—N2A—N3A—C7A179.04 (14)C4C—N2C—N3C—C7C178.84 (14)
O2A—N1A—C1A—C6A178.12 (16)O2C—N1C—C1C—C6C176.57 (17)
O3A—N1A—C1A—C6A1.8 (2)O3C—N1C—C1C—C6C3.9 (2)
O2A—N1A—C1A—C2A1.7 (2)O2C—N1C—C1C—C2C3.0 (2)
O3A—N1A—C1A—C2A178.42 (16)O3C—N1C—C1C—C2C176.54 (15)
C6A—C1A—C2A—C3A0.9 (3)C6C—C1C—C2C—C3C1.0 (3)
N1A—C1A—C2A—C3A179.37 (15)N1C—C1C—C2C—C3C179.44 (15)
C1A—C2A—C3A—C4A0.1 (3)C1C—C2C—C3C—C4C0.8 (3)
C2A—C3A—C4A—C5A1.7 (3)C2C—C3C—C4C—C5C2.2 (3)
C2A—C3A—C4A—N2A178.71 (16)C2C—C3C—C4C—N2C177.34 (16)
N3A—N2A—C4A—C3A6.4 (2)N3C—N2C—C4C—C5C173.60 (15)
N3A—N2A—C4A—C5A173.98 (14)N3C—N2C—C4C—C3C5.9 (2)
C3A—C4A—C5A—C6A2.4 (3)C3C—C4C—C5C—C6C1.7 (3)
N2A—C4A—C5A—C6A177.98 (16)N2C—C4C—C5C—C6C177.81 (16)
C2A—C1A—C6A—C5A0.2 (3)C2C—C1C—C6C—C5C1.5 (3)
N1A—C1A—C6A—C5A179.97 (15)N1C—C1C—C6C—C5C179.03 (15)
C4A—C5A—C6A—C1A1.5 (3)C4C—C5C—C6C—C1C0.0 (3)
N2A—N3A—C7A—C8A179.77 (15)N2C—N3C—C7C—C8C176.74 (14)
N2A—N3A—C7A—C12A0.8 (2)N2C—N3C—C7C—C12C3.7 (2)
C12A—C7A—C8A—C9A0.8 (3)C12C—C7C—C8C—C9C0.3 (3)
N3A—C7A—C8A—C9A178.24 (16)N3C—C7C—C8C—C9C179.83 (15)
C7A—C8A—C9A—C10A0.2 (3)C7C—C8C—C9C—C10C1.0 (3)
C8A—C9A—C10A—O1A179.82 (17)C8C—C9C—C10C—O1C178.82 (16)
C8A—C9A—C10A—C11A1.0 (3)C8C—C9C—C10C—C11C1.1 (3)
O1A—C10A—C11A—C12A179.50 (17)O1C—C10C—C11C—C12C179.54 (16)
C9A—C10A—C11A—C12A1.6 (3)C9C—C10C—C11C—C12C0.4 (3)
C10A—C11A—C12A—C7A1.0 (3)C10C—C11C—C12C—C7C0.4 (3)
C8A—C7A—C12A—C11A0.2 (3)C8C—C7C—C12C—C11C0.4 (3)
N3A—C7A—C12A—C11A178.75 (16)N3C—C7C—C12C—C11C179.07 (16)
C4B—N2B—N3B—C7B179.42 (13)C4D—N2D—N3D—C7D179.51 (13)
O3B—N1B—C1B—C6B0.3 (2)O2D—N1D—C1D—C6D175.51 (16)
O2B—N1B—C1B—C6B179.10 (16)O3D—N1D—C1D—C6D3.7 (2)
O3B—N1B—C1B—C2B179.46 (16)O2D—N1D—C1D—C2D3.2 (2)
O2B—N1B—C1B—C2B0.7 (2)O3D—N1D—C1D—C2D177.59 (16)
C6B—C1B—C2B—C3B0.7 (3)C6D—C1D—C2D—C3D1.0 (3)
N1B—C1B—C2B—C3B179.03 (15)N1D—C1D—C2D—C3D177.63 (15)
C1B—C2B—C3B—C4B1.0 (3)C1D—C2D—C3D—C4D0.2 (3)
C2B—C3B—C4B—C5B0.1 (3)C2D—C3D—C4D—C5D0.9 (3)
C2B—C3B—C4B—N2B179.14 (16)C2D—C3D—C4D—N2D178.64 (16)
N3B—N2B—C4B—C5B178.09 (15)N3D—N2D—C4D—C5D177.15 (15)
N3B—N2B—C4B—C3B1.0 (2)N3D—N2D—C4D—C3D2.4 (2)
C3B—C4B—C5B—C6B1.1 (3)C3D—C4D—C5D—C6D1.2 (3)
N2B—C4B—C5B—C6B178.03 (15)N2D—C4D—C5D—C6D178.40 (15)
C2B—C1B—C6B—C5B0.4 (3)C2D—C1D—C6D—C5D0.7 (3)
N1B—C1B—C6B—C5B179.80 (15)N1D—C1D—C6D—C5D177.89 (15)
C4B—C5B—C6B—C1B1.4 (3)C4D—C5D—C6D—C1D0.4 (3)
N2B—N3B—C7B—C8B179.12 (15)N2D—N3D—C7D—C8D178.77 (15)
N2B—N3B—C7B—C12B0.2 (2)N2D—N3D—C7D—C12D1.4 (2)
C12B—C7B—C8B—C9B1.2 (3)C12D—C7D—C8D—C9D0.2 (3)
N3B—C7B—C8B—C9B179.48 (15)N3D—C7D—C8D—C9D179.93 (15)
C7B—C8B—C9B—C10B0.3 (3)C7D—C8D—C9D—C10D1.2 (3)
C8B—C9B—C10B—O1B179.28 (16)C8D—C9D—C10D—O1D177.74 (16)
C8B—C9B—C10B—C11B1.2 (3)C8D—C9D—C10D—C11D2.1 (3)
O1B—C10B—C11B—C12B178.47 (15)O1D—C10D—C11D—C12D178.29 (15)
C9B—C10B—C11B—C12B2.0 (3)C9D—C10D—C11D—C12D1.6 (3)
C10B—C11B—C12B—C7B1.2 (3)C10D—C11D—C12D—C7D0.1 (3)
C8B—C7B—C12B—C11B0.4 (3)C8D—C7D—C12D—C11D0.8 (3)
N3B—C7B—C12B—C11B179.70 (16)N3D—C7D—C12D—C11D179.40 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···O2Bi0.842.022.753 (2)146
O1B—H1B···O2A0.842.122.811 (2)140
O1C—H1C···O3D0.842.062.903 (2)177
O1D—H1D···O3Ci0.842.072.904 (2)174
Symmetry code: (i) x1, y, z1.
(IIIa) (E)-(4-methoxyphenyl)(4-nitrophenyl)diazene top
Crystal data top
C13H11N3O3Z = 2
Mr = 257.25F(000) = 268
Triclinic, P1Dx = 1.406 Mg m3
Hall symbol: -P1Melting point: 421 K
a = 6.1530 (12) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.5500 (15) ÅCell parameters from 24 reflections
c = 13.683 (3) Åθ = 11–12°
α = 100.80 (3)°µ = 0.10 mm1
β = 102.68 (3)°T = 298 K
γ = 91.74 (3)°Parallelepiped prism, yellow
V = 607.5 (2) Å30.45 × 0.35 × 0.30 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.058
Radiation source: fine-focus sealed tubeθmax = 26.0°, θmin = 2.8°
Graphite monochromatorh = 07
θ/2θ scansk = 99
2618 measured reflectionsl = 1616
2382 independent reflections3 standard reflections every 97 reflections
1717 reflections with I > 2σ(I) intensity decay: 3%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.079P)2 + 0.0794P]
where P = (Fo2 + 2Fc2)/3
2382 reflections(Δ/σ)max < 0.001
173 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C13H11N3O3γ = 91.74 (3)°
Mr = 257.25V = 607.5 (2) Å3
Triclinic, P1Z = 2
a = 6.1530 (12) ÅMo Kα radiation
b = 7.5500 (15) ŵ = 0.10 mm1
c = 13.683 (3) ÅT = 298 K
α = 100.80 (3)°0.45 × 0.35 × 0.30 mm
β = 102.68 (3)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.058
2618 measured reflections3 standard reflections every 97 reflections
2382 independent reflections intensity decay: 3%
1717 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.144H-atom parameters constrained
S = 1.04Δρmax = 0.16 e Å3
2382 reflectionsΔρmin = 0.19 e Å3
173 parameters
Special details top

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. All H atoms were placed in geometrically calculeted positions and refined using a riding model.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.24178 (19)0.11783 (17)0.16573 (9)0.0648 (4)
O21.3612 (2)0.66378 (19)0.83739 (9)0.0787 (4)
O31.1712 (2)0.6266 (2)0.94592 (9)0.0886 (5)
N11.1933 (2)0.60681 (18)0.85842 (10)0.0532 (3)
N20.47598 (19)0.25706 (16)0.54580 (9)0.0461 (3)
N30.49461 (19)0.23619 (15)0.45539 (9)0.0443 (3)
C11.0110 (2)0.51416 (18)0.77543 (10)0.0433 (3)
C21.0340 (2)0.49594 (19)0.67598 (11)0.0459 (4)
H2A1.16430.54000.66200.055*
C30.8599 (2)0.4111 (2)0.59786 (11)0.0460 (4)
H3A0.87170.39750.53030.055*
C40.6661 (2)0.34566 (17)0.62027 (10)0.0416 (3)
C50.6484 (2)0.3642 (2)0.72077 (11)0.0490 (4)
H5A0.51930.31880.73520.059*
C60.8215 (3)0.4496 (2)0.79974 (11)0.0504 (4)
H6A0.81050.46330.86740.060*
C70.3032 (2)0.14801 (17)0.38274 (10)0.0409 (3)
C80.3135 (2)0.1157 (2)0.28108 (11)0.0484 (4)
H8A0.44240.15290.26320.058*
C90.1339 (3)0.0283 (2)0.20552 (11)0.0522 (4)
H9A0.14200.00730.13730.063*
C100.0577 (2)0.0275 (2)0.23241 (11)0.0471 (4)
C110.0697 (2)0.0070 (2)0.33423 (11)0.0488 (4)
H11A0.19910.02910.35210.059*
C120.1078 (2)0.0939 (2)0.40852 (11)0.0456 (4)
H12A0.09810.11690.47660.055*
C130.2495 (4)0.1463 (3)0.05961 (13)0.0806 (6)
H13B0.39050.20750.02200.121*
H13A0.13080.21880.04490.121*
H13C0.23240.03190.04010.121*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0535 (7)0.0752 (8)0.0525 (7)0.0132 (6)0.0047 (5)0.0021 (6)
O20.0544 (7)0.1048 (10)0.0650 (7)0.0289 (7)0.0065 (6)0.0009 (7)
O30.0788 (9)0.1285 (13)0.0445 (7)0.0347 (8)0.0069 (6)0.0025 (7)
N10.0506 (7)0.0551 (8)0.0469 (7)0.0062 (6)0.0040 (6)0.0030 (6)
N20.0443 (7)0.0448 (7)0.0455 (7)0.0046 (5)0.0058 (5)0.0060 (5)
N30.0440 (7)0.0408 (7)0.0457 (7)0.0021 (5)0.0069 (5)0.0074 (5)
C10.0431 (8)0.0375 (7)0.0446 (8)0.0001 (6)0.0039 (6)0.0040 (6)
C20.0417 (7)0.0449 (8)0.0491 (8)0.0037 (6)0.0086 (6)0.0080 (6)
C30.0482 (8)0.0465 (8)0.0418 (7)0.0030 (6)0.0088 (6)0.0075 (6)
C40.0416 (7)0.0344 (7)0.0452 (8)0.0000 (5)0.0049 (6)0.0056 (6)
C50.0431 (8)0.0513 (8)0.0517 (8)0.0058 (6)0.0121 (6)0.0080 (6)
C60.0527 (8)0.0550 (9)0.0418 (7)0.0027 (7)0.0112 (6)0.0063 (6)
C70.0417 (7)0.0348 (7)0.0443 (7)0.0003 (5)0.0058 (6)0.0083 (6)
C80.0443 (8)0.0524 (9)0.0491 (8)0.0024 (6)0.0119 (6)0.0114 (7)
C90.0557 (9)0.0596 (9)0.0393 (7)0.0001 (7)0.0087 (6)0.0080 (7)
C100.0451 (8)0.0432 (8)0.0467 (8)0.0004 (6)0.0003 (6)0.0066 (6)
C110.0415 (7)0.0513 (8)0.0524 (8)0.0058 (6)0.0091 (6)0.0107 (7)
C120.0482 (8)0.0472 (8)0.0401 (7)0.0026 (6)0.0097 (6)0.0071 (6)
C130.0763 (13)0.0940 (15)0.0508 (10)0.0076 (11)0.0108 (9)0.0053 (9)
Geometric parameters (Å, º) top
O1—C101.3591 (18)C5—C61.382 (2)
O1—C131.417 (2)C5—H5A0.9300
O1—C131.417 (2)C6—H6A0.9300
O2—N11.2186 (17)C7—C81.3826 (19)
O3—N11.2166 (17)C7—C121.3954 (19)
N1—C11.4604 (19)C8—C91.387 (2)
N2—N31.2485 (17)C8—H8A0.9300
N2—C41.4242 (18)C9—C101.386 (2)
N3—C71.4175 (18)C9—H9A0.9300
C1—C61.380 (2)C10—C111.387 (2)
C1—C21.381 (2)C11—C121.370 (2)
C2—C31.379 (2)C11—H11A0.9300
C2—H2A0.9300C12—H12A0.9300
C3—C41.393 (2)C13—H13B0.9600
C3—H3A0.9300C13—H13A0.9600
C4—C51.385 (2)C13—H13C0.9600
C10—O1—C13118.66 (14)C8—C7—C12119.10 (13)
O3—N1—O2122.30 (14)C8—C7—N3117.27 (12)
O3—N1—C1118.94 (13)C12—C7—N3123.63 (13)
O2—N1—C1118.75 (13)C7—C8—C9120.71 (13)
N3—N2—C4114.99 (12)C7—C8—H8A119.6
N2—N3—C7113.92 (12)C9—C8—H8A119.6
C6—C1—C2122.66 (14)C10—C9—C8119.56 (14)
C6—C1—N1118.48 (13)C10—C9—H9A120.2
C2—C1—N1118.85 (13)C8—C9—H9A120.2
C3—C2—C1118.60 (13)O1—C10—C9124.94 (14)
C3—C2—H2A120.7O1—C10—C11115.20 (13)
C1—C2—H2A120.7C9—C10—C11119.86 (14)
C2—C3—C4119.90 (14)C12—C11—C10120.36 (13)
C2—C3—H3A120.1C12—C11—H11A119.8
C4—C3—H3A120.1C10—C11—H11A119.8
C5—C4—C3120.28 (13)C11—C12—C7120.39 (13)
C5—C4—N2115.10 (12)C11—C12—H12A119.8
C3—C4—N2124.62 (13)C7—C12—H12A119.8
C6—C5—C4120.38 (13)O1—C13—H13B109.5
C6—C5—H5A119.8O1—C13—H13A109.5
C4—C5—H5A119.8H13B—C13—H13A109.5
C1—C6—C5118.18 (14)O1—C13—H13C109.5
C1—C6—H6A120.9H13B—C13—H13C109.5
C5—C6—H6A120.9H13A—C13—H13C109.5
C4—N2—N3—C7179.90 (10)C4—C5—C6—C10.4 (2)
O3—N1—C1—C61.1 (2)N2—N3—C7—C8178.29 (13)
O2—N1—C1—C6179.87 (15)N2—N3—C7—C122.0 (2)
O3—N1—C1—C2178.34 (15)C12—C7—C8—C90.9 (2)
O2—N1—C1—C20.7 (2)N3—C7—C8—C9179.31 (13)
C6—C1—C2—C30.5 (2)C7—C8—C9—C100.2 (2)
N1—C1—C2—C3178.91 (13)C13—O1—C10—C95.3 (3)
C1—C2—C3—C40.1 (2)C13—O1—C10—C11175.30 (15)
C2—C3—C4—C50.5 (2)C8—C9—C10—O1178.36 (14)
C2—C3—C4—N2179.60 (12)C8—C9—C10—C111.0 (2)
N3—N2—C4—C5178.17 (13)O1—C10—C11—C12178.63 (13)
N3—N2—C4—C31.7 (2)C9—C10—C11—C120.8 (2)
C3—C4—C5—C60.8 (2)C10—C11—C12—C70.3 (2)
N2—C4—C5—C6179.32 (13)C8—C7—C12—C111.1 (2)
C2—C1—C6—C50.3 (2)N3—C7—C12—C11179.11 (13)
N1—C1—C6—C5179.17 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8A···O2i0.932.573.412 (2)150
Symmetry code: (i) x+2, y+1, z+1.
(IIIc) (E)-[4-(6-bromohexyloxy)phenyl](4-cyanophenyl)diazene top
Crystal data top
C19H20BrN3OZ = 4
Mr = 386.29F(000) = 792
Triclinic, P1Dx = 1.495 Mg m3
Hall symbol: -P1Melting point: 376 K
a = 7.4279 (18) ÅMo Kα radiation, λ = 0.71073 Å
b = 12.009 (3) ÅCell parameters from 320 reflections
c = 19.552 (5) Åθ = 4–24°
α = 86.502 (5)°µ = 2.41 mm1
β = 80.511 (5)°T = 110 K
γ = 87.604 (5)°Plate, yellow
V = 1716.2 (7) Å30.50 × 0.35 × 0.15 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
9845 independent reflections
Radiation source: fine-focus sealed tube3353 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.083
ϕ and ω scansθmax = 30.1°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
h = 1010
Tmin = 0.403, Tmax = 0.697k = 1616
20166 measured reflectionsl = 2627
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094H-atom parameters constrained
S = 0.68 w = 1/[σ2(Fo2) + (0.02P)2]
where P = (Fo2 + 2Fc2)/3
9845 reflections(Δ/σ)max < 0.001
433 parametersΔρmax = 1.17 e Å3
0 restraintsΔρmin = 0.48 e Å3
Crystal data top
C19H20BrN3Oγ = 87.604 (5)°
Mr = 386.29V = 1716.2 (7) Å3
Triclinic, P1Z = 4
a = 7.4279 (18) ÅMo Kα radiation
b = 12.009 (3) ŵ = 2.41 mm1
c = 19.552 (5) ÅT = 110 K
α = 86.502 (5)°0.50 × 0.35 × 0.15 mm
β = 80.511 (5)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
9845 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
3353 reflections with I > 2σ(I)
Tmin = 0.403, Tmax = 0.697Rint = 0.083
20166 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.094H-atom parameters constrained
S = 0.68Δρmax = 1.17 e Å3
9845 reflectionsΔρmin = 0.48 e Å3
433 parameters
Special details top

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. All H atoms were placed in geometrically calculated positions and refined using a riding model.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br1A0.06933 (6)0.11321 (3)0.07294 (2)0.03930 (14)
O1A0.5947 (3)0.25090 (19)0.25472 (13)0.0287 (6)
N1A0.1448 (5)0.8239 (3)0.77340 (17)0.0388 (9)
N2A0.2520 (4)0.4768 (2)0.52729 (16)0.0232 (7)
N3A0.2536 (4)0.5135 (2)0.46568 (16)0.0225 (7)
C1A0.0073 (5)0.6891 (3)0.68080 (18)0.0222 (9)
C2A0.0242 (5)0.7274 (3)0.61082 (18)0.0233 (9)
H2AB0.01890.80040.59880.028*
C3A0.1027 (5)0.6595 (3)0.56028 (18)0.0232 (9)
H3AB0.11320.68520.51290.028*
C4A0.1677 (5)0.5529 (3)0.57728 (19)0.0220 (9)
C5A0.1530 (5)0.5149 (3)0.64745 (19)0.0257 (9)
H5AA0.19970.44280.65940.031*
C6A0.0707 (5)0.5827 (3)0.69868 (19)0.0258 (9)
H6AA0.05730.55670.74610.031*
C7A0.3367 (5)0.4415 (3)0.41379 (19)0.0211 (9)
C8A0.3483 (5)0.4841 (3)0.34616 (19)0.0234 (9)
H8AA0.29980.55690.33710.028*
C9A0.4303 (5)0.4219 (3)0.29110 (19)0.0250 (9)
H9AA0.43550.45130.24460.030*
C10A0.5043 (5)0.3164 (3)0.30449 (19)0.0243 (9)
C11A0.4877 (5)0.2714 (3)0.37308 (19)0.0259 (9)
H11A0.53310.19770.38220.031*
C12A0.4057 (5)0.3337 (3)0.42727 (19)0.0234 (9)
H12A0.39610.30350.47370.028*
C13A0.0769 (5)0.7636 (3)0.7332 (2)0.0269 (9)
C14A0.6199 (5)0.2953 (3)0.18423 (18)0.0273 (9)
H14A0.68420.36660.18020.033*
H14B0.50000.30980.16900.033*
C15A0.7316 (5)0.2108 (3)0.1394 (2)0.0347 (10)
H15A0.76190.24390.09150.042*
H15B0.84770.19410.15710.042*
C16A0.6353 (5)0.1029 (3)0.13753 (19)0.0295 (10)
H16A0.58490.07700.18560.035*
H16B0.72580.04550.11810.035*
C17A0.4806 (5)0.1130 (3)0.09452 (19)0.0286 (9)
H17A0.53290.12810.04500.034*
H17B0.39880.17720.10960.034*
C18A0.3691 (5)0.0075 (3)0.10173 (19)0.0282 (9)
H18A0.44830.05590.08340.034*
H18B0.32300.01070.15140.034*
C19A0.2112 (5)0.0234 (3)0.0628 (2)0.0322 (10)
H19A0.25700.04130.01310.039*
H19B0.13170.08670.08110.039*
Br1B0.90469 (5)0.58117 (3)0.90418 (2)0.03685 (14)
O1B0.4040 (3)0.27510 (19)0.72551 (12)0.0265 (6)
N1B1.1512 (4)0.3268 (3)0.22147 (16)0.0334 (9)
N2B0.7523 (4)0.0223 (2)0.46623 (16)0.0241 (7)
N3B0.7438 (4)0.0135 (2)0.52915 (16)0.0241 (7)
C1B0.9971 (4)0.1935 (3)0.31539 (19)0.0223 (9)
C2B0.9820 (5)0.2303 (3)0.38463 (18)0.0219 (9)
H2BB1.02720.30270.39690.026*
C3B0.9017 (5)0.1619 (3)0.43503 (18)0.0236 (9)
H3BB0.88890.18760.48250.028*
C4B0.8382 (5)0.0547 (3)0.41744 (19)0.0217 (9)
C5B0.8551 (5)0.0185 (3)0.34788 (19)0.0239 (9)
H5BA0.81030.05410.33580.029*
C6B0.9354 (5)0.0856 (3)0.29638 (19)0.0250 (9)
H6BA0.94900.05980.24900.030*
C7B0.6596 (5)0.0621 (3)0.57813 (19)0.0208 (9)
C8B0.6449 (5)0.0283 (3)0.64709 (19)0.0252 (9)
H8BA0.69270.04320.65990.030*
C9B0.5607 (5)0.0975 (3)0.69883 (19)0.0243 (9)
H9BA0.55040.07360.74650.029*
C10B0.4924 (5)0.2016 (3)0.67924 (19)0.0234 (9)
C11B0.5102 (5)0.2373 (3)0.60966 (18)0.0214 (9)
H11B0.46580.30950.59670.026*
C12B0.5915 (5)0.1686 (3)0.55995 (18)0.0223 (9)
H12B0.60220.19310.51240.027*
C13B1.0837 (5)0.2672 (3)0.2627 (2)0.0258 (9)
C14B0.3921 (5)0.2462 (3)0.79858 (18)0.0275 (9)
H14C0.51560.23080.81040.033*
H14D0.31930.17870.81150.033*
C15B0.3010 (5)0.3444 (3)0.83716 (18)0.0271 (9)
H15C0.36270.41340.81740.033*
H15D0.17230.35190.82980.033*
C16B0.3054 (5)0.3335 (3)0.91401 (19)0.0323 (10)
H16C0.24970.26220.93280.039*
H16D0.22800.39460.93630.039*
C17B0.4943 (5)0.3365 (3)0.93525 (19)0.0282 (9)
H17C0.48120.32590.98640.034*
H17D0.57100.27360.91490.034*
C18B0.5911 (5)0.4451 (3)0.91217 (19)0.0262 (9)
H18C0.60460.45670.86100.031*
H18D0.51690.50850.93310.031*
C19B0.7783 (5)0.4415 (3)0.93413 (19)0.0297 (9)
H19C0.85220.37790.91330.036*
H19D0.76470.43020.98530.036*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br1A0.0309 (3)0.0316 (3)0.0571 (3)0.0023 (2)0.0119 (2)0.0021 (2)
O1A0.0300 (16)0.0271 (15)0.0306 (16)0.0037 (12)0.0064 (13)0.0139 (13)
N1A0.049 (2)0.035 (2)0.028 (2)0.0147 (18)0.0047 (19)0.0083 (17)
N2A0.0214 (18)0.0230 (18)0.0249 (19)0.0009 (14)0.0026 (15)0.0024 (15)
N3A0.0187 (17)0.0226 (18)0.0261 (19)0.0002 (14)0.0022 (15)0.0059 (15)
C1A0.018 (2)0.020 (2)0.028 (2)0.0020 (16)0.0001 (18)0.0052 (18)
C2A0.019 (2)0.020 (2)0.032 (2)0.0025 (16)0.0052 (19)0.0041 (18)
C3A0.023 (2)0.023 (2)0.024 (2)0.0001 (17)0.0069 (19)0.0032 (18)
C4A0.015 (2)0.021 (2)0.028 (2)0.0012 (16)0.0012 (18)0.0064 (18)
C5A0.022 (2)0.018 (2)0.037 (2)0.0019 (16)0.006 (2)0.0047 (19)
C6A0.032 (2)0.026 (2)0.020 (2)0.0012 (18)0.0044 (19)0.0028 (18)
C7A0.015 (2)0.021 (2)0.028 (2)0.0022 (16)0.0037 (18)0.0066 (18)
C8A0.019 (2)0.018 (2)0.033 (2)0.0021 (16)0.0062 (19)0.0037 (18)
C9A0.029 (2)0.025 (2)0.020 (2)0.0013 (17)0.0024 (18)0.0002 (18)
C10A0.019 (2)0.027 (2)0.026 (2)0.0031 (17)0.0013 (18)0.0076 (19)
C11A0.022 (2)0.022 (2)0.036 (2)0.0057 (17)0.0095 (19)0.0075 (19)
C12A0.022 (2)0.024 (2)0.025 (2)0.0030 (17)0.0062 (18)0.0027 (18)
C13A0.024 (2)0.029 (2)0.029 (2)0.0039 (18)0.009 (2)0.0016 (19)
C14A0.032 (2)0.028 (2)0.022 (2)0.0082 (18)0.0005 (19)0.0077 (18)
C15A0.023 (2)0.040 (3)0.041 (3)0.0014 (19)0.001 (2)0.010 (2)
C16A0.034 (2)0.023 (2)0.033 (2)0.0057 (18)0.006 (2)0.0102 (18)
C17A0.026 (2)0.027 (2)0.033 (2)0.0046 (17)0.004 (2)0.0096 (18)
C18A0.023 (2)0.027 (2)0.036 (2)0.0025 (17)0.009 (2)0.0058 (19)
C19A0.026 (2)0.027 (2)0.044 (3)0.0019 (17)0.007 (2)0.0076 (19)
Br1B0.0338 (3)0.0364 (3)0.0393 (3)0.0085 (2)0.0007 (2)0.0060 (2)
O1B0.0245 (15)0.0263 (15)0.0284 (15)0.0026 (11)0.0007 (13)0.0122 (12)
N1B0.038 (2)0.034 (2)0.028 (2)0.0033 (16)0.0022 (18)0.0039 (17)
N2B0.0229 (18)0.0219 (18)0.0271 (19)0.0004 (14)0.0031 (16)0.0034 (15)
N3B0.0192 (18)0.0212 (18)0.032 (2)0.0016 (14)0.0021 (16)0.0072 (16)
C1B0.014 (2)0.022 (2)0.031 (2)0.0006 (16)0.0016 (18)0.0075 (18)
C2B0.020 (2)0.021 (2)0.025 (2)0.0035 (16)0.0050 (18)0.0029 (18)
C3B0.022 (2)0.027 (2)0.023 (2)0.0007 (17)0.0067 (19)0.0023 (19)
C4B0.016 (2)0.019 (2)0.030 (2)0.0004 (16)0.0020 (18)0.0043 (18)
C5B0.023 (2)0.019 (2)0.030 (2)0.0006 (17)0.0061 (19)0.0025 (18)
C6B0.026 (2)0.026 (2)0.023 (2)0.0019 (18)0.0052 (19)0.0016 (18)
C7B0.015 (2)0.023 (2)0.025 (2)0.0011 (16)0.0037 (17)0.0067 (18)
C8B0.023 (2)0.020 (2)0.034 (2)0.0008 (17)0.010 (2)0.0023 (19)
C9B0.023 (2)0.024 (2)0.026 (2)0.0033 (17)0.0027 (18)0.0014 (18)
C10B0.016 (2)0.023 (2)0.032 (2)0.0017 (16)0.0048 (18)0.0109 (19)
C11B0.018 (2)0.018 (2)0.028 (2)0.0025 (16)0.0044 (18)0.0017 (18)
C12B0.025 (2)0.018 (2)0.024 (2)0.0036 (16)0.0049 (19)0.0029 (17)
C13B0.026 (2)0.028 (2)0.025 (2)0.0019 (18)0.0077 (19)0.0035 (19)
C14B0.032 (2)0.027 (2)0.024 (2)0.0040 (18)0.0055 (19)0.0117 (18)
C15B0.024 (2)0.031 (2)0.026 (2)0.0007 (18)0.0037 (19)0.0058 (19)
C16B0.025 (2)0.033 (2)0.037 (3)0.0014 (18)0.002 (2)0.011 (2)
C17B0.030 (2)0.028 (2)0.028 (2)0.0043 (18)0.0039 (19)0.0120 (18)
C18B0.024 (2)0.024 (2)0.031 (2)0.0071 (16)0.0049 (19)0.0063 (18)
C19B0.032 (2)0.024 (2)0.034 (2)0.0040 (17)0.008 (2)0.0034 (18)
Geometric parameters (Å, º) top
Br1A—C19A1.970 (3)Br1B—C19B1.966 (3)
O1A—C10A1.360 (4)O1B—C10B1.372 (4)
O1A—C14A1.433 (4)O1B—C14B1.439 (4)
N1A—C13A1.143 (4)N1B—C13B1.150 (4)
N2A—N3A1.256 (4)N2B—N3B1.271 (4)
N2A—C4A1.430 (4)N2B—C4B1.425 (4)
N3A—C7A1.420 (4)N3B—C7B1.412 (4)
C1A—C6A1.388 (5)C1B—C2B1.386 (5)
C1A—C2A1.404 (5)C1B—C6B1.405 (5)
C1A—C13A1.447 (5)C1B—C13B1.450 (5)
C2A—C3A1.360 (4)C2B—C3B1.366 (4)
C2A—H2AB0.9500C2B—H2BB0.9500
C3A—C4A1.390 (5)C3B—C4B1.396 (5)
C3A—H3AB0.9500C3B—H3BB0.9500
C4A—C5A1.407 (5)C4B—C5B1.389 (5)
C5A—C6A1.377 (4)C5B—C6B1.371 (4)
C5A—H5AA0.9500C5B—H5BA0.9500
C6A—H6AA0.9500C6B—H6BA0.9500
C7A—C8A1.379 (5)C7B—C8B1.373 (5)
C7A—C12A1.398 (5)C7B—C12B1.403 (5)
C8A—C9A1.390 (4)C8B—C9B1.399 (5)
C8A—H8AA0.9500C8B—H8BA0.9500
C9A—C10A1.387 (5)C9B—C10B1.386 (5)
C9A—H9AA0.9500C9B—H9BA0.9500
C10A—C11A1.403 (5)C10B—C11B1.388 (5)
C11A—C12A1.379 (4)C11B—C12B1.361 (4)
C11A—H11A0.9500C11B—H11B0.9500
C12A—H12A0.9500C12B—H12B0.9500
C14A—C15A1.512 (5)C14B—C15B1.513 (4)
C14A—H14A0.9900C14B—H14C0.9900
C14A—H14B0.9900C14B—H14D0.9900
C15A—C16A1.511 (5)C15B—C16B1.506 (5)
C15A—H15A0.9900C15B—H15C0.9900
C15A—H15B0.9900C15B—H15D0.9900
C16A—C17A1.529 (5)C16B—C17B1.530 (5)
C16A—H16A0.9900C16B—H16C0.9900
C16A—H16B0.9900C16B—H16D0.9900
C17A—C18A1.530 (4)C17B—C18B1.523 (5)
C17A—H17A0.9900C17B—H17C0.9900
C17A—H17B0.9900C17B—H17D0.9900
C18A—C19A1.499 (5)C18B—C19B1.520 (5)
C18A—H18A0.9900C18B—H18C0.9900
C18A—H18B0.9900C18B—H18D0.9900
C19A—H19A0.9900C19B—H19C0.9900
C19A—H19B0.9900C19B—H19D0.9900
C10A—O1A—C14A117.7 (3)C10B—O1B—C14B118.5 (3)
N3A—N2A—C4A113.2 (3)N3B—N2B—C4B113.8 (3)
N2A—N3A—C7A115.6 (3)N2B—N3B—C7B114.4 (3)
C6A—C1A—C2A120.4 (3)C2B—C1B—C6B120.9 (3)
C6A—C1A—C13A121.4 (3)C2B—C1B—C13B118.7 (3)
C2A—C1A—C13A118.2 (3)C6B—C1B—C13B120.4 (3)
C3A—C2A—C1A119.7 (3)C3B—C2B—C1B119.6 (3)
C3A—C2A—H2AB120.2C3B—C2B—H2BB120.2
C1A—C2A—H2AB120.2C1B—C2B—H2BB120.2
C2A—C3A—C4A120.6 (3)C2B—C3B—C4B120.6 (3)
C2A—C3A—H3AB119.7C2B—C3B—H3BB119.7
C4A—C3A—H3AB119.7C4B—C3B—H3BB119.7
C3A—C4A—C5A119.8 (3)C5B—C4B—C3B119.3 (3)
C3A—C4A—N2A124.0 (3)C5B—C4B—N2B116.1 (3)
C5A—C4A—N2A116.2 (3)C3B—C4B—N2B124.6 (3)
C6A—C5A—C4A119.7 (3)C6B—C5B—C4B121.2 (4)
C6A—C5A—H5AA120.1C6B—C5B—H5BA119.4
C4A—C5A—H5AA120.1C4B—C5B—H5BA119.4
C5A—C6A—C1A119.7 (3)C5B—C6B—C1B118.4 (3)
C5A—C6A—H6AA120.1C5B—C6B—H6BA120.8
C1A—C6A—H6AA120.1C1B—C6B—H6BA120.8
C8A—C7A—C12A119.7 (3)C8B—C7B—C12B119.0 (3)
C8A—C7A—N3A115.8 (3)C8B—C7B—N3B117.4 (3)
C12A—C7A—N3A124.5 (3)C12B—C7B—N3B123.6 (3)
C7A—C8A—C9A120.8 (3)C7B—C8B—C9B120.9 (3)
C7A—C8A—H8AA119.6C7B—C8B—H8BA119.5
C9A—C8A—H8AA119.6C9B—C8B—H8BA119.5
C10A—C9A—C8A119.5 (3)C10B—C9B—C8B118.7 (3)
C10A—C9A—H9AA120.2C10B—C9B—H9BA120.6
C8A—C9A—H9AA120.2C8B—C9B—H9BA120.6
O1A—C10A—C9A124.2 (3)O1B—C10B—C9B123.6 (3)
O1A—C10A—C11A116.0 (3)O1B—C10B—C11B115.9 (3)
C9A—C10A—C11A119.8 (3)C9B—C10B—C11B120.6 (3)
C12A—C11A—C10A120.1 (3)C12B—C11B—C10B119.9 (3)
C12A—C11A—H11A119.9C12B—C11B—H11B120.0
C10A—C11A—H11A119.9C10B—C11B—H11B120.0
C11A—C12A—C7A119.9 (3)C11B—C12B—C7B120.8 (3)
C11A—C12A—H12A120.0C11B—C12B—H12B119.6
C7A—C12A—H12A120.0C7B—C12B—H12B119.6
N1A—C13A—C1A178.5 (4)N1B—C13B—C1B179.1 (4)
O1A—C14A—C15A108.1 (3)O1B—C14B—C15B107.4 (3)
O1A—C14A—H14A110.1O1B—C14B—H14C110.2
C15A—C14A—H14A110.1C15B—C14B—H14C110.2
O1A—C14A—H14B110.1O1B—C14B—H14D110.2
C15A—C14A—H14B110.1C15B—C14B—H14D110.2
H14A—C14A—H14B108.4H14C—C14B—H14D108.5
C16A—C15A—C14A113.5 (3)C16B—C15B—C14B113.3 (3)
C16A—C15A—H15A108.9C16B—C15B—H15C108.9
C14A—C15A—H15A108.9C14B—C15B—H15C108.9
C16A—C15A—H15B108.9C16B—C15B—H15D108.9
C14A—C15A—H15B108.9C14B—C15B—H15D108.9
H15A—C15A—H15B107.7H15C—C15B—H15D107.7
C15A—C16A—C17A113.6 (3)C15B—C16B—C17B115.9 (3)
C15A—C16A—H16A108.8C15B—C16B—H16C108.3
C17A—C16A—H16A108.8C17B—C16B—H16C108.3
C15A—C16A—H16B108.8C15B—C16B—H16D108.3
C17A—C16A—H16B108.8C17B—C16B—H16D108.3
H16A—C16A—H16B107.7H16C—C16B—H16D107.4
C16A—C17A—C18A112.4 (3)C18B—C17B—C16B113.4 (3)
C16A—C17A—H17A109.1C18B—C17B—H17C108.9
C18A—C17A—H17A109.1C16B—C17B—H17C108.9
C16A—C17A—H17B109.1C18B—C17B—H17D108.9
C18A—C17A—H17B109.1C16B—C17B—H17D108.9
H17A—C17A—H17B107.9H17C—C17B—H17D107.7
C19A—C18A—C17A110.8 (3)C19B—C18B—C17B110.4 (3)
C19A—C18A—H18A109.5C19B—C18B—H18C109.6
C17A—C18A—H18A109.5C17B—C18B—H18C109.6
C19A—C18A—H18B109.5C19B—C18B—H18D109.6
C17A—C18A—H18B109.5C17B—C18B—H18D109.6
H18A—C18A—H18B108.1H18C—C18B—H18D108.1
C18A—C19A—Br1A110.1 (2)C18B—C19B—Br1B110.7 (2)
C18A—C19A—H19A109.6C18B—C19B—H19C109.5
Br1A—C19A—H19A109.6Br1B—C19B—H19C109.5
C18A—C19A—H19B109.6C18B—C19B—H19D109.5
Br1A—C19A—H19B109.6Br1B—C19B—H19D109.5
H19A—C19A—H19B108.2H19C—C19B—H19D108.1
C4A—N2A—N3A—C7A179.7 (3)C4B—N2B—N3B—C7B179.8 (3)
C6A—C1A—C2A—C3A0.2 (5)C6B—C1B—C2B—C3B1.7 (5)
C13A—C1A—C2A—C3A180.0 (3)C13B—C1B—C2B—C3B179.7 (3)
C1A—C2A—C3A—C4A0.5 (5)C1B—C2B—C3B—C4B1.3 (5)
C2A—C3A—C4A—C5A0.3 (5)C2B—C3B—C4B—C5B0.9 (5)
C2A—C3A—C4A—N2A179.9 (3)C2B—C3B—C4B—N2B179.8 (3)
N3A—N2A—C4A—C3A3.4 (5)N3B—N2B—C4B—C5B178.4 (3)
N3A—N2A—C4A—C5A176.9 (3)N3B—N2B—C4B—C3B2.6 (5)
C3A—C4A—C5A—C6A1.4 (5)C3B—C4B—C5B—C6B1.0 (5)
N2A—C4A—C5A—C6A178.9 (3)N2B—C4B—C5B—C6B180.0 (3)
C4A—C5A—C6A—C1A1.7 (5)C4B—C5B—C6B—C1B1.4 (5)
C2A—C1A—C6A—C5A0.9 (5)C2B—C1B—C6B—C5B1.8 (5)
C13A—C1A—C6A—C5A178.9 (3)C13B—C1B—C6B—C5B179.7 (3)
N2A—N3A—C7A—C8A176.3 (3)N2B—N3B—C7B—C8B179.6 (3)
N2A—N3A—C7A—C12A3.3 (5)N2B—N3B—C7B—C12B0.5 (5)
C12A—C7A—C8A—C9A0.9 (5)C12B—C7B—C8B—C9B1.1 (5)
N3A—C7A—C8A—C9A178.7 (3)N3B—C7B—C8B—C9B178.9 (3)
C7A—C8A—C9A—C10A1.3 (5)C7B—C8B—C9B—C10B0.2 (5)
C14A—O1A—C10A—C9A2.1 (5)C14B—O1B—C10B—C9B4.4 (5)
C14A—O1A—C10A—C11A178.0 (3)C14B—O1B—C10B—C11B175.8 (3)
C8A—C9A—C10A—O1A176.9 (3)C8B—C9B—C10B—O1B178.6 (3)
C8A—C9A—C10A—C11A3.2 (5)C8B—C9B—C10B—C11B1.1 (5)
O1A—C10A—C11A—C12A177.0 (3)O1B—C10B—C11B—C12B178.2 (3)
C9A—C10A—C11A—C12A3.1 (5)C9B—C10B—C11B—C12B1.6 (5)
C10A—C11A—C12A—C7A0.9 (5)C10B—C11B—C12B—C7B0.7 (5)
C8A—C7A—C12A—C11A1.1 (5)C8B—C7B—C12B—C11B0.7 (5)
N3A—C7A—C12A—C11A178.5 (3)N3B—C7B—C12B—C11B179.4 (3)
C10A—O1A—C14A—C15A177.0 (3)C10B—O1B—C14B—C15B176.0 (3)
O1A—C14A—C15A—C16A65.0 (4)O1B—C14B—C15B—C16B171.0 (3)
C14A—C15A—C16A—C17A73.2 (4)C14B—C15B—C16B—C17B66.4 (4)
C15A—C16A—C17A—C18A172.0 (3)C15B—C16B—C17B—C18B60.7 (4)
C16A—C17A—C18A—C19A176.1 (3)C16B—C17B—C18B—C19B179.2 (3)
C17A—C18A—C19A—Br1A179.9 (2)C17B—C18B—C19B—Br1B179.8 (2)

Experimental details

(Ia)(IIIa)(IIIc)
Crystal data
Chemical formulaC12H9N3O3C13H11N3O3C19H20BrN3O
Mr243.22257.25386.29
Crystal system, space groupTriclinic, P1Triclinic, P1Triclinic, P1
Temperature (K)110298110
a, b, c (Å)7.290 (4), 10.648 (6), 28.353 (16)6.1530 (12), 7.5500 (15), 13.683 (3)7.4279 (18), 12.009 (3), 19.552 (5)
α, β, γ (°)93.685 (10), 94.922 (11), 100.811 (10)100.80 (3), 102.68 (3), 91.74 (3)86.502 (5), 80.511 (5), 87.604 (5)
V3)2147 (2)607.5 (2)1716.2 (7)
Z824
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.110.102.41
Crystal size (mm)0.50 × 0.40 × 0.150.45 × 0.35 × 0.300.50 × 0.35 × 0.15
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Enraf-Nonius CAD-4
diffractometer
Bruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1998)
Tmin, Tmax0.403, 0.697
No. of measured, independent and
observed [I > 2σ(I)] reflections
24813, 12208, 6579 2618, 2382, 1717 20166, 9845, 3353
Rint0.0310.0580.083
(sin θ/λ)max1)0.7060.6170.705
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.143, 0.89 0.046, 0.144, 1.04 0.047, 0.094, 0.68
No. of reflections1220823829845
No. of parameters649173433
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.47, 0.270.16, 0.191.17, 0.48

Computer programs: SMART (Bruker, 1998), CAD-4 Software (Enraf-Nonius, 1989), SMART, CAD-4 Software, SAINT (Bruker, 1998), SHELXTL-Plus (Sheldrick, 1994), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus, SHELXL97.

Selected geometric parameters (Å, º) for (Ia) top
N2A—N3A1.2601 (19)N2C—N3C1.2571 (19)
N2A—C4A1.421 (2)N2C—C4C1.423 (2)
N3A—C7A1.414 (2)N3C—C7C1.418 (2)
N2B—N3B1.263 (2)N2D—N3D1.2616 (19)
N2B—C4B1.424 (2)N2D—C4D1.424 (2)
N3B—C7B1.416 (2)N3D—C7D1.418 (2)
N3A—N2A—C4A113.87 (14)N3C—N2C—C4C114.31 (14)
N2A—N3A—C7A114.54 (14)N2C—N3C—C7C113.77 (14)
N3B—N2B—C4B114.43 (14)N3D—N2D—C4D113.83 (13)
N2B—N3B—C7B114.25 (14)N2D—N3D—C7D114.22 (14)
C4A—N2A—N3A—C7A179.04 (14)C4C—N2C—N3C—C7C178.84 (14)
N3A—N2A—C4A—C3A6.4 (2)N3C—N2C—C4C—C3C5.9 (2)
N2A—N3A—C7A—C8A179.77 (15)N2C—N3C—C7C—C8C176.74 (14)
C4B—N2B—N3B—C7B179.42 (13)C4D—N2D—N3D—C7D179.51 (13)
N3B—N2B—C4B—C3B1.0 (2)N3D—N2D—C4D—C3D2.4 (2)
N2B—N3B—C7B—C8B179.12 (15)N2D—N3D—C7D—C8D178.77 (15)
Hydrogen-bond geometry (Å, º) for (Ia) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···O2Bi0.842.022.753 (2)146
O1B—H1B···O2A0.842.122.811 (2)140
O1C—H1C···O3D0.842.062.903 (2)177
O1D—H1D···O3Ci0.842.072.904 (2)174
Symmetry code: (i) x1, y, z1.
Selected geometric parameters (Å, º) for (IIIa) top
N2—N31.2485 (17)N3—C71.4175 (18)
N2—C41.4242 (18)
N3—N2—C4114.99 (12)N2—N3—C7113.92 (12)
C4—N2—N3—C7179.90 (10)N2—N3—C7—C8178.29 (13)
N3—N2—C4—C31.7 (2)
Hydrogen-bond geometry (Å, º) for (IIIa) top
D—H···AD—HH···AD···AD—H···A
C8—H8A···O2i0.932.573.412 (2)150
Symmetry code: (i) x+2, y+1, z+1.
Selected geometric parameters (Å, º) for (IIIc) top
N2A—N3A1.256 (4)N2B—N3B1.271 (4)
N2A—C4A1.430 (4)N2B—C4B1.425 (4)
N3A—C7A1.420 (4)N3B—C7B1.412 (4)
N3A—N2A—C4A113.2 (3)N3B—N2B—C4B113.8 (3)
N2A—N3A—C7A115.6 (3)N2B—N3B—C7B114.4 (3)
C4A—N2A—N3A—C7A179.7 (3)C4B—N2B—N3B—C7B179.8 (3)
N3A—N2A—C4A—C3A3.4 (5)N3B—N2B—C4B—C3B2.6 (5)
N2A—N3A—C7A—C8A176.3 (3)N2B—N3B—C7B—C8B179.6 (3)
C14A—O1A—C10A—C9A2.1 (5)C14B—O1B—C10B—C9B4.4 (5)
C10A—O1A—C14A—C15A177.0 (3)C10B—O1B—C14B—C15B176.0 (3)
O1A—C14A—C15A—C16A65.0 (4)O1B—C14B—C15B—C16B171.0 (3)
C14A—C15A—C16A—C17A73.2 (4)C14B—C15B—C16B—C17B66.4 (4)
C15A—C16A—C17A—C18A172.0 (3)C15B—C16B—C17B—C18B60.7 (4)
C16A—C17A—C18A—C19A176.1 (3)C16B—C17B—C18B—C19B179.2 (3)
C17A—C18A—C19A—Br1A179.9 (2)C17B—C18B—C19B—Br1B179.8 (2)
 

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