5,6-Dimeth­yl-1,10-phenanthroline

Rozenel, S.S.

doi:10.1107/S1600536813025087

organic compounds

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ISSN: 2056-9890

Volume 69| Part 10| October 2013| Page o1560

doi:10.1107/S1600536813025087

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5,6-Dimethyl-1,10-phenanthroline

Sergio S. Rozenel ^a ^*

^aChemistry Department and Chemical Sciences Division of Lawrence Berkeley National Laboratory, University of California, Berkeley, California 94720, USA
^*Correspondence e-mail: SSrozenel@lbl.gov

(Received 29 August 2013; accepted 9 September 2013; online 18 September 2013)

In the title compound, C₁₄H₁₂N₂, the N⋯N distance is 2.719 (1) Å. The N—C—C—N torsion angle [0.9 (1)°] is close to the ideal value of 0° as expected. Bond lengths and angles are consistent with those observed for [1,10]phenanthroline and coordinated 5,6 dimethyl[1,10]phenanthroline. In the crystal, C—H⋯N hydrogen bonds link the molecules into C(4) chains running parallel to the b axis. Weak π–π interactions between benzene and pyridine rings [centroid–centroid distance = 3.5337 (7) Å] and between benzene rings [centroid–centroid distances = 3.6627 (7) and 3.8391 (7)Å] also occur.

CCDC reference: 960120

Related literature

For [1,10]phenanthroline and 5,6-dimethyl[1,10]phenanthroline, see: Ton & Bolte (2005 ) and Gasque et al. (1999 ), respectively. For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₄H₁₂N₂
M_r = 208.26
Monoclinic, P 2₁ /c
a = 7.1932 (7) Å
b = 10.0572 (10) Å
c = 13.8729 (13) Å
β = 93.673 (5)°
V = 1001.55 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.11 × 0.10 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.991, T_max = 0.993
16500 measured reflections
1855 independent reflections
1613 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.100
S = 1.06
1855 reflections
171 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯N1ⁱ	0.945 (14)	2.439 (13)	3.3718 (15)	169.0 (10)
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare, et al. 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-32 (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 960120

Crystal structure: contains datablocks srd3013, I. DOI: 10.1107/S1600536813025087/bx2451sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813025087/bx2451Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813025087/bx2451Isup3.cml

checkCIF report

Comment top

5,6-dimethyl-1,10-phenanthroline was obtained from Sigma-Aldrich. The distances and angles are consistent with those observed for [1,10]phenanthroline (Ton & Bolte, 2005) and coordinated 5,6-dimethyl-1,10-phenanthroline (Gasque, et al., 1999). The crystal packing is stabilized by an intermolecular C—H···N hydrogen bond interaction which links the molecules into chains with graph-set notation C(4) (Bernstein, et al., 1995) running parallel to the b axis. Weak intermolecular π-π interactions, involving the benzene rings, and the pyridine rings, respectively with an average plane-to plane separation of 3.5982 (7) Å further stabilize and reinforce the crystal structure.

Related literature top

For [1,10]phenanthroline and 5,6-dimethyl-1,10-phenanthroline, see: Ton & Bolte (2005) and Gasque et al. (1999), respectively. For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

Crystals of the title compound, 5,6-dimethyl-1,10-phenanthroline, were obtained by sublimation at 160 °C under dynamic vacuum.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SIR97 (Altomare, et al. 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-32 (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

Fig. 1. Top view of the structure of 5,6-dimethyl-1,10-phenanthroline, displacement ellipsoids drawn at the 50% probability level.

5,6-Dimethyl-1,10-phenanthroline top

Crystal data top

C₁₄H₁₂N₂	F(000) = 440
M_r = 208.26	SHELXL-97
Monoclinic, P2₁/c	D_x = 1.381 Mg m⁻³
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.1932 (7) Å	Cell parameters from 9819 reflections
b = 10.0572 (10) Å	θ = 2.5–25.4°
c = 13.8729 (13) Å	µ = 0.08 mm⁻¹
β = 93.673 (5)°	T = 100 K
V = 1001.55 (17) Å³	Block, colourless
Z = 4	0.11 × 0.10 × 0.09 mm

Data collection top

Bruker APEXII CCD diffractometer	1855 independent reflections
Radiation source: microfocus sealed tube	1613 reflections with I > 2σ(I)
QUAZAR multilayer mirrors monochromator	R_int = 0.022
Detector resolution: 8.366 pixels mm^-1	θ_max = 25.5°, θ_min = 2.5°
ϕ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −12→12
T_min = 0.991, T_max = 0.993	l = −16→16
16500 measured reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0576P)² + 0.2458P] where P = (F_o² + 2F_c²)/3
1855 reflections	(Δ/σ)_max < 0.001
171 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₄H₁₂N₂	V = 1001.55 (17) Å³
M_r = 208.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.1932 (7) Å	µ = 0.08 mm⁻¹
b = 10.0572 (10) Å	T = 100 K
c = 13.8729 (13) Å	0.11 × 0.10 × 0.09 mm
β = 93.673 (5)°

Data collection top

Bruker APEXII CCD diffractometer	1855 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1613 reflections with I > 2σ(I)
T_min = 0.991, T_max = 0.993	R_int = 0.022
16500 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.16 e Å⁻³
1855 reflections	Δρ_min = −0.20 e Å⁻³
171 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
C1	0.42701 (15)	0.02490 (12)	0.23673 (8)	0.0163 (3)
C2	0.42141 (15)	0.15376 (12)	0.19967 (8)	0.0169 (3)
C3	0.35250 (15)	0.17126 (12)	0.10622 (8)	0.0155 (3)
C4	0.29281 (14)	0.06112 (11)	0.04921 (8)	0.0133 (3)
C5	0.22138 (14)	0.07469 (11)	−0.05047 (8)	0.0140 (3)
C6	0.17602 (14)	−0.03576 (11)	−0.10406 (8)	0.0140 (3)
C7	0.19526 (14)	−0.16667 (11)	−0.06034 (8)	0.0136 (3)
C8	0.15222 (15)	−0.28403 (12)	−0.11278 (8)	0.0168 (3)
C9	0.17425 (16)	−0.40516 (12)	−0.06876 (8)	0.0192 (3)
C10	0.24086 (16)	−0.40937 (12)	0.02795 (9)	0.0193 (3)
C11	0.26123 (14)	−0.18229 (11)	0.03706 (8)	0.0132 (3)
C12	0.31061 (14)	−0.06488 (11)	0.09349 (8)	0.0128 (3)
C13	0.20306 (16)	0.21432 (12)	−0.08965 (8)	0.0182 (3)
H13A	0.3273	0.2519	−0.0961	0.027*
H13B	0.1353	0.2692	−0.0452	0.027*
H13C	0.1347	0.2125	−0.1530	0.027*
C14	0.10570 (15)	−0.03036 (12)	−0.20896 (8)	0.0188 (3)
H14A	−0.0264	−0.0549	−0.2148	0.028*
H14B	0.1771	−0.0926	−0.2464	0.028*
H14C	0.1207	0.0600	−0.2337	0.028*
N1	0.37466 (12)	−0.08243 (9)	0.18696 (7)	0.0150 (2)
N2	0.28440 (13)	−0.30292 (9)	0.08056 (7)	0.0163 (3)
H1	0.4752 (17)	0.0073 (13)	0.3036 (9)	0.019 (3)*
H2	0.4698 (17)	0.2240 (14)	0.2390 (9)	0.020 (3)*
H3	0.3500 (18)	0.2604 (15)	0.0801 (9)	0.023 (3)*
H8	0.1103 (18)	−0.2799 (14)	−0.1809 (10)	0.026 (3)*
H9	0.1465 (17)	−0.4866 (14)	−0.1012 (9)	0.022 (3)*
H10	0.2560 (18)	−0.4966 (14)	0.0606 (9)	0.024 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0132 (5)	0.0220 (7)	0.0137 (6)	−0.0005 (4)	0.0003 (4)	−0.0018 (5)
C2	0.0141 (6)	0.0184 (6)	0.0183 (6)	−0.0024 (4)	0.0026 (4)	−0.0061 (5)
C3	0.0146 (6)	0.0130 (6)	0.0194 (6)	0.0002 (4)	0.0043 (4)	0.0005 (5)
C4	0.0086 (5)	0.0157 (6)	0.0160 (6)	0.0004 (4)	0.0031 (4)	0.0004 (5)
C5	0.0095 (5)	0.0160 (6)	0.0167 (6)	0.0014 (4)	0.0030 (4)	0.0034 (5)
C6	0.0098 (5)	0.0184 (6)	0.0141 (6)	0.0011 (4)	0.0023 (4)	0.0007 (5)
C7	0.0093 (5)	0.0169 (6)	0.0149 (6)	0.0007 (4)	0.0020 (4)	−0.0005 (5)
C8	0.0154 (6)	0.0210 (7)	0.0142 (6)	−0.0015 (5)	0.0008 (4)	−0.0024 (5)
C9	0.0201 (6)	0.0157 (6)	0.0217 (6)	−0.0018 (5)	0.0014 (5)	−0.0045 (5)
C10	0.0209 (6)	0.0126 (6)	0.0241 (7)	0.0004 (5)	0.0001 (5)	0.0012 (5)
C11	0.0101 (5)	0.0145 (6)	0.0151 (6)	0.0005 (4)	0.0026 (4)	0.0012 (5)
C12	0.0091 (5)	0.0165 (6)	0.0130 (6)	0.0004 (4)	0.0019 (4)	0.0013 (4)
C13	0.0197 (6)	0.0169 (7)	0.0177 (6)	0.0004 (5)	0.0000 (5)	0.0029 (5)
C14	0.0192 (6)	0.0218 (7)	0.0150 (6)	0.0019 (5)	−0.0014 (4)	0.0023 (5)
N1	0.0138 (5)	0.0180 (5)	0.0131 (5)	0.0002 (4)	−0.0002 (4)	0.0002 (4)
N2	0.0172 (5)	0.0135 (5)	0.0178 (5)	−0.0001 (4)	−0.0003 (4)	0.0013 (4)

Geometric parameters (Å, º) top

C1—N1	1.3230 (15)	C8—C9	1.3673 (17)
C1—C2	1.3939 (17)	C8—H8	0.975 (14)
C1—H1	0.985 (13)	C9—C10	1.3960 (17)
C2—C3	1.3695 (16)	C9—H9	0.950 (14)
C2—H2	0.945 (14)	C10—N2	1.3220 (15)
C3—C4	1.4118 (16)	C10—H10	0.990 (14)
C3—H3	0.967 (15)	C11—N2	1.3605 (14)
C4—C12	1.4105 (16)	C11—C12	1.4483 (15)
C4—C5	1.4505 (16)	C12—N1	1.3595 (14)
C5—C6	1.3645 (16)	C13—H13A	0.9800
C5—C13	1.5085 (15)	C13—H13B	0.9800
C6—C7	1.4525 (16)	C13—H13C	0.9800
C6—C14	1.5108 (15)	C14—H14A	0.9800
C7—C8	1.4104 (15)	C14—H14B	0.9800
C7—C11	1.4118 (15)	C14—H14C	0.9800

N1—C1—C2	124.44 (10)	C8—C9—H9	122.8 (8)
N1—C1—H1	114.6 (8)	C10—C9—H9	118.6 (8)
C2—C1—H1	121.0 (7)	N2—C10—C9	124.10 (11)
C3—C2—C1	117.96 (10)	N2—C10—H10	116.7 (8)
C3—C2—H2	123.3 (8)	C9—C10—H10	119.2 (8)
C1—C2—H2	118.7 (8)	N2—C11—C7	123.22 (10)
C2—C3—C4	120.54 (11)	N2—C11—C12	117.93 (10)
C2—C3—H3	118.1 (8)	C7—C11—C12	118.84 (10)
C4—C3—H3	121.3 (8)	N1—C12—C4	123.21 (10)
C12—C4—C3	116.43 (10)	N1—C12—C11	117.78 (10)
C12—C4—C5	121.10 (10)	C4—C12—C11	119.00 (10)
C3—C4—C5	122.46 (10)	C5—C13—H13A	109.5
C6—C5—C4	120.03 (10)	C5—C13—H13B	109.5
C6—C5—C13	123.31 (10)	H13A—C13—H13B	109.5
C4—C5—C13	116.65 (10)	C5—C13—H13C	109.5
C5—C6—C7	119.83 (10)	H13A—C13—H13C	109.5
C5—C6—C14	123.31 (10)	H13B—C13—H13C	109.5
C7—C6—C14	116.87 (10)	C6—C14—H14A	109.5
C8—C7—C11	116.73 (10)	C6—C14—H14B	109.5
C8—C7—C6	122.09 (10)	H14A—C14—H14B	109.5
C11—C7—C6	121.17 (10)	C6—C14—H14C	109.5
C9—C8—C7	119.99 (10)	H14A—C14—H14C	109.5
C9—C8—H8	119.4 (8)	H14B—C14—H14C	109.5
C7—C8—H8	120.6 (8)	C1—N1—C12	117.36 (9)
C8—C9—C10	118.62 (11)	C10—N2—C11	117.34 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N1ⁱ	0.945 (14)	2.439 (13)	3.3718 (15)	169.0 (10)

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N1ⁱ	0.945 (14)	2.439 (13)	3.3718 (15)	169.0 (10)

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Acknowledgements

The author thanks Professor Richard Andersen and Dr DiPasquale for their support. This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, and the Division of Chemical Sciences, Geosciences, and Biosciences of the US Department of Energy under contract No. DE–AC02-05CH11231.

References

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