A 3,5-dinitro-benzoyl derivative of a stereoisomer of glycerol menthonide.

The title compound, [(2S,5R,6S,9R)-6-isopropyl-9-methyl-1,4-dioxaspiro-[4.5]dec-2-yl]methyl 3,5-dinitro-benzoate, C(20)H(26)N(2)O(8), was synthesized as part of a study of three-carbon stereochemical systems. The crystallographic assignment of the absolute stereochemistry is consistent with having started with (-)-menthone, the acetal carbon is R and the secondary alcohol is S. This brings the dinitro-benzoate into approximately the same plane as the menthyl ring and anti to the isopropyl group. Close inter-molecular C=O⋯NO(2) contacts between neighboring mol-ecules [2.8341 (16) Å] contribute to the packing arrangement. The structure was refined as a pseudo-merohedral twin (monoclinic space group P2(1) emulating the ortho-rhom-bic space group C222(1)). Application of the twin law 100, 00, 0 gave a 2:1 ratio of twin moieties [refined BASF value = 0.3790 (7)].

Related literature

For the synthesis of glycerol menthonide, see: Greenberg (1999 ▶). For the synthesis and NMR spectra of the title compound, see: Kiessling et al. (2009 ▶). Glidewell et al. (2003 ▶) report a related structure with a very short C=O ⋯ NO2 distance. Allen et al. (1998 ▶) discuss inter­molecular C=O ⋯ C=O inter­actions. For a description of the Cambridge Crystallographic Database, see: Allen (2002 ▶).

Experimental

Crystal data

C20H26N2O8

M = 422.43

Monoclinic,

a = 9.4396 (5) Å

b = 5.8825 (3) Å

c = 19.6719 (10) Å

β = 103.923 (3)°

V = 1060.26 (9) Å3

Z = 2

Cu Kα radiation

μ = 0.87 mm−1

T = 100 K

0.38 × 0.09 × 0.02 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.602, T max = 0.977

16481 measured reflections

3275 independent reflections

3254 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.018

wR(F 2) = 0.045

S = 1.06

3275 reflections

276 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.10 e Å−3

Δρmin = −0.11 e Å−3

Absolute structure: Flack (1983 ▶), 1131 Friedel pairs

Flack parameter: 0.03 (13)

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809020960/zl2211sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809020960/zl2211Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C20H26N2O8	F(000) = 448
Mr = 422.43	Dx = 1.323 Mg m−3
Monoclinic, P21	Melting point: 368 K
Hall symbol: P 2yb	Cu Kα radiation, λ = 1.54178 Å
a = 9.4396 (5) Å	Cell parameters from 9947 reflections
b = 5.8825 (3) Å	θ = 2.3–68.2°
c = 19.6719 (10) Å	µ = 0.87 mm−1
β = 103.923 (3)°	T = 100 K
V = 1060.26 (9) Å3	Needle, colourless
Z = 2	0.38 × 0.09 × 0.02 mm

Bruker SMART APEXII CCD area-detector diffractometer	3275 independent reflections
Radiation source: fine-focus sealed tube	3254 reflections with I > 2σ(I)
graphite	Rint = 0.025
φ and ω scans	θmax = 68.2°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→11
Tmin = 0.602, Tmax = 0.977	k = −6→5
16481 measured reflections	l = −23→23

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.018	w = 1/[σ2(Fo2) + (0.0245P)2 + 0.0832P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.045	(Δ/σ)max = 0.001
S = 1.06	Δρmax = 0.10 e Å−3
3275 reflections	Δρmin = −0.11 e Å−3
276 parameters	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraint	Extinction coefficient: 0.0009 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1131 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.03 (13)

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. The structure was refined as a pseudo-merohedral twin (monoclinic space group P21 emulating orthorhombic space group C2221); Twin law 1 0 0 0 - 1 0 - 1 0 - 1; Refined ratio (BASF) 0.3790 (7).Hydrogen positions were calculated and refined using a riding model using the following C—H distances: methyne 1.000 Å, methylene 0.990 Å, methyl 0.980Å and aromatic 0.950 Å. The isotropic U values for the H atoms were set at 50% above that of bonded carbon for methyl H atoms and 20% above that of the bonded carbon for all other H atoms.

	x	y	z	Uiso*/Ueq
O1	0.72662 (12)	−0.12929 (19)	0.71101 (5)	0.0258 (3)
C2	0.81610 (17)	−0.1291 (3)	0.78046 (7)	0.0227 (3)
H2	0.9171	−0.1783	0.7796	0.027*
C3	0.81810 (17)	0.1200 (3)	0.80073 (8)	0.0222 (3)
H3A	0.7329	0.1589	0.8196	0.027*
H3B	0.9088	0.1591	0.8359	0.027*
O4	0.81137 (12)	0.23300 (19)	0.73591 (5)	0.0227 (2)
C5	0.72348 (19)	0.0946 (3)	0.68212 (8)	0.0232 (3)
C6	0.78923 (18)	0.0943 (3)	0.61799 (8)	0.0266 (4)
H6	0.7245	−0.0053	0.5824	0.032*
C7	0.7763 (2)	0.3330 (3)	0.58613 (8)	0.0329 (4)
H7A	0.8359	0.4400	0.6202	0.039*
H7B	0.8154	0.3319	0.5437	0.039*
C8	0.6194 (2)	0.4149 (4)	0.56676 (8)	0.0365 (4)
H8A	0.5619	0.3166	0.5293	0.044*
H8B	0.6163	0.5717	0.5482	0.044*
C9	0.54978 (19)	0.4117 (3)	0.62943 (8)	0.0308 (4)
H9	0.6041	0.5223	0.6649	0.037*
C10	0.56642 (18)	0.1768 (3)	0.66303 (8)	0.0270 (4)
H10A	0.5289	0.1811	0.7059	0.032*
H10B	0.5063	0.0670	0.6302	0.032*
C11	0.3900 (2)	0.4850 (4)	0.60923 (11)	0.0461 (5)
H11A	0.3347	0.3813	0.5736	0.069*
H11B	0.3831	0.6400	0.5904	0.069*
H11C	0.3497	0.4809	0.6507	0.069*
C12	0.9428 (2)	−0.0117 (4)	0.63175 (9)	0.0344 (4)
H12	0.9459	−0.1414	0.6649	0.041*
C13	0.9717 (2)	−0.1084 (4)	0.56378 (9)	0.0400 (5)
H13A	0.9693	0.0152	0.5301	0.060*
H13B	0.8964	−0.2206	0.5439	0.060*
H13C	1.0678	−0.1814	0.5740	0.060*
C14	1.0663 (2)	0.1510 (5)	0.66460 (13)	0.0633 (8)
H14A	1.1582	0.0664	0.6782	0.095*
H14B	1.0452	0.2222	0.7061	0.095*
H14C	1.0748	0.2687	0.6306	0.095*
C15	0.75391 (17)	−0.2914 (3)	0.82456 (8)	0.0241 (3)
H15A	0.7341	−0.4403	0.8007	0.029*
H15B	0.8241	−0.3148	0.8703	0.029*
O16	0.61928 (12)	−0.19409 (19)	0.83493 (5)	0.0219 (3)
C17	0.55649 (16)	−0.3039 (3)	0.87874 (7)	0.0204 (3)
C18	0.43170 (16)	−0.1728 (3)	0.89389 (7)	0.0195 (3)
C19	0.36462 (15)	−0.2611 (3)	0.94374 (7)	0.0207 (3)
H19	0.3984	−0.3989	0.9673	0.025*
C20	0.24814 (16)	−0.1456 (3)	0.95844 (7)	0.0196 (3)
C21	0.19642 (16)	0.0567 (3)	0.92634 (7)	0.0197 (3)
H21	0.1167	0.1350	0.9373	0.024*
C22	0.26696 (16)	0.1397 (3)	0.87730 (8)	0.0203 (3)
C23	0.38314 (16)	0.0311 (3)	0.86020 (8)	0.0196 (3)
H23	0.4288	0.0936	0.8264	0.024*
O24	0.59532 (12)	−0.4860 (2)	0.90476 (6)	0.0267 (3)
N25	0.21586 (14)	0.3563 (2)	0.84164 (6)	0.0219 (3)
O26	0.28039 (12)	0.4291 (2)	0.79908 (5)	0.0270 (3)
O27	0.11232 (11)	0.4517 (2)	0.85721 (6)	0.0275 (3)
N28	0.17654 (13)	−0.2454 (3)	1.01017 (6)	0.0222 (3)
O29	0.07569 (12)	−0.1400 (2)	1.02463 (6)	0.0299 (3)
O30	0.22049 (12)	−0.4300 (2)	1.03556 (6)	0.0271 (3)

	U11	U22	U33	U12	U13	U23
O1	0.0394 (6)	0.0178 (6)	0.0215 (5)	−0.0057 (5)	0.0101 (5)	−0.0007 (4)
C2	0.0236 (7)	0.0238 (9)	0.0229 (7)	0.0038 (7)	0.0097 (6)	0.0018 (7)
C3	0.0224 (7)	0.0251 (10)	0.0197 (7)	−0.0025 (7)	0.0061 (6)	−0.0017 (7)
O4	0.0302 (5)	0.0196 (6)	0.0189 (5)	−0.0046 (5)	0.0068 (4)	−0.0012 (5)
C5	0.0325 (8)	0.0158 (9)	0.0218 (7)	−0.0054 (7)	0.0075 (7)	−0.0010 (6)
C6	0.0348 (9)	0.0263 (10)	0.0196 (7)	−0.0092 (8)	0.0083 (7)	−0.0040 (7)
C7	0.0457 (11)	0.0308 (11)	0.0237 (7)	−0.0144 (8)	0.0114 (7)	0.0002 (8)
C8	0.0484 (11)	0.0313 (11)	0.0249 (8)	−0.0089 (9)	−0.0011 (7)	0.0060 (7)
C9	0.0340 (9)	0.0238 (11)	0.0299 (8)	−0.0050 (8)	−0.0013 (7)	0.0004 (7)
C10	0.0279 (8)	0.0261 (10)	0.0266 (7)	−0.0081 (7)	0.0057 (6)	−0.0018 (7)
C11	0.0405 (11)	0.0406 (14)	0.0503 (11)	0.0012 (10)	−0.0023 (9)	0.0048 (10)
C12	0.0388 (10)	0.0405 (12)	0.0272 (8)	−0.0038 (9)	0.0144 (8)	−0.0053 (8)
C13	0.0560 (12)	0.0388 (12)	0.0327 (8)	−0.0020 (10)	0.0253 (9)	0.0000 (8)
C14	0.0360 (11)	0.093 (2)	0.0638 (13)	−0.0085 (12)	0.0177 (10)	−0.0370 (15)
C15	0.0248 (8)	0.0232 (10)	0.0266 (7)	0.0072 (7)	0.0110 (6)	0.0023 (7)
O16	0.0232 (5)	0.0213 (7)	0.0236 (5)	0.0020 (4)	0.0102 (4)	0.0035 (5)
C17	0.0229 (7)	0.0205 (9)	0.0169 (6)	−0.0020 (6)	0.0034 (6)	−0.0026 (6)
C18	0.0196 (7)	0.0211 (9)	0.0172 (6)	−0.0025 (6)	0.0031 (6)	−0.0007 (6)
C19	0.0204 (8)	0.0217 (9)	0.0181 (6)	−0.0002 (7)	0.0007 (6)	0.0010 (6)
C20	0.0200 (7)	0.0222 (9)	0.0163 (6)	−0.0051 (7)	0.0036 (5)	−0.0024 (6)
C21	0.0162 (7)	0.0218 (9)	0.0208 (7)	−0.0004 (6)	0.0037 (5)	−0.0041 (6)
C22	0.0203 (7)	0.0193 (9)	0.0198 (6)	−0.0037 (6)	0.0019 (6)	−0.0015 (6)
C23	0.0206 (7)	0.0202 (9)	0.0184 (7)	−0.0032 (6)	0.0052 (6)	−0.0010 (6)
O24	0.0283 (6)	0.0241 (7)	0.0291 (5)	0.0049 (5)	0.0100 (5)	0.0089 (5)
N25	0.0209 (6)	0.0193 (8)	0.0236 (6)	−0.0027 (6)	0.0017 (5)	−0.0011 (6)
O26	0.0296 (6)	0.0245 (7)	0.0277 (5)	−0.0002 (5)	0.0083 (5)	0.0060 (5)
O27	0.0217 (5)	0.0223 (7)	0.0379 (6)	0.0024 (5)	0.0060 (5)	0.0005 (5)
N28	0.0194 (6)	0.0283 (9)	0.0186 (6)	−0.0040 (6)	0.0043 (5)	−0.0008 (6)
O29	0.0245 (6)	0.0357 (7)	0.0328 (5)	0.0008 (6)	0.0137 (5)	0.0043 (6)
O30	0.0278 (6)	0.0276 (7)	0.0263 (5)	−0.0007 (5)	0.0074 (5)	0.0068 (5)

O1—C2	1.4230 (17)	C12—C13	1.537 (2)
O1—C5	1.432 (2)	C12—H12	1.0000
C2—C15	1.501 (2)	C13—H13A	0.9800
C2—C3	1.518 (2)	C13—H13B	0.9800
C2—H2	1.0000	C13—H13C	0.9800
C3—O4	1.4259 (18)	C14—H14A	0.9800
C3—H3A	0.9900	C14—H14B	0.9800
C3—H3B	0.9900	C14—H14C	0.9800
O4—C5	1.4310 (19)	C15—O16	1.4523 (18)
C5—C10	1.518 (2)	C15—H15A	0.9900
C5—C6	1.534 (2)	C15—H15B	0.9900
C6—C7	1.531 (3)	O16—C17	1.3257 (19)
C6—C12	1.541 (2)	C17—O24	1.206 (2)
C6—H6	1.0000	C17—C18	1.497 (2)
C7—C8	1.517 (3)	C18—C19	1.390 (2)
C7—H7A	0.9900	C18—C23	1.393 (2)
C7—H7B	0.9900	C19—C20	1.381 (2)
C8—C9	1.530 (2)	C19—H19	0.9500
C8—H8A	0.9900	C20—C21	1.380 (2)
C8—H8B	0.9900	C20—N28	1.4726 (19)
C9—C10	1.523 (3)	C21—C22	1.386 (2)
C9—C11	1.526 (3)	C21—H21	0.9500
C9—H9	1.0000	C22—C23	1.379 (2)
C10—H10A	0.9900	C22—N25	1.478 (2)
C10—H10B	0.9900	C23—H23	0.9500
C11—H11A	0.9800	N25—O26	1.2253 (17)
C11—H11B	0.9800	N25—O27	1.2280 (17)
C11—H11C	0.9800	N28—O30	1.2254 (18)
C12—C14	1.526 (3)	N28—O29	1.2256 (18)
C2—O1—C5	109.35 (12)	H11A—C11—H11C	109.5
O1—C2—C15	109.28 (13)	H11B—C11—H11C	109.5
O1—C2—C3	102.70 (13)	C14—C12—C13	108.84 (16)
C15—C2—C3	116.37 (13)	C14—C12—C6	114.26 (18)
O1—C2—H2	109.4	C13—C12—C6	110.70 (15)
C15—C2—H2	109.4	C14—C12—H12	107.6
C3—C2—H2	109.4	C13—C12—H12	107.6
O4—C3—C2	102.72 (12)	C6—C12—H12	107.6
O4—C3—H3A	111.2	C12—C13—H13A	109.5
C2—C3—H3A	111.2	C12—C13—H13B	109.5
O4—C3—H3B	111.2	H13A—C13—H13B	109.5
C2—C3—H3B	111.2	C12—C13—H13C	109.5
H3A—C3—H3B	109.1	H13A—C13—H13C	109.5
C3—O4—C5	106.81 (11)	H13B—C13—H13C	109.5
O4—C5—O1	106.07 (11)	C12—C14—H14A	109.5
O4—C5—C10	111.08 (13)	C12—C14—H14B	109.5
O1—C5—C10	108.47 (14)	H14A—C14—H14B	109.5
O4—C5—C6	109.35 (13)	C12—C14—H14C	109.5
O1—C5—C6	110.57 (14)	H14A—C14—H14C	109.5
C10—C5—C6	111.17 (13)	H14B—C14—H14C	109.5
C7—C6—C5	109.12 (14)	O16—C15—C2	107.91 (13)
C7—C6—C12	114.98 (15)	O16—C15—H15A	110.1
C5—C6—C12	113.93 (14)	C2—C15—H15A	110.1
C7—C6—H6	106.0	O16—C15—H15B	110.1
C5—C6—H6	106.0	C2—C15—H15B	110.1
C12—C6—H6	106.0	H15A—C15—H15B	108.4
C8—C7—C6	111.77 (15)	C17—O16—C15	116.25 (13)
C8—C7—H7A	109.3	O24—C17—O16	124.84 (15)
C6—C7—H7A	109.3	O24—C17—C18	123.15 (14)
C8—C7—H7B	109.3	O16—C17—C18	112.00 (14)
C6—C7—H7B	109.3	C19—C18—C23	120.27 (14)
H7A—C7—H7B	107.9	C19—C18—C17	117.49 (15)
C7—C8—C9	112.11 (14)	C23—C18—C17	122.24 (13)
C7—C8—H8A	109.2	C20—C19—C18	118.97 (15)
C9—C8—H8A	109.2	C20—C19—H19	120.5
C7—C8—H8B	109.2	C18—C19—H19	120.5
C9—C8—H8B	109.2	C21—C20—C19	122.72 (14)
H8A—C8—H8B	107.9	C21—C20—N28	119.29 (14)
C10—C9—C11	111.20 (15)	C19—C20—N28	117.99 (15)
C10—C9—C8	109.96 (15)	C20—C21—C22	116.46 (14)
C11—C9—C8	112.06 (15)	C20—C21—H21	121.8
C10—C9—H9	107.8	C22—C21—H21	121.8
C11—C9—H9	107.8	C23—C22—C21	123.38 (15)
C8—C9—H9	107.8	C23—C22—N25	118.12 (13)
C5—C10—C9	112.88 (14)	C21—C22—N25	118.50 (13)
C5—C10—H10A	109.0	C22—C23—C18	118.20 (14)
C9—C10—H10A	109.0	C22—C23—H23	120.9
C5—C10—H10B	109.0	C18—C23—H23	120.9
C9—C10—H10B	109.0	O26—N25—O27	124.54 (14)
H10A—C10—H10B	107.8	O26—N25—C22	117.82 (13)
C9—C11—H11A	109.5	O27—N25—C22	117.64 (12)
C9—C11—H11B	109.5	O30—N28—O29	124.03 (13)
H11A—C11—H11B	109.5	O30—N28—C20	117.93 (13)
C9—C11—H11C	109.5	O29—N28—C20	118.03 (14)
C5—O1—C2—C15	145.19 (13)	C5—C6—C12—C13	153.37 (16)
C5—O1—C2—C3	21.05 (15)	O1—C2—C15—O16	−70.24 (16)
O1—C2—C3—O4	−33.31 (15)	C3—C2—C15—O16	45.44 (18)
C15—C2—C3—O4	−152.61 (12)	C2—C15—O16—C17	−173.43 (12)
C2—C3—O4—C5	33.85 (16)	C15—O16—C17—O24	−7.2 (2)
C3—O4—C5—O1	−21.48 (16)	C15—O16—C17—C18	171.59 (12)
C3—O4—C5—C10	96.20 (14)	O24—C17—C18—C19	4.1 (2)
C3—O4—C5—C6	−140.74 (14)	O16—C17—C18—C19	−174.70 (13)
C2—O1—C5—O4	−0.87 (16)	O24—C17—C18—C23	−176.18 (15)
C2—O1—C5—C10	−120.27 (13)	O16—C17—C18—C23	5.01 (19)
C2—O1—C5—C6	117.59 (14)	C23—C18—C19—C20	1.0 (2)
O4—C5—C6—C7	−66.69 (17)	C17—C18—C19—C20	−179.32 (13)
O1—C5—C6—C7	176.87 (13)	C18—C19—C20—C21	−1.0 (2)
C10—C5—C6—C7	56.32 (18)	C18—C19—C20—N28	178.53 (13)
O4—C5—C6—C12	63.30 (19)	C19—C20—C21—C22	0.6 (2)
O1—C5—C6—C12	−53.14 (19)	N28—C20—C21—C22	−178.93 (13)
C10—C5—C6—C12	−173.69 (15)	C20—C21—C22—C23	−0.1 (2)
C5—C6—C7—C8	−56.89 (18)	C20—C21—C22—N25	−179.81 (12)
C12—C6—C7—C8	173.69 (14)	C21—C22—C23—C18	0.2 (2)
C6—C7—C8—C9	56.6 (2)	N25—C22—C23—C18	179.83 (13)
C7—C8—C9—C10	−53.50 (19)	C19—C18—C23—C22	−0.6 (2)
C7—C8—C9—C11	−177.71 (18)	C17—C18—C23—C22	179.73 (14)
O4—C5—C10—C9	65.68 (16)	C23—C22—N25—O26	−0.60 (19)
O1—C5—C10—C9	−178.11 (12)	C21—C22—N25—O26	179.08 (14)
C6—C5—C10—C9	−56.33 (18)	C23—C22—N25—O27	179.99 (13)
C11—C9—C10—C5	178.43 (15)	C21—C22—N25—O27	−0.33 (19)
C8—C9—C10—C5	53.72 (17)	C21—C20—N28—O30	176.82 (13)
C7—C6—C12—C14	43.7 (2)	C19—C20—N28—O30	−2.68 (19)
C5—C6—C12—C14	−83.3 (2)	C21—C20—N28—O29	−2.41 (19)
C7—C6—C12—C13	−79.62 (19)	C19—C20—N28—O29	178.08 (13)