catena-Poly[[[aqua­manganese(II)]-di-μ-sulfato-[aqua­manganese(II)]-μ-N,N,N′,N′-tetra­kis(2-pyridylmeth­yl)hexane-1,6-diamine] hexa­hydrate]

Song, A.-R.; Hwang, I.-C.; Ha, K.

doi:10.1107/S1600536807063313

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page m44

https://doi.org/10.1107/S1600536807063313

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catena-Poly[[[aquamanganese(II)]-di-μ-sulfato-[aquamanganese(II)]-μ-N,N,N′,N′-tetrakis(2-pyridylmethyl)hexane-1,6-diamine] hexahydrate]

Ah-Ran Song,^a In-Chul Hwang ^b and Kwang Ha ^a ^*

^aSchool of Applied Chemical Engineering, Center for Functional Nano Fine Chemicals, Chonnam National University, Gwangju 500-757, Republic of Korea, and ^bDepartment of Chemistry, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea
^*Correspondence e-mail: hakwang@chonnam.ac.kr

(Received 23 November 2007; accepted 26 November 2007; online 6 December 2007)

In the polymeric title compound, {[Mn₂(SO₄)₂(C₃₀H₃₆N₆)(H₂O)₂]·6H₂O}_n, the two Mn²⁺ ions are bridged by two sulfate anions to form dinuclear complexes, and these dinuclear species are linked by the hexadentate ligand N,N,N′,N′-tetrakis(2-pyridylmethyl)hexane-1,6-diamine (tphn), forming a one-dimensional chain structure running in the [101] direction. The repeat unit of the polymer, Mn₂(SO₄)₂(H₂O)₂(tphn), is disposed about a twofold axis passing through the centre of the dinuclear unit. The coordination geometry around the Mn centre is distorted octahedral. Two methylene groups are each disordered equally over two positions.

Related literature

For a related Mn-complex involving the tphn ligand, see: Hwang & Ha (2007 ).

Experimental

Crystal data

[Mn₂(SO₄)₂(C₃₀H₃₆N₆)(H₂O)₂]·6H₂O
M_r = 926.78
Monoclinic, C 2/c
a = 20.910 (3) Å
b = 12.5820 (17) Å
c = 15.752 (2) Å
β = 99.888 (3)°
V = 4082.7 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.80 mm⁻¹
T = 243 (2) K
0.21 × 0.20 × 0.15 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.734, T_max = 0.888
11793 measured reflections
4165 independent reflections
3158 reflections with I > 2σs(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.079
wR(F²) = 0.145
S = 1.22
4165 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5W—H5W1⋯O7Wⁱ	0.96	1.76	2.703 (5)	166
O5W—H5W2⋯O3ⁱⁱ	0.94	1.85	2.727 (4)	153
O6W—H6W1⋯O2ⁱⁱⁱ	0.96	1.91	2.865 (5)	171
O6W—H6W2⋯O3^iv	0.86	2.26	2.899 (5)	130
O7W—H7W1⋯O8W	1.00	1.85	2.829 (6)	165
O7W—H7W2⋯O6W	0.93	2.53	3.044 (6)	115
O7W—H7W2⋯O6W^v	0.93	2.35	3.162 (6)	146
O8W—H8W1⋯O3^vi	1.03	1.91	2.860 (5)	152
O8W—H8W2⋯O1^vii	0.97	1.96	2.913 (5)	166
O8W—H8W2⋯O3^vii	0.97	2.59	3.317 (5)	132
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iv) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (v) $[-x, y, -z+{\script{1\over 2}}]$ ; (vi) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807063313/ln2016sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063313/ln2016Isup2.hkl

checkCIF report

Comment top

The title compound consists of a Mn^II complex polymer with solvent H₂O molecules. In the polymer, two Mn²⁺ ions are first bridged by two SO₄ anion ligands to form dinuclear complexes (Fig. 1), and these dinuclear species are anew bridged by the hexadentate ligand N,N,N',N'-tetrakis(2-pyridylmethyl)hexane-1,6-diamine (tphn) to form a one-dimensional chain structure running in the [101] direction (Fig. 2). The Mn ion is six-coordinated in a distorted octahedral structure by three N atoms from the tphn ligand in the facial position, two O atoms from the two SO₄ ligands and an O atom from H₂O ligand. The constitutional repeating unit of the polymer, Mn₂(SO₄)₂(H₂O)₂(tphn), is disposed about a twofold axis passing through the centre of the dinuclear unit. As the twofold axis is parallel to the b axis, the unit lies in the (010) plane. The Mn—N(amine) bond length [2.360 (4) Å] is slightly longer than the Mn—N(pyridyl) bond lengths [2.300 (4) and 2.256 (4) Å], and the Mn—O(H₂O) bond length [2.206 (3) Å] is slightly longer than the Mn—O(SO₄) bond lengths [2.139 (3) and 2.143 (3) Å]. The geometry of the bridging SO₄ ligand is nearly tetrahedral with the O—S—O bond angles of 107.96 (18)–110.23 (18)°, and the S—O bond distances are almost equal [1.456 (3)–1.486 (3) Å]. The compound displays intra- and intermolecular O—H···O hydrogen bonds among the H₂O ligand, solvent molecules and SO₄ anions (Fig. 2, Table 1).

Related literature top

For a related Mn-complex involving the tphn ligand, see: Hwang & Ha (2007).

Experimental top

To a solution of MnSO₄.5H₂O (0.25 g, 1.04 mmol) in H₂O (10 ml) was added a solution of N,N,N',N'-tetrakis(2-pyridylmethyl)hexane-1,6-diamine (0.50 g, 1.04 mmol) in EtOH (10 ml) and stirred for 1 h at room temparature, and then filtered. The solvent was removed under vacuum, the residue washed with EtOH/acetone and dried, to give a pale yellow powder (0.41 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from an aqueous solution. MS (FAB): m/z 632 (Mn(tphn)HSO₄⁺); IR (KBr): 3405 cm^-1 (broad).

Structure description top

For a related Mn-complex involving the tphn ligand, see: Hwang & Ha (2007).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

	Fig. 1. The structure of the constitutional repeating unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms and the solvent H₂O molecules have been omitted for clarity. The bonds of the disordered hexylene chains are shown with dashed lines.
	Fig. 2. View of the unit-cell contents and chain structure of the title compound. H atoms at C atoms have been omitted for clarity. Hydrogen-bond interactions are drawn with dashed lines.

catena-Poly[[[aquamanganese(II)]-di-µ-sulfato-[aquamanganese(II)]-µ- N,N,N',N'-tetrakis(2-pyridylmethyl)hexane-1,6-diamine] hexahydrate] top

Crystal data top

[Mn₂(SO₄)₂(C₃₀H₃₆N₆)(H₂O)₂]·6H₂O	F(000) = 1936
M_r = 926.78	D_x = 1.508 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2250 reflections
a = 20.910 (3) Å	θ = 2.2–24.3°
b = 12.5820 (17) Å	µ = 0.80 mm⁻¹
c = 15.752 (2) Å	T = 243 K
β = 99.888 (3)°	Block, colorless
V = 4082.7 (10) Å³	0.21 × 0.20 × 0.15 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD diffractometer	4165 independent reflections
Radiation source: fine-focus sealed tube	3158 reflections with I > 2σs(I)
Graphite monochromator	R_int = 0.050
φ and ω scans	θ_max = 26.4°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −26→20
T_min = 0.734, T_max = 0.888	k = −15→15
11793 measured reflections	l = −18→19

Refinement top

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)] = 0.079	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 1.22	w = 1/[σ²(F_o²) + (0.0516P)²] where P = (F_o² + 2F_c²)/3
4165 reflections	(Δ/σ)_max < 0.001
271 parameters	Δρ_max = 0.56 e Å⁻³
0 restraints	Δρ_min = −0.67 e Å⁻³

Crystal data top

[Mn₂(SO₄)₂(C₃₀H₃₆N₆)(H₂O)₂]·6H₂O	V = 4082.7 (10) Å³
M_r = 926.78	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 20.910 (3) Å	µ = 0.80 mm⁻¹
b = 12.5820 (17) Å	T = 243 K
c = 15.752 (2) Å	0.21 × 0.20 × 0.15 mm
β = 99.888 (3)°

Data collection top

Bruker SMART 1000 CCD diffractometer	4165 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3158 reflections with I > 2σs(I)
T_min = 0.734, T_max = 0.888	R_int = 0.050
11793 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.079	0 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.22	Δρ_max = 0.56 e Å⁻³
4165 reflections	Δρ_min = −0.67 e Å⁻³
271 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mn1	0.39214 (3)	0.24391 (5)	0.21343 (4)	0.0214 (2)
N1	0.41270 (18)	0.4176 (3)	0.1814 (2)	0.0258 (9)
N2	0.28972 (18)	0.2294 (3)	0.1407 (2)	0.0263 (9)
N3	0.32712 (19)	0.3532 (3)	0.2857 (2)	0.0275 (9)
C1	0.4377 (2)	0.4535 (4)	0.1136 (3)	0.0317 (12)
H1	0.4496	0.4033	0.0749	0.038*
C2	0.4467 (3)	0.5585 (4)	0.0978 (4)	0.0515 (16)
H2	0.4644	0.5802	0.0497	0.062*
C3	0.4295 (4)	0.6309 (4)	0.1537 (5)	0.082 (3)
H3	0.4347	0.7040	0.1446	0.098*
C4	0.4040 (4)	0.5958 (4)	0.2244 (4)	0.072 (2)
H4	0.3923	0.6449	0.2641	0.086*
C5	0.3960 (2)	0.4891 (4)	0.2360 (3)	0.0329 (12)
C6	0.3681 (2)	0.4466 (4)	0.3113 (3)	0.0334 (12)
H6A	0.4034	0.4269	0.3579	0.040*
H6B	0.3421	0.5020	0.3330	0.040*
C7	0.2691 (2)	0.1531 (4)	0.0829 (3)	0.0310 (12)
H7	0.3000	0.1055	0.0678	0.037*
C8	0.2056 (3)	0.1406 (4)	0.0446 (3)	0.0376 (13)
H8	0.1934	0.0860	0.0043	0.045*
C9	0.1602 (3)	0.2099 (4)	0.0664 (3)	0.0419 (14)
H9	0.1162	0.2034	0.0411	0.050*
C10	0.1798 (3)	0.2889 (4)	0.1256 (3)	0.0375 (13)
H10	0.1496	0.3373	0.1411	0.045*
C11	0.2447 (2)	0.2960 (4)	0.1620 (3)	0.0283 (11)
C12	0.2683 (2)	0.3835 (4)	0.2250 (3)	0.0349 (12)
H12A	0.2775	0.4469	0.1931	0.042*
H12B	0.2338	0.4016	0.2576	0.042*
C13	0.3108 (3)	0.2990 (4)	0.3633 (3)	0.0414 (13)
H13A	0.2808	0.2414	0.3420	0.050*	0.50
H13B	0.3509	0.2651	0.3922	0.050*	0.50
H13C	0.3506	0.2664	0.3945	0.050*	0.50
H13D	0.2973	0.3533	0.4011	0.050*	0.50
C14A	0.2846 (6)	0.3505 (7)	0.4266 (6)	0.039 (3)	0.50
H14A	0.2435	0.3831	0.4000	0.047*	0.50
H14B	0.3141	0.4079	0.4500	0.047*	0.50
C15A	0.2719 (5)	0.2795 (8)	0.5022 (6)	0.033 (2)	0.50
H15A	0.2409	0.2235	0.4800	0.040*	0.50
H15B	0.3125	0.2453	0.5288	0.040*	0.50
C14B	0.2607 (5)	0.2176 (8)	0.3489 (6)	0.038 (3)	0.50
H14C	0.2708	0.1673	0.3056	0.046*	0.50
H14D	0.2189	0.2511	0.3260	0.046*	0.50
C15B	0.2545 (6)	0.1568 (7)	0.4313 (6)	0.042 (3)	0.50
H15C	0.2262	0.0953	0.4157	0.050*	0.50
H15D	0.2975	0.1299	0.4569	0.050*	0.50
S1	0.50266 (6)	0.19295 (9)	0.09722 (7)	0.0224 (3)
O1	0.43452 (15)	0.1790 (2)	0.11052 (18)	0.0311 (8)
O2	0.50341 (16)	0.2496 (2)	0.01682 (18)	0.0340 (8)
O3	0.53263 (16)	0.0869 (2)	0.09408 (18)	0.0304 (8)
O4	0.53755 (16)	0.2547 (2)	0.17063 (18)	0.0332 (8)
O5W	0.37252 (16)	0.0856 (2)	0.26352 (19)	0.0335 (8)
H5W1	0.3706	0.0210	0.2304	0.080*
H5W2	0.3952	0.0746	0.3200	0.080*
O6W	0.0222 (2)	0.3660 (3)	0.1421 (2)	0.0555 (11)
H6W1	0.0116	0.3339	0.0860	0.080*
H6W2	0.0000	0.4224	0.1267	0.080*
O7W	0.11759 (19)	0.3934 (3)	0.3098 (3)	0.0633 (12)
H7W1	0.1173	0.4122	0.3717	0.080*
H7W2	0.0723	0.3913	0.2988	0.080*
O8W	0.1124 (2)	0.4811 (3)	0.4739 (3)	0.0716 (14)
H8W1	0.0798	0.4383	0.5024	0.080*
H8W2	0.0897	0.5429	0.4459	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0244 (4)	0.0200 (4)	0.0213 (3)	0.0010 (3)	0.0082 (3)	0.0018 (3)
N1	0.026 (2)	0.025 (2)	0.029 (2)	0.0012 (17)	0.0125 (18)	−0.0024 (17)
N2	0.026 (2)	0.030 (2)	0.0251 (19)	0.0024 (17)	0.0088 (17)	0.0064 (17)
N3	0.031 (2)	0.032 (2)	0.0216 (19)	−0.0001 (18)	0.0123 (18)	0.0043 (17)
C1	0.040 (3)	0.029 (3)	0.031 (3)	0.003 (2)	0.019 (2)	0.003 (2)
C2	0.064 (4)	0.034 (3)	0.067 (4)	0.000 (3)	0.041 (3)	0.015 (3)
C3	0.130 (7)	0.022 (3)	0.117 (6)	−0.007 (4)	0.084 (6)	0.003 (3)
C4	0.113 (6)	0.026 (3)	0.095 (5)	−0.008 (3)	0.072 (5)	−0.014 (3)
C5	0.040 (3)	0.028 (3)	0.035 (3)	−0.002 (2)	0.018 (2)	−0.004 (2)
C6	0.046 (3)	0.030 (3)	0.030 (3)	0.000 (2)	0.020 (2)	−0.007 (2)
C7	0.035 (3)	0.029 (3)	0.029 (3)	0.000 (2)	0.006 (2)	−0.002 (2)
C8	0.042 (4)	0.040 (3)	0.029 (3)	−0.012 (3)	0.000 (3)	0.006 (2)
C9	0.027 (3)	0.061 (4)	0.037 (3)	−0.004 (3)	0.001 (2)	0.018 (3)
C10	0.034 (3)	0.047 (3)	0.034 (3)	0.009 (3)	0.012 (2)	0.015 (2)
C11	0.029 (3)	0.035 (3)	0.023 (2)	0.003 (2)	0.012 (2)	0.013 (2)
C12	0.036 (3)	0.038 (3)	0.035 (3)	0.010 (2)	0.017 (2)	0.004 (2)
C13	0.046 (4)	0.054 (3)	0.027 (3)	−0.004 (3)	0.013 (3)	0.006 (2)
C14A	0.056 (8)	0.024 (5)	0.042 (6)	0.004 (5)	0.023 (6)	0.004 (5)
C15A	0.041 (7)	0.035 (6)	0.026 (5)	−0.002 (4)	0.012 (5)	0.003 (4)
C14B	0.058 (8)	0.036 (6)	0.024 (5)	0.009 (5)	0.021 (5)	0.004 (4)
C15B	0.055 (8)	0.030 (6)	0.042 (6)	0.014 (5)	0.016 (6)	0.012 (5)
S1	0.0259 (7)	0.0213 (6)	0.0212 (6)	0.0008 (5)	0.0076 (5)	−0.0024 (5)
O1	0.033 (2)	0.0322 (18)	0.0319 (18)	−0.0025 (15)	0.0158 (16)	−0.0072 (14)
O2	0.043 (2)	0.0343 (19)	0.0269 (16)	−0.0004 (17)	0.0138 (16)	0.0022 (15)
O3	0.035 (2)	0.0259 (17)	0.0302 (17)	0.0045 (15)	0.0063 (15)	−0.0066 (14)
O4	0.039 (2)	0.0248 (17)	0.0328 (17)	0.0084 (16)	−0.0009 (15)	−0.0086 (14)
O5W	0.042 (2)	0.0243 (17)	0.0338 (18)	−0.0047 (16)	0.0057 (16)	0.0018 (14)
O6W	0.074 (3)	0.048 (2)	0.046 (2)	−0.003 (2)	0.015 (2)	−0.0042 (18)
O7W	0.054 (3)	0.045 (2)	0.095 (3)	0.011 (2)	0.026 (3)	0.025 (2)
O8W	0.060 (3)	0.069 (3)	0.096 (3)	0.022 (2)	0.044 (3)	0.041 (2)

Geometric parameters (Å, º) top

Mn1—O1	2.139 (3)	C11—C12	1.507 (6)
Mn1—O4ⁱ	2.143 (3)	C12—H12A	0.9800
Mn1—O5W	2.206 (3)	C12—H12B	0.9800
Mn1—N2	2.256 (4)	C13—C14A	1.379 (10)
Mn1—N1	2.300 (4)	C13—C14B	1.456 (11)
Mn1—N3	2.360 (4)	C13—H13A	0.9800
N1—C5	1.332 (5)	C13—H13B	0.9800
N1—C1	1.345 (5)	C13—H13C	0.9800
N2—C7	1.342 (5)	C13—H13D	0.9800
N2—C11	1.346 (6)	C14A—C15A	1.547 (12)
N3—C6	1.468 (6)	C14A—H14A	0.9800
N3—C12	1.473 (6)	C14A—H14B	0.9800
N3—C13	1.489 (5)	C15A—C15Bⁱⁱ	1.499 (13)
C1—C2	1.364 (6)	C15A—H15A	0.9800
C1—H1	0.9400	C15A—H15B	0.9800
C2—C3	1.358 (7)	C14B—C15B	1.531 (12)
C2—H2	0.9400	C14B—H14C	0.9800
C3—C4	1.387 (7)	C14B—H14D	0.9800
C3—H3	0.9400	C15B—H15C	0.9800
C4—C5	1.370 (7)	C15B—H15D	0.9800
C4—H4	0.9400	S1—O2	1.456 (3)
C5—C6	1.507 (6)	S1—O4	1.477 (3)
C6—H6A	0.9800	S1—O3	1.479 (3)
C6—H6B	0.9800	S1—O1	1.486 (3)
C7—C8	1.370 (7)	O5W—H5W1	0.963
C7—H7	0.9400	O5W—H5W2	0.944
C8—C9	1.376 (7)	O6W—H6W1	0.962
C8—H8	0.9400	O6W—H6W2	0.860
C9—C10	1.377 (7)	O7W—H7W1	1.004
C9—H9	0.9400	O7W—H7W2	0.933
C10—C11	1.381 (7)	O8W—H8W1	1.030
C10—H10	0.9400	O8W—H8W2	0.977

O1—Mn1—O4ⁱ	110.92 (13)	C10—C11—C12	120.5 (4)
O1—Mn1—O5W	93.05 (11)	N3—C12—C11	112.4 (4)
O4ⁱ—Mn1—O5W	83.96 (11)	N3—C12—H12A	109.1
O1—Mn1—N2	93.72 (12)	C11—C12—H12A	109.1
O4ⁱ—Mn1—N2	152.92 (13)	N3—C12—H12B	109.1
O5W—Mn1—N2	83.68 (12)	C11—C12—H12B	109.1
O1—Mn1—N1	94.54 (12)	H12A—C12—H12B	107.9
O4ⁱ—Mn1—N1	90.01 (12)	C14A—C13—C14B	94.5 (7)
O5W—Mn1—N1	171.62 (12)	C14A—C13—N3	123.6 (6)
N2—Mn1—N1	99.36 (13)	C14B—C13—N3	117.1 (5)
O1—Mn1—N3	159.47 (12)	C14A—C13—H13A	106.4
O4ⁱ—Mn1—N3	85.39 (13)	N3—C13—H13A	106.4
O5W—Mn1—N3	101.28 (12)	C14A—C13—H13B	106.4
N2—Mn1—N3	73.57 (13)	C14B—C13—H13B	107.5
N1—Mn1—N3	72.36 (12)	N3—C13—H13B	106.4
C5—N1—C1	117.8 (4)	H13A—C13—H13B	106.5
C5—N1—Mn1	114.9 (3)	C14A—C13—H13C	104.0
C1—N1—Mn1	127.3 (3)	C14B—C13—H13C	108.0
C7—N2—C11	117.3 (4)	N3—C13—H13C	108.0
C7—N2—Mn1	124.6 (3)	H13A—C13—H13C	107.5
C11—N2—Mn1	117.8 (3)	C14B—C13—H13D	108.0
C6—N3—C12	110.7 (4)	N3—C13—H13D	108.0
C6—N3—C13	110.2 (3)	H13A—C13—H13D	119.2
C12—N3—C13	111.6 (4)	H13B—C13—H13D	109.6
C6—N3—Mn1	104.0 (3)	H13C—C13—H13D	107.3
C12—N3—Mn1	108.9 (3)	C13—C14A—C15A	115.3 (8)
C13—N3—Mn1	111.2 (3)	C13—C14A—H14A	108.4
N1—C1—C2	123.7 (4)	C15A—C14A—H14A	108.4
N1—C1—H1	118.2	C13—C14A—H14B	108.4
C2—C1—H1	118.2	C15A—C14A—H14B	108.4
C3—C2—C1	118.2 (5)	H14A—C14A—H14B	107.5
C3—C2—H2	120.9	C15Bⁱⁱ—C15A—C14A	111.2 (8)
C1—C2—H2	120.9	C15Bⁱⁱ—C15A—H15A	109.4
C2—C3—C4	119.2 (5)	C14A—C15A—H15A	109.4
C2—C3—H3	120.4	C15Bⁱⁱ—C15A—H15B	109.4
C4—C3—H3	120.4	C14A—C15A—H15B	109.4
C5—C4—C3	119.5 (5)	H15A—C15A—H15B	108.0
C5—C4—H4	120.3	C13—C14B—C15B	112.5 (8)
C3—C4—H4	120.3	C13—C14B—H14C	109.1
N1—C5—C4	121.6 (5)	C15B—C14B—H14C	109.1
N1—C5—C6	116.7 (4)	C13—C14B—H14D	109.1
C4—C5—C6	121.7 (4)	C15B—C14B—H14D	109.1
N3—C6—C5	110.7 (3)	H14C—C14B—H14D	107.8
N3—C6—H6A	109.5	C15Aⁱⁱ—C15B—C14B	114.9 (8)
C5—C6—H6A	109.5	C15Aⁱⁱ—C15B—H15C	108.5
N3—C6—H6B	109.5	C14B—C15B—H15C	108.5
C5—C6—H6B	109.5	C15Aⁱⁱ—C15B—H15D	108.5
H6A—C6—H6B	108.1	C14B—C15B—H15D	108.5
N2—C7—C8	123.7 (5)	H15C—C15B—H15D	107.5
N2—C7—H7	118.2	O2—S1—O4	110.23 (18)
C8—C7—H7	118.2	O2—S1—O3	110.17 (18)
C7—C8—C9	118.5 (5)	O4—S1—O3	110.21 (18)
C7—C8—H8	120.8	O2—S1—O1	109.54 (19)
C9—C8—H8	120.8	O4—S1—O1	107.96 (18)
C8—C9—C10	119.1 (5)	O3—S1—O1	108.69 (18)
C8—C9—H9	120.4	S1—O1—Mn1	126.45 (18)
C10—C9—H9	120.4	S1—O4—Mn1ⁱ	143.91 (19)
C9—C10—C11	119.1 (5)	H5W1—O5W—H5W2	110.7
C9—C10—H10	120.5	H6W1—O6W—H6W2	93.4
C11—C10—H10	120.5	H7W1—O7W—H7W2	90.7
N2—C11—C10	122.3 (5)	H8W1—O8W—H8W2	107.8
N2—C11—C12	117.1 (4)

O1—Mn1—N1—C5	−176.5 (3)	C12—N3—C6—C5	−67.5 (5)
O4ⁱ—Mn1—N1—C5	−65.5 (3)	C13—N3—C6—C5	168.5 (4)
N2—Mn1—N1—C5	88.9 (3)	Mn1—N3—C6—C5	49.3 (4)
N3—Mn1—N1—C5	19.6 (3)	N1—C5—C6—N3	−36.5 (6)
O1—Mn1—N1—C1	5.3 (4)	C4—C5—C6—N3	143.6 (6)
O4ⁱ—Mn1—N1—C1	116.3 (4)	C11—N2—C7—C8	0.6 (6)
N2—Mn1—N1—C1	−89.2 (4)	Mn1—N2—C7—C8	174.5 (3)
N3—Mn1—N1—C1	−158.5 (4)	N2—C7—C8—C9	−0.1 (7)
O1—Mn1—N2—C7	31.8 (3)	C7—C8—C9—C10	−0.1 (7)
O4ⁱ—Mn1—N2—C7	−124.2 (4)	C8—C9—C10—C11	−0.4 (7)
O5W—Mn1—N2—C7	−60.9 (3)	C7—N2—C11—C10	−1.1 (6)
N1—Mn1—N2—C7	127.0 (3)	Mn1—N2—C11—C10	−175.4 (3)
N3—Mn1—N2—C7	−164.6 (4)	C7—N2—C11—C12	−178.3 (4)
O1—Mn1—N2—C11	−154.4 (3)	Mn1—N2—C11—C12	7.4 (5)
O4ⁱ—Mn1—N2—C11	49.7 (4)	C9—C10—C11—N2	1.0 (7)
O5W—Mn1—N2—C11	113.0 (3)	C9—C10—C11—C12	178.1 (4)
N1—Mn1—N2—C11	−59.1 (3)	C6—N3—C12—C11	148.8 (4)
N3—Mn1—N2—C11	9.2 (3)	C13—N3—C12—C11	−88.0 (5)
O1—Mn1—N3—C6	−88.2 (4)	Mn1—N3—C12—C11	35.0 (4)
O4ⁱ—Mn1—N3—C6	55.5 (3)	N2—C11—C12—N3	−29.7 (6)
O5W—Mn1—N3—C6	138.4 (3)	C10—C11—C12—N3	153.1 (4)
N2—Mn1—N3—C6	−141.7 (3)	C6—N3—C13—C14A	52.1 (8)
N1—Mn1—N3—C6	−35.9 (3)	C12—N3—C13—C14A	−71.4 (8)
O1—Mn1—N3—C12	29.9 (5)	Mn1—N3—C13—C14A	166.8 (7)
O4ⁱ—Mn1—N3—C12	173.6 (3)	C6—N3—C13—C14B	168.5 (6)
O5W—Mn1—N3—C12	−103.5 (3)	C12—N3—C13—C14B	45.0 (7)
N2—Mn1—N3—C12	−23.6 (3)	Mn1—N3—C13—C14B	−76.8 (7)
N1—Mn1—N3—C12	82.1 (3)	C14B—C13—C14A—C15A	53.7 (10)
O1—Mn1—N3—C13	153.2 (3)	N3—C13—C14A—C15A	−179.5 (7)
O4ⁱ—Mn1—N3—C13	−63.1 (3)	C13—C14A—C15A—C15Bⁱⁱ	178.2 (9)
O5W—Mn1—N3—C13	19.8 (3)	C14A—C13—C14B—C15B	−56.4 (9)
N2—Mn1—N3—C13	99.7 (3)	N3—C13—C14B—C15B	172.1 (6)
N1—Mn1—N3—C13	−154.5 (3)	C13—C14B—C15B—C15Aⁱⁱ	68.7 (12)
C5—N1—C1—C2	−0.1 (7)	O2—S1—O1—Mn1	−116.8 (2)
Mn1—N1—C1—C2	178.1 (4)	O4—S1—O1—Mn1	3.3 (3)
N1—C1—C2—C3	−0.1 (9)	O3—S1—O1—Mn1	122.8 (2)
C1—C2—C3—C4	0.5 (11)	O4ⁱ—Mn1—O1—S1	−32.5 (3)
C2—C3—C4—C5	−0.8 (11)	O5W—Mn1—O1—S1	−117.2 (2)
C1—N1—C5—C4	−0.2 (8)	N2—Mn1—O1—S1	158.9 (2)
Mn1—N1—C5—C4	−178.6 (5)	N1—Mn1—O1—S1	59.2 (2)
C1—N1—C5—C6	179.9 (4)	N3—Mn1—O1—S1	108.3 (4)
Mn1—N1—C5—C6	1.5 (5)	O2—S1—O4—Mn1ⁱ	−134.1 (3)
C3—C4—C5—N1	0.6 (10)	O3—S1—O4—Mn1ⁱ	−12.3 (4)
C3—C4—C5—C6	−179.5 (6)	O1—S1—O4—Mn1ⁱ	106.3 (4)

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5W—H5W1···O7Wⁱⁱⁱ	0.963	1.758	2.703 (5)	166
O5W—H5W2···O3ⁱ	0.944	1.852	2.727 (4)	153
O6W—H6W1···O2^iv	0.962	1.911	2.865 (5)	171
O6W—H6W2···O3^v	0.860	2.266	2.899 (5)	130
O7W—H7W1···O8W	1.004	1.847	2.829 (6)	165
O7W—H7W2···O6W	0.933	2.530	3.044 (6)	115
O7W—H7W2···O6W^vi	0.933	2.347	3.162 (6)	146
O8W—H8W1···O3^vii	1.030	1.910	2.860 (5)	152
O8W—H8W2···O1^viii	0.977	1.956	2.913 (5)	166
O8W—H8W2···O3^viii	0.977	2.587	3.317 (5)	132

Symmetry codes: (i) −x+1, y, −z+1/2; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x+1/2, −y+1/2, −z; (v) x−1/2, y+1/2, z; (vi) −x, y, −z+1/2; (vii) x−1/2, −y+1/2, z+1/2; (viii) −x+1/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Mn₂(SO₄)₂(C₃₀H₃₆N₆)(H₂O)₂]·6H₂O
M_r	926.78
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	243
a, b, c (Å)	20.910 (3), 12.5820 (17), 15.752 (2)
β (°)	99.888 (3)
V (Å³)	4082.7 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.80
Crystal size (mm)	0.21 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART 1000 CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.734, 0.888
No. of measured, independent and observed [I > 2σs(I)] reflections	11793, 4165, 3158
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.079, 0.145, 1.22
No. of reflections	4165
No. of parameters	271
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.67

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5W—H5W1···O7Wⁱ	0.963	1.758	2.703 (5)	166
O5W—H5W2···O3ⁱⁱ	0.944	1.852	2.727 (4)	153
O6W—H6W1···O2ⁱⁱⁱ	0.962	1.911	2.865 (5)	171
O6W—H6W2···O3^iv	0.860	2.266	2.899 (5)	130
O7W—H7W1···O8W	1.004	1.847	2.829 (6)	165
O7W—H7W2···O6W	0.933	2.530	3.044 (6)	115
O7W—H7W2···O6W^v	0.933	2.347	3.162 (6)	146
O8W—H8W1···O3^vi	1.030	1.910	2.860 (5)	152
O8W—H8W2···O1^vii	0.977	1.956	2.913 (5)	166
O8W—H8W2···O3^vii	0.977	2.587	3.317 (5)	132

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1, y, −z+1/2; (iii) −x+1/2, −y+1/2, −z; (iv) x−1/2, y+1/2, z; (v) −x, y, −z+1/2; (vi) x−1/2, −y+1/2, z+1/2; (vii) −x+1/2, y+1/2, −z+1/2.

Acknowledgements

This research was supported in part by the BK21 program of the Ministry of Education & Human Resources Development, Republic of Korea.

References

Bruker (2000). SADABS (Version 2.03), SMART (Version 5.618) and SAINT (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Hwang, I.-C. & Ha, K. (2007). Acta Cryst. E63, m2302. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

catena-Poly[[[aqua­manganese(II)]-di-μ-sulfato-[aqua­manganese(II)]-μ-N,N,N′,N′-tetra­kis(2-pyridylmeth­yl)hexane-1,6-di­amine] hexa­hydrate]

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

catena-Poly[[[aquamanganese(II)]-di-μ-sulfato-[aquamanganese(II)]-μ-N,N,N′,N′-tetrakis(2-pyridylmethyl)hexane-1,6-diamine] hexahydrate]