catena-Poly[[tris­(1H-benzimidazole-κN3)manganese(II)]-μ-maleato-κ2O,O′:κO′′]

Hu, Z.-Q.; Ni, Y.; Lai, G.-Q.

doi:10.1107/S1600536805028333

catena-Poly[[tris(1H-benzimidazole-κN³)manganese(II)]-μ-maleato-κ²O,O′:κO′′]

In the title compound, [Mn(C₄H₂O₄)(C₇H₆N₂)₃]_n, maleate dianions bridge neighbouring Mn^II ions to form helical polymeric chains. The Mn ion assumes a distorted octahedral coordination geometry, formed by two maleate and three benzimidazole ligands. One maleate carboxyl group chelates to the Mn atom with longer Mn—O bond distances while the other carboxyl group coordinates in a monodentate manner to the Mn atom.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805028333/hb6259sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805028333/hb6259Isup2.hkl Contains datablock I

CCDC reference: 287563

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Key indicators

Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.006 Å
R factor = 0.038
wR factor = 0.106
Data-to-parameter ratio = 13.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.86 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C16

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.50
           From the CIF: _reflns_number_total               4528
           Count of symmetry unique reflns         2593
           Completeness (_total/calc)            174.62%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1935
           Fraction of Friedel pairs measured     0.746
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The chemical behavior of manganese complexes has attracted much attention in terms of their catalytic activity in some industrial and biochemical process (Kono & Fridovich, 1983; Wu et al., 2001). As part of our ongoing investigation on polymerization reactions catalysed by variable valance manganese complexes, we present here the X-ray structure of the title Mn^II complex, (I).

The crystal of (I) consists of polymeric complex chains (Fig. 1). The maleate dianions bridge neighboring Mn^II ions through both carboxyl groups, one in a chelating mode and the other in a monodentate mode. The Mn—O bond distances involving the chelating carboxyl group [O1—Mn—O2 = 55.76 (7)°] are much longer than that involving the monodentate carboxyl group (Table 1). Three benzimidazole N atoms coordinate to the Mn atom to complete the distorted octahedral coordination geometry. The large N23—Mn—O3ⁱ angle of 117.82 (10)° [symmetry code: (i) −1/2 + x, 3/2 − y, 1 − z] indicates a significant degree of distortion.

The C1-carboxyl group of the maleate dianion is twisted with respect to the carbon backbone mean plane by 28.1 (3)°; the Mn ion bonded to the C1-carboxyl group is thus displaced from the backbone mean plane by a relatively small amount [0.145 (8) Å]. The maleate C3-carboxyl group is nearly perpendicular to the carbon backbone [dihedral angle = 80.6 (2)°], resulting in the O3-bridging Mnⁱⁱ atom being out of the backbone best plane by −1.318 (8) Å [symmetry code: (ii) 1/2 + x, 3/2 − y, 1 − z]. Overall, the maleate dianions bridge neighboring Mn atoms to form a helical polymeric chain (Fig. 2), in agreement with the situation found in the isostructural Co^II analogue (Xue et al., 2003).

The crystal packing is stabilized by N—H···O hydrogen bonds between benzimidazole ligands and neighbouring carboxyl groups (Table 2).

Experimental top

A hot aqueous solution (5 ml) of maleic acid (2 mmol) and Na₂CO₃ (2 mmol) was mixed with an aqueous solution (5 ml) of MnCl₂·2H₂O (2 mmol). The mixture was refluxed for 1 h, after which time an ethanol solution (5 ml) of benzimidazole (4 mmol) was added dropwise and the resulting mixture refluxed for another 3 h and filtered. Single crystals of (I) were obtained from the solution after 10 d.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A segment of polymeric structure of (I), shown with 30% probability displacement ellipsoids (arbitrary spheres for H atoms). [Symmetry codes: (i) x − 1/2, 3/2 − y, 1 − z; (ii) 1/2 + x, 3/2 − y, 1 − z.]
	Fig. 2. The packing of (I), showing a fragment of the helical complex chain. H atoms have been omitted for clarity.

catena-Poly[[tris(1H-benzimidazole-κN³)manganese(II)]-µ-maleato- κ³O,O':κO''] top

Crystal data top

[Mn(C₄H₂O₄)(C₇H₆N₂)₃]	F(000) = 1076
M_r = 523.41	D_x = 1.421 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 17602 reflections
a = 9.3455 (13) Å	θ = 2.4–25.0°
b = 12.2596 (13) Å	µ = 0.58 mm⁻¹
c = 21.3592 (19) Å	T = 295 K
V = 2447.2 (5) Å³	Block, colourless
Z = 4	0.29 × 0.13 × 0.10 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	4528 independent reflections
Radiation source: fine-focus sealed tube	3945 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 10.00 pixels mm^-1	θ_max = 25.5°, θ_min = 1.9°
ω scans	h = −10→11
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −14→14
T_min = 0.838, T_max = 0.935	l = −25→25
19932 measured reflections

Refinement top

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)] = 0.038	H-atom parameters constrained
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.0618P)²] where P = (F_o² + 2F_c²)/3
S = 1.18	(Δ/σ)_max = 0.001
4528 reflections	Δρ_max = 0.39 e Å⁻³
325 parameters	Δρ_min = −0.54 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1935 Friedel Pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (2)

Crystal data top

[Mn(C₄H₂O₄)(C₇H₆N₂)₃]	V = 2447.2 (5) Å³
M_r = 523.41	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.3455 (13) Å	µ = 0.58 mm⁻¹
b = 12.2596 (13) Å	T = 295 K
c = 21.3592 (19) Å	0.29 × 0.13 × 0.10 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	4528 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3945 reflections with I > 2σ(I)
T_min = 0.838, T_max = 0.935	R_int = 0.048
19932 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.106	Δρ_max = 0.39 e Å⁻³
S = 1.18	Δρ_min = −0.54 e Å⁻³
4528 reflections	Absolute structure: Flack (1983), 1935 Friedel Pairs
325 parameters	Absolute structure parameter: 0.01 (2)
0 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
Mn	0.51711 (5)	0.72570 (4)	0.387056 (19)	0.03921 (14)
O1	0.6373 (2)	0.8878 (2)	0.37049 (9)	0.0466 (6)
O2	0.6163 (2)	0.83497 (19)	0.46816 (10)	0.0469 (5)
O3	0.9331 (2)	0.8778 (2)	0.53924 (10)	0.0474 (6)
O4	0.7556 (3)	0.9371 (2)	0.59944 (10)	0.0562 (7)
N11	0.1215 (3)	0.8881 (3)	0.43417 (13)	0.0539 (8)
H11	0.0612	0.9036	0.4633	0.065*
N13	0.3171 (3)	0.8235 (2)	0.38927 (13)	0.0460 (6)
N21	0.4436 (3)	0.5595 (3)	0.20920 (13)	0.0542 (8)
H21	0.4001	0.5097	0.1882	0.065*
N23	0.4995 (3)	0.6668 (2)	0.28923 (11)	0.0477 (6)
N31	0.9542 (3)	0.5962 (3)	0.40759 (14)	0.0528 (7)
H31	1.0446	0.6083	0.4104	0.063*
N33	0.7229 (3)	0.6293 (2)	0.39332 (14)	0.0449 (6)
C1	0.6533 (3)	0.9048 (3)	0.42852 (14)	0.0378 (7)
C2	0.7174 (3)	1.0094 (3)	0.44882 (16)	0.0444 (8)
H2	0.7054	1.0697	0.4229	0.053*
C3	0.7912 (4)	1.0231 (3)	0.50160 (16)	0.0468 (8)
H3	0.8253	1.0931	0.5093	0.056*
C4	0.8255 (3)	0.9379 (3)	0.55029 (14)	0.0411 (7)
C12	0.2448 (4)	0.8362 (3)	0.44091 (15)	0.0481 (8)
H12	0.2771	0.8108	0.4794	0.058*
C14	0.2542 (5)	0.8828 (4)	0.27967 (17)	0.0693 (12)
H14	0.3359	0.8553	0.2604	0.083*
C15	0.1490 (6)	0.9362 (6)	0.2458 (2)	0.0995 (19)
H15	0.1608	0.9446	0.2028	0.119*
C16	0.0274 (5)	0.9772 (6)	0.2738 (2)	0.107 (2)
H16	−0.0406	1.0124	0.2493	0.129*
C17	0.0044 (4)	0.9673 (4)	0.3368 (2)	0.0813 (14)
H17	−0.0770	0.9957	0.3558	0.098*
C18	0.1087 (3)	0.9126 (3)	0.37103 (16)	0.0492 (8)
C19	0.2324 (3)	0.8720 (3)	0.34372 (15)	0.0446 (8)
C22	0.4181 (4)	0.5872 (3)	0.26893 (15)	0.0528 (9)
H22	0.3493	0.5531	0.2936	0.063*
C24	0.6949 (4)	0.7699 (4)	0.23258 (18)	0.0665 (11)
H24	0.7191	0.8154	0.2658	0.080*
C25	0.7651 (5)	0.7763 (5)	0.1761 (2)	0.0872 (15)
H25	0.8387	0.8266	0.1712	0.105*
C26	0.7280 (5)	0.7085 (4)	0.12605 (19)	0.0802 (13)
H26	0.7768	0.7159	0.0883	0.096*
C27	0.6228 (5)	0.6321 (4)	0.13064 (17)	0.0627 (11)
H27	0.5996	0.5867	0.0973	0.075*
C28	0.5517 (4)	0.6254 (3)	0.18777 (15)	0.0492 (8)
C29	0.5869 (4)	0.6933 (3)	0.23818 (15)	0.0471 (8)
C32	0.8529 (3)	0.6693 (3)	0.39397 (16)	0.0505 (8)
H32	0.8729	0.7422	0.3857	0.061*
C34	0.6439 (4)	0.4334 (3)	0.4079 (2)	0.0642 (10)
H34	0.5471	0.4456	0.4008	0.077*
C35	0.6941 (6)	0.3308 (4)	0.4200 (3)	0.0893 (16)
H35	0.6306	0.2725	0.4205	0.107*
C36	0.8400 (6)	0.3120 (4)	0.4318 (3)	0.0910 (16)
H36	0.8703	0.2416	0.4410	0.109*
C37	0.9380 (5)	0.3939 (3)	0.4301 (2)	0.0683 (11)
H37	1.0345	0.3810	0.4377	0.082*
C38	0.8869 (4)	0.4981 (3)	0.41630 (15)	0.0482 (8)
C39	0.7413 (4)	0.5187 (3)	0.40648 (15)	0.0430 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn	0.0426 (2)	0.0406 (2)	0.0345 (2)	−0.0008 (2)	0.0000 (2)	−0.0006 (2)
O1	0.0595 (14)	0.0467 (14)	0.0337 (11)	−0.0007 (11)	−0.0030 (10)	0.0008 (9)
O2	0.0548 (13)	0.0442 (13)	0.0417 (12)	−0.0031 (11)	−0.0060 (11)	0.0057 (11)
O3	0.0361 (11)	0.0531 (14)	0.0531 (13)	0.0059 (10)	0.0025 (10)	0.0097 (11)
O4	0.0525 (13)	0.0746 (19)	0.0414 (13)	0.0087 (13)	−0.0007 (11)	−0.0056 (12)
N11	0.0560 (18)	0.060 (2)	0.0452 (15)	0.0069 (15)	0.0137 (14)	0.0057 (14)
N13	0.0538 (15)	0.0489 (16)	0.0353 (13)	0.0047 (13)	0.0009 (14)	0.0025 (13)
N21	0.0587 (17)	0.065 (2)	0.0389 (14)	−0.0095 (15)	−0.0036 (13)	−0.0109 (14)
N23	0.0483 (15)	0.0573 (17)	0.0375 (12)	−0.0028 (16)	0.0025 (13)	−0.0051 (12)
N31	0.0393 (14)	0.0564 (19)	0.0626 (17)	−0.0024 (13)	−0.0093 (13)	−0.0054 (14)
N33	0.0433 (14)	0.0432 (16)	0.0482 (15)	−0.0007 (12)	0.0014 (13)	−0.0033 (13)
C1	0.0356 (15)	0.0349 (17)	0.0430 (16)	0.0035 (13)	−0.0040 (13)	−0.0004 (14)
C2	0.0497 (18)	0.0356 (18)	0.0480 (18)	0.0033 (15)	−0.0080 (15)	0.0046 (14)
C3	0.0522 (19)	0.0353 (19)	0.0528 (19)	0.0009 (15)	−0.0067 (16)	−0.0014 (14)
C4	0.0374 (16)	0.0435 (19)	0.0425 (17)	−0.0044 (14)	−0.0065 (14)	−0.0049 (14)
C12	0.058 (2)	0.049 (2)	0.0365 (17)	0.0089 (18)	0.0015 (15)	0.0046 (15)
C14	0.058 (2)	0.106 (4)	0.044 (2)	0.006 (2)	0.0014 (18)	0.018 (2)
C15	0.081 (3)	0.164 (6)	0.054 (2)	0.015 (4)	−0.005 (2)	0.038 (3)
C16	0.068 (3)	0.180 (6)	0.075 (3)	0.032 (4)	−0.008 (3)	0.053 (3)
C17	0.049 (2)	0.115 (4)	0.080 (3)	0.019 (3)	0.004 (2)	0.030 (3)
C18	0.0405 (17)	0.059 (2)	0.0478 (19)	−0.0011 (16)	0.0022 (14)	0.0126 (16)
C19	0.0404 (17)	0.056 (2)	0.0377 (16)	−0.0072 (16)	−0.0001 (14)	0.0054 (15)
C22	0.0486 (19)	0.069 (3)	0.0407 (17)	−0.0110 (18)	0.0002 (15)	−0.0006 (17)
C24	0.082 (3)	0.065 (3)	0.053 (2)	−0.021 (2)	0.0153 (19)	−0.013 (2)
C25	0.097 (3)	0.093 (4)	0.072 (3)	−0.031 (3)	0.025 (3)	−0.005 (3)
C26	0.098 (3)	0.091 (4)	0.051 (2)	−0.011 (3)	0.029 (2)	−0.005 (2)
C27	0.077 (3)	0.069 (3)	0.0415 (19)	0.000 (2)	0.0056 (18)	−0.0066 (17)
C28	0.054 (2)	0.057 (2)	0.0363 (16)	0.0047 (17)	−0.0046 (15)	−0.0025 (15)
C29	0.055 (2)	0.047 (2)	0.0393 (17)	0.0027 (16)	0.0049 (15)	−0.0039 (14)
C32	0.0503 (18)	0.0440 (19)	0.057 (2)	−0.0044 (15)	−0.0020 (17)	0.0040 (17)
C34	0.054 (2)	0.049 (2)	0.089 (3)	−0.0059 (18)	0.012 (2)	−0.014 (2)
C35	0.084 (3)	0.047 (3)	0.137 (5)	−0.007 (2)	0.022 (3)	−0.002 (3)
C36	0.102 (4)	0.052 (3)	0.119 (4)	0.008 (3)	0.012 (3)	0.018 (3)
C37	0.068 (2)	0.061 (3)	0.076 (3)	0.016 (2)	−0.008 (2)	0.004 (2)
C38	0.058 (2)	0.048 (2)	0.0382 (16)	0.0073 (17)	−0.0035 (15)	−0.0035 (15)
C39	0.0472 (17)	0.0431 (19)	0.0385 (16)	0.0006 (15)	0.0037 (14)	−0.0075 (14)

Geometric parameters (Å, º) top

Mn—O1	2.310 (2)	C14—C19	1.389 (5)
Mn—O2	2.378 (2)	C14—H14	0.9300
Mn—O3ⁱ	2.169 (2)	C15—C16	1.380 (7)
Mn—N13	2.221 (3)	C15—H15	0.9300
Mn—N23	2.217 (2)	C16—C17	1.367 (6)
Mn—N33	2.261 (3)	C16—H16	0.9300
O1—C1	1.266 (4)	C17—C18	1.391 (5)
O2—C1	1.253 (4)	C17—H17	0.9300
O3—C4	1.269 (4)	C18—C19	1.388 (5)
O4—C4	1.237 (4)	C22—H22	0.9300
N11—C12	1.324 (5)	C24—C25	1.375 (5)
N11—C18	1.387 (4)	C24—C29	1.385 (5)
N11—H11	0.8600	C24—H24	0.9300
N13—C12	1.303 (4)	C25—C26	1.397 (6)
N13—C19	1.388 (4)	C25—H25	0.9300
N21—C22	1.341 (4)	C26—C27	1.362 (6)
N21—C28	1.372 (5)	C26—H26	0.9300
N21—H21	0.8600	C27—C28	1.392 (5)
N23—C22	1.311 (5)	C27—H27	0.9300
N23—C29	1.400 (4)	C28—C29	1.400 (5)
N31—C32	1.336 (5)	C32—H32	0.9300
N31—C38	1.369 (5)	C34—C35	1.366 (6)
N31—H31	0.8600	C34—C39	1.387 (5)
N33—C32	1.310 (4)	C34—H34	0.9300
N33—C39	1.395 (4)	C35—C36	1.405 (7)
C1—C2	1.480 (5)	C35—H35	0.9300
C2—C3	1.332 (5)	C36—C37	1.359 (7)
C2—H2	0.9300	C36—H36	0.9300
C3—C4	1.509 (5)	C37—C38	1.396 (5)
C3—H3	0.9300	C37—H37	0.9300
C12—H12	0.9300	C38—C39	1.400 (5)
C14—C15	1.385 (6)

O3ⁱ—Mn—N23	117.82 (10)	C14—C15—H15	119.0
O3ⁱ—Mn—N13	89.76 (10)	C17—C16—C15	121.6 (4)
N23—Mn—N13	97.68 (10)	C17—C16—H16	119.2
O3ⁱ—Mn—N33	87.67 (10)	C15—C16—H16	119.2
N23—Mn—N33	87.06 (11)	C16—C17—C18	116.7 (4)
N13—Mn—N33	175.25 (11)	C16—C17—H17	121.6
O3ⁱ—Mn—O1	142.22 (8)	C18—C17—H17	121.6
N23—Mn—O1	99.91 (9)	N11—C18—C19	105.0 (3)
N13—Mn—O1	87.02 (10)	N11—C18—C17	132.6 (4)
N33—Mn—O1	92.58 (9)	C19—C18—C17	122.4 (3)
O3ⁱ—Mn—O2	86.66 (8)	C18—C19—N13	109.5 (3)
N23—Mn—O2	154.04 (9)	C18—C19—C14	120.1 (3)
N13—Mn—O2	90.48 (9)	N13—C19—C14	130.3 (3)
N33—Mn—O2	85.38 (9)	N23—C22—N21	113.5 (3)
O1—Mn—O2	55.76 (7)	N23—C22—H22	123.2
C1—O1—Mn	92.84 (19)	N21—C22—H22	123.2
C1—O2—Mn	90.02 (18)	C25—C24—C29	117.5 (4)
C4—O3—Mnⁱⁱ	119.5 (2)	C25—C24—H24	121.2
C12—N11—C18	106.6 (3)	C29—C24—H24	121.2
C12—N11—H11	126.7	C24—C25—C26	121.3 (4)
C18—N11—H11	126.7	C24—C25—H25	119.4
C12—N13—C19	104.3 (3)	C26—C25—H25	119.4
C12—N13—Mn	121.3 (2)	C27—C26—C25	122.2 (4)
C19—N13—Mn	134.1 (2)	C27—C26—H26	118.9
C22—N21—C28	107.4 (3)	C25—C26—H26	118.9
C22—N21—H21	126.3	C26—C27—C28	116.7 (4)
C28—N21—H21	126.3	C26—C27—H27	121.7
C22—N23—C29	104.7 (3)	C28—C27—H27	121.7
C22—N23—Mn	126.7 (2)	N21—C28—C27	132.8 (3)
C29—N23—Mn	127.9 (2)	N21—C28—C29	105.5 (3)
C32—N31—C38	107.1 (3)	C27—C28—C29	121.8 (4)
C32—N31—H31	126.5	C24—C29—N23	130.6 (3)
C38—N31—H31	126.5	C24—C29—C28	120.6 (3)
C32—N33—C39	104.4 (3)	N23—C29—C28	108.9 (3)
C32—N33—Mn	126.4 (2)	N33—C32—N31	114.1 (3)
C39—N33—Mn	128.6 (2)	N33—C32—H32	123.0
O2—C1—O1	121.1 (3)	N31—C32—H32	123.0
O2—C1—C2	120.4 (3)	C35—C34—C39	118.2 (4)
O1—C1—C2	118.5 (3)	C35—C34—H34	120.9
C3—C2—C1	124.5 (3)	C39—C34—H34	120.9
C3—C2—H2	117.7	C34—C35—C36	121.2 (5)
C1—C2—H2	117.7	C34—C35—H35	119.4
C2—C3—C4	127.3 (3)	C36—C35—H35	119.4
C2—C3—H3	116.3	C37—C36—C35	121.9 (4)
C4—C3—H3	116.3	C37—C36—H36	119.1
O4—C4—O3	124.9 (3)	C35—C36—H36	119.1
O4—C4—C3	118.6 (3)	C36—C37—C38	116.8 (4)
O3—C4—C3	116.3 (3)	C36—C37—H37	121.6
N13—C12—N11	114.6 (3)	C38—C37—H37	121.6
N13—C12—H12	122.7	N31—C38—C37	132.5 (4)
N11—C12—H12	122.7	N31—C38—C39	105.5 (3)
C15—C14—C19	117.1 (4)	C37—C38—C39	122.0 (4)
C15—C14—H14	121.5	C34—C39—N33	131.1 (3)
C19—C14—H14	121.5	C34—C39—C38	119.9 (3)
C16—C15—C14	122.0 (4)	N33—C39—C38	109.0 (3)
C16—C15—H15	119.0

Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O3ⁱⁱⁱ	0.86	2.04	2.855 (3)	158
N21—H21···O1^iv	0.86	1.98	2.811 (4)	162
N31—H31···O4ⁱⁱ	0.86	2.06	2.850 (4)	152

Symmetry codes: (ii) x+1/2, −y+3/2, −z+1; (iii) x−1, y, z; (iv) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Mn(C₄H₂O₄)(C₇H₆N₂)₃]
M_r	523.41
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	9.3455 (13), 12.2596 (13), 21.3592 (19)
V (Å³)	2447.2 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.58
Crystal size (mm)	0.29 × 0.13 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.838, 0.935
No. of measured, independent and observed [I > 2σ(I)] reflections	19932, 4528, 3945
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.106, 1.18
No. of reflections	4528
No. of parameters	325
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.54
Absolute structure	Flack (1983), 1935 Friedel Pairs
Absolute structure parameter	0.01 (2)

Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Mn—O1	2.310 (2)	Mn—N13	2.221 (3)
Mn—O2	2.378 (2)	Mn—N23	2.217 (2)
Mn—O3ⁱ	2.169 (2)	Mn—N33	2.261 (3)

C1—O1—Mn	92.84 (19)	C4—O3—Mnⁱⁱ	119.5 (2)
C1—O2—Mn	90.02 (18)