Oxalatobis(propane-1,3-diamine)manganese(II) chloride monohydrate

Meng, Q.-G.; Wang, L.-T.; Liu, Y.-Z.; Pang, Y.

doi:10.1107/S1600536807065361

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Pages m170-m171

https://doi.org/10.1107/S1600536807065361

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RETRACTED ARTICLE

This article has been retracted. To view the retraction notice, click here.

Retracted: Oxalatobis(propane-1,3-diamine)manganese(II) chloride monohydrate

Qing-Guo Meng,^a ^* Lin-Tong Wang,^a Yan-Zhen Liu ^a and Yan Pang ^a

^aCollege of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: qgmeng_weifang@yahoo.cn

(Received 18 November 2007; accepted 4 December 2007; online 12 December 2007)

In the asymmetric unit of the title compound, [Mn(C₂O₄)(C₃H₁₀N₂)₂]Cl·H₂O, there are two independent Mn^III complexes, two Cl⁻ anions and two uncoordinated water molecules. Each Mn^III atom is hexacoordinated by four N atoms from two propane-1,3-diamine ligands and two O atoms from one oxalate ligand, resulting in a slightly distorted octahedral MnO₂N₄ geometry. Mn—O and Mn—N bond lengths are in the ranges 1.969 (2)–2.020 (3) and 2.068 (3)–2.113 (4) Å, respectively. There are weak intermolecular O—H⋯O, O—H⋯Cl, N—H⋯O and N—H⋯Cl hydrogen bonds with D⋯A distances in the range 2.831 (4)–3.423 (3) Å.

Related literature

For related literature, see: Chung et al. (1971 ); Church & Halvorson (1959 ); Okabe & Oya (2000 ); Pocker & Fong (1980 ); Poowell (1953 ); Scapin et al. (1997 ); Serre et al. (2005 ).

Experimental

Crystal data

[Mn(C₂O₄)(C₃H₁₀N₂)₂]Cl·H₂O
M_r = 344.69
Monoclinic, P n
a = 9.1286 (17) Å
b = 11.807 (2) Å
c = 13.912 (3) Å
β = 100.037 (14)°
V = 1476.6 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.10 mm⁻¹
T = 293 (2) K
0.43 × 0.28 × 0.23 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.650, T_max = 0.787
3373 measured reflections
3060 independent reflections
3032 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.085
S = 1.00
3060 reflections
356 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.43 e Å⁻³
Absolute structure: Flack (1983 ), 521 Friedel pairs
Flack parameter: 0.040 (15)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H3W⋯Cl2	0.81 (6)	2.70 (7)	3.205 (5)	122 (7)
O10—H4W⋯O6	0.81 (5)	2.71 (7)	3.078 (5)	110 (5)
O9—H2W⋯Cl1ⁱ	0.83 (3)	2.55 (2)	3.348 (4)	163 (5)
O9—H1W⋯O10ⁱⁱ	0.82 (5)	2.03 (5)	2.845 (6)	170 (6)
N8—H8B⋯Cl2ⁱ	0.90	2.61	3.366 (3)	142
N8—H8A⋯O3ⁱⁱⁱ	0.90	2.59	3.426 (4)	154
N7—H7B⋯O4ⁱⁱⁱ	0.90	2.45	3.195 (4)	141
N7—H7A⋯O8^iv	0.90	2.13	3.014 (4)	169
N6—H6D⋯O9	0.90	2.20	3.054 (4)	157
N6—H6C⋯O8^iv	0.90	2.21	3.046 (4)	155
N5—H5D⋯O4ⁱⁱⁱ	0.90	2.04	2.942 (4)	176
N5—H5C⋯Cl1^v	0.90	2.41	3.299 (3)	172
N4—H4D⋯Cl1^vi	0.90	2.53	3.423 (3)	170
N4—H4C⋯O2^vii	0.90	2.42	3.206 (4)	147
N3—H3D⋯Cl2	0.90	2.25	3.115 (3)	162
N3—H3C⋯O5^viii	0.90	2.02	2.831 (4)	149
N2—H2D⋯Cl1^vi	0.90	2.54	3.317 (4)	144
N2—H2C⋯O8^viii	0.90	2.15	3.024 (5)	163
N1—H1D⋯Cl2	0.90	2.71	3.404 (3)	135
N1—H1C⋯Cl1ⁱⁱⁱ	0.90	2.55	3.388 (3)	155
Symmetry codes: (i) x-1, y, z; (ii) $[x-{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (iv) x-1, y-1, z; (v) $[x-{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (vi) x, y+1, z; (vii) x+1, y+1, z; (viii) $[x-{\script{1\over 2}}, -y+2, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807065361/is2256sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807065361/is2256Isup2.hkl

checkCIF report

Comment top

During the past decades, dicarboxylic acid has been widely used as one poly-dentate ligand involved in various metal chelation reactions to form transition or rare earth metal complexes that own thermal resistance of certain bacteria spores (Poowell, 1953; Church & Halvorson, 1959; Chung et al., 1971; Okabe & Oya, 2000) and the activation (Serre et al., 2005) or inhabitation (Pocker & Fong, 1980; Scapin et al., 1997) in some metallo-enzymes. In this paper, we report the structure of the title compound, (I).

In the title compound, the Mn atom is hexa-coordinated by four nitrogen atoms from two chealating propane-1,3-diamine ligands and two oxygen atoms from one oxalic acid, resulting in a slightly distorted octahedral MnO₂N₄ geometry for the metal (Fig. 1, Table 1). Mn—O and Mn—N bond lengths are in the range of 1.969 (2) - 2.020 (3) Å and 2.068 (3) - 2.113 (4) Å, respectively. Moreover, there exist weak intermolecular hydrogen bonds with the distance range of 2.830–3.423 Å (Table 2), forming a three-dimensional structure (Fig. 2).

Related literature top

For related literature, see: Chung et al. (1971); Church & Halvorson (1959); Okabe & Oya (2000); Pocker & Fong (1980); Poowell (1953); Scapin et al. (1997); Serre et al. (2005).

Experimental top

A mixed water and ethanol solution of manganese(III) acetate (1 mmoL) and oxalic acid (1 mmoL) was neutralized by propane-1,3-diamine. The resulted solution was saturated with 1 g sodium hydrochloride and evaporated at room temperature for one week. yellow block crystals were obtained with a yield of 21%. Anal. Calc. for C₈H₂₂ClMnN₄O₅: C 27.83, H 6.38, N 16.23%; Found: C 27.80, H 6.42, N 16.18%.

Structure description top

For related literature, see: Chung et al. (1971); Church & Halvorson (1959); Okabe & Oya (2000); Pocker & Fong (1980); Poowell (1953); Scapin et al. (1997); Serre et al. (2005).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top

	Fig. 1. The asymmetric unit of the title compound, drawn with 30% probability displacement ellipsoids for the non-hydrogen atoms.
	Fig. 2. A packing diagram of the title compound. Hydrogen bonds are indicated by dashed lines.

Oxalatobis(propane-1,3-diamine)manganese(II) chloride monohydrate top

Crystal data top

[Mn(C₂O₄)(C₃H₁₀N₂)₂]Cl·H₂O	F(000) = 720
M_r = 344.69	D_x = 1.551 Mg m⁻³
Monoclinic, Pn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yac	Cell parameters from 3060 reflections
a = 9.1286 (17) Å	θ = 2.9–25.0°
b = 11.807 (2) Å	µ = 1.10 mm⁻¹
c = 13.912 (3) Å	T = 293 K
β = 100.037 (14)°	Block, yellow
V = 1476.6 (5) Å³	0.43 × 0.28 × 0.23 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	3060 independent reflections
Radiation source: fine-focus sealed tube	3032 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
φ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −1→10
T_min = 0.650, T_max = 0.787	k = −14→1
3373 measured reflections	l = −16→16

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.032	w = 1/[σ²(F_o²) + (0.072P)² + 0.2126P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.085	(Δ/σ)_max < 0.001
S = 1.00	Δρ_max = 0.53 e Å⁻³
3060 reflections	Δρ_min = −0.43 e Å⁻³
356 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
8 restraints	Extinction coefficient: 0.0164 (13)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 521 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.040 (15)

Crystal data top

[Mn(C₂O₄)(C₃H₁₀N₂)₂]Cl·H₂O	V = 1476.6 (5) Å³
M_r = 344.69	Z = 4
Monoclinic, Pn	Mo Kα radiation
a = 9.1286 (17) Å	µ = 1.10 mm⁻¹
b = 11.807 (2) Å	T = 293 K
c = 13.912 (3) Å	0.43 × 0.28 × 0.23 mm
β = 100.037 (14)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3060 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3032 reflections with I > 2σ(I)
T_min = 0.650, T_max = 0.787	R_int = 0.023
3373 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.085	Δρ_max = 0.53 e Å⁻³
S = 1.00	Δρ_min = −0.43 e Å⁻³
3060 reflections	Absolute structure: Flack (1983), 521 Friedel pairs
356 parameters	Absolute structure parameter: 0.040 (15)
8 restraints

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
Mn1	0.11279 (5)	0.45504 (4)	0.50737 (3)	0.02681 (15)
Mn2	0.91703 (6)	0.99201 (4)	0.36505 (4)	0.02996 (16)
C1	0.3604 (4)	0.3805 (3)	0.3916 (3)	0.0360 (8)
H1A	0.3263	0.4355	0.3409	0.043*
H1B	0.4034	0.3172	0.3619	0.043*
C2	0.4805 (5)	0.4350 (4)	0.4694 (3)	0.0404 (9)
H2A	0.5053	0.3832	0.5239	0.048*
H2B	0.5697	0.4471	0.4417	0.048*
C3	0.4322 (5)	0.5455 (3)	0.5062 (3)	0.0378 (9)
H3A	0.3975	0.5942	0.4508	0.045*
H3B	0.5178	0.5818	0.5453	0.045*
C4	−0.1361 (5)	0.5164 (3)	0.6257 (3)	0.0373 (8)
H4A	−0.2080	0.4832	0.5738	0.045*
H4B	−0.1848	0.5778	0.6541	0.045*
C5	−0.0860 (5)	0.4271 (3)	0.7035 (3)	0.0401 (9)
H5A	−0.0135	0.4604	0.7550	0.048*
H5B	−0.1709	0.4035	0.7319	0.048*
C6	−0.0192 (5)	0.3260 (3)	0.6642 (3)	0.0351 (8)
H6A	−0.0886	0.2967	0.6090	0.042*
H6B	−0.0038	0.2677	0.7140	0.042*
C7	−0.1264 (4)	0.4394 (3)	0.3465 (3)	0.0289 (7)
C8	−0.0207 (4)	0.5353 (3)	0.3226 (3)	0.0308 (8)
C9	0.5848 (5)	0.9640 (4)	0.3832 (3)	0.0417 (9)
H9A	0.4953	0.9199	0.3620	0.050*
H9B	0.6156	0.9518	0.4527	0.050*
C10	0.5504 (5)	1.0872 (4)	0.3649 (4)	0.0486 (10)
H10A	0.4667	1.1079	0.3957	0.058*
H10B	0.5214	1.0994	0.2952	0.058*
C11	0.6810 (5)	1.1632 (3)	0.4035 (3)	0.0431 (9)
H11A	0.6490	1.2416	0.3972	0.052*
H11B	0.7139	1.1477	0.4723	0.052*
C12	1.0022 (5)	1.0344 (3)	0.5651 (3)	0.0377 (9)
C13	1.1333 (5)	1.0806 (3)	0.5152 (3)	0.0360 (8)
C14	1.1008 (6)	0.9676 (4)	0.1977 (3)	0.0478 (11)
H14A	1.1031	0.9793	0.1290	0.057*
H14B	1.1750	1.0167	0.2349	0.057*
C15	1.1384 (6)	0.8483 (4)	0.2233 (4)	0.0516 (11)
H15A	1.2274	0.8282	0.1979	0.062*
H15B	1.0582	0.8004	0.1913	0.062*
C16	1.1650 (5)	0.8233 (4)	0.3342 (3)	0.0428 (9)
H16A	1.2009	0.7463	0.3452	0.051*
H16B	1.2415	0.8738	0.3670	0.051*
N1	1.0262 (4)	0.8377 (2)	0.3781 (2)	0.0324 (6)
H1C	1.0502	0.8218	0.4422	0.039*
H1D	0.9606	0.7847	0.3515	0.039*
N2	0.9487 (5)	0.9993 (3)	0.2183 (2)	0.0375 (8)
H2C	0.8814	0.9534	0.1829	0.045*
H2D	0.9284	1.0704	0.1965	0.045*
N3	0.7056 (4)	0.9230 (2)	0.3304 (2)	0.0327 (7)
H3C	0.6738	0.9341	0.2662	0.039*
H3D	0.7143	0.8477	0.3398	0.039*
N4	0.8095 (4)	1.1468 (3)	0.3503 (2)	0.0340 (7)
H4C	0.8773	1.2009	0.3706	0.041*
H4D	0.7762	1.1586	0.2863	0.041*
N5	0.3116 (4)	0.5354 (2)	0.5663 (2)	0.0291 (6)
H5C	0.2889	0.6059	0.5835	0.035*
H5D	0.3501	0.4987	0.6217	0.035*
N6	0.2302 (4)	0.3396 (2)	0.4346 (2)	0.0297 (6)
H6C	0.2630	0.2837	0.4769	0.036*
H6D	0.1648	0.3083	0.3860	0.036*
N7	0.1268 (4)	0.3507 (2)	0.6321 (2)	0.0313 (6)
H7A	0.1688	0.2845	0.6197	0.038*
H7B	0.1877	0.3841	0.6818	0.038*
N8	−0.0078 (4)	0.5630 (2)	0.5835 (2)	0.0319 (6)
H8A	0.0568	0.5937	0.6330	0.038*
H8B	−0.0430	0.6199	0.5430	0.038*
O1	0.0942 (3)	0.55365 (19)	0.39175 (18)	0.0302 (5)
O2	−0.0783 (3)	0.3917 (2)	0.43141 (18)	0.0301 (5)
O3	−0.2391 (3)	0.4152 (2)	0.2880 (2)	0.0402 (6)
O4	−0.0474 (4)	0.5855 (3)	0.24339 (19)	0.0440 (7)
O5	1.0023 (5)	1.0508 (3)	0.6534 (2)	0.0583 (9)
O6	0.8993 (3)	0.9836 (2)	0.50604 (19)	0.0362 (6)
O7	1.1132 (3)	1.0658 (2)	0.42064 (19)	0.0365 (6)
O8	1.2408 (4)	1.1305 (2)	0.5639 (2)	0.0457 (7)
O9	0.0571 (4)	0.2740 (3)	0.2343 (2)	0.0600 (9)
H1W	0.114 (5)	0.246 (5)	0.201 (4)	0.072*
H2W	−0.031 (2)	0.256 (6)	0.214 (4)	0.072*
O10	0.7709 (7)	0.7953 (3)	0.6200 (3)	0.0795 (13)
H3W	0.828 (7)	0.772 (6)	0.586 (4)	0.095*
H4W	0.728 (8)	0.854 (4)	0.603 (5)	0.095*
Cl1	0.72741 (14)	0.19856 (8)	0.10470 (7)	0.0495 (3)
Cl2	0.72971 (12)	0.67594 (8)	0.41008 (8)	0.0427 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0300 (3)	0.0243 (2)	0.0252 (2)	−0.0010 (2)	0.00198 (19)	0.00041 (19)
Mn2	0.0339 (3)	0.0262 (3)	0.0277 (3)	−0.0024 (2)	−0.0005 (2)	0.00098 (18)
C1	0.0375 (19)	0.0338 (18)	0.0389 (18)	−0.0004 (16)	0.0132 (17)	−0.0015 (14)
C2	0.034 (2)	0.0431 (19)	0.044 (2)	0.0002 (18)	0.0074 (18)	0.0010 (17)
C3	0.038 (2)	0.036 (2)	0.039 (2)	−0.0106 (16)	0.0072 (17)	−0.0029 (15)
C4	0.039 (2)	0.0368 (18)	0.0375 (19)	0.0047 (16)	0.0108 (17)	−0.0016 (15)
C5	0.044 (2)	0.040 (2)	0.038 (2)	0.0020 (19)	0.0125 (18)	0.0046 (16)
C6	0.042 (2)	0.0303 (17)	0.0341 (18)	−0.0043 (16)	0.0088 (17)	0.0045 (14)
C7	0.0311 (19)	0.0277 (15)	0.0270 (16)	−0.0012 (14)	0.0025 (15)	−0.0032 (12)
C8	0.037 (2)	0.0277 (17)	0.0276 (17)	0.0020 (15)	0.0042 (16)	0.0006 (13)
C9	0.037 (2)	0.044 (2)	0.045 (2)	−0.0050 (18)	0.0078 (18)	0.0003 (17)
C10	0.037 (2)	0.045 (2)	0.062 (3)	0.0071 (19)	0.005 (2)	−0.002 (2)
C11	0.049 (2)	0.0307 (18)	0.051 (2)	0.0075 (18)	0.0103 (19)	−0.0051 (16)
C12	0.048 (2)	0.0302 (17)	0.032 (2)	0.0042 (17)	−0.0012 (18)	0.0017 (14)
C13	0.036 (2)	0.0230 (15)	0.043 (2)	0.0026 (16)	−0.0082 (17)	0.0000 (15)
C14	0.061 (3)	0.044 (2)	0.044 (2)	0.001 (2)	0.022 (2)	0.0083 (18)
C15	0.068 (3)	0.040 (2)	0.052 (2)	0.013 (2)	0.025 (2)	0.0015 (19)
C16	0.039 (2)	0.0382 (19)	0.052 (2)	0.0076 (17)	0.0103 (18)	0.0076 (17)
N1	0.0350 (15)	0.0268 (13)	0.0335 (15)	−0.0003 (13)	0.0005 (13)	0.0046 (12)
N2	0.052 (2)	0.0294 (16)	0.0305 (16)	0.0041 (14)	0.0041 (15)	0.0026 (11)
N3	0.0333 (16)	0.0261 (14)	0.0348 (15)	−0.0006 (13)	−0.0049 (13)	0.0040 (12)
N4	0.0404 (17)	0.0233 (13)	0.0361 (16)	−0.0014 (13)	0.0003 (14)	0.0002 (11)
N5	0.0293 (16)	0.0256 (14)	0.0298 (15)	−0.0026 (12)	−0.0021 (13)	−0.0019 (11)
N6	0.0374 (16)	0.0235 (12)	0.0284 (14)	−0.0014 (13)	0.0063 (12)	0.0001 (11)
N7	0.0385 (16)	0.0265 (13)	0.0276 (14)	−0.0007 (13)	0.0023 (13)	0.0000 (11)
N8	0.0369 (17)	0.0257 (12)	0.0322 (15)	0.0019 (13)	0.0033 (14)	−0.0001 (11)
O1	0.0371 (14)	0.0263 (11)	0.0244 (11)	−0.0045 (10)	−0.0022 (10)	0.0027 (9)
O2	0.0336 (12)	0.0258 (10)	0.0291 (11)	−0.0037 (10)	0.0003 (10)	−0.0006 (9)
O3	0.0378 (16)	0.0410 (14)	0.0380 (13)	−0.0050 (13)	−0.0041 (13)	−0.0037 (12)
O4	0.0555 (18)	0.0412 (14)	0.0300 (13)	−0.0042 (14)	−0.0072 (13)	0.0097 (11)
O5	0.073 (2)	0.069 (2)	0.0287 (15)	−0.0011 (19)	−0.0039 (16)	−0.0109 (13)
O6	0.0444 (17)	0.0346 (12)	0.0281 (13)	−0.0032 (12)	0.0018 (12)	0.0045 (10)
O7	0.0375 (15)	0.0334 (13)	0.0356 (14)	−0.0069 (12)	−0.0019 (12)	0.0007 (11)
O8	0.0472 (17)	0.0290 (13)	0.0522 (16)	−0.0039 (12)	−0.0155 (14)	−0.0002 (12)
O9	0.059 (2)	0.074 (2)	0.0471 (17)	0.0031 (19)	0.0081 (16)	−0.0112 (16)
O10	0.122 (4)	0.048 (2)	0.081 (3)	−0.007 (2)	0.052 (3)	−0.0004 (19)
Cl1	0.0658 (7)	0.0332 (4)	0.0420 (5)	−0.0013 (5)	−0.0118 (5)	0.0025 (4)
Cl2	0.0448 (5)	0.0307 (4)	0.0529 (5)	0.0008 (4)	0.0090 (4)	0.0068 (4)

Geometric parameters (Å, º) top

Mn1—O1	1.969 (2)	C10—C11	1.514 (7)
Mn1—O2	2.019 (3)	C10—H10A	0.9700
Mn1—N5	2.085 (3)	C10—H10B	0.9700
Mn1—N8	2.089 (3)	C11—N4	1.504 (5)
Mn1—N6	2.100 (3)	C11—H11A	0.9700
Mn1—N7	2.113 (3)	C11—H11B	0.9700
Mn2—O6	1.999 (3)	C12—O5	1.243 (5)
Mn2—O7	2.020 (3)	C12—O6	1.284 (5)
Mn2—N4	2.068 (3)	C12—C13	1.582 (6)
Mn2—N1	2.069 (3)	C13—O8	1.241 (5)
Mn2—N3	2.073 (3)	C13—O7	1.307 (5)
Mn2—N2	2.113 (4)	C14—C15	1.478 (6)
C1—N6	1.500 (5)	C14—N2	1.513 (7)
C1—C2	1.541 (6)	C14—H14A	0.9700
C1—H1A	0.9700	C14—H14B	0.9700
C1—H1B	0.9700	C15—C16	1.548 (6)
C2—C3	1.495 (6)	C15—H15A	0.9700
C2—H2A	0.9700	C15—H15B	0.9700
C2—H2B	0.9700	C16—N1	1.509 (5)
C3—N5	1.499 (5)	C16—H16A	0.9700
C3—H3A	0.9700	C16—H16B	0.9700
C3—H3B	0.9700	N1—H1C	0.9000
C4—N8	1.503 (5)	N1—H1D	0.9000
C4—C5	1.523 (6)	N2—H2C	0.9000
C4—H4A	0.9700	N2—H2D	0.9000
C4—H4B	0.9700	N3—H3C	0.9000
C5—C6	1.488 (6)	N3—H3D	0.9000
C5—H5A	0.9700	N4—H4C	0.9000
C5—H5B	0.9700	N4—H4D	0.9000
C6—N7	1.506 (5)	N5—H5C	0.9000
C6—H6A	0.9700	N5—H5D	0.9000
C6—H6B	0.9700	N6—H6C	0.9000
C7—O3	1.229 (5)	N6—H6D	0.9000
C7—O2	1.314 (4)	N7—H7A	0.9000
C7—C8	1.560 (5)	N7—H7B	0.9000
C8—O4	1.238 (5)	N8—H8A	0.9000
C8—O1	1.311 (5)	N8—H8B	0.9000
C9—C10	1.501 (6)	O9—H1W	0.82 (5)
C9—N3	1.507 (6)	O9—H2W	0.83 (3)
C9—H9A	0.9700	O10—H3W	0.81 (6)
C9—H9B	0.9700	O10—H4W	0.81 (5)

O1—Mn1—O2	81.23 (11)	N4—C11—C10	112.5 (3)
O1—Mn1—N5	89.86 (12)	N4—C11—H11A	109.1
O2—Mn1—N5	171.03 (11)	C10—C11—H11A	109.1
O1—Mn1—N8	94.33 (11)	N4—C11—H11B	109.1
O2—Mn1—N8	90.45 (12)	C10—C11—H11B	109.1
N5—Mn1—N8	91.28 (13)	H11A—C11—H11B	107.8
O1—Mn1—N6	88.21 (11)	O5—C12—O6	125.4 (4)
O2—Mn1—N6	88.53 (11)	O5—C12—C13	120.6 (4)
N5—Mn1—N6	90.15 (12)	O6—C12—C13	113.9 (3)
N8—Mn1—N6	177.09 (12)	O8—C13—O7	124.9 (4)
O1—Mn1—N7	178.39 (13)	O8—C13—C12	120.7 (4)
O2—Mn1—N7	97.88 (11)	O7—C13—C12	114.3 (3)
N5—Mn1—N7	91.05 (12)	C15—C14—N2	111.9 (4)
N8—Mn1—N7	84.33 (12)	C15—C14—H14A	109.2
N6—Mn1—N7	93.11 (12)	N2—C14—H14A	109.2
O6—Mn2—O7	82.17 (12)	C15—C14—H14B	109.2
O6—Mn2—N4	91.31 (12)	N2—C14—H14B	109.2
O7—Mn2—N4	91.72 (12)	H14A—C14—H14B	107.9
O6—Mn2—N1	89.44 (12)	C14—C15—C16	114.3 (4)
O7—Mn2—N1	88.01 (12)	C14—C15—H15A	108.7
N4—Mn2—N1	179.16 (14)	C16—C15—H15A	108.7
O6—Mn2—N3	88.68 (13)	C14—C15—H15B	108.7
O7—Mn2—N3	170.31 (13)	C16—C15—H15B	108.7
N4—Mn2—N3	85.28 (13)	H15A—C15—H15B	107.6
N1—Mn2—N3	95.11 (13)	N1—C16—C15	112.7 (4)
O6—Mn2—N2	176.79 (16)	N1—C16—H16A	109.1
O7—Mn2—N2	95.20 (14)	C15—C16—H16A	109.1
N4—Mn2—N2	90.61 (13)	N1—C16—H16B	109.1
N1—Mn2—N2	88.62 (13)	C15—C16—H16B	109.1
N3—Mn2—N2	94.04 (15)	H16A—C16—H16B	107.8
N6—C1—C2	111.7 (3)	C16—N1—Mn2	119.3 (2)
N6—C1—H1A	109.3	C16—N1—H1C	107.5
C2—C1—H1A	109.3	Mn2—N1—H1C	107.5
N6—C1—H1B	109.3	C16—N1—H1D	107.5
C2—C1—H1B	109.3	Mn2—N1—H1D	107.5
H1A—C1—H1B	107.9	H1C—N1—H1D	107.0
C3—C2—C1	112.9 (3)	C14—N2—Mn2	117.2 (3)
C3—C2—H2A	109.0	C14—N2—H2C	108.0
C1—C2—H2A	109.0	Mn2—N2—H2C	108.0
C3—C2—H2B	109.0	C14—N2—H2D	108.0
C1—C2—H2B	109.0	Mn2—N2—H2D	108.0
H2A—C2—H2B	107.8	H2C—N2—H2D	107.2
C2—C3—N5	114.3 (3)	C9—N3—Mn2	119.5 (2)
C2—C3—H3A	108.7	C9—N3—H3C	107.5
N5—C3—H3A	108.7	Mn2—N3—H3C	107.5
C2—C3—H3B	108.7	C9—N3—H3D	107.5
N5—C3—H3B	108.7	Mn2—N3—H3D	107.5
H3A—C3—H3B	107.6	H3C—N3—H3D	107.0
N8—C4—C5	111.9 (3)	C11—N4—Mn2	117.5 (2)
N8—C4—H4A	109.2	C11—N4—H4C	107.9
C5—C4—H4A	109.2	Mn2—N4—H4C	107.9
N8—C4—H4B	109.2	C11—N4—H4D	107.9
C5—C4—H4B	109.2	Mn2—N4—H4D	107.9
H4A—C4—H4B	107.9	H4C—N4—H4D	107.2
C6—C5—C4	112.7 (3)	C3—N5—Mn1	119.4 (2)
C6—C5—H5A	109.1	C3—N5—H5C	107.5
C4—C5—H5A	109.1	Mn1—N5—H5C	107.5
C6—C5—H5B	109.1	C3—N5—H5D	107.5
C4—C5—H5B	109.1	Mn1—N5—H5D	107.5
H5A—C5—H5B	107.8	H5C—N5—H5D	107.0
C5—C6—N7	113.2 (3)	C1—N6—Mn1	119.3 (2)
C5—C6—H6A	108.9	C1—N6—H6C	107.5
N7—C6—H6A	108.9	Mn1—N6—H6C	107.5
C5—C6—H6B	108.9	C1—N6—H6D	107.5
N7—C6—H6B	108.9	Mn1—N6—H6D	107.5
H6A—C6—H6B	107.7	H6C—N6—H6D	107.0
O3—C7—O2	127.3 (4)	C6—N7—Mn1	115.2 (2)
O3—C7—C8	120.4 (3)	C6—N7—H7A	108.5
O2—C7—C8	112.3 (3)	Mn1—N7—H7A	108.5
O4—C8—O1	125.6 (4)	C6—N7—H7B	108.5
O4—C8—C7	120.2 (3)	Mn1—N7—H7B	108.5
O1—C8—C7	114.2 (3)	H7A—N7—H7B	107.5
C10—C9—N3	112.2 (4)	C4—N8—Mn1	119.4 (2)
C10—C9—H9A	109.2	C4—N8—H8A	107.5
N3—C9—H9A	109.2	Mn1—N8—H8A	107.5
C10—C9—H9B	109.2	C4—N8—H8B	107.5
N3—C9—H9B	109.2	Mn1—N8—H8B	107.5
H9A—C9—H9B	107.9	H8A—N8—H8B	107.0
C9—C10—C11	112.7 (4)	C8—O1—Mn1	116.5 (2)
C9—C10—H10A	109.1	C7—O2—Mn1	115.8 (2)
C11—C10—H10A	109.1	C12—O6—Mn2	115.4 (3)
C9—C10—H10B	109.1	C13—O7—Mn2	113.7 (3)
C11—C10—H10B	109.1	H1W—O9—H2W	112 (5)
H10A—C10—H10B	107.8	H3W—O10—H4W	117 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H3W···Cl2	0.81 (6)	2.70 (7)	3.205 (5)	122 (7)
O10—H4W···O6	0.81 (5)	2.71 (7)	3.078 (5)	110 (5)
O9—H2W···Cl1ⁱ	0.83 (3)	2.55 (2)	3.348 (4)	163 (5)
O9—H1W···O10ⁱⁱ	0.82 (5)	2.03 (5)	2.845 (6)	170 (6)
N8—H8B···Cl2ⁱ	0.90	2.61	3.366 (3)	142
N8—H8A···O3ⁱⁱⁱ	0.90	2.59	3.426 (4)	154
N7—H7B···O4ⁱⁱⁱ	0.90	2.45	3.195 (4)	141
N7—H7A···O8^iv	0.90	2.13	3.014 (4)	169
N6—H6D···O9	0.90	2.20	3.054 (4)	157
N6—H6C···O8^iv	0.90	2.21	3.046 (4)	155
N5—H5D···O4ⁱⁱⁱ	0.90	2.04	2.942 (4)	176
N5—H5C···Cl1^v	0.90	2.41	3.299 (3)	172
N4—H4D···Cl1^vi	0.90	2.53	3.423 (3)	170
N4—H4C···O2^vii	0.90	2.42	3.206 (4)	147
N3—H3D···Cl2	0.90	2.25	3.115 (3)	162
N3—H3C···O5^viii	0.90	2.02	2.831 (4)	149
N2—H2D···Cl1^vi	0.90	2.54	3.317 (4)	144
N2—H2C···O8^viii	0.90	2.15	3.024 (5)	163
N1—H1D···Cl2	0.90	2.71	3.404 (3)	135
N1—H1C···Cl1ⁱⁱⁱ	0.90	2.55	3.388 (3)	155

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

Experimental details

Crystal data
Chemical formula	[Mn(C₂O₄)(C₃H₁₀N₂)₂]Cl·H₂O
M_r	344.69
Crystal system, space group	Monoclinic, Pn
Temperature (K)	293
a, b, c (Å)	9.1286 (17), 11.807 (2), 13.912 (3)
β (°)	100.037 (14)
V (Å³)	1476.6 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.10
Crystal size (mm)	0.43 × 0.28 × 0.23

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.650, 0.787
No. of measured, independent and observed [I > 2σ(I)] reflections	3373, 3060, 3032
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.085, 1.00
No. of reflections	3060
No. of parameters	356
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.43
Absolute structure	Flack (1983), 521 Friedel pairs
Absolute structure parameter	0.040 (15)

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H3W···Cl2	0.81 (6)	2.70 (7)	3.205 (5)	122 (7)
O10—H4W···O6	0.81 (5)	2.71 (7)	3.078 (5)	110 (5)
O9—H2W···Cl1ⁱ	0.83 (3)	2.55 (2)	3.348 (4)	163 (5)
O9—H1W···O10ⁱⁱ	0.82 (5)	2.03 (5)	2.845 (6)	170 (6)
N8—H8B···Cl2ⁱ	0.90	2.61	3.366 (3)	141.7
N8—H8A···O3ⁱⁱⁱ	0.90	2.59	3.426 (4)	153.9
N7—H7B···O4ⁱⁱⁱ	0.90	2.45	3.195 (4)	140.7
N7—H7A···O8^iv	0.90	2.13	3.014 (4)	168.9
N6—H6D···O9	0.90	2.20	3.054 (4)	157.2
N6—H6C···O8^iv	0.90	2.21	3.046 (4)	155.3
N5—H5D···O4ⁱⁱⁱ	0.90	2.04	2.942 (4)	175.6
N5—H5C···Cl1^v	0.90	2.41	3.299 (3)	171.6
N4—H4D···Cl1^vi	0.90	2.53	3.423 (3)	170.4
N4—H4C···O2^vii	0.90	2.42	3.206 (4)	146.7
N3—H3D···Cl2	0.90	2.25	3.115 (3)	162.2
N3—H3C···O5^viii	0.90	2.02	2.831 (4)	148.9
N2—H2D···Cl1^vi	0.90	2.54	3.317 (4)	144.3
N2—H2C···O8^viii	0.90	2.15	3.024 (5)	163.4
N1—H1D···Cl2	0.90	2.71	3.404 (3)	134.6
N1—H1C···Cl1ⁱⁱⁱ	0.90	2.55	3.388 (3)	154.8

Acknowledgements

The authors thank the Education Department of Shandong Province for research and development projects (No. J06A55)

References

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