Literature DB >> 21581034

(±)-Cyclo-hexane-1,2-diyl bis-(4-nitro-benzoate).

Sok Teng Tong¹, David Barker, Ka Wai Choi, Peter D W Boyd, Margaret A Brimble.

Abstract

The crystal structure of the title compound, C(20)H(18)N(2)O(8), has been investigated to establish the relative stereochemistry between the ester groups. The cyclo-hexane ring adopts a chair conformation, in which the two ester groups occupy the adjacent equatorial positions in a trans relationship with each other. The mol-ecules assemble in the crystal as chains along the c axis via C-H⋯π inter-actions between the cyclo-hexane ring and a pair of nitro-phenyl rings of the neighbouring mol-ecule. Also observed are π-π stacking inter-actions between the nitro-phenyl rings of neighbouring chains, with a perpendicular distance between these rings of 3.409 Å and a slippage of 0.969 Å.

Entities: Chemical Disease Gene

Year: 2008 PMID： 21581034 PMCID： PMC2959677 DOI： 10.1107/S1600536808033874

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For the related synthesis of cyclohexane-1,2-diyl-bis(4-bromobenzoate) from trans-cyclohexane-1,2-diol, see: Hayashi et al. (2004 ▶); for non-conventional hydrogen contacts and stacking interactions, see: Desiraju & Steiner (2001 ▶) and Ciunik & Jarosz (1998 ▶).

Experimental

Crystal data

C20H18N2O8 M = 414.36 Monoclinic, a = 12.6510 (2) Å b = 12.2720 (2) Å c = 13.2186 (2) Å β = 108.8300 (10)° V = 1942.39 (5) Å3 Z = 4 Mo Kα radiation μ = 0.11 mm−1 T = 89 (2) K 0.2 × 0.1 × 0.05 mm

Data collection

Siemens SMART diffractometer with an APEXII CCD detector Absorption correction: none 15207 measured reflections 4973 independent reflections 2999 reflections with I > 2σ(I) R int = 0.077

Refinement

R[F 2 > 2σ(F 2)] = 0.041 wR(F 2) = 0.098 S = 0.91 4973 reflections 271 parameters H-atom parameters constrained Δρmax = 0.28 e Å−3 Δρmin = −0.30 e Å−3 Data collection: SMART (Siemens, 1995 ▶); cell refinement: SAINT (Siemens, 1995 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and publCIF (Westrip, 2008 ▶). Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808033874/si2117sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536808033874/si2117Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₂₀H₁₈N₂O₈	D_x = 1.417 Mg m⁻³
M_r = 414.36	Melting point: 381(1) K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.6510 (2) Å	Cell parameters from 4298 reflections
b = 12.2720 (2) Å	θ = 1.7–25.1°
c = 13.2186 (2) Å	µ = 0.11 mm⁻¹
β = 108.830 (1)°	T = 89 K
V = 1942.39 (5) Å³	Needle, yellow
Z = 4	0.2 × 0.1 × 0.05 mm
F(000) = 864

Siemens SMART diffractometer with an APEXII CCD detector	2999 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.077
graphite	θ_max = 28.8°, θ_min = 1.7°
area–detector ω scans	h = −16→17
15207 measured reflections	k = −16→16
4973 independent reflections	l = −17→17

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 0.91	w = 1/[σ²(F_o²) + (0.0453P)²] where P = (F_o² + 2F_c²)/3
4973 reflections	(Δ/σ)_max < 0.001
271 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

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	U_iso*/U_eq
O2	0.13143 (8)	0.12316 (9)	0.12240 (8)	0.0237 (2)
O4	0.07109 (9)	0.29575 (9)	0.08144 (8)	0.0294 (3)
O1	0.36109 (8)	0.08691 (8)	0.21140 (7)	0.0238 (3)
O3	0.26940 (8)	−0.03067 (9)	0.28553 (8)	0.0263 (3)
O6	0.62313 (9)	0.29785 (10)	0.71389 (8)	0.0337 (3)
O7	−0.20229 (9)	0.24599 (10)	0.45414 (8)	0.0341 (3)
O5	0.55152 (10)	0.16681 (9)	0.78095 (8)	0.0368 (3)
O8	−0.16503 (10)	0.07314 (10)	0.46935 (9)	0.0371 (3)
C9	0.39653 (12)	0.09399 (12)	0.39838 (11)	0.0213 (3)
N1	0.56407 (11)	0.21667 (11)	0.70528 (10)	0.0280 (3)
N2	−0.16168 (10)	0.16318 (12)	0.42995 (10)	0.0269 (3)
C18	−0.10386 (12)	0.17208 (13)	0.34967 (11)	0.0221 (3)
C1	0.29657 (12)	0.04900 (13)	0.10370 (11)	0.0224 (3)
H1	0.2646	−0.0229	0.1080	0.027*
C12	0.50482 (13)	0.17579 (12)	0.59718 (11)	0.0236 (3)
C6	0.20401 (12)	0.13022 (13)	0.05672 (11)	0.0235 (3)
H6	0.2354	0.2038	0.0614	0.028*
C15	0.00784 (12)	0.19370 (13)	0.20538 (10)	0.0206 (3)
C16	0.02556 (12)	0.10200 (13)	0.27072 (11)	0.0238 (4)
H16	0.0757	0.0487	0.2655	0.029*
C14	0.35143 (13)	0.07916 (13)	0.48064 (12)	0.0261 (4)
H14	0.2843	0.0420	0.4676	0.031*
C17	−0.03163 (12)	0.09018 (13)	0.34374 (11)	0.0247 (4)
H17	−0.0215	0.0289	0.3873	0.030*
C10	0.49575 (13)	0.15077 (13)	0.41674 (11)	0.0240 (3)
H10	0.5254	0.1603	0.3615	0.029*
C20	−0.06729 (12)	0.27323 (13)	0.21196 (11)	0.0226 (3)
H20	−0.0799	0.3335	0.1669	0.027*
C13	0.40625 (13)	0.11952 (13)	0.58144 (12)	0.0270 (4)
H13	0.3776	0.1091	0.6373	0.032*
C4	0.21805 (13)	0.09860 (14)	−0.12498 (12)	0.0315 (4)
H4A	0.1763	0.0791	−0.1981	0.038*
H4B	0.2514	0.1697	−0.1257	0.038*
C11	0.55089 (13)	0.19336 (13)	0.51698 (12)	0.0254 (4)
H11	0.6169	0.2326	0.5299	0.031*
C7	0.33501 (12)	0.04317 (13)	0.29358 (12)	0.0225 (3)
C5	0.13918 (13)	0.10373 (15)	−0.05883 (11)	0.0302 (4)
H5A	0.0829	0.1592	−0.0878	0.036*
H5B	0.1016	0.0342	−0.0625	0.036*
C8	0.07180 (12)	0.21209 (13)	0.12914 (11)	0.0226 (3)
C19	−0.12367 (12)	0.26323 (13)	0.28548 (11)	0.0226 (3)
H19	−0.1735	0.3166	0.2914	0.027*
C3	0.30937 (13)	0.01510 (14)	−0.07859 (12)	0.0297 (4)
H3A	0.3599	0.0142	−0.1203	0.036*
H3B	0.2763	−0.0568	−0.0826	0.036*
C2	0.37471 (12)	0.04183 (14)	0.03779 (11)	0.0259 (4)
H2A	0.4302	−0.0143	0.0670	0.031*
H2B	0.4134	0.1107	0.0412	0.031*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0232 (5)	0.0264 (6)	0.0246 (5)	0.0030 (5)	0.0120 (4)	0.0016 (5)
O4	0.0333 (6)	0.0289 (6)	0.0296 (6)	0.0057 (6)	0.0154 (5)	0.0067 (5)
O1	0.0238 (6)	0.0269 (6)	0.0198 (5)	−0.0028 (5)	0.0057 (4)	−0.0001 (5)
O3	0.0266 (6)	0.0235 (6)	0.0279 (6)	−0.0040 (5)	0.0077 (5)	−0.0001 (5)
O6	0.0331 (6)	0.0315 (7)	0.0330 (6)	−0.0044 (6)	0.0057 (5)	−0.0059 (6)
O7	0.0320 (6)	0.0451 (8)	0.0290 (6)	0.0127 (6)	0.0150 (5)	0.0018 (6)
O5	0.0551 (8)	0.0320 (7)	0.0227 (6)	0.0051 (6)	0.0118 (5)	0.0032 (5)
O8	0.0417 (7)	0.0364 (7)	0.0406 (7)	−0.0056 (6)	0.0236 (6)	0.0053 (6)
C9	0.0220 (8)	0.0188 (8)	0.0218 (7)	0.0018 (7)	0.0053 (6)	0.0023 (7)
N1	0.0317 (8)	0.0258 (8)	0.0247 (7)	0.0069 (7)	0.0065 (6)	−0.0003 (6)
N2	0.0208 (7)	0.0354 (9)	0.0248 (7)	−0.0002 (7)	0.0078 (6)	0.0009 (7)
C18	0.0185 (7)	0.0299 (9)	0.0183 (7)	0.0004 (7)	0.0066 (6)	−0.0008 (7)
C1	0.0207 (8)	0.0255 (9)	0.0197 (7)	−0.0011 (7)	0.0046 (6)	−0.0016 (7)
C12	0.0279 (8)	0.0198 (8)	0.0205 (7)	0.0033 (7)	0.0041 (6)	0.0003 (7)
C6	0.0221 (8)	0.0273 (9)	0.0240 (8)	0.0009 (7)	0.0114 (6)	0.0018 (7)
C15	0.0190 (7)	0.0251 (8)	0.0165 (7)	−0.0001 (7)	0.0043 (6)	−0.0020 (7)
C16	0.0224 (8)	0.0255 (9)	0.0245 (8)	0.0056 (7)	0.0087 (6)	0.0006 (7)
C14	0.0242 (8)	0.0257 (9)	0.0292 (8)	−0.0031 (8)	0.0098 (7)	0.0003 (7)
C17	0.0260 (8)	0.0242 (9)	0.0235 (8)	0.0009 (7)	0.0075 (6)	0.0030 (7)
C10	0.0268 (8)	0.0232 (9)	0.0225 (7)	0.0002 (8)	0.0087 (6)	0.0025 (7)
C20	0.0230 (8)	0.0237 (9)	0.0189 (7)	0.0018 (7)	0.0038 (6)	0.0014 (7)
C13	0.0336 (9)	0.0265 (9)	0.0245 (8)	0.0009 (8)	0.0142 (7)	0.0014 (7)
C4	0.0302 (9)	0.0416 (11)	0.0220 (8)	0.0001 (9)	0.0077 (7)	−0.0028 (8)
C11	0.0249 (8)	0.0234 (9)	0.0271 (8)	−0.0015 (7)	0.0071 (7)	0.0002 (7)
C7	0.0205 (8)	0.0217 (8)	0.0251 (8)	0.0032 (7)	0.0072 (6)	0.0033 (7)
C5	0.0248 (8)	0.0420 (11)	0.0233 (8)	0.0040 (8)	0.0069 (7)	−0.0009 (8)
C8	0.0219 (8)	0.0238 (9)	0.0204 (7)	0.0026 (7)	0.0044 (6)	−0.0005 (7)
C19	0.0203 (8)	0.0248 (9)	0.0221 (7)	0.0041 (7)	0.0057 (6)	−0.0013 (7)
C3	0.0283 (9)	0.0353 (10)	0.0277 (8)	−0.0006 (8)	0.0122 (7)	−0.0057 (8)
C2	0.0214 (8)	0.0294 (9)	0.0285 (8)	−0.0004 (8)	0.0101 (7)	−0.0018 (7)

O2—C8	1.3459 (18)	C15—C16	1.392 (2)
O2—C6	1.4557 (16)	C15—C8	1.499 (2)
O4—C8	1.2034 (17)	C16—C17	1.388 (2)
O1—C7	1.3447 (17)	C16—H16	0.9300
O1—C1	1.4694 (16)	C14—C13	1.380 (2)
O3—C7	1.2101 (17)	C14—H14	0.9300
O6—N1	1.2283 (16)	C17—H17	0.9300
O7—N2	1.2267 (16)	C10—C11	1.385 (2)
O5—N1	1.2258 (16)	C10—H10	0.9300
O8—N2	1.2281 (17)	C20—C19	1.384 (2)
C9—C10	1.387 (2)	C20—H20	0.9300
C9—C14	1.393 (2)	C13—H13	0.9300
C9—C7	1.489 (2)	C4—C3	1.518 (2)
N1—C12	1.4710 (19)	C4—C5	1.526 (2)
N2—C18	1.4746 (18)	C4—H4A	0.9700
C18—C17	1.378 (2)	C4—H4B	0.9700
C18—C19	1.377 (2)	C11—H11	0.9300
C1—C6	1.510 (2)	C5—H5A	0.9700
C1—C2	1.5166 (19)	C5—H5B	0.9700
C1—H1	0.9800	C19—H19	0.9300
C12—C11	1.382 (2)	C3—C2	1.529 (2)
C12—C13	1.381 (2)	C3—H3A	0.9700
C6—C5	1.517 (2)	C3—H3B	0.9700
C6—H6	0.9800	C2—H2A	0.9700
C15—C20	1.385 (2)	C2—H2B	0.9700

C8—O2—C6	117.78 (12)	C9—C10—H10	119.8
C7—O1—C1	116.87 (11)	C15—C20—C19	120.09 (14)
C10—C9—C14	120.30 (13)	C15—C20—H20	120.0
C10—C9—C7	123.02 (13)	C19—C20—H20	120.0
C14—C9—C7	116.65 (13)	C14—C13—C12	118.21 (14)
O6—N1—O5	124.36 (13)	C14—C13—H13	120.9
O6—N1—C12	118.07 (13)	C12—C13—H13	120.9
O5—N1—C12	117.57 (13)	C3—C4—C5	110.47 (13)
O7—N2—O8	124.06 (13)	C3—C4—H4A	109.6
O7—N2—C18	118.23 (14)	C5—C4—H4A	109.6
O8—N2—C18	117.70 (14)	C3—C4—H4B	109.6
C17—C18—C19	123.34 (13)	C5—C4—H4B	109.6
C17—C18—N2	118.64 (14)	H4A—C4—H4B	108.1
C19—C18—N2	118.01 (13)	C12—C11—C10	117.91 (15)
O1—C1—C6	107.69 (12)	C12—C11—H11	121.0
O1—C1—C2	108.28 (11)	C10—C11—H11	121.0
C6—C1—C2	111.39 (12)	O3—C7—O1	124.61 (14)
O1—C1—H1	109.8	O3—C7—C9	122.21 (14)
C6—C1—H1	109.8	O1—C7—C9	113.17 (13)
C2—C1—H1	109.8	C6—C5—C4	110.17 (12)
C11—C12—C13	123.12 (14)	C6—C5—H5A	109.6
C11—C12—N1	118.90 (14)	C4—C5—H5A	109.6
C13—C12—N1	117.97 (13)	C6—C5—H5B	109.6
O2—C6—C1	105.67 (11)	C4—C5—H5B	109.6
O2—C6—C5	110.34 (12)	H5A—C5—H5B	108.1
C1—C6—C5	111.59 (13)	O4—C8—O2	124.52 (13)
O2—C6—H6	109.7	O4—C8—C15	124.49 (14)
C1—C6—H6	109.7	O2—C8—C15	110.98 (13)
C5—C6—H6	109.7	C18—C19—C20	118.17 (14)
C20—C15—C16	120.49 (14)	C18—C19—H19	120.9
C20—C15—C8	117.80 (14)	C20—C19—H19	120.9
C16—C15—C8	121.67 (14)	C4—C3—C2	110.83 (13)
C17—C16—C15	120.01 (14)	C4—C3—H3A	109.5
C17—C16—H16	120.0	C2—C3—H3A	109.5
C15—C16—H16	120.0	C4—C3—H3B	109.5
C13—C14—C9	120.12 (14)	C2—C3—H3B	109.5
C13—C14—H14	119.9	H3A—C3—H3B	108.1
C9—C14—H14	119.9	C1—C2—C3	110.46 (12)
C18—C17—C16	117.87 (14)	C1—C2—H2A	109.6
C18—C17—H17	121.1	C3—C2—H2A	109.6
C16—C17—H17	121.1	C1—C2—H2B	109.6
C11—C10—C9	120.32 (14)	C3—C2—H2B	109.6
C11—C10—H10	119.8	H2A—C2—H2B	108.1

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O8ⁱ	0.93	2.40	3.240 (2)	150
C16—H16···O3	0.93	2.57	3.4374 (19)	156
C19—H19···O3ⁱⁱ	0.93	2.29	3.0919 (19)	145
C5—H5A···Cg2ⁱⁱⁱ	0.97	2.79	3.7273 (18)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯O8ⁱ	0.93	2.40	3.240 (2)	150
C16—H16⋯O3	0.93	2.57	3.4374 (19)	156
C19—H19⋯O3ⁱⁱ	0.93	2.29	3.0919 (19)	145
C5—H5A⋯Cg2ⁱⁱⁱ	0.97	2.79	3.7273 (18)	162

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

2 in total

1. Direct proline-catalyzed asymmetric alpha-aminoxylation of aldehydes and ketones.

Authors: Yujiro Hayashi; Junichiro Yamaguchi; Tatsunobu Sumiya; Kazuhiro Hibino; Mitsuru Shoji
Journal: J Org Chem Date: 2004-09-03 Impact factor: 4.354

2. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2 in total