Methyl [8-(3,5-di­methyl­pyrazol-1-yl­methyl)-4-methyl-2-oxo-2H-chromen-7-yl­oxy]­acetate 0.19-hydrate

In the title compound, C₁₉H₂₀N₂O₅·0.19H₂O, the coumarin moiety is oriented almost perpendicular to the plane of the pyrazole ring. The crystal structure is stabilized by weak intermolecular C—H...π interactions.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.003 Å
• H-atom completeness 99%
• Disorder in solvent or counterion
• R factor = 0.059
• wR factor = 0.161
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level A
REFLT03_ALERT_3_A  Reflection count < 85% complete (theta max?)
           From the CIF: _diffrn_reflns_theta_max           28.03
           From the CIF: _diffrn_reflns_theta_full           0.00
           From the CIF: _reflns_number_total               3630
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         4358
           Completeness (_total/calc)             83.30%
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.83

Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact  O19A   ..  O1W     ..       2.75 Ang.

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms ..          ?
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....        C19
PLAT301_ALERT_3_C Main Residue  Disorder .........................       4.00 Perc.
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      19.00 Perc.
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) .....       <O1W
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              O

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C19 H20.38 N2 O5.19
            Atom count from the _atom_site data:  C19 H20 N2 O5.19
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    2
           From the CIF: _chemical_formula_sum  C19 H20.38 N2 O5.19
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         38.00     38.00    0.00
           H         40.76     40.00    0.76
           N          4.00      4.00    0.00
           O         10.38     10.38    0.00

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

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

---

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Methyl [8-(3,5-dimethylpyrazol-1-ylmethyl)-4-methyl-2-oxo-2H-chromen-7- yloxy]acetate 0.19-hydrate

Crystal data

C19H20N2O5·0.19H2O	Z = 2
Mr = 359.79	F(000) = 380
Triclinic, P1	Dx = 1.327 Mg m^−3
Hall symbol: -P 1	Melting point: 423 K
a = 8.8151 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.6692 (11) Å	Cell parameters from 1506 reflections
c = 10.9050 (11) Å	θ = 2.5–25.0°
α = 96.281 (2)°	µ = 0.10 mm^−1
β = 108.032 (2)°	T = 273 K
γ = 108.383 (2)°	Prism, colourless
V = 900.79 (16) Å^3	0.22 × 0.14 × 0.08 mm

Data collection

Siemens SMART CCD area-detector diffractometer	2476 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.013
Graphite monochromator	θmax = 28.0°, θmin = 2.0°
ω scans	h = −11→10
5544 measured reflections	k = −13→14
3630 independent reflections	l = −14→14

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.161	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0818P)^2 + 0.1112P] where P = (Fo^2 + 2Fc^2)/3
3630 reflections	(Δ/σ)max < 0.001
258 parameters	Δρmax = 0.21 e Å^−3
7 restraints	Δρmin = −0.12 e Å^−3

Special details

Experimental. Due to the poor quality of the crystals, we could collect only 83% of X-ray data.

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)
O1W	0.349 (2)	0.0407 (18)	−0.5177 (16)	0.176 (6)	0.19
O7	0.42928 (18)	0.60375 (14)	−0.19790 (15)	0.0609 (4)
O8	0.5345 (3)	0.6198 (2)	−0.3553 (2)	0.0953 (6)
O17	0.24280 (19)	0.60755 (14)	0.15617 (16)	0.0651 (4)
O19A	0.234 (4)	0.7726 (9)	0.355 (2)	0.093 (3)	0.51 (6)
O19B	0.307 (5)	0.7657 (17)	0.3811 (19)	0.109 (6)	0.49 (6)
O20	0.1330 (2)	0.60040 (18)	0.43844 (16)	0.0817 (5)
N1	0.30457 (19)	0.82419 (15)	−0.01084 (16)	0.0495 (4)
N2	0.1761 (2)	0.78195 (16)	−0.13131 (17)	0.0538 (4)
C3	0.1024 (3)	0.8738 (2)	−0.1342 (2)	0.0574 (5)
C4	0.1848 (3)	0.9734 (2)	−0.0175 (2)	0.0620 (6)
H4	0.1575	1.0484	0.0036	0.074*
C5	0.3142 (3)	0.94001 (19)	0.0607 (2)	0.0541 (5)
C6	0.4219 (2)	0.75274 (18)	0.0244 (2)	0.0543 (5)
H61	0.4798	0.7761	0.1199	0.065*
H62	0.5084	0.7823	−0.0146	0.065*
C8	0.4468 (3)	0.5443 (3)	−0.3088 (3)	0.0692 (6)
C9	0.3611 (3)	0.3997 (3)	−0.3546 (3)	0.0724 (7)
H9	0.3706	0.3572	−0.4295	0.087*
C10	0.2677 (3)	0.3230 (2)	−0.2943 (2)	0.0628 (6)
C11	0.1615 (3)	0.3220 (2)	−0.1046 (2)	0.0612 (6)
H11	0.1028	0.2286	−0.1326	0.073*
C12	0.1549 (3)	0.3896 (2)	0.0063 (2)	0.0629 (6)
H12	0.0935	0.3426	0.0534	0.076*
C13	0.2409 (2)	0.5296 (2)	0.0482 (2)	0.0541 (5)
C14	0.3316 (2)	0.60168 (19)	−0.0218 (2)	0.0494 (5)
C15	0.3362 (2)	0.52935 (19)	−0.1322 (2)	0.0510 (5)
C16	0.2533 (3)	0.3884 (2)	−0.1774 (2)	0.0548 (5)
C18	0.1695 (3)	0.5443 (2)	0.2429 (2)	0.0626 (6)
H181	0.2236	0.4823	0.2762	0.075*
H182	0.0476	0.4933	0.1965	0.075*
C19	0.1980 (3)	0.6538 (3)	0.3544 (2)	0.0698 (6)
C21	0.1533 (4)	0.6912 (3)	0.5547 (3)	0.0979 (9)
H211	0.2732	0.7370	0.6069	0.147*
H212	0.0967	0.6406	0.6060	0.147*
H213	0.1034	0.7568	0.5290	0.147*
C22	−0.0503 (3)	0.8585 (3)	−0.2513 (3)	0.0817 (8)
H221	−0.0347	0.8277	−0.3309	0.123*
H222	−0.0635	0.9444	−0.2518	0.123*
H223	−0.1511	0.7934	−0.2464	0.123*
C23	0.4437 (3)	1.0070 (2)	0.1963 (2)	0.0744 (7)
H231	0.4313	0.9453	0.2535	0.112*
H232	0.4266	1.0865	0.2297	0.112*
H233	0.5569	1.0325	0.1933	0.112*
C24	0.1813 (4)	0.1727 (2)	−0.3457 (3)	0.0865 (8)
H241	0.2142	0.1449	−0.4171	0.130*
H242	0.0591	0.1483	−0.3772	0.130*
H243	0.2152	0.1283	−0.2758	0.130*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1W	0.191 (15)	0.192 (15)	0.152 (13)	0.073 (13)	0.072 (12)	0.029 (12)
O7	0.0608 (8)	0.0600 (8)	0.0702 (10)	0.0208 (7)	0.0349 (8)	0.0191 (8)
O8	0.0951 (13)	0.0987 (14)	0.1058 (15)	0.0233 (11)	0.0676 (12)	0.0233 (11)
O17	0.0751 (9)	0.0587 (8)	0.0676 (10)	0.0200 (7)	0.0372 (8)	0.0193 (8)
O19A	0.130 (8)	0.065 (3)	0.093 (6)	0.033 (3)	0.054 (6)	0.022 (2)
O19B	0.149 (10)	0.072 (4)	0.091 (6)	0.012 (5)	0.056 (7)	0.017 (3)
O20	0.0887 (12)	0.0908 (12)	0.0614 (11)	0.0213 (9)	0.0350 (10)	0.0147 (9)
N1	0.0491 (9)	0.0439 (8)	0.0538 (10)	0.0142 (7)	0.0189 (8)	0.0128 (7)
N2	0.0532 (9)	0.0513 (9)	0.0561 (11)	0.0160 (7)	0.0211 (8)	0.0155 (8)
C3	0.0525 (11)	0.0563 (12)	0.0694 (14)	0.0189 (9)	0.0265 (11)	0.0293 (11)
C4	0.0653 (13)	0.0482 (11)	0.0825 (16)	0.0235 (10)	0.0360 (12)	0.0196 (11)
C5	0.0565 (11)	0.0439 (10)	0.0640 (13)	0.0136 (8)	0.0296 (10)	0.0128 (9)
C6	0.0478 (10)	0.0507 (11)	0.0630 (13)	0.0160 (8)	0.0202 (10)	0.0143 (9)
C8	0.0631 (14)	0.0805 (16)	0.0739 (17)	0.0304 (12)	0.0343 (13)	0.0177 (13)
C9	0.0732 (15)	0.0782 (16)	0.0681 (16)	0.0360 (13)	0.0242 (13)	0.0064 (13)
C10	0.0630 (13)	0.0595 (12)	0.0629 (14)	0.0300 (10)	0.0127 (11)	0.0109 (11)
C11	0.0641 (13)	0.0458 (10)	0.0684 (15)	0.0177 (9)	0.0176 (11)	0.0196 (10)
C12	0.0647 (13)	0.0546 (12)	0.0705 (15)	0.0176 (10)	0.0262 (12)	0.0271 (11)
C13	0.0525 (11)	0.0551 (11)	0.0588 (13)	0.0228 (9)	0.0207 (10)	0.0191 (10)
C14	0.0457 (10)	0.0487 (10)	0.0579 (13)	0.0197 (8)	0.0201 (9)	0.0176 (9)
C15	0.0445 (10)	0.0520 (11)	0.0612 (13)	0.0208 (8)	0.0196 (9)	0.0212 (10)
C16	0.0531 (11)	0.0519 (11)	0.0573 (13)	0.0245 (9)	0.0113 (10)	0.0150 (10)
C18	0.0617 (12)	0.0656 (13)	0.0668 (14)	0.0220 (10)	0.0295 (11)	0.0263 (11)
C19	0.0720 (15)	0.0742 (16)	0.0609 (15)	0.0227 (13)	0.0239 (12)	0.0205 (12)
C21	0.110 (2)	0.120 (2)	0.0642 (17)	0.0449 (19)	0.0323 (16)	0.0127 (16)
C22	0.0714 (15)	0.0854 (17)	0.0894 (19)	0.0329 (13)	0.0223 (14)	0.0332 (14)
C23	0.0797 (16)	0.0598 (13)	0.0705 (16)	0.0178 (11)	0.0223 (13)	0.0025 (11)
C24	0.1037 (19)	0.0639 (14)	0.0757 (17)	0.0318 (14)	0.0140 (15)	0.0055 (13)

Geometric parameters (Å, º)

O7—C15	1.377 (2)	C10—C24	1.495 (3)
O7—C8	1.378 (3)	C11—C12	1.366 (3)
O8—C8	1.201 (3)	C11—C16	1.395 (3)
O17—C13	1.358 (3)	C11—H11	0.9300
O17—C18	1.418 (3)	C12—C13	1.391 (3)
O19A—C19	1.205 (5)	C12—H12	0.9300
O19B—C19	1.207 (5)	C13—C14	1.391 (3)
O20—C19	1.314 (3)	C14—C15	1.375 (3)
O20—C21	1.435 (3)	C15—C16	1.400 (3)
N1—C5	1.351 (3)	C18—C19	1.491 (3)
N1—N2	1.356 (2)	C18—H181	0.9700
N1—C6	1.454 (2)	C18—H182	0.9700
N2—C3	1.334 (3)	C21—H211	0.9600
C3—C4	1.386 (3)	C21—H212	0.9600
C3—C22	1.490 (3)	C21—H213	0.9600
C4—C5	1.370 (3)	C22—H221	0.9600
C4—H4	0.9300	C22—H222	0.9600
C5—C23	1.486 (3)	C22—H223	0.9600
C6—C14	1.500 (3)	C23—H231	0.9600
C6—H61	0.9700	C23—H232	0.9600
C6—H62	0.9700	C23—H233	0.9600
C8—C9	1.436 (3)	C24—H241	0.9600
C9—C10	1.344 (3)	C24—H242	0.9600
C9—H9	0.9300	C24—H243	0.9600
C10—C16	1.447 (3)
C15—O7—C8	122.26 (17)	C13—C14—C6	120.1 (2)
C13—O17—C18	119.41 (16)	C14—C15—O7	116.04 (17)
C19—O20—C21	117.5 (2)	C14—C15—C16	123.42 (19)
C5—N1—N2	112.48 (16)	O7—C15—C16	120.5 (2)
C5—N1—C6	127.08 (17)	C11—C16—C15	116.3 (2)
N2—N1—C6	120.24 (16)	C11—C16—C10	125.07 (19)
C3—N2—N1	104.63 (16)	C15—C16—C10	118.6 (2)
N2—C3—C4	110.70 (18)	O17—C18—C19	107.30 (18)
N2—C3—C22	120.3 (2)	O17—C18—H181	110.3
C4—C3—C22	129.0 (2)	C19—C18—H181	110.3
C5—C4—C3	106.63 (19)	O17—C18—H182	110.3
C5—C4—H4	126.7	C19—C18—H182	110.3
C3—C4—H4	126.7	H181—C18—H182	108.5
N1—C5—C4	105.55 (18)	O19A—C19—O20	121.4 (8)
N1—C5—C23	123.02 (19)	O19B—C19—O20	124.4 (8)
C4—C5—C23	131.4 (2)	O19A—C19—C18	126.4 (8)
N1—C6—C14	112.34 (15)	O19B—C19—C18	122.4 (12)
N1—C6—H61	109.1	O20—C19—C18	109.8 (2)
C14—C6—H61	109.1	O20—C21—H211	109.5
N1—C6—H62	109.1	O20—C21—H212	109.5
C14—C6—H62	109.1	H211—C21—H212	109.5
H61—C6—H62	107.9	O20—C21—H213	109.5
O8—C8—O7	115.9 (2)	H211—C21—H213	109.5
O8—C8—C9	127.3 (3)	H212—C21—H213	109.5
O7—C8—C9	116.8 (2)	C3—C22—H221	109.5
C10—C9—C8	123.1 (2)	C3—C22—H222	109.5
C10—C9—H9	118.5	H221—C22—H222	109.5
C8—C9—H9	118.5	C3—C22—H223	109.5
C9—C10—C16	118.7 (2)	H221—C22—H223	109.5
C9—C10—C24	121.1 (2)	H222—C22—H223	109.5
C16—C10—C24	120.2 (2)	C5—C23—H231	109.5
C12—C11—C16	122.21 (19)	C5—C23—H232	109.5
C12—C11—H11	118.9	H231—C23—H232	109.5
C16—C11—H11	118.9	C5—C23—H233	109.5
C11—C12—C13	119.3 (2)	H231—C23—H233	109.5
C11—C12—H12	120.3	H232—C23—H233	109.5
C13—C12—H12	120.3	C10—C24—H241	109.5
O17—C13—C14	114.28 (17)	C10—C24—H242	109.5
O17—C13—C12	124.6 (2)	H241—C24—H242	109.5
C14—C13—C12	121.1 (2)	C10—C24—H243	109.5
C15—C14—C13	117.60 (18)	H241—C24—H243	109.5
C15—C14—C6	122.25 (18)	H242—C24—H243	109.5
C5—N1—N2—C3	−0.6 (2)	O17—C13—C14—C6	0.4 (3)
C6—N1—N2—C3	−175.80 (16)	C12—C13—C14—C6	179.36 (18)
N1—N2—C3—C4	0.7 (2)	N1—C6—C14—C15	102.4 (2)
N1—N2—C3—C22	−177.86 (18)	N1—C6—C14—C13	−78.3 (2)
N2—C3—C4—C5	−0.5 (2)	C13—C14—C15—O7	−179.06 (15)
C22—C3—C4—C5	177.9 (2)	C6—C14—C15—O7	0.3 (3)
N2—N1—C5—C4	0.3 (2)	C13—C14—C15—C16	0.6 (3)
C6—N1—C5—C4	175.11 (18)	C6—C14—C15—C16	179.92 (17)
N2—N1—C5—C23	179.81 (18)	C8—O7—C15—C14	179.04 (17)
C6—N1—C5—C23	−5.4 (3)	C8—O7—C15—C16	−0.6 (3)
C3—C4—C5—N1	0.1 (2)	C12—C11—C16—C15	−1.3 (3)
C3—C4—C5—C23	−179.3 (2)	C12—C11—C16—C10	179.08 (19)
C5—N1—C6—C14	144.92 (19)	C14—C15—C16—C11	0.6 (3)
N2—N1—C6—C14	−40.6 (2)	O7—C15—C16—C11	−179.70 (16)
C15—O7—C8—O8	−178.34 (19)	C14—C15—C16—C10	−179.68 (17)
C15—O7—C8—C9	0.8 (3)	O7—C15—C16—C10	0.0 (3)
O8—C8—C9—C10	178.8 (3)	C9—C10—C16—C11	−179.83 (19)
O7—C8—C9—C10	−0.2 (3)	C24—C10—C16—C11	−0.4 (3)
C8—C9—C10—C16	−0.4 (3)	C9—C10—C16—C15	0.5 (3)
C8—C9—C10—C24	−179.8 (2)	C24—C10—C16—C15	179.94 (19)
C16—C11—C12—C13	0.6 (3)	C13—O17—C18—C19	177.25 (18)
C18—O17—C13—C14	−173.71 (16)	C21—O20—C19—O19A	−18.5 (17)
C18—O17—C13—C12	7.3 (3)	C21—O20—C19—O19B	19 (3)
C11—C12—C13—O17	179.62 (19)	C21—O20—C19—C18	178.2 (2)
C11—C12—C13—C14	0.7 (3)	O17—C18—C19—O19A	18.0 (18)
O17—C13—C14—C15	179.69 (16)	O17—C18—C19—O19B	−20 (2)
C12—C13—C14—C15	−1.3 (3)	O17—C18—C19—O20	−179.69 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H182···Cg1^i	0.97	2.78	3.564 (3)	139

Symmetry code: (i) −x+1, −y+2, −z.