catena-Poly[[bis­(ethanol-κO)mangan­ese(II)]-μ-2,5-di­chloro-3,6-di­oxo­cyclo­hexa-1,4-diene-1,4-bis­(olato)-κ4O1,O6:O3,O4]

Tanaka, S.; Himegi, A.; Ohishi, T.; Fuyuhiro, A.; Kawata, S.

doi:10.1107/S1600536814002396

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 3| March 2014| Pages m90-m91

doi:10.1107/S1600536814002396

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catena-Poly[[bis(ethanol-κO)manganese(II)]-μ-2,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,4-bis(olato)-κ⁴O¹,O⁶:O³,O⁴]

Seiya Tanaka,^a Akiko Himegi,^a Tomomi Ohishi,^a Akira Fuyuhiro ^b and Satoshi Kawata ^a ^*

^aDepartment of Chemistry, Faculty of Science, Fukuoka University, Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan, and ^bDepartment of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan
^*Correspondence e-mail: kawata@fukuoka-u.ac.jp

(Received 12 January 2014; accepted 2 February 2014; online 8 February 2014)

In the title coordination polymer, [Mn(C₆Cl₂O₄)(C₂H₅OH)₂]_n, the Mn^II atom and the chloranilate [systematic name: 2,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,4-bis(olate)] ion lie on crystallographic inversion centers. The geometry around the Mn^II atom is a distorted octahedron involving four O atoms of two chloranilate ions and two O atoms from two ethanol molecules. The chloranilate ion serves as a bridging ligand between the Mn^II ions, leading to an infinite linear chain along the b-axis direction. The chains are linked by O—H⋯O hydrogen bonds between the apically coordinating ethanol molecule and the chloranilate ion, affording a two-dimensional layer expanding parallel to the ab plane.

CCDC reference: 984709

Related literature

For metal complexes of chloranilic acid, see: Kawata et al. (1995 , 1998 ); Kitagawa et al. (1996 ); Kitagawa & Kawata (2002 ); Abrahams et al. (2011 ).

Experimental

Crystal data

[Mn(C₆Cl₂O₄)(C₂H₆O)₂]
M_r = 354.05
Triclinic, $[P \overline 1]$
a = 5.0784 (5) Å
b = 8.1255 (8) Å
c = 8.9003 (9) Å
α = 102.718 (4)°
β = 105.175 (5)°
γ = 101.092 (3)°
V = 333.35 (6) Å³
Z = 1
Mo Kα radiation
μ = 1.41 mm⁻¹
T = 200 K
0.50 × 0.25 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID II diffractometer
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995 ) T_min = 0.406, T_max = 0.869
3298 measured reflections
1534 independent reflections
1434 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.095
S = 1.17
1534 reflections
93 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—O1	2.1884 (13)
Mn1—O2	2.1491 (11)
Mn1—O3	2.2042 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1⋯O1ⁱ	0.76 (4)	2.07 (3)	2.8200 (17)	167 (4)
Symmetry code: (i) x-1, y, z.

Data collection: RAPID-AUTO (Rigaku, 2002 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: CrystalStructure; software used to prepare material for publication: CrystalStructure (Rigaku, 2010 ).

Supporting information

CCDC reference: 984709

Crystal structure: contains datablocks General, I. DOI: 10.1107/S1600536814002396/is5335sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814002396/is5335Isup2.hkl

checkCIF report

Comment top

Benzoquinones and their derivatives have been used and known as bis-bidentate ligands and are good candidates to provide transition metal coordination polymers (Kawata et al., 1995, 1998; Kitagawa et al., 1996; Kitagawa & Kawata, 2002; Abrahams et al., 2011). The background of this chemistry prompts us to utilize chloranilate (CA) chains of Mn as a building block for high dimensional structures. We have succeeded in the synthesis and characterization of a one-dimensional coordination polymer having a hydrogen-bonding link, [Mn(CA)(EtOH)₂]_n (Fig. 1). The four O atoms of the CA^2- anion and the Mn^II atom form a basal plane, because the Mn—O distances [2.1884 (13) and 2.1491 (11) Å] are shorter than the two apical Mn—O(EtOH) distances [2.2042 (16) Å]. The hydrogen-bond donor EtOH serves as a woof in the synthesis of a woven polymer: the straight one-dimensional [Mn(CA)(EtOH)₂]_n chains are linked by two hydrogen bonds [O3—H1···O1 distance: 2.8200 (17) Å] between the apically coordinated EtOH molecule and the O atom of CA^2- anion in the nearest neighbor chain to afford a two-dimensional layer (Fig. 2). A similar hydrogen bond is also found between O atoms of water molecules and CA^2- anion in [Mn(CA)(H₂O)₂(phz)]_n (Kawata et al., 1998), where the straight chains are linked by hydrogen bonds [2.751 (2) Å] shorter than those in the title compound. The inter-chain hydrogen bonds lead to short nearest neighbor Mn···Mn distances [5.6784 (5) Å], and the geometry of the two-dimensional sheet can be regarded as a rectangular array of manganese atoms. The title complex is a good example of lattice structures formed by hydrogen bonds. The fabrication of two-dimensional polymers from warp and woof components has been shown to be quite useful in the construction of tetragonal Mn lattices. This concept can also be applied to a wide variety of compounds having square lattices.

Related literature top

For metal complexes of chloranilic acid, see: Kawata et al. (1995, 1998); Kitagawa et al. (1996); Kitagawa & Kawata (2002); Abrahams et al. (2011).

Experimental top

Aqueous solution of MnCl₂·4H₂O (5 ml, 30 mmolL^-1) was transferred to a glass tube, and ethanolic solution of H₂CA (5 ml, 90 mmolL^-1) was poured into the glass tube without mixing the solutions. Green crystals began to form at ambient temperature within one week.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2002); cell refinement: RAPID-AUTO (Rigaku, 2002); data reduction: RAPID-AUTO (Rigaku, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).

Figures top

	Fig. 1. An ORTEP drawing of the title complex, showing 50% probability displacement ellipsoids.
	Fig. 2. A packing view of the title compound, showing a two-dimensional structure. Blue lines indicate O—H···O hydrogen bonds. H atoms have been omitted for clarity.

catena-Poly[[bis(ethanol-κO)manganese(II)]-µ-2,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,4-bis(olato)-κ⁴O¹,O⁶:O³,O⁴] top

Crystal data top

[Mn(C₆Cl₂O₄)(C₂H₆O)₂]	Z = 1
M_r = 354.05	F(000) = 179.00
Triclinic, P1	D_x = 1.764 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 5.0784 (5) Å	Cell parameters from 3040 reflections
b = 8.1255 (8) Å	θ = 3.1–27.5°
c = 8.9003 (9) Å	µ = 1.41 mm⁻¹
α = 102.718 (4)°	T = 200 K
β = 105.175 (5)°	Block, green
γ = 101.092 (3)°	0.50 × 0.25 × 0.10 mm
V = 333.35 (6) Å³

Data collection top

Rigaku R-AXIS RAPID II diffractometer	1434 reflections with F² > 2σ(F²)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.029
ω scans	θ_max = 27.5°
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995)	h = −6→6
T_min = 0.406, T_max = 0.869	k = −10→9
3298 measured reflections	l = −11→11
1534 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ²(F_o²) + (0.0605P)² + 0.0437P] where P = (F_o² + 2F_c²)/3
1534 reflections	(Δ/σ)_max < 0.001
93 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

[Mn(C₆Cl₂O₄)(C₂H₆O)₂]	γ = 101.092 (3)°
M_r = 354.05	V = 333.35 (6) Å³
Triclinic, P1	Z = 1
a = 5.0784 (5) Å	Mo Kα radiation
b = 8.1255 (8) Å	µ = 1.41 mm⁻¹
c = 8.9003 (9) Å	T = 200 K
α = 102.718 (4)°	0.50 × 0.25 × 0.10 mm
β = 105.175 (5)°

Data collection top

Rigaku R-AXIS RAPID II diffractometer	1534 independent reflections
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995)	1434 reflections with F² > 2σ(F²)
T_min = 0.406, T_max = 0.869	R_int = 0.029
3298 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	Δρ_max = 0.70 e Å⁻³
1534 reflections	Δρ_min = −0.32 e Å⁻³
93 parameters

Special details top

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	U_iso*/U_eq
Mn1	1.0000	1.0000	0.0000	0.01772 (15)
Cl1	0.38362 (8)	0.36866 (5)	−0.26023 (5)	0.02047 (16)
O1	1.2640 (3)	0.84608 (14)	0.10826 (15)	0.0196 (3)
O2	0.7400 (3)	0.73489 (15)	−0.09699 (15)	0.0197 (3)
O3	0.8359 (3)	1.03778 (16)	0.20763 (16)	0.0256 (3)
C1	1.1523 (3)	0.68293 (19)	0.06530 (18)	0.0154 (3)
C2	0.8514 (3)	0.6189 (2)	−0.05794 (18)	0.0152 (3)
C3	0.7193 (4)	0.43901 (19)	−0.11994 (19)	0.0162 (3)
C4	0.8660 (5)	1.2048 (3)	0.3176 (3)	0.0278 (4)
C5	0.7319 (5)	1.1860 (4)	0.4470 (3)	0.0426 (6)
H1	0.691 (7)	0.975 (4)	0.187 (4)	0.049 (8)*
H4A	0.7772	1.2778	0.2552	0.0334*
H4B	1.0697	1.2656	0.3696	0.0334*
H5A	0.5295	1.1279	0.3960	0.0511*
H5B	0.7570	1.3021	0.5189	0.0511*
H5C	0.8219	1.1158	0.5104	0.0511*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0186 (3)	0.0085 (2)	0.0267 (3)	0.00490 (15)	0.00650 (16)	0.00590 (15)
Cl1	0.0161 (3)	0.0159 (3)	0.0247 (3)	0.00325 (16)	0.00050 (17)	0.00448 (17)
O1	0.0177 (6)	0.0086 (5)	0.0296 (7)	0.0025 (5)	0.0034 (5)	0.0055 (5)
O2	0.0183 (6)	0.0107 (6)	0.0296 (7)	0.0049 (5)	0.0041 (5)	0.0078 (5)
O3	0.0236 (7)	0.0177 (6)	0.0340 (7)	0.0020 (6)	0.0125 (6)	0.0037 (5)
C1	0.0157 (8)	0.0110 (7)	0.0204 (8)	0.0039 (6)	0.0071 (6)	0.0043 (6)
C2	0.0149 (7)	0.0128 (7)	0.0204 (8)	0.0051 (6)	0.0069 (6)	0.0065 (6)
C3	0.0148 (7)	0.0109 (7)	0.0215 (8)	0.0035 (6)	0.0033 (6)	0.0049 (6)
C4	0.0275 (10)	0.0221 (9)	0.0308 (10)	0.0060 (7)	0.0092 (8)	0.0022 (7)
C5	0.0331 (11)	0.0515 (14)	0.0345 (12)	0.0023 (10)	0.0145 (9)	−0.0018 (10)

Geometric parameters (Å, º) top

Mn1—O1	2.1884 (13)	C1—C2	1.5410 (19)
Mn1—O1ⁱ	2.1884 (13)	C1—C3ⁱⁱ	1.392 (3)
Mn1—O2	2.1491 (11)	C2—C3	1.402 (2)
Mn1—O2ⁱ	2.1491 (11)	C4—C5	1.504 (4)
Mn1—O3	2.2042 (16)	O3—H1	0.76 (3)
Mn1—O3ⁱ	2.2042 (16)	C4—H4A	0.990
Cl1—C3	1.7285 (15)	C4—H4B	0.990
O1—C1	1.2646 (18)	C5—H5A	0.980
O2—C2	1.255 (3)	C5—H5B	0.980
O3—C4	1.442 (3)	C5—H5C	0.980

O1—Mn1—O1ⁱ	180.00 (7)	O2—C2—C1	116.48 (13)
O1—Mn1—O2	75.40 (5)	O2—C2—C3	124.00 (13)
O1—Mn1—O2ⁱ	104.60 (5)	C1—C2—C3	119.52 (15)
O1—Mn1—O3	89.94 (6)	Cl1—C3—C1ⁱⁱ	119.54 (10)
O1—Mn1—O3ⁱ	90.06 (6)	Cl1—C3—C2	119.10 (13)
O1ⁱ—Mn1—O2	104.60 (5)	C1ⁱⁱ—C3—C2	121.29 (13)
O1ⁱ—Mn1—O2ⁱ	75.40 (5)	O3—C4—C5	112.07 (17)
O1ⁱ—Mn1—O3	90.06 (6)	Mn1—O3—H1	112 (3)
O1ⁱ—Mn1—O3ⁱ	89.94 (6)	C4—O3—H1	112 (3)
O2—Mn1—O2ⁱ	180.00 (8)	O3—C4—H4A	109.195
O2—Mn1—O3	90.47 (5)	O3—C4—H4B	109.194
O2—Mn1—O3ⁱ	89.53 (5)	C5—C4—H4A	109.198
O2ⁱ—Mn1—O3	89.53 (5)	C5—C4—H4B	109.199
O2ⁱ—Mn1—O3ⁱ	90.47 (5)	H4A—C4—H4B	107.893
O3—Mn1—O3ⁱ	180.00 (7)	C4—C5—H5A	109.468
Mn1—O1—C1	115.42 (10)	C4—C5—H5B	109.470
Mn1—O2—C2	116.70 (9)	C4—C5—H5C	109.467
Mn1—O3—C4	125.08 (13)	H5A—C5—H5B	109.476
O1—C1—C2	115.83 (15)	H5A—C5—H5C	109.471
O1—C1—C3ⁱⁱ	125.09 (13)	H5B—C5—H5C	109.475
C2—C1—C3ⁱⁱ	119.07 (13)

O1—Mn1—O2—C2	−3.21 (9)	O3—Mn1—O2ⁱ—C2ⁱ	−86.98 (10)
O2—Mn1—O1—C1	0.99 (9)	O2ⁱ—Mn1—O3ⁱ—C4ⁱ	165.27 (10)
O1—Mn1—O2ⁱ—C2ⁱ	−176.79 (9)	O3ⁱ—Mn1—O2ⁱ—C2ⁱ	93.02 (10)
O2ⁱ—Mn1—O1—C1	−179.01 (9)	Mn1—O1—C1—C2	0.92 (19)
O1—Mn1—O3—C4	119.34 (10)	Mn1—O1—C1—C3ⁱⁱ	−179.43 (11)
O3—Mn1—O1—C1	91.49 (10)	Mn1—O2—C2—C1	4.67 (19)
O1—Mn1—O3ⁱ—C4ⁱ	60.66 (10)	Mn1—O2—C2—C3	−175.03 (11)
O3ⁱ—Mn1—O1—C1	−88.51 (10)	Mn1—O3—C4—C5	−179.70 (9)
O1ⁱ—Mn1—O2—C2	176.79 (9)	O1—C1—C2—O2	−3.8 (3)
O2—Mn1—O1ⁱ—C1ⁱ	179.01 (9)	O1—C1—C2—C3	175.92 (15)
O1ⁱ—Mn1—O2ⁱ—C2ⁱ	3.21 (9)	O1—C1—C3ⁱⁱ—Cl1ⁱⁱ	1.2 (3)
O2ⁱ—Mn1—O1ⁱ—C1ⁱ	−0.99 (9)	O1—C1—C3ⁱⁱ—C2ⁱⁱ	−175.82 (16)
O1ⁱ—Mn1—O3—C4	−60.66 (10)	C2—C1—C3ⁱⁱ—Cl1ⁱⁱ	−179.14 (13)
O3—Mn1—O1ⁱ—C1ⁱ	88.51 (10)	C2—C1—C3ⁱⁱ—C2ⁱⁱ	3.8 (3)
O1ⁱ—Mn1—O3ⁱ—C4ⁱ	−119.34 (10)	C3ⁱⁱ—C1—C2—O2	176.54 (15)
O3ⁱ—Mn1—O1ⁱ—C1ⁱ	−91.49 (10)	C3ⁱⁱ—C1—C2—C3	−3.7 (3)
O2—Mn1—O3—C4	−165.27 (10)	O2—C2—C3—Cl1	0.6 (3)
O3—Mn1—O2—C2	−93.02 (10)	O2—C2—C3—C1ⁱⁱ	−176.48 (16)
O2—Mn1—O3ⁱ—C4ⁱ	−14.73 (10)	C1—C2—C3—Cl1	−179.11 (13)
O3ⁱ—Mn1—O2—C2	86.98 (10)	C1—C2—C3—C1ⁱⁱ	3.8 (3)
O2ⁱ—Mn1—O3—C4	14.73 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···O1ⁱⁱⁱ	0.76 (4)	2.07 (3)	2.8200 (17)	167 (4)

Symmetry code: (iii) x−1, y, z.

Selected bond lengths (Å) top

Mn1—O1	2.1884 (13)	Mn1—O3	2.2042 (16)
Mn1—O2	2.1491 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···O1ⁱ	0.76 (4)	2.07 (3)	2.8200 (17)	167 (4)

Symmetry code: (i) x−1, y, z.

Acknowledgements

This work was supported by the fund Grant-in-Aids for Science Research (No. 25410078) from the Ministry of Education, Culture, Sports, Science and Technology of Japan.

References

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