Methyl [4-methoxy-3-(methyl­sulfonyl­oxy)­benzoyl]­formate

The crystal structure of the title compound, C₁₁H₁₂O₇S, confirms an earlier proposal concerning the regioselectivity of electrophilic substitution reactions of mesyl guaiacol.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.044
• wR factor = 0.124
• Data-to-parameter ratio = 13.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.80
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C7     -   C9     ...       1.53 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 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
   1 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: COLLECT (Nonius, 1998); cell refinement: COLLECT; data reduction: CORINC (Dräger, 1971); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Jonhson, 1976); software used to prepare material for publication: SHELXL97.

Methyl [4-methoxy-3-(methylsulfonyloxy)benzoyl]formate

Crystal data

C11H12O7S	Z = 2
Mr = 288.27	F(000) = 300
Triclinic, P1	Dx = 1.478 Mg m^−3
Hall symbol: -P 1	Melting point: 70 K
a = 8.4530 (15) Å	Cu Kα radiation, λ = 1.54178 Å
b = 8.6560 (12) Å	Cell parameters from 24 reflections
c = 10.7923 (12) Å	θ = 60–69°
α = 105.221 (10)°	µ = 2.50 mm^−1
β = 98.919 (12)°	T = 295 K
γ = 116.400 (13)°	Block, colourless
V = 647.9 (2) Å^3	0.32 × 0.22 × 0.22 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	2297 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.055
Graphite monochromator	θmax = 69.9°, θmin = 4.5°
θ/2ω scans	h = −10→0
Absorption correction: psi-scan (CORINC; Dräger, 1971)	k = −9→10
Tmin = 0.379, Tmax = 0.577	l = −12→13
2633 measured reflections	3 standard reflections every 60 min
2456 independent reflections	intensity decay: 3%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	Only H-atom displacement parameters refined
wR(F^2) = 0.124	w = 1/[σ^2(Fo^2) + (0.0747P)^2 + 0.1755P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
2456 reflections	Δρmax = 0.35 e Å^−3
182 parameters	Δρmin = −0.47 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0122 (15)

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	0.1418 (3)	0.3830 (3)	0.59345 (19)	0.0428 (4)
C2	0.2864 (3)	0.3464 (3)	0.5863 (2)	0.0474 (4)
C3	0.2529 (3)	0.1968 (3)	0.4756 (2)	0.0538 (5)
H3	0.3457	0.1681	0.4686	0.070 (7)*
C4	0.0822 (3)	0.0914 (3)	0.3763 (2)	0.0517 (5)
H4	0.0614	−0.0087	0.3034	0.057 (6)*
C5	−0.0601 (3)	0.1307 (3)	0.38233 (19)	0.0460 (4)
C6	−0.0266 (3)	0.2804 (2)	0.49425 (18)	0.0438 (4)
H6	−0.1190	0.3099	0.5010	0.056 (6)*
C7	−0.2371 (3)	0.0131 (3)	0.2719 (2)	0.0520 (5)
O8	−0.2684 (3)	−0.1227 (2)	0.17868 (18)	0.0762 (5)
C9	−0.3954 (3)	0.0539 (3)	0.27472 (19)	0.0487 (5)
O10	−0.4350 (2)	0.0957 (3)	0.37461 (16)	0.0691 (5)
O11	−0.4845 (2)	0.0264 (2)	0.15242 (14)	0.0559 (4)
C12	−0.6435 (3)	0.0519 (3)	0.1408 (2)	0.0613 (6)
H12A	−0.6898	0.0426	0.0505	0.081 (5)*
H12B	−0.6068	0.1725	0.2039	0.081 (5)*
H12C	−0.7394	−0.0423	0.1603	0.081 (5)*
O13	0.4475 (2)	0.4613 (2)	0.68826 (16)	0.0601 (4)
C14	0.6031 (3)	0.4362 (4)	0.6798 (3)	0.0696 (7)
H14A	0.7112	0.5329	0.7543	0.085 (5)*
H14B	0.6264	0.4416	0.5963	0.085 (5)*
H14C	0.5756	0.3174	0.6830	0.085 (5)*
O15	0.17735 (19)	0.53873 (18)	0.70199 (13)	0.0470 (3)
S16	0.09370 (6)	0.51135 (6)	0.82312 (5)	0.0474 (2)
O17	−0.0653 (2)	0.3305 (2)	0.77589 (16)	0.0647 (4)
O18	0.0740 (2)	0.6684 (2)	0.87165 (17)	0.0678 (5)
C19	0.2728 (4)	0.5294 (4)	0.9418 (2)	0.0671 (6)
H19A	0.3012	0.4357	0.9019	0.095 (6)*
H19B	0.2346	0.5121	1.0187	0.095 (6)*
H19C	0.3814	0.6502	0.9700	0.095 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0496 (10)	0.0413 (9)	0.0443 (9)	0.0278 (8)	0.0168 (8)	0.0164 (7)
C2	0.0479 (10)	0.0529 (10)	0.0522 (10)	0.0304 (9)	0.0184 (8)	0.0252 (9)
C3	0.0608 (12)	0.0619 (12)	0.0614 (12)	0.0441 (11)	0.0287 (10)	0.0270 (10)
C4	0.0629 (12)	0.0531 (11)	0.0517 (11)	0.0379 (10)	0.0253 (9)	0.0183 (9)
C5	0.0563 (11)	0.0449 (10)	0.0444 (10)	0.0310 (9)	0.0178 (8)	0.0171 (8)
C6	0.0508 (10)	0.0441 (10)	0.0459 (10)	0.0311 (8)	0.0157 (8)	0.0175 (8)
C7	0.0620 (12)	0.0476 (10)	0.0470 (10)	0.0310 (9)	0.0163 (9)	0.0134 (8)
O8	0.0840 (12)	0.0658 (10)	0.0625 (10)	0.0474 (10)	0.0035 (9)	−0.0050 (8)
C9	0.0484 (10)	0.0433 (10)	0.0436 (10)	0.0190 (8)	0.0120 (8)	0.0097 (8)
O10	0.0611 (10)	0.0965 (13)	0.0499 (8)	0.0433 (9)	0.0208 (7)	0.0199 (8)
O11	0.0526 (8)	0.0654 (9)	0.0452 (7)	0.0320 (7)	0.0120 (6)	0.0126 (6)
C12	0.0521 (12)	0.0668 (14)	0.0588 (13)	0.0327 (11)	0.0114 (10)	0.0136 (10)
O13	0.0471 (8)	0.0683 (10)	0.0647 (9)	0.0340 (7)	0.0122 (7)	0.0194 (8)
C14	0.0500 (12)	0.0877 (17)	0.0878 (17)	0.0422 (13)	0.0232 (12)	0.0432 (15)
O15	0.0504 (7)	0.0412 (7)	0.0467 (7)	0.0248 (6)	0.0122 (6)	0.0115 (5)
S16	0.0449 (3)	0.0491 (3)	0.0460 (3)	0.0271 (2)	0.0121 (2)	0.0101 (2)
O17	0.0571 (9)	0.0584 (9)	0.0640 (9)	0.0208 (7)	0.0232 (7)	0.0155 (7)
O18	0.0709 (10)	0.0654 (10)	0.0695 (10)	0.0470 (9)	0.0198 (8)	0.0074 (8)
C19	0.0701 (15)	0.0896 (17)	0.0523 (12)	0.0517 (14)	0.0142 (11)	0.0249 (12)

Geometric parameters (Å, º)

C1—C6	1.366 (3)	S16—O18	1.4160 (16)
C1—C2	1.401 (3)	S16—O17	1.4192 (17)
C1—O15	1.407 (2)	S16—C19	1.744 (2)
C2—O13	1.346 (3)	C3—H3	0.9300
C2—C3	1.393 (3)	C4—H4	0.9300
C3—C4	1.377 (3)	C6—H6	0.9300
C4—C5	1.394 (3)	C12—H12A	0.9600
C5—C6	1.402 (3)	C12—H12B	0.9600
C5—C7	1.467 (3)	C12—H12C	0.9600
C7—O8	1.218 (2)	C14—H14A	0.9600
C7—C9	1.531 (3)	C14—H14B	0.9600
C9—O10	1.192 (3)	C14—H14C	0.9600
C9—O11	1.317 (2)	C19—H19A	0.9600
O11—C12	1.449 (3)	C19—H19B	0.9600
O13—C14	1.437 (3)	C19—H19C	0.9600
O15—S16	1.6017 (15)
C6—C1—C2	122.07 (17)	O15—S16—C19	103.13 (10)
C6—C1—O15	119.50 (16)	C2—C3—H3	120.00
C2—C1—O15	118.28 (17)	C4—C3—H3	120.00
O13—C2—C3	125.66 (18)	C3—C4—H4	119.00
O13—C2—C1	116.33 (18)	C5—C4—H4	119.00
C3—C2—C1	118.02 (19)	C1—C6—H6	120.00
C4—C3—C2	120.04 (18)	C5—C6—H6	120.00
C3—C4—C5	121.78 (18)	O11—C12—H12A	109.00
C4—C5—C6	118.16 (19)	O11—C12—H12B	109.00
C4—C5—C7	118.46 (18)	O11—C12—H12C	109.00
C6—C5—C7	123.37 (18)	H12A—C12—H12B	110.00
C1—C6—C5	119.91 (17)	H12A—C12—H12C	109.00
O8—C7—C5	123.0 (2)	H12B—C12—H12C	109.00
O8—C7—C9	117.2 (2)	O13—C14—H14A	109.00
C5—C7—C9	119.74 (17)	O13—C14—H14B	109.00
O10—C9—O11	125.9 (2)	O13—C14—H14C	109.00
O10—C9—C7	123.21 (19)	H14A—C14—H14B	109.00
O11—C9—C7	110.75 (17)	H14A—C14—H14C	110.00
C9—O11—C12	116.00 (17)	H14B—C14—H14C	109.00
C2—O13—C14	117.93 (19)	S16—C19—H19A	109.00
C1—O15—S16	120.17 (12)	S16—C19—H19B	110.00
O18—S16—O17	119.22 (11)	S16—C19—H19C	109.00
O18—S16—O15	103.96 (9)	H19A—C19—H19B	109.00
O17—S16—O15	109.09 (9)	H19A—C19—H19C	109.00
O18—S16—C19	109.93 (12)	H19B—C19—H19C	110.00
O17—S16—C19	110.14 (13)
C6—C1—C2—O13	177.89 (17)	C4—C5—C7—C9	−179.34 (18)
O15—C1—C2—O13	2.4 (3)	C6—C5—C7—C9	1.0 (3)
C6—C1—C2—C3	−1.8 (3)	O8—C7—C9—O10	135.4 (2)
O15—C1—C2—C3	−177.29 (17)	C5—C7—C9—O10	−41.7 (3)
O13—C2—C3—C4	−178.84 (19)	O8—C7—C9—O11	−41.1 (3)
C1—C2—C3—C4	0.8 (3)	C5—C7—C9—O11	141.75 (18)
C2—C3—C4—C5	0.6 (3)	O10—C9—O11—C12	0.7 (3)
C3—C4—C5—C6	−1.0 (3)	C7—C9—O11—C12	177.17 (18)
C3—C4—C5—C7	179.34 (19)	C3—C2—O13—C14	3.9 (3)
C2—C1—C6—C5	1.4 (3)	C1—C2—O13—C14	−175.74 (19)
O15—C1—C6—C5	176.83 (16)	C6—C1—O15—S16	78.1 (2)
C4—C5—C6—C1	0.0 (3)	C2—C1—O15—S16	−106.28 (18)
C7—C5—C6—C1	179.68 (18)	C1—O15—S16—O18	−151.89 (14)
C4—C5—C7—O8	3.7 (3)	C1—O15—S16—O17	−23.70 (16)
C6—C5—C7—O8	−176.0 (2)	C1—O15—S16—C19	93.36 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O10^i	0.93	2.48	3.371 (3)	161
C19—H19A···O8^ii	0.96	2.49	3.399 (3)	158

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