5,6-Dioxo-1,10-phenanthrolin-1-ium chloride

Borel, C.; Bond, A.D.

doi:10.1107/S1600536807061788

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o34

https://doi.org/10.1107/S1600536807061788

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5,6-Dioxo-1,10-phenanthrolin-1-ium chloride

Cedric Borel ^a and Andrew D. Bond ^b ^*

^aChalmers Tekniska Högskola, Department of Chemical and Biological Engineering, 41296 Göteborg, Sweden, and ^bUniversity of Southern Denmark, Department of Physics and Chemistry, Campusvej 55, 5230 Odense, Denmark
^*Correspondence e-mail: adb@chem.sdu.dk

(Received 26 July 2007; accepted 21 November 2007; online 6 December 2007)

The title compound, C₁₂H₇N₂O₂⁺·Cl⁻, is isostructural with its bromide analogue. The compound exhibits a layered structure in which all atoms lie on a crystallographic mirror plane. N⁺—H⋯Cl⁻ hydrogen bonds, C—H⋯O and C—H⋯Cl⁻ contacts are formed within each layer. The perpendicular separation between the layers is 3.141 (1) Å.

Related literature

For the isostructural bromide analogue, see: Bomfim et al. (2003 ).

Experimental

Crystal data

C₁₂H₇N₂O₂⁺·Cl⁻
M_r = 246.65
Orthorhombic, P n m a
a = 14.2870 (11) Å
b = 6.2833 (5) Å
c = 12.0019 (10) Å
V = 1077.40 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 298 (2) K
0.40 × 0.07 × 0.04 mm

Data collection

Bruker Nonius X8-APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.744, T_max = 0.986
4229 measured reflections
1028 independent reflections
758 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.093
S = 1.04
1028 reflections
106 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1	0.88 (1)	2.27 (2)	3.067 (2)	150 (3)
C1—H1A⋯O1ⁱ	0.93	2.27	3.074 (3)	145
C3—H3A⋯Cl1ⁱⁱ	0.93	2.87	3.755 (3)	161
C8—H8A⋯Cl1ⁱⁱⁱ	0.93	2.91	3.545 (3)	127
C9—H9A⋯Cl1ⁱⁱⁱ	0.93	2.93	3.556 (3)	126
C10—H10A⋯O2^iv	0.93	2.27	3.196 (3)	177
Symmetry codes: (i) $[x-{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker Nonius, 2004 ); cell refinement: SAINT (Bruker, 2003 ); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807061788/pr2019sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807061788/pr2019Isup2.hkl

checkCIF report

Comment top

The title compound, C₁₂H₇N₂O₂⁺.Cl^-, was obtained as a by-product from an attempted synthesis of a metal-organic framework (MOF). It is isostructural with its bromide analogue (Bomfim, et al., 2003).

Related literature top

For the isostructural bromide analogue, see: Bomfim et al. (2003).

Experimental top

5,6-Dioxo-1,10-phenanthroline (40 mg, 0.19 mmol) was dissolved in 10 ml of water at room temperature with stirring and HCl(aq) was added until the pH was 4. When all of the compound had dissolved, K₃[Mn(CN)₆] (31 mg, 0.1 mmol) and NH₄Cl (5 mg, 0.1 mmol) were added and the mixture was left to stand overnight at 277 K, yielding yellow crystals of the title compound.

Structure description top

For the isostructural bromide analogue, see: Bomfim et al. (2003).

Computing details top

Data collection: APEX2 (Bruker Nonius, 2004); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL (Sheldrick, 2000); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL (Sheldrick, 2000).

Figures top

Fig. 1. Molecular structure of the title compound showing displacement ellipsoids at the 50% probability level for non-H atoms. The dashed line denotes the N⁺—H···Cl^- hydrogen bond.

5,6-Dioxo-1,10-phenanthrolin-1-ium chloride top

Crystal data top

C₁₂H₇N₂O₂⁺·Cl⁻	F(000) = 504
M_r = 246.65	D_x = 1.521 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 1190 reflections
a = 14.2870 (11) Å	θ = 2.9–24.1°
b = 6.2833 (5) Å	µ = 0.34 mm⁻¹
c = 12.0019 (10) Å	T = 298 K
V = 1077.40 (15) Å³	Needle, yellow
Z = 4	0.40 × 0.07 × 0.04 mm

Data collection top

Bruker Nonius X8-APEXII CCD diffractometer	1028 independent reflections
Radiation source: fine-focus sealed tube	758 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω and φ scans	θ_max = 25.1°, θ_min = 3.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −16→12
T_min = 0.744, T_max = 0.986	k = −7→4
4229 measured reflections	l = −14→14

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0554P)²] where P = (F_o² + 2F_c²)/3
1028 reflections	(Δ/σ)_max < 0.001
106 parameters	Δρ_max = 0.27 e Å⁻³
1 restraint	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₂H₇N₂O₂⁺·Cl⁻	V = 1077.40 (15) Å³
M_r = 246.65	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 14.2870 (11) Å	µ = 0.34 mm⁻¹
b = 6.2833 (5) Å	T = 298 K
c = 12.0019 (10) Å	0.40 × 0.07 × 0.04 mm

Data collection top

Bruker Nonius X8-APEXII CCD diffractometer	1028 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	758 reflections with I > 2σ(I)
T_min = 0.744, T_max = 0.986	R_int = 0.028
4229 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	1 restraint
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.27 e Å⁻³
1028 reflections	Δρ_min = −0.16 e Å⁻³
106 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
Cl1	0.29410 (5)	0.2500	0.51333 (6)	0.0466 (3)
O1	0.82632 (14)	0.2500	0.63231 (19)	0.0638 (7)
O2	0.85156 (15)	0.2500	0.4091 (2)	0.0956 (10)
N1	0.50089 (15)	0.2500	0.58192 (19)	0.0360 (6)
H1	0.4519 (15)	0.2500	0.538 (2)	0.071 (11)*
N2	0.52192 (15)	0.2500	0.36021 (18)	0.0401 (6)
C1	0.4820 (2)	0.2500	0.6909 (2)	0.0447 (7)
H1A	0.4202	0.2500	0.7153	0.054*
C2	0.5539 (2)	0.2500	0.7667 (2)	0.0482 (8)
H2A	0.5413	0.2500	0.8427	0.058*
C3	0.6444 (2)	0.2500	0.7295 (2)	0.0438 (7)
H3A	0.6938	0.2500	0.7799	0.053*
C4	0.66185 (18)	0.2500	0.6159 (2)	0.0376 (7)
C5	0.7592 (2)	0.2500	0.5718 (2)	0.0452 (7)
C6	0.7731 (2)	0.2500	0.4455 (3)	0.0511 (8)
C7	0.68991 (19)	0.2500	0.3738 (2)	0.0399 (7)
C8	0.6968 (2)	0.2500	0.2584 (2)	0.0479 (8)
H8A	0.7553	0.2500	0.2243	0.057*
C9	0.6174 (2)	0.2500	0.1954 (2)	0.0515 (8)
H9A	0.6209	0.2500	0.1180	0.062*
C10	0.5318 (2)	0.2500	0.2487 (2)	0.0481 (8)
H10A	0.4780	0.2500	0.2052	0.058*
C11	0.60042 (18)	0.2500	0.4196 (2)	0.0328 (6)
C12	0.58855 (18)	0.2500	0.5415 (2)	0.0333 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0402 (5)	0.0572 (5)	0.0423 (5)	0.000	−0.0037 (3)	0.000
O1	0.0424 (12)	0.0960 (18)	0.0529 (14)	0.000	−0.0163 (10)	0.000
O2	0.0350 (14)	0.194 (3)	0.0580 (17)	0.000	0.0115 (11)	0.000
N1	0.0338 (14)	0.0369 (12)	0.0372 (15)	0.000	0.0020 (11)	0.000
N2	0.0422 (14)	0.0412 (13)	0.0367 (14)	0.000	−0.0096 (11)	0.000
C1	0.0453 (17)	0.0453 (17)	0.0436 (19)	0.000	0.0167 (14)	0.000
C2	0.060 (2)	0.0528 (18)	0.0314 (17)	0.000	0.0067 (15)	0.000
C3	0.0484 (18)	0.0486 (17)	0.0346 (17)	0.000	−0.0045 (14)	0.000
C4	0.0368 (17)	0.0424 (16)	0.0337 (16)	0.000	−0.0033 (12)	0.000
C5	0.0343 (17)	0.0584 (18)	0.0428 (18)	0.000	−0.0063 (14)	0.000
C6	0.0348 (18)	0.076 (2)	0.0425 (18)	0.000	0.0052 (14)	0.000
C7	0.0392 (17)	0.0458 (17)	0.0348 (16)	0.000	0.0033 (12)	0.000
C8	0.0483 (18)	0.0588 (18)	0.0365 (17)	0.000	0.0096 (14)	0.000
C9	0.066 (2)	0.057 (2)	0.0312 (18)	0.000	−0.0008 (15)	0.000
C10	0.0542 (19)	0.0502 (17)	0.0397 (18)	0.000	−0.0159 (15)	0.000
C11	0.0369 (16)	0.0310 (14)	0.0305 (15)	0.000	0.0011 (12)	0.000
C12	0.0349 (17)	0.0301 (14)	0.0348 (16)	0.000	0.0016 (12)	0.000

Geometric parameters (Å, º) top

O1—C5	1.202 (3)	C4—C12	1.376 (3)
O2—C6	1.203 (3)	C4—C5	1.488 (4)
N1—C1	1.335 (3)	C5—C6	1.530 (4)
N1—C12	1.343 (3)	C6—C7	1.468 (4)
N1—H1	0.88 (1)	C7—C8	1.388 (4)
N2—C11	1.329 (3)	C7—C11	1.392 (4)
N2—C10	1.345 (3)	C8—C9	1.363 (4)
C1—C2	1.373 (4)	C8—H8A	0.930
C1—H1A	0.930	C9—C10	1.381 (4)
C2—C3	1.368 (4)	C9—H9A	0.930
C2—H2A	0.930	C10—H10A	0.930
C3—C4	1.386 (4)	C11—C12	1.473 (3)
C3—H3A	0.930

C1—N1—C12	122.8 (2)	O2—C6—C5	118.8 (3)
C1—N1—H1	115 (2)	C7—C6—C5	118.4 (2)
C12—N1—H1	122 (2)	C8—C7—C11	117.4 (3)
C11—N2—C10	116.4 (2)	C8—C7—C6	121.8 (3)
N1—C1—C2	119.8 (3)	C11—C7—C6	120.8 (3)
N1—C1—H1A	120.1	C9—C8—C7	119.6 (3)
C2—C1—H1A	120.1	C9—C8—H8A	120.2
C3—C2—C1	119.4 (3)	C7—C8—H8A	120.2
C3—C2—H2A	120.3	C8—C9—C10	118.7 (3)
C1—C2—H2A	120.3	C8—C9—H9A	120.6
C2—C3—C4	119.4 (3)	C10—C9—H9A	120.6
C2—C3—H3A	120.3	N2—C10—C9	123.6 (3)
C4—C3—H3A	120.3	N2—C10—H10A	118.2
C12—C4—C3	120.1 (2)	C9—C10—H10A	118.2
C12—C4—C5	118.8 (3)	N2—C11—C7	124.3 (2)
C3—C4—C5	121.1 (2)	N2—C11—C12	115.8 (2)
O1—C5—C4	122.1 (3)	C7—C11—C12	119.9 (2)
O1—C5—C6	119.7 (3)	N1—C12—C4	118.4 (3)
C4—C5—C6	118.3 (2)	N1—C12—C11	117.8 (2)
O2—C6—C7	122.8 (3)	C4—C12—C11	123.8 (2)

C12—N1—C1—C2	0.0	C7—C8—C9—C10	0.0
N1—C1—C2—C3	0.0	C11—N2—C10—C9	0.0
C1—C2—C3—C4	0.0	C8—C9—C10—N2	0.0
C2—C3—C4—C12	0.0	C10—N2—C11—C7	0.0
C2—C3—C4—C5	180.0	C10—N2—C11—C12	180.0
C12—C4—C5—O1	180.0	C8—C7—C11—N2	0.0
C3—C4—C5—O1	0.0	C6—C7—C11—N2	180.0
C12—C4—C5—C6	0.0	C8—C7—C11—C12	180.0
C3—C4—C5—C6	180.0	C6—C7—C11—C12	0.0
O1—C5—C6—O2	0.0	C1—N1—C12—C4	0.0
C4—C5—C6—O2	180.0	C1—N1—C12—C11	180.0
O1—C5—C6—C7	180.0	C3—C4—C12—N1	0.0
C4—C5—C6—C7	0.0	C5—C4—C12—N1	180.0
O2—C6—C7—C8	0.0	C3—C4—C12—C11	180.0
C5—C6—C7—C8	180.0	C5—C4—C12—C11	0.0
O2—C6—C7—C11	180.0	N2—C11—C12—N1	0.0
C5—C6—C7—C11	0.0	C7—C11—C12—N1	180.0
C11—C7—C8—C9	0.0	N2—C11—C12—C4	180.0
C6—C7—C8—C9	180.0	C7—C11—C12—C4	0.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.88 (1)	2.27 (2)	3.067 (2)	150 (3)
C1—H1A···O1ⁱ	0.93	2.27	3.074 (3)	145
C3—H3A···Cl1ⁱⁱ	0.93	2.87	3.755 (3)	161
C8—H8A···Cl1ⁱⁱⁱ	0.93	2.91	3.545 (3)	127
C9—H9A···Cl1ⁱⁱⁱ	0.93	2.93	3.556 (3)	126
C10—H10A···O2^iv	0.93	2.27	3.196 (3)	177

Symmetry codes: (i) x−1/2, y, −z+3/2; (ii) x+1/2, y, −z+3/2; (iii) x+1/2, y, −z+1/2; (iv) x−1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₇N₂O₂⁺·Cl⁻
M_r	246.65
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	298
a, b, c (Å)	14.2870 (11), 6.2833 (5), 12.0019 (10)
V (Å³)	1077.40 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.40 × 0.07 × 0.04

Data collection
Diffractometer	Bruker Nonius X8-APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.744, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	4229, 1028, 758
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.093, 1.04
No. of reflections	1028
No. of parameters	106
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.16

Computer programs: APEX2 (Bruker Nonius, 2004), SAINT (Bruker, 2003), SHELXTL (Sheldrick, 2000).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.88 (1)	2.27 (2)	3.067 (2)	150 (3)
C1—H1A···O1ⁱ	0.93	2.27	3.074 (3)	145
C3—H3A···Cl1ⁱⁱ	0.93	2.87	3.755 (3)	161
C8—H8A···Cl1ⁱⁱⁱ	0.93	2.91	3.545 (3)	127
C9—H9A···Cl1ⁱⁱⁱ	0.93	2.93	3.556 (3)	126
C10—H10A···O2^iv	0.93	2.27	3.196 (3)	177

Symmetry codes: (i) x−1/2, y, −z+3/2; (ii) x+1/2, y, −z+3/2; (iii) x+1/2, y, −z+1/2; (iv) x−1/2, y, −z+1/2.

Acknowledgements

This work was undertaken as part of the Nordic–Baltic Network in Crystal Engineering and Supramolecular Materials, funded by Nordforsk. ADB is grateful to the Danish Natural Science Research Council and the Carlsberg Foundation for provision of the X-ray equipment.

References

Bomfim, J. A. S., Filgueiras, C. A. L., Howie, R. A. & Wardell, J. L. (2003). Acta Cryst. E59, o244–o246. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2003). SAINT. Version 7.06a. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker Nonius (2004). APEX2. Version 1.0-22. Bruker Nonius BV, Delft, The Netherlands. Google Scholar
Sheldrick, G. M. (2000). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2003). SADABS. Version 2.10. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar