1,1′-Bicyclo­hexyl-1,1′-diyl 2,2′-bipyridine-3,3′-dicarboxyl­ate

Fun, H.-K.; Lim, M.Y.; Quah, C.K.; Wu, D.

doi:10.1107/S1600536812018508

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1629

doi:10.1107/S1600536812018508

Open

access

1,1′-Bicyclohexyl-1,1′-diyl 2,2′-bipyridine-3,3′-dicarboxylate

Hoong-Kun Fun,^a ^*‡ Ming Yeng Lim,^a Ching Kheng Quah ^a § and Dongdong Wu ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bSchool of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: hkfun@usm.my

(Received 20 April 2012; accepted 25 April 2012; online 5 May 2012)

The title compound, C₂₄H₂₆N₂O₄, lies about a crystallographic twofold rotation axis. The cyclohexane rings adopts a chair conformation. The two pyridine rings form a dihedral angle of 41.02 (4)°. In the crystal, molecules are linked via C—H⋯O and C—H⋯N hydrogen bonds into a layer parallel to the bc plane.

Related literature

For the background to this study, see the first paper in this series: Fun, Quah, Wu & Zhang (2012 ). For a related structure, see: Fun, Quah & Wu (2012 ). For the stability of the temperature controller used in the the data collection, see: Cosier & Glazer (1986 ). For standard bond-length data, see: Allen et al. (1987 ). For ring conformations, see: Cremer & Pople (1975 ). For the preparation, see: Wu et al. (2012 ).

Experimental

Crystal data

C₂₄H₂₆N₂O₄
M_r = 406.47
Monoclinic, C 2/c
a = 16.7647 (3) Å
b = 10.2618 (2) Å
c = 11.5755 (2) Å
β = 99.810 (1)°
V = 1962.28 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.53 × 0.24 × 0.12 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.952, T_max = 0.989
11734 measured reflections
3578 independent reflections
2972 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.119
S = 1.04
3578 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯O2ⁱ	0.95	2.60	3.5319 (12)	168
C12—H12A⋯N1ⁱⁱ	0.99	2.54	3.4641 (12)	156
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) x, y+1, z.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812018508/is5124sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812018508/is5124Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812018508/is5124Isup3.cml

checkCIF report

Comment top

The title compound is a ten-membered bislactone with biaryl moiety fused. Easy preparation of this compound could be achieved through a concise photochemical method (Wu et al., 2012). The title compound, Fig. 1, lies about a crystallographic twofold axis generated by the symmetry code -x, y, -z + 1/2. The cyclohexane ring (C7–C12) adopts a chair conformation with puckering parameters (Cremer & Pople, 1975) Q = 0.5773 (10) Å, Θ = 177.88 (10)° and ϕ = 256 (3)°. The two pyridine rings (N1/C1–C5 & N1A/C1A–C5A) are essentially planar [maximum deviation of 0.018 (1) Å at atom C4/C4A] and form a dihedral angle of 41.02 (4)°. Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to related structures (Fun, Quah, Wu & Zhang, 2012; Fun, Quah & Wu, 2012). In the crystal (Fig. 2), molecules are linked via intermolecular C3—H3A···O2 and C12—H12A···N1 hydrogen bonds (Table 1) into layers parallel to the (100) plane.

Related literature top

For the background to this study, see the first paper in this series: Fun, Quah, Wu & Zhang (2012). For a related structure, see: Fun, Quah & Wu (2012). For the stability of the temperature controller used in the the data collection, see: Cosier & Glazer (1986). For standard bond-length data, see: Allen et al. (1987). For ring conformations, see: Cremer & Pople (1975). For the preparation, see: Wu et al. (2012).

Experimental top

The title compound was the product from the photo-oxidation between 2,3-dispirohexyl-2,3-dihydro-[1,4]dioxino[2,3-f][1,10]phenanthroline and oxygen. The compound was purified by flash column chromatography with ethyl acetate/petroleum ether (1:10) as eluents. X-ray quality crystals of the title compound (m.p. 180–183 °C), were obtained from slow evaporation of an acetone and petroleum ether solution (1:10).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids for non-H atoms. Atoms with suffix A have been generated by the symmetry code -x, y, -z + 1/2.
	Fig. 2. A packing diagram of the title compound, viewed along the c axis. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity.

1,1'-Bicyclohexyl-1,1'-diyl 2,2'-bipyridine-3,3'-dicarboxylate top

Crystal data top

C₂₄H₂₆N₂O₄	F(000) = 864
M_r = 406.47	D_x = 1.376 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4821 reflections
a = 16.7647 (3) Å	θ = 2.3–32.4°
b = 10.2618 (2) Å	µ = 0.09 mm⁻¹
c = 11.5755 (2) Å	T = 100 K
β = 99.810 (1)°	Block, colourless
V = 1962.28 (6) Å³	0.53 × 0.24 × 0.12 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3578 independent reflections
Radiation source: fine-focus sealed tube	2972 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 32.7°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −24→25
T_min = 0.952, T_max = 0.989	k = −15→15
11734 measured reflections	l = −14→17

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0602P)² + 1.2358P] where P = (F_o² + 2F_c²)/3
3578 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₂₄H₂₆N₂O₄	V = 1962.28 (6) Å³
M_r = 406.47	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.7647 (3) Å	µ = 0.09 mm⁻¹
b = 10.2618 (2) Å	T = 100 K
c = 11.5755 (2) Å	0.53 × 0.24 × 0.12 mm
β = 99.810 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3578 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2972 reflections with I > 2σ(I)
T_min = 0.952, T_max = 0.989	R_int = 0.027
11734 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.04	Δρ_max = 0.50 e Å⁻³
3578 reflections	Δρ_min = −0.27 e Å⁻³
136 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.07035 (4)	0.91569 (6)	0.32195 (5)	0.01138 (14)
O2	0.08919 (4)	0.79994 (7)	0.15933 (6)	0.01480 (15)
N1	0.03750 (5)	0.47163 (8)	0.36731 (7)	0.01641 (17)
C1	0.13527 (6)	0.68507 (10)	0.44475 (8)	0.01575 (18)
H1A	0.1678	0.7583	0.4717	0.019*
C2	0.13993 (6)	0.57190 (10)	0.51086 (8)	0.01792 (19)
H2A	0.1757	0.5658	0.5837	0.022*
C3	0.09090 (6)	0.46750 (10)	0.46771 (8)	0.01813 (19)
H3A	0.0955	0.3889	0.5117	0.022*
C4	0.03211 (5)	0.58187 (9)	0.30384 (8)	0.01315 (17)
C5	0.08212 (5)	0.68998 (9)	0.33802 (8)	0.01229 (16)
C6	0.08110 (5)	0.80731 (9)	0.26097 (8)	0.01163 (16)
C7	0.04781 (5)	1.04426 (9)	0.26757 (7)	0.01063 (16)
C8	0.09239 (5)	1.07527 (9)	0.16519 (8)	0.01365 (17)
H8A	0.0760	1.0116	0.1013	0.016*
H8B	0.0764	1.1631	0.1343	0.016*
C9	0.18467 (6)	1.07060 (10)	0.20256 (9)	0.01769 (19)
H9A	0.2013	0.9814	0.2289	0.021*
H9B	0.2110	1.0921	0.1346	0.021*
C10	0.21245 (6)	1.16711 (11)	0.30191 (9)	0.0207 (2)
H10A	0.2716	1.1591	0.3280	0.025*
H10B	0.2007	1.2572	0.2734	0.025*
C11	0.16867 (6)	1.13963 (10)	0.40464 (8)	0.01758 (19)
H11A	0.1842	1.2065	0.4660	0.021*
H11B	0.1860	1.0537	0.4388	0.021*
C12	0.07650 (5)	1.14012 (9)	0.36753 (8)	0.01346 (17)
H12A	0.0585	1.2291	0.3422	0.016*
H12B	0.0510	1.1171	0.4359	0.016*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0130 (3)	0.0087 (3)	0.0120 (3)	0.0012 (2)	0.0009 (2)	0.0006 (2)
O2	0.0162 (3)	0.0141 (3)	0.0145 (3)	0.0007 (2)	0.0040 (2)	−0.0013 (2)
N1	0.0203 (4)	0.0111 (4)	0.0178 (3)	0.0014 (3)	0.0030 (3)	0.0021 (3)
C1	0.0156 (4)	0.0141 (4)	0.0164 (4)	0.0025 (3)	−0.0004 (3)	−0.0002 (3)
C2	0.0196 (4)	0.0177 (5)	0.0154 (4)	0.0054 (4)	−0.0002 (3)	0.0016 (3)
C3	0.0223 (4)	0.0140 (4)	0.0180 (4)	0.0052 (4)	0.0032 (3)	0.0039 (3)
C4	0.0156 (4)	0.0099 (4)	0.0138 (4)	0.0012 (3)	0.0022 (3)	0.0001 (3)
C5	0.0132 (3)	0.0097 (4)	0.0139 (3)	0.0020 (3)	0.0020 (3)	0.0005 (3)
C6	0.0094 (3)	0.0098 (4)	0.0151 (4)	−0.0001 (3)	0.0003 (3)	−0.0002 (3)
C7	0.0118 (3)	0.0076 (3)	0.0119 (3)	−0.0002 (3)	0.0003 (3)	0.0009 (3)
C8	0.0132 (4)	0.0137 (4)	0.0140 (4)	−0.0011 (3)	0.0023 (3)	0.0021 (3)
C9	0.0134 (4)	0.0198 (5)	0.0203 (4)	−0.0020 (3)	0.0040 (3)	0.0032 (4)
C10	0.0143 (4)	0.0193 (5)	0.0271 (5)	−0.0050 (4)	−0.0001 (3)	0.0018 (4)
C11	0.0141 (4)	0.0167 (4)	0.0200 (4)	−0.0014 (3)	−0.0028 (3)	−0.0025 (4)
C12	0.0142 (4)	0.0101 (4)	0.0148 (4)	−0.0005 (3)	−0.0011 (3)	−0.0023 (3)

Geometric parameters (Å, º) top

O1—C6	1.3458 (11)	C7—C7ⁱ	1.5854 (17)
O1—C7	1.4828 (11)	C8—C9	1.5344 (13)
O2—C6	1.2094 (11)	C8—H8A	0.9900
N1—C3	1.3414 (12)	C8—H8B	0.9900
N1—C4	1.3435 (12)	C9—C10	1.5290 (15)
C1—C2	1.3856 (14)	C9—H9A	0.9900
C1—C5	1.3956 (12)	C9—H9B	0.9900
C1—H1A	0.9500	C10—C11	1.5264 (15)
C2—C3	1.3903 (15)	C10—H10A	0.9900
C2—H2A	0.9500	C10—H10B	0.9900
C3—H3A	0.9500	C11—C12	1.5317 (13)
C4—C5	1.4061 (13)	C11—H11A	0.9900
C4—C4ⁱ	1.5018 (18)	C11—H11B	0.9900
C5—C6	1.4968 (12)	C12—H12A	0.9900
C7—C12	1.5324 (12)	C12—H12B	0.9900
C7—C8	1.5382 (12)

C6—O1—C7	124.05 (6)	C7—C8—H8A	109.2
C3—N1—C4	118.24 (9)	C9—C8—H8B	109.2
C2—C1—C5	119.12 (9)	C7—C8—H8B	109.2
C2—C1—H1A	120.4	H8A—C8—H8B	107.9
C5—C1—H1A	120.4	C10—C9—C8	110.80 (8)
C1—C2—C3	118.24 (9)	C10—C9—H9A	109.5
C1—C2—H2A	120.9	C8—C9—H9A	109.5
C3—C2—H2A	120.9	C10—C9—H9B	109.5
N1—C3—C2	123.60 (9)	C8—C9—H9B	109.5
N1—C3—H3A	118.2	H9A—C9—H9B	108.1
C2—C3—H3A	118.2	C11—C10—C9	109.94 (8)
N1—C4—C5	121.94 (8)	C11—C10—H10A	109.7
N1—C4—C4ⁱ	115.20 (6)	C9—C10—H10A	109.7
C5—C4—C4ⁱ	122.84 (6)	C11—C10—H10B	109.7
C1—C5—C4	118.74 (8)	C9—C10—H10B	109.7
C1—C5—C6	119.82 (8)	H10A—C10—H10B	108.2
C4—C5—C6	121.42 (8)	C10—C11—C12	112.15 (8)
O2—C6—O1	127.53 (8)	C10—C11—H11A	109.2
O2—C6—C5	122.52 (8)	C12—C11—H11A	109.2
O1—C6—C5	109.95 (7)	C10—C11—H11B	109.2
O1—C7—C12	103.07 (6)	C12—C11—H11B	109.2
O1—C7—C8	112.90 (7)	H11A—C11—H11B	107.9
C12—C7—C8	108.53 (7)	C11—C12—C7	112.42 (8)
O1—C7—C7ⁱ	106.40 (5)	C11—C12—H12A	109.1
C12—C7—C7ⁱ	111.54 (7)	C7—C12—H12A	109.1
C8—C7—C7ⁱ	113.91 (8)	C11—C12—H12B	109.1
C9—C8—C7	112.04 (7)	C7—C12—H12B	109.1
C9—C8—H8A	109.2	H12A—C12—H12B	107.9

C5—C1—C2—C3	−0.15 (14)	C1—C5—C6—O1	−53.79 (11)
C4—N1—C3—C2	1.26 (15)	C4—C5—C6—O1	128.11 (9)
C1—C2—C3—N1	−2.13 (16)	C6—O1—C7—C12	−157.78 (7)
C3—N1—C4—C5	1.90 (14)	C6—O1—C7—C8	−40.90 (10)
C3—N1—C4—C4ⁱ	−176.74 (10)	C6—O1—C7—C7ⁱ	84.75 (10)
C2—C1—C5—C4	3.07 (14)	O1—C7—C8—C9	−56.99 (10)
C2—C1—C5—C6	−175.08 (8)	C12—C7—C8—C9	56.61 (10)
N1—C4—C5—C1	−4.06 (14)	C7ⁱ—C7—C8—C9	−178.48 (6)
C4ⁱ—C4—C5—C1	174.47 (10)	C7—C8—C9—C10	−58.49 (11)
N1—C4—C5—C6	174.05 (8)	C8—C9—C10—C11	56.01 (11)
C4ⁱ—C4—C5—C6	−7.41 (15)	C9—C10—C11—C12	−54.88 (11)
C7—O1—C6—O2	14.66 (13)	C10—C11—C12—C7	55.67 (11)
C7—O1—C6—C5	−165.46 (7)	O1—C7—C12—C11	65.03 (9)
C1—C5—C6—O2	126.10 (10)	C8—C7—C12—C11	−54.90 (10)
C4—C5—C6—O2	−52.00 (13)	C7ⁱ—C7—C12—C11	178.81 (7)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O2ⁱⁱ	0.95	2.60	3.5319 (12)	168
C12—H12A···N1ⁱⁱⁱ	0.99	2.54	3.4641 (12)	156

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

Experimental details

Crystal data
Chemical formula	C₂₄H₂₆N₂O₄
M_r	406.47
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	16.7647 (3), 10.2618 (2), 11.5755 (2)
β (°)	99.810 (1)
V (Å³)	1962.28 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.53 × 0.24 × 0.12

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.952, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	11734, 3578, 2972
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.759

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.119, 1.04
No. of reflections	3578
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.27

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SAINT (Bruker, 2009, SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O2ⁱ	0.95	2.60	3.5319 (12)	168
C12—H12A···N1ⁱⁱ	0.99	2.54	3.4641 (12)	156

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5525-2009.

Acknowledgements

HKF and CKQ thank Universiti Sains Malaysia for the Research University Grant (No. 1001/PFIZIK/811160). Financial support from the Ministry of Science and Technology of China of the Austria–China Cooperation project (2007DFA41590) is acknowledged.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Fun, H.-K., Quah, C. K. & Wu, D. (2012). Acta Cryst. E68, o1628. CSD CrossRef IUCr Journals Google Scholar
Fun, H.-K., Quah, C. K., Wu, D. & Zhang, Y. (2012). Acta Cryst. E68, o1627. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wu, D., Wang, L., Xu, K., Song, J., Fun, H.-K., Xu, J. & Zhang, Y. (2012). Chem. Commun. 48, 1168–1170. Web of Science CSD CrossRef CAS Google Scholar