4-[(3-Chloro­phenyl)­diazenyl]-6-methoxy-2-{[tris­(hydroxy­methyl)­methyl]­aminomethyl­ene}cyclo­hexa-3,5-dien-1(2H)-one

The title compound, C₁₈H₂₀ClN₃O₅, adopts the keto–amine tautomeric form and displays an intramolecular N—H...O hydrogen bond. The configuration around the azo N=N double bond is trans and the dihedral angle between the two aromatic rings is 10.0 (1)°. Intermolecular O—H...O hydrogen bonds form a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.043
• wR factor = 0.116
• Data-to-parameter ratio = 11.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of .      48.00 A   3  

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

   0 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
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1998).

4-[(3-Chlorophenyl)diazenyl]-6-methoxy- 2-{[tris(hydroxymethyl)methyl]aminomethylene}cyclohexa-3,5-dien-1(2H)-one

Crystal data

C18H20ClN3O5	F(000) = 824
Mr = 393.82	Dx = 1.363 Mg m^−3
Monoclinic, P21/c	Melting point = 496–498 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.6950 (8) Å	Cell parameters from 12137 reflections
b = 12.3204 (10) Å	θ = 1.9–28.3°
c = 14.8486 (12) Å	µ = 0.23 mm^−1
β = 101.144 (6)°	T = 291 K
V = 1919.7 (3) Å^3	Plate, orange
Z = 4	0.50 × 0.50 × 0.16 mm

Data collection

Stoe IPDS 2 diffractometer	3776 independent reflections
Radiation source: fine-focus sealed tube	2571 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.075
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 1.9°
ω scans	h = −13→13
Absorption correction: integration (X-RED; Stoe & Cie, 2002)	k = −15→15
Tmin = 0.850, Tmax = 0.963	l = −18→18
13394 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)] = 0.043	Hydrogen site location: difference Fourier map
wR(F^2) = 0.116	All H-atom parameters refined
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0703P)^2] where P = (Fo^2 + 2Fc^2)/3
3776 reflections	(Δ/σ)max = 0.001
324 parameters	Δρmax = 0.64 e Å^−3
0 restraints	Δρmin = −0.49 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
C1	0.13433 (18)	0.72957 (16)	0.65642 (13)	0.0410 (4)
C2	0.16422 (19)	0.83632 (17)	0.64022 (14)	0.0440 (5)
C3	0.1306 (2)	0.91626 (16)	0.69517 (14)	0.0464 (5)
C4	0.0684 (2)	0.89373 (19)	0.76638 (16)	0.0545 (6)
C5	0.0367 (2)	0.7879 (2)	0.78045 (17)	0.0606 (6)
C6	0.0688 (2)	0.70593 (19)	0.72557 (16)	0.0532 (5)
C7	0.2758 (2)	0.58065 (16)	0.49854 (13)	0.0418 (4)
C8	0.3566 (2)	0.60867 (16)	0.44155 (13)	0.0433 (5)
C9	0.40194 (18)	0.53031 (15)	0.38629 (12)	0.0389 (4)
C10	0.36574 (19)	0.41905 (15)	0.39086 (12)	0.0381 (4)
C11	0.27705 (19)	0.39445 (15)	0.45030 (12)	0.0401 (4)
C12	0.2347 (2)	0.47114 (16)	0.50230 (13)	0.0418 (4)
C13	0.47883 (19)	0.56439 (16)	0.32441 (12)	0.0397 (4)
C14	0.59204 (17)	0.52936 (15)	0.19671 (12)	0.0364 (4)
C15	0.6282 (2)	0.42291 (18)	0.15547 (15)	0.0480 (5)
C16	0.5021 (2)	0.59626 (17)	0.12506 (13)	0.0417 (4)
C17	0.7151 (2)	0.58994 (18)	0.23637 (15)	0.0449 (5)
C18	0.1609 (3)	0.2513 (2)	0.50459 (17)	0.0569 (6)
Cl1	0.17021 (7)	1.05007 (5)	0.67634 (5)	0.0717 (2)
N1	0.16723 (16)	0.63944 (13)	0.60500 (11)	0.0445 (4)
N2	0.23912 (17)	0.66560 (13)	0.55063 (11)	0.0456 (4)
N3	0.52193 (16)	0.49935 (13)	0.26894 (10)	0.0387 (4)
O1	0.40725 (14)	0.34422 (10)	0.34544 (9)	0.0458 (3)
O2	0.52391 (17)	0.35069 (12)	0.13317 (11)	0.0555 (4)
O3	0.56250 (17)	0.63071 (14)	0.05367 (10)	0.0556 (4)
O4	0.69757 (15)	0.68903 (12)	0.27946 (10)	0.0516 (4)
O5	0.24392 (15)	0.28706 (11)	0.44664 (10)	0.0510 (4)
H1	0.498 (3)	0.432 (2)	0.2777 (18)	0.081 (9)*
H2	0.207 (2)	0.8569 (19)	0.5927 (16)	0.057 (6)*
H4	0.049 (2)	0.949 (2)	0.8062 (17)	0.069 (7)*
H5	−0.004 (3)	0.775 (2)	0.835 (2)	0.087 (8)*
H6	0.050 (2)	0.632 (2)	0.7372 (16)	0.063 (7)*
H8	0.381 (2)	0.680 (2)	0.4389 (15)	0.055 (6)*
H12	0.176 (2)	0.4506 (18)	0.5458 (14)	0.051 (6)*
H13	0.5001 (19)	0.6411 (18)	0.3206 (13)	0.044 (5)*
H15A	0.690 (2)	0.386 (2)	0.1993 (17)	0.067 (7)*
H15B	0.663 (2)	0.4365 (19)	0.1003 (16)	0.062 (7)*
H16A	0.427 (2)	0.5507 (18)	0.0979 (14)	0.049 (6)*
H16B	0.4684 (19)	0.6597 (18)	0.1522 (13)	0.044 (5)*
H17A	0.756 (2)	0.5984 (17)	0.1854 (14)	0.045 (5)*
H17B	0.770 (2)	0.5435 (17)	0.2845 (14)	0.047 (5)*
H18A	0.200 (2)	0.2584 (19)	0.5703 (17)	0.060 (6)*
H18B	0.144 (3)	0.178 (3)	0.4868 (18)	0.080 (8)*
H18C	0.077 (3)	0.296 (3)	0.4899 (19)	0.088 (9)*
H22	0.492 (3)	0.361 (2)	0.0746 (19)	0.074 (8)*
H33	0.598 (3)	0.686 (3)	0.069 (2)	0.088 (10)*
H44	0.673 (3)	0.737 (2)	0.232 (2)	0.081 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0415 (10)	0.0362 (10)	0.0478 (10)	0.0016 (8)	0.0147 (8)	−0.0018 (8)
C2	0.0476 (11)	0.0401 (11)	0.0480 (11)	0.0024 (9)	0.0181 (9)	−0.0004 (9)
C3	0.0485 (12)	0.0339 (10)	0.0583 (11)	0.0029 (9)	0.0141 (10)	−0.0022 (9)
C4	0.0616 (14)	0.0469 (13)	0.0610 (13)	0.0081 (11)	0.0264 (11)	−0.0085 (10)
C5	0.0713 (15)	0.0534 (14)	0.0692 (14)	0.0048 (12)	0.0435 (13)	0.0012 (11)
C6	0.0584 (13)	0.0397 (12)	0.0694 (14)	0.0010 (10)	0.0321 (11)	0.0019 (10)
C7	0.0519 (11)	0.0321 (10)	0.0442 (9)	0.0012 (9)	0.0162 (9)	−0.0029 (8)
C8	0.0595 (13)	0.0289 (10)	0.0451 (10)	−0.0033 (9)	0.0193 (9)	−0.0027 (8)
C9	0.0482 (11)	0.0306 (9)	0.0404 (9)	−0.0016 (8)	0.0149 (8)	−0.0012 (7)
C10	0.0485 (11)	0.0297 (9)	0.0375 (9)	0.0011 (8)	0.0114 (8)	−0.0008 (7)
C11	0.0501 (11)	0.0292 (9)	0.0422 (9)	−0.0033 (8)	0.0121 (9)	0.0021 (8)
C12	0.0510 (11)	0.0360 (10)	0.0419 (9)	−0.0018 (9)	0.0174 (9)	0.0005 (8)
C13	0.0504 (11)	0.0307 (10)	0.0401 (9)	−0.0029 (9)	0.0136 (8)	−0.0015 (8)
C14	0.0423 (10)	0.0330 (9)	0.0364 (9)	0.0005 (8)	0.0139 (8)	0.0019 (7)
C15	0.0572 (13)	0.0409 (12)	0.0492 (11)	0.0080 (10)	0.0183 (11)	−0.0006 (9)
C16	0.0487 (12)	0.0342 (10)	0.0422 (10)	−0.0013 (9)	0.0089 (9)	0.0023 (8)
C17	0.0443 (11)	0.0474 (12)	0.0439 (10)	−0.0044 (9)	0.0109 (9)	0.0035 (9)
C18	0.0727 (16)	0.0478 (14)	0.0546 (13)	−0.0202 (12)	0.0236 (12)	0.0003 (11)
Cl1	0.0942 (5)	0.0360 (3)	0.0923 (5)	−0.0010 (3)	0.0366 (4)	−0.0023 (3)
N1	0.0514 (10)	0.0371 (9)	0.0499 (9)	0.0030 (8)	0.0222 (8)	−0.0021 (7)
N2	0.0561 (10)	0.0364 (9)	0.0488 (9)	0.0025 (8)	0.0214 (8)	−0.0039 (7)
N3	0.0501 (10)	0.0299 (9)	0.0396 (8)	−0.0014 (7)	0.0169 (7)	0.0015 (7)
O1	0.0617 (9)	0.0297 (7)	0.0511 (7)	0.0001 (6)	0.0236 (6)	−0.0041 (6)
O2	0.0852 (11)	0.0348 (8)	0.0492 (8)	−0.0057 (8)	0.0192 (8)	−0.0052 (7)
O3	0.0731 (11)	0.0510 (10)	0.0416 (7)	−0.0193 (8)	0.0080 (7)	0.0075 (7)
O4	0.0620 (9)	0.0417 (8)	0.0480 (8)	−0.0097 (7)	0.0032 (7)	−0.0011 (7)
O5	0.0705 (9)	0.0307 (7)	0.0590 (8)	−0.0096 (7)	0.0301 (7)	−0.0025 (6)

Geometric parameters (Å, º)

C1—C6	1.381 (3)	C13—N3	1.296 (2)
C1—C2	1.385 (3)	C13—H13	0.98 (2)
C1—N1	1.430 (2)	C14—N3	1.470 (2)
C2—C3	1.370 (3)	C14—C17	1.528 (3)
C2—H2	0.94 (2)	C14—C15	1.529 (3)
C3—C4	1.382 (3)	C14—C16	1.530 (3)
C3—Cl1	1.738 (2)	C15—O2	1.415 (3)
C4—C5	1.373 (3)	C15—H15A	0.95 (3)
C4—H4	0.95 (3)	C15—H15B	0.98 (2)
C5—C6	1.382 (3)	C16—O3	1.409 (2)
C5—H5	1.00 (3)	C16—H16A	1.00 (2)
C6—H6	0.96 (3)	C16—H16B	0.98 (2)
C7—C8	1.366 (3)	C17—O4	1.408 (3)
C7—N2	1.402 (2)	C17—H17A	0.95 (2)
C7—C12	1.424 (3)	C17—H17B	1.01 (2)
C8—C9	1.412 (3)	C18—O5	1.421 (3)
C8—H8	0.92 (2)	C18—H18A	0.99 (2)
C9—C13	1.410 (3)	C18—H18B	0.94 (3)
C9—C10	1.430 (3)	C18—H18C	1.04 (3)
C10—O1	1.272 (2)	N1—N2	1.260 (2)
C10—C11	1.447 (3)	N3—H1	0.88 (3)
C11—C12	1.353 (3)	O2—H22	0.88 (3)
C11—O5	1.368 (2)	O3—H33	0.80 (3)
C12—H12	1.02 (2)	O4—H44	0.91 (3)
C6—C1—C2	119.77 (19)	N3—C14—C17	111.37 (15)
C6—C1—N1	116.47 (18)	N3—C14—C15	106.31 (15)
C2—C1—N1	123.76 (17)	C17—C14—C15	107.91 (16)
C3—C2—C1	118.88 (19)	N3—C14—C16	107.59 (15)
C3—C2—H2	118.1 (14)	C17—C14—C16	112.56 (16)
C1—C2—H2	123.0 (14)	C15—C14—C16	110.95 (16)
C2—C3—C4	122.1 (2)	O2—C15—C14	112.57 (17)
C2—C3—Cl1	119.07 (17)	O2—C15—H15A	105.9 (16)
C4—C3—Cl1	118.80 (16)	C14—C15—H15A	109.3 (15)
C5—C4—C3	118.5 (2)	O2—C15—H15B	108.9 (14)
C5—C4—H4	119.8 (15)	C14—C15—H15B	110.9 (14)
C3—C4—H4	121.7 (15)	H15A—C15—H15B	109 (2)
C4—C5—C6	120.5 (2)	O3—C16—C14	111.55 (17)
C4—C5—H5	115.5 (16)	O3—C16—H16A	108.2 (12)
C6—C5—H5	123.9 (17)	C14—C16—H16A	109.0 (12)
C1—C6—C5	120.3 (2)	O3—C16—H16B	109.1 (12)
C1—C6—H6	119.5 (14)	C14—C16—H16B	112.1 (11)
C5—C6—H6	120.2 (14)	H16A—C16—H16B	106.7 (17)
C8—C7—N2	115.56 (17)	O4—C17—C14	114.74 (17)
C8—C7—C12	120.08 (18)	O4—C17—H17A	112.9 (13)
N2—C7—C12	124.36 (18)	C14—C17—H17A	103.9 (12)
C7—C8—C9	121.11 (19)	O4—C17—H17B	106.3 (12)
C7—C8—H8	119.1 (14)	C14—C17—H17B	109.6 (12)
C9—C8—H8	119.8 (14)	H17A—C17—H17B	109.4 (17)
C13—C9—C8	118.94 (18)	O5—C18—H18A	112.2 (13)
C13—C9—C10	120.91 (17)	O5—C18—H18B	103.4 (16)
C8—C9—C10	120.10 (17)	H18A—C18—H18B	112 (2)
O1—C10—C9	122.98 (17)	O5—C18—H18C	108.9 (16)
O1—C10—C11	120.59 (17)	H18A—C18—H18C	110 (2)
C9—C10—C11	116.44 (16)	H18B—C18—H18C	110 (2)
C12—C11—O5	125.83 (18)	N2—N1—C1	112.79 (16)
C12—C11—C10	122.23 (17)	N1—N2—C7	115.68 (17)
O5—C11—C10	111.94 (16)	C13—N3—C14	127.05 (16)
C11—C12—C7	119.97 (18)	C13—N3—H1	109.8 (18)
C11—C12—H12	120.4 (12)	C14—N3—H1	123.0 (18)
C7—C12—H12	119.6 (12)	C15—O2—H22	106.4 (18)
N3—C13—C9	123.63 (18)	C16—O3—H33	108 (2)
N3—C13—H13	116.5 (12)	C17—O4—H44	105.0 (17)
C9—C13—H13	119.9 (12)	C11—O5—C18	117.58 (17)
C6—C1—C2—C3	1.7 (3)	C8—C7—C12—C11	0.9 (3)
N1—C1—C2—C3	−178.48 (19)	N2—C7—C12—C11	−178.96 (19)
C1—C2—C3—C4	0.2 (3)	C8—C9—C13—N3	−177.91 (18)
C1—C2—C3—Cl1	178.96 (16)	C10—C9—C13—N3	−0.4 (3)
C2—C3—C4—C5	−1.7 (4)	N3—C14—C15—O2	48.7 (2)
Cl1—C3—C4—C5	179.58 (19)	C17—C14—C15—O2	168.23 (17)
C3—C4—C5—C6	1.3 (4)	C16—C14—C15—O2	−68.0 (2)
C2—C1—C6—C5	−2.1 (3)	N3—C14—C16—O3	178.78 (15)
N1—C1—C6—C5	178.0 (2)	C17—C14—C16—O3	55.7 (2)
C4—C5—C6—C1	0.6 (4)	C15—C14—C16—O3	−65.3 (2)
N2—C7—C8—C9	179.20 (18)	N3—C14—C17—O4	−62.0 (2)
C12—C7—C8—C9	−0.7 (3)	C15—C14—C17—O4	−178.30 (17)
C7—C8—C9—C13	176.11 (19)	C16—C14—C17—O4	58.9 (2)
C7—C8—C9—C10	−1.4 (3)	C6—C1—N1—N2	−172.28 (18)
C13—C9—C10—O1	5.3 (3)	C2—C1—N1—N2	7.8 (3)
C8—C9—C10—O1	−177.26 (18)	C1—N1—N2—C7	179.53 (16)
C13—C9—C10—C11	−174.34 (18)	C8—C7—N2—N1	−178.24 (18)
C8—C9—C10—C11	3.1 (3)	C12—C7—N2—N1	1.6 (3)
O1—C10—C11—C12	177.41 (18)	C9—C13—N3—C14	173.79 (18)
C9—C10—C11—C12	−3.0 (3)	C17—C14—N3—C13	59.2 (2)
O1—C10—C11—O5	−2.4 (3)	C15—C14—N3—C13	176.47 (19)
C9—C10—C11—O5	177.16 (16)	C16—C14—N3—C13	−64.6 (2)
O5—C11—C12—C7	−179.17 (19)	C12—C11—O5—C18	−2.2 (3)
C10—C11—C12—C7	1.0 (3)	C10—C11—O5—C18	177.67 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···O1	0.88 (3)	1.88 (3)	2.643 (2)	145 (3)
O2—H22···O3^i	0.88 (3)	1.88 (3)	2.759 (2)	173 (3)
O3—H33···O1^ii	0.80 (3)	2.33 (3)	3.014 (2)	144 (3)
O3—H33···O5^ii	0.80 (3)	2.14 (3)	2.829 (2)	144 (3)
O4—H44···O1^ii	0.91 (3)	1.85 (3)	2.747 (2)	165 (3)

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