4-(2,4-Dichloro­benz­yloxy)-3-ethoxy­benzaldehyde

In the title compound, C₁₆H₁₄Cl₂O₃, the ethylvanillin group makes a dihedral angle of 6.15 (3)° with the dichloro­benzene ring. Inter­molecular C—H...O inter­actions lead to trimeric associations of mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.029
• wR factor = 0.083
• Data-to-parameter ratio = 8.4

checkCIF/PLATON results

No syntax errors found



Alert level B
SYMMS02_ALERT_1_B  The unit-cell lengths a and c should be equal for a
            rhombohedral cell
  Cell      19.8490   19.8490   10.3400
  Angles    90.0000   90.0000  120.0000
SYMMS02_ALERT_1_B  Cell angles alpha and gamma should be equal for a
            rhombohedral cell
  Cell      19.8490   19.8490   10.3400
  Angles    90.0000   90.0000  120.0000
SYMMS02_ALERT_1_B  All angles should not be 90 for a rhombohedral cell
  Cell      19.8490   19.8490   10.3400
  Angles    90.0000   90.0000  120.0000

Alert level C
PLAT034_ALERT_1_C No Flack Parameter Given. Z .GT. Si, NonCentro .          ?
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          6
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl1    ..  O3      ..       3.23 Ang.

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           26.40
           From the CIF: _reflns_number_total               1601
           Count of symmetry unique reflns         1606
           Completeness (_total/calc)             99.69%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   3 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   4 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

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

4–4-(2,4-Dichlorobenzyloxy)-3-ethoxybenzaldehyde

Crystal data

C16H14Cl2O3	F(000) = 1512
Mr = 325.17	Dx = 1.378 Mg m^−3
Rhombohedral, R3	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: R 3	Cell parameters from 2629 reflections
a = 19.849 (3) Å	θ = 2.3–25.6°
c = 10.340 (2) Å	µ = 0.42 mm^−1
α = 90°	T = 294 K
γ = 120°	Block, colorless
V = 3528.0 (10) Å^3	0.26 × 0.24 × 0.20 mm
Z = 9

Data collection

Bruker SMART APEX CCD diffractometer	1601 independent reflections
Radiation source: fine-focus sealed tube	1263 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ and ω scans	θmax = 26.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→24
Tmin = 0.878, Tmax = 0.919	k = −13→24
6567 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0472P)^2 + 0.7953P] where P = (Fo^2 + 2Fc^2)/3
1601 reflections	(Δ/σ)max < 0.001
191 parameters	Δρmax = 0.24 e Å^−3
1 restraint	Δρmin = −0.18 e Å^−3

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 > 2σ(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
Cl1	0.34754 (6)	0.27838 (8)	0.36798 (11)	0.0759 (4)
Cl2	0.03498 (6)	0.11165 (5)	0.35177 (12)	0.0645 (3)
O1	0.04996 (14)	0.34052 (14)	0.3773 (2)	0.0490 (6)
O2	0.08296 (14)	0.48186 (13)	0.3796 (2)	0.0494 (6)
O3	−0.18716 (18)	0.4669 (2)	0.3739 (4)	0.0851 (10)
C1	−0.0130 (2)	0.35061 (18)	0.3790 (3)	0.0399 (8)
C2	0.0054 (2)	0.42927 (18)	0.3809 (3)	0.0395 (8)
C3	−0.05343 (19)	0.4456 (2)	0.3825 (3)	0.0436 (8)
H3	−0.0417	0.4972	0.3854	0.052*
C4	−0.1311 (2)	0.3863 (2)	0.3798 (4)	0.0467 (8)
C5	−0.1483 (2)	0.3095 (2)	0.3787 (4)	0.0498 (8)
H5	−0.2000	0.2698	0.3778	0.060*
C6	−0.0890 (2)	0.2909 (2)	0.3787 (4)	0.0464 (8)
H6	−0.1007	0.2393	0.3786	0.056*
C7	0.1066 (2)	0.56240 (19)	0.3905 (4)	0.0518 (9)
H7A	0.0876	0.5719	0.4709	0.062*
H7B	0.0856	0.5780	0.3193	0.062*
C8	0.1932 (2)	0.6076 (3)	0.3877 (4)	0.0680 (12)
H8A	0.2134	0.5925	0.4595	0.102*
H8B	0.2106	0.6622	0.3936	0.102*
H8C	0.2115	0.5973	0.3083	0.102*
C9	−0.1945 (3)	0.4037 (3)	0.3779 (4)	0.0617 (11)
H9	−0.2450	0.3617	0.3799	0.074*
C10	0.0363 (2)	0.26315 (17)	0.3830 (4)	0.0427 (8)
H10A	0.0044	0.2330	0.3106	0.051*
H10B	0.0095	0.2382	0.4625	0.051*
C11	0.11434 (19)	0.26784 (18)	0.3780 (3)	0.0397 (7)
C12	0.1836 (2)	0.3378 (2)	0.3905 (4)	0.0502 (8)
H12	0.1822	0.3837	0.4000	0.060*
C13	0.2549 (2)	0.3407 (2)	0.3891 (4)	0.0536 (9)
H13	0.3008	0.3881	0.3980	0.064*
C14	0.2576 (2)	0.2729 (2)	0.3744 (3)	0.0527 (9)
C15	0.1912 (2)	0.2029 (2)	0.3622 (4)	0.0496 (8)
H15	0.1932	0.1573	0.3526	0.060*
C16	0.1198 (2)	0.2014 (2)	0.3646 (4)	0.0467 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0493 (6)	0.1038 (10)	0.0871 (8)	0.0477 (7)	0.0021 (5)	−0.0068 (6)
Cl2	0.0511 (5)	0.0338 (4)	0.1065 (8)	0.0196 (4)	−0.0117 (5)	−0.0054 (5)
O1	0.0402 (12)	0.0350 (12)	0.0758 (18)	0.0219 (11)	0.0015 (11)	−0.0022 (11)
O2	0.0390 (13)	0.0362 (13)	0.0725 (16)	0.0184 (11)	0.0033 (11)	−0.0023 (11)
O3	0.066 (2)	0.076 (2)	0.135 (3)	0.0517 (19)	−0.0093 (18)	−0.0039 (19)
C1	0.0407 (18)	0.0389 (18)	0.0433 (19)	0.0224 (15)	−0.0018 (14)	−0.0024 (14)
C2	0.0399 (17)	0.0375 (16)	0.0418 (19)	0.0198 (15)	0.0000 (13)	−0.0006 (13)
C3	0.0463 (19)	0.0401 (18)	0.053 (2)	0.0280 (15)	0.0007 (15)	−0.0011 (14)
C4	0.0417 (18)	0.052 (2)	0.0509 (19)	0.0267 (17)	−0.0027 (15)	−0.0015 (16)
C5	0.0376 (18)	0.048 (2)	0.058 (2)	0.0175 (16)	−0.0041 (15)	−0.0051 (17)
C6	0.0443 (18)	0.0374 (18)	0.054 (2)	0.0177 (16)	−0.0013 (15)	−0.0012 (15)
C7	0.051 (2)	0.0341 (18)	0.067 (2)	0.0187 (16)	−0.0009 (17)	−0.0056 (16)
C8	0.052 (2)	0.050 (2)	0.086 (3)	0.0129 (19)	−0.003 (2)	−0.007 (2)
C9	0.045 (2)	0.068 (3)	0.078 (3)	0.033 (2)	−0.0067 (18)	−0.005 (2)
C10	0.0412 (19)	0.0344 (16)	0.054 (2)	0.0196 (15)	0.0009 (15)	−0.0001 (14)
C11	0.0446 (18)	0.0314 (17)	0.0444 (19)	0.0200 (15)	0.0011 (14)	−0.0012 (12)
C12	0.049 (2)	0.0348 (17)	0.067 (2)	0.0213 (16)	0.0033 (17)	−0.0042 (16)
C13	0.0391 (18)	0.0375 (19)	0.073 (3)	0.0106 (15)	0.0024 (16)	−0.0033 (16)
C14	0.044 (2)	0.067 (2)	0.055 (2)	0.034 (2)	−0.0024 (16)	−0.0079 (19)
C15	0.051 (2)	0.048 (2)	0.058 (2)	0.0303 (17)	−0.0033 (16)	−0.0040 (17)
C16	0.0411 (18)	0.0375 (17)	0.059 (2)	0.0180 (15)	−0.0064 (15)	−0.0045 (15)

Geometric parameters (Å, º)

Cl1—C14	1.735 (4)	C7—H7A	0.9700
Cl2—C16	1.740 (4)	C7—H7B	0.9700
O1—C1	1.360 (4)	C8—H8A	0.9600
O1—C10	1.421 (4)	C8—H8B	0.9600
O2—C2	1.361 (4)	C8—H8C	0.9600
O2—C7	1.428 (4)	C9—H9	0.9300
O3—C9	1.189 (5)	C10—C11	1.505 (5)
C1—C6	1.376 (5)	C10—H10A	0.9700
C1—C2	1.415 (4)	C10—H10B	0.9700
C2—C3	1.359 (4)	C11—C16	1.383 (5)
C3—C4	1.395 (5)	C11—C12	1.388 (5)
C3—H3	0.9300	C12—C13	1.389 (5)
C4—C5	1.386 (5)	C12—H12	0.9300
C4—C9	1.463 (5)	C13—C14	1.381 (5)
C5—C6	1.399 (5)	C13—H13	0.9300
C5—H5	0.9300	C14—C15	1.361 (5)
C6—H6	0.9300	C15—C16	1.403 (5)
C7—C8	1.490 (5)	C15—H15	0.9300
C1—O1—C10	117.8 (3)	H8A—C8—H8C	109.5
C2—O2—C7	118.1 (3)	H8B—C8—H8C	109.5
O1—C1—C6	124.4 (3)	O3—C9—C4	125.7 (4)
O1—C1—C2	114.5 (3)	O3—C9—H9	117.2
C6—C1—C2	121.1 (3)	C4—C9—H9	117.2
C3—C2—O2	126.5 (3)	O1—C10—C11	107.3 (3)
C3—C2—C1	119.0 (3)	O1—C10—H10A	110.3
O2—C2—C1	114.5 (3)	C11—C10—H10A	110.3
C2—C3—C4	121.2 (3)	O1—C10—H10B	110.3
C2—C3—H3	119.4	C11—C10—H10B	110.3
C4—C3—H3	119.4	H10A—C10—H10B	108.5
C5—C4—C3	119.2 (3)	C16—C11—C12	116.9 (3)
C5—C4—C9	119.4 (3)	C16—C11—C10	120.9 (3)
C3—C4—C9	121.3 (4)	C12—C11—C10	122.1 (3)
C4—C5—C6	120.9 (3)	C11—C12—C13	121.3 (3)
C4—C5—H5	119.6	C11—C12—H12	119.4
C6—C5—H5	119.6	C13—C12—H12	119.4
C1—C6—C5	118.5 (3)	C14—C13—C12	119.7 (3)
C1—C6—H6	120.7	C14—C13—H13	120.1
C5—C6—H6	120.7	C12—C13—H13	120.1
O2—C7—C8	107.9 (3)	C15—C14—C13	121.1 (3)
O2—C7—H7A	110.1	C15—C14—Cl1	120.0 (3)
C8—C7—H7A	110.1	C13—C14—Cl1	118.9 (3)
O2—C7—H7B	110.1	C14—C15—C16	118.1 (3)
C8—C7—H7B	110.1	C14—C15—H15	120.9
H7A—C7—H7B	108.4	C16—C15—H15	120.9
C7—C8—H8A	109.5	C11—C16—C15	122.8 (3)
C7—C8—H8B	109.5	C11—C16—Cl2	119.1 (3)
H8A—C8—H8B	109.5	C15—C16—Cl2	118.1 (3)
C7—C8—H8C	109.5
C10—O1—C1—C6	−3.8 (5)	C5—C4—C9—O3	−177.1 (4)
C10—O1—C1—C2	176.4 (3)	C3—C4—C9—O3	2.7 (7)
C7—O2—C2—C3	5.0 (5)	C1—O1—C10—C11	179.3 (3)
C7—O2—C2—C1	−175.7 (3)	O1—C10—C11—C16	−171.3 (3)
O1—C1—C2—C3	179.9 (3)	O1—C10—C11—C12	10.7 (5)
C6—C1—C2—C3	0.0 (5)	C16—C11—C12—C13	0.2 (5)
O1—C1—C2—O2	0.5 (4)	C10—C11—C12—C13	178.2 (4)
C6—C1—C2—O2	−179.3 (3)	C11—C12—C13—C14	0.3 (6)
O2—C2—C3—C4	178.0 (3)	C12—C13—C14—C15	−0.5 (6)
C1—C2—C3—C4	−1.2 (5)	C12—C13—C14—Cl1	178.0 (3)
C2—C3—C4—C5	1.6 (5)	C13—C14—C15—C16	0.2 (6)
C2—C3—C4—C9	−178.3 (3)	Cl1—C14—C15—C16	−178.3 (3)
C3—C4—C5—C6	−0.7 (5)	C12—C11—C16—C15	−0.5 (6)
C9—C4—C5—C6	179.1 (3)	C10—C11—C16—C15	−178.6 (4)
O1—C1—C6—C5	−179.0 (3)	C12—C11—C16—Cl2	178.7 (3)
C2—C1—C6—C5	0.8 (5)	C10—C11—C16—Cl2	0.7 (5)
C4—C5—C6—C1	−0.5 (5)	C14—C15—C16—C11	0.4 (6)
C2—O2—C7—C8	179.5 (3)	C14—C15—C16—Cl2	−178.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O3^i	0.93	2.52	3.429 (5)	167

Symmetry code: (i) −x+y−1, −x, z.