5,6-Dihydr­oxy-1,10-phenanthrolin-1-ium chloride dihydrate

Lin, X.-Y.; Tang, S.-J.; Wu, W.-S.

doi:10.1107/S1600536809033777

organic compounds

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Volume 65| Part 10| October 2009| Page o2367

doi:10.1107/S1600536809033777

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5,6-Dihydroxy-1,10-phenanthrolin-1-ium chloride dihydrate

Xin-Yong Lin,^a Sheng-Jiao Tang ^a and Wen-Shi Wu ^a ^*

^aCollege of Materials Science and Engineering, Huaqiao University, Xiamen, Fujian 361021, People's Republic of China
^*Correspondence e-mail: wws@hqu.edu.cn

(Received 4 August 2009; accepted 24 August 2009; online 5 September 2009)

The title compound, C₁₂H₉N₂O₂⁺·Cl⁻·2H₂O, exhibits a layered structure which is stabilized by intermolecular O—H⋯O, O—H⋯Cl⁻ and N⁺—H⋯Cl⁻ hydrogen bonds, and π–π interactions (centroid–centroid distances = 3.654 and 3.583 Å). The distances between the molecules are 3.371 and 3.294 Å.

Related literature

For a related structure, see: Borel & Bond (2008 ).

Experimental

Crystal data

C₁₂H₉N₂O₂⁺·Cl⁻·2H₂O
M_r = 284.69
Triclinic, $[P \overline 1]$
a = 7.7627 (1) Å
b = 8.6974 (1) Å
c = 9.6432 (1) Å
α = 86.116 (1)°
β = 86.859 (1)°
γ = 74.580 (1)°
V = 625.73 (1) Å³
Z = 2
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 296 K
0.25 × 0.12 × 0.03 mm

Data collection

Bruker P4 diffractometer
Absorption correction: none
9780 measured reflections
2872 independent reflections
2336 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.111
S = 1.06
2872 reflections
180 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H01⋯O4	0.82	1.86	2.6782 (18)	179
O2—H02⋯O3	0.82	1.89	2.6669 (18)	157
O3—H03B⋯Cl1	0.81 (3)	2.40 (3)	3.2133 (15)	174 (3)
O3—H03A⋯Cl1ⁱ	0.78 (3)	2.45 (3)	3.2323 (15)	176 (3)
O4—H04B⋯Cl1	0.91 (3)	2.33 (3)	3.2185 (14)	165 (3)
O4—H04A⋯Cl1ⁱⁱ	0.94 (3)	2.30 (3)	3.2216 (14)	168 (3)
N2—H9⋯Cl1ⁱⁱⁱ	0.86	2.37	3.1635 (13)	153
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x, -y+1, -z; (iii) x, y-1, z+1.

Data collection: XSCANS (Bruker, 1999 ); cell refinement: XSCANS); data reduction: SHELXTL (Sheldrick, 2008 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033777/hg2548sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809033777/hg2548Isup2.hkl

checkCIF report

Comment top

The title compound, [C₁₂H₉N₂O₂]Cl.2H₂O, was obtained unintentionally as the product of an attempted synthesis of a condensation product between 1,10-phenanthroline-5,6-dione and picoloylhydrazide. Compared with a similar compound (5,6-dioxo-1,10-phenanthrolin-1-ium chloride) reported (Borel & Bond, 2008), the Cl—H distance is slightly longer (2.372 vs 2.274Å).

The structure of the title compound is shown in Fig. 1. It exhibits a layered structure which is stabilized by inter-molecular O—H···O, O—H···Cl^-, N⁺—H···Cl^- hydrogen bonds, detailed in Fig. 2 and Table 1, as well as π-π interactions and C—H···O, C—H···Cl^- interactions. With Cl^- as the connecting point, it occurs two different shape parallelograms made up of O and Cl^-. The dihedral angle between the two planes, which possess different shapes, is 78.67°. The distances between the layers, which belong to offset face to face, are 3.371 Å and 3.294 Å, reflecting π-π interactions.

Related literature top

For a related structure, see: Borel & Bond (2008).

Experimental top

1,10-phenanthroline-5,6-dione (300 mg, 1.53 mmol) was dissolved in a mixed solution of 10 ml CH₂Cl₂ and 30 ml EtOH when heating with stirring. When all of the compound dissolved, picoloylhydrazide (200 mg, 1.46 mmol) was added and refluxed 8hrs. Then HCl(aq) was added until the pH was 6. Red crystals of the title compound were obtained by slow evaporation of solvent at room temperature. Analysis: Found C 50.45, H 4.82, N 9.71%, calc. for C₁₂H₁₃ClN₂O₄, C 50.63, H 4.60, N 9.84%.

Computing details top

Data collection: XSCANS (Bruker, 1999); cell refinement: XSCANS (Bruker, 1999); data reduction: SHELXTL (Sheldrick, 2008); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented by circles of arbitrary radius.
	Fig. 2. Crystal Packing diagram of the title compound, showing the H-bonded interactions (dashed lines). Cl11, Cl12, Cl13 represent Cl1ⁱ, Cl1ⁱⁱ, Cl1ⁱⁱⁱ, respectively.

5,6-Dihydroxy-1,10-phenanthrolin-1-ium chloride dihydrate top

Crystal data top

C₁₂H₉N₂O₂⁺·Cl⁻·2H₂O	Z = 2
M_r = 284.69	F(000) = 296
Triclinic, P1	D_x = 1.511 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7627 (1) Å	Cell parameters from 2922 reflections
b = 8.6974 (1) Å	θ = 2.1–27.7°
c = 9.6432 (1) Å	µ = 0.32 mm⁻¹
α = 86.116 (1)°	T = 296 K
β = 86.859 (1)°	Block, red
γ = 74.580 (1)°	0.25 × 0.12 × 0.03 mm
V = 625.73 (1) Å³

Data collection top

Bruker P4 diffractometer	2336 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 27.7°, θ_min = 2.1°
Detector resolution: 0 pixels mm^-1	h = −9→9
ω scans	k = −11→11
9780 measured reflections	l = −12→12
2872 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0638P)² + 0.0835P] where P = (F_o² + 2F_c²)/3
2872 reflections	(Δ/σ)_max < 0.001
180 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₂H₉N₂O₂⁺·Cl⁻·2H₂O	γ = 74.580 (1)°
M_r = 284.69	V = 625.73 (1) Å³
Triclinic, P1	Z = 2
a = 7.7627 (1) Å	Mo Kα radiation
b = 8.6974 (1) Å	µ = 0.32 mm⁻¹
c = 9.6432 (1) Å	T = 296 K
α = 86.116 (1)°	0.25 × 0.12 × 0.03 mm
β = 86.859 (1)°

Data collection top

Bruker P4 diffractometer	2336 reflections with I > 2σ(I)
9780 measured reflections	R_int = 0.023
2872 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.29 e Å⁻³
2872 reflections	Δρ_min = −0.22 e Å⁻³
180 parameters

Special details top

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 > 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	0.19595 (6)	0.69904 (5)	0.01405 (4)	0.04841 (15)
O1	0.30334 (16)	0.13935 (13)	0.25607 (10)	0.0444 (3)
H01	0.2307	0.2235	0.2339	0.067*
O2	0.37121 (17)	0.34384 (13)	0.45497 (11)	0.0463 (3)
H02	0.3972	0.3484	0.3715	0.069*
O3	0.4713 (2)	0.4352 (2)	0.20054 (15)	0.0614 (4)
H03B	0.404 (3)	0.497 (3)	0.148 (3)	0.078 (8)*
H03A	0.555 (4)	0.400 (3)	0.152 (3)	0.086 (9)*
O4	0.06665 (19)	0.41360 (17)	0.18085 (14)	0.0554 (3)
H04B	0.089 (4)	0.492 (4)	0.121 (3)	0.105 (9)*
H04A	−0.024 (4)	0.389 (4)	0.133 (3)	0.101 (9)*
N1	0.18014 (17)	−0.20833 (15)	0.63900 (12)	0.0357 (3)
N2	0.24864 (16)	−0.00702 (15)	0.82063 (12)	0.0351 (3)
H9	0.2179	−0.0925	0.8478	0.042*
C1	0.1482 (2)	−0.30386 (18)	0.54877 (16)	0.0392 (3)
H1	0.1168	−0.3958	0.5828	0.047*
C2	0.1591 (2)	−0.27406 (19)	0.40435 (16)	0.0394 (3)
H2	0.1357	−0.3454	0.3451	0.047*
C3	0.2039 (2)	−0.14094 (18)	0.35128 (15)	0.0358 (3)
H3	0.2101	−0.1197	0.2556	0.043*
C4	0.28852 (19)	0.10836 (17)	0.39662 (13)	0.0321 (3)
C5	0.32397 (19)	0.20722 (16)	0.48912 (14)	0.0318 (3)
C6	0.3461 (2)	0.26396 (19)	0.73659 (16)	0.0389 (3)
H6	0.3798	0.3567	0.7090	0.047*
C7	0.3317 (2)	0.2208 (2)	0.87618 (16)	0.0456 (4)
H7	0.3559	0.2838	0.9428	0.055*
C8	0.2811 (2)	0.0834 (2)	0.91623 (15)	0.0436 (4)
H8	0.2696	0.0541	1.0102	0.052*
C9	0.22636 (18)	−0.07646 (16)	0.58613 (13)	0.0298 (3)
C10	0.24091 (17)	−0.03478 (16)	0.44305 (13)	0.0298 (3)
C11	0.26175 (17)	0.02913 (16)	0.68159 (13)	0.0299 (3)
C12	0.31023 (18)	0.16851 (16)	0.63634 (14)	0.0309 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0659 (3)	0.0498 (3)	0.0337 (2)	−0.0246 (2)	−0.00378 (17)	0.00808 (16)
O1	0.0661 (8)	0.0399 (6)	0.0248 (5)	−0.0116 (5)	0.0009 (5)	0.0034 (4)
O2	0.0697 (8)	0.0360 (6)	0.0367 (6)	−0.0223 (5)	0.0041 (5)	0.0027 (5)
O3	0.0576 (9)	0.0664 (9)	0.0517 (8)	−0.0087 (7)	0.0078 (7)	0.0172 (7)
O4	0.0623 (8)	0.0580 (8)	0.0512 (7)	−0.0280 (6)	−0.0123 (6)	0.0164 (6)
N1	0.0414 (7)	0.0340 (6)	0.0329 (6)	−0.0132 (5)	0.0009 (5)	0.0003 (5)
N2	0.0447 (7)	0.0361 (7)	0.0263 (6)	−0.0146 (5)	0.0005 (5)	0.0019 (5)
C1	0.0455 (9)	0.0327 (8)	0.0410 (8)	−0.0138 (6)	0.0024 (6)	−0.0018 (6)
C2	0.0442 (9)	0.0366 (8)	0.0392 (8)	−0.0115 (6)	−0.0011 (6)	−0.0112 (6)
C3	0.0396 (8)	0.0382 (8)	0.0283 (7)	−0.0074 (6)	−0.0011 (5)	−0.0036 (6)
C4	0.0369 (7)	0.0333 (7)	0.0235 (6)	−0.0061 (5)	0.0002 (5)	0.0021 (5)
C5	0.0347 (7)	0.0279 (7)	0.0318 (7)	−0.0078 (5)	0.0000 (5)	0.0037 (5)
C6	0.0454 (9)	0.0364 (8)	0.0380 (8)	−0.0160 (6)	−0.0007 (6)	−0.0045 (6)
C7	0.0586 (10)	0.0495 (10)	0.0343 (8)	−0.0218 (8)	−0.0033 (7)	−0.0102 (7)
C8	0.0556 (10)	0.0525 (10)	0.0251 (7)	−0.0183 (7)	−0.0004 (6)	−0.0029 (6)
C9	0.0306 (7)	0.0306 (7)	0.0273 (6)	−0.0070 (5)	−0.0004 (5)	0.0002 (5)
C10	0.0297 (7)	0.0313 (7)	0.0271 (6)	−0.0056 (5)	−0.0008 (5)	−0.0019 (5)
C11	0.0297 (7)	0.0335 (7)	0.0256 (6)	−0.0072 (5)	−0.0012 (5)	0.0003 (5)
C12	0.0305 (7)	0.0323 (7)	0.0296 (7)	−0.0081 (5)	−0.0005 (5)	−0.0006 (5)

Geometric parameters (Å, º) top

O1—C4	1.3685 (16)	C2—H2	0.9300
O1—H01	0.8200	C3—C10	1.414 (2)
O2—C5	1.3491 (18)	C3—H3	0.9300
O2—H02	0.8200	C4—C5	1.367 (2)
O3—H03B	0.81 (3)	C4—C10	1.428 (2)
O3—H03A	0.78 (3)	C5—C12	1.4415 (18)
O4—H04B	0.91 (3)	C6—C7	1.380 (2)
O4—H04A	0.94 (3)	C6—C12	1.401 (2)
N1—C1	1.3192 (19)	C6—H6	0.9300
N1—C9	1.3504 (18)	C7—C8	1.379 (2)
N2—C8	1.327 (2)	C7—H7	0.9300
N2—C11	1.3608 (17)	C8—H8	0.9300
N2—H9	0.8600	C9—C10	1.4088 (18)
C1—C2	1.401 (2)	C9—C11	1.4293 (19)
C1—H1	0.9300	C11—C12	1.3980 (19)
C2—C3	1.355 (2)

C4—O1—H01	109.5	C4—C5—C12	119.73 (13)
C5—O2—H02	109.5	C7—C6—C12	120.17 (14)
H03B—O3—H03A	103 (2)	C7—C6—H6	119.9
H04B—O4—H04A	99 (2)	C12—C6—H6	119.9
C1—N1—C9	116.77 (12)	C8—C7—C6	119.53 (14)
C8—N2—C11	123.10 (13)	C8—C7—H7	120.2
C8—N2—H9	118.4	C6—C7—H7	120.2
C11—N2—H9	118.4	N2—C8—C7	119.93 (14)
N1—C1—C2	123.39 (14)	N2—C8—H8	120.0
N1—C1—H1	118.3	C7—C8—H8	120.0
C2—C1—H1	118.3	N1—C9—C10	124.54 (12)
C3—C2—C1	119.85 (14)	N1—C9—C11	117.94 (12)
C3—C2—H2	120.1	C10—C9—C11	117.52 (12)
C1—C2—H2	120.1	C9—C10—C3	116.20 (13)
C2—C3—C10	119.24 (13)	C9—C10—C4	120.66 (12)
C2—C3—H3	120.4	C3—C10—C4	123.13 (12)
C10—C3—H3	120.4	N2—C11—C12	118.90 (12)
C5—C4—O1	121.50 (13)	N2—C11—C9	119.19 (12)
C5—C4—C10	121.14 (12)	C12—C11—C9	121.91 (12)
O1—C4—C10	117.32 (12)	C11—C12—C6	118.36 (13)
O2—C5—C4	125.29 (12)	C11—C12—C5	119.02 (12)
O2—C5—C12	114.97 (12)	C6—C12—C5	122.62 (13)

C9—N1—C1—C2	−0.4 (2)	O1—C4—C10—C9	178.79 (12)
N1—C1—C2—C3	−0.2 (2)	C5—C4—C10—C3	−179.72 (13)
C1—C2—C3—C10	0.7 (2)	O1—C4—C10—C3	−2.0 (2)
O1—C4—C5—O2	1.8 (2)	C8—N2—C11—C12	−0.5 (2)
C10—C4—C5—O2	179.45 (13)	C8—N2—C11—C9	179.24 (13)
O1—C4—C5—C12	−178.75 (12)	N1—C9—C11—N2	0.33 (19)
C10—C4—C5—C12	−1.1 (2)	C10—C9—C11—N2	179.86 (12)
C12—C6—C7—C8	−0.3 (3)	N1—C9—C11—C12	−179.92 (12)
C11—N2—C8—C7	−0.4 (2)	C10—C9—C11—C12	−0.4 (2)
C6—C7—C8—N2	0.8 (3)	N2—C11—C12—C6	1.0 (2)
C1—N1—C9—C10	0.5 (2)	C9—C11—C12—C6	−178.75 (13)
C1—N1—C9—C11	−179.99 (13)	N2—C11—C12—C5	−179.91 (12)
N1—C9—C10—C3	−0.1 (2)	C9—C11—C12—C5	0.3 (2)
C11—C9—C10—C3	−179.56 (12)	C7—C6—C12—C11	−0.6 (2)
N1—C9—C10—C4	179.20 (12)	C7—C6—C12—C5	−179.68 (14)
C11—C9—C10—C4	−0.29 (19)	O2—C5—C12—C11	179.92 (12)
C2—C3—C10—C9	−0.5 (2)	C4—C5—C12—C11	0.4 (2)
C2—C3—C10—C4	−179.81 (14)	O2—C5—C12—C6	−1.0 (2)
C5—C4—C10—C9	1.1 (2)	C4—C5—C12—C6	179.47 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H01···O4	0.82	1.86	2.6782 (18)	179
O2—H02···O3	0.82	1.89	2.6669 (18)	157
O3—H03B···Cl1	0.81 (3)	2.40 (3)	3.2133 (15)	174 (3)
O3—H03A···Cl1ⁱ	0.78 (3)	2.45 (3)	3.2323 (15)	176 (3)
O4—H04B···Cl1	0.91 (3)	2.33 (3)	3.2185 (14)	165 (3)
O4—H04A···Cl1ⁱⁱ	0.94 (3)	2.30 (3)	3.2216 (14)	168 (3)
N2—H9···Cl1ⁱⁱⁱ	0.86	2.37	3.1635 (13)	153

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

Experimental details

Crystal data
Chemical formula	C₁₂H₉N₂O₂⁺·Cl⁻·2H₂O
M_r	284.69
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.7627 (1), 8.6974 (1), 9.6432 (1)
α, β, γ (°)	86.116 (1), 86.859 (1), 74.580 (1)
V (Å³)	625.73 (1)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.25 × 0.12 × 0.03

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9780, 2872, 2336
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.653

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.111, 1.06
No. of reflections	2872
No. of parameters	180
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.22

Computer programs: XSCANS (Bruker, 1999), SHELXTL (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H01···O4	0.820	1.861	2.6782 (18)	179.22
O2—H02···O3	0.820	1.891	2.6669 (18)	157.35
O3—H03B···Cl1	0.81 (3)	2.40 (3)	3.2133 (15)	174 (3)
O3—H03A···Cl1ⁱ	0.78 (3)	2.45 (3)	3.2323 (15)	176 (3)
O4—H04B···Cl1	0.91 (3)	2.33 (3)	3.2185 (14)	165 (3)
O4—H04A···Cl1ⁱⁱ	0.94 (3)	2.30 (3)	3.2216 (14)	168 (3)
N2—H9···Cl1ⁱⁱⁱ	0.860	2.372	3.1635 (13)	153.22

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

Acknowledgements

We are grateful for financial support from the National Science Foundation of Fujian Province of China (No. E0610017, 2003 F006).

References

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