A quasi-planar polyaromatic compound containing an azo and a Schiff base linkage

The title compound, 2-{(E)-3-[(E)-4-chloro­phenyl­imino]-4-hydroxy­phenyl­diazenyl}benzoic acid hemihydrate, C₂₀H₁₄ClN₃O₃·0.5H₂O, forms sheets, parallel to the (100) plane, that are linked by weak aromatic C—H...O interactions. These sheets are in turn linked by strong hydrogen bonds to interstitial water mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.076
• wR factor = 0.216
• Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT731_ALERT_1_B Bond    Calc     0.85(7), Rep   0.852(10) ......       7.00 su-Rat
              O1W  -H1W1    1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.85(7), Rep   0.852(10) ......       7.00 su-Rat
              O1W  -H1#     1.555   1.555

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
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT199_ALERT_1_C Check the Reported cell_measurement_temperature         293
PLAT200_ALERT_1_C Check the Reported cell_ambient_temperature ....        293
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          7
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          1
PLAT736_ALERT_1_C H...A   Calc     2.05(7), Rep     2.05(3) ......       2.33 su-Rat
              H1#  -O1      1.555   1.555
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              H2 O

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

   8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   3 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL97 (Sheldrick, 1997); program(s) used to solve structure: SHELXTL97; program(s) used to refine structure: SHELXTL97; molecular graphics: SHELXTL97; software used to prepare material for publication: SHELXTL97.

2-{(E)-3-[(E)-4-chlorophenylimino]-4-hydroxyphenyldiazenyl}benzoic acid hemihydrate

Crystal data

C20H14ClN3O3·0.5H2O	Dx = 1.422 Mg m^−3
Mr = 388.80	Melting point = 498–499 K
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
a = 13.2451 (19) Å	Cell parameters from 49 reflections
b = 21.668 (4) Å	θ = 5.4–27.8°
c = 12.664 (2) Å	µ = 2.12 mm^−1
β = 91.69 (2)°	T = 293 K
V = 3632.8 (10) Å^3	Prism, red
Z = 8	0.50 × 0.35 × 0.28 mm
F(000) = 1608

Data collection

Bruker P4 diffractometer	1707 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.037
Graphite monochromator	θmax = 69.1°, θmin = 3.9°
2θ/ω scans	h = 0→16
Absorption correction: part of the refinement model (ΔF) (SHELX97; Sheldrick, 1998)	k = 0→26
Tmin = 0.415, Tmax = 0.552	l = −15→15
3534 measured reflections	3 standard reflections every 97 reflections
3382 independent reflections	intensity decay: 0.3%

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.216	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0577P)^2 + 7.4356P] where P = (Fo^2 + 2Fc^2)/3
3382 reflections	(Δ/σ)max < 0.001
254 parameters	Δρmax = 0.20 e Å^−3
1 restraint	Δρmin = −0.25 e Å^−3

Special details

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

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

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

	x	y	z	Uiso*/Ueq
Cl	0.40742 (17)	0.07579 (9)	1.12841 (12)	0.1232 (8)
O1	0.4080 (4)	0.37481 (19)	−0.0762 (3)	0.1179 (17)
O2	0.3795 (3)	0.30536 (16)	0.0423 (3)	0.0853 (11)
H2O	0.3767	0.3029	0.1067	0.102*
O3	0.3182 (4)	0.09637 (16)	0.4948 (3)	0.0943 (13)
H3O	0.3265	0.0968	0.5592	0.113*
O1W	0.5000	0.3132 (3)	−0.2500	0.117 (2)
H1W1	0.480 (7)	0.337 (3)	−0.202 (5)	0.176*
N1	0.3712 (3)	0.33810 (18)	0.2377 (3)	0.0639 (10)
N2	0.3807 (3)	0.33039 (18)	0.3368 (3)	0.0671 (10)
N3	0.3639 (3)	0.13951 (18)	0.6768 (3)	0.0648 (10)
C1	0.3930 (4)	0.3631 (2)	0.0152 (4)	0.0778 (15)
C2	0.3843 (4)	0.4122 (2)	0.0964 (4)	0.0653 (12)
C3	0.3863 (4)	0.4728 (2)	0.0619 (4)	0.0793 (15)
H3A	0.3932	0.4808	−0.0096	0.095*
C4	0.3782 (4)	0.5214 (2)	0.1313 (4)	0.0815 (16)
H4A	0.3793	0.5617	0.1064	0.098*
C5	0.3685 (4)	0.5101 (2)	0.2382 (4)	0.0796 (15)
H5A	0.3629	0.5428	0.2851	0.096*
C6	0.3671 (4)	0.4502 (2)	0.2751 (4)	0.0689 (13)
H6A	0.3603	0.4426	0.3468	0.083*
C7	0.3758 (3)	0.4010 (2)	0.2049 (4)	0.0621 (12)
C8	0.3666 (4)	0.2690 (2)	0.3703 (4)	0.0647 (12)
C9	0.3358 (4)	0.2192 (2)	0.3061 (4)	0.0796 (15)
H9A	0.3265	0.2249	0.2337	0.096*
C10	0.3195 (5)	0.1626 (3)	0.3493 (4)	0.0884 (17)
H10A	0.2982	0.1301	0.3060	0.106*
C11	0.3340 (4)	0.1527 (2)	0.4566 (4)	0.0736 (14)
C12	0.3668 (3)	0.2014 (2)	0.5231 (4)	0.0627 (12)
C13	0.3816 (3)	0.2593 (2)	0.4780 (4)	0.0635 (12)
H13A	0.4020	0.2921	0.5210	0.076*
C14	0.3806 (4)	0.1925 (2)	0.6351 (4)	0.0687 (13)
H14A	0.4018	0.2253	0.6777	0.082*
C15	0.3749 (3)	0.1282 (2)	0.7860 (4)	0.0628 (12)
C16	0.3841 (4)	0.0665 (2)	0.8162 (4)	0.0704 (13)
H16A	0.3838	0.0360	0.7646	0.084*
C17	0.3936 (4)	0.0501 (2)	0.9204 (4)	0.0758 (14)
H17A	0.3999	0.0088	0.9395	0.091*
C18	0.3939 (4)	0.0952 (2)	0.9963 (4)	0.0769 (14)
C19	0.3828 (4)	0.1565 (2)	0.9695 (4)	0.0742 (14)
H19A	0.3817	0.1867	1.0218	0.089*
C20	0.3733 (4)	0.1726 (2)	0.8645 (4)	0.0688 (13)
H20A	0.3658	0.2140	0.8460	0.083*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl	0.190 (2)	0.1074 (13)	0.0734 (10)	0.0265 (13)	0.0230 (11)	0.0125 (9)
O1	0.192 (5)	0.091 (3)	0.073 (3)	0.024 (3)	0.040 (3)	0.009 (2)
O2	0.113 (3)	0.066 (2)	0.078 (2)	0.005 (2)	0.022 (2)	−0.0022 (18)
O3	0.140 (4)	0.064 (2)	0.079 (2)	−0.014 (2)	0.006 (3)	0.0007 (19)
O1W	0.169 (7)	0.078 (4)	0.107 (5)	0.000	0.033 (5)	0.000
N1	0.059 (2)	0.064 (2)	0.070 (3)	0.0050 (19)	0.0088 (19)	0.009 (2)
N2	0.067 (3)	0.061 (2)	0.073 (3)	−0.001 (2)	0.009 (2)	0.006 (2)
N3	0.065 (3)	0.062 (2)	0.068 (2)	−0.0007 (19)	0.0080 (19)	0.0076 (19)
C1	0.093 (4)	0.066 (3)	0.075 (3)	0.008 (3)	0.013 (3)	0.002 (3)
C2	0.068 (3)	0.061 (3)	0.067 (3)	0.004 (2)	0.008 (2)	0.009 (2)
C3	0.094 (4)	0.065 (3)	0.079 (4)	−0.001 (3)	0.008 (3)	0.013 (3)
C4	0.100 (4)	0.055 (3)	0.089 (4)	−0.001 (3)	0.003 (3)	0.007 (3)
C5	0.090 (4)	0.057 (3)	0.091 (4)	−0.005 (3)	0.000 (3)	−0.008 (3)
C6	0.077 (3)	0.066 (3)	0.064 (3)	−0.002 (3)	0.006 (2)	−0.002 (2)
C7	0.054 (3)	0.061 (3)	0.072 (3)	0.000 (2)	0.007 (2)	0.007 (2)
C8	0.065 (3)	0.063 (3)	0.067 (3)	−0.002 (2)	0.013 (2)	0.006 (2)
C9	0.105 (4)	0.070 (3)	0.066 (3)	−0.009 (3)	0.020 (3)	−0.002 (3)
C10	0.121 (5)	0.070 (3)	0.074 (3)	−0.016 (3)	0.011 (3)	−0.005 (3)
C11	0.089 (4)	0.057 (3)	0.076 (3)	−0.001 (3)	0.013 (3)	0.003 (2)
C12	0.058 (3)	0.062 (3)	0.069 (3)	−0.003 (2)	0.013 (2)	−0.001 (2)
C13	0.055 (3)	0.063 (3)	0.072 (3)	−0.005 (2)	0.006 (2)	0.003 (2)
C14	0.063 (3)	0.073 (3)	0.070 (3)	−0.002 (3)	0.007 (2)	0.003 (2)
C15	0.054 (3)	0.064 (3)	0.070 (3)	−0.007 (2)	0.004 (2)	0.009 (2)
C16	0.079 (3)	0.058 (3)	0.074 (3)	−0.004 (2)	0.012 (3)	−0.001 (2)
C17	0.094 (4)	0.059 (3)	0.075 (3)	0.006 (3)	0.010 (3)	0.008 (2)
C18	0.090 (4)	0.071 (3)	0.070 (3)	0.005 (3)	0.011 (3)	−0.002 (3)
C19	0.085 (4)	0.064 (3)	0.074 (3)	−0.005 (3)	0.012 (3)	−0.005 (3)
C20	0.071 (3)	0.054 (3)	0.081 (3)	−0.002 (2)	0.007 (3)	0.002 (2)

Geometric parameters (Å, º)

Cl—C18	1.730 (5)	C6—H6A	0.9300
O1—C1	1.207 (6)	C8—C13	1.389 (6)
O2—C1	1.311 (6)	C8—C9	1.403 (7)
O2—H2O	0.8200	C9—C10	1.364 (7)
O3—C11	1.333 (6)	C9—H9A	0.9300
O3—H3O	0.8200	C10—C11	1.383 (7)
O1W—H1W1	0.852 (10)	C10—H10A	0.9300
N1—N2	1.269 (5)	C11—C12	1.409 (7)
N1—C7	1.426 (6)	C12—C13	1.396 (6)
N2—C8	1.411 (6)	C12—C14	1.438 (6)
N3—C14	1.287 (6)	C13—H13A	0.9300
N3—C15	1.407 (6)	C14—H14A	0.9300
C1—C2	1.487 (7)	C15—C20	1.385 (6)
C2—C3	1.383 (6)	C15—C16	1.395 (6)
C2—C7	1.404 (6)	C16—C17	1.369 (6)
C3—C4	1.378 (7)	C16—H16A	0.9300
C3—H3A	0.9300	C17—C18	1.371 (7)
C4—C5	1.385 (7)	C17—H17A	0.9300
C4—H4A	0.9300	C18—C19	1.378 (7)
C5—C6	1.379 (6)	C19—C20	1.378 (6)
C5—H5A	0.9300	C19—H19A	0.9300
C6—C7	1.395 (6)	C20—H20A	0.9300
C1—O2—H2O	109.5	C9—C10—H10A	119.6
C11—O3—H3O	109.5	C11—C10—H10A	119.6
N2—N1—C7	114.2 (4)	O3—C11—C10	118.6 (5)
N1—N2—C8	114.3 (4)	O3—C11—C12	121.1 (5)
C14—N3—C15	123.0 (4)	C10—C11—C12	120.2 (5)
O1—C1—O2	118.6 (5)	C13—C12—C11	118.2 (5)
O1—C1—C2	122.1 (5)	C13—C12—C14	120.5 (5)
O2—C1—C2	119.2 (5)	C11—C12—C14	121.2 (5)
C3—C2—C7	118.4 (5)	C8—C13—C12	121.3 (5)
C3—C2—C1	117.3 (5)	C8—C13—H13A	119.4
C7—C2—C1	124.3 (4)	C12—C13—H13A	119.4
C4—C3—C2	121.4 (5)	N3—C14—C12	120.3 (5)
C4—C3—H3A	119.3	N3—C14—H14A	119.8
C2—C3—H3A	119.3	C12—C14—H14A	119.8
C3—C4—C5	120.0 (5)	C20—C15—C16	118.2 (5)
C3—C4—H4A	120.0	C20—C15—N3	125.5 (4)
C5—C4—H4A	120.0	C16—C15—N3	116.3 (4)
C6—C5—C4	120.0 (5)	C17—C16—C15	121.3 (5)
C6—C5—H5A	120.0	C17—C16—H16A	119.4
C4—C5—H5A	120.0	C15—C16—H16A	119.4
C5—C6—C7	120.1 (5)	C16—C17—C18	119.2 (5)
C5—C6—H6A	120.0	C16—C17—H17A	120.4
C7—C6—H6A	120.0	C18—C17—H17A	120.4
C6—C7—C2	120.1 (4)	C17—C18—C19	121.2 (5)
C6—C7—N1	122.6 (4)	C17—C18—Cl	120.2 (4)
C2—C7—N1	117.1 (4)	C19—C18—Cl	118.7 (4)
C13—C8—C9	119.0 (5)	C20—C19—C18	119.2 (5)
C13—C8—N2	114.9 (4)	C20—C19—H19A	120.4
C9—C8—N2	126.1 (4)	C18—C19—H19A	120.4
C10—C9—C8	120.4 (5)	C19—C20—C15	120.9 (5)
C10—C9—H9A	119.8	C19—C20—H20A	119.5
C8—C9—H9A	119.8	C15—C20—H20A	119.5
C9—C10—C11	120.9 (5)
C7—N1—N2—C8	174.3 (4)	C9—C10—C11—C12	−0.4 (9)
O1—C1—C2—C3	4.9 (9)	O3—C11—C12—C13	−179.8 (5)
O2—C1—C2—C3	−172.0 (5)	C10—C11—C12—C13	1.4 (8)
O1—C1—C2—C7	−174.1 (6)	O3—C11—C12—C14	−2.3 (8)
O2—C1—C2—C7	9.0 (8)	C10—C11—C12—C14	178.8 (5)
C7—C2—C3—C4	−1.3 (8)	C9—C8—C13—C12	0.0 (7)
C1—C2—C3—C4	179.7 (5)	N2—C8—C13—C12	177.7 (4)
C2—C3—C4—C5	0.4 (9)	C11—C12—C13—C8	−1.2 (7)
C3—C4—C5—C6	0.1 (9)	C14—C12—C13—C8	−178.6 (4)
C4—C5—C6—C7	0.2 (8)	C15—N3—C14—C12	−179.2 (4)
C5—C6—C7—C2	−1.1 (8)	C13—C12—C14—N3	177.9 (4)
C5—C6—C7—N1	−177.6 (5)	C11—C12—C14—N3	0.5 (7)
C3—C2—C7—C6	1.6 (7)	C14—N3—C15—C20	21.2 (7)
C1—C2—C7—C6	−179.4 (5)	C14—N3—C15—C16	−161.4 (5)
C3—C2—C7—N1	178.3 (5)	C20—C15—C16—C17	−1.4 (8)
C1—C2—C7—N1	−2.7 (7)	N3—C15—C16—C17	−179.0 (4)
N2—N1—C7—C6	−14.7 (6)	C15—C16—C17—C18	0.1 (8)
N2—N1—C7—C2	168.7 (4)	C16—C17—C18—C19	1.3 (9)
N1—N2—C8—C13	177.0 (4)	C16—C17—C18—Cl	−179.2 (4)
N1—N2—C8—C9	−5.5 (7)	C17—C18—C19—C20	−1.3 (9)
C13—C8—C9—C10	1.0 (8)	Cl—C18—C19—C20	179.2 (4)
N2—C8—C9—C10	−176.4 (5)	C18—C19—C20—C15	0.0 (8)
C8—C9—C10—C11	−0.9 (9)	C16—C15—C20—C19	1.4 (7)
C9—C10—C11—O3	−179.2 (5)	N3—C15—C20—C19	178.7 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···N1	0.82	1.83	2.580 (5)	152
O3—H3O···N3	0.82	1.81	2.544 (5)	148
O1W—H1W1···O1	0.85 (1)	2.05 (3)	2.875 (5)	164 (8)
C5—H5A···O1^i	0.93	2.56	3.457 (7)	161
C14—H14A···O1W^ii	0.93	2.47	3.364 (7)	162
C19—H19A···O2^ii	0.93	2.59	3.355 (6)	140

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