1,5-Dimethyl-2-phenyl-4-[(1E)-(2,3,4-trihydroxy­benzyl­idene)amino]-1H-pyrazol-3(2H)-one

The title compound, C₁₈H₁₇N₃O₄, was synthesized by the condensation of 2,3,4-trihydroxy­benzaldehyde with 4-amino­anti­pyrine. The mol­ecule adopts a trans configuration about the central C=N double bond and exists in the phenol–imine form. Mol­ecules are linked into a two-dimensional framework by inter­molecular O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.060
• wR factor = 0.138
• Data-to-parameter ratio = 11.0

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.93

Author Response: This problem has arisen because there is not good quality crystals and the ata collected with a R-AXIS-IV. Several samples were screened. The selected sample exhibited the strongest diffraction behavior. Hence the precision of the structure is lowered.Validation issues a number of other alerts which are related to this issue.

Alert level C
REFLT03_ALERT_3_C  Reflection count < 95% complete
           From the CIF: _diffrn_reflns_theta_max           25.00
           From the CIF: _diffrn_reflns_theta_full          25.00
           From the CIF: _reflns_number_total               2633
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         2828
           Completeness (_total/calc)             93.10%
PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low ....       0.93
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?

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

   1 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
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: R-AXIS (Rigaku, 1996); cell refinement: R-AXIS; data reduction: R-AXIS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN (Molecular Structure Corporation, 1999); software used to prepare material for publication: SHELXL97'.

1,5-Dimethyl-2-phenyl-4-[(1E)-(2,3,4-trihydroxybenzylidene)amino]-1H-pyrazol- 3(2H)-one

Crystal data

C18H17N3O4	F(000) = 712
Mr = 339.35	Dx = 1.407 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 356 reflections
a = 12.916 (3) Å	θ = 2–25.1°
b = 7.3123 (15) Å	µ = 0.10 mm^−1
c = 17.328 (4) Å	T = 291 K
β = 101.85 (3)°	Prism, red
V = 1601.7 (6) Å^3	0.20 × 0.17 × 0.17 mm
Z = 4

Data collection

Rigaku-R-AXIS-IV diffractometer	2633 independent reflections
Radiation source: fine-focus sealed tube	1994 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 0 pixels mm^-1	θmax = 25.0°, θmin = 1.8°
Oscillation frame scans	h = 0→15
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −8→8
Tmin = 0.980, Tmax = 0.983	l = −20→20
4561 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)] = 0.060	Hydrogen site location: difference Fourier map
wR(F^2) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0587P)^2 + 1.302P] where P = (Fo^2 + 2Fc^2)/3
2633 reflections	(Δ/σ)max = 0.003
240 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.26 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
N1	0.63583 (18)	0.4622 (3)	0.16149 (13)	0.0289 (6)
N2	0.6474 (2)	0.6384 (3)	−0.02835 (14)	0.0354 (6)
N3	0.69346 (19)	0.4670 (3)	−0.03351 (13)	0.0304 (6)
O1	0.62884 (17)	0.6038 (3)	0.29773 (13)	0.0376 (5)
O2	0.59121 (19)	0.5512 (3)	0.44688 (13)	0.0421 (6)
O3	0.55812 (19)	0.2059 (3)	0.49698 (12)	0.0458 (6)
O4	0.71807 (17)	0.2030 (3)	0.04213 (11)	0.0376 (5)
C1	0.6142 (2)	0.4307 (4)	0.32141 (17)	0.0286 (7)
C2	0.5957 (2)	0.4054 (4)	0.39706 (17)	0.0313 (7)
C3	0.5781 (2)	0.2310 (4)	0.42301 (17)	0.0335 (7)
C4	0.5806 (2)	0.0800 (4)	0.37511 (18)	0.0381 (8)
H4	0.5685	−0.0365	0.3929	0.046*
C5	0.6010 (2)	0.1041 (4)	0.30121 (17)	0.0355 (7)
H5	0.6041	0.0020	0.2697	0.043*
C6	0.6173 (2)	0.2783 (4)	0.27153 (16)	0.0297 (7)
C7	0.6346 (2)	0.3029 (4)	0.19234 (16)	0.0315 (7)
H7	0.6450	0.2006	0.1630	0.038*
C8	0.6905 (2)	0.3675 (4)	0.03385 (16)	0.0275 (7)
C9	0.6503 (2)	0.4897 (4)	0.08449 (15)	0.0265 (6)
C10	0.6279 (2)	0.6533 (4)	0.04548 (16)	0.0306 (7)
C11	0.5889 (3)	0.8272 (4)	0.0741 (2)	0.0491 (9)
H11A	0.6332	0.9265	0.0644	0.074*
H11B	0.5909	0.8181	0.1296	0.074*
H11C	0.5176	0.8492	0.0466	0.074*
C12	0.6685 (3)	0.7861 (4)	−0.07953 (19)	0.0468 (9)
H12A	0.6442	0.8997	−0.0619	0.070*
H12B	0.6321	0.7624	−0.1327	0.070*
H12C	0.7432	0.7935	−0.0777	0.070*
C13	0.7022 (2)	0.3842 (4)	−0.10676 (16)	0.0287 (7)
C14	0.7971 (2)	0.3063 (4)	−0.11206 (18)	0.0392 (8)
H14	0.8560	0.3196	−0.0713	0.047*
C15	0.8040 (3)	0.2079 (5)	−0.1787 (2)	0.0519 (9)
H15	0.8676	0.1526	−0.1826	0.062*
C16	0.7174 (3)	0.1909 (5)	−0.2395 (2)	0.0492 (9)
H16	0.7223	0.1223	−0.2838	0.059*
C17	0.6238 (3)	0.2751 (5)	−0.23497 (19)	0.0451 (8)
H17	0.5661	0.2665	−0.2769	0.054*
C18	0.6150 (2)	0.3726 (4)	−0.16828 (18)	0.0363 (7)
H18	0.5517	0.4293	−0.1648	0.044*
H1	0.642 (3)	0.596 (5)	0.247 (2)	0.070 (12)*
H3	0.536 (3)	0.315 (6)	0.515 (2)	0.072 (13)*
H2	0.653 (4)	0.616 (6)	0.450 (3)	0.097 (16)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0303 (14)	0.0358 (14)	0.0225 (13)	−0.0004 (10)	0.0095 (10)	−0.0002 (10)
N2	0.0487 (16)	0.0294 (14)	0.0332 (14)	0.0073 (11)	0.0203 (12)	0.0056 (11)
N3	0.0431 (16)	0.0263 (13)	0.0241 (13)	0.0072 (10)	0.0120 (11)	0.0005 (10)
O1	0.0542 (15)	0.0330 (11)	0.0285 (12)	−0.0089 (10)	0.0152 (11)	−0.0019 (9)
O2	0.0505 (15)	0.0456 (13)	0.0363 (13)	−0.0129 (11)	0.0229 (11)	−0.0121 (10)
O3	0.0603 (17)	0.0511 (15)	0.0313 (13)	−0.0066 (12)	0.0214 (11)	0.0037 (11)
O4	0.0519 (14)	0.0312 (11)	0.0331 (12)	0.0138 (10)	0.0170 (10)	0.0075 (9)
C1	0.0255 (16)	0.0330 (16)	0.0272 (16)	−0.0038 (12)	0.0058 (12)	0.0036 (12)
C2	0.0297 (17)	0.0409 (17)	0.0248 (15)	−0.0060 (13)	0.0090 (13)	−0.0077 (13)
C3	0.0315 (17)	0.0432 (18)	0.0261 (16)	−0.0037 (13)	0.0068 (13)	0.0081 (13)
C4	0.044 (2)	0.0316 (17)	0.0394 (19)	0.0001 (14)	0.0101 (16)	0.0090 (14)
C5	0.0431 (19)	0.0314 (16)	0.0324 (18)	0.0020 (13)	0.0086 (14)	0.0002 (13)
C6	0.0302 (17)	0.0331 (16)	0.0265 (16)	0.0021 (12)	0.0077 (13)	−0.0010 (12)
C7	0.0365 (18)	0.0326 (16)	0.0271 (16)	−0.0010 (13)	0.0106 (13)	−0.0031 (12)
C8	0.0273 (16)	0.0284 (15)	0.0268 (16)	0.0022 (12)	0.0055 (13)	0.0018 (12)
C9	0.0250 (16)	0.0332 (16)	0.0223 (15)	−0.0011 (12)	0.0074 (12)	−0.0020 (12)
C10	0.0349 (17)	0.0312 (16)	0.0297 (16)	0.0014 (12)	0.0161 (14)	−0.0012 (12)
C11	0.072 (3)	0.0318 (17)	0.053 (2)	0.0078 (16)	0.036 (2)	−0.0003 (15)
C12	0.070 (2)	0.0387 (18)	0.0366 (19)	0.0066 (17)	0.0227 (17)	0.0089 (15)
C13	0.0374 (18)	0.0282 (14)	0.0225 (15)	0.0008 (12)	0.0109 (13)	0.0029 (12)
C14	0.0363 (19)	0.0501 (19)	0.0321 (18)	0.0108 (15)	0.0093 (14)	−0.0010 (15)
C15	0.050 (2)	0.067 (2)	0.043 (2)	0.0207 (18)	0.0179 (18)	−0.0067 (18)
C16	0.064 (3)	0.054 (2)	0.036 (2)	0.0019 (18)	0.0234 (18)	−0.0153 (16)
C17	0.045 (2)	0.055 (2)	0.0349 (19)	−0.0086 (16)	0.0072 (15)	−0.0074 (16)
C18	0.0331 (18)	0.0420 (17)	0.0353 (18)	−0.0007 (13)	0.0105 (15)	−0.0018 (14)

Geometric parameters (Å, º)

N1—C7	1.283 (4)	C6—C7	1.446 (4)
N1—C9	1.400 (3)	C7—H7	0.93
N2—C10	1.358 (4)	C8—C9	1.422 (4)
N2—N3	1.398 (3)	C9—C10	1.376 (4)
N2—C12	1.458 (4)	C10—C11	1.489 (4)
N3—C8	1.383 (3)	C11—H11A	0.96
N3—C13	1.431 (3)	C11—H11B	0.96
O1—C1	1.356 (3)	C11—H11C	0.96
O1—H1	0.93 (4)	C12—H12A	0.96
O2—C2	1.381 (3)	C12—H12B	0.96
O2—H2	0.93 (5)	C12—H12C	0.96
O3—C3	1.371 (3)	C13—C14	1.373 (4)
O3—H3	0.92 (4)	C13—C18	1.385 (4)
O4—C8	1.255 (3)	C14—C15	1.379 (4)
C1—C2	1.392 (4)	C14—H14	0.93
C1—C6	1.416 (4)	C15—C16	1.376 (5)
C2—C3	1.386 (4)	C15—H15	0.93
C3—C4	1.386 (4)	C16—C17	1.374 (5)
C4—C5	1.371 (4)	C16—H16	0.93
C4—H4	0.93	C17—C18	1.382 (4)
C5—C6	1.406 (4)	C17—H17	0.93
C5—H5	0.93	C18—H18	0.93
C7—N1—C9	122.9 (2)	C10—C9—C8	108.1 (2)
C10—N2—N3	107.2 (2)	N1—C9—C8	129.4 (2)
C10—N2—C12	127.4 (2)	N2—C10—C9	109.4 (2)
N3—N2—C12	119.3 (2)	N2—C10—C11	121.5 (3)
C8—N3—N2	109.4 (2)	C9—C10—C11	129.1 (3)
C8—N3—C13	123.2 (2)	C10—C11—H11A	109.5
N2—N3—C13	123.2 (2)	C10—C11—H11B	109.5
C1—O1—H1	107 (2)	H11A—C11—H11B	109.5
C2—O2—H2	107 (3)	C10—C11—H11C	109.5
C3—O3—H3	109 (3)	H11A—C11—H11C	109.5
O1—C1—C2	118.1 (2)	H11B—C11—H11C	109.5
O1—C1—C6	121.8 (2)	N2—C12—H12A	109.5
C2—C1—C6	120.1 (2)	N2—C12—H12B	109.5
O2—C2—C3	118.5 (2)	H12A—C12—H12B	109.5
O2—C2—C1	121.6 (3)	N2—C12—H12C	109.5
C3—C2—C1	120.0 (3)	H12A—C12—H12C	109.5
O3—C3—C2	120.1 (3)	H12B—C12—H12C	109.5
O3—C3—C4	119.0 (3)	C14—C13—C18	121.3 (3)
C2—C3—C4	120.9 (3)	C14—C13—N3	118.0 (3)
C5—C4—C3	119.3 (3)	C18—C13—N3	120.6 (3)
C5—C4—H4	120.3	C13—C14—C15	119.0 (3)
C3—C4—H4	120.3	C13—C14—H14	120.5
C4—C5—C6	122.0 (3)	C15—C14—H14	120.5
C4—C5—H5	119.0	C16—C15—C14	120.4 (3)
C6—C5—H5	119.0	C16—C15—H15	119.8
C5—C6—C1	117.7 (2)	C14—C15—H15	119.8
C5—C6—C7	121.6 (3)	C17—C16—C15	120.2 (3)
C1—C6—C7	120.7 (3)	C17—C16—H16	119.9
N1—C7—C6	121.7 (3)	C15—C16—H16	119.9
N1—C7—H7	119.1	C16—C17—C18	120.3 (3)
C6—C7—H7	119.1	C16—C17—H17	119.9
O4—C8—N3	123.0 (2)	C18—C17—H17	119.9
O4—C8—C9	131.5 (3)	C17—C18—C13	118.8 (3)
N3—C8—C9	105.5 (2)	C17—C18—H18	120.6
C10—C9—N1	122.5 (2)	C13—C18—H18	120.6
C10—N2—N3—C8	7.2 (3)	C13—N3—C8—C9	−163.0 (3)
C12—N2—N3—C8	161.9 (3)	C7—N1—C9—C10	164.7 (3)
C10—N2—N3—C13	164.7 (3)	C7—N1—C9—C8	−16.9 (5)
C12—N2—N3—C13	−40.6 (4)	O4—C8—C9—C10	−177.2 (3)
O1—C1—C2—O2	0.7 (4)	N3—C8—C9—C10	1.9 (3)
C6—C1—C2—O2	−179.4 (3)	O4—C8—C9—N1	4.2 (5)
O1—C1—C2—C3	178.6 (3)	N3—C8—C9—N1	−176.7 (3)
C6—C1—C2—C3	−1.4 (4)	N3—N2—C10—C9	−6.0 (3)
O2—C2—C3—O3	−0.9 (4)	C12—N2—C10—C9	−158.0 (3)
C1—C2—C3—O3	−178.9 (3)	N3—N2—C10—C11	173.6 (3)
O2—C2—C3—C4	179.3 (3)	C12—N2—C10—C11	21.6 (5)
C1—C2—C3—C4	1.3 (5)	N1—C9—C10—N2	−178.7 (3)
O3—C3—C4—C5	−179.7 (3)	C8—C9—C10—N2	2.6 (3)
C2—C3—C4—C5	0.1 (5)	N1—C9—C10—C11	1.8 (5)
C3—C4—C5—C6	−1.4 (5)	C8—C9—C10—C11	−177.0 (3)
C4—C5—C6—C1	1.3 (5)	C8—N3—C13—C14	−71.2 (4)
C4—C5—C6—C7	−177.5 (3)	N2—N3—C13—C14	134.4 (3)
O1—C1—C6—C5	−179.9 (3)	C8—N3—C13—C18	104.4 (3)
C2—C1—C6—C5	0.2 (4)	N2—N3—C13—C18	−50.0 (4)
O1—C1—C6—C7	−1.1 (4)	C18—C13—C14—C15	−2.8 (5)
C2—C1—C6—C7	178.9 (3)	N3—C13—C14—C15	172.7 (3)
C9—N1—C7—C6	−178.7 (3)	C13—C14—C15—C16	1.1 (5)
C5—C6—C7—N1	170.8 (3)	C14—C15—C16—C17	1.3 (6)
C1—C6—C7—N1	−7.9 (4)	C15—C16—C17—C18	−2.0 (5)
N2—N3—C8—O4	173.7 (3)	C16—C17—C18—C13	0.3 (5)
C13—N3—C8—O4	16.2 (4)	C14—C13—C18—C17	2.1 (4)
N2—N3—C8—C9	−5.5 (3)	N3—C13—C18—C17	−173.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2^i	0.92 (4)	2.13 (4)	2.931 (3)	144 (3)
O2—H2···O4^ii	0.93 (5)	1.76 (5)	2.673 (3)	170 (4)
O1—H1···N1	0.93 (4)	1.77 (4)	2.596 (3)	147 (3)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+3/2, y+1/2, −z+1/2.