Bis(μ-2-carboxymethyl-2-hydroxy-butane-dioato)bis-[diaqua-manganese(II)]-1,2-bis-(pyridin-4-yl)ethane-water (1/1/2).

The asymmetric unit of the title compound, [Mn(2)(C(6)H(6)O(7))(2)(H(2)O)(4)]·C(12)H(12)N(2)·2H(2)O, comprises half of a centrosymmetric dimer, half of a 1,2-bis-(pyridin-4-yl)ethane and one water mol-ecule. Two citrate ligands bridge two Mn(II) ions, the Mn(II) ion being coordinated by four O atoms from the citrate(2-) ligands and two water O atoms, forming a distorted octa-hedral environment. In the crystal, O-H⋯O hydrogen bonds link the centrosymmetric dimers and lattice water mol-ecules into a three-dimensional structure which is further stabilized by inter-molecular π-π inter-actions [centroid-centroid distance = 3.792 (2) Å].

Related literature

For inter­actions of metal ions with biologically active mol­ecules, see: Daniele et al. (2008 ▶); Parkin (2004 ▶); Tshuva & Lippard (2004 ▶); Stoumpos et al. (2009 ▶). For related complexes, see: Lee et al. (2008 ▶); Park et al. (2008 ▶); Shin et al. (2009 ▶); Song et al. (2009 ▶); Yu et al. (2008 ▶, 2009 ▶); Kim et al. (2011 ▶).

Experimental

Crystal data

[Mn2(C6H6O7)2(H2O)4]·C12H12N2·2H2O

M = 782.43

Triclinic,

a = 9.3950 (19) Å

b = 9.5880 (19) Å

c = 10.252 (2) Å

α = 68.90 (3)°

β = 67.74 (3)°

γ = 78.16 (3)°

V = 794.8 (3) Å3

Z = 1

Mo Kα radiation

μ = 0.88 mm−1

T = 293 K

0.40 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T min = 0.719, T max = 0.843

4449 measured reflections

3048 independent reflections

2780 reflections with I > 2σ(I)

R int = 0.014

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.092

S = 1.05

3048 reflections

239 parameters

7 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.52 e Å−3

Δρmin = −0.42 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); 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/S1600536812032771/bx2421sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032771/bx2421Isup2.hkl

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

[Mn2(C6H6O7)2(H2O)4]·C12H12N2·2H2O	Z = 1
Mr = 782.43	F(000) = 404
Triclinic, P1	Dx = 1.635 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3950 (19) Å	Cell parameters from 11909 reflections
b = 9.5880 (19) Å	θ = 2.7–27.6°
c = 10.252 (2) Å	µ = 0.88 mm−1
α = 68.90 (3)°	T = 293 K
β = 67.74 (3)°	Block, colourless
γ = 78.16 (3)°	0.40 × 0.20 × 0.20 mm
V = 794.8 (3) Å3

Bruker SMART CCD diffractometer	3048 independent reflections
Radiation source: fine-focus sealed tube	2780 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
φ and ω scans	θmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −11→11
Tmin = 0.719, Tmax = 0.843	k = −8→11
4449 measured reflections	l = −12→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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0603P)2 + 0.2356P] where P = (Fo2 + 2Fc2)/3
3048 reflections	(Δ/σ)max = 0.001
239 parameters	Δρmax = 0.52 e Å−3
7 restraints	Δρmin = −0.42 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
Mn1	0.59630 (3)	0.69243 (3)	0.60317 (3)	0.02605 (12)
O1	0.42810 (14)	0.50818 (14)	0.71524 (14)	0.0253 (3)
H1O	0.422 (3)	0.467 (2)	0.648 (2)	0.038*
O2	0.38654 (15)	0.79182 (15)	0.54871 (15)	0.0344 (3)
O3	0.13155 (17)	0.80099 (18)	0.6601 (2)	0.0491 (4)
O4	0.47047 (16)	0.73580 (18)	0.81310 (15)	0.0377 (3)
O5	0.34758 (17)	0.66928 (18)	1.05400 (15)	0.0400 (4)
H5	0.4213	0.7042	1.0522	0.060*
O6	0.31979 (15)	0.40470 (17)	0.57203 (15)	0.0355 (3)
O7	0.06796 (18)	0.4110 (3)	0.6235 (2)	0.0632 (6)
O8	0.76699 (16)	0.56448 (18)	0.70557 (16)	0.0389 (3)
H8A	0.738 (3)	0.4919 (19)	0.7866 (15)	0.047*
H8B	0.8528 (15)	0.525 (3)	0.659 (2)	0.047*
O9	0.70528 (19)	0.89824 (18)	0.5069 (2)	0.0498 (4)
H9A	0.8044 (3)	0.892 (3)	0.476 (3)	0.060*
H9B	0.672 (3)	0.9906 (10)	0.498 (3)	0.060*
C1	0.27525 (19)	0.5802 (2)	0.76103 (19)	0.0243 (4)
C2	0.2623 (2)	0.7377 (2)	0.6467 (2)	0.0289 (4)
C3	0.2476 (2)	0.5940 (2)	0.9129 (2)	0.0294 (4)
H3A	0.1475	0.6478	0.9430	0.035*
H3B	0.2421	0.4939	0.9836	0.035*
C4	0.3654 (2)	0.6717 (2)	0.9252 (2)	0.0277 (4)
C5	0.1528 (2)	0.4839 (2)	0.7782 (2)	0.0285 (4)
H5A	0.1468	0.3963	0.8648	0.034*
H5B	0.0535	0.5413	0.7976	0.034*
C6	0.1791 (2)	0.4310 (2)	0.6473 (2)	0.0295 (4)
N11	0.4324 (2)	0.18749 (19)	0.9584 (2)	0.0367 (4)
C11	0.4410 (3)	0.1513 (2)	0.8411 (2)	0.0392 (5)
H11	0.5245	0.1776	0.7540	0.047*
C12	0.3275 (3)	0.0755 (2)	0.8483 (3)	0.0401 (5)
H12	0.3343	0.0505	0.7664	0.048*
C13	0.2026 (2)	0.0363 (2)	0.9784 (3)	0.0397 (5)
C14	0.1958 (3)	0.0774 (3)	1.0979 (3)	0.0433 (5)
H14	0.1126	0.0544	1.1857	0.052*
C15	0.3128 (3)	0.1524 (3)	1.0851 (3)	0.0408 (5)
H15	0.3090	0.1790	1.1652	0.049*
C16	0.0763 (3)	−0.0475 (3)	0.9912 (3)	0.0521 (6)
H16A	0.0643	−0.1376	1.0761	0.062*
H16B	0.1053	−0.0777	0.9032	0.062*
O1W	0.0166 (2)	0.8352 (2)	0.4269 (2)	0.0644 (5)
H1WA	0.061 (3)	0.824 (4)	0.501 (3)	0.077*
H1WB	0.023 (4)	0.7418 (18)	0.410 (4)	0.077*

	U11	U22	U33	U12	U13	U23
Mn1	0.02480 (17)	0.02764 (18)	0.02587 (17)	−0.00515 (11)	−0.00565 (12)	−0.00986 (12)
O1	0.0215 (6)	0.0254 (6)	0.0297 (6)	0.0000 (5)	−0.0076 (5)	−0.0114 (5)
O2	0.0298 (7)	0.0293 (7)	0.0357 (7)	−0.0044 (6)	−0.0089 (6)	−0.0016 (6)
O3	0.0295 (8)	0.0379 (9)	0.0649 (11)	0.0061 (6)	−0.0130 (7)	−0.0066 (8)
O4	0.0375 (8)	0.0463 (8)	0.0320 (7)	−0.0179 (6)	−0.0006 (6)	−0.0189 (6)
O5	0.0428 (8)	0.0539 (9)	0.0291 (7)	−0.0222 (7)	−0.0092 (6)	−0.0126 (7)
O6	0.0265 (7)	0.0492 (9)	0.0378 (7)	−0.0015 (6)	−0.0071 (6)	−0.0263 (7)
O7	0.0296 (8)	0.1139 (16)	0.0738 (12)	−0.0066 (9)	−0.0134 (8)	−0.0644 (12)
O8	0.0288 (7)	0.0465 (9)	0.0312 (7)	−0.0008 (6)	−0.0072 (6)	−0.0048 (7)
O9	0.0355 (8)	0.0282 (8)	0.0753 (12)	−0.0089 (7)	−0.0104 (8)	−0.0094 (8)
C1	0.0204 (8)	0.0253 (9)	0.0265 (8)	−0.0026 (7)	−0.0042 (7)	−0.0108 (7)
C2	0.0267 (9)	0.0263 (9)	0.0346 (10)	−0.0004 (7)	−0.0106 (8)	−0.0110 (8)
C3	0.0294 (9)	0.0308 (10)	0.0273 (9)	−0.0082 (8)	−0.0032 (7)	−0.0119 (8)
C4	0.0281 (9)	0.0262 (9)	0.0297 (9)	−0.0019 (7)	−0.0078 (7)	−0.0121 (8)
C5	0.0223 (8)	0.0310 (10)	0.0317 (9)	−0.0056 (7)	−0.0032 (7)	−0.0133 (8)
C6	0.0261 (9)	0.0318 (10)	0.0328 (9)	−0.0038 (7)	−0.0083 (7)	−0.0135 (8)
N11	0.0367 (9)	0.0311 (9)	0.0455 (10)	−0.0044 (7)	−0.0202 (8)	−0.0078 (8)
C11	0.0400 (11)	0.0335 (11)	0.0415 (11)	−0.0017 (9)	−0.0152 (9)	−0.0077 (9)
C12	0.0450 (12)	0.0367 (11)	0.0487 (12)	0.0040 (9)	−0.0244 (10)	−0.0193 (10)
C13	0.0350 (11)	0.0345 (11)	0.0600 (14)	0.0020 (9)	−0.0235 (10)	−0.0209 (10)
C14	0.0341 (11)	0.0492 (13)	0.0496 (13)	−0.0077 (10)	−0.0124 (10)	−0.0180 (11)
C15	0.0446 (12)	0.0429 (12)	0.0438 (12)	−0.0066 (10)	−0.0208 (10)	−0.0154 (10)
C16	0.0394 (13)	0.0454 (14)	0.0871 (19)	0.0007 (11)	−0.0266 (13)	−0.0350 (13)
O1W	0.0568 (11)	0.0585 (12)	0.0768 (13)	−0.0075 (9)	−0.0278 (10)	−0.0126 (11)

Mn1—O6i	2.1319 (15)	C3—C4	1.518 (3)
Mn1—O9	2.1395 (17)	C3—H3A	0.9700
Mn1—O4	2.1720 (15)	C3—H3B	0.9700
Mn1—O8	2.1725 (16)	C5—C6	1.519 (3)
Mn1—O2	2.1871 (15)	C5—H5A	0.9700
Mn1—O1	2.2905 (16)	C5—H5B	0.9700
O1—C1	1.440 (2)	N11—C11	1.337 (3)
O1—H1O	0.930 (2)	N11—C15	1.341 (3)
O2—C2	1.275 (2)	C11—C12	1.375 (3)
O3—C2	1.234 (2)	C11—H11	0.9300
O4—C4	1.246 (2)	C12—C13	1.389 (3)
O5—C4	1.259 (2)	C12—H12	0.9300
O5—H5	0.8200	C13—C14	1.392 (3)
O6—C6	1.280 (2)	C13—C16	1.506 (3)
O6—Mn1i	2.1319 (15)	C14—C15	1.375 (3)
O7—C6	1.223 (2)	C14—H14	0.9300
O8—H8A	0.860 (2)	C15—H15	0.9300
O8—H8B	0.859 (2)	C16—C16ii	1.518 (5)
O9—H9A	0.860 (2)	C16—H16A	0.9700
O9—H9B	0.860 (2)	C16—H16B	0.9700
C1—C3	1.529 (3)	O1W—H1WA	0.960 (2)
C1—C5	1.540 (2)	O1W—H1WB	0.959 (2)
C1—C2	1.558 (3)
O6i—Mn1—O9	103.57 (7)	C1—C3—H3A	108.0
O6i—Mn1—O4	163.30 (6)	C4—C3—H3B	108.0
O9—Mn1—O4	93.05 (7)	C1—C3—H3B	108.0
O6i—Mn1—O8	93.96 (6)	H3A—C3—H3B	107.2
O9—Mn1—O8	95.36 (7)	O4—C4—O5	122.97 (17)
O4—Mn1—O8	85.97 (6)	O4—C4—C3	121.25 (16)
O6i—Mn1—O2	92.00 (6)	O5—C4—C3	115.76 (16)
O9—Mn1—O2	94.89 (6)	C6—C5—C1	116.30 (15)
O4—Mn1—O2	84.89 (6)	C6—C5—H5A	108.2
O8—Mn1—O2	166.60 (5)	C1—C5—H5A	108.2
O6i—Mn1—O1	83.80 (6)	C6—C5—H5B	108.2
O9—Mn1—O1	166.66 (6)	C1—C5—H5B	108.2
O4—Mn1—O1	79.57 (6)	H5A—C5—H5B	107.4
O8—Mn1—O1	95.19 (6)	O7—C6—O6	124.37 (18)
O2—Mn1—O1	73.53 (5)	O7—C6—C5	119.40 (17)
C1—O1—Mn1	107.05 (10)	O6—C6—C5	116.17 (16)
C1—O1—H1O	101.9 (14)	C11—N11—C15	121.11 (18)
Mn1—O1—H1O	112.3 (14)	N11—C11—C12	120.5 (2)
C2—O2—Mn1	114.86 (12)	N11—C11—H11	119.7
C4—O4—Mn1	132.39 (13)	C12—C11—H11	119.7
C4—O5—H5	109.5	C11—C12—C13	119.8 (2)
C6—O6—Mn1i	127.51 (12)	C11—C12—H12	120.1
Mn1—O8—H8A	118.4 (17)	C13—C12—H12	120.1
Mn1—O8—H8B	123.3 (17)	C12—C13—C14	118.3 (2)
H8A—O8—H8B	101 (2)	C12—C13—C16	121.5 (2)
Mn1—O9—H9A	117.2 (19)	C14—C13—C16	120.2 (2)
Mn1—O9—H9B	134 (2)	C15—C14—C13	119.5 (2)
H9A—O9—H9B	109 (3)	C15—C14—H14	120.2
O1—C1—C3	106.79 (14)	C13—C14—H14	120.2
O1—C1—C5	110.98 (14)	N11—C15—C14	120.7 (2)
C3—C1—C5	108.23 (15)	N11—C15—H15	119.7
O1—C1—C2	110.46 (14)	C14—C15—H15	119.7
C3—C1—C2	110.69 (15)	C13—C16—C16ii	111.7 (2)
C5—C1—C2	109.64 (15)	C13—C16—H16A	109.3
O3—C2—O2	125.25 (18)	C16ii—C16—H16A	109.3
O3—C2—C1	116.81 (17)	C13—C16—H16B	109.3
O2—C2—C1	117.94 (16)	C16ii—C16—H16B	109.3
C4—C3—C1	117.19 (15)	H16A—C16—H16B	107.9
C4—C3—H3A	108.0	H1WA—O1W—H1WB	111 (3)
O6i—Mn1—O1—C1	−128.46 (11)	C5—C1—C2—O2	−134.76 (17)
O9—Mn1—O1—C1	−4.0 (3)	O1—C1—C3—C4	54.5 (2)
O4—Mn1—O1—C1	53.18 (11)	C5—C1—C3—C4	174.00 (15)
O8—Mn1—O1—C1	138.10 (11)	C2—C1—C3—C4	−65.8 (2)
O2—Mn1—O1—C1	−34.53 (10)	Mn1—O4—C4—O5	150.23 (16)
O6i—Mn1—O2—C2	113.17 (14)	Mn1—O4—C4—C3	−31.3 (3)
O9—Mn1—O2—C2	−143.02 (14)	C1—C3—C4—O4	7.7 (3)
O4—Mn1—O2—C2	−50.38 (14)	C1—C3—C4—O5	−173.68 (17)
O8—Mn1—O2—C2	−3.2 (3)	O1—C1—C5—C6	−51.4 (2)
O1—Mn1—O2—C2	30.23 (13)	C3—C1—C5—C6	−168.30 (16)
O6i—Mn1—O4—C4	−3.7 (3)	C2—C1—C5—C6	70.9 (2)
O9—Mn1—O4—C4	170.83 (19)	Mn1i—O6—C6—O7	−4.3 (3)
O8—Mn1—O4—C4	−94.01 (19)	Mn1i—O6—C6—C5	172.89 (12)
O2—Mn1—O4—C4	76.19 (19)	C1—C5—C6—O7	−150.0 (2)
O1—Mn1—O4—C4	2.03 (18)	C1—C5—C6—O6	32.6 (3)
Mn1—O1—C1—C3	−85.32 (13)	C15—N11—C11—C12	−0.6 (3)
Mn1—O1—C1—C5	156.92 (12)	N11—C11—C12—C13	0.1 (3)
Mn1—O1—C1—C2	35.10 (15)	C11—C12—C13—C14	0.8 (3)
Mn1—O2—C2—O3	158.86 (17)	C11—C12—C13—C16	−179.6 (2)
Mn1—O2—C2—C1	−20.1 (2)	C12—C13—C14—C15	−1.2 (3)
O1—C1—C2—O3	168.78 (17)	C16—C13—C14—C15	179.2 (2)
C3—C1—C2—O3	−73.2 (2)	C11—N11—C15—C14	0.2 (3)
C5—C1—C2—O3	46.2 (2)	C13—C14—C15—N11	0.7 (4)
O1—C1—C2—O2	−12.2 (2)	C12—C13—C16—C16ii	−113.7 (3)
C3—C1—C2—O2	105.91 (19)	C14—C13—C16—C16ii	65.8 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O3	0.96 (1)	1.91 (1)	2.869 (3)	175 (3)
O1—H1O···O6	0.93 (1)	1.74 (1)	2.6020 (19)	153 (2)
O1W—H1WB···O7iii	0.96 (1)	2.02 (2)	2.903 (3)	152 (3)
O5—H5···N11iv	0.82	1.84	2.649 (2)	171
O8—H8A···O5iv	0.86 (1)	1.84 (1)	2.694 (2)	170 (2)
O8—H8B···O7v	0.86 (1)	2.06 (1)	2.872 (2)	158 (2)
O8—H8B···O7i	0.86 (1)	2.56 (2)	3.075 (3)	119 (2)
O9—H9A···O1Wv	0.86 (1)	1.88 (1)	2.722 (3)	168 (3)
O9—H9B···O2vi	0.86 (1)	1.97 (1)	2.829 (2)	173 (3)
C5—H5B···O3	0.97	2.48	2.834 (3)	101
C14—H14···O1Wvii	0.93	2.59	3.357 (4)	141
C15—H15···O4iv	0.93	2.49	3.114 (3)	125

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O3	0.96 (1)	1.91 (1)	2.869 (3)	175 (3)
O1—H1O⋯O6	0.93 (1)	1.74 (1)	2.6020 (19)	153 (2)
O1W—H1WB⋯O7i	0.96 (1)	2.02 (2)	2.903 (3)	152 (3)
O5—H5⋯N11ii	0.82	1.84	2.649 (2)	171
O8—H8A⋯O5ii	0.86 (1)	1.84 (1)	2.694 (2)	170 (2)
O8—H8B⋯O7iii	0.86 (1)	2.06 (1)	2.872 (2)	158 (2)
O8—H8B⋯O7iv	0.86 (1)	2.56 (2)	3.075 (3)	119 (2)
O9—H9A⋯O1W iii	0.86 (1)	1.88 (1)	2.722 (3)	168 (3)
O9—H9B⋯O2v	0.86 (1)	1.97 (1)	2.829 (2)	173 (3)

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