Poly[tetra-aqua-(μ(6)-9,10-dioxo-9,10-dihydro-anthracene-1,4,5,8-tetra-carboxyl-ato)dimanganese(II)].

The title complex, [Mn(2)(C(18)H(4)O(10))(H(2)O)(4)](n), was synthesized from manganese(II) chloride tetra-hydrate and 9,10-dioxo-9,10-dihydro-anthracene-1,4,5,8-tetra-carb-oxy-lic acid (H(4)AQTC) in water. The anthraquinone unit is located about a crystallographic center of inversion. Each asymmetric unit therefore contains one Mn(II) atom, two water ligands and one half AQTC(4-) anion. The Mn(II) atom is coordinated in a distorted octa-hedral geometry by four O atoms from three AQTC(4-) ligands and two water O atoms. Two of the carboxyl-ate groups coordinate one Mn(II) atom in a chelating mode, whereas the others each coordinate two Mn(II) atoms. Each AQTC(4-) tetra-anion therefore coordinates six different Mn(II) ions and, as a result, a three-dimensional coordination polymer is formed. O-H⋯O hydrogen bonds, some of them bifurcated, between water ligands and neighboring water or anthraquinone ligands are observed in the crystal structure.

Related literature

For general background to metal-organic frameworks, see: Li et al. (1999 ▶, 2012 ▶); Cheng et al. (2010 ▶); Hong et al. (2009 ▶); Miller & Gatteschi (2011 ▶); Liu et al. (2010 ▶).

Experimental

Crystal data

[Mn2(C18H4O10)(H2O)4]

M = 562.16

Monoclinic,

a = 11.2255 (16) Å

b = 8.4153 (13) Å

c = 9.7252 (14) Å

β = 92.355 (2)°

V = 917.9 (2) Å3

Z = 2

Mo Kα radiation

μ = 1.46 mm−1

T = 273 K

0.46 × 0.32 × 0.26 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.553, T max = 0.702

4340 measured reflections

1609 independent reflections

1499 reflections with I > 2σ(I)

R int = 0.065

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.076

S = 1.08

1609 reflections

170 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.35 e Å−3

Δρmin = −0.41 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); 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 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812027158/im2383sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027158/im2383Isup2.hkl

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

[Mn2(C18H4O10)(H2O)4]	F(000) = 564
Mr = 562.16	Dx = 2.034 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5133 reflections
a = 11.2255 (16) Å	θ = 2.2–27.6°
b = 8.4153 (13) Å	µ = 1.46 mm−1
c = 9.7252 (14) Å	T = 273 K
β = 92.355 (2)°	Block, brown
V = 917.9 (2) Å3	0.46 × 0.32 × 0.26 mm
Z = 2

Bruker SMART APEX CCD area-detector diffractometer	1609 independent reflections
Radiation source: fine-focus sealed tube	1499 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.065
phi and ω scans	θmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −12→13
Tmin = 0.553, Tmax = 0.702	k = −10→7
4340 measured reflections	l = −11→11

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0357P)2 + 0.3487P] where P = (Fo2 + 2Fc2)/3
1609 reflections	(Δ/σ)max < 0.001
170 parameters	Δρmax = 0.35 e Å−3
2 restraints	Δρmin = −0.41 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
C1	0.32095 (18)	0.3515 (2)	0.3203 (2)	0.0199 (4)
C2	0.44180 (17)	0.2999 (2)	0.37593 (19)	0.0182 (4)
C3	0.47029 (17)	0.1544 (2)	0.43842 (19)	0.0174 (4)
C4	0.58569 (16)	0.1290 (2)	0.49497 (19)	0.0168 (4)
C5	0.67291 (17)	0.2464 (2)	0.4857 (2)	0.0176 (4)
C6	0.64515 (18)	0.3863 (2)	0.4181 (2)	0.0214 (4)
H1	0.7036	0.4632	0.4081	0.026*
C7	0.53093 (18)	0.4128 (2)	0.3654 (2)	0.0214 (4)
H2	0.5133	0.5087	0.3217	0.026*
C8	0.79987 (17)	0.2271 (2)	0.5408 (2)	0.0187 (4)
C9	0.38273 (18)	0.0223 (2)	0.4344 (2)	0.0173 (4)
Mn1	0.14215 (3)	0.50978 (3)	0.21336 (3)	0.02054 (15)
O1	0.31881 (13)	0.4118 (2)	0.20209 (15)	0.0305 (4)
O2	0.23044 (12)	0.35278 (18)	0.39148 (15)	0.0261 (4)
O3	0.87242 (12)	0.15778 (18)	0.46563 (15)	0.0245 (3)
O6	0.82943 (13)	0.28802 (18)	0.65405 (15)	0.0274 (4)
O7	0.28972 (13)	0.03344 (17)	0.36714 (16)	0.0244 (4)
O8	0.09489 (15)	0.2961 (2)	0.08600 (17)	0.0267 (4)
O9	−0.04028 (17)	0.5190 (3)	0.2639 (2)	0.0489 (6)
H3	0.143 (3)	0.273 (4)	0.034 (3)	0.053 (10)*
H4	0.024 (3)	0.306 (4)	0.042 (4)	0.068 (10)*
H5	−0.064 (3)	0.590 (3)	0.312 (3)	0.079 (13)*
H6	−0.091 (3)	0.457 (5)	0.239 (5)	0.114 (17)*

	U11	U22	U33	U12	U13	U23
C1	0.0197 (10)	0.0151 (10)	0.0247 (11)	−0.0006 (8)	−0.0031 (8)	0.0011 (8)
C2	0.0176 (10)	0.0206 (10)	0.0166 (10)	0.0002 (8)	0.0007 (7)	0.0003 (8)
C3	0.0157 (9)	0.0201 (10)	0.0163 (10)	0.0020 (8)	0.0004 (7)	−0.0001 (8)
C4	0.0171 (9)	0.0186 (10)	0.0147 (10)	0.0016 (8)	−0.0007 (7)	−0.0010 (7)
C5	0.0172 (10)	0.0191 (10)	0.0163 (10)	0.0015 (8)	−0.0002 (7)	−0.0031 (8)
C6	0.0183 (10)	0.0225 (11)	0.0233 (11)	−0.0042 (8)	0.0000 (8)	0.0011 (8)
C7	0.0223 (10)	0.0191 (10)	0.0225 (10)	0.0012 (8)	−0.0008 (8)	0.0042 (8)
C8	0.0177 (10)	0.0154 (10)	0.0228 (11)	−0.0029 (8)	−0.0027 (8)	0.0029 (8)
C9	0.0158 (10)	0.0183 (10)	0.0178 (10)	0.0016 (8)	0.0002 (8)	−0.0015 (8)
Mn1	0.0173 (2)	0.0225 (2)	0.0215 (2)	0.00180 (12)	−0.00320 (14)	−0.00052 (12)
O1	0.0221 (8)	0.0426 (10)	0.0265 (8)	0.0031 (7)	−0.0023 (6)	0.0113 (7)
O2	0.0205 (8)	0.0280 (8)	0.0299 (8)	0.0030 (6)	0.0035 (6)	0.0038 (6)
O3	0.0166 (7)	0.0319 (8)	0.0247 (8)	0.0000 (6)	−0.0016 (6)	−0.0063 (6)
O6	0.0260 (8)	0.0289 (8)	0.0266 (8)	−0.0003 (7)	−0.0069 (6)	−0.0097 (7)
O7	0.0183 (8)	0.0225 (7)	0.0315 (9)	0.0000 (6)	−0.0105 (6)	0.0041 (6)
O8	0.0185 (8)	0.0339 (9)	0.0276 (9)	0.0005 (7)	−0.0007 (7)	−0.0065 (7)
O9	0.0217 (9)	0.0638 (14)	0.0617 (14)	−0.0095 (9)	0.0059 (9)	−0.0353 (11)

C1—O2	1.253 (3)	C8—O3	1.260 (2)
C1—O1	1.256 (2)	C9—O7	1.212 (2)
C1—C2	1.504 (3)	C9—C4i	1.483 (3)
C2—C7	1.386 (3)	Mn1—O9	2.1270 (19)
C2—C3	1.398 (3)	Mn1—O3ii	2.1412 (15)
C3—C4	1.403 (3)	Mn1—O6iii	2.1508 (15)
C3—C9	1.483 (3)	Mn1—O1	2.1547 (15)
C4—C5	1.396 (3)	Mn1—O8	2.2350 (16)
C4—C9i	1.483 (3)	Mn1—O2	2.3637 (15)
C5—C6	1.378 (3)	O3—Mn1iv	2.1412 (15)
C5—C8	1.511 (3)	O6—Mn1iii	2.1508 (15)
C6—C7	1.379 (3)	O8—H3	0.78 (3)
C6—H1	0.9300	O8—H4	0.89 (4)
C7—H2	0.9300	O9—H5	0.812 (10)
C8—O6	1.247 (2)	O9—H6	0.809 (10)
O2—C1—O1	121.11 (18)	C4i—C9—C3	119.05 (17)
O2—C1—C2	122.96 (18)	O9—Mn1—O3ii	97.16 (8)
O1—C1—C2	115.40 (17)	O9—Mn1—O6iii	87.31 (7)
C7—C2—C3	118.63 (18)	O3ii—Mn1—O6iii	91.81 (6)
C7—C2—C1	114.76 (17)	O9—Mn1—O1	157.30 (8)
C3—C2—C1	126.59 (18)	O3ii—Mn1—O1	102.77 (5)
C2—C3—C4	119.69 (18)	O6iii—Mn1—O1	102.67 (6)
C2—C3—C9	120.34 (17)	O9—Mn1—O8	87.05 (7)
C4—C3—C9	119.75 (18)	O3ii—Mn1—O8	90.52 (6)
C5—C4—C3	120.36 (18)	O6iii—Mn1—O8	174.13 (6)
C5—C4—C9i	118.84 (17)	O1—Mn1—O8	82.05 (6)
C3—C4—C9i	120.80 (17)	O9—Mn1—O2	103.28 (8)
C6—C5—C4	119.34 (17)	O3ii—Mn1—O2	159.49 (5)
C6—C5—C8	116.90 (17)	O6iii—Mn1—O2	87.45 (6)
C4—C5—C8	123.71 (17)	O1—Mn1—O2	57.61 (5)
C5—C6—C7	120.24 (19)	O8—Mn1—O2	92.25 (6)
C5—C6—H1	119.9	C1—O1—Mn1	95.23 (12)
C7—C6—H1	119.9	C1—O2—Mn1	85.71 (12)
C6—C7—C2	121.64 (19)	C8—O3—Mn1iv	135.36 (13)
C6—C7—H2	119.2	C8—O6—Mn1iii	151.88 (14)
C2—C7—H2	119.2	Mn1—O8—H3	114 (2)
O6—C8—O3	123.22 (18)	Mn1—O8—H4	112 (2)
O6—C8—C5	118.82 (17)	H3—O8—H4	110 (3)
O3—C8—C5	117.82 (17)	Mn1—O9—H5	120 (3)
O7—C9—C4i	120.01 (18)	Mn1—O9—H6	126 (4)
O7—C9—C3	120.77 (18)	H5—O9—H6	114 (5)
O2—C1—C2—C7	−122.6 (2)	C4—C5—C8—O3	84.0 (2)
O1—C1—C2—C7	49.1 (3)	C2—C3—C9—O7	6.4 (3)
O2—C1—C2—C3	55.6 (3)	C4—C3—C9—O7	−168.17 (19)
O1—C1—C2—C3	−132.7 (2)	C2—C3—C9—C4i	−178.27 (17)
C7—C2—C3—C4	3.3 (3)	C4—C3—C9—C4i	7.1 (3)
C1—C2—C3—C4	−174.94 (18)	O2—C1—O1—Mn1	6.2 (2)
C7—C2—C3—C9	−171.33 (17)	C2—C1—O1—Mn1	−165.70 (15)
C1—C2—C3—C9	10.5 (3)	O9—Mn1—O1—C1	−39.0 (2)
C2—C3—C4—C5	−1.8 (3)	O3ii—Mn1—O1—C1	170.17 (12)
C9—C3—C4—C5	172.81 (17)	O6iii—Mn1—O1—C1	75.34 (13)
C2—C3—C4—C9i	178.11 (17)	O8—Mn1—O1—C1	−101.11 (13)
C9—C3—C4—C9i	−7.3 (3)	O2—Mn1—O1—C1	−3.32 (11)
C3—C4—C5—C6	−1.2 (3)	O1—C1—O2—Mn1	−5.63 (19)
C9i—C4—C5—C6	178.86 (18)	C2—C1—O2—Mn1	165.63 (18)
C3—C4—C5—C8	−178.52 (18)	O9—Mn1—O2—C1	169.94 (12)
C9i—C4—C5—C8	1.6 (3)	O3ii—Mn1—O2—C1	−15.1 (2)
C4—C5—C6—C7	2.8 (3)	O6iii—Mn1—O2—C1	−103.43 (12)
C8—C5—C6—C7	−179.76 (18)	O1—Mn1—O2—C1	3.32 (11)
C5—C6—C7—C2	−1.3 (3)	O8—Mn1—O2—C1	82.44 (12)
C3—C2—C7—C6	−1.8 (3)	O6—C8—O3—Mn1iv	168.36 (14)
C1—C2—C7—C6	176.64 (19)	C5—C8—O3—Mn1iv	−15.9 (3)
C6—C5—C8—O6	82.5 (2)	O3—C8—O6—Mn1iii	112.0 (3)
C4—C5—C8—O6	−100.1 (2)	C5—C8—O6—Mn1iii	−63.7 (4)
C6—C5—C8—O3	−93.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H3···O2v	0.78 (3)	2.03 (3)	2.775 (2)	160 (3)
O8—H4···O3vi	0.89 (4)	1.86 (4)	2.742 (2)	174 (3)
O8—H4···O6vi	0.89 (4)	2.60 (3)	3.159 (2)	121 (3)
O9—H5···O8vii	0.81 (1)	2.03 (1)	2.832 (3)	168 (4)
O9—H6···O6vi	0.81 (1)	2.38 (2)	3.135 (3)	157 (5)
O9—H6···O7vii	0.81 (1)	2.50 (4)	3.031 (3)	124 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H3⋯O2i	0.78 (3)	2.03 (3)	2.775 (2)	160 (3)
O8—H4⋯O3ii	0.89 (4)	1.86 (4)	2.742 (2)	174 (3)
O8—H4⋯O6ii	0.89 (4)	2.60 (3)	3.159 (2)	121 (3)
O9—H5⋯O8iii	0.81 (1)	2.03 (1)	2.832 (3)	168 (4)
O9—H6⋯O6ii	0.81 (1)	2.38 (2)	3.135 (3)	157 (5)
O9—H6⋯O7iii	0.81 (1)	2.50 (4)	3.031 (3)	124 (4)

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