2-{(E)-3-[(E)-4-Bromo­phenyl­imino­meth­yl]-4-hydroxy­phenyl­diazen­yl}benzoic acid toluene hemisolvate

The polyaromatic title compound, C₂₀H₁₄BrN₃O₃·0.5C₇H₈, has an extended and reasonably flat conformation. The hydr­oxy H atoms are involved in intra­molecular hydrogen bonds only, while C—H...O and C—H...Br inter­actions link the molecules into two-dimensional networks.

Key indicators

• Single-crystal X-ray study
• T = 160 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in solvent or counterion
• R factor = 0.037
• wR factor = 0.098
• Data-to-parameter ratio = 15.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       1.07
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.86
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      50.00 Perc.

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      1.069
            Tmax scaled      0.850 Tmin scaled      0.717

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

2-{(E)-3-[(E)-4-bromophenyliminomethyl]-4-hydroxyphenyldiazenyl}benzoic acid toluene hemisolvate

Crystal data

C20H14BrN3O3·0.5C7H8	Z = 2
Mr = 470.32	F(000) = 478
Triclinic, P1	Dx = 1.516 Mg m^−3
Hall symbol: -P 1	Melting point: 488 K
a = 8.2708 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.7547 (3) Å	Cell parameters from 15871 reflections
c = 12.3929 (3) Å	θ = 2.0–27.5°
α = 88.1844 (17)°	µ = 2.03 mm^−1
β = 85.3535 (16)°	T = 160 K
γ = 69.6152 (13)°	Tablet, orange
V = 1029.91 (5) Å^3	0.20 × 0.13 × 0.08 mm

Data collection

Nonius KappaCCD area-detector diffractometer	4718 independent reflections
Radiation source: Nonius FR590 sealed tube generator	3707 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.047
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 2.0°
φ and ω scans with κ offsets	h = −10→10
Absorption correction: multi-scan (Blessing, 1995)	k = −13→13
Tmin = 0.671, Tmax = 0.795	l = −16→16
23736 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: geom & difmap
wR(F^2) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.053P)^2 + 0.3064P] where P = (Fo^2 + 2Fc^2)/3
4718 reflections	(Δ/σ)max = 0.001
304 parameters	Δρmax = 0.39 e Å^−3
42 restraints	Δρmin = −0.54 e Å^−3

Special details

Experimental. Solvent used: toluene Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.516 (1) Frames collected: 361 Seconds exposure per frame: 24 Degrees rotation per frame: 2.0 Crystal-Detector distance (mm): 33.0

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br	0.44009 (4)	0.04891 (3)	0.766823 (18)	0.05472 (12)
O1	1.3161 (2)	0.42359 (16)	−0.20657 (14)	0.0430 (4)
H1	1.284 (4)	0.418 (3)	−0.151 (3)	0.065 (10)*
O2	1.4231 (2)	0.55577 (18)	−0.30282 (13)	0.0528 (4)
O3	0.9806 (2)	0.01190 (14)	0.16860 (13)	0.0379 (3)
H3	0.935 (4)	0.018 (3)	0.235 (3)	0.064 (9)*
N1	1.2353 (2)	0.46922 (16)	−0.00150 (13)	0.0301 (4)
N2	1.1797 (2)	0.44947 (16)	0.09301 (13)	0.0307 (4)
N3	0.8637 (2)	0.10556 (17)	0.35734 (14)	0.0321 (4)
C1	1.3672 (3)	0.5279 (2)	−0.21609 (18)	0.0377 (5)
C2	1.3519 (3)	0.6092 (2)	−0.11623 (17)	0.0323 (4)
C3	1.2868 (2)	0.58301 (19)	−0.01285 (16)	0.0299 (4)
C4	1.2786 (3)	0.6647 (2)	0.07402 (18)	0.0351 (5)
H4	1.2337	0.6470	0.1435	0.042*
C5	1.3351 (3)	0.7707 (2)	0.0599 (2)	0.0393 (5)
H5	1.3295	0.8259	0.1194	0.047*
C6	1.4002 (3)	0.7969 (2)	−0.0416 (2)	0.0409 (5)
H6	1.4399	0.8697	−0.0513	0.049*
C7	1.4076 (3)	0.7175 (2)	−0.12851 (19)	0.0385 (5)
H7	1.4512	0.7370	−0.1978	0.046*
C8	1.1351 (2)	0.33465 (19)	0.10655 (16)	0.0292 (4)
C9	1.0639 (3)	0.3183 (2)	0.20855 (16)	0.0302 (4)
H9	1.0518	0.3815	0.2633	0.036*
C10	1.0092 (2)	0.21081 (19)	0.23262 (15)	0.0289 (4)
C11	1.0312 (3)	0.11612 (19)	0.15073 (16)	0.0308 (4)
C12	1.1057 (3)	0.1325 (2)	0.04804 (17)	0.0336 (4)
H12	1.1212	0.0686	−0.0067	0.040*
C13	1.1561 (3)	0.2394 (2)	0.02591 (16)	0.0319 (4)
H13	1.2056	0.2496	−0.0442	0.038*
C14	0.9216 (3)	0.2012 (2)	0.33750 (16)	0.0320 (4)
H14	0.9071	0.2657	0.3915	0.038*
C15	0.7677 (3)	0.0982 (2)	0.45573 (16)	0.0326 (4)
C16	0.6688 (3)	0.2086 (2)	0.51642 (18)	0.0394 (5)
H16	0.6655	0.2944	0.4933	0.047*
C17	0.5748 (3)	0.1940 (2)	0.61074 (18)	0.0424 (5)
H17	0.5088	0.2691	0.6534	0.051*
C18	0.5788 (3)	0.0681 (2)	0.64176 (16)	0.0376 (5)
C19	0.6741 (3)	−0.0424 (2)	0.58207 (18)	0.0379 (5)
H19	0.6750	−0.1279	0.6045	0.046*
C20	0.7687 (3)	−0.0268 (2)	0.48883 (17)	0.0356 (5)
H20	0.8352	−0.1024	0.4468	0.043*
C21	−0.0859 (13)	0.3670 (8)	0.6524 (6)	0.090 (2)	0.50
H21A	−0.1945	0.4248	0.6888	0.135*	0.50
H21B	0.0030	0.3373	0.7046	0.135*	0.50
H21C	−0.1036	0.2898	0.6227	0.135*	0.50
C22	−0.0283 (7)	0.4422 (5)	0.5623 (3)	0.0560 (14)	0.50
C23	−0.1486 (5)	0.5402 (5)	0.5054 (4)	0.059 (2)	0.50
H23	−0.2687	0.5610	0.5240	0.070*	0.50
C24	−0.0929 (10)	0.6079 (4)	0.4215 (4)	0.076 (2)	0.50
H24	−0.1751	0.6749	0.3826	0.091*	0.50
C25	0.0829 (11)	0.5775 (6)	0.3943 (3)	0.080 (2)	0.50
H25	0.1210	0.6238	0.3369	0.096*	0.50
C26	0.2032 (7)	0.4795 (7)	0.4511 (4)	0.075 (2)	0.50
H26	0.3233	0.4587	0.4326	0.090*	0.50
C27	0.1475 (6)	0.4118 (5)	0.5351 (4)	0.0517 (18)	0.50
H27	0.2297	0.3448	0.5739	0.062*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br	0.0791 (2)	0.0700 (2)	0.03262 (14)	−0.05045 (16)	0.00867 (11)	−0.00286 (11)
O1	0.0588 (11)	0.0394 (9)	0.0303 (8)	−0.0175 (8)	0.0041 (8)	−0.0060 (7)
O2	0.0641 (11)	0.0561 (10)	0.0358 (9)	−0.0208 (9)	0.0101 (8)	0.0005 (8)
O3	0.0499 (9)	0.0324 (8)	0.0354 (8)	−0.0209 (7)	0.0077 (7)	−0.0081 (6)
N1	0.0308 (8)	0.0283 (8)	0.0313 (9)	−0.0103 (7)	−0.0026 (7)	−0.0007 (7)
N2	0.0323 (9)	0.0301 (8)	0.0305 (8)	−0.0115 (7)	−0.0015 (7)	−0.0027 (7)
N3	0.0363 (9)	0.0321 (9)	0.0290 (8)	−0.0135 (8)	−0.0012 (7)	−0.0011 (7)
C1	0.0363 (11)	0.0354 (11)	0.0364 (11)	−0.0067 (9)	−0.0008 (9)	0.0019 (9)
C2	0.0271 (10)	0.0309 (10)	0.0350 (11)	−0.0054 (8)	−0.0024 (8)	0.0013 (8)
C3	0.0272 (10)	0.0264 (9)	0.0349 (10)	−0.0077 (8)	−0.0023 (8)	−0.0005 (8)
C4	0.0367 (11)	0.0326 (11)	0.0359 (11)	−0.0120 (9)	−0.0025 (9)	−0.0028 (9)
C5	0.0396 (12)	0.0300 (11)	0.0492 (13)	−0.0113 (9)	−0.0089 (10)	−0.0049 (9)
C6	0.0352 (11)	0.0318 (11)	0.0580 (14)	−0.0140 (10)	−0.0073 (10)	0.0039 (10)
C7	0.0323 (11)	0.0364 (11)	0.0455 (12)	−0.0112 (9)	−0.0023 (9)	0.0083 (10)
C8	0.0301 (10)	0.0275 (10)	0.0304 (10)	−0.0099 (8)	−0.0030 (8)	−0.0037 (8)
C9	0.0328 (10)	0.0298 (10)	0.0281 (9)	−0.0105 (8)	−0.0025 (8)	−0.0063 (8)
C10	0.0299 (10)	0.0292 (10)	0.0274 (9)	−0.0098 (8)	−0.0018 (8)	−0.0045 (8)
C11	0.0305 (10)	0.0269 (10)	0.0347 (10)	−0.0097 (8)	−0.0004 (8)	−0.0036 (8)
C12	0.0382 (11)	0.0304 (10)	0.0319 (10)	−0.0118 (9)	0.0029 (8)	−0.0098 (8)
C13	0.0341 (10)	0.0305 (10)	0.0289 (10)	−0.0092 (9)	0.0024 (8)	−0.0042 (8)
C14	0.0366 (11)	0.0327 (10)	0.0272 (10)	−0.0121 (9)	−0.0038 (8)	−0.0033 (8)
C15	0.0369 (11)	0.0353 (11)	0.0280 (10)	−0.0154 (9)	−0.0030 (8)	0.0007 (8)
C16	0.0520 (13)	0.0334 (11)	0.0358 (11)	−0.0203 (10)	0.0043 (10)	−0.0003 (9)
C17	0.0549 (14)	0.0403 (12)	0.0353 (11)	−0.0224 (11)	0.0077 (10)	−0.0071 (9)
C18	0.0485 (12)	0.0490 (13)	0.0257 (10)	−0.0300 (11)	−0.0041 (9)	0.0028 (9)
C19	0.0460 (12)	0.0363 (11)	0.0374 (11)	−0.0210 (10)	−0.0085 (10)	0.0070 (9)
C20	0.0399 (11)	0.0326 (11)	0.0363 (11)	−0.0145 (9)	−0.0047 (9)	−0.0006 (9)
C21	0.133 (6)	0.082 (5)	0.071 (5)	−0.064 (4)	0.029 (4)	−0.026 (4)
C22	0.072 (4)	0.058 (3)	0.049 (3)	−0.038 (3)	0.015 (3)	−0.026 (3)
C23	0.060 (4)	0.047 (4)	0.069 (5)	−0.016 (3)	−0.010 (3)	−0.022 (4)
C24	0.110 (6)	0.057 (4)	0.070 (5)	−0.036 (4)	−0.029 (4)	−0.009 (4)
C25	0.145 (6)	0.073 (4)	0.048 (4)	−0.070 (4)	0.004 (4)	−0.022 (3)
C26	0.091 (5)	0.082 (4)	0.067 (4)	−0.055 (4)	0.032 (3)	−0.035 (3)
C27	0.057 (3)	0.056 (4)	0.047 (4)	−0.024 (3)	−0.006 (3)	−0.007 (3)

Geometric parameters (Å, º)

Br—C18	1.902 (2)	C12—C13	1.366 (3)
O1—C1	1.329 (3)	C12—H12	0.9500
O1—H1	0.73 (3)	C13—H13	0.9500
O2—C1	1.206 (3)	C14—H14	0.9500
O3—C11	1.333 (2)	C15—C16	1.387 (3)
O3—H3	0.87 (3)	C15—C20	1.391 (3)
N1—N2	1.262 (2)	C16—C17	1.386 (3)
N1—C3	1.429 (3)	C16—H16	0.9500
N2—C8	1.408 (3)	C17—C18	1.387 (3)
N3—C14	1.286 (3)	C17—H17	0.9500
N3—C15	1.416 (3)	C18—C19	1.374 (3)
C1—C2	1.509 (3)	C19—C20	1.381 (3)
C2—C7	1.394 (3)	C19—H19	0.9500
C2—C3	1.408 (3)	C20—H20	0.9500
C3—C4	1.393 (3)	C21—C22	1.501 (8)
C4—C5	1.377 (3)	C21—H21A	0.9800
C4—H4	0.9500	C21—H21B	0.9800
C5—C6	1.387 (3)	C21—H21C	0.9800
C5—H5	0.9500	C22—C23	1.3900
C6—C7	1.380 (3)	C22—C27	1.3900
C6—H6	0.9500	C23—C24	1.3900
C7—H7	0.9500	C23—H23	0.9500
C8—C9	1.383 (3)	C24—C25	1.3900
C8—C13	1.411 (3)	C24—H24	0.9500
C9—C10	1.396 (3)	C25—C26	1.3900
C9—H9	0.9500	C25—H25	0.9500
C10—C11	1.417 (3)	C26—C27	1.3900
C10—C14	1.455 (3)	C26—H26	0.9500
C11—C12	1.402 (3)	C27—H27	0.9500
C1—O1—H1	110 (3)	N3—C14—H14	119.9
C11—O3—H3	107 (2)	C10—C14—H14	119.9
N2—N1—C3	114.77 (16)	C16—C15—C20	119.55 (19)
N1—N2—C8	115.49 (16)	C16—C15—N3	123.41 (18)
C14—N3—C15	121.65 (18)	C20—C15—N3	116.98 (19)
O2—C1—O1	120.1 (2)	C17—C16—C15	120.2 (2)
O2—C1—C2	121.8 (2)	C17—C16—H16	119.9
O1—C1—C2	118.12 (18)	C15—C16—H16	119.9
C7—C2—C3	118.3 (2)	C16—C17—C18	118.9 (2)
C7—C2—C1	116.84 (19)	C16—C17—H17	120.6
C3—C2—C1	124.82 (18)	C18—C17—H17	120.6
C4—C3—C2	120.05 (18)	C19—C18—C17	121.8 (2)
C4—C3—N1	122.57 (18)	C19—C18—Br	119.18 (16)
C2—C3—N1	117.36 (18)	C17—C18—Br	118.92 (17)
C5—C4—C3	120.5 (2)	C18—C19—C20	118.79 (19)
C5—C4—H4	119.8	C18—C19—H19	120.6
C3—C4—H4	119.8	C20—C19—H19	120.6
C4—C5—C6	119.9 (2)	C19—C20—C15	120.7 (2)
C4—C5—H5	120.1	C19—C20—H20	119.6
C6—C5—H5	120.1	C15—C20—H20	119.6
C7—C6—C5	120.3 (2)	C22—C21—H21A	109.5
C7—C6—H6	119.9	C22—C21—H21B	109.5
C5—C6—H6	119.9	H21A—C21—H21B	109.5
C6—C7—C2	121.0 (2)	C22—C21—H21C	109.5
C6—C7—H7	119.5	H21A—C21—H21C	109.5
C2—C7—H7	119.5	H21B—C21—H21C	109.5
C9—C8—N2	115.10 (17)	C23—C22—C27	120.0
C9—C8—C13	119.31 (18)	C23—C22—C21	120.8 (6)
N2—C8—C13	125.58 (18)	C27—C22—C21	119.2 (6)
C8—C9—C10	121.28 (18)	C24—C23—C22	120.0
C8—C9—H9	119.4	C24—C23—H23	120.0
C10—C9—H9	119.4	C22—C23—H23	120.0
C9—C10—C11	118.66 (18)	C23—C24—C25	120.0
C9—C10—C14	120.44 (18)	C23—C24—H24	120.0
C11—C10—C14	120.78 (18)	C25—C24—H24	120.0
O3—C11—C12	118.90 (18)	C24—C25—C26	120.0
O3—C11—C10	121.44 (18)	C24—C25—H25	120.0
C12—C11—C10	119.66 (18)	C26—C25—H25	120.0
C13—C12—C11	120.66 (18)	C27—C26—C25	120.0
C13—C12—H12	119.7	C27—C26—H26	120.0
C11—C12—H12	119.7	C25—C26—H26	120.0
C12—C13—C8	120.41 (19)	C26—C27—C22	120.0
C12—C13—H13	119.8	C26—C27—H27	120.0
C8—C13—H13	119.8	C22—C27—H27	120.0
N3—C14—C10	120.22 (18)
C3—N1—N2—C8	−177.49 (15)	O3—C11—C12—C13	178.73 (18)
O2—C1—C2—C7	−0.8 (3)	C10—C11—C12—C13	−0.5 (3)
O1—C1—C2—C7	179.60 (19)	C11—C12—C13—C8	0.5 (3)
O2—C1—C2—C3	179.5 (2)	C9—C8—C13—C12	0.4 (3)
O1—C1—C2—C3	−0.1 (3)	N2—C8—C13—C12	−179.05 (19)
C7—C2—C3—C4	0.2 (3)	C15—N3—C14—C10	−175.66 (17)
C1—C2—C3—C4	179.93 (19)	C9—C10—C14—N3	176.46 (18)
C7—C2—C3—N1	−178.19 (17)	C11—C10—C14—N3	0.4 (3)
C1—C2—C3—N1	1.5 (3)	C14—N3—C15—C16	27.4 (3)
N2—N1—C3—C4	0.9 (3)	C14—N3—C15—C20	−155.52 (19)
N2—N1—C3—C2	179.22 (17)	C20—C15—C16—C17	1.5 (3)
C2—C3—C4—C5	−0.5 (3)	N3—C15—C16—C17	178.5 (2)
N1—C3—C4—C5	177.81 (18)	C15—C16—C17—C18	−1.3 (4)
C3—C4—C5—C6	0.2 (3)	C16—C17—C18—C19	0.5 (4)
C4—C5—C6—C7	0.4 (3)	C16—C17—C18—Br	−176.64 (17)
C5—C6—C7—C2	−0.7 (3)	C17—C18—C19—C20	0.2 (3)
C3—C2—C7—C6	0.4 (3)	Br—C18—C19—C20	177.29 (16)
C1—C2—C7—C6	−179.37 (19)	C18—C19—C20—C15	0.0 (3)
N1—N2—C8—C9	−175.97 (17)	C16—C15—C20—C19	−0.8 (3)
N1—N2—C8—C13	3.5 (3)	N3—C15—C20—C19	−177.98 (18)
N2—C8—C9—C10	178.24 (17)	C27—C22—C23—C24	0.0
C13—C8—C9—C10	−1.3 (3)	C21—C22—C23—C24	−179.3 (5)
C8—C9—C10—C11	1.2 (3)	C22—C23—C24—C25	0.0
C8—C9—C10—C14	−174.88 (18)	C23—C24—C25—C26	0.0
C9—C10—C11—O3	−179.55 (18)	C24—C25—C26—C27	0.0
C14—C10—C11—O3	−3.4 (3)	C25—C26—C27—C22	0.0
C9—C10—C11—C12	−0.4 (3)	C23—C22—C27—C26	0.0
C14—C10—C11—C12	175.75 (18)	C21—C22—C27—C26	179.3 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.73 (3)	1.92 (3)	2.593 (2)	154 (4)
O3—H3···N3	0.87 (3)	1.76 (3)	2.554 (2)	151 (3)
C6—H6···Br^i	0.95	2.92	3.630 (2)	133
C12—H12···O3^ii	0.95	2.53	3.388 (3)	151
C17—H17···O1^iii	0.95	2.49	3.419 (3)	166
C26—H26···O2^iv	0.95	2.50	3.374 (6)	153

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