Biphenyl-4,4′-diyl bis­(2,2,5,5-tetra­methyl-1-oxyl-3-pyrroline-3-carboxyl­ate)

Margraf, D.; Schuetz, D.; Prisner, T.F.; Bats, J.W.

doi:10.1107/S1600536809024659

organic compounds

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Volume 65| Part 8| August 2009| Page o1784

doi:10.1107/S1600536809024659

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Biphenyl-4,4′-diyl bis(2,2,5,5-tetramethyl-1-oxyl-3-pyrroline-3-carboxylate)

Dominik Margraf,^a Denise Schuetz,^a Thomas F. Prisner ^a and Jan W. Bats ^b ^*

^aInstitut für Physikalische und Theoretische Chemie, Universität Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main, Germany, and ^bInstitut für Organische Chemie, Universität Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main, Germany
^*Correspondence e-mail: bats@chemie.uni-frankfurt.de

(Received 18 June 2009; accepted 26 June 2009; online 4 July 2009)

In the title compound, C₃₀H₃₄N₂O₆, the complete molecule is generated by a crystallographic 2/m symmetry operation. The 1-oxyl-3-pyrroline-3-carboxylate group lies on a mirror plane. The dihedral angle between the ring planes of the biphenyl fragment is constrained by symmetry to be zero, resulting in rather short intramolecular H⋯H contact distances of 2.02 Å. In the crystal, molecules are connected along the a-axis direction by very weak intermolecular methyl–phenyl C—H⋯π interactions. The C—H bond is not directed to the center of the benzene ring, but mainly to one C atom [C—H⋯C(x − 1, y, z): H⋯C = 2.91 Å and C—H⋯C = 143°].

Related literature

For the preparation of the title compound see: Weber et al. (2002 ). For the crystal structures of related compounds see: Boeyens & Kruger (1970 ); Bolte (2006 ); Duskova et al. (2001 ); Godt et al., 2000 ; Papoutsakis et al. (1999 ); Wiley et al., 1989 and Wiley et al., 1991 .

Experimental

Crystal data

C₃₀H₃₄N₂O₆
M_r = 518.59
Monoclinic, C 2/m
a = 6.931 (2) Å
b = 9.461 (3) Å
c = 20.805 (4) Å
β = 96.059 (14)°
V = 1356.6 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 169 K
0.44 × 0.30 × 0.10 mm

Data collection

Siemens SMART 1K CCD diffractometer
Absorption correction: none
11267 measured reflections
2074 independent reflections
1552 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.126
S = 1.03
2074 reflections
105 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11C⋯C3ⁱ	0.98	2.91	3.745 (2)	143
Symmetry code: (i) x-1, y, z.

Data collection: SMART (Siemens, 1995 ); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809024659/lh2852sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024659/lh2852Isup2.hkl

checkCIF report

Comment top

The title compound was prepared as a reference compound for pulsed electron-electron double resonance measurements (Weber et al., 2002).

The molecular structure is shown in Fig. 1. The molecule has 2/m symmetry: atoms C1, C4, O1, C5, O2, C6, C7, C8, C9, N1 and O3 lie on a mirror plane. There is a twofold axis perpendicular to this mirror plane and passing through the center of the central C—C single bond. There also is an inversion center at the midpoint of the central C—C single bond. The two six-membered rings of the biphenyl group are coplanar by symmetry, resulting in rather short intramolecular H···H contact distances of 2.02 A. The 1-oxyl-3-pyrroline-3-carboxylate group is planar. Approximate planarity of this group also has been observed in a number of related crystal structures (Papoutsakis et al., 1999; Boeyens & Kruger, 1970; Bolte, 2006; Duskova et al., 2001; Godt et al., 2000; Wiley et al., 1989 and Wiley et al., 1991)

The crystal packing is shown in Fig 2. The molecules are connected along the a-direction by four symmetry-equivalent very weak intermolecular C_methyl—H···π(phenyl) interactions (Table 1). The C_methyl—H bond is not directed to the center of the phenyl ring, but mainly to one C atom. There are no other short intermolecular contacts.

Related literature top

For the preparation of the title compound see: Weber et al. (2002). For the crystal structures of related compounds see: Boeyens & Kruger (1970); Bolte (2006); Duskova et al. (2001); Godt et al., 2000; Papoutsakis et al. (1999); Wiley et al., 1989 and Wiley et al., 1991.

Experimental top

The title compound was prepared similar to the procedure described by Weber et al. (2002). Single crystals were obtained by recrystallization of the compound from a mixture of toluene and n-hexane (3:1).

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT (Siemens, 1995); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound shown with 50% probability displacement ellipsoids. The H atoms are drawn as small spheres of arbitrary radius. Symmetry equivalent atoms are related by i: x, -y, z, ii: 2 - x, -y, 1 - z and iii: 2 - x, y, 1 - z.
	Fig. 2. The crystal packing of the title compound, viewed down the a axis.

Biphenyl-4,4'-diyl bis(2,2,5,5-tetramethyl-1-oxyl-3-pyrroline-3-carboxylate) top

Crystal data top

C₃₀H₃₄N₂O₆	F(000) = 552
M_r = 518.59	D_x = 1.270 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 77 reflections
a = 6.931 (2) Å	θ = 3–23°
b = 9.461 (3) Å	µ = 0.09 mm⁻¹
c = 20.805 (4) Å	T = 169 K
β = 96.059 (14)°	Plate, yellow
V = 1356.6 (6) Å³	0.44 × 0.30 × 0.10 mm
Z = 2

Data collection top

Siemens SMART 1K CCD diffractometer	1552 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	R_int = 0.056
Graphite monochromator	θ_max = 30.5°, θ_min = 2.0°
ω scans	h = −9→9
11267 measured reflections	k = −13→12
2074 independent reflections	l = −29→29

Refinement top

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.06P)² + 0.9P] where P = (F_o² + 2F_c²)/3
2074 reflections	(Δ/σ)_max = 0.001
105 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₃₀H₃₄N₂O₆	V = 1356.6 (6) Å³
M_r = 518.59	Z = 2
Monoclinic, C2/m	Mo Kα radiation
a = 6.931 (2) Å	µ = 0.09 mm⁻¹
b = 9.461 (3) Å	T = 169 K
c = 20.805 (4) Å	0.44 × 0.30 × 0.10 mm
β = 96.059 (14)°

Data collection top

Siemens SMART 1K CCD diffractometer	1552 reflections with I > 2σ(I)
11267 measured reflections	R_int = 0.056
2074 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 1.03	Δρ_max = 0.39 e Å⁻³
2074 reflections	Δρ_min = −0.21 e Å⁻³
105 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.58234 (19)	0.0000	0.29187 (6)	0.0310 (3)
O2	0.2989 (2)	0.0000	0.33551 (6)	0.0396 (4)
O3	−0.0951 (2)	0.0000	0.09831 (7)	0.0323 (3)
N1	0.0672 (2)	0.0000	0.13356 (7)	0.0231 (3)
C1	0.9329 (3)	0.0000	0.46943 (8)	0.0231 (4)
C2	0.8678 (2)	0.12604 (16)	0.43958 (6)	0.0317 (3)
H2A	0.9076	0.2135	0.4592	0.038*
C3	0.7462 (2)	0.12691 (16)	0.38187 (7)	0.0321 (3)
H3A	0.7036	0.2137	0.3622	0.039*
C4	0.6887 (3)	0.0000	0.35376 (8)	0.0261 (4)
C5	0.3862 (3)	0.0000	0.28870 (8)	0.0211 (4)
C6	0.2971 (2)	0.0000	0.22093 (8)	0.0179 (3)
C7	0.3911 (3)	0.0000	0.16826 (8)	0.0190 (3)
H7A	0.5285	0.0000	0.1696	0.023*
C8	0.2570 (3)	0.0000	0.10658 (8)	0.0205 (3)
C9	0.0794 (2)	0.0000	0.20539 (8)	0.0185 (3)
C10	0.2784 (2)	0.13302 (16)	0.06612 (7)	0.0324 (3)
H10A	0.1799	0.1325	0.0287	0.049*
H10B	0.4079	0.1348	0.0512	0.049*
H10C	0.2611	0.2169	0.0925	0.049*
C11	−0.01778 (19)	0.13337 (14)	0.22809 (7)	0.0261 (3)
H11A	−0.1535	0.1360	0.2093	0.039*
H11B	0.0503	0.2170	0.2142	0.039*
H11C	−0.0125	0.1327	0.2753	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0170 (6)	0.0590 (9)	0.0159 (6)	0.000	−0.0032 (5)	0.000
O2	0.0240 (7)	0.0753 (12)	0.0194 (6)	0.000	0.0022 (5)	0.000
O3	0.0215 (7)	0.0429 (8)	0.0295 (7)	0.000	−0.0116 (5)	0.000
N1	0.0176 (7)	0.0302 (8)	0.0200 (7)	0.000	−0.0050 (5)	0.000
C1	0.0194 (8)	0.0309 (9)	0.0182 (8)	0.000	−0.0018 (6)	0.000
C2	0.0363 (8)	0.0306 (7)	0.0256 (7)	0.0027 (6)	−0.0087 (6)	−0.0022 (5)
C3	0.0340 (8)	0.0360 (8)	0.0244 (6)	0.0067 (6)	−0.0066 (5)	0.0026 (6)
C4	0.0166 (8)	0.0452 (11)	0.0157 (8)	0.000	−0.0023 (6)	0.000
C5	0.0183 (8)	0.0246 (8)	0.0195 (8)	0.000	−0.0017 (6)	0.000
C6	0.0164 (7)	0.0172 (7)	0.0192 (8)	0.000	−0.0020 (6)	0.000
C7	0.0179 (8)	0.0188 (8)	0.0193 (8)	0.000	−0.0021 (6)	0.000
C8	0.0211 (8)	0.0226 (8)	0.0169 (7)	0.000	−0.0015 (6)	0.000
C9	0.0159 (7)	0.0193 (8)	0.0199 (8)	0.000	−0.0006 (6)	0.000
C10	0.0376 (8)	0.0321 (7)	0.0262 (7)	−0.0044 (6)	−0.0032 (6)	0.0093 (6)
C11	0.0200 (6)	0.0234 (6)	0.0346 (7)	0.0024 (5)	0.0012 (5)	−0.0035 (5)

Geometric parameters (Å, º) top

O1—C5	1.354 (2)	C6—C7	1.332 (2)
O1—C4	1.414 (2)	C6—C9	1.509 (2)
O2—C5	1.199 (2)	C7—C8	1.503 (2)
O3—N1	1.2766 (19)	C7—H7A	0.9500
N1—C8	1.484 (2)	C8—C10ⁱ	1.5299 (17)
N1—C9	1.488 (2)	C8—C10	1.5299 (17)
C1—C2ⁱ	1.3970 (17)	C9—C11	1.5285 (16)
C1—C2	1.3971 (17)	C9—C11ⁱ	1.5285 (16)
C1—C1ⁱⁱ	1.495 (3)	C10—H10A	0.9800
C2—C3	1.3922 (19)	C10—H10B	0.9800
C2—H2A	0.9500	C10—H10C	0.9800
C3—C4	1.3760 (17)	C11—H11A	0.9800
C3—H3A	0.9500	C11—H11B	0.9800
C4—C3ⁱ	1.3761 (17)	C11—H11C	0.9800
C5—C6	1.478 (2)

C5—O1—C4	117.92 (14)	N1—C8—C7	99.78 (13)
O3—N1—C8	123.07 (14)	N1—C8—C10ⁱ	110.45 (10)
O3—N1—C9	122.02 (15)	C7—C8—C10ⁱ	112.51 (9)
C8—N1—C9	114.91 (13)	N1—C8—C10	110.45 (10)
C2ⁱ—C1—C2	117.19 (16)	C7—C8—C10	112.51 (9)
C2ⁱ—C1—C1ⁱⁱ	121.40 (8)	C10ⁱ—C8—C10	110.69 (15)
C2—C1—C1ⁱⁱ	121.40 (8)	N1—C9—C6	99.50 (13)
C3—C2—C1	121.74 (13)	N1—C9—C11	109.27 (9)
C3—C2—H2A	119.1	C6—C9—C11	113.40 (9)
C1—C2—H2A	119.1	N1—C9—C11ⁱ	109.28 (9)
C4—C3—C2	118.90 (13)	C6—C9—C11ⁱ	113.40 (9)
C4—C3—H3A	120.6	C11—C9—C11ⁱ	111.28 (15)
C2—C3—H3A	120.6	C8—C10—H10A	109.5
C3—C4—C3ⁱ	121.52 (17)	C8—C10—H10B	109.5
C3—C4—O1	119.12 (8)	H10A—C10—H10B	109.5
C3ⁱ—C4—O1	119.12 (8)	C8—C10—H10C	109.5
O2—C5—O1	123.36 (16)	H10A—C10—H10C	109.5
O2—C5—C6	125.39 (17)	H10B—C10—H10C	109.5
O1—C5—C6	111.25 (14)	C9—C11—H11A	109.5
C7—C6—C5	126.39 (16)	C9—C11—H11B	109.5
C7—C6—C9	112.83 (14)	H11A—C11—H11B	109.5
C5—C6—C9	120.78 (14)	C9—C11—H11C	109.5
C6—C7—C8	112.99 (16)	H11A—C11—H11C	109.5
C6—C7—H7A	123.5	H11B—C11—H11C	109.5
C8—C7—H7A	123.5

C2ⁱ—C1—C2—C3	−1.2 (3)	C9—N1—C8—C10ⁱ	118.61 (10)
C1ⁱⁱ—C1—C2—C3	178.55 (19)	O3—N1—C8—C10	61.39 (10)
C1—C2—C3—C4	0.1 (2)	C9—N1—C8—C10	−118.61 (10)
C2—C3—C4—C3ⁱ	1.0 (3)	C6—C7—C8—N1	0.0
C2—C3—C4—O1	−173.34 (14)	C6—C7—C8—C10ⁱ	−117.08 (11)
C5—O1—C4—C3	−92.77 (15)	C6—C7—C8—C10	117.08 (11)
C5—O1—C4—C3ⁱ	92.77 (15)	O3—N1—C9—C6	180.0
C4—O1—C5—O2	0.0	C8—N1—C9—C6	0.0
C4—O1—C5—C6	180.0	O3—N1—C9—C11	−60.99 (10)
O2—C5—C6—C7	180.0	C8—N1—C9—C11	119.01 (10)
O1—C5—C6—C7	0.0	O3—N1—C9—C11ⁱ	60.99 (10)
O2—C5—C6—C9	0.0	C8—N1—C9—C11ⁱ	−119.01 (10)
O1—C5—C6—C9	180.0	C7—C6—C9—N1	0.0
C5—C6—C7—C8	180.0	C5—C6—C9—N1	180.0
C9—C6—C7—C8	0.0	C7—C6—C9—C11	−115.91 (11)
O3—N1—C8—C7	180.0	C5—C6—C9—C11	64.09 (11)
C9—N1—C8—C7	0.0	C7—C6—C9—C11ⁱ	115.92 (11)
O3—N1—C8—C10ⁱ	−61.39 (10)	C5—C6—C9—C11ⁱ	−64.08 (11)

Symmetry codes: (i) x, −y, z; (ii) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11C···C3ⁱⁱⁱ	0.98	2.91	3.745 (2)	143

Symmetry code: (iii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₃₀H₃₄N₂O₆
M_r	518.59
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	169
a, b, c (Å)	6.931 (2), 9.461 (3), 20.805 (4)
β (°)	96.059 (14)
V (Å³)	1356.6 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.44 × 0.30 × 0.10

Data collection
Diffractometer	Siemens SMART 1K CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11267, 2074, 1552
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.126, 1.03
No. of reflections	2074
No. of parameters	105
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.21

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11C···C3ⁱ	0.98	2.91	3.745 (2)	143

Symmetry code: (i) x−1, y, z.

References

Boeyens, J. C. A. & Kruger, G. J. (1970). Acta Cryst. B26, 668–672. CSD CrossRef CAS IUCr Journals Google Scholar
Bolte, M. (2006). Acta Cryst. E62, m1609–m1610. Web of Science CSD CrossRef IUCr Journals Google Scholar
Duskova, J., Labsky, J., Hasek, J. & Cisarova, I. (2001). Acta Cryst. E57, o85–o86. Web of Science CSD CrossRef IUCr Journals Google Scholar
Godt, A., Franzen, C., Veit, S., Enkelmann, V., Pannier, M. & Jeschke, G. (2000). J. Org. Chem. 65, 7575–7582. Web of Science CSD CrossRef PubMed CAS Google Scholar
Papoutsakis, D., Kirby, J. P., Jackson, J. E. & Nocera, D. G. (1999). Chem. Eur. J. 5, 1474–1480. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1995). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Weber, A., Schiemann, O., Bode, B. & Prisner, T. F. (2002). J. Magn. Reson. 157, 277–285. Web of Science CrossRef PubMed CAS Google Scholar
Wiley, D. W., Calabrese, J. C., Harlow, R. L. & Miller, J. S. (1991). Angew. Chem. Int. Ed. 30, 450–452. CSD CrossRef Google Scholar
Wiley, D. W., Calabrese, J. C. & Miller, J. S. (1989). Chem. Commun. pp. 1523–1526. CrossRef Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bi­phenyl-4,4′-diyl bis­­(2,2,5,5-tetra­methyl-1-oxyl-3-pyrroline-3-carboxyl­ate)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

Biphenyl-4,4′-diyl bis(2,2,5,5-tetramethyl-1-oxyl-3-pyrroline-3-carboxylate)