3,9-Dimethyl-3,9-bis-(4-nitro-phen-yl)-2,4,8,10-tetra-oxaspiro-[5.5]undeca-ne.

In the title compound, C(21)H(22)N(2)O(8), both of the nonplanar six-membered heterocycles adopt chair conformations. The dihedral angle between the terminal benzene rings is 58.22 (11)°. Weak inter-molecular C-H⋯O inter-actions are observed in the crystal structure.

Related literature

For general background to spiranes, see: Cismaş et al. (2005 ▶); Mihiş et al. (2008 ▶); Sun et al. (2010 ▶).

Experimental

Crystal data

C21H22N2O8

M = 430.41

Triclinic,

a = 7.4215 (12) Å

b = 11.8790 (18) Å

c = 13.522 (3) Å

α = 115.280 (4)°

β = 94.426 (4)°

γ = 103.444 (3)°

V = 1027.0 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.11 mm−1

T = 295 K

0.21 × 0.21 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.976, T max = 0.986

5588 measured reflections

3563 independent reflections

2980 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.187

S = 1.07

3563 reflections

282 parameters

12 restraints

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015017/is2689sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015017/is2689Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811015017/is2689Isup3.cml

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

Enhanced figure: interactive version of Fig. 1

C21H22N2O8	Z = 2
Mr = 430.41	F(000) = 452
Triclinic, P1	Dx = 1.392 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4215 (12) Å	Cell parameters from 3502 reflections
b = 11.8790 (18) Å	θ = 2.9–30.2°
c = 13.522 (3) Å	µ = 0.11 mm−1
α = 115.280 (4)°	T = 295 K
β = 94.426 (4)°	Block, colorless
γ = 103.444 (3)°	0.21 × 0.21 × 0.16 mm
V = 1027.0 (3) Å3

Bruker APEXII CCD diffractometer	3563 independent reflections
Radiation source: fine-focus sealed tube	2980 reflections with I > 2σ(I)
graphite	Rint = 0.022
φ and ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→8
Tmin = 0.976, Tmax = 0.986	k = −14→14
5588 measured reflections	l = −16→11

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.187	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.135P)2 + 0.1621P] where P = (Fo2 + 2Fc2)/3
3563 reflections	(Δ/σ)max < 0.001
282 parameters	Δρmax = 0.37 e Å−3
12 restraints	Δρmin = −0.26 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	Uiso*/Ueq
N1	1.2247 (3)	0.6344 (2)	0.63022 (16)	0.0321 (5)
N2	0.1620 (3)	0.14798 (18)	−0.42929 (16)	0.0254 (5)
O1	1.2782 (3)	0.5766 (2)	0.67765 (15)	0.0451 (5)
O2	1.1755 (3)	0.73336 (19)	0.67867 (14)	0.0424 (5)
O3	0.2195 (3)	0.18113 (19)	−0.49758 (15)	0.0398 (5)
O4	−0.0012 (2)	0.13861 (17)	−0.41184 (15)	0.0346 (4)
O5	1.2135 (2)	0.31399 (14)	0.10612 (12)	0.0205 (4)
O6	1.1156 (2)	0.48954 (14)	0.11022 (12)	0.0209 (4)
O7	0.86957 (19)	0.10427 (13)	−0.16096 (12)	0.0192 (4)
O8	0.6406 (2)	0.06651 (14)	−0.06059 (12)	0.0238 (4)
C1	1.2214 (3)	0.5840 (2)	0.51053 (18)	0.0242 (5)
C2	1.2715 (3)	0.4717 (2)	0.45462 (19)	0.0254 (5)
H2A	1.3038	0.4270	0.4920	0.030*
C3	1.2728 (3)	0.4269 (2)	0.34267 (18)	0.0231 (5)
H3A	1.3069	0.3515	0.3041	0.028*
C4	1.2233 (3)	0.4939 (2)	0.28631 (17)	0.0195 (5)
C5	1.1707 (3)	0.6059 (2)	0.34539 (18)	0.0224 (5)
H5	1.1353	0.6501	0.3083	0.027*
C6	1.1703 (3)	0.6524 (2)	0.45800 (18)	0.0244 (5)
H6	1.1366	0.7278	0.4973	0.029*
C7	1.2414 (3)	0.4498 (2)	0.16478 (17)	0.0199 (5)
C8	1.4377 (3)	0.5140 (2)	0.15867 (19)	0.0264 (5)
H8A	1.5284	0.4917	0.1958	0.040*
H8B	1.4615	0.6069	0.1944	0.040*
H8C	1.4484	0.4846	0.0819	0.040*
C9	1.0213 (3)	0.2363 (2)	0.08616 (17)	0.0215 (5)
H9A	0.9863	0.2480	0.1568	0.026*
H9B	1.0111	0.1449	0.0421	0.026*
C10	0.9207 (3)	0.4212 (2)	0.09267 (17)	0.0211 (5)
H10A	0.8431	0.4507	0.0534	0.025*
H10B	0.8844	0.4397	0.1641	0.025*
C11	0.8872 (3)	0.2752 (2)	0.02479 (17)	0.0200 (5)
C12	0.9199 (3)	0.2421 (2)	−0.09323 (17)	0.0187 (5)
H12A	0.8447	0.2786	−0.1264	0.022*
H12B	1.0520	0.2806	−0.0901	0.022*
C13	0.6814 (3)	0.2026 (2)	0.01311 (18)	0.0236 (5)
H13A	0.6576	0.2144	0.0859	0.028*
H13B	0.5984	0.2386	−0.0156	0.028*
C14	0.6799 (3)	0.0390 (2)	−0.16773 (17)	0.0205 (5)
C15	0.6618 (3)	−0.1047 (2)	−0.22524 (19)	0.0282 (5)
H15A	0.7513	−0.1229	−0.1834	0.042*
H15B	0.6865	−0.1289	−0.2991	0.042*
H15C	0.5360	−0.1537	−0.2298	0.042*
C16	0.5415 (3)	0.07090 (19)	−0.23489 (17)	0.0192 (5)
C17	0.5956 (3)	0.0991 (2)	−0.31997 (17)	0.0195 (5)
H17	0.7169	0.1014	−0.3338	0.023*
C18	0.4722 (3)	0.1238 (2)	−0.38398 (17)	0.0204 (5)
H18	0.5097	0.1443	−0.4398	0.024*
C19	0.2916 (3)	0.1176 (2)	−0.36354 (17)	0.0208 (5)
C20	0.2302 (3)	0.0863 (2)	−0.28153 (18)	0.0232 (5)
H20	0.1073	0.0812	−0.2699	0.028*
C21	0.3573 (3)	0.0631 (2)	−0.21751 (18)	0.0236 (5)
H21	0.3192	0.0419	−0.1621	0.028*

	U11	U22	U33	U12	U13	U23
N1	0.0187 (10)	0.0450 (13)	0.0191 (10)	−0.0053 (9)	−0.0021 (8)	0.0112 (9)
N2	0.0205 (10)	0.0278 (10)	0.0265 (10)	0.0095 (8)	0.0042 (8)	0.0100 (9)
O1	0.0418 (11)	0.0681 (14)	0.0253 (9)	0.0071 (10)	0.0027 (8)	0.0266 (10)
O2	0.0362 (10)	0.0535 (12)	0.0220 (9)	0.0097 (9)	0.0090 (8)	0.0045 (8)
O3	0.0348 (10)	0.0605 (13)	0.0410 (11)	0.0205 (9)	0.0092 (8)	0.0349 (10)
O4	0.0220 (9)	0.0451 (10)	0.0416 (10)	0.0175 (8)	0.0069 (7)	0.0203 (9)
O5	0.0209 (8)	0.0203 (8)	0.0193 (8)	0.0082 (6)	0.0035 (6)	0.0072 (6)
O6	0.0240 (8)	0.0224 (8)	0.0189 (8)	0.0084 (6)	0.0036 (6)	0.0111 (6)
O7	0.0163 (7)	0.0208 (8)	0.0186 (7)	0.0058 (6)	0.0036 (6)	0.0072 (6)
O8	0.0253 (8)	0.0256 (8)	0.0206 (8)	0.0037 (7)	0.0038 (6)	0.0127 (7)
C1	0.0158 (10)	0.0328 (12)	0.0165 (11)	−0.0022 (9)	0.0014 (8)	0.0097 (10)
C2	0.0214 (11)	0.0306 (12)	0.0237 (11)	0.0004 (9)	−0.0023 (9)	0.0168 (10)
C3	0.0224 (11)	0.0208 (11)	0.0239 (11)	0.0031 (9)	0.0002 (9)	0.0106 (9)
C4	0.0149 (10)	0.0222 (11)	0.0194 (11)	0.0027 (8)	0.0020 (8)	0.0094 (9)
C5	0.0220 (11)	0.0233 (11)	0.0216 (11)	0.0064 (9)	0.0024 (9)	0.0105 (9)
C6	0.0191 (11)	0.0256 (11)	0.0216 (11)	0.0041 (9)	0.0042 (9)	0.0059 (9)
C7	0.0225 (11)	0.0203 (11)	0.0185 (11)	0.0082 (9)	0.0037 (9)	0.0096 (9)
C8	0.0265 (12)	0.0297 (12)	0.0236 (12)	0.0069 (10)	0.0086 (9)	0.0131 (10)
C9	0.0250 (11)	0.0197 (11)	0.0180 (10)	0.0056 (9)	0.0031 (9)	0.0076 (9)
C10	0.0231 (11)	0.0253 (11)	0.0159 (10)	0.0092 (9)	0.0032 (8)	0.0095 (9)
C11	0.0217 (11)	0.0234 (11)	0.0174 (11)	0.0086 (9)	0.0057 (8)	0.0103 (9)
C12	0.0188 (10)	0.0192 (10)	0.0175 (11)	0.0048 (8)	0.0030 (8)	0.0085 (9)
C13	0.0245 (11)	0.0287 (12)	0.0171 (10)	0.0089 (9)	0.0056 (9)	0.0092 (9)
C14	0.0191 (11)	0.0227 (11)	0.0184 (11)	0.0054 (9)	0.0040 (8)	0.0086 (9)
C15	0.0284 (12)	0.0228 (12)	0.0296 (12)	0.0057 (10)	−0.0020 (10)	0.0107 (10)
C16	0.0179 (10)	0.0158 (10)	0.0202 (11)	0.0043 (8)	0.0030 (8)	0.0055 (9)
C17	0.0163 (10)	0.0228 (11)	0.0174 (10)	0.0056 (8)	0.0059 (8)	0.0070 (9)
C18	0.0188 (10)	0.0234 (11)	0.0171 (10)	0.0045 (9)	0.0057 (8)	0.0080 (9)
C19	0.0193 (11)	0.0186 (10)	0.0199 (11)	0.0065 (8)	0.0006 (8)	0.0048 (9)
C20	0.0167 (10)	0.0281 (12)	0.0242 (11)	0.0080 (9)	0.0090 (9)	0.0099 (10)
C21	0.0206 (11)	0.0268 (12)	0.0243 (11)	0.0054 (9)	0.0087 (9)	0.0127 (10)

N1—O1	1.226 (3)	C8—H8C	0.9600
N1—O2	1.234 (3)	C9—C11	1.519 (3)
N1—C1	1.462 (3)	C9—H9A	0.9700
N2—O3	1.218 (2)	C9—H9B	0.9700
N2—O4	1.240 (2)	C10—C11	1.522 (3)
N2—C19	1.466 (3)	C10—H10A	0.9700
O5—C7	1.414 (2)	C10—H10B	0.9700
O5—C9	1.441 (2)	C11—C12	1.526 (3)
O6—C7	1.426 (2)	C11—C13	1.528 (3)
O6—C10	1.430 (2)	C12—H12A	0.9700
O7—C14	1.415 (2)	C12—H12B	0.9700
O7—C12	1.428 (2)	C13—H13A	0.9700
O8—C14	1.413 (2)	C13—H13B	0.9700
O8—C13	1.431 (3)	C14—C15	1.510 (3)
C1—C2	1.379 (3)	C14—C16	1.534 (3)
C1—C6	1.379 (3)	C15—H15A	0.9600
C2—C3	1.375 (3)	C15—H15B	0.9600
C2—H2A	0.9300	C15—H15C	0.9600
C3—C4	1.400 (3)	C16—C17	1.391 (3)
C3—H3A	0.9300	C16—C21	1.393 (3)
C4—C5	1.393 (3)	C17—C18	1.376 (3)
C4—C7	1.525 (3)	C17—H17	0.9300
C5—C6	1.381 (3)	C18—C19	1.381 (3)
C5—H5	0.9300	C18—H18	0.9300
C6—H6	0.9300	C19—C20	1.388 (3)
C7—C8	1.506 (3)	C20—C21	1.384 (3)
C8—H8A	0.9600	C20—H20	0.9300
C8—H8B	0.9600	C21—H21	0.9300
O1—N1—O2	123.3 (2)	C11—C10—H10B	109.6
O1—N1—C1	118.2 (2)	H10A—C10—H10B	108.1
O2—N1—C1	118.6 (2)	C9—C11—C10	107.29 (16)
O3—N2—O4	123.52 (19)	C9—C11—C12	111.57 (17)
O3—N2—C19	118.69 (18)	C10—C11—C12	110.46 (16)
O4—N2—C19	117.79 (18)	C9—C11—C13	111.03 (16)
C7—O5—C9	113.97 (15)	C10—C11—C13	109.82 (17)
C7—O6—C10	113.62 (14)	C12—C11—C13	106.70 (17)
C14—O7—C12	113.49 (15)	O7—C12—C11	110.82 (16)
C14—O8—C13	113.91 (15)	O7—C12—H12A	109.5
C2—C1—C6	122.4 (2)	C11—C12—H12A	109.5
C2—C1—N1	119.3 (2)	O7—C12—H12B	109.5
C6—C1—N1	118.3 (2)	C11—C12—H12B	109.5
C3—C2—C1	118.90 (19)	H12A—C12—H12B	108.1
C3—C2—H2A	120.5	O8—C13—C11	110.95 (16)
C1—C2—H2A	120.5	O8—C13—H13A	109.4
C2—C3—C4	120.5 (2)	C11—C13—H13A	109.4
C2—C3—H3A	119.7	O8—C13—H13B	109.4
C4—C3—H3A	119.7	C11—C13—H13B	109.4
C5—C4—C3	118.81 (19)	H13A—C13—H13B	108.0
C5—C4—C7	121.08 (18)	O8—C14—O7	111.31 (16)
C3—C4—C7	119.96 (19)	O8—C14—C15	106.00 (17)
C6—C5—C4	121.19 (19)	O7—C14—C15	106.04 (16)
C6—C5—H5	119.4	O8—C14—C16	111.73 (16)
C4—C5—H5	119.4	O7—C14—C16	111.13 (16)
C1—C6—C5	118.1 (2)	C15—C14—C16	110.34 (17)
C1—C6—H6	120.9	C14—C15—H15A	109.5
C5—C6—H6	120.9	C14—C15—H15B	109.5
O5—C7—O6	111.16 (15)	H15A—C15—H15B	109.5
O5—C7—C8	106.19 (17)	C14—C15—H15C	109.5
O6—C7—C8	106.18 (16)	H15A—C15—H15C	109.5
O5—C7—C4	112.31 (16)	H15B—C15—H15C	109.5
O6—C7—C4	110.65 (16)	C17—C16—C21	119.12 (19)
C8—C7—C4	110.07 (17)	C17—C16—C14	119.69 (18)
C7—C8—H8A	109.5	C21—C16—C14	121.04 (18)
C7—C8—H8B	109.5	C18—C17—C16	120.94 (19)
H8A—C8—H8B	109.5	C18—C17—H17	119.5
C7—C8—H8C	109.5	C16—C17—H17	119.5
H8A—C8—H8C	109.5	C17—C18—C19	118.60 (19)
H8B—C8—H8C	109.5	C17—C18—H18	120.7
O5—C9—C11	110.63 (16)	C19—C18—H18	120.7
O5—C9—H9A	109.5	C18—C19—C20	122.33 (19)
C11—C9—H9A	109.5	C18—C19—N2	118.64 (18)
O5—C9—H9B	109.5	C20—C19—N2	119.01 (18)
C11—C9—H9B	109.5	C21—C20—C19	118.04 (19)
H9A—C9—H9B	108.1	C21—C20—H20	121.0
O6—C10—C11	110.27 (16)	C19—C20—H20	121.0
O6—C10—H10A	109.6	C20—C21—C16	120.92 (19)
C11—C10—H10A	109.6	C20—C21—H21	119.5
O6—C10—H10B	109.6	C16—C21—H21	119.5
O1—N1—C1—C2	2.3 (3)	C14—O7—C12—C11	57.4 (2)
O2—N1—C1—C2	−178.41 (19)	C9—C11—C12—O7	66.9 (2)
O1—N1—C1—C6	−176.8 (2)	C10—C11—C12—O7	−173.87 (15)
O2—N1—C1—C6	2.5 (3)	C13—C11—C12—O7	−54.5 (2)
C6—C1—C2—C3	0.8 (3)	C14—O8—C13—C11	−56.1 (2)
N1—C1—C2—C3	−178.31 (18)	C9—C11—C13—O8	−68.0 (2)
C1—C2—C3—C4	−0.3 (3)	C10—C11—C13—O8	173.56 (15)
C2—C3—C4—C5	−0.7 (3)	C12—C11—C13—O8	53.8 (2)
C2—C3—C4—C7	174.82 (19)	C13—O8—C14—O7	55.3 (2)
C3—C4—C5—C6	1.2 (3)	C13—O8—C14—C15	170.19 (16)
C7—C4—C5—C6	−174.24 (19)	C13—O8—C14—C16	−69.6 (2)
C2—C1—C6—C5	−0.3 (3)	C12—O7—C14—O8	−55.9 (2)
N1—C1—C6—C5	178.84 (18)	C12—O7—C14—C15	−170.77 (15)
C4—C5—C6—C1	−0.8 (3)	C12—O7—C14—C16	69.3 (2)
C9—O5—C7—O6	−54.6 (2)	O8—C14—C16—C17	155.17 (18)
C9—O5—C7—C8	−169.62 (16)	O7—C14—C16—C17	30.2 (2)
C9—O5—C7—C4	70.0 (2)	C15—C14—C16—C17	−87.2 (2)
C10—O6—C7—O5	55.6 (2)	O8—C14—C16—C21	−29.4 (3)
C10—O6—C7—C8	170.66 (16)	O7—C14—C16—C21	−154.43 (19)
C10—O6—C7—C4	−69.9 (2)	C15—C14—C16—C21	88.2 (2)
C5—C4—C7—O5	−154.14 (18)	C21—C16—C17—C18	2.3 (3)
C3—C4—C7—O5	30.5 (3)	C14—C16—C17—C18	177.83 (18)
C5—C4—C7—O6	−29.3 (3)	C16—C17—C18—C19	−1.2 (3)
C3—C4—C7—O6	155.32 (18)	C17—C18—C19—C20	−0.5 (3)
C5—C4—C7—C8	87.8 (2)	C17—C18—C19—N2	178.06 (18)
C3—C4—C7—C8	−87.6 (2)	O3—N2—C19—C18	−2.0 (3)
C7—O5—C9—C11	55.9 (2)	O4—N2—C19—C18	178.18 (19)
C7—O6—C10—C11	−57.5 (2)	O3—N2—C19—C20	176.7 (2)
O5—C9—C11—C10	−54.6 (2)	O4—N2—C19—C20	−3.2 (3)
O5—C9—C11—C12	66.6 (2)	C18—C19—C20—C21	1.1 (3)
O5—C9—C11—C13	−174.56 (16)	N2—C19—C20—C21	−177.47 (18)
O6—C10—C11—C9	55.5 (2)	C19—C20—C21—C16	0.0 (3)
O6—C10—C11—C12	−66.3 (2)	C17—C16—C21—C20	−1.7 (3)
O6—C10—C11—C13	176.29 (15)	C14—C16—C21—C20	−177.16 (19)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O2i	0.97	2.56	3.515 (3)	168.
C10—H10B···O1i	0.97	2.59	3.533 (3)	164.
C17—H17···O4ii	0.93	2.45	3.337 (3)	160.
C20—H20···O7iii	0.93	2.37	3.242 (3)	155.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯O2i	0.97	2.56	3.515 (3)	168
C10—H10B⋯O1i	0.97	2.59	3.533 (3)	164
C17—H17⋯O4ii	0.93	2.45	3.337 (3)	160
C20—H20⋯O7iii	0.93	2.37	3.242 (3)	155

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