Bis(1,10-phenanthrolin-1-ium) 9,10-di­oxo-9,10-dihydroanthracene-1,5-disul­fonate hexa­hydrate

Jia, J.

doi:10.1107/S1600536810053456

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o250

doi:10.1107/S1600536810053456

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Bis(1,10-phenanthrolin-1-ium) 9,10-dioxo-9,10-dihydroanthracene-1,5-disulfonate hexahydrate

Jia Jia ^a

^aDepartment of Chemistry, Baicheng Normal College, Baicheng, Jilin 137000, People's Republic of China

(Received 11 December 2010; accepted 20 December 2010; online 8 January 2011)

The title hydrated molecular salt, 2C₁₂H₉N₂⁺·C₁₄H₆O₈S₂²⁻·6H₂O, consists of 1,10-phenanthrolinium (phen-H⁺) cations, anthraquinone-1,5-disulfonate (AQDS²⁻) anions, which occupy a centre of inversion, and water molecules of crystallization. In the crystal, a supramolecular network structure is formed via N—H⋯O and O—H⋯O hydrogen bonds and weak C—H⋯O and π–π stacking interactions [centroid–centroid distances = 3.651 (6) and 3.545 (8) Å].

Related literature

For examples of multiple binding of 1,5-naphthalenedisulfonate, see: Gao et al. (2005 ); Voogt & Blanch (2005 ). For the crystal structure of o-phenanthroline, see: Nishigaki et al. (1978 ). For the changes in protonated o-phenanthroline, see: Shriver et al. (1994 ). For weakly N—H⋯O hydrogen-bonded sulfonate ligands, see: Onoda et al. (2001 ). For graph-set analysis of hydrogen-bond patterns, see: Bernstein et al. (1995 ).

Experimental

Crystal data

2C₁₂H₉N₂⁺·C₁₄H₆O₈S₂²⁻·6H₂O
M_r = 836.83
Triclinic, $[P \overline 1]$
a = 10.0439 (6) Å
b = 10.1978 (6) Å
c = 11.1070 (6) Å
α = 111.591 (1)°
β = 98.848 (1)°
γ = 111.234 (1)°
V = 930.34 (9) Å³
Z = 1
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 296 K
0.24 × 0.22 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.782, T_max = 1.000
5035 measured reflections
3499 independent reflections
2964 reflections with I > 2σ(I)
R_int = 0.009

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.100
S = 1.06
3499 reflections
265 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O5	0.87 (3)	1.91 (3)	2.713 (3)	153 (3)
O5—H5A⋯O2ⁱ	0.82	1.97	2.776 (3)	168
O5—H5B⋯O2	0.82	2.19	2.931 (3)	150
O5—H5B⋯O4	0.82	2.48	3.131 (3)	138
O6—H6A⋯O3ⁱⁱ	0.82	1.96	2.775 (3)	170
O6—H6B⋯O1ⁱⁱⁱ	0.82	1.92	2.739 (3)	172
O7—H7A⋯O6	0.82	1.97	2.774 (4)	167
O7—H7B⋯O7^iv	0.82	2.20	3.021 (6)	178
O7—H7C⋯O5	0.82	2.48	3.301 (4)	179
C2—H2A⋯O7	0.93	2.39	3.300 (4)	167
C4—H4A⋯O1^v	0.93	2.58	3.418 (4)	151
C6—H6⋯O4^v	0.93	2.54	3.350 (3)	145
C18—H18⋯O3^vi	0.93	2.51	3.357 (4)	152
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) x, y, z+1; (iii) -x+1, -y, -z+1; (iv) -x+2, -y+1, -z+2; (v) -x+1, -y+1, -z+1; (vi) -x+2, -y, -z.

Data collection: APEX2 (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2001 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810053456/si2318sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810053456/si2318Isup2.hkl

checkCIF report

Comment top

The anthraquinone-1,5-disulfonate (AQDS ^2-) possesses six sulfonate O atoms and has been also employed either as a counter ion, forming extensive hydrogen-bonding interaction with water molecules or as a ligand with multiple binding sites available to construct coordination polymers with varying dimensionalities (Gao et al., 2005; Voogt & Blanch, 2005). Hydrogen bonding patterns involving sulfonate in biological systems and metal complexes are of current interest (Onoda et al., 2001). In the molecular structure of the title cocrystal, (phen-H⁺)₂(AQDS^2-).6H₂O (I), the dianion exhibits crystallographic inversion symmetry (Fig. 1). A supramolecular network structure is formed via N—H···O and O—H···O hydrogen bonds, and weak C—H···O and π-π stacking interactions (Fig. 2 and Table 1) support the stability of the crystal packing.

The phen-H⁺ cation is planar, with deviations of the non-H atoms from the least-squares plane of less than 0.021 (1) Å in the phen-H⁺ cation consisting of N1, N2, C1 to C12. The angle between the planar cation and planar anion in the asymmetric unit is 2.133 (3)°. Compared with the neutral base, 1,10-phenanthroline (Nishigaki et al., 1978), the bond distances in the phen-H⁺ cations show no significant differences, but some internal bond angles vary significantly, at the protonated N1 atom angle C2—N1—C1 = 123.1 (3)° and angle at neutral N2, C11—N2—C12 = 116.6 (3)°, which makes a difference of 6.5 (3)°. This is due to the formation of N—H bonds, which have a less repulsive effect on the N—C bonds than the lone electron pair (Shriver et al., 1994).

The phen-H⁺ cations and AQDS ^2- anions are held together by weak hydrogen bonds C6—H6···O4^v. Such adjacent units are assembled into 1-D chain through π-π stacking interactions between the adjacent phen-H⁺ rings (Fig. 2). Cg3···Cg4^v distance is 3.651 (6) Å, the perpendicular distance between the inversion-related planes (therefore the dihedral angle is zero) is 3.395 (6) Å. Cg3 is the centroid of the ring (N1, C2, C3, C4, C5, C1), Cg4 is the centroid of the ring (N2, C12, C8, C9, C10, C11), and the symmetry code v = 1 - x, 1 - y, 1 - z. Additionally, the adjacent 1-D chains are extended into a two-dimensional structure also by π-π stacking interaction between the anthraquinone ring and phen-H⁺ ring. Cg2···Cg4ⁱⁱⁱ distance is 3.545 (8) Å, Cg2 is the centroid of the ring (C15, C14, C16, C15A, C14A, C16A), and the symmetry code iii = 1 - x, - y, 1 - z.

Meanwhile, the lattice water molecules are anchored on the layer via hydrogen bonds (O5—H5A···O2ⁱ, O5—H5B···O2), resulting in the hydrogen-bonded ring motifs of R₄² (8) (Bernstein et al., 1995). Such rings are linked to phen-H⁺ cations by hydrogen bond N1—H1A···O5. Dimeric water molecules are linked via O7—H7A···O6, and are connected to the sulfonate oxygen O3 atom by O6—H6A···O3ⁱⁱ (Fig. 2). The hydrogen-bond geometries and symmetry codes are listed in Table 1. In conclusion, this work indicates that anthraquinone-1,5-disulfonate is also a good participant in hydrogen-bonding and π-π stacking networks for the formation of acid-base molecular cocrystals.

Related literature top

For examples of multiple binding of 1,5-naphthalenedisulfonate, see: Gao et al. (2005); Voogt & Blanch (2005). For the crystal structure of o-phenanthroline, see: Nishigaki et al. (1978). For the changes in protonated o-phenanthroline, see: Shriver et al. (1994). For weakly N—H···O hydrogen-bonded sulfonate ligands, see: Onoda et al. (2001). For graph-set analysis of hydrogen-bond patterns, see: Bernstein et al. (1995).

Experimental top

A mixture of disodium anthraquinone-1,5-disulfonate (0.2 mmol, 82.4 mg), FeCl₃.6H₂O (0.2 mmol, 54.06 mg), 1,10-phenanthroline (0.2 mmol, 39.64 mg), and H₂O (10 mL) was sealed in a 23 ml teflonlined stainless steel vessel under autogenous pressure; the vessel was heated to 150°C for 4 days and then cooled to room temperature at a rate of 2.6°C/h. The reaction mixture was filtered and yellow block-shaped crystals were collected by slow evaporation of the solvent.

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I) drawn with 30% probability displacement ellipsoids.[symmetry code: 2 – x, 1 – y, 1 – z.]
	Fig. 2. A perspective view of the two-dimensional structure. Hydrogen bonds and π-π stacking interactions are indicated by dashed lines. H atoms not involved in the hydrogen bonds shown have been omitted.

Bis(1,10-phenanthrolin-1-ium) 9,10-dioxo-9,10-dihydroanthracene-1,5-disulfonate hexahydrate top

Crystal data top

2C₁₂H₉N₂⁺·C₁₄H₆O₈S₂²⁻·6H₂O	Z = 1
M_r = 836.83	F(000) = 436
Triclinic, P1	D_x = 1.494 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.0439 (6) Å	Cell parameters from 3063 reflections
b = 10.1978 (6) Å	θ = 2.4–27.6°
c = 11.1070 (6) Å	µ = 0.22 mm⁻¹
α = 111.591 (1)°	T = 296 K
β = 98.848 (1)°	Block, yellow
γ = 111.234 (1)°	0.24 × 0.22 × 0.20 mm
V = 930.34 (9) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	3499 independent reflections
Radiation source: fine-focus sealed tube	2964 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.009
ϕ and ω scans	θ_max = 25.7°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→9
T_min = 0.782, T_max = 1.000	k = −11→12
5035 measured reflections	l = −11→13

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)] = 0.047	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.P)² + 1.1P] where P = (F_o² + 2F_c²)/3
3499 reflections	(Δ/σ)_max < 0.001
265 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

2C₁₂H₉N₂⁺·C₁₄H₆O₈S₂²⁻·6H₂O	γ = 111.234 (1)°
M_r = 836.83	V = 930.34 (9) Å³
Triclinic, P1	Z = 1
a = 10.0439 (6) Å	Mo Kα radiation
b = 10.1978 (6) Å	µ = 0.22 mm⁻¹
c = 11.1070 (6) Å	T = 296 K
α = 111.591 (1)°	0.24 × 0.22 × 0.20 mm
β = 98.848 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3499 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2964 reflections with I > 2σ(I)
T_min = 0.782, T_max = 1.000	R_int = 0.009
5035 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.42 e Å⁻³
3499 reflections	Δρ_min = −0.39 e Å⁻³
265 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	Occ. (<1)
N1	0.7261 (2)	0.6318 (3)	0.6490 (2)	0.0508 (5)
H1A	0.777 (3)	0.583 (3)	0.616 (3)	0.061*
N2	0.7525 (2)	0.5796 (3)	0.3953 (2)	0.0529 (5)
C1	0.6554 (3)	0.6801 (3)	0.5725 (3)	0.0473 (6)
C2	0.7199 (3)	0.6540 (3)	0.7734 (3)	0.0614 (7)
H2A	0.7702	0.6189	0.8220	0.074*
C3	0.6388 (4)	0.7293 (4)	0.8305 (3)	0.0678 (8)
H3A	0.6351	0.7461	0.9179	0.081*
C4	0.5642 (3)	0.7788 (3)	0.7575 (3)	0.0654 (8)
H4A	0.5086	0.8285	0.7953	0.078*
C5	0.5701 (3)	0.7558 (3)	0.6260 (3)	0.0547 (7)
C6	0.4937 (3)	0.8035 (3)	0.5441 (4)	0.0657 (8)
H6	0.4366	0.8533	0.5779	0.079*
C7	0.5030 (3)	0.7776 (3)	0.4189 (4)	0.0661 (8)
H7	0.4522	0.8101	0.3678	0.079*
C8	0.5896 (3)	0.7008 (3)	0.3618 (3)	0.0536 (7)
C9	0.6022 (3)	0.6695 (3)	0.2310 (3)	0.0643 (8)
H9A	0.5532	0.6992	0.1756	0.077*
C10	0.6866 (4)	0.5954 (4)	0.1856 (3)	0.0652 (8)
H10A	0.6953	0.5735	0.0990	0.078*
C11	0.7599 (3)	0.5531 (4)	0.2714 (3)	0.0610 (7)
H11A	0.8174	0.5030	0.2392	0.073*
C12	0.6670 (3)	0.6521 (3)	0.4392 (3)	0.0469 (6)
S1	0.78814 (8)	0.11641 (9)	0.22241 (7)	0.05292 (19)
O1	0.6380 (2)	0.0104 (3)	0.2065 (3)	0.0829 (7)
O2	0.8478 (2)	0.2720 (2)	0.3366 (2)	0.0633 (5)
O3	0.8023 (3)	0.1250 (4)	0.0977 (2)	0.1002 (9)
O4	0.7954 (2)	0.1068 (3)	0.4845 (2)	0.0661 (6)
C13	0.9069 (3)	0.0280 (3)	0.2540 (2)	0.0395 (5)
C14	0.9501 (2)	0.0149 (3)	0.3743 (2)	0.0346 (5)
C15	0.8932 (3)	0.0643 (3)	0.4908 (2)	0.0383 (5)
C16	1.0474 (2)	−0.0535 (3)	0.3832 (2)	0.0365 (5)
C17	1.0957 (3)	−0.1127 (3)	0.2735 (3)	0.0506 (6)
H17	1.1599	−0.1583	0.2805	0.061*
C18	1.0489 (3)	−0.1042 (4)	0.1554 (3)	0.0602 (8)
H18	1.0788	−0.1465	0.0812	0.072*
C19	0.9570 (3)	−0.0324 (3)	0.1471 (3)	0.0524 (6)
H19	0.9281	−0.0245	0.0674	0.063*
O5	0.8925 (2)	0.4707 (2)	0.6231 (2)	0.0661 (6)
H5A	0.9758	0.5440	0.6439	0.099*
H5B	0.8657	0.3892	0.5524	0.099*
O6	0.6538 (3)	0.2203 (3)	0.9409 (3)	0.1278 (13)
H6A	0.6893	0.1913	0.9919	0.192*
H6B	0.5678	0.1470	0.9015	0.192*
O7	0.8515 (4)	0.4711 (3)	0.9125 (3)	0.1289 (12)
H7A	0.7860	0.3911	0.9080	0.193*
H7B	0.9314	0.4878	0.9619	0.193*	0.50
H7C	0.8613	0.4715	0.8406	0.193*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0456 (13)	0.0436 (12)	0.0565 (14)	0.0198 (10)	0.0116 (10)	0.0190 (11)
N2	0.0491 (13)	0.0509 (13)	0.0583 (14)	0.0265 (11)	0.0134 (11)	0.0228 (11)
C1	0.0359 (13)	0.0337 (12)	0.0602 (16)	0.0118 (10)	0.0078 (11)	0.0169 (12)
C2	0.0577 (18)	0.0542 (17)	0.0579 (18)	0.0174 (14)	0.0096 (14)	0.0233 (14)
C3	0.0648 (19)	0.0566 (18)	0.0622 (19)	0.0178 (16)	0.0222 (16)	0.0171 (15)
C4	0.0542 (17)	0.0481 (16)	0.077 (2)	0.0190 (14)	0.0266 (16)	0.0151 (15)
C5	0.0419 (14)	0.0389 (14)	0.0711 (19)	0.0155 (12)	0.0154 (13)	0.0173 (13)
C6	0.0515 (17)	0.0521 (17)	0.094 (2)	0.0305 (14)	0.0218 (16)	0.0285 (17)
C7	0.0518 (17)	0.0539 (17)	0.095 (2)	0.0287 (14)	0.0111 (16)	0.0376 (17)
C8	0.0426 (14)	0.0402 (14)	0.0718 (19)	0.0154 (12)	0.0078 (13)	0.0275 (13)
C9	0.0605 (18)	0.0559 (17)	0.076 (2)	0.0212 (15)	0.0093 (15)	0.0398 (16)
C10	0.0660 (19)	0.0627 (19)	0.0659 (19)	0.0239 (16)	0.0191 (15)	0.0350 (16)
C11	0.0562 (17)	0.0614 (18)	0.0654 (19)	0.0291 (15)	0.0193 (14)	0.0271 (15)
C12	0.0368 (13)	0.0355 (13)	0.0595 (16)	0.0132 (11)	0.0079 (11)	0.0196 (12)
S1	0.0617 (4)	0.0595 (4)	0.0475 (4)	0.0369 (4)	0.0117 (3)	0.0279 (3)
O1	0.0439 (12)	0.0733 (15)	0.1110 (19)	0.0275 (11)	0.0012 (12)	0.0309 (14)
O2	0.0819 (14)	0.0497 (11)	0.0684 (13)	0.0355 (11)	0.0266 (11)	0.0308 (10)
O3	0.161 (3)	0.153 (3)	0.0635 (14)	0.122 (2)	0.0502 (16)	0.0712 (16)
O4	0.0783 (14)	0.1073 (17)	0.0764 (14)	0.0750 (14)	0.0483 (12)	0.0644 (13)
C13	0.0372 (12)	0.0404 (12)	0.0392 (12)	0.0173 (10)	0.0100 (10)	0.0182 (10)
C14	0.0320 (11)	0.0330 (11)	0.0369 (12)	0.0143 (9)	0.0106 (9)	0.0151 (9)
C15	0.0385 (12)	0.0396 (12)	0.0464 (13)	0.0227 (10)	0.0181 (10)	0.0229 (11)
C16	0.0356 (12)	0.0370 (12)	0.0375 (12)	0.0179 (10)	0.0138 (9)	0.0160 (10)
C17	0.0522 (15)	0.0625 (17)	0.0479 (15)	0.0370 (14)	0.0225 (12)	0.0228 (13)
C18	0.0671 (19)	0.083 (2)	0.0429 (15)	0.0455 (17)	0.0283 (14)	0.0256 (15)
C19	0.0560 (16)	0.0664 (18)	0.0388 (13)	0.0302 (14)	0.0160 (12)	0.0258 (13)
O5	0.0582 (12)	0.0608 (12)	0.0744 (14)	0.0309 (10)	0.0177 (10)	0.0243 (11)
O6	0.0916 (19)	0.0847 (18)	0.170 (3)	0.0179 (15)	−0.0330 (19)	0.074 (2)
O7	0.123 (2)	0.091 (2)	0.150 (3)	0.0416 (19)	−0.005 (2)	0.061 (2)

Geometric parameters (Å, º) top

N1—C2	1.330 (4)	S1—O1	1.439 (2)
N1—C1	1.359 (3)	S1—O2	1.443 (2)
N1—H1A	0.87 (3)	S1—O3	1.445 (2)
N2—C11	1.320 (4)	S1—C13	1.801 (2)
N2—C12	1.359 (3)	O4—C15	1.211 (3)
C1—C5	1.408 (4)	C13—C19	1.384 (3)
C1—C12	1.433 (4)	C13—C14	1.409 (3)
C2—C3	1.382 (4)	C14—C16	1.402 (3)
C2—H2A	0.9300	C14—C15	1.487 (3)
C3—C4	1.364 (4)	C15—C16ⁱ	1.494 (3)
C3—H3A	0.9300	C16—C17	1.391 (3)
C4—C5	1.406 (4)	C16—C15ⁱ	1.494 (3)
C4—H4A	0.9300	C17—C18	1.369 (4)
C5—C6	1.427 (4)	C17—H17	0.9300
C6—C7	1.341 (4)	C18—C19	1.381 (4)
C6—H6	0.9300	C18—H18	0.9300
C7—C8	1.439 (4)	C19—H19	0.9300
C7—H7	0.9300	O5—H5A	0.8200
C8—C9	1.405 (4)	O5—H5B	0.8200
C8—C12	1.406 (3)	O6—H6A	0.8201
C9—C10	1.363 (4)	O6—H6B	0.8200
C9—H9A	0.9300	O7—H7A	0.8199
C10—C11	1.398 (4)	O7—H7B	0.8200
C10—H10A	0.9300	O7—H7C	0.8200
C11—H11A	0.9300

C2—N1—C1	123.0 (3)	C10—C11—H11A	117.9
C2—N1—H1A	117.5 (19)	N2—C12—C8	123.9 (3)
C1—N1—H1A	119.5 (19)	N2—C12—C1	117.7 (2)
C11—N2—C12	116.6 (2)	C8—C12—C1	118.4 (2)
N1—C1—C5	118.8 (3)	O1—S1—O2	113.37 (14)
N1—C1—C12	120.0 (2)	O1—S1—O3	113.36 (17)
C5—C1—C12	121.2 (2)	O2—S1—O3	111.51 (15)
N1—C2—C3	120.1 (3)	O1—S1—C13	106.06 (12)
N1—C2—H2A	119.9	O2—S1—C13	108.18 (11)
C3—C2—H2A	119.9	O3—S1—C13	103.59 (12)
C4—C3—C2	119.3 (3)	C19—C13—C14	119.0 (2)
C4—C3—H3A	120.3	C19—C13—S1	114.84 (18)
C2—C3—H3A	120.3	C14—C13—S1	126.17 (18)
C3—C4—C5	121.0 (3)	C16—C14—C13	118.6 (2)
C3—C4—H4A	119.5	C16—C14—C15	117.95 (19)
C5—C4—H4A	119.5	C13—C14—C15	123.4 (2)
C4—C5—C1	117.7 (3)	O4—C15—C14	122.0 (2)
C4—C5—C6	123.7 (3)	O4—C15—C16ⁱ	118.9 (2)
C1—C5—C6	118.6 (3)	C14—C15—C16ⁱ	119.07 (19)
C7—C6—C5	121.0 (3)	C17—C16—C14	120.7 (2)
C7—C6—H6	119.5	C17—C16—C15ⁱ	116.5 (2)
C5—C6—H6	119.5	C14—C16—C15ⁱ	122.7 (2)
C6—C7—C8	121.6 (3)	C18—C17—C16	120.1 (2)
C6—C7—H7	119.2	C18—C17—H17	119.9
C8—C7—H7	119.2	C16—C17—H17	119.9
C9—C8—C12	116.7 (3)	C17—C18—C19	119.7 (2)
C9—C8—C7	124.0 (3)	C17—C18—H18	120.2
C12—C8—C7	119.3 (3)	C19—C18—H18	120.2
C10—C9—C8	119.8 (3)	C18—C19—C13	121.8 (2)
C10—C9—H9A	120.1	C18—C19—H19	119.1
C8—C9—H9A	120.1	C13—C19—H19	119.1
C9—C10—C11	118.9 (3)	H5A—O5—H5B	117.0
C9—C10—H10A	120.5	H6A—O6—H6B	100.6
C11—C10—H10A	120.5	H7A—O7—H7B	106.1
N2—C11—C10	124.1 (3)	H7A—O7—H7C	118.2
N2—C11—H11A	117.9	H7B—O7—H7C	109.6

C2—N1—C1—C5	−0.7 (4)	C5—C1—C12—N2	179.5 (2)
C2—N1—C1—C12	180.0 (2)	N1—C1—C12—C8	178.7 (2)
C1—N1—C2—C3	0.0 (4)	C5—C1—C12—C8	−0.6 (4)
N1—C2—C3—C4	0.7 (4)	O1—S1—C13—C19	109.1 (2)
C2—C3—C4—C5	−0.7 (4)	O2—S1—C13—C19	−129.0 (2)
C3—C4—C5—C1	0.0 (4)	O3—S1—C13—C19	−10.6 (2)
C3—C4—C5—C6	179.5 (3)	O1—S1—C13—C14	−70.5 (2)
N1—C1—C5—C4	0.7 (4)	O2—S1—C13—C14	51.5 (2)
C12—C1—C5—C4	180.0 (2)	O3—S1—C13—C14	169.9 (2)
N1—C1—C5—C6	−178.8 (2)	C19—C13—C14—C16	2.4 (3)
C12—C1—C5—C6	0.5 (4)	S1—C13—C14—C16	−178.08 (17)
C4—C5—C6—C7	−179.7 (3)	C19—C13—C14—C15	−175.1 (2)
C1—C5—C6—C7	−0.2 (4)	S1—C13—C14—C15	4.4 (3)
C5—C6—C7—C8	0.1 (5)	C16—C14—C15—O4	−171.1 (2)
C6—C7—C8—C9	179.4 (3)	C13—C14—C15—O4	6.4 (4)
C6—C7—C8—C12	−0.3 (4)	C16—C14—C15—C16ⁱ	5.7 (3)
C12—C8—C9—C10	0.0 (4)	C13—C14—C15—C16ⁱ	−176.7 (2)
C7—C8—C9—C10	−179.7 (3)	C13—C14—C16—C17	−2.4 (3)
C8—C9—C10—C11	−0.4 (4)	C15—C14—C16—C17	175.3 (2)
C12—N2—C11—C10	0.3 (4)	C13—C14—C16—C15ⁱ	176.4 (2)
C9—C10—C11—N2	0.3 (5)	C15—C14—C16—C15ⁱ	−5.9 (4)
C11—N2—C12—C8	−0.8 (4)	C14—C16—C17—C18	0.3 (4)
C11—N2—C12—C1	179.1 (2)	C15ⁱ—C16—C17—C18	−178.6 (2)
C9—C8—C12—N2	0.7 (4)	C16—C17—C18—C19	1.8 (4)
C7—C8—C12—N2	−179.6 (2)	C17—C18—C19—C13	−1.8 (5)
C9—C8—C12—C1	−179.2 (2)	C14—C13—C19—C18	−0.4 (4)
C7—C8—C12—C1	0.5 (4)	S1—C13—C19—C18	−179.9 (2)
N1—C1—C12—N2	−1.3 (3)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O5	0.87 (3)	1.91 (3)	2.713 (3)	153 (3)
O5—H5A···O2ⁱⁱ	0.82	1.97	2.776 (3)	168
O5—H5B···O2	0.82	2.19	2.931 (3)	150
O5—H5B···O4	0.82	2.48	3.131 (3)	138
O6—H6A···O3ⁱⁱⁱ	0.82	1.96	2.775 (3)	170
O6—H6B···O1^iv	0.82	1.92	2.739 (3)	172
O7—H7A···O6	0.82	1.97	2.774 (4)	167
O7—H7B···O7^v	0.82	2.20	3.021 (6)	178
O7—H7C···O5	0.82	2.48	3.301 (4)	179
C2—H2A···O7	0.93	2.39	3.300 (4)	167
C4—H4A···O1^vi	0.93	2.58	3.418 (4)	151
C6—H6···O4^vi	0.93	2.54	3.350 (3)	145
C18—H18···O3^vii	0.93	2.51	3.357 (4)	152

Symmetry codes: (ii) −x+2, −y+1, −z+1; (iii) x, y, z+1; (iv) −x+1, −y, −z+1; (v) −x+2, −y+1, −z+2; (vi) −x+1, −y+1, −z+1; (vii) −x+2, −y, −z.

Experimental details

Crystal data
Chemical formula	2C₁₂H₉N₂⁺·C₁₄H₆O₈S₂²⁻·6H₂O
M_r	836.83
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	10.0439 (6), 10.1978 (6), 11.1070 (6)
α, β, γ (°)	111.591 (1), 98.848 (1), 111.234 (1)
V (Å³)	930.34 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.24 × 0.22 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.782, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5035, 3499, 2964
R_int	0.009
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.100, 1.06
No. of reflections	3499
No. of parameters	265
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.39

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O5	0.87 (3)	1.91 (3)	2.713 (3)	153 (3)
O5—H5A···O2ⁱ	0.82	1.97	2.776 (3)	168
O5—H5B···O2	0.82	2.19	2.931 (3)	150
O5—H5B···O4	0.82	2.48	3.131 (3)	138
O6—H6A···O3ⁱⁱ	0.82	1.96	2.775 (3)	170
O6—H6B···O1ⁱⁱⁱ	0.82	1.92	2.739 (3)	172
O7—H7A···O6	0.82	1.97	2.774 (4)	167
O7—H7B···O7^iv	0.82	2.20	3.021 (6)	178
O7—H7C···O5	0.82	2.48	3.301 (4)	179
C2—H2A···O7	0.93	2.39	3.300 (4)	167
C4—H4A···O1^v	0.93	2.58	3.418 (4)	151
C6—H6···O4^v	0.93	2.54	3.350 (3)	145
C18—H18···O3^vi	0.93	2.51	3.357 (4)	152

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

Acknowledgements

The author gratefully acknowledges financial support from the Youth Fund of Baicheng Normal College.

References

Bernstein, J., Davies, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Brandenburg, K. & Berndt, M. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis(1,10-phenanthrolin-1-ium) 9,10-di­oxo-9,10-di­hydroanthracene-1,5-disul­fonate hexa­hydrate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Bis(1,10-phenanthrolin-1-ium) 9,10-dioxo-9,10-dihydroanthracene-1,5-disulfonate hexahydrate