Bis(μ-carboxyl-atoethyl-phospho-nato)bis-[aqua-(2,2'-bipyridine)manganese(II)].

The title compound, [Mn(2)(HO(3)PCH(2)CH(2)COO)(2)(C(8)H(8)N(2))(2)(H(2)O)(2)], was obtained by hydro-thermal synthesis. The manganese(II) ions are six-coordinate and are linked by two 2-carboxy-ethyl-phospho-nate ligands, forming a centrosymmetric dimer. The Mn ions adopts a distorted octahedral coordination geometry. The dimers are further linked by O-H⋯O hydrogen bonds and π-π stacking inter-actions [centroid-centroid distance 4.2754 (4) Å].

Related literature

For related literature, see: Clearfield (1998 ▶); Cheetham et al. (1999 ▶); Stock et al. (2000 ▶); Serpaggi & Férey (1999 ▶); Ying & Mao et al. (2004 ▶); Ying et al. (2007 ▶). For the isostructural Zn(II) complex, see: Ying et al. (2006 ▶).

Experimental

Crystal data

[Mn2(C5H5O5P)2(C8H8N2)2(H2O)2]

M = 762.36

Orthorhombic,

a = 8.7553 (13) Å

b = 18.060 (3) Å

c = 20.682 (3) Å

V = 3270.3 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.94 mm−1

T = 293 (2) K

0.32 × 0.30 × 0.26 mm

Data collection

Bruker APEX area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▶) T min = 0.754, T max = 0.796

23111 measured reflections

4057 independent reflections

2893 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.090

S = 0.99

4057 reflections

208 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.60 e Å−3

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a ▶); molecular graphics: SHELXTL (Sheldrick, 1997b ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807065142/om2188sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807065142/om2188Isup2.hkl

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

[Mn2(C5H5O5P1)2(C8H8N2)2(H2O)2]	F000 = 1560
Mr = 762.36	Dx = 1.548 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5461 reflections
a = 8.7553 (13) Å	θ = 2.5–28.2º
b = 18.060 (3) Å	µ = 0.94 mm−1
c = 20.682 (3) Å	T = 293 (2) K
V = 3270.3 (8) Å3	Block, colourless
Z = 4	0.32 × 0.30 × 0.26 mm

Bruker APEX area-detector diffractometer	4057 independent reflections
Radiation source: fine-focus sealed tube	2893 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.038
T = 293(2) K	θmax = 28.3º
φ and ω scans	θmin = 2.0º
Absorption correction: multi-scan(SADABS; Sheldrick, 2002)	h = −11→11
Tmin = 0.754, Tmax = 0.796	k = −24→24
23111 measured reflections	l = −27→27

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030	H-atom parameters constrained
wR(F2) = 0.090	w = 1/[σ2(Fo2) + (0.0521P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99	(Δ/σ)max = 0.001
4057 reflections	Δρmax = 0.47 e Å−3
208 parameters	Δρmin = −0.60 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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	0.67540 (3)	0.073021 (14)	0.408219 (13)	0.02994 (10)
P1	0.84779 (5)	0.19961 (2)	0.50438 (2)	0.03026 (12)
N1	0.70029 (19)	0.11228 (9)	0.30583 (8)	0.0409 (4)
N2	0.5539 (2)	−0.01013 (9)	0.34242 (7)	0.0427 (4)
O1	0.71646 (15)	0.22186 (7)	0.55235 (6)	0.0417 (3)
H1B	0.6353	0.2240	0.5327	0.062*
O2	0.78629 (14)	0.16537 (7)	0.44369 (6)	0.0364 (3)
O3	0.94774 (14)	0.26603 (7)	0.49251 (7)	0.0441 (3)
O4	1.29300 (14)	0.01457 (7)	0.51674 (6)	0.0378 (3)
O5	1.11488 (16)	0.00513 (7)	0.59060 (6)	0.0419 (3)
O6	0.45857 (14)	0.10698 (7)	0.44337 (6)	0.0415 (3)
H6A	0.4491	0.1514	0.4658	0.050*
H6B	0.3731	0.0775	0.4363	0.050*
C1	0.7756 (3)	0.17412 (12)	0.29085 (11)	0.0538 (6)
H1A	0.8182	0.2023	0.3239	0.065*
C2	0.7923 (3)	0.19769 (14)	0.22728 (12)	0.0667 (7)
H2A	0.8457	0.2408	0.2177	0.080*
C3	0.7284 (3)	0.15608 (16)	0.17906 (12)	0.0703 (8)
H3A	0.7376	0.1709	0.1362	0.084*
C4	0.6509 (3)	0.09242 (14)	0.19413 (11)	0.0600 (7)
H4A	0.6078	0.0636	0.1616	0.072*
C5	0.6375 (2)	0.07146 (11)	0.25805 (9)	0.0402 (5)
C6	0.5559 (2)	0.00356 (11)	0.27852 (9)	0.0412 (5)
C7	0.4850 (3)	−0.04431 (14)	0.23502 (10)	0.0582 (6)
H7A	0.4878	−0.0345	0.1909	0.070*
C8	0.4116 (3)	−0.10562 (16)	0.25773 (12)	0.0758 (8)
H8A	0.3634	−0.1377	0.2291	0.091*
C9	0.4089 (3)	−0.12002 (14)	0.32312 (12)	0.0773 (9)
H9A	0.3599	−0.1616	0.3396	0.093*
C10	0.4818 (3)	−0.07028 (12)	0.36322 (11)	0.0632 (7)
H10A	0.4803	−0.0794	0.4075	0.076*
C11	1.0934 (2)	0.10444 (10)	0.51376 (9)	0.0380 (4)
H11A	1.0651	0.0930	0.4695	0.046*
H11B	1.1671	0.1445	0.5123	0.046*
C12	1.1699 (2)	0.03742 (10)	0.54257 (9)	0.0314 (4)
C13	0.9522 (2)	0.13154 (10)	0.54921 (9)	0.0393 (4)
H13A	0.9828	0.1526	0.5904	0.047*
H13B	0.8860	0.0897	0.5580	0.047*

	U11	U22	U33	U12	U13	U23
Mn1	0.03305 (17)	0.02699 (15)	0.02977 (16)	0.00015 (11)	−0.00014 (11)	0.00075 (11)
P1	0.0241 (2)	0.0261 (2)	0.0406 (3)	0.00079 (18)	−0.0006 (2)	−0.00313 (19)
N1	0.0446 (10)	0.0396 (9)	0.0386 (9)	0.0034 (7)	0.0020 (8)	0.0085 (7)
N2	0.0506 (11)	0.0449 (10)	0.0325 (9)	−0.0091 (8)	−0.0030 (8)	0.0000 (7)
O1	0.0308 (7)	0.0512 (8)	0.0430 (8)	0.0083 (6)	0.0008 (6)	−0.0065 (6)
O2	0.0366 (7)	0.0329 (7)	0.0396 (7)	−0.0046 (5)	−0.0019 (6)	−0.0030 (6)
O3	0.0311 (7)	0.0292 (7)	0.0719 (10)	−0.0051 (5)	−0.0002 (7)	−0.0057 (6)
O4	0.0338 (7)	0.0338 (7)	0.0457 (8)	0.0075 (6)	0.0078 (6)	0.0066 (6)
O5	0.0443 (8)	0.0411 (8)	0.0403 (8)	0.0082 (6)	0.0105 (7)	0.0098 (6)
O6	0.0337 (7)	0.0318 (7)	0.0591 (8)	−0.0018 (6)	0.0060 (6)	−0.0074 (6)
C1	0.0614 (15)	0.0473 (13)	0.0527 (13)	−0.0027 (11)	0.0044 (12)	0.0119 (11)
C2	0.0764 (19)	0.0570 (15)	0.0667 (17)	0.0022 (13)	0.0152 (14)	0.0280 (13)
C3	0.092 (2)	0.0752 (18)	0.0435 (13)	0.0132 (15)	0.0154 (14)	0.0201 (13)
C4	0.0825 (19)	0.0638 (15)	0.0337 (11)	0.0127 (13)	0.0043 (11)	0.0085 (11)
C5	0.0437 (11)	0.0464 (11)	0.0305 (10)	0.0134 (9)	0.0009 (8)	0.0031 (9)
C6	0.0420 (12)	0.0462 (11)	0.0354 (10)	0.0080 (9)	−0.0041 (9)	−0.0008 (9)
C7	0.0699 (16)	0.0699 (15)	0.0348 (12)	−0.0029 (13)	−0.0109 (11)	−0.0052 (11)
C8	0.092 (2)	0.0759 (18)	0.0590 (16)	−0.0260 (17)	−0.0192 (16)	−0.0155 (14)
C9	0.102 (2)	0.0702 (17)	0.0596 (16)	−0.0440 (17)	−0.0095 (16)	−0.0037 (13)
C10	0.0830 (18)	0.0629 (15)	0.0437 (12)	−0.0296 (14)	−0.0059 (12)	0.0006 (11)
C11	0.0330 (10)	0.0335 (10)	0.0475 (11)	0.0045 (8)	0.0011 (9)	0.0085 (8)
C12	0.0310 (10)	0.0264 (9)	0.0367 (10)	−0.0005 (7)	−0.0034 (8)	−0.0027 (8)
C13	0.0378 (11)	0.0378 (10)	0.0422 (11)	0.0106 (8)	0.0002 (9)	0.0008 (8)

Mn1—O2	2.0646 (12)	C1—H1A	0.9300
Mn1—O6	2.1233 (13)	C2—C3	1.368 (4)
Mn1—O4i	2.2334 (13)	C2—H2A	0.9300
Mn1—N1	2.2437 (16)	C3—C4	1.371 (4)
Mn1—N2	2.2890 (16)	C3—H3A	0.9300
Mn1—O5i	2.3161 (14)	C4—C5	1.380 (3)
Mn1—C12i	2.6170 (18)	C4—H4A	0.9300
P1—O2	1.4993 (13)	C5—C6	1.481 (3)
P1—O3	1.5050 (13)	C6—C7	1.394 (3)
P1—O1	1.5710 (13)	C7—C8	1.364 (3)
P1—C13	1.7909 (18)	C7—H7A	0.9300
N1—C1	1.334 (2)	C8—C9	1.377 (3)
N1—C5	1.350 (3)	C8—H8A	0.9300
N2—C10	1.328 (2)	C9—C10	1.379 (3)
N2—C6	1.345 (2)	C9—H9A	0.9300
O1—H1B	0.8200	C10—H10A	0.9300
O4—C12	1.272 (2)	C11—C12	1.506 (2)
O4—Mn1i	2.2334 (13)	C11—C13	1.518 (2)
O5—C12	1.248 (2)	C11—H11A	0.9700
O5—Mn1i	2.3161 (14)	C11—H11B	0.9700
O6—H6A	0.9300	C12—Mn1i	2.6170 (18)
O6—H6B	0.9300	C13—H13A	0.9700
C1—C2	1.390 (3)	C13—H13B	0.9700
O2—Mn1—O6	93.75 (5)	C3—C2—H2A	120.7
O2—Mn1—O4i	105.49 (5)	C1—C2—H2A	120.7
O6—Mn1—O4i	94.44 (5)	C2—C3—C4	119.8 (2)
O2—Mn1—N1	91.97 (6)	C2—C3—H3A	120.1
O6—Mn1—N1	108.58 (6)	C4—C3—H3A	120.1
O4i—Mn1—N1	150.19 (5)	C3—C4—C5	119.3 (2)
O2—Mn1—N2	163.71 (5)	C3—C4—H4A	120.3
O6—Mn1—N2	88.71 (6)	C5—C4—H4A	120.3
O4i—Mn1—N2	90.35 (6)	N1—C5—C4	121.1 (2)
N1—Mn1—N2	72.02 (6)	N1—C5—C6	116.05 (16)
O2—Mn1—O5i	96.64 (5)	C4—C5—C6	122.8 (2)
O6—Mn1—O5i	151.79 (5)	N2—C6—C7	120.96 (19)
O4i—Mn1—O5i	57.51 (4)	N2—C6—C5	116.09 (17)
N1—Mn1—O5i	97.21 (5)	C7—C6—C5	122.95 (18)
N2—Mn1—O5i	88.57 (6)	C8—C7—C6	119.4 (2)
O2—Mn1—C12i	103.54 (5)	C8—C7—H7A	120.3
O6—Mn1—C12i	123.35 (6)	C6—C7—H7A	120.3
O4i—Mn1—C12i	29.05 (5)	C7—C8—C9	120.0 (2)
N1—Mn1—C12i	123.89 (6)	C7—C8—H8A	120.0
N2—Mn1—C12i	88.38 (6)	C9—C8—H8A	120.0
O5i—Mn1—C12i	28.49 (5)	C8—C9—C10	117.4 (2)
O2—P1—O3	113.64 (8)	C8—C9—H9A	121.3
O2—P1—O1	111.80 (8)	C10—C9—H9A	121.3
O3—P1—O1	108.95 (8)	N2—C10—C9	123.9 (2)
O2—P1—C13	109.49 (8)	N2—C10—H10A	118.0
O3—P1—C13	109.55 (9)	C9—C10—H10A	118.0
O1—P1—C13	102.85 (8)	C12—C11—C13	115.46 (16)
C1—N1—C5	119.24 (18)	C12—C11—H11A	108.4
C1—N1—Mn1	122.14 (15)	C13—C11—H11A	108.4
C5—N1—Mn1	118.61 (13)	C12—C11—H11B	108.4
C10—N2—C6	118.37 (18)	C13—C11—H11B	108.4
C10—N2—Mn1	124.41 (14)	H11A—C11—H11B	107.5
C6—N2—Mn1	117.22 (13)	O5—C12—O4	120.64 (17)
P1—O1—H1B	109.5	O5—C12—C11	121.25 (16)
P1—O2—Mn1	143.09 (8)	O4—C12—C11	118.11 (16)
C12—O4—Mn1i	92.45 (11)	O5—C12—Mn1i	62.24 (10)
C12—O5—Mn1i	89.27 (11)	O4—C12—Mn1i	58.50 (9)
Mn1—O6—H6A	120.0	C11—C12—Mn1i	175.17 (13)
Mn1—O6—H6B	120.0	C11—C13—P1	112.77 (13)
H6A—O6—H6B	120.0	C11—C13—H13A	109.0
N1—C1—C2	121.9 (2)	P1—C13—H13A	109.0
N1—C1—H1A	119.1	C11—C13—H13B	109.0
C2—C1—H1A	119.1	P1—C13—H13B	109.0
C3—C2—C1	118.6 (2)	H13A—C13—H13B	107.8

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6B···O4ii	0.93	2.13	2.6813 (18)	117
O1—H1B···O3iii	0.82	1.73	2.5385 (19)	167

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6B⋯O4i	0.93	2.13	2.6813 (18)	117
O1—H1B⋯O3ii	0.82	1.73	2.5385 (19)	167

Symmetry codes: (i) ; (ii) .