Meth­yl 4,6-dichloro­chroman-2-carboxyl­ate

In the title compound, C₁₁H₁₀Cl₂O₃, the six-membered heterocyclic ring adopts a half-chair conformation. An inter­molecular C—H...O hydrogen bond and π–π stacking are observed in the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 283 K
• R factor = 0.033
• wR factor = 0.091
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found


No errors found in this datablock

---

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Methyl 4,6-dichlorochroman-2-carboxylate

Crystal data

C11H10Cl2O3	F(000) = 1072
Mr = 261.09	Dx = 1.556 Mg m^−3
Monoclinic, C2/c	Melting point: 446 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 19.7026 (15) Å	Cell parameters from 4252 reflections
b = 11.2427 (8) Å	θ = 2.5–27.9°
c = 12.2043 (9) Å	µ = 0.57 mm^−1
β = 124.450 (1)°	T = 283 K
V = 2229.3 (3) Å^3	Block, colourless
Z = 8	0.60 × 0.30 × 0.20 mm

Data collection

Bruker SMART 4K CCD area-detector diffractometer	2187 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.019
Graphite monochromator	θmax = 27.0°, θmin = 2.2°
φ and ω scans	h = −17→24
6401 measured reflections	k = −14→13
2415 independent reflections	l = −15→14

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)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.092	w = 1/[σ^2(Fo^2) + (0.0513P)^2 + 1.1147P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.004
2415 reflections	Δρmax = 0.27 e Å^−3
147 parameters	Δρmin = −0.24 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0017 (4)

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
Cl2	0.07933 (2)	0.54872 (4)	0.19050 (4)	0.04866 (15)
Cl1	0.39805 (3)	0.78975 (4)	0.49626 (4)	0.04976 (15)
O2	0.04682 (7)	0.22256 (11)	0.40385 (12)	0.0525 (3)
O1	0.21511 (7)	0.42000 (10)	0.56485 (10)	0.0398 (3)
O3	0.16772 (7)	0.21170 (11)	0.60085 (12)	0.0493 (3)
C1	0.34196 (9)	0.67929 (13)	0.51253 (15)	0.0346 (3)
C6	0.28010 (9)	0.62034 (13)	0.40150 (14)	0.0335 (3)
H6	0.2679	0.6398	0.3181	0.040*
C3	0.31705 (10)	0.56669 (14)	0.65154 (14)	0.0385 (3)
H3	0.3292	0.5485	0.7352	0.046*
C5	0.23568 (8)	0.53123 (12)	0.41437 (13)	0.0296 (3)
C4	0.25430 (9)	0.50581 (13)	0.54028 (13)	0.0321 (3)
C10	0.12203 (9)	0.26120 (14)	0.49826 (14)	0.0346 (3)
C9	0.14010 (9)	0.37441 (13)	0.45157 (13)	0.0325 (3)
H9	0.0956	0.4319	0.4224	0.039*
C2	0.36101 (9)	0.65355 (14)	0.63818 (15)	0.0395 (3)
H2	0.4029	0.6944	0.7122	0.047*
C8	0.14883 (9)	0.34781 (13)	0.33758 (13)	0.0334 (3)
H8A	0.1911	0.2880	0.3652	0.040*
H8B	0.0973	0.3166	0.2624	0.040*
C7	0.17162 (9)	0.45997 (13)	0.29667 (13)	0.0326 (3)
H7	0.1938	0.4371	0.2452	0.039*
C11	0.02430 (13)	0.10921 (17)	0.4289 (2)	0.0619 (5)
H11A	0.0618	0.0494	0.4375	0.093*
H11B	−0.0306	0.0892	0.3562	0.093*
H11C	0.0266	0.1133	0.5095	0.093*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl2	0.0379 (2)	0.0486 (3)	0.0384 (2)	0.00029 (16)	0.00891 (18)	0.01002 (16)
Cl1	0.0497 (3)	0.0463 (3)	0.0532 (3)	−0.01560 (17)	0.0291 (2)	−0.00275 (17)
O2	0.0417 (6)	0.0473 (7)	0.0496 (7)	−0.0117 (5)	0.0144 (5)	0.0121 (5)
O1	0.0446 (6)	0.0444 (6)	0.0268 (5)	−0.0127 (5)	0.0180 (5)	−0.0017 (4)
O3	0.0470 (7)	0.0488 (7)	0.0426 (6)	0.0004 (5)	0.0196 (6)	0.0142 (5)
C1	0.0335 (7)	0.0303 (7)	0.0399 (8)	−0.0021 (5)	0.0206 (6)	−0.0004 (6)
C6	0.0344 (7)	0.0345 (7)	0.0309 (7)	0.0005 (6)	0.0181 (6)	0.0013 (5)
C3	0.0435 (8)	0.0412 (8)	0.0262 (7)	−0.0045 (6)	0.0169 (6)	−0.0027 (6)
C5	0.0288 (6)	0.0305 (7)	0.0267 (6)	0.0008 (5)	0.0141 (5)	−0.0009 (5)
C4	0.0326 (7)	0.0327 (7)	0.0296 (7)	−0.0006 (5)	0.0167 (6)	−0.0004 (5)
C10	0.0353 (7)	0.0357 (8)	0.0351 (7)	0.0014 (6)	0.0212 (6)	0.0024 (6)
C9	0.0323 (7)	0.0322 (7)	0.0302 (7)	−0.0018 (5)	0.0161 (6)	0.0013 (5)
C2	0.0372 (8)	0.0388 (8)	0.0330 (7)	−0.0059 (6)	0.0140 (6)	−0.0070 (6)
C8	0.0344 (7)	0.0333 (7)	0.0289 (7)	−0.0028 (5)	0.0157 (6)	−0.0027 (5)
C7	0.0323 (7)	0.0368 (7)	0.0255 (6)	−0.0020 (5)	0.0143 (6)	−0.0014 (5)
C11	0.0581 (11)	0.0456 (10)	0.0741 (13)	−0.0152 (9)	0.0327 (10)	0.0069 (9)

Geometric parameters (Å, º)

Cl2—C7	1.8208 (15)	C5—C4	1.3928 (19)
Cl1—C1	1.7467 (15)	C5—C7	1.4990 (18)
O2—C10	1.3344 (19)	C10—C9	1.517 (2)
O2—C11	1.438 (2)	C9—C8	1.5249 (18)
O1—C4	1.3707 (17)	C9—H9	0.9800
O1—C9	1.4306 (17)	C2—H2	0.9300
O3—C10	1.1885 (18)	C8—C7	1.5148 (19)
C1—C6	1.376 (2)	C8—H8A	0.9700
C1—C2	1.387 (2)	C8—H8B	0.9700
C6—C5	1.396 (2)	C7—H7	0.9800
C6—H6	0.9300	C11—H11A	0.9600
C3—C2	1.375 (2)	C11—H11B	0.9600
C3—C4	1.393 (2)	C11—H11C	0.9600
C3—H3	0.9300
C10—O2—C11	115.50 (13)	C10—C9—H9	109.7
C4—O1—C9	116.27 (10)	C8—C9—H9	109.7
C6—C1—C2	121.54 (13)	C3—C2—C1	118.98 (14)
C6—C1—Cl1	119.71 (11)	C3—C2—H2	120.5
C2—C1—Cl1	118.75 (12)	C1—C2—H2	120.5
C1—C6—C5	119.83 (13)	C7—C8—C9	110.18 (11)
C1—C6—H6	120.1	C7—C8—H8A	109.6
C5—C6—H6	120.1	C9—C8—H8A	109.6
C2—C3—C4	120.30 (14)	C7—C8—H8B	109.6
C2—C3—H3	119.8	C9—C8—H8B	109.6
C4—C3—H3	119.8	H8A—C8—H8B	108.1
C4—C5—C6	118.73 (13)	C5—C7—C8	112.02 (11)
C4—C5—C7	120.07 (12)	C5—C7—Cl2	110.46 (10)
C6—C5—C7	121.15 (12)	C8—C7—Cl2	109.14 (10)
O1—C4—C5	123.81 (12)	C5—C7—H7	108.4
O1—C4—C3	115.57 (12)	C8—C7—H7	108.4
C5—C4—C3	120.60 (13)	Cl2—C7—H7	108.4
O3—C10—O2	124.51 (14)	O2—C11—H11A	109.5
O3—C10—C9	126.14 (14)	O2—C11—H11B	109.5
O2—C10—C9	109.32 (12)	H11A—C11—H11B	109.5
O1—C9—C10	105.74 (11)	O2—C11—H11C	109.5
O1—C9—C8	111.34 (11)	H11A—C11—H11C	109.5
C10—C9—C8	110.47 (12)	H11B—C11—H11C	109.5
O1—C9—H9	109.7
C2—C1—C6—C5	−0.9 (2)	O3—C10—C9—O1	−11.0 (2)
Cl1—C1—C6—C5	179.40 (11)	O2—C10—C9—O1	170.92 (12)
C1—C6—C5—C4	1.3 (2)	O3—C10—C9—C8	109.61 (17)
C1—C6—C5—C7	−176.02 (13)	O2—C10—C9—C8	−68.50 (16)
C9—O1—C4—C5	−14.2 (2)	C4—C3—C2—C1	−0.1 (2)
C9—O1—C4—C3	167.20 (13)	C6—C1—C2—C3	0.3 (2)
C6—C5—C4—O1	−179.66 (13)	Cl1—C1—C2—C3	180.00 (12)
C7—C5—C4—O1	−2.3 (2)	O1—C9—C8—C7	−59.63 (15)
C6—C5—C4—C3	−1.1 (2)	C10—C9—C8—C7	−176.80 (12)
C7—C5—C4—C3	176.20 (13)	C4—C5—C7—C8	−13.47 (18)
C2—C3—C4—O1	179.19 (14)	C6—C5—C7—C8	163.80 (13)
C2—C3—C4—C5	0.5 (2)	C4—C5—C7—Cl2	108.42 (13)
C11—O2—C10—O3	−4.1 (3)	C6—C5—C7—Cl2	−74.31 (15)
C11—O2—C10—C9	174.08 (15)	C9—C8—C7—C5	42.64 (16)
C4—O1—C9—C10	164.99 (12)	C9—C8—C7—Cl2	−80.00 (12)
C4—O1—C9—C8	44.98 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O3^i	0.97	2.57	3.3173 (19)	134

Symmetry code: (i) −x+1/2, −y+1/2, −z+1.