Penta­erythrit­yl tetra­kis­(4-bromo­benz­yl ether)

The title compound {alternatively called tetra­kis­[(4-bromo­benz­yl­oxy)meth­yl]methane}, C₃₃H₃₂Br₄O₄, was crystallized from eth­yl acetate. The molecule has crystallographic twofold rotation symmetry. Key features of the structure include intra­molecular edge-to-face aromatic inter­actions, inter­molecular Br...π inter­actions and inter­molecular Br...O contacts.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.055
• wR factor = 0.165
• Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found





Alert level C
PLAT199_ALERT_1_C Check the Reported cell_measurement_temperature         293
PLAT200_ALERT_1_C Check the Reported cell_ambient_temperature ....        293
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C7
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C15
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          9
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br2    ..  O1      ..       3.30 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C33 H32 Br4 O4

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           68.36
           From the CIF: _reflns_number_total               2814
           Count of symmetry unique reflns         1658
           Completeness (_total/calc)            169.72%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1156
           Fraction of Friedel pairs measured     0.697
           Are heavy atom types Z>Si present        yes

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2003); 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, 2000); software used to prepare material for publication: SHELXTL.

tetrakis[(4-bromobenzyloxy)methyl]methane

Crystal data

C33H32Br4O4	Dx = 1.646 Mg m^−3
Mr = 812.23	Melting point: 400.5 K
Orthorhombic, Fdd2	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: F 2 -2d	Cell parameters from 9698 reflections
a = 25.342 (5) Å	θ = 4.0–68.1°
b = 44.671 (5) Å	µ = 6.28 mm^−1
c = 5.7889 (9) Å	T = 293 K
V = 6553.3 (18) Å^3	Block, colorless
Z = 8	0.25 × 0.05 × 0.05 mm
F(000) = 3216

Data collection

Bruker SMART6000 diffractometer	2814 independent reflections
Radiation source: rotating anode	2559 reflections with I > 2σ(I)
Montel 200 optics monochromator	Rint = 0.044
Detector resolution: 5.5 pixels mm^-1	θmax = 68.4°, θmin = 4.0°
ω scans	h = −30→29
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	k = −53→53
Tmin = 0.620, Tmax = 0.730	l = −6→6
16557 measured reflections

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)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.165	w = 1/[σ^2(Fo^2) + (0.1152P)^2 + 3.049P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.035
2814 reflections	Δρmax = 0.59 e Å^−3
187 parameters	Δρmin = −0.47 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 1156 Friedel Pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.11 (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. The structure was solved by direct methods with SHELXS97. All non-Hydrogen atoms were refined by full-matrix least-squares with anisotropic displacement parameters. 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
Br1	0.00316 (3)	0.16962 (2)	0.09172 (18)	0.1113 (4)
Br2	0.39446 (4)	0.422886 (15)	−0.11444 (16)	0.1110 (4)
C1	0.2500	0.2500	−0.5811 (12)	0.0571 (14)
C2	0.2044 (2)	0.25914 (11)	−0.4211 (9)	0.0641 (11)
H2A	0.1968	0.2431	−0.3137	0.077*
H2B	0.2143	0.2767	−0.3328	0.077*
C3	0.1148 (2)	0.27315 (13)	−0.4190 (13)	0.0828 (16)
H3A	0.0875	0.2812	−0.5184	0.099*
H3B	0.1249	0.2887	−0.3110	0.099*
C4	0.0925 (2)	0.24687 (13)	−0.2850 (12)	0.0724 (13)
C5	0.0903 (3)	0.21833 (14)	−0.3810 (14)	0.0883 (17)
H5	0.1067	0.2147	−0.5220	0.106*
C6	0.0642 (3)	0.19520 (16)	−0.2701 (15)	0.0909 (18)
H6	0.0628	0.1762	−0.3360	0.109*
C7	0.0404 (2)	0.20076 (14)	−0.0609 (12)	0.0797 (16)
C8	0.0415 (2)	0.22854 (16)	0.0383 (13)	0.0875 (17)
H8	0.0251	0.2319	0.1796	0.105*
C9	0.0676 (3)	0.25183 (15)	−0.0753 (14)	0.0896 (19)
H9	0.0683	0.2708	−0.0096	0.107*
C10	0.2665 (2)	0.27579 (10)	−0.7407 (9)	0.0636 (11)
H10A	0.2948	0.2693	−0.8415	0.076*
H10B	0.2368	0.2818	−0.8360	0.076*
C11	0.3033 (3)	0.32387 (12)	−0.7418 (12)	0.0768 (14)
H11A	0.2750	0.3324	−0.8340	0.092*
H11B	0.3303	0.3164	−0.8458	0.092*
C12	0.3263 (2)	0.34754 (10)	−0.5871 (10)	0.0653 (12)
C13	0.3705 (2)	0.36331 (12)	−0.6475 (12)	0.0763 (14)
H13	0.3873	0.3587	−0.7857	0.092*
C14	0.3909 (2)	0.38558 (13)	−0.5128 (13)	0.0814 (16)
H14	0.4206	0.3961	−0.5606	0.098*
C15	0.3669 (2)	0.39231 (11)	−0.3037 (10)	0.0727 (14)
C16	0.3225 (2)	0.37655 (12)	−0.2330 (12)	0.0776 (14)
H16	0.3066	0.3809	−0.0922	0.093*
C17	0.3023 (2)	0.35438 (12)	−0.3736 (13)	0.0763 (13)
H17	0.2724	0.3438	−0.3270	0.092*
O1	0.15938 (14)	0.26539 (9)	−0.5568 (8)	0.0752 (9)
O2	0.28338 (14)	0.30002 (7)	−0.6047 (7)	0.0704 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0782 (4)	0.1168 (6)	0.1390 (8)	−0.0089 (3)	0.0025 (4)	0.0456 (6)
Br2	0.1545 (8)	0.0727 (4)	0.1056 (6)	−0.0352 (4)	−0.0218 (5)	0.0005 (4)
C1	0.066 (4)	0.049 (3)	0.056 (4)	0.003 (2)	0.000	0.000
C2	0.073 (3)	0.063 (2)	0.056 (3)	−0.007 (2)	0.008 (2)	−0.006 (2)
C3	0.084 (3)	0.069 (3)	0.095 (4)	0.010 (2)	0.021 (3)	0.008 (3)
C4	0.061 (3)	0.080 (3)	0.076 (3)	0.007 (2)	0.007 (3)	−0.004 (3)
C5	0.094 (4)	0.077 (3)	0.094 (4)	0.001 (3)	0.022 (4)	−0.008 (3)
C6	0.088 (4)	0.079 (4)	0.105 (5)	−0.006 (3)	0.013 (3)	−0.002 (4)
C7	0.057 (3)	0.096 (4)	0.086 (4)	0.000 (2)	0.008 (3)	0.015 (3)
C8	0.076 (3)	0.108 (5)	0.078 (4)	0.001 (3)	0.018 (3)	0.000 (3)
C9	0.088 (4)	0.098 (4)	0.083 (5)	0.001 (3)	0.015 (3)	−0.014 (3)
C10	0.079 (3)	0.055 (2)	0.057 (3)	−0.009 (2)	0.001 (2)	0.004 (2)
C11	0.089 (3)	0.063 (3)	0.078 (4)	−0.019 (2)	−0.003 (3)	0.010 (2)
C12	0.073 (3)	0.048 (2)	0.075 (3)	−0.0001 (18)	0.000 (2)	0.010 (2)
C13	0.073 (3)	0.069 (3)	0.087 (4)	−0.003 (2)	0.007 (3)	0.010 (3)
C14	0.076 (3)	0.072 (3)	0.097 (4)	−0.020 (3)	0.001 (3)	0.009 (3)
C15	0.088 (3)	0.051 (2)	0.079 (4)	−0.007 (2)	−0.014 (3)	0.005 (2)
C16	0.085 (3)	0.064 (3)	0.084 (4)	−0.009 (2)	0.010 (3)	−0.002 (3)
C17	0.069 (3)	0.067 (3)	0.093 (4)	−0.006 (2)	0.009 (3)	0.007 (3)
O1	0.072 (2)	0.078 (2)	0.075 (2)	0.0009 (17)	0.0054 (18)	0.0015 (18)
O2	0.092 (2)	0.0503 (15)	0.069 (2)	−0.0151 (15)	0.0041 (18)	0.0010 (15)

Geometric parameters (Å, º)

Br1—C7	1.899 (6)	C8—C9	1.397 (10)
Br2—C15	1.885 (5)	C8—H8	0.93
C1—C10	1.534 (6)	C9—H9	0.93
C1—C10^i	1.534 (6)	C10—O2	1.405 (6)
C1—C2^i	1.536 (6)	C10—H10A	0.97
C1—C2	1.536 (6)	C10—H10B	0.97
C2—O1	1.414 (7)	C11—O2	1.421 (6)
C2—H2A	0.97	C11—C12	1.503 (8)
C2—H2B	0.97	C11—H11A	0.97
C3—O1	1.426 (7)	C11—H11B	0.97
C3—C4	1.516 (8)	C12—C13	1.369 (8)
C3—H3A	0.97	C12—C17	1.411 (9)
C3—H3B	0.97	C13—C14	1.366 (9)
C4—C9	1.386 (10)	C13—H13	0.93
C4—C5	1.391 (8)	C14—C15	1.388 (9)
C5—C6	1.385 (10)	C14—H14	0.93
C5—H5	0.93	C15—C16	1.388 (8)
C6—C7	1.375 (10)	C16—C17	1.381 (9)
C6—H6	0.93	C16—H16	0.93
C7—C8	1.368 (10)	C17—H17	0.93
C10—C1—C10^i	106.0 (6)	C4—C9—H9	119.7
C10—C1—C2^i	111.0 (3)	C8—C9—H9	119.7
C10^i—C1—C2^i	111.6 (3)	O2—C10—C1	108.9 (4)
C10—C1—C2	111.6 (3)	O2—C10—H10A	109.9
C10^i—C1—C2	111.0 (3)	C1—C10—H10A	109.9
C2^i—C1—C2	105.8 (6)	O2—C10—H10B	109.9
O1—C2—C1	108.9 (4)	C1—C10—H10B	109.9
O1—C2—H2A	109.9	H10A—C10—H10B	108.3
C1—C2—H2A	109.9	O2—C11—C12	109.4 (5)
O1—C2—H2B	109.9	O2—C11—H11A	109.8
C1—C2—H2B	109.9	C12—C11—H11A	109.8
H2A—C2—H2B	108.3	O2—C11—H11B	109.8
O1—C3—C4	113.2 (4)	C12—C11—H11B	109.8
O1—C3—H3A	108.9	H11A—C11—H11B	108.2
C4—C3—H3A	108.9	C13—C12—C17	117.7 (5)
O1—C3—H3B	108.9	C13—C12—C11	121.8 (6)
C4—C3—H3B	108.9	C17—C12—C11	120.5 (5)
H3A—C3—H3B	107.8	C14—C13—C12	122.6 (6)
C9—C4—C5	118.6 (6)	C14—C13—H13	118.7
C9—C4—C3	119.6 (5)	C12—C13—H13	118.7
C5—C4—C3	121.3 (6)	C13—C14—C15	119.3 (5)
C6—C5—C4	121.1 (7)	C13—C14—H14	120.3
C6—C5—H5	119.4	C15—C14—H14	120.3
C4—C5—H5	119.4	C14—C15—C16	120.2 (5)
C7—C6—C5	118.9 (7)	C14—C15—Br2	120.1 (4)
C7—C6—H6	120.6	C16—C15—Br2	119.8 (5)
C5—C6—H6	120.6	C17—C16—C15	119.4 (6)
C8—C7—C6	121.7 (6)	C17—C16—H16	120.3
C8—C7—Br1	118.6 (5)	C15—C16—H16	120.3
C6—C7—Br1	119.7 (5)	C16—C17—C12	120.7 (5)
C7—C8—C9	119.2 (6)	C16—C17—H17	119.6
C7—C8—H8	120.4	C12—C17—H17	119.6
C9—C8—H8	120.4	C2—O1—C3	112.2 (5)
C4—C9—C8	120.6 (6)	C10—O2—C11	111.9 (4)
C10—C1—C2—O1	64.2 (5)	C2—C1—C10—O2	60.5 (5)
C10^i—C1—C2—O1	−53.7 (5)	O2—C11—C12—C13	143.4 (5)
C2^i—C1—C2—O1	−174.9 (4)	O2—C11—C12—C17	−37.1 (7)
O1—C3—C4—C9	150.4 (6)	C17—C12—C13—C14	−1.8 (9)
O1—C3—C4—C5	−37.9 (9)	C11—C12—C13—C14	177.7 (6)
C9—C4—C5—C6	−0.4 (10)	C12—C13—C14—C15	1.4 (9)
C3—C4—C5—C6	−172.0 (7)	C13—C14—C15—C16	−0.1 (9)
C4—C5—C6—C7	−0.3 (11)	C13—C14—C15—Br2	179.8 (5)
C5—C6—C7—C8	0.7 (10)	C14—C15—C16—C17	−0.7 (9)
C5—C6—C7—Br1	178.7 (5)	Br2—C15—C16—C17	179.4 (5)
C6—C7—C8—C9	−0.2 (9)	C15—C16—C17—C12	0.3 (9)
Br1—C7—C8—C9	−178.3 (6)	C13—C12—C17—C16	0.9 (8)
C5—C4—C9—C8	0.9 (10)	C11—C12—C17—C16	−178.6 (6)
C3—C4—C9—C8	172.6 (7)	C1—C2—O1—C3	178.1 (4)
C7—C8—C9—C4	−0.6 (10)	C4—C3—O1—C2	−70.5 (6)
C10^i—C1—C10—O2	−178.5 (5)	C1—C10—O2—C11	175.2 (4)
C2^i—C1—C10—O2	−57.2 (5)	C12—C11—O2—C10	−173.7 (5)

Symmetry code: (i) −x+1/2, −y+1/2, z.