Bis(1,10-phenanthrolin-1-ium) 9,10-di-oxo-9,10-dihydroanthracene-1,5-disul-fonate hexa-hydrate.

The title hydrated molecular salt, 2C(12)H(9)N(2) (+)·C(14)H(6)O(8)S(2) (2-)·6H(2)O, consists of 1,10-phenanthrolinium (phen-H(+)) cations, anthraquinone-1,5-disulfonate (AQDS(2-)) anions, which occupy a centre of inversion, and water molecules of crystal-lization. In the crystal, a supra-molecular network structure is formed via N-H⋯O and O-H⋯O hydrogen bonds and weak C-H⋯O and π-π stacking inter-actions [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 +·C14H6O8S2 2−·6H2O

M = 836.83

Triclinic,

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[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.100

S = 1.06

3499 reflections

265 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.42 e Å−3

Δρmin = −0.39 e Å−3

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 ▶).

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

2C12H9N2+·C14H6O8S22−·6H2O	Z = 1
Mr = 836.83	F(000) = 436
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.P)2 + 1.1P] where P = (Fo2 + 2Fc2)/3
3499 reflections	(Δ/σ)max < 0.001
265 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

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.

	x	y	z	Uiso*/Ueq	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

	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)

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)

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···O1iv	0.82	1.92	2.739 (3)	172
O7—H7A···O6	0.82	1.97	2.774 (4)	167
O7—H7B···O7v	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···O1vi	0.93	2.58	3.418 (4)	151
C6—H6···O4vi	0.93	2.54	3.350 (3)	145
C18—H18···O3vii	0.93	2.51	3.357 (4)	152

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⋯O7iv	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⋯O1v	0.93	2.58	3.418 (4)	151
C6—H6⋯O4v	0.93	2.54	3.350 (3)	145
C18—H18⋯O3vi	0.93	2.51	3.357 (4)	152

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .