Bis(1-bromo-9-chloro­homocub-9-yl) ether

The title compound, C₁₈H₁₄Br₂Cl₂O, is an ether-bridged pair of identical homocubanes. It is an unexpected product obtained in an attempt to chlorinate a bromo-keto-homocubane. No homocubyl or cubyl ethers are currently found in the crystal structure literature.

Key indicators

• Single-crystal X-ray study
• T = 93 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.022
• wR factor = 0.045
• Data-to-parameter ratio = 19.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_320  Alert C Check Hybridisation of  C(4A)  in main residue          ?

PLAT_320  Alert C Check Hybridisation of  C(4B)  in main residue          ?

PLAT_320  Alert C Check Hybridisation of  C(5A)  in main residue          ?

PLAT_320  Alert C Check Hybridisation of  C(5B)  in main residue          ?


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 4 Alert Level C = Please check

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Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXTL (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

1-bromo-9-(7-bromo-8-chloropentacyclo[4.3.0.0^2,5.0^3,9.0^4,7]non-8-yloxy)- 9-chloropentacyclo[4.3.0.0^2,5.0^3,8.0^4,7]nonane

Crystal data

C18H14Br2Cl2O	Dx = 1.899 Mg m^−3
Mr = 477.01	Melting point: not measured K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
a = 13.763 (4) Å	Cell parameters from 5103 reflections
b = 11.909 (4) Å	θ = 2.5–28.3°
c = 20.357 (6) Å	µ = 5.18 mm^−1
V = 3336 (3) Å^3	T = 93 K
Z = 8	Irregular chunk, colorless
F(000) = 1872	0.31 × 0.26 × 0.22 mm

Data collection

Bruker CCD area detector diffractometer	4074 independent reflections
Radiation source: fine-focus sealed tube	2956 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
φ and ω scans	θmax = 28.3°, θmin = 2.0°
Absorption correction: integration (Wuensch & Prewitt, 1965)	h = −17→18
Tmin = 0.255, Tmax = 0.389	k = −15→15
20768 measured reflections	l = −26→24

Refinement

Refinement on F^2	Secondary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	H-atom parameters constrained
wR(F^2) = 0.045	w = 1/[σ^2(Fo^2) + (0.0202P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.86	(Δ/σ)max = 0.001
4074 reflections	Δρmax = 0.48 e Å^−3
209 parameters	Δρmin = −0.64 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: 0.0037 (1)

Special details

Experimental. One hundred area-detector frames were repeated at beginning and end of experiment. The decay was estimated to be negligible from the 455 duplicate reflections found in these frames.

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
Br1A	−0.154700 (16)	0.40838 (2)	0.161237 (11)	0.03003 (7)
C1A	−0.03942 (14)	0.41530 (17)	0.21499 (9)	0.0145 (4)
C2A	−0.02408 (15)	0.31924 (18)	0.26545 (9)	0.0188 (5)
H15A	−0.0574	0.2450	0.2610	0.023*
C3A	0.08719 (15)	0.32852 (17)	0.28158 (9)	0.0177 (5)
H17A	0.1283	0.2603	0.2886	0.021*
C4A	0.06295 (15)	0.41132 (17)	0.33921 (10)	0.0204 (5)
H10A	0.0925	0.4094	0.3841	0.025*
C5A	−0.04730 (16)	0.40174 (17)	0.32350 (9)	0.0203 (5)
H9A	−0.1005	0.3924	0.3565	0.024*
C6A	−0.03804 (15)	0.50009 (18)	0.27276 (9)	0.0175 (5)
H19A	−0.0819	0.5670	0.2740	0.021*
C7A	0.07361 (15)	0.50904 (17)	0.28855 (9)	0.0169 (5)
H4A	0.1042	0.5822	0.3010	0.020*
C8A	0.12233 (15)	0.42873 (16)	0.23761 (9)	0.0150 (4)
H6A	0.1938	0.4369	0.2300	0.018*
C9A	0.05601 (15)	0.42924 (16)	0.17775 (9)	0.0131 (4)
Cl9A	0.05822 (4)	0.56624 (4)	0.13837 (2)	0.02018 (12)
O1	0.06362 (9)	0.34204 (11)	0.13133 (6)	0.0132 (3)
Br1B	0.055013 (16)	0.112951 (17)	0.048532 (10)	0.02090 (6)
C1B	0.13379 (14)	0.24601 (16)	0.03996 (9)	0.0139 (4)
C2B	0.23199 (15)	0.23324 (17)	0.00388 (9)	0.0166 (5)
H16A	0.2656	0.1591	0.0000	0.020*
C3B	0.28769 (15)	0.34290 (17)	0.02507 (10)	0.0173 (5)
H14A	0.3589	0.3418	0.0349	0.021*
C4B	0.24654 (16)	0.40533 (18)	−0.03647 (10)	0.0193 (5)
H20A	0.2844	0.4559	−0.0662	0.023*
C5B	0.19094 (15)	0.29705 (17)	−0.05800 (10)	0.0184 (5)
H7A	0.1869	0.2665	−0.1037	0.022*
C6B	0.10269 (15)	0.33171 (17)	−0.01356 (9)	0.0159 (5)
H13A	0.0348	0.3342	−0.0310	0.019*
C7B	0.15839 (15)	0.44133 (17)	0.00728 (9)	0.0167 (4)
H5A	0.1280	0.5173	0.0031	0.020*
C8B	0.21401 (14)	0.40512 (17)	0.07100 (9)	0.0147 (4)
H8A	0.2399	0.4658	0.1001	0.018*
C9B	0.15310 (14)	0.31343 (16)	0.10266 (9)	0.0130 (4)
Cl9B	0.22657 (4)	0.22900 (4)	0.15852 (2)	0.01782 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1A	0.01368 (11)	0.05486 (18)	0.02156 (12)	0.00160 (11)	−0.00178 (10)	−0.00620 (11)
C1A	0.0108 (10)	0.0201 (12)	0.0127 (9)	−0.0005 (8)	−0.0025 (8)	−0.0002 (8)
C2A	0.0255 (13)	0.0162 (12)	0.0147 (10)	−0.0039 (9)	0.0027 (9)	−0.0005 (9)
C3A	0.0265 (13)	0.0132 (11)	0.0133 (10)	0.0045 (9)	−0.0034 (9)	0.0004 (8)
C4A	0.0279 (12)	0.0198 (12)	0.0136 (9)	0.0047 (10)	−0.0027 (10)	−0.0015 (9)
C5A	0.0262 (12)	0.0208 (12)	0.0138 (10)	−0.0019 (10)	0.0047 (9)	−0.0017 (9)
C6A	0.0211 (13)	0.0167 (12)	0.0148 (10)	0.0036 (9)	0.0005 (9)	−0.0010 (8)
C7A	0.0231 (13)	0.0129 (11)	0.0146 (10)	0.0000 (9)	−0.0026 (9)	−0.0024 (8)
C8A	0.0148 (10)	0.0153 (11)	0.0148 (10)	−0.0009 (8)	−0.0035 (8)	−0.0009 (8)
C9A	0.0160 (10)	0.0106 (10)	0.0126 (9)	0.0011 (8)	0.0003 (8)	0.0028 (8)
Cl9A	0.0296 (3)	0.0132 (3)	0.0177 (2)	0.0036 (2)	0.0030 (2)	0.0033 (2)
O1	0.0118 (7)	0.0151 (7)	0.0127 (7)	−0.0001 (6)	0.0009 (6)	−0.0022 (5)
Br1B	0.02475 (12)	0.01482 (11)	0.02315 (11)	−0.00566 (9)	−0.00094 (10)	−0.00121 (9)
C1B	0.0153 (11)	0.0108 (10)	0.0157 (10)	−0.0020 (8)	−0.0013 (8)	0.0003 (8)
C2B	0.0188 (11)	0.0161 (11)	0.0150 (10)	0.0029 (9)	0.0022 (9)	−0.0024 (9)
C3B	0.0144 (11)	0.0197 (12)	0.0178 (11)	−0.0008 (9)	0.0017 (9)	−0.0006 (9)
C4B	0.0226 (12)	0.0199 (12)	0.0155 (10)	−0.0032 (9)	0.0032 (9)	0.0015 (9)
C5B	0.0230 (12)	0.0186 (12)	0.0136 (10)	0.0008 (9)	0.0015 (9)	−0.0014 (9)
C6B	0.0183 (11)	0.0161 (12)	0.0133 (10)	0.0004 (9)	−0.0042 (9)	−0.0005 (9)
C7B	0.0222 (12)	0.0117 (11)	0.0163 (10)	0.0010 (9)	0.0020 (9)	0.0020 (8)
C8B	0.0162 (11)	0.0139 (11)	0.0141 (10)	−0.0027 (9)	−0.0004 (8)	0.0000 (8)
C9B	0.0128 (10)	0.0139 (11)	0.0123 (10)	0.0025 (8)	−0.0025 (8)	0.0014 (8)
Cl9B	0.0182 (3)	0.0190 (3)	0.0162 (2)	0.0047 (2)	−0.0026 (2)	0.0022 (2)

Geometric parameters (Å, º)

Br1A—C1A	1.9291 (19)	O1—C9B	1.405 (2)
C1A—C9A	1.525 (3)	Br1B—C1B	1.928 (2)
C1A—C6A	1.550 (3)	C1B—C9B	1.531 (3)
C1A—C2A	1.552 (3)	C1B—C2B	1.546 (3)
C2A—C5A	1.570 (3)	C1B—C6B	1.553 (3)
C2A—C3A	1.570 (3)	C2B—C3B	1.574 (3)
C2A—H15A	1.000	C2B—C5B	1.576 (3)
C3A—C8A	1.568 (3)	C2B—H16A	1.000
C3A—C4A	1.568 (3)	C3B—C4B	1.563 (3)
C3A—H17A	1.000	C3B—C8B	1.566 (3)
C4A—C5A	1.555 (3)	C3B—H14A	1.000
C4A—C7A	1.562 (3)	C4B—C5B	1.562 (3)
C4A—H10A	1.000	C4B—C7B	1.565 (3)
C5A—C6A	1.567 (3)	C4B—H20A	1.000
C5A—H9A	1.000	C5B—C6B	1.570 (3)
C6A—C7A	1.573 (3)	C5B—H7A	1.000
C6A—H19A	1.000	C6B—C7B	1.572 (3)
C7A—C8A	1.562 (3)	C6B—H13A	1.000
C7A—H4A	1.000	C7B—C8B	1.567 (3)
C8A—C9A	1.522 (3)	C7B—H5A	1.000
C8A—H6A	1.000	C8B—C9B	1.520 (3)
C9A—O1	1.408 (2)	C8B—H8A	1.000
C9A—Cl9A	1.818 (2)	C9B—Cl9B	1.8240 (19)
C9A—C1A—C6A	107.19 (16)	C9B—C1B—C2B	107.22 (15)
C9A—C1A—C2A	106.98 (16)	C9B—C1B—C6B	106.74 (15)
C6A—C1A—C2A	88.64 (15)	C2B—C1B—C6B	88.41 (15)
C9A—C1A—Br1A	115.52 (13)	C9B—C1B—Br1B	116.95 (13)
C6A—C1A—Br1A	117.92 (14)	C2B—C1B—Br1B	116.99 (14)
C2A—C1A—Br1A	117.12 (14)	C6B—C1B—Br1B	116.66 (13)
C1A—C2A—C5A	90.53 (15)	C1B—C2B—C3B	102.35 (16)
C1A—C2A—C3A	102.66 (16)	C1B—C2B—C5B	91.08 (15)
C5A—C2A—C3A	89.84 (15)	C3B—C2B—C5B	89.63 (15)
C1A—C2A—H15A	121.9	C1B—C2B—H16A	121.9
C5A—C2A—H15A	121.9	C3B—C2B—H16A	121.9
C3A—C2A—H15A	121.9	C5B—C2B—H16A	121.9
C8A—C3A—C4A	90.81 (15)	C4B—C3B—C8B	91.08 (15)
C8A—C3A—C2A	103.59 (16)	C4B—C3B—C2B	89.92 (15)
C4A—C3A—C2A	89.61 (15)	C8B—C3B—C2B	103.94 (16)
C8A—C3A—H17A	121.6	C4B—C3B—H14A	121.4
C4A—C3A—H17A	121.6	C8B—C3B—H14A	121.4
C2A—C3A—H17A	121.6	C2B—C3B—H14A	121.4
C5A—C4A—C7A	90.60 (15)	C5B—C4B—C3B	90.56 (15)
C5A—C4A—C3A	90.43 (15)	C5B—C4B—C7B	90.35 (15)
C7A—C4A—C3A	87.40 (15)	C3B—C4B—C7B	87.42 (15)
C5A—C4A—H10A	125.6	C5B—C4B—H20A	125.6
C7A—C4A—H10A	125.6	C3B—C4B—H20A	125.6
C3A—C4A—H10A	125.6	C7B—C4B—H20A	125.6
C4A—C5A—C6A	90.08 (16)	C4B—C5B—C6B	90.01 (15)
C4A—C5A—C2A	90.11 (15)	C4B—C5B—C2B	89.89 (15)
C6A—C5A—C2A	87.42 (15)	C6B—C5B—C2B	86.76 (14)
C4A—C5A—H9A	125.8	C4B—C5B—H7A	126.0
C6A—C5A—H9A	125.8	C6B—C5B—H7A	126.0
C2A—C5A—H9A	125.8	C2B—C5B—H7A	126.0
C1A—C6A—C5A	90.70 (15)	C1B—C6B—C5B	91.05 (15)
C1A—C6A—C7A	102.18 (16)	C1B—C6B—C7B	102.83 (15)
C5A—C6A—C7A	89.73 (15)	C5B—C6B—C7B	89.81 (15)
C1A—C6A—H19A	122.0	C1B—C6B—H13A	121.8
C5A—C6A—H19A	122.0	C5B—C6B—H13A	121.8
C7A—C6A—H19A	122.0	C7B—C6B—H13A	121.8
C4A—C7A—C8A	91.28 (15)	C4B—C7B—C8B	90.98 (15)
C4A—C7A—C6A	89.59 (15)	C4B—C7B—C6B	89.83 (15)
C8A—C7A—C6A	104.01 (16)	C8B—C7B—C6B	103.48 (15)
C4A—C7A—H4A	121.4	C4B—C7B—H5A	121.6
C8A—C7A—H4A	121.4	C8B—C7B—H5A	121.6
C6A—C7A—H4A	121.4	C6B—C7B—H5A	121.6
C9A—C8A—C7A	105.76 (16)	C9B—C8B—C3B	105.68 (16)
C9A—C8A—C3A	105.97 (16)	C9B—C8B—C7B	106.22 (16)
C7A—C8A—C3A	87.40 (15)	C3B—C8B—C7B	87.26 (15)
C9A—C8A—H6A	117.7	C9B—C8B—H8A	117.7
C7A—C8A—H6A	117.7	C3B—C8B—H8A	117.7
C3A—C8A—H6A	117.7	C7B—C8B—H8A	117.7
O1—C9A—C8A	119.32 (16)	O1—C9B—C8B	119.04 (16)
O1—C9A—C1A	108.50 (16)	O1—C9B—C1B	108.75 (15)
C8A—C9A—C1A	96.77 (15)	C8B—C9B—C1B	96.84 (15)
O1—C9A—Cl9A	111.39 (13)	O1—C9B—Cl9B	111.13 (13)
C8A—C9A—Cl9A	110.28 (14)	C8B—C9B—Cl9B	110.78 (14)
C1A—C9A—Cl9A	109.34 (13)	C1B—C9B—Cl9B	109.08 (13)
C9B—O1—C9A	121.53 (15)