Crystal structure of tetraaquabis(8-chloro-9,10-dioxo-9,10-dihydroanthracene-1-carboxyl-ato-κO (1))cobalt(II) dihydrate.

In the title complex, [Co(C15H6ClO4)2(H2O)4]·2H2O, the Co(II) ion is bound by two carboxylate O atoms of two 5-chloro-9,10-anthra-quinone-1-carboxyl-ate anions and four water O atoms in a trans conformation, forming an irregular octa-hedral coordination geometry. This arrangement is stabilized by intra-molecular O-H⋯O hydrogen bonds between water and carboxyl-ate. Further O-H⋯O hydrogen bonds between coordinating and non-coordinating water and carboxyl-ate produce layers of mol-ecules that extend parallel to (001). The organic ligands project above and below the plane. Those ligands of adjacent planes are inter-digitated and there are π-π inter-actions between them with centroid-centroid distances of 3.552 (2) and 3.767 (2) Å that generate a three-dimensional supra-molecular structure.

Related literature

For the synthesis of the title complex, see: George et al. (2006 ▶). The major advantage of metal-based over organic-based drugs is the ability to vary coordination number, geometry and redox states, and metals can also change the pharmacological properties of organic-based drugs by forming coordination complexes with them, see: Hambley (2007 ▶). Anthra­quinones are highly effective chemotherapeutic agents with a wide spectrum of anti­tumor activity, see: Unverferth et al. (1983 ▶); Kantrowitz & Bristow (1984 ▶); Stuart et al. (1984 ▶); Arcamone (1987 ▶). For related compounds, see: Bruijnincx & Sadler (2008 ▶); Gruber et al. (2010 ▶); Neufeind et al. (2011 ▶).

Experimental

Crystal data

[Co(C15H6ClO4)2(H2O)4]·2H2O

M = 738.32

Triclinic,

a = 6.8655 (14) Å

b = 8.1623 (16) Å

c = 14.285 (3) Å

α = 73.97 (3)°

β = 88.86 (3)°

γ = 73.35 (3)°

V = 735.6 (3) Å3

Z = 1

Mo Kα radiation

μ = 0.84 mm−1

T = 293 K

0.22 × 0.19 × 0.17 mm

Data collection

Rigaku MM007-HF CCD (Saturn 724+) diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.837, T max = 0.870

7246 measured reflections

3329 independent reflections

2171 reflections with I > 2σ(I)

R int = 0.041

2 standard reflections every 150 reflections intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.179

S = 1.12

3329 reflections

235 parameters

9 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.59 e Å−3

Δρmin = −0.64 e Å−3

Data collection: CrystalStructure (Rigaku/MSC, 2006 ▶); cell refinement: CrystalStructure; data reduction: CrystalStructure; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) I, new_global_publ_block. DOI: 10.1107/S1600536814020972/pj2015sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814020972/pj2015Isup2.hkl

Click here for additional data file.

x y z . DOI: 10.1107/S1600536814020972/pj2015fig1.tif

The mol­ecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids. Symmetry equivalent atoms labelled with an A (eg O1A) are generated by the symmetry operator 1–x, –y, 1–z.

Click here for additional data file.

. DOI: 10.1107/S1600536814020972/pj2015fig2.tif

A view of the crystal packing. Hydrogen bonds are shown as brown dashed lines.

CCDC reference: 1025297

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Co(C15H6ClO4)2(H2O)4]·2H2O	Z = 1
Mr = 738.32	F(000) = 377
Triclinic, P1	Dx = 1.667 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8655 (14) Å	Cell parameters from 25 reflections
b = 8.1623 (16) Å	θ = 3.1–25.0°
c = 14.285 (3) Å	µ = 0.84 mm−1
α = 73.97 (3)°	T = 293 K
β = 88.86 (3)°	Block, red
γ = 73.35 (3)°	0.22 × 0.19 × 0.17 mm
V = 735.6 (3) Å3

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	3329 independent reflections
Radiation source: rotating anode	2171 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.041
ω scans at fixed χ = 45°	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −7→8
Tmin = 0.837, Tmax = 0.870	k = −10→10
7246 measured reflections	l = −18→18

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.179	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ2(Fo2) + (0.0859P)2 + 0.2785P] where P = (Fo2 + 2Fc2)/3
3329 reflections	(Δ/σ)max < 0.001
235 parameters	Δρmax = 0.59 e Å−3
9 restraints	Δρmin = −0.64 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
Co1	0.5000	0.0000	0.5000	0.0521 (3)
O1	0.2123 (5)	0.3055 (4)	1.0202 (2)	0.0734 (8)
O2	0.2651 (4)	−0.0771 (3)	0.76542 (19)	0.0618 (7)
O3	0.3637 (4)	0.1703 (3)	0.58318 (18)	0.0565 (6)
O4	0.0299 (4)	0.1985 (4)	0.5694 (2)	0.0631 (7)
O5	0.4564 (6)	−0.2191 (4)	0.6077 (2)	0.0798 (10)
H5A	0.431 (8)	−0.222 (7)	0.663 (3)	0.101 (9)*
H5B	0.469 (8)	−0.317 (5)	0.607 (4)	0.101 (9)*
O6	0.2118 (5)	0.0420 (4)	0.4326 (2)	0.0664 (8)
H6A	0.181 (8)	−0.050 (6)	0.442 (4)	0.101 (9)*
H6B	0.141 (7)	0.079 (7)	0.474 (3)	0.101 (9)*
O7	0.6143 (6)	0.4206 (5)	0.6095 (3)	0.0832 (9)
H7A	0.724 (7)	0.371 (10)	0.591 (6)	0.16 (2)*
H7B	0.527 (8)	0.385 (10)	0.594 (6)	0.16 (2)*
C1	0.1499 (5)	0.3019 (5)	0.6896 (3)	0.0497 (8)
C2	0.0846 (6)	0.4864 (5)	0.6614 (3)	0.0624 (10)
H2	0.0601	0.5482	0.5955	0.075*
C3	0.0552 (7)	0.5804 (5)	0.7312 (3)	0.0666 (11)
H3	0.0103	0.7043	0.7116	0.080*
C4	0.0924 (6)	0.4908 (5)	0.8284 (3)	0.0590 (10)
H4	0.0715	0.5541	0.8746	0.071*
C5	0.2727 (5)	−0.0750 (5)	1.0984 (3)	0.0506 (8)
C6	0.3092 (5)	−0.2598 (5)	1.1281 (3)	0.0583 (9)
H6	0.3266	−0.3212	1.1942	0.070*
C7	0.3193 (6)	−0.3514 (5)	1.0589 (3)	0.0619 (10)
H7	0.3390	−0.4738	1.0783	0.074*
C8	0.3001 (6)	−0.2605 (5)	0.9614 (3)	0.0562 (9)
H8	0.3107	−0.3230	0.9152	0.067*
C9	0.2065 (5)	0.2169 (5)	0.9648 (3)	0.0508 (8)
C10	0.2436 (5)	0.0117 (5)	0.8235 (3)	0.0466 (8)
C11	0.1858 (5)	0.2093 (5)	0.7891 (3)	0.0476 (8)
C12	0.1613 (5)	0.3057 (5)	0.8584 (3)	0.0482 (8)
C13	0.2495 (5)	0.0193 (5)	1.0001 (2)	0.0459 (8)
C14	0.2651 (5)	−0.0773 (5)	0.9307 (3)	0.0477 (8)
C15	0.1838 (6)	0.2122 (5)	0.6087 (3)	0.0525 (8)
Cl1	0.25829 (17)	0.02230 (15)	1.19317 (7)	0.0696 (3)

	U11	U22	U33	U12	U13	U23
Co1	0.0629 (5)	0.0479 (4)	0.0531 (4)	−0.0121 (3)	0.0195 (3)	−0.0316 (3)
O1	0.106 (2)	0.0652 (17)	0.0646 (17)	−0.0219 (16)	0.0088 (16)	−0.0472 (14)
O2	0.0817 (18)	0.0561 (14)	0.0632 (16)	−0.0195 (13)	0.0199 (13)	−0.0434 (12)
O3	0.0627 (15)	0.0581 (15)	0.0598 (15)	−0.0146 (12)	0.0214 (12)	−0.0389 (12)
O4	0.0655 (16)	0.0728 (18)	0.0649 (16)	−0.0171 (14)	0.0081 (13)	−0.0453 (14)
O5	0.121 (3)	0.0548 (16)	0.0705 (19)	−0.0255 (17)	0.0424 (19)	−0.0311 (15)
O6	0.0744 (19)	0.0636 (17)	0.0722 (19)	−0.0160 (14)	0.0169 (14)	−0.0419 (15)
O7	0.083 (2)	0.065 (2)	0.104 (3)	−0.0127 (17)	0.012 (2)	−0.0370 (18)
C1	0.0487 (18)	0.0543 (19)	0.055 (2)	−0.0088 (15)	0.0092 (15)	−0.0359 (16)
C2	0.076 (3)	0.054 (2)	0.058 (2)	−0.0064 (19)	0.0075 (19)	−0.0311 (18)
C3	0.082 (3)	0.050 (2)	0.073 (3)	−0.0062 (19)	0.009 (2)	−0.0377 (19)
C4	0.067 (2)	0.056 (2)	0.066 (2)	−0.0103 (18)	0.0129 (19)	−0.0445 (19)
C5	0.0410 (17)	0.065 (2)	0.056 (2)	−0.0157 (16)	0.0121 (15)	−0.0355 (17)
C6	0.054 (2)	0.063 (2)	0.062 (2)	−0.0151 (18)	0.0108 (17)	−0.0269 (18)
C7	0.061 (2)	0.055 (2)	0.075 (3)	−0.0146 (18)	0.0123 (19)	−0.0302 (19)
C8	0.055 (2)	0.058 (2)	0.070 (2)	−0.0168 (17)	0.0136 (18)	−0.0410 (19)
C9	0.0468 (18)	0.058 (2)	0.061 (2)	−0.0128 (15)	0.0140 (16)	−0.0421 (17)
C10	0.0423 (17)	0.0548 (19)	0.057 (2)	−0.0143 (15)	0.0128 (15)	−0.0385 (16)
C11	0.0428 (17)	0.0524 (18)	0.060 (2)	−0.0111 (15)	0.0124 (15)	−0.0387 (16)
C12	0.0446 (17)	0.0546 (19)	0.058 (2)	−0.0133 (15)	0.0136 (15)	−0.0384 (16)
C13	0.0394 (16)	0.0551 (19)	0.0528 (19)	−0.0117 (14)	0.0112 (14)	−0.0332 (16)
C14	0.0404 (16)	0.0548 (19)	0.059 (2)	−0.0126 (15)	0.0102 (15)	−0.0346 (16)
C15	0.065 (2)	0.0494 (19)	0.0489 (19)	−0.0108 (17)	0.0078 (17)	−0.0300 (15)
Cl1	0.0773 (7)	0.0832 (7)	0.0594 (6)	−0.0203 (6)	0.0136 (5)	−0.0419 (5)

Co1—O3i	2.083 (2)	C2—H2	0.9300
Co1—O3	2.083 (2)	C3—C4	1.369 (6)
Co1—O5i	2.104 (3)	C3—H3	0.9300
Co1—O5	2.104 (3)	C4—C12	1.390 (5)
Co1—O6i	2.113 (3)	C4—H4	0.9300
Co1—O6	2.113 (3)	C5—C13	1.390 (5)
O1—C9	1.219 (4)	C5—C6	1.397 (5)
O2—C10	1.225 (4)	C5—Cl1	1.737 (3)
O3—C15	1.259 (4)	C6—C7	1.385 (5)
O4—C15	1.253 (4)	C6—H6	0.9300
O5—H5A	0.81 (3)	C7—C8	1.373 (6)
O5—H5B	0.78 (3)	C7—H7	0.9300
O6—H6A	0.82 (3)	C8—C14	1.387 (5)
O6—H6B	0.82 (3)	C8—H8	0.9300
O7—H7A	0.82 (3)	C9—C12	1.487 (5)
O7—H7B	0.80 (4)	C9—C13	1.492 (5)
C1—C2	1.385 (5)	C10—C11	1.485 (5)
C1—C11	1.402 (5)	C10—C14	1.493 (5)
C1—C15	1.511 (4)	C11—C12	1.405 (4)
C2—C3	1.395 (5)	C13—C14	1.412 (4)
O3i—Co1—O3	180.00 (10)	C12—C4—H4	119.8
O3i—Co1—O5i	90.64 (11)	C13—C5—C6	121.2 (3)
O3—Co1—O5i	89.36 (11)	C13—C5—Cl1	124.1 (3)
O3i—Co1—O5	89.36 (11)	C6—C5—Cl1	114.7 (3)
O3—Co1—O5	90.64 (11)	C7—C6—C5	119.8 (4)
O5i—Co1—O5	180.0	C7—C6—H6	120.1
O3i—Co1—O6i	89.78 (11)	C5—C6—H6	120.1
O3—Co1—O6i	90.22 (11)	C8—C7—C6	119.7 (4)
O5i—Co1—O6i	89.38 (15)	C8—C7—H7	120.1
O5—Co1—O6i	90.62 (15)	C6—C7—H7	120.1
O3i—Co1—O6	90.22 (11)	C7—C8—C14	121.2 (3)
O3—Co1—O6	89.78 (11)	C7—C8—H8	119.4
O5i—Co1—O6	90.62 (15)	C14—C8—H8	119.4
O5—Co1—O6	89.38 (15)	O1—C9—C12	119.7 (3)
O6i—Co1—O6	180.0	O1—C9—C13	121.8 (3)
C15—O3—Co1	130.3 (2)	C12—C9—C13	118.4 (3)
Co1—O5—H5A	126 (4)	O2—C10—C11	120.9 (3)
Co1—O5—H5B	131 (4)	O2—C10—C14	120.3 (3)
H5A—O5—H5B	103 (4)	C11—C10—C14	118.7 (3)
Co1—O6—H6A	112 (4)	C1—C11—C12	119.4 (3)
Co1—O6—H6B	98 (4)	C1—C11—C10	121.7 (3)
H6A—O6—H6B	96 (4)	C12—C11—C10	118.9 (3)
H7A—O7—H7B	110 (5)	C4—C12—C11	120.0 (3)
C2—C1—C11	119.5 (3)	C4—C12—C9	117.6 (3)
C2—C1—C15	116.7 (3)	C11—C12—C9	122.4 (3)
C11—C1—C15	123.8 (3)	C5—C13—C14	118.0 (3)
C1—C2—C3	120.6 (4)	C5—C13—C9	123.2 (3)
C1—C2—H2	119.7	C14—C13—C9	118.8 (3)
C3—C2—H2	119.7	C8—C14—C13	120.1 (3)
C4—C3—C2	120.2 (4)	C8—C14—C10	117.9 (3)
C4—C3—H3	119.9	C13—C14—C10	122.1 (3)
C2—C3—H3	119.9	O4—C15—O3	126.6 (3)
C3—C4—C12	120.3 (3)	O4—C15—C1	117.3 (3)
C3—C4—H4	119.8	O3—C15—C1	115.9 (3)
O3i—Co1—O3—C15	−8 (100)	C13—C9—C12—C4	170.7 (3)
O5i—Co1—O3—C15	115.4 (3)	O1—C9—C12—C11	169.1 (3)
O5—Co1—O3—C15	−64.6 (3)	C13—C9—C12—C11	−9.3 (5)
O6i—Co1—O3—C15	−155.2 (3)	C6—C5—C13—C14	−0.3 (5)
O6—Co1—O3—C15	24.8 (3)	Cl1—C5—C13—C14	180.0 (2)
C11—C1—C2—C3	0.3 (6)	C6—C5—C13—C9	178.8 (3)
C15—C1—C2—C3	−178.1 (4)	Cl1—C5—C13—C9	−0.9 (5)
C1—C2—C3—C4	0.5 (7)	O1—C9—C13—C5	8.6 (5)
C2—C3—C4—C12	0.5 (6)	C12—C9—C13—C5	−173.1 (3)
C13—C5—C6—C7	−1.1 (6)	O1—C9—C13—C14	−172.2 (3)
Cl1—C5—C6—C7	178.6 (3)	C12—C9—C13—C14	6.1 (5)
C5—C6—C7—C8	2.1 (6)	C7—C8—C14—C13	0.3 (6)
C6—C7—C8—C14	−1.7 (6)	C7—C8—C14—C10	−179.3 (3)
C2—C1—C11—C12	−2.1 (5)	C5—C13—C14—C8	0.8 (5)
C15—C1—C11—C12	176.1 (3)	C9—C13—C14—C8	−178.5 (3)
C2—C1—C11—C10	176.2 (3)	C5—C13—C14—C10	−179.7 (3)
C15—C1—C11—C10	−5.6 (5)	C9—C13—C14—C10	1.1 (5)
O2—C10—C11—C1	1.2 (5)	O2—C10—C14—C8	−3.0 (5)
C14—C10—C11—C1	−175.8 (3)	C11—C10—C14—C8	174.0 (3)
O2—C10—C11—C12	179.5 (3)	O2—C10—C14—C13	177.4 (3)
C14—C10—C11—C12	2.5 (5)	C11—C10—C14—C13	−5.6 (5)
C3—C4—C12—C11	−2.4 (6)	Co1—O3—C15—O4	−20.4 (6)
C3—C4—C12—C9	177.6 (4)	Co1—O3—C15—C1	165.0 (2)
C1—C11—C12—C4	3.2 (5)	C2—C1—C15—O4	−80.0 (5)
C10—C11—C12—C4	−175.2 (3)	C11—C1—C15—O4	101.7 (4)
C1—C11—C12—C9	−176.8 (3)	C2—C1—C15—O3	95.1 (4)
C10—C11—C12—C9	4.8 (5)	C11—C1—C15—O3	−83.2 (4)
O1—C9—C12—C4	−11.0 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7B···O3	0.80 (4)	2.37 (5)	3.121 (5)	157 (8)
O7—H7A···O4ii	0.82 (3)	2.24 (4)	3.049 (4)	169 (8)
O6—H6B···O4	0.82 (3)	1.92 (3)	2.717 (4)	164 (5)
O6—H6A···O4iii	0.82 (3)	2.17 (4)	2.916 (4)	152 (6)
O5—H5B···O7iv	0.78 (3)	2.08 (4)	2.821 (4)	159 (5)
O5—H5A···O2	0.81 (3)	2.22 (4)	2.932 (4)	147 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7B⋯O3	0.80 (4)	2.37 (5)	3.121 (5)	157 (8)
O7—H7A⋯O4i	0.82 (3)	2.24 (4)	3.049 (4)	169 (8)
O6—H6B⋯O4	0.82 (3)	1.92 (3)	2.717 (4)	164 (5)
O6—H6A⋯O4ii	0.82 (3)	2.17 (4)	2.916 (4)	152 (6)
O5—H5B⋯O7iii	0.78 (3)	2.08 (4)	2.821 (4)	159 (5)
O5—H5A⋯O2	0.81 (3)	2.22 (4)	2.932 (4)	147 (5)

Symmetry codes: (i) ; (ii) ; (iii) .