(Z)-6-{[1,3-Dihydr­oxy-2-(hydroxy­meth­yl)propan-2-ylamino]methyl­ene}-4-[(E)-(4-ethyl­phen­yl)diazen­yl]cyclohexa-2,4-dienone

The title compound, C₁₉H₂₃N₃O₄, adopts the keto-amine tautomeric form, with the H atom located on N rather than on O. This H atom is involved in a strong intra­molecular hydrogen bond. The configuration around the azo N=N double bond is trans and the dihedral angle between the two aromatic rings is 8.94 (2)°. The mol­ecules, with intra­molecular N—H...O hydrogen bonding, are linked by intermolecular O—H...O hydrogen bonds, forming a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.010 Å
• Disorder in main residue
• R factor = 0.107
• wR factor = 0.313
• Data-to-parameter ratio = 15.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low ....         36 Perc.

Alert level C
RFACG01_ALERT_3_C  The value of the R factor is > 0.10
            R factor given   0.107
RFACR01_ALERT_3_C  The value of the weighted R factor is > 0.25
            Weighted R factor given   0.313
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.129
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.13
PLAT082_ALERT_2_C High R1 Value ..................................       0.11
PLAT084_ALERT_2_C High R2 Value ..................................       0.31
PLAT301_ALERT_3_C Main Residue  Disorder .........................       7.00 Perc.
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         10
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         10
PLAT731_ALERT_1_C Bond    Calc     0.83(6), Rep     0.83(2) ......       3.00 su-Rat
              O2   -H2      1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(5), Rep     0.84(2) ......       2.50 su-Rat
              O3   -H3      1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.83(6), Rep     0.83(2) ......       3.00 su-Rat
              O2   -H2      1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(5), Rep     0.84(2) ......       2.50 su-Rat
              O3   -H3      1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.85(5), Rep     1.85(2) ......       2.50 su-Rat
              H3   -O1      1.555   4.556
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      25.80 Deg.
              C2A  -C3   -C2B     1.555   1.555   1.555

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

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

---

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (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).

(Z)-4-[(E)-(4-ethylphenyl)diazenyl]-6-{[1,3-dihydroxy-2-(hydroxymethyl)propan- 2-ylamino]methylene}cyclohexa-2,4-dienone

Crystal data

C19H23N3O4	F(000) = 760
Mr = 357.40	Dx = 1.258 Mg m^−3
Monoclinic, P21/c	Melting point = 463–465 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 18.441 (4) Å	Cell parameters from 7373 reflections
b = 7.8992 (10) Å	θ = 1.6–23.5°
c = 13.014 (3) Å	µ = 0.09 mm^−1
β = 95.516 (16)°	T = 296 K
V = 1887.0 (6) Å^3	Plate, brown
Z = 4	0.50 × 0.40 × 0.12 mm

Data collection

Stoe IPDS 2 diffractometer	1336 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.129
Graphite monochromator	θmax = 26.0°, θmin = 2.2°
Detector resolution: 6.67 pixels mm^-1	h = −22→22
w scan rotation	k = −9→9
9340 measured reflections	l = −13→16
3690 independent 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)] = 0.107	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.313	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	w = 1/[σ^2(Fo^2) + (0.157P)^2] where P = (Fo^2 + 2Fc^2)/3
3690 reflections	(Δ/σ)max < 0.001
238 parameters	Δρmax = 0.47 e Å^−3
27 restraints	Δρmin = −0.31 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	Occ. (<1)
C1A	0.5523 (13)	1.205 (3)	0.452 (2)	0.1031 (4)	0.396 (14)
H1A1	0.5873	1.2835	0.4834	0.155*	0.396 (14)
H1A2	0.5616	1.0943	0.4802	0.155*	0.396 (14)
H1A3	0.5042	1.2405	0.4640	0.155*	0.396 (14)
C1B	0.5824 (8)	1.295 (2)	0.4066 (13)	0.1031 (4)	0.604 (14)
H1B1	0.6215	1.2487	0.4519	0.155*	0.604 (14)
H1B2	0.5546	1.3722	0.4445	0.155*	0.604 (14)
H1B3	0.6021	1.3552	0.3514	0.155*	0.604 (14)
C2A	0.5588 (15)	1.200 (4)	0.331 (2)	0.1031 (4)	0.396 (14)
H2A1	0.5116	1.2214	0.2940	0.124*	0.396 (14)
H2A2	0.5925	1.2862	0.3126	0.124*	0.396 (14)
C2B	0.5360 (9)	1.161 (2)	0.3648 (15)	0.1031 (4)	0.604 (14)
H2B1	0.4971	1.2070	0.3174	0.124*	0.604 (14)
H2B2	0.5144	1.1027	0.4198	0.124*	0.604 (14)
C3	0.5851 (5)	1.0320 (10)	0.3049 (8)	0.0949 (3)
C4	0.6131 (4)	0.8970 (10)	0.3654 (8)	0.0989 (3)
H4A	0.6092	0.8982	0.4361	0.119*
C5	0.6462 (5)	0.7624 (10)	0.3222 (8)	0.098 (3)
H5	0.6627	0.6705	0.3626	0.117*
C6	0.6547 (4)	0.7655 (8)	0.2171 (7)	0.074 (2)
C7	0.6292 (4)	0.9013 (9)	0.1591 (8)	0.093 (3)
H7	0.6354	0.9057	0.0891	0.111*
C8	0.5942 (4)	1.0323 (9)	0.2052 (7)	0.0876 (3)
H8	0.5766	1.1232	0.1648	0.105*
C9	0.7394 (3)	0.3735 (7)	0.1700 (5)	0.0513 (14)
C10	0.7604 (3)	0.2391 (7)	0.2308 (5)	0.0559 (15)
H10	0.7448	0.2329	0.2965	0.067*
C11	0.8045 (3)	0.1101 (7)	0.1984 (4)	0.0504 (14)
C12	0.8252 (3)	0.1123 (7)	0.0960 (4)	0.0489 (14)
C13	0.8007 (4)	0.2521 (8)	0.0339 (5)	0.0707 (19)
H13	0.8135	0.2580	−0.0334	0.085*
C14	0.7599 (3)	0.3765 (8)	0.0685 (5)	0.0635 (17)
H14	0.7449	0.4658	0.0249	0.076*
C15	0.8328 (3)	−0.0110 (7)	0.2720 (5)	0.0565 (15)
H15	0.8160	−0.0086	0.3371	0.068*
C16	0.9197 (3)	−0.2418 (6)	0.3291 (4)	0.0463 (13)
C17	0.9191 (4)	−0.1766 (7)	0.4412 (5)	0.0613 (17)
H17A	0.9515	−0.2468	0.4862	0.074*
H17B	0.9383	−0.0622	0.4448	0.074*
C18	0.8815 (3)	−0.4126 (6)	0.3149 (5)	0.0525 (15)
H18A	0.8317	−0.4018	0.3320	0.063*
H18B	0.8802	−0.4468	0.2432	0.063*
C19	0.9975 (3)	−0.2505 (8)	0.3034 (5)	0.0594 (16)
H19A	1.0215	−0.1433	0.3197	0.071*
H19B	1.0233	−0.3379	0.3447	0.071*
N1	0.6890 (3)	0.6339 (7)	0.1643 (5)	0.0746 (16)
N2	0.7006 (3)	0.5033 (7)	0.2180 (5)	0.0658 (15)
N3	0.8805 (3)	−0.1247 (6)	0.2540 (4)	0.0484 (12)
O1	0.8664 (2)	−0.0040 (5)	0.0630 (3)	0.0576 (11)
O2	0.9996 (2)	−0.2874 (5)	0.1966 (3)	0.0623 (12)
O3	0.9180 (3)	−0.5395 (5)	0.3787 (3)	0.0620 (12)
O4	0.8506 (3)	−0.1763 (5)	0.4778 (3)	0.0724 (13)
H2	1.033 (3)	−0.221 (8)	0.186 (7)	0.109*
H3	0.903 (4)	−0.527 (11)	0.437 (3)	0.109*
H3A	0.899 (4)	−0.136 (9)	0.191 (6)	0.087*
H4	0.847 (4)	−0.275 (4)	0.498 (6)	0.109*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1A	0.107	0.105	0.100	0.026 (4)	0.026 (6)	−0.026 (5)
C1B	0.107	0.105	0.100	0.026 (4)	0.026 (6)	−0.026 (5)
C2A	0.107	0.105	0.100	0.026 (4)	0.026 (6)	−0.026 (5)
C2B	0.107	0.105	0.100	0.026 (4)	0.026 (6)	−0.026 (5)
C3	0.102	0.071	0.108	0.026 (4)	−0.009 (5)	−0.027 (5)
C4	0.102	0.085	0.108	0.026 (5)	0.004 (5)	−0.013 (5)
C5	0.115 (6)	0.066 (5)	0.112 (8)	0.040 (5)	0.010 (5)	−0.009 (5)
C6	0.073 (4)	0.053 (4)	0.094 (6)	0.006 (3)	0.005 (4)	−0.010 (4)
C7	0.091 (5)	0.056 (4)	0.127 (8)	−0.003 (4)	−0.009 (5)	0.009 (5)
C8	0.090	0.060	0.109	0.014 (4)	−0.007 (5)	−0.006 (5)
C9	0.059 (4)	0.039 (3)	0.056 (4)	0.006 (3)	0.004 (3)	−0.005 (3)
C10	0.067 (4)	0.050 (3)	0.051 (4)	0.005 (3)	0.008 (3)	−0.001 (3)
C11	0.060 (4)	0.046 (3)	0.044 (3)	−0.003 (3)	0.001 (3)	0.003 (3)
C12	0.063 (4)	0.043 (3)	0.041 (3)	−0.002 (3)	0.004 (3)	−0.001 (3)
C13	0.102 (5)	0.064 (4)	0.047 (4)	0.016 (4)	0.014 (3)	0.014 (3)
C14	0.077 (4)	0.051 (4)	0.061 (4)	0.008 (3)	−0.002 (3)	0.011 (3)
C15	0.073 (4)	0.053 (4)	0.044 (3)	0.004 (3)	0.009 (3)	0.006 (3)
C16	0.067 (4)	0.038 (3)	0.033 (3)	0.000 (3)	0.002 (2)	0.006 (2)
C17	0.094 (5)	0.040 (3)	0.047 (4)	0.001 (3)	−0.005 (3)	−0.001 (3)
C18	0.076 (4)	0.039 (3)	0.043 (3)	−0.005 (3)	0.008 (3)	−0.001 (2)
C19	0.064 (4)	0.048 (3)	0.065 (5)	−0.010 (3)	0.004 (3)	0.012 (3)
N1	0.083 (4)	0.065 (4)	0.074 (4)	0.006 (3)	0.000 (3)	0.003 (3)
N2	0.061 (3)	0.053 (3)	0.081 (4)	0.006 (3)	0.000 (3)	0.005 (3)
N3	0.062 (3)	0.042 (3)	0.041 (3)	0.006 (2)	0.004 (2)	0.002 (2)
O1	0.081 (3)	0.054 (2)	0.038 (2)	0.006 (2)	0.0093 (18)	−0.0019 (19)
O2	0.082 (3)	0.051 (3)	0.055 (3)	−0.007 (2)	0.017 (2)	−0.002 (2)
O3	0.103 (3)	0.037 (2)	0.049 (3)	0.009 (2)	0.019 (2)	0.0068 (19)
O4	0.116 (4)	0.058 (3)	0.047 (3)	0.019 (3)	0.025 (2)	0.007 (2)

Geometric parameters (Å, º)

C1A—C2A	1.58 (4)	C10—H10	0.9300
C1A—H1A1	0.9600	C11—C15	1.416 (8)
C1A—H1A2	0.9600	C11—C12	1.421 (8)
C1A—H1A3	0.9600	C12—O1	1.292 (7)
C1B—C2B	1.44 (2)	C12—C13	1.416 (8)
C1B—H1B1	0.9600	C13—C14	1.342 (9)
C1B—H1B2	0.9600	C13—H13	0.9300
C1B—H1B3	0.9600	C14—H14	0.9300
C2A—C3	1.46 (3)	C15—N3	1.295 (7)
C2A—H2A1	0.9700	C15—H15	0.9300
C2A—H2A2	0.9700	C16—N3	1.482 (7)
C2B—C3	1.614 (18)	C16—C19	1.506 (8)
C2B—H2B1	0.9700	C16—C18	1.525 (7)
C2B—H2B2	0.9700	C16—C17	1.548 (8)
C3—C8	1.324 (12)	C17—O4	1.392 (8)
C3—C4	1.394 (12)	C17—H17A	0.9700
C4—C5	1.373 (11)	C17—H17B	0.9700
C4—H4A	0.9300	C18—O3	1.428 (7)
C5—C6	1.391 (12)	C18—H18A	0.9700
C5—H5	0.9300	C18—H18B	0.9700
C6—C7	1.368 (10)	C19—O2	1.425 (7)
C6—N1	1.428 (9)	C19—H19A	0.9700
C7—C8	1.386 (11)	C19—H19B	0.9700
C7—H7	0.9300	N1—N2	1.253 (7)
C8—H8	0.9300	N3—H3A	0.93 (8)
C9—C10	1.357 (8)	O2—H2	0.83 (2)
C9—C14	1.409 (9)	O3—H3	0.84 (2)
C9—N2	1.428 (8)	O4—H4	0.82 (2)
C10—C11	1.394 (8)
C2B—C1B—H1B1	109.5	C10—C11—C12	119.4 (5)
C2B—C1B—H1B2	109.5	C15—C11—C12	121.9 (5)
H1B1—C1B—H1B2	109.5	O1—C12—C13	122.0 (6)
C2B—C1B—H1B3	109.5	O1—C12—C11	121.5 (5)
H1B1—C1B—H1B3	109.5	C13—C12—C11	116.4 (6)
H1B2—C1B—H1B3	109.5	C14—C13—C12	122.5 (6)
C3—C2A—C1A	108 (2)	C14—C13—H13	118.7
C3—C2A—H2A1	110.0	C12—C13—H13	118.7
C1A—C2A—H2A1	110.0	C13—C14—C9	120.8 (6)
C3—C2A—H2A2	110.0	C13—C14—H14	119.6
C1A—C2A—H2A2	110.0	C9—C14—H14	119.6
H2A1—C2A—H2A2	108.4	N3—C15—C11	124.0 (6)
C1B—C2B—C3	108.0 (13)	N3—C15—H15	118.0
C1B—C2B—H2B1	110.1	C11—C15—H15	118.0
C3—C2B—H2B1	110.1	N3—C16—C19	107.3 (5)
C1B—C2B—H2B2	110.1	N3—C16—C18	106.4 (4)
C3—C2B—H2B2	110.1	C19—C16—C18	111.8 (5)
H2B1—C2B—H2B2	108.4	N3—C16—C17	111.5 (5)
C8—C3—C4	118.7 (8)	C19—C16—C17	108.5 (5)
C8—C3—C2A	107.7 (14)	C18—C16—C17	111.3 (5)
C4—C3—C2A	132.3 (14)	O4—C17—C16	114.3 (5)
C8—C3—C2B	127.0 (10)	O4—C17—H17A	108.7
C4—C3—C2B	113.9 (11)	C16—C17—H17A	108.7
C2A—C3—C2B	25.8 (11)	O4—C17—H17B	108.7
C5—C4—C3	121.1 (10)	C16—C17—H17B	108.7
C5—C4—H4A	119.5	H17A—C17—H17B	107.6
C3—C4—H4A	119.5	O3—C18—C16	111.4 (5)
C4—C5—C6	119.0 (8)	O3—C18—H18A	109.4
C4—C5—H5	120.5	C16—C18—H18A	109.4
C6—C5—H5	120.5	O3—C18—H18B	109.4
C7—C6—C5	119.4 (7)	C16—C18—H18B	109.4
C7—C6—N1	116.7 (8)	H18A—C18—H18B	108.0
C5—C6—N1	123.9 (6)	O2—C19—C16	110.0 (4)
C6—C7—C8	119.7 (9)	O2—C19—H19A	109.7
C6—C7—H7	120.1	C16—C19—H19A	109.7
C8—C7—H7	120.1	O2—C19—H19B	109.7
C3—C8—C7	122.0 (8)	C16—C19—H19B	109.7
C3—C8—H8	119.0	H19A—C19—H19B	108.2
C7—C8—H8	119.0	N2—N1—C6	113.0 (6)
C10—C9—C14	118.2 (5)	N1—N2—C9	114.4 (6)
C10—C9—N2	115.7 (6)	C15—N3—C16	127.7 (5)
C14—C9—N2	126.0 (5)	C15—N3—H3A	123 (4)
C9—C10—C11	122.5 (6)	C16—N3—H3A	109 (4)
C9—C10—H10	118.7	C19—O2—H2	97 (6)
C11—C10—H10	118.7	C18—O3—H3	106 (6)
C10—C11—C15	118.5 (6)	C17—O4—H4	102 (6)
C1A—C2A—C3—C8	−176.5 (17)	O1—C12—C13—C14	−177.8 (6)
C1A—C2A—C3—C4	−10 (3)	C11—C12—C13—C14	−0.4 (9)
C1A—C2A—C3—C2B	41 (3)	C12—C13—C14—C9	0.2 (10)
C1B—C2B—C3—C8	−94.3 (16)	C10—C9—C14—C13	−1.8 (9)
C1B—C2B—C3—C4	93.4 (16)	N2—C9—C14—C13	175.3 (6)
C1B—C2B—C3—C2A	−47 (3)	C10—C11—C15—N3	−172.0 (5)
C8—C3—C4—C5	−3.3 (13)	C12—C11—C15—N3	2.2 (9)
C2A—C3—C4—C5	−168.4 (17)	N3—C16—C17—O4	67.3 (6)
C2B—C3—C4—C5	169.7 (10)	C19—C16—C17—O4	−174.8 (5)
C3—C4—C5—C6	2.9 (13)	C18—C16—C17—O4	−51.4 (6)
C4—C5—C6—C7	−0.7 (12)	N3—C16—C18—O3	175.9 (5)
C4—C5—C6—N1	179.2 (7)	C19—C16—C18—O3	59.1 (6)
C5—C6—C7—C8	−1.2 (11)	C17—C16—C18—O3	−62.4 (6)
N1—C6—C7—C8	178.9 (6)	N3—C16—C19—O2	−51.4 (6)
C4—C3—C8—C7	1.3 (13)	C18—C16—C19—O2	64.9 (6)
C2A—C3—C8—C7	169.8 (14)	C17—C16—C19—O2	−172.0 (4)
C2B—C3—C8—C7	−170.7 (11)	C7—C6—N1—N2	−169.6 (6)
C6—C7—C8—C3	0.9 (12)	C5—C6—N1—N2	10.5 (10)
C14—C9—C10—C11	3.7 (9)	C6—N1—N2—C9	−175.9 (5)
N2—C9—C10—C11	−173.8 (5)	C10—C9—N2—N1	172.4 (5)
C9—C10—C11—C15	170.5 (5)	C14—C9—N2—N1	−4.8 (8)
C9—C10—C11—C12	−3.8 (8)	C11—C15—N3—C16	171.8 (5)
C10—C11—C12—O1	179.5 (5)	C19—C16—N3—C15	−138.9 (6)
C15—C11—C12—O1	5.4 (8)	C18—C16—N3—C15	101.3 (6)
C10—C11—C12—C13	2.0 (8)	C17—C16—N3—C15	−20.2 (8)
C15—C11—C12—C13	−172.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3^i	0.83 (2)	1.93 (4)	2.718 (6)	158 (8)
O3—H3···O1^ii	0.84 (2)	1.85 (2)	2.685 (6)	177 (8)
N3—H3A···O1	0.93 (8)	2.00 (7)	2.652 (6)	125 (6)
N3—H3A···O2	0.93 (8)	2.20 (7)	2.712 (7)	114 (5)
O4—H4···O1^ii	0.82 (2)	1.96 (3)	2.762 (6)	163 (8)

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