1,10-Phenanthroline-5,6-dione ethanol monosolvate

Dai, J.-W.; Li, Z.-Y.; Sato, O.

doi:10.1107/S1600536814008241

organic compounds

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1,10-Phenanthroline-5,6-dione ethanol monosolvate

Jing-Wei Dai,^a Zhao-Yang Li ^b and Osamu Sato ^a ^*

^aInstitute for Materials Chemistry and Engineering, Kyushu University, 6-1 Kasuga-koen, Kasuga, Fukuoka 816-8580, Japan, and ^bDepartment of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, Sendai 980-8578, Japan
^*Correspondence e-mail: sato@cm.kyushu-u.ac.jp

(Received 30 March 2014; accepted 11 April 2014; online 18 April 2014)

In the title compound, C₁₂H₆N₂O₂·C₂H₅OH, the molecule of the 1,10-phenanthroline-5,6-dione is approximately planar, with a maximum deviation of 0.051 (1) Å. In the crystal, molecules are linked by O—H⋯N and weak C—H⋯O hydrogen bonds, forming supramolecular chains propagating along [110]. π–π stacking interactions are observed between the pyridine rings of neighbouring chains, the centroid–centroid separations being 3.6226 (11) and 3.7543 (11) Å.

CCDC reference: 996896

Related literature

For background to and applications of 1,10-phenanthroline-5,6-dione, see: Smith & Cagle (1947 ); Ma et al. (2010 ); Goss & Abruna (1985 ); Murphy et al. (2011 ); Wu et al. (1996 ); Pinczewska et al. (2012 ); Poteet & MacDonnell (2013 ); Wu et al. (2002 ); Poteet et al. 2013 ); Paw et al. (1998 ). For the synthesis, see: Paw & Eisenberg (1997 ). For a related structure, see: Calderazzo et al. (1999 ).

Experimental

Crystal data

C₁₂H₆N₂O₂·C₂H₆O
M_r = 256.26
Triclinic, $[P \overline 1]$
a = 7.3064 (15) Å
b = 9.1055 (18) Å
c = 9.7291 (19) Å
α = 96.47 (3)°
β = 101.68 (3)°
γ = 109.83 (3)°
V = 584.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 123 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Saturn724+ diffractometer
5059 measured reflections
2252 independent reflections
2074 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.114
S = 1.06
2252 reflections
185 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯N1ⁱ	0.85 (1)	2.08 (1)	2.8258 (19)	146 (2)
C1—H1⋯O2ⁱⁱ	0.95	2.53	3.3381 (19)	143
Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) x+1, y+1, z.

Data collection: CrystalClear (Rigaku, 2008 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 996896

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814008241/xu5783sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814008241/xu5783Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814008241/xu5783Isup3.cml

checkCIF report

Experimental top

Synthesis and crystallization top

The title compound was prepared according to literature method (Paw & Eisenberg, 1997). An ice-cold mixture of concentrated H₂SO₄ (40 mL) and HNO₃ (20 mL) was added to 4 g of 1,10-phenanthroline (0.02 mol) and 4 g of KBr (0.03 mol). The mixture was heated at 90 ^oC for 3 h. The hot yellow solution was poured over 200 mL of ice and neutralized carefully with sodium hydroxide until neutral to slightly acidic pH. Extraction with CH₂Cl₂ (4*100 mL) followed by drying with Na₂SO₄ and removal of solvent gave 2.8 g (yield = 67%) of 1,10-phenanthroline-5,6-dione. This product was purified further by crystallization from ethanol.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. Carbon-bound H-atoms were placed in calculated positions and were included in the refinement in the riding model approximation with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for the others. The hydroxy H atom was located in a difference Fourier map, and was refined with distance restraints of O—H = 0.84±0.01, U_iso(H) = 1.2U_eq(O).

Results and discussion top

1,10-Phenanthroline-5,6-dione has been known for many years (Smith & Cagle, 1947), and its chelating ability as either a diimine or a catecholate was important in coordination chemistry (Ma et al., 2010, Goss & Abruna, 1985, Murphy et al., 2011), analytical chemistry (Wu et al., 1996, Pinczewska et al., 2012) and biophysical chemistry (Poteet & MacDonnell, 2013, Wu et al., 2002, Poteet et al., 2013). Moreover, it can become as the bridging ligand, which has shown very interesting function in multinuclear complexes (Paw et al., 1998, Paw & Eisenberg, 1997, Calderazzo et al., 1999).

According to the structural analysis, the bond lengths and angles of the title compound are generally within normal ranges. The asymmetric unit of the title compound consists of one 1,10-phenanthroline-5,6-dione molecule and one ethanol molecule. Between molecules, O—H···N and C—H···O hydrogen bonds can be found that further form one-dimensional chain. The weak π···π stacking interactions between adjacent chains are also observed [centroid– centroid separations being 3.6226 (11) and 3.7543 (11) Å].

Related literature top

For background to and applications of 1,10-phenanthroline-5,6-dione, see: Smith & Cagle (1947); Ma et al. (2010); Goss & Abruna (1985); Murphy et al. (2011); Wu et al. (1996); Pinczewska et al. (2012); Poteet & MacDonnell (2013); Wu et al. (2002); Poteet et al. 2013); Paw et al. (1998). For the synthesis, see: Paw & Eisenberg (1997). For a related structure, see: Calderazzo et al. (1999).

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Crystal packing of the title compound. Intermolecular O—H···N and C—H···O hydrogen bonds are shown as green dashed lines, and π-π stacking interactions between molecules are shown as blue dashed lines.

1,10-Phenanthroline-5,6-dione ethanol monosolvate top

Crystal data top

C₁₂H₆N₂O₂·C₂H₆O	Z = 2
M_r = 256.26	F(000) = 268
Triclinic, P1	D_x = 1.456 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3064 (15) Å	Cell parameters from 2355 reflections
b = 9.1055 (18) Å	θ = 3.1–30.2°
c = 9.7291 (19) Å	µ = 0.10 mm⁻¹
α = 96.47 (3)°	T = 123 K
β = 101.68 (3)°	Block, yellow
γ = 109.83 (3)°	0.20 × 0.20 × 0.20 mm
V = 584.6 (2) Å³

Data collection top

Rigaku Saturn724+ diffractometer	2074 reflections with I > 2σ(I)
Radiation source: Rotating Anode	R_int = 0.020
Confocal monochromator	θ_max = 26.0°, θ_min = 3.1°
Detector resolution: 28.5714 pixels mm^-1	h = −9→9
ω scans	k = −11→11
5059 measured reflections	l = −11→11
2252 independent 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0709P)² + 0.118P] where P = (F_o² + 2F_c²)/3
2252 reflections	(Δ/σ)_max < 0.001
185 parameters	Δρ_max = 0.24 e Å⁻³
1 restraint	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₂H₆N₂O₂·C₂H₆O	γ = 109.83 (3)°
M_r = 256.26	V = 584.6 (2) Å³
Triclinic, P1	Z = 2
a = 7.3064 (15) Å	Mo Kα radiation
b = 9.1055 (18) Å	µ = 0.10 mm⁻¹
c = 9.7291 (19) Å	T = 123 K
α = 96.47 (3)°	0.20 × 0.20 × 0.20 mm
β = 101.68 (3)°

Data collection top

Rigaku Saturn724+ diffractometer	2074 reflections with I > 2σ(I)
5059 measured reflections	R_int = 0.020
2252 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	1 restraint
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.24 e Å⁻³
2252 reflections	Δρ_min = −0.17 e Å⁻³
185 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
C4	0.66468 (17)	0.96363 (14)	0.27101 (12)	0.0211 (3)
C11	0.69855 (17)	0.93910 (13)	0.52865 (12)	0.0196 (3)
C5	0.50156 (18)	0.80403 (14)	0.22423 (12)	0.0237 (3)
C7	0.54977 (17)	0.78514 (14)	0.49173 (12)	0.0211 (3)
C6	0.43997 (17)	0.70995 (13)	0.34035 (13)	0.0239 (3)
C12	0.75757 (16)	1.02974 (13)	0.41609 (12)	0.0200 (3)
C8	0.50365 (18)	0.70329 (14)	0.60099 (13)	0.0250 (3)
H8	0.4042	0.5987	0.5794	0.030*
C9	0.60544 (18)	0.77748 (15)	0.74108 (13)	0.0270 (3)
H9	0.5787	0.7248	0.8179	0.032*
C3	0.72616 (18)	1.05260 (15)	0.16952 (13)	0.0252 (3)
H3	0.6651	1.0108	0.0704	0.030*
C1	0.95979 (18)	1.25750 (14)	0.36088 (14)	0.0262 (3)
H1	1.0632	1.3603	0.3919	0.031*
C10	0.74812 (18)	0.93131 (15)	0.76688 (13)	0.0261 (3)
H10	0.8166	0.9818	0.8636	0.031*
C2	0.87625 (19)	1.20164 (15)	0.21448 (14)	0.0272 (3)
H2	0.9213	1.2644	0.1475	0.033*
O1	0.41332 (14)	0.74720 (11)	0.09901 (9)	0.0331 (3)
O2	0.30275 (14)	0.58111 (10)	0.30567 (10)	0.0333 (3)
N2	0.79532 (15)	1.01274 (12)	0.66490 (10)	0.0237 (2)
N1	0.90359 (15)	1.17542 (12)	0.46054 (11)	0.0233 (2)
C15	0.8686 (2)	0.65765 (16)	0.07549 (14)	0.0336 (3)
H15A	0.8325	0.7503	0.0621	0.050*
H15B	0.8372	0.5885	−0.0177	0.050*
H15C	1.0130	0.6934	0.1211	0.050*
C14	0.7508 (2)	0.56671 (15)	0.16901 (14)	0.0312 (3)
O3	0.76490 (13)	0.66129 (10)	0.30034 (9)	0.0291 (2)
H14A	0.598 (3)	0.5214 (19)	0.1167 (17)	0.042 (4)*
H14B	0.797 (3)	0.479 (2)	0.1910 (18)	0.048 (5)*
H3O	0.8864 (17)	0.719 (2)	0.3431 (19)	0.058 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C4	0.0190 (6)	0.0245 (6)	0.0236 (6)	0.0108 (5)	0.0073 (4)	0.0073 (5)
C11	0.0173 (5)	0.0214 (6)	0.0226 (6)	0.0091 (4)	0.0069 (4)	0.0051 (4)
C5	0.0215 (6)	0.0259 (6)	0.0238 (6)	0.0102 (5)	0.0044 (5)	0.0036 (5)
C7	0.0188 (6)	0.0219 (6)	0.0252 (6)	0.0091 (5)	0.0077 (4)	0.0064 (4)
C6	0.0205 (6)	0.0222 (6)	0.0291 (6)	0.0078 (5)	0.0068 (5)	0.0043 (5)
C12	0.0168 (5)	0.0216 (6)	0.0238 (6)	0.0086 (4)	0.0070 (4)	0.0053 (4)
C8	0.0217 (6)	0.0231 (6)	0.0330 (7)	0.0085 (5)	0.0107 (5)	0.0100 (5)
C9	0.0266 (6)	0.0333 (7)	0.0277 (6)	0.0138 (5)	0.0118 (5)	0.0145 (5)
C3	0.0242 (6)	0.0326 (7)	0.0240 (6)	0.0143 (5)	0.0085 (5)	0.0095 (5)
C1	0.0215 (6)	0.0234 (6)	0.0355 (7)	0.0065 (5)	0.0113 (5)	0.0107 (5)
C10	0.0260 (6)	0.0332 (7)	0.0215 (6)	0.0124 (5)	0.0077 (5)	0.0069 (5)
C2	0.0268 (6)	0.0324 (7)	0.0318 (7)	0.0150 (5)	0.0157 (5)	0.0163 (5)
O1	0.0338 (5)	0.0333 (5)	0.0238 (5)	0.0072 (4)	0.0005 (4)	0.0019 (4)
O2	0.0290 (5)	0.0249 (5)	0.0346 (5)	−0.0012 (4)	0.0051 (4)	0.0027 (4)
N2	0.0234 (5)	0.0257 (5)	0.0222 (5)	0.0088 (4)	0.0070 (4)	0.0044 (4)
N1	0.0200 (5)	0.0223 (5)	0.0276 (5)	0.0068 (4)	0.0076 (4)	0.0060 (4)
C15	0.0321 (7)	0.0332 (7)	0.0282 (7)	0.0040 (5)	0.0083 (5)	0.0019 (5)
C14	0.0388 (8)	0.0250 (6)	0.0296 (7)	0.0104 (5)	0.0116 (6)	0.0043 (5)
O3	0.0255 (5)	0.0329 (5)	0.0261 (5)	0.0092 (4)	0.0059 (4)	0.0007 (4)

Geometric parameters (Å, º) top

C4—C3	1.3950 (17)	C3—C2	1.3776 (19)
C4—C12	1.3995 (17)	C3—H3	0.9500
C4—C5	1.4818 (18)	C1—N1	1.3355 (16)
C11—N2	1.3436 (16)	C1—C2	1.3907 (18)
C11—C7	1.4037 (17)	C1—H1	0.9500
C11—C12	1.4899 (16)	C10—N2	1.3357 (16)
C5—O1	1.2171 (15)	C10—H10	0.9500
C5—C6	1.5411 (17)	C2—H2	0.9500
C7—C8	1.3972 (17)	C15—C14	1.5026 (18)
C7—C6	1.4843 (18)	C15—H15A	0.9800
C6—O2	1.2128 (16)	C15—H15B	0.9800
C12—N1	1.3448 (16)	C15—H15C	0.9800
C8—C9	1.3813 (18)	C14—O3	1.4225 (15)
C8—H8	0.9500	C14—H14A	1.040 (18)
C9—C10	1.3914 (19)	C14—H14B	0.995 (18)
C9—H9	0.9500	O3—H3O	0.850 (10)

C3—C4—C12	118.58 (11)	C4—C3—H3	120.3
C3—C4—C5	119.93 (11)	N1—C1—C2	124.01 (11)
C12—C4—C5	121.48 (11)	N1—C1—H1	118.0
N2—C11—C7	122.79 (11)	C2—C1—H1	118.0
N2—C11—C12	116.36 (10)	N2—C10—C9	124.42 (12)
C7—C11—C12	120.85 (11)	N2—C10—H10	117.8
O1—C5—C4	122.47 (12)	C9—C10—H10	117.8
O1—C5—C6	119.54 (11)	C3—C2—C1	117.99 (11)
C4—C5—C6	117.97 (10)	C3—C2—H2	121.0
C8—C7—C11	118.69 (11)	C1—C2—H2	121.0
C8—C7—C6	119.96 (11)	C10—N2—C11	117.08 (11)
C11—C7—C6	121.35 (11)	C1—N1—C12	117.77 (11)
O2—C6—C7	122.90 (12)	C14—C15—H15A	109.5
O2—C6—C5	119.48 (11)	C14—C15—H15B	109.5
C7—C6—C5	117.60 (10)	H15A—C15—H15B	109.5
N1—C12—C4	122.28 (11)	C14—C15—H15C	109.5
N1—C12—C11	117.04 (10)	H15A—C15—H15C	109.5
C4—C12—C11	120.68 (11)	H15B—C15—H15C	109.5
C9—C8—C7	118.69 (11)	O3—C14—C15	114.19 (11)
C9—C8—H8	120.7	O3—C14—H14A	104.6 (9)
C7—C8—H8	120.7	C15—C14—H14A	109.3 (9)
C8—C9—C10	118.31 (11)	O3—C14—H14B	108.5 (10)
C8—C9—H9	120.8	C15—C14—H14B	109.8 (10)
C10—C9—H9	120.8	H14A—C14—H14B	110.5 (14)
C2—C3—C4	119.37 (12)	C14—O3—H3O	111.5 (14)
C2—C3—H3	120.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···N1ⁱ	0.85 (1)	2.08 (1)	2.8258 (19)	146 (2)
C1—H1···O2ⁱⁱ	0.95	2.53	3.3381 (19)	143

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···N1ⁱ	0.850 (10)	2.080 (14)	2.8258 (19)	146.2 (18)
C1—H1···O2ⁱⁱ	0.95	2.53	3.3381 (19)	143.1

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

Acknowledgements

The authors would like to thank the China Scholarship Council (CSC).

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