Dimethyl (7-hy­droxy-4-methyl-2-oxo-2H-chromen-3-yl)phospho­nate

In the title compound, C₁₂H₁₃O₆P, the coumarin ring system is essentially planar [dihedral angle between the rings = 1.32 (16)°] and the meth­oxy groups and double-bonded O atom of the phospho­nate group are disordered over two sets of sites [occupancy ratio 0.537 (2):0.463 (2)]. In the crystal, C—H...O hydrogen bonds involving the disordered phospho­nate O atom as acceptor occur, which generate [100] chains. Weak C—H...O and aromatic π–π stacking inter­actions [minimum centroid–centroid separation = 3.713 (2) Å] are also observed.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.058
• wR factor = 0.173
• Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0048 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      7.999 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2 Report
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Note

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          4 Note
PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ...          4 Report
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          1 Report
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          5 Report
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          2 Report
PLAT186_ALERT_4_G The CIF-Embedded .res File Contains ISOR Records          2 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1)..         26 % Note
PLAT395_ALERT_2_G Deviating  X-O-Y  Angle from 120 Deg for >O5          119.4 Degree
PLAT395_ALERT_2_G Deviating  X-O-Y  Angle from 120 Deg for >O6          125.4 Degree
PLAT395_ALERT_2_G Deviating  X-O-Y  Angle from 120 Deg for <O5A         123.3 Degree
PLAT395_ALERT_2_G Deviating  X-O-Y  Angle from 120 Deg for <O6A         117.2 Degree
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          ! Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         26 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          2 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          1 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  17 ALERT level G = General information/check it is not something unexpected

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


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

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Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Dimethyl (7-hydroxy-4-methyl-2-oxo-2H-chromen-3-yl)phosphonate

Crystal data

C12H13O6P	F(000) = 592
Mr = 284.19	Dx = 1.500 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.9684 (7) Å	Cell parameters from 1046 reflections
b = 7.8695 (6) Å	θ = 3.8–25.4°
c = 16.6927 (10) Å	µ = 0.24 mm^−1
β = 106.097 (7)°	T = 293 K
V = 1258.13 (16) Å^3	Prism, colourless
Z = 4	0.25 × 0.12 × 0.1 mm

Data collection

Agilent Xcalibur Eos diffractometer	2572 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	1364 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
Detector resolution: 16.2312 pixels mm^-1	θmax = 26.4°, θmin = 2.1°
ω scans	h = −12→11
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	k = −6→9
Tmin = 0.007, Tmax = 1.000	l = −20→20
5507 measured reflections

Refinement

Refinement on F^2	26 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.058	H-atom parameters constrained
wR(F^2) = 0.173	w = 1/[σ^2(Fo^2) + (0.0763P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
2572 reflections	Δρmax = 0.30 e Å^−3
194 parameters	Δρmin = −0.28 e Å^−3

Special details

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

Refinement. Aromatic H atoms were placed geometrically and refined as riding, with C—H = 0.93–0.97 Å, and with U_iso(H) = 1.2 U_eq(C). The H atoms associated to hydroxyl and methyl groups were refined as rotating groups, with U_iso(H) = 1.5 U_eq(C). The O5A—C11A and O6A—C12A bonds were refined with restrained distances of 1.55 (2) Å.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.4062 (3)	0.3873 (5)	0.6581 (2)	0.0552 (10)
C2	0.2791 (3)	0.3234 (4)	0.6012 (2)	0.0468 (8)
C3	0.2797 (3)	0.2579 (5)	0.5251 (2)	0.0486 (9)
C4	0.4104 (3)	0.2502 (4)	0.5029 (2)	0.0451 (8)
C5	0.5316 (3)	0.3061 (4)	0.56004 (19)	0.0450 (8)
C6	0.6615 (3)	0.3005 (5)	0.5456 (2)	0.0547 (10)
H6	0.7404	0.3383	0.5858	0.066*
C7	0.6715 (4)	0.2381 (5)	0.4706 (2)	0.0552 (10)
C8	0.5532 (4)	0.1831 (5)	0.4109 (2)	0.0617 (10)
H8	0.5604	0.1421	0.3600	0.074*
C9	0.4261 (4)	0.1891 (5)	0.4269 (2)	0.0562 (10)
H9	0.3476	0.1516	0.3862	0.067*
C10	0.1510 (3)	0.1924 (6)	0.4629 (2)	0.0725 (12)
H10A	0.0967	0.2863	0.4345	0.109*
H10B	0.0965	0.1275	0.4912	0.109*
H10C	0.1774	0.1213	0.4230	0.109*
C11	0.209 (3)	0.077 (3)	0.733 (2)	0.086 (5)	0.537 (2)
H11A	0.1408	0.0093	0.6941	0.129*	0.537 (2)
H11B	0.2170	0.0382	0.7888	0.129*	0.537 (2)
H11C	0.2979	0.0652	0.7215	0.129*	0.537 (2)
C11A	0.209 (4)	0.036 (4)	0.723 (2)	0.086 (5)	0.463 (2)
H11D	0.2358	−0.0589	0.6947	0.129*	0.463 (2)
H11E	0.1707	−0.0036	0.7660	0.129*	0.463 (2)
H11F	0.2893	0.1057	0.7466	0.129*	0.463 (2)
C12	0.151 (5)	0.598 (2)	0.738 (2)	0.085 (3)	0.537 (2)
H12A	0.2501	0.6123	0.7468	0.127*	0.537 (2)
H12B	0.1341	0.5309	0.7816	0.127*	0.537 (2)
H12C	0.1082	0.7076	0.7366	0.127*	0.537 (2)
C12A	0.153 (6)	0.609 (3)	0.727 (3)	0.085 (3)	0.463 (2)
H12D	0.1767	0.6525	0.6793	0.127*	0.463 (2)
H12E	0.2202	0.6479	0.7770	0.127*	0.463 (2)
H12F	0.0618	0.6493	0.7272	0.127*	0.463 (2)
O1	0.4182 (3)	0.4547 (4)	0.72427 (15)	0.0756 (9)
O2	0.5290 (2)	0.3705 (3)	0.63588 (13)	0.0581 (7)
O3	0.7946 (3)	0.2292 (4)	0.45079 (16)	0.0806 (9)
H3	0.8580	0.2619	0.4905	0.121*
O4	0.0015 (5)	0.2510 (8)	0.5818 (3)	0.0693 (13)	0.537 (2)
O4A	0.0032 (6)	0.3910 (9)	0.5761 (4)	0.0693 (13)	0.463 (2)
O5	0.1688 (5)	0.2446 (7)	0.7256 (3)	0.0615 (10)	0.537 (2)
O5A	0.1013 (5)	0.1394 (7)	0.6613 (3)	0.0615 (10)	0.463 (2)
O6	0.0938 (5)	0.5143 (6)	0.6592 (3)	0.0679 (11)	0.537 (2)
O6A	0.1527 (6)	0.4150 (8)	0.7252 (3)	0.0679 (11)	0.463 (2)
P1	0.12560 (9)	0.32787 (13)	0.63845 (6)	0.0535 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0398 (19)	0.077 (3)	0.052 (2)	0.0053 (19)	0.0172 (17)	0.003 (2)
C2	0.0335 (16)	0.054 (2)	0.0544 (19)	0.0022 (16)	0.0142 (15)	0.0028 (18)
C3	0.0357 (18)	0.050 (2)	0.059 (2)	0.0072 (16)	0.0105 (16)	0.0102 (18)
C4	0.0351 (17)	0.051 (2)	0.0491 (19)	0.0040 (16)	0.0114 (15)	0.0039 (16)
C5	0.0386 (18)	0.052 (2)	0.0452 (18)	0.0016 (16)	0.0134 (15)	0.0002 (16)
C6	0.0325 (17)	0.076 (3)	0.055 (2)	−0.0001 (17)	0.0104 (16)	0.0016 (19)
C7	0.0388 (19)	0.076 (3)	0.054 (2)	0.0070 (19)	0.0188 (17)	0.0088 (19)
C8	0.052 (2)	0.081 (3)	0.055 (2)	0.009 (2)	0.0203 (19)	−0.002 (2)
C9	0.0441 (19)	0.074 (3)	0.0492 (19)	0.0051 (19)	0.0100 (16)	−0.0008 (18)
C10	0.038 (2)	0.106 (4)	0.070 (2)	−0.003 (2)	0.0088 (18)	−0.015 (2)
C11	0.106 (4)	0.060 (11)	0.104 (5)	0.016 (7)	0.048 (5)	0.017 (7)
C11A	0.106 (4)	0.060 (11)	0.104 (5)	0.016 (7)	0.048 (5)	0.017 (7)
C12	0.081 (4)	0.076 (4)	0.102 (8)	0.012 (3)	0.035 (5)	−0.012 (3)
C12A	0.081 (4)	0.076 (4)	0.102 (8)	0.012 (3)	0.035 (5)	−0.012 (3)
O1	0.0553 (15)	0.117 (3)	0.0575 (15)	−0.0005 (16)	0.0202 (13)	−0.0220 (16)
O2	0.0334 (12)	0.088 (2)	0.0542 (14)	−0.0038 (12)	0.0136 (11)	−0.0117 (13)
O3	0.0454 (15)	0.130 (3)	0.0747 (17)	0.0084 (18)	0.0302 (14)	0.0004 (18)
O4	0.0325 (15)	0.106 (4)	0.069 (2)	−0.003 (3)	0.0146 (15)	−0.004 (3)
O4A	0.0325 (15)	0.106 (4)	0.069 (2)	−0.003 (3)	0.0146 (15)	−0.004 (3)
O5	0.059 (2)	0.064 (3)	0.069 (2)	0.0066 (19)	0.030 (2)	0.0139 (18)
O5A	0.059 (2)	0.064 (3)	0.069 (2)	0.0066 (19)	0.030 (2)	0.0139 (18)
O6	0.069 (3)	0.067 (3)	0.076 (3)	0.018 (2)	0.033 (2)	0.008 (2)
O6A	0.069 (3)	0.067 (3)	0.076 (3)	0.018 (2)	0.033 (2)	0.008 (2)
P1	0.0368 (5)	0.0680 (7)	0.0595 (6)	0.0055 (5)	0.0196 (4)	0.0059 (5)

Geometric parameters (Å, º)

C1—C2	1.446 (5)	C11—H11B	0.9600
C1—O1	1.200 (4)	C11—H11C	0.9600
C1—O2	1.381 (4)	C11—O5	1.38 (2)
C2—C3	1.373 (4)	C11A—H11D	0.9600
C2—P1	1.805 (3)	C11A—H11E	0.9600
C3—C4	1.451 (4)	C11A—H11F	0.9600
C3—C10	1.501 (5)	C11A—O5A	1.499 (19)
C4—C5	1.387 (4)	C12—H12A	0.9600
C4—C9	1.405 (4)	C12—H12B	0.9600
C5—C6	1.382 (4)	C12—H12C	0.9600
C5—O2	1.370 (4)	C12—O6	1.43 (4)
C6—H6	0.9300	C12A—H12D	0.9600
C6—C7	1.374 (5)	C12A—H12E	0.9600
C7—C8	1.385 (5)	C12A—H12F	0.9600
C7—O3	1.358 (4)	C12A—O6A	1.529 (19)
C8—H8	0.9300	O3—H3	0.8200
C8—C9	1.366 (4)	O4—P1	1.464 (5)
C9—H9	0.9300	O4A—P1	1.454 (6)
C10—H10A	0.9600	O5—P1	1.543 (4)
C10—H10B	0.9600	O5A—P1	1.567 (5)
C10—H10C	0.9600	O6—P1	1.561 (5)
C11—H11A	0.9600	O6A—P1	1.556 (6)
O1—C1—C2	127.1 (3)	O5—C11—H11C	109.5
O1—C1—O2	114.8 (3)	H11D—C11A—H11E	109.5
O2—C1—C2	118.0 (3)	H11D—C11A—H11F	109.5
C1—C2—P1	116.0 (2)	H11E—C11A—H11F	109.5
C3—C2—C1	120.7 (3)	O5A—C11A—H11D	109.5
C3—C2—P1	123.2 (3)	O5A—C11A—H11E	109.5
C2—C3—C4	119.1 (3)	O5A—C11A—H11F	109.5
C2—C3—C10	123.2 (3)	H12A—C12—H12B	109.5
C4—C3—C10	117.7 (3)	H12A—C12—H12C	109.5
C5—C4—C3	118.9 (3)	H12B—C12—H12C	109.5
C5—C4—C9	115.9 (3)	O6—C12—H12A	109.5
C9—C4—C3	125.2 (3)	O6—C12—H12B	109.5
C6—C5—C4	123.3 (3)	O6—C12—H12C	109.5
O2—C5—C4	121.1 (3)	H12D—C12A—H12E	109.5
O2—C5—C6	115.5 (3)	H12D—C12A—H12F	109.5
C5—C6—H6	120.7	H12E—C12A—H12F	109.5
C7—C6—C5	118.6 (3)	O6A—C12A—H12D	109.5
C7—C6—H6	120.7	O6A—C12A—H12E	109.5
C6—C7—C8	120.3 (3)	O6A—C12A—H12F	109.5
O3—C7—C6	122.6 (3)	C5—O2—C1	121.9 (3)
O3—C7—C8	117.1 (3)	C7—O3—H3	109.5
C7—C8—H8	120.0	C11—O5—P1	119.4 (15)
C9—C8—C7	120.0 (3)	C11A—O5A—P1	123.3 (17)
C9—C8—H8	120.0	C12—O6—P1	125.5 (12)
C4—C9—H9	119.0	C12A—O6A—P1	117.5 (19)
C8—C9—C4	121.9 (3)	O4—P1—C2	114.5 (2)
C8—C9—H9	119.0	O4—P1—O5	113.5 (3)
C3—C10—H10A	109.5	O4—P1—O6	110.2 (3)
C3—C10—H10B	109.5	O4A—P1—C2	112.6 (2)
C3—C10—H10C	109.5	O4A—P1—O5A	110.0 (3)
H10A—C10—H10B	109.5	O4A—P1—O6A	114.2 (3)
H10A—C10—H10C	109.5	O5—P1—C2	105.91 (19)
H10B—C10—H10C	109.5	O5—P1—O6	102.1 (3)
H11A—C11—H11B	109.5	O5A—P1—C2	105.6 (2)
H11A—C11—H11C	109.5	O6—P1—C2	109.8 (2)
H11B—C11—H11C	109.5	O6A—P1—C2	112.6 (2)
O5—C11—H11A	109.5	O6A—P1—O5A	100.9 (3)
O5—C11—H11B	109.5
C1—C2—C3—C4	1.3 (5)	C7—C8—C9—C4	0.0 (6)
C1—C2—C3—C10	−179.0 (3)	C9—C4—C5—C6	−1.2 (5)
C1—C2—P1—O4	−175.7 (4)	C9—C4—C5—O2	179.1 (3)
C1—C2—P1—O4A	135.4 (4)	C10—C3—C4—C5	−178.5 (3)
C1—C2—P1—O5	−49.9 (4)	C10—C3—C4—C9	1.3 (5)
C1—C2—P1—O5A	−104.6 (3)	C11—O5—P1—C2	−63.3 (18)
C1—C2—P1—O6	59.7 (3)	C11—O5—P1—O4	63.1 (18)
C1—C2—P1—O6A	4.6 (4)	C11—O5—P1—O6	−178.3 (18)
C2—C1—O2—C5	4.3 (5)	C11A—O5A—P1—C2	57 (2)
C2—C3—C4—C5	1.3 (5)	C11A—O5A—P1—O4A	179 (2)
C2—C3—C4—C9	−178.9 (3)	C11A—O5A—P1—O6A	−60 (2)
C3—C2—P1—O4	1.8 (4)	C12—O6—P1—C2	−87 (2)
C3—C2—P1—O4A	−47.0 (4)	C12—O6—P1—O4	146 (2)
C3—C2—P1—O5	127.6 (3)	C12—O6—P1—O5	25 (2)
C3—C2—P1—O5A	73.0 (4)	C12A—O6A—P1—C2	80 (2)
C3—C2—P1—O6	−122.8 (3)	C12A—O6A—P1—O4A	−50 (2)
C3—C2—P1—O6A	−177.9 (3)	C12A—O6A—P1—O5A	−168 (2)
C3—C4—C5—C6	178.6 (3)	O1—C1—C2—C3	176.1 (4)
C3—C4—C5—O2	−1.1 (5)	O1—C1—C2—P1	−6.3 (5)
C3—C4—C9—C8	−178.9 (4)	O1—C1—O2—C5	−175.8 (3)
C4—C5—C6—C7	0.6 (6)	O2—C1—C2—C3	−4.1 (5)
C4—C5—O2—C1	−1.8 (5)	O2—C1—C2—P1	173.5 (2)
C5—C4—C9—C8	0.9 (5)	O2—C5—C6—C7	−179.7 (3)
C5—C6—C7—C8	0.4 (6)	O3—C7—C8—C9	−179.9 (4)
C5—C6—C7—O3	179.5 (3)	P1—C2—C3—C4	−176.1 (2)
C6—C5—O2—C1	178.5 (3)	P1—C2—C3—C10	3.6 (5)
C6—C7—C8—C9	−0.7 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4^i	0.82	1.78	2.562 (6)	159
O3—H3···O4A^i	0.82	2.01	2.812 (7)	168
C8—H8···O1^ii	0.93	2.44	3.220 (4)	142
C10—H10B···O4	0.96	2.22	2.831 (6)	121
C12—H12A···O1	0.96	2.20	2.96 (5)	135

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