rac-3,9-Bis(3-chloro-phen-yl)-2,4,8,10-tetra-oxaspiro-[5.5]undeca-ne.

In the title compound, C(19)H(18)Cl(2)O(4), the two non-planar six-membered heterocycles passing through the spiro-C atom both adopt chair conformations, and the dihedral angle between the two benzene rings is 7.2 (1)°. In the crystal, the enanti-omers with R and S configurations are generated by the symmetry elements of the centrosymmetric space group, forming a racemic crystal. Inter-molecular C-H⋯π and weak C-H⋯O inter-actions link the mol-ecules in the crystal structure.

Related literature

For general background to spiranes, see: Cismaş et al. (2005 ▶); Mihiş et al. (2008 ▶); Sun et al. (2010 ▶).

Experimental

Crystal data

C19H18Cl2O4

M = 381.23

Monoclinic,

a = 13.0924 (13) Å

b = 5.8473 (6) Å

c = 23.061 (2) Å

β = 92.865 (2)°

V = 1763.2 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.39 mm−1

T = 296 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.892, T max = 0.926

9216 measured reflections

3083 independent reflections

2669 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.091

S = 1.01

3083 reflections

227 parameters

H-atom parameters constrained

Δρmax = 0.23 e Å−3

Δρmin = −0.37 e Å−3

Data collection: APEX2 (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811037172/kp2345sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037172/kp2345Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811037172/kp2345Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C19H18Cl2O4	F(000) = 792
Mr = 381.23	Dx = 1.436 Mg m−3
Monoclinic, P21/c	Melting point: 397 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.0924 (13) Å	Cell parameters from 5568 reflections
b = 5.8473 (6) Å	θ = 2.4–30.2°
c = 23.061 (2) Å	µ = 0.39 mm−1
β = 92.865 (2)°	T = 296 K
V = 1763.2 (3) Å3	PRISM, colourless
Z = 4	0.30 × 0.20 × 0.20 mm

Bruker APEXII CCD diffractometer	3083 independent reflections
Radiation source: fine-focus sealed tube	2669 reflections with I > 2σ(I)
graphite	Rint = 0.044
φ and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −15→15
Tmin = 0.892, Tmax = 0.926	k = −6→6
9216 measured reflections	l = −27→23

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034	H-atom parameters constrained
wR(F2) = 0.091	w = 1/[σ2(Fo2) + (0.045P)2 + 0.585P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max = 0.001
3083 reflections	Δρmax = 0.23 e Å−3
227 parameters	Δρmin = −0.37 e Å−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0101 (15)

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.

	x	y	z	Uiso*/Ueq
Cl1	1.44666 (4)	−0.09142 (9)	0.42374 (2)	0.06281 (18)
Cl2	0.60790 (4)	0.03575 (11)	0.87193 (2)	0.0707 (2)
C10	1.00108 (11)	−0.0663 (3)	0.63687 (6)	0.0355 (3)
C7	1.18050 (11)	0.0270 (3)	0.57866 (6)	0.0381 (4)
H7	1.2282	−0.0646	0.6032	0.046*
C13	0.81522 (11)	0.0410 (3)	0.68608 (6)	0.0367 (3)
H13	0.7765	−0.0790	0.6650	0.044*
C14	0.74431 (11)	0.1662 (3)	0.72470 (6)	0.0365 (3)
C6	1.23665 (11)	0.1316 (3)	0.52994 (6)	0.0360 (3)
C9	1.08461 (12)	0.0975 (3)	0.65948 (7)	0.0437 (4)
H9A	1.0544	0.2177	0.6820	0.052*
H9B	1.1333	0.0154	0.6848	0.052*
C12	0.91461 (12)	0.0658 (3)	0.60524 (6)	0.0426 (4)
H12A	0.9431	0.1715	0.5779	0.051*
H12B	0.8704	−0.0401	0.5835	0.051*
C19	0.71569 (12)	0.0629 (3)	0.77554 (7)	0.0407 (4)
H19	0.7439	−0.0767	0.7871	0.049*
C18	0.64487 (12)	0.1693 (3)	0.80883 (7)	0.0452 (4)
C1	1.31014 (11)	−0.0007 (3)	0.50473 (7)	0.0383 (3)
H1	1.3269	−0.1442	0.5198	0.046*
C11	0.95635 (13)	−0.2022 (3)	0.68599 (7)	0.0466 (4)
H11A	0.9156	−0.3274	0.6697	0.056*
H11B	1.0116	−0.2670	0.7103	0.056*
C15	0.70256 (13)	0.3758 (3)	0.70861 (8)	0.0475 (4)
H15	0.7217	0.4465	0.6747	0.057*
C2	1.35834 (12)	0.0819 (3)	0.45714 (7)	0.0413 (4)
C8	1.04953 (14)	−0.2341 (3)	0.59572 (8)	0.0479 (4)
H8A	1.0958	−0.3346	0.6178	0.057*
H8B	0.9965	−0.3276	0.5768	0.057*
C3	1.33736 (13)	0.2967 (3)	0.43493 (7)	0.0471 (4)
H3	1.3716	0.3520	0.4035	0.057*
C5	1.21370 (13)	0.3469 (3)	0.50771 (7)	0.0451 (4)
H5	1.1645	0.4368	0.5244	0.054*
C17	0.60229 (13)	0.3780 (3)	0.79319 (8)	0.0533 (5)
H17	0.5546	0.4477	0.8160	0.064*
C4	1.26424 (14)	0.4277 (3)	0.46054 (8)	0.0505 (4)
H4	1.2487	0.5724	0.4459	0.061*
C16	0.63242 (14)	0.4803 (3)	0.74285 (9)	0.0567 (5)
H16	0.6052	0.6216	0.7318	0.068*
O3	0.89369 (8)	−0.06191 (19)	0.72093 (4)	0.0415 (3)
O1	1.10447 (8)	−0.11743 (19)	0.55266 (5)	0.0421 (3)
O4	0.85569 (8)	0.1908 (2)	0.64567 (4)	0.0429 (3)
O2	1.13674 (8)	0.19688 (19)	0.61245 (5)	0.0441 (3)

	U11	U22	U33	U12	U13	U23
Cl1	0.0534 (3)	0.0747 (4)	0.0629 (3)	0.0064 (2)	0.0281 (2)	−0.0002 (2)
Cl2	0.0728 (3)	0.0869 (4)	0.0552 (3)	−0.0017 (3)	0.0312 (2)	0.0047 (3)
C10	0.0400 (8)	0.0339 (8)	0.0332 (7)	0.0029 (6)	0.0077 (6)	−0.0012 (6)
C7	0.0375 (8)	0.0435 (9)	0.0333 (8)	0.0046 (7)	0.0032 (6)	−0.0027 (6)
C13	0.0374 (8)	0.0396 (8)	0.0333 (8)	−0.0012 (6)	0.0030 (6)	−0.0001 (6)
C14	0.0320 (7)	0.0410 (8)	0.0365 (8)	−0.0008 (6)	0.0015 (6)	−0.0031 (6)
C6	0.0364 (8)	0.0403 (8)	0.0314 (7)	−0.0037 (6)	0.0015 (6)	−0.0043 (6)
C9	0.0440 (8)	0.0575 (10)	0.0301 (8)	−0.0008 (8)	0.0061 (6)	−0.0084 (7)
C12	0.0412 (8)	0.0578 (10)	0.0293 (7)	0.0037 (7)	0.0056 (6)	0.0027 (7)
C19	0.0395 (8)	0.0414 (9)	0.0415 (8)	−0.0005 (7)	0.0050 (7)	−0.0017 (7)
C18	0.0392 (8)	0.0554 (10)	0.0417 (9)	−0.0061 (8)	0.0099 (7)	−0.0063 (7)
C1	0.0373 (8)	0.0393 (8)	0.0384 (8)	−0.0006 (7)	0.0029 (6)	0.0014 (6)
C11	0.0546 (10)	0.0402 (9)	0.0467 (9)	0.0128 (8)	0.0180 (7)	0.0077 (7)
C15	0.0473 (9)	0.0479 (10)	0.0478 (9)	0.0060 (8)	0.0067 (7)	0.0053 (8)
C2	0.0353 (8)	0.0496 (9)	0.0394 (8)	−0.0052 (7)	0.0057 (6)	−0.0027 (7)
C8	0.0592 (10)	0.0354 (9)	0.0511 (9)	−0.0028 (8)	0.0229 (8)	−0.0051 (7)
C3	0.0516 (9)	0.0505 (10)	0.0395 (8)	−0.0119 (8)	0.0049 (7)	0.0046 (7)
C5	0.0533 (9)	0.0393 (9)	0.0426 (9)	0.0041 (7)	0.0032 (7)	−0.0061 (7)
C17	0.0423 (9)	0.0600 (11)	0.0587 (11)	0.0058 (8)	0.0130 (8)	−0.0143 (9)
C4	0.0662 (11)	0.0379 (9)	0.0471 (9)	−0.0035 (8)	0.0004 (8)	0.0042 (7)
C16	0.0528 (10)	0.0491 (10)	0.0686 (12)	0.0148 (9)	0.0065 (9)	−0.0016 (9)
O3	0.0461 (6)	0.0455 (6)	0.0338 (5)	0.0124 (5)	0.0106 (5)	0.0071 (5)
O1	0.0510 (6)	0.0384 (6)	0.0382 (6)	−0.0059 (5)	0.0149 (5)	−0.0094 (5)
O4	0.0453 (6)	0.0475 (6)	0.0369 (6)	0.0117 (5)	0.0112 (5)	0.0103 (5)
O2	0.0475 (6)	0.0464 (6)	0.0395 (6)	−0.0082 (5)	0.0139 (5)	−0.0138 (5)

Cl1—C2	1.7456 (16)	C12—H12B	0.9700
Cl2—C18	1.7413 (17)	C19—C18	1.381 (2)
C10—C11	1.524 (2)	C19—H19	0.9300
C10—C8	1.525 (2)	C18—C17	1.382 (3)
C10—C9	1.526 (2)	C1—C2	1.380 (2)
C10—C12	1.526 (2)	C1—H1	0.9300
C7—O2	1.4026 (18)	C11—O3	1.4356 (18)
C7—O1	1.4153 (19)	C11—H11A	0.9700
C7—C6	1.503 (2)	C11—H11B	0.9700
C7—H7	0.9800	C15—C16	1.383 (2)
C13—O4	1.4019 (18)	C15—H15	0.9300
C13—O3	1.4074 (18)	C2—C3	1.379 (2)
C13—C14	1.508 (2)	C8—O1	1.4285 (19)
C13—H13	0.9800	C8—H8A	0.9700
C14—C15	1.385 (2)	C8—H8B	0.9700
C14—C19	1.387 (2)	C3—C4	1.382 (2)
C6—C1	1.385 (2)	C3—H3	0.9300
C6—C5	1.387 (2)	C5—C4	1.384 (2)
C9—O2	1.4332 (19)	C5—H5	0.9300
C9—H9A	0.9700	C17—C16	1.381 (3)
C9—H9B	0.9700	C17—H17	0.9300
C12—O4	1.4388 (18)	C4—H4	0.9300
C12—H12A	0.9700	C16—H16	0.9300
C11—C10—C8	108.33 (13)	C17—C18—Cl2	119.26 (13)
C11—C10—C9	111.63 (14)	C2—C1—C6	119.55 (15)
C8—C10—C9	107.65 (13)	C2—C1—H1	120.2
C11—C10—C12	108.41 (13)	C6—C1—H1	120.2
C8—C10—C12	110.49 (13)	O3—C11—C10	111.77 (12)
C9—C10—C12	110.32 (14)	O3—C11—H11A	109.3
O2—C7—O1	111.08 (12)	C10—C11—H11A	109.3
O2—C7—C6	110.82 (13)	O3—C11—H11B	109.3
O1—C7—C6	106.63 (12)	C10—C11—H11B	109.3
O2—C7—H7	109.4	H11A—C11—H11B	107.9
O1—C7—H7	109.4	C16—C15—C14	120.17 (16)
C6—C7—H7	109.4	C16—C15—H15	119.9
O4—C13—O3	110.93 (12)	C14—C15—H15	119.9
O4—C13—C14	110.70 (12)	C3—C2—C1	121.58 (15)
O3—C13—C14	108.89 (12)	C3—C2—Cl1	119.28 (12)
O4—C13—H13	108.8	C1—C2—Cl1	119.14 (13)
O3—C13—H13	108.8	O1—C8—C10	111.40 (13)
C14—C13—H13	108.8	O1—C8—H8A	109.3
C15—C14—C19	119.48 (15)	C10—C8—H8A	109.3
C15—C14—C13	121.20 (14)	O1—C8—H8B	109.3
C19—C14—C13	119.21 (14)	C10—C8—H8B	109.3
C1—C6—C5	119.62 (14)	H8A—C8—H8B	108.0
C1—C6—C7	117.54 (14)	C2—C3—C4	118.41 (15)
C5—C6—C7	122.74 (14)	C2—C3—H3	120.8
O2—C9—C10	110.88 (12)	C4—C3—H3	120.8
O2—C9—H9A	109.5	C4—C5—C6	119.81 (16)
C10—C9—H9A	109.5	C4—C5—H5	120.1
O2—C9—H9B	109.5	C6—C5—H5	120.1
C10—C9—H9B	109.5	C16—C17—C18	118.26 (16)
H9A—C9—H9B	108.1	C16—C17—H17	120.9
O4—C12—C10	110.87 (12)	C18—C17—H17	120.9
O4—C12—H12A	109.5	C3—C4—C5	121.02 (16)
C10—C12—H12A	109.5	C3—C4—H4	119.5
O4—C12—H12B	109.5	C5—C4—H4	119.5
C10—C12—H12B	109.5	C17—C16—C15	120.94 (17)
H12A—C12—H12B	108.1	C17—C16—H16	119.5
C18—C19—C14	119.40 (15)	C15—C16—H16	119.5
C18—C19—H19	120.3	C13—O3—C11	110.19 (12)
C14—C19—H19	120.3	C7—O1—C8	111.00 (12)
C19—C18—C17	121.73 (16)	C13—O4—C12	110.26 (12)
C19—C18—Cl2	119.00 (14)	C7—O2—C9	110.87 (12)
O4—C13—C14—C15	19.0 (2)	C6—C1—C2—Cl1	−177.16 (11)
O3—C13—C14—C15	141.19 (15)	C11—C10—C8—O1	−172.53 (14)
O4—C13—C14—C19	−164.95 (13)	C9—C10—C8—O1	−51.68 (18)
O3—C13—C14—C19	−42.74 (18)	C12—C10—C8—O1	68.85 (18)
O2—C7—C6—C1	159.48 (13)	C1—C2—C3—C4	−1.7 (2)
O1—C7—C6—C1	−79.51 (16)	Cl1—C2—C3—C4	177.45 (13)
O2—C7—C6—C5	−24.2 (2)	C1—C6—C5—C4	0.1 (2)
O1—C7—C6—C5	96.80 (17)	C7—C6—C5—C4	−176.16 (15)
C11—C10—C9—O2	170.89 (12)	C19—C18—C17—C16	−0.1 (3)
C8—C10—C9—O2	52.13 (17)	Cl2—C18—C17—C16	−179.73 (15)
C12—C10—C9—O2	−68.50 (16)	C2—C3—C4—C5	0.6 (3)
C11—C10—C12—O4	50.16 (18)	C6—C5—C4—C3	0.2 (3)
C8—C10—C12—O4	168.73 (13)	C18—C17—C16—C15	0.7 (3)
C9—C10—C12—O4	−72.36 (16)	C14—C15—C16—C17	−0.4 (3)
C15—C14—C19—C18	0.9 (2)	O4—C13—O3—C11	−63.94 (16)
C13—C14—C19—C18	−175.20 (14)	C14—C13—O3—C11	173.99 (12)
C14—C19—C18—C17	−0.7 (2)	C10—C11—O3—C13	56.69 (18)
C14—C19—C18—Cl2	178.92 (12)	O2—C7—O1—C8	−61.88 (16)
C5—C6—C1—C2	−1.1 (2)	C6—C7—O1—C8	177.28 (12)
C7—C6—C1—C2	175.31 (14)	C10—C8—O1—C7	57.07 (18)
C8—C10—C11—O3	−169.67 (13)	O3—C13—O4—C12	64.98 (15)
C9—C10—C11—O3	71.97 (18)	C14—C13—O4—C12	−174.01 (11)
C12—C10—C11—O3	−49.75 (18)	C10—C12—O4—C13	−58.23 (16)
C19—C14—C15—C16	−0.4 (3)	O1—C7—O2—C9	62.62 (16)
C13—C14—C15—C16	175.67 (16)	C6—C7—O2—C9	−179.05 (12)
C6—C1—C2—C3	2.0 (2)	C10—C9—O2—C7	−58.53 (16)

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···Cg1i	0.97	2.70	3.632 (2)	162.
C9—H9A···O3ii	0.97	2.64	3.402 (2)	135.
C11—H11B···O3iii	0.97	2.61	3.530 (2)	158.

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12B⋯Cg1i	0.97	2.70	3.632 (2)	162
C9—H9A⋯O3ii	0.97	2.64	3.402 (2)	135
C11—H11B⋯O3iii	0.97	2.61	3.530 (2)	158

Symmetry codes: (i) ; (ii) ; (iii) .