3,4:9,10-Dibenzo-1,12-di­formyl-5,8-dioxodo­decane

In the title compound, C₁₆H₁₄O₄, the dihedral angle between the two aromatic rings is 75.8 (1)°. The torsion angle about the central C—C bond is 77.2 (3)°. The packing of the mol­ecules in the solid state is stabilized by C—H...O, C—H...π and π–π intermolecular interactions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.086
• wR factor = 0.240
• Data-to-parameter ratio = 17.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Polyether compounds are of much recent interest due to their remarkable metal ion selectivity, ability to transport alkali metal ion through biological and artificial membranes and their utilization to organic synthetic procedures (Armstrong & Lindoy, 1975; Grimsley et al., 1977).

The bond lengths and angles of the title compound, (I), agree with the values reported for 2,2'-[1,2-ethanediylbis(oxy)](benzenemethanol) (Bailey et al., 1989). The dihedral angle between the phenyl rings A (C2–C7) and B (C10–C15) is 75.9 (1)°. Atoms O1/C1/O2/C8 and atoms O4/C16/O3/C9 lie almost on their respective phenyl ring planes [the deviations of the above atoms are 0.020 (3), 0.058 (4), −0.010 (2) and −0.040 (4) Å, and −0.101 (4), −0.030 (5), 0.050 (3) and 0.012 (4) Å, respectively]. The methylene group between the phenyl rings has the gauche form and the torsion angle about the C8—C9 bond is 77.2 (4)°, so the molecule is twisted.

The molecules are linked by weak C—H···O interactions and form an infinite chain running along the a direction (Fig. 2). The face-to-face interactions are between A and A^iv, and B and B^v, which stack in the lattice along b and a axis, respectively, with centroid–centroid distances of 3.784 (2) and 3.731 (2) Å, respectively [symmetry codes: (iv) 1 − x, 1 − y, −z; (v) −x, 2 − y, 1 − z]. Apart from these weak π–π interactions, the packing of the molecules in the solid state is stabilized by C—H···O and C—H···π intermolecular interactions (Table 2).

S2. Experimental

1,2-Dibromoethane (9.396 g, 0.05 mol) in methanol (10 ml) was added to salicylaldehyde (9.052 g, 0.1 mol) in methanol (30 ml) and the solution was heated. Sodium hydroxide pellets (4 g, 0.1 mol) in water (15 ml) was added and the reaction mixture was refluxed under N₂ atmosphere for nearly 48 h. Then the resulting solution was allowed to cool at room temperature (298 K). The solid obtained was filtered and washed with water and methanol. The crystals were obtained by recrystallization from chloroform.

S3. Refinement

All the H atoms were geometrically positioned and were treated as riding on their parent atoms, with C—H distances in the range 0.93–0.97 Å.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997) and PLATON (Spek, 1990); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).

Figures

	Fig. 1. The molecular structure, with the atom-numbering scheme. Ellipsoids are drawn at the 35% probability level.
	Fig. 2. A packing diagram of the molecule, viewed down the a axis. π–π and C—H···O interactions are indicated by dashed lines.

3,4:9,10-dibenzo-1,12-diformyl-5,8-dioxododecane

Crystal data

C16H14O4	Z = 2
Mr = 270.27	F(000) = 284
Triclinic, P1	Dx = 1.334 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7956 (7) Å	Cell parameters from 1815 reflections
b = 8.4511 (8) Å	θ = 1.8–28.3°
c = 11.4697 (11) Å	µ = 0.10 mm^−1
α = 83.054 (2)°	T = 293 K
β = 75.008 (2)°	Block, yellow
γ = 67.219 (2)°	0.36 × 0.24 × 0.16 mm
V = 672.80 (11) Å^3

Data collection

Siemens SMART CCD area-detector diffractometer	1273 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.064
Graphite monochromator	θmax = 28.3°, θmin = 1.8°
ω scans	h = −10→9
4829 measured reflections	k = −10→11
3172 independent reflections	l = −15→15

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)] = 0.086	H-atom parameters constrained
wR(F^2) = 0.240	w = 1/[σ^2(Fo^2) + (0.1202P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.83	(Δ/σ)max < 0.001
3172 reflections	Δρmax = 0.37 e Å^−3
182 parameters	Δρmin = −0.38 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: 0.036 (10)

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
O1	0.0784 (4)	0.7888 (4)	−0.0461 (2)	0.0759 (9)
O2	0.4719 (3)	0.8211 (3)	0.09749 (19)	0.0488 (7)
O3	0.4016 (3)	0.8694 (3)	0.35573 (18)	0.0482 (7)
O4	0.2152 (5)	0.5866 (4)	0.6190 (3)	0.0837 (10)
C1	0.2041 (5)	0.7996 (5)	−0.0087 (3)	0.0537 (10)
H1	0.1678	0.8658	0.0589	0.064*
C2	0.4092 (5)	0.7172 (4)	−0.0607 (3)	0.0412 (8)
C3	0.4717 (5)	0.6241 (4)	−0.1657 (3)	0.0512 (9)
H3	0.3831	0.6114	−0.2009	0.061*
C4	0.6634 (6)	0.5510 (5)	−0.2176 (3)	0.0598 (10)
H4	0.7047	0.4898	−0.2882	0.072*
C5	0.7954 (5)	0.5688 (5)	−0.1642 (3)	0.0568 (10)
H5	0.9251	0.5198	−0.2001	0.068*
C6	0.7384 (5)	0.6571 (4)	−0.0596 (3)	0.0471 (9)
H6	0.8284	0.6681	−0.0247	0.056*
C7	0.5440 (4)	0.7302 (4)	−0.0063 (3)	0.0385 (8)
C8	0.6004 (5)	0.8395 (5)	0.1585 (3)	0.0501 (9)
H8A	0.6890	0.8842	0.1031	0.060*
H8B	0.6734	0.7289	0.1900	0.060*
C9	0.4851 (5)	0.9606 (5)	0.2593 (3)	0.0494 (9)
H9A	0.5663	1.0036	0.2868	0.059*
H9B	0.3856	1.0574	0.2321	0.059*
C10	0.2935 (4)	0.9571 (4)	0.4586 (3)	0.0396 (8)
C11	0.2198 (5)	0.8611 (4)	0.5527 (3)	0.0426 (8)
C12	0.1026 (5)	0.9452 (5)	0.6585 (3)	0.0537 (9)
H12	0.0524	0.8838	0.7215	0.064*
C13	0.0600 (6)	1.1148 (5)	0.6716 (3)	0.0606 (10)
H13	−0.0202	1.1691	0.7423	0.073*
C14	0.1370 (6)	1.2064 (5)	0.5788 (3)	0.0598 (10)
H14	0.1107	1.3218	0.5883	0.072*
C15	0.2512 (5)	1.1281 (5)	0.4734 (3)	0.0498 (9)
H15	0.3006	1.1912	0.4114	0.060*
C16	0.2658 (6)	0.6784 (5)	0.5405 (3)	0.0594 (10)
H16	0.3395	0.6293	0.4669	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0534 (17)	0.103 (2)	0.087 (2)	−0.0422 (17)	−0.0279 (15)	0.0081 (17)
O2	0.0387 (13)	0.0626 (16)	0.0484 (13)	−0.0209 (11)	−0.0072 (11)	−0.0129 (12)
O3	0.0607 (15)	0.0429 (14)	0.0437 (13)	−0.0250 (12)	−0.0075 (12)	−0.0010 (11)
O4	0.115 (3)	0.0615 (19)	0.083 (2)	−0.0504 (19)	−0.0168 (18)	0.0162 (16)
C1	0.048 (2)	0.070 (3)	0.048 (2)	−0.0315 (19)	−0.0087 (18)	0.0065 (19)
C2	0.0451 (19)	0.0428 (19)	0.0406 (17)	−0.0235 (15)	−0.0097 (15)	0.0056 (15)
C3	0.064 (2)	0.048 (2)	0.052 (2)	−0.0286 (19)	−0.0203 (19)	0.0044 (18)
C4	0.077 (3)	0.053 (2)	0.046 (2)	−0.026 (2)	−0.004 (2)	−0.0108 (18)
C5	0.050 (2)	0.054 (2)	0.055 (2)	−0.0159 (18)	0.0041 (18)	−0.0071 (18)
C6	0.042 (2)	0.050 (2)	0.052 (2)	−0.0220 (16)	−0.0084 (17)	−0.0016 (17)
C7	0.0402 (19)	0.0394 (18)	0.0359 (16)	−0.0181 (14)	−0.0039 (15)	−0.0003 (15)
C8	0.0418 (19)	0.065 (2)	0.050 (2)	−0.0265 (17)	−0.0120 (17)	−0.0013 (18)
C9	0.052 (2)	0.056 (2)	0.0446 (18)	−0.0286 (18)	−0.0079 (17)	0.0022 (17)
C10	0.0429 (18)	0.042 (2)	0.0403 (17)	−0.0176 (15)	−0.0173 (15)	−0.0030 (15)
C11	0.049 (2)	0.044 (2)	0.0434 (18)	−0.0225 (16)	−0.0198 (16)	0.0065 (16)
C12	0.057 (2)	0.064 (3)	0.0440 (19)	−0.0267 (19)	−0.0128 (18)	0.0022 (18)
C13	0.068 (3)	0.058 (3)	0.051 (2)	−0.020 (2)	−0.0053 (19)	−0.014 (2)
C14	0.075 (3)	0.050 (2)	0.060 (2)	−0.025 (2)	−0.020 (2)	−0.005 (2)
C15	0.060 (2)	0.046 (2)	0.049 (2)	−0.0254 (18)	−0.0153 (18)	0.0005 (17)
C16	0.071 (3)	0.055 (2)	0.058 (2)	−0.028 (2)	−0.018 (2)	0.003 (2)

Geometric parameters (Å, º)

O1—C1	1.204 (4)	C8—C9	1.493 (4)
O2—C7	1.365 (3)	C8—H8A	0.9700
O2—C8	1.423 (3)	C8—H8B	0.9700
O3—C10	1.365 (4)	C9—H9A	0.9700
O3—C9	1.432 (3)	C9—H9B	0.9700
O4—C16	1.205 (4)	C10—C15	1.374 (4)
C1—C2	1.464 (5)	C10—C11	1.408 (4)
C1—H1	0.9300	C11—C12	1.394 (5)
C2—C3	1.391 (4)	C11—C16	1.459 (5)
C2—C7	1.397 (4)	C12—C13	1.358 (5)
C3—C4	1.372 (5)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.386 (5)
C4—C5	1.387 (5)	C13—H13	0.9300
C4—H4	0.9300	C14—C15	1.368 (5)
C5—C6	1.370 (4)	C14—H14	0.9300
C5—H5	0.9300	C15—H15	0.9300
C6—C7	1.393 (4)	C16—H16	0.9300
C6—H6	0.9300
C7—O2—C8	119.2 (2)	H8A—C8—H8B	108.4
C10—O3—C9	117.3 (2)	O3—C9—C8	108.1 (3)
O1—C1—C2	125.5 (4)	O3—C9—H9A	110.1
O1—C1—H1	117.2	C8—C9—H9A	110.1
C2—C1—H1	117.2	O3—C9—H9B	110.1
C3—C2—C7	119.3 (3)	C8—C9—H9B	110.1
C3—C2—C1	119.8 (3)	H9A—C9—H9B	108.4
C7—C2—C1	121.0 (3)	O3—C10—C15	124.7 (3)
C4—C3—C2	120.4 (3)	O3—C10—C11	115.4 (3)
C4—C3—H3	119.8	C15—C10—C11	119.8 (3)
C2—C3—H3	119.8	C12—C11—C10	118.1 (3)
C3—C4—C5	119.7 (3)	C12—C11—C16	120.8 (3)
C3—C4—H4	120.2	C10—C11—C16	121.1 (3)
C5—C4—H4	120.2	C13—C12—C11	121.5 (3)
C6—C5—C4	121.3 (3)	C13—C12—H12	119.2
C6—C5—H5	119.3	C11—C12—H12	119.2
C4—C5—H5	119.3	C12—C13—C14	119.5 (4)
C5—C6—C7	119.1 (3)	C12—C13—H13	120.2
C5—C6—H6	120.5	C14—C13—H13	120.2
C7—C6—H6	120.5	C15—C14—C13	120.4 (3)
O2—C7—C6	123.9 (3)	C15—C14—H14	119.8
O2—C7—C2	115.9 (3)	C13—C14—H14	119.8
C6—C7—C2	120.2 (3)	C14—C15—C10	120.6 (3)
O2—C8—C9	108.0 (3)	C14—C15—H15	119.7
O2—C8—H8A	110.1	C10—C15—H15	119.7
C9—C8—H8A	110.1	O4—C16—C11	124.7 (4)
O2—C8—H8B	110.1	O4—C16—H16	117.6
C9—C8—H8B	110.1	C11—C16—H16	117.6
O1—C1—C2—C3	3.4 (5)	O2—C8—C9—O3	77.2 (3)
O1—C1—C2—C7	−176.4 (3)	C9—O3—C10—C15	3.6 (4)
C7—C2—C3—C4	−2.3 (5)	C9—O3—C10—C11	−177.8 (2)
C1—C2—C3—C4	177.9 (3)	O3—C10—C11—C12	−177.7 (3)
C2—C3—C4—C5	0.6 (5)	C15—C10—C11—C12	0.9 (4)
C3—C4—C5—C6	0.5 (5)	O3—C10—C11—C16	2.8 (4)
C4—C5—C6—C7	0.0 (5)	C15—C10—C11—C16	−178.6 (3)
C8—O2—C7—C6	−2.1 (4)	C10—C11—C12—C13	−0.2 (5)
C8—O2—C7—C2	179.8 (3)	C16—C11—C12—C13	179.3 (3)
C5—C6—C7—O2	−179.8 (3)	C11—C12—C13—C14	−1.1 (5)
C5—C6—C7—C2	−1.7 (5)	C12—C13—C14—C15	1.6 (6)
C3—C2—C7—O2	−178.9 (3)	C13—C14—C15—C10	−0.9 (5)
C1—C2—C7—O2	0.9 (4)	O3—C10—C15—C14	178.1 (3)
C3—C2—C7—C6	2.9 (5)	C11—C10—C15—C14	−0.4 (5)
C1—C2—C7—C6	−177.3 (3)	C12—C11—C16—O4	−3.0 (6)
C7—O2—C8—C9	173.3 (3)	C10—C11—C16—O4	176.5 (3)
C10—O3—C9—C8	178.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2	0.93	2.40	2.746 (4)	102
C16—H16···O3	0.93	2.41	2.748 (4)	102
C6—H6···O1^i	0.93	2.48	3.290 (4)	146
C9—H9A···CgB^ii	0.97	2.84	3.712 (2)	150
C9—H9B···CgA^iii	0.97	2.76	3.473 (2)	131

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