Aqua(N,N'-disalicyl­idene­ethyl­enedi­amino-N,N',O,O')(4,5-imidazole­di­carboxyl­ato-O)­manganese(III) monohydrate

In the title compound, [Mn^III(salen)(OCOC₃H₂N₂COOH)(H₂O)]·H₂O, (H₂salen = N,N'-disalicyl­idene­ethyl­ene­di­amine, C₁₆H₁₄N₂O₂), two N and two O atoms from salen chelate to the Mn^III ion, forming a distorted octahedral coordination sphere together with two other axial O atoms from a carboxyl group and a water mol­ecule. Extended intermolecular hydrogen bonds are observed to link the complex mol­ecules, forming a one-dimensional chain structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.037
• wR factor = 0.130
• Data-to-parameter ratio = 11.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

The imidazole N atom of histidine have been described as a functional group (Wieghardt, 1989) in the oxygen-evolving complex (EOC) of photosystem II (PS II). 4,5-Imidazoledicarboxylate was suggested as a bridging ligand (Rypniewski et al., 1995; Tainer et al., 1982) and a dinuclear Mn^IV cluster with 4,5-imidazoledicarboxylate-bridged dimanganese(IV) has been reported (Caudle et al., 1997). It is interesting to study the differing coordination behavior of 4,5-dicarboxyimidazole. We present here a new complex, [Mn(salen)(OCOC₃H₂N₂COOH)(H₂O)]·H₂O, (I), in which 4,5-imidazoledicarboxylate coordinates to Mn^III as a terminal ligand. The structure of (I) is shown in Fig. 1. The Mn atom is chelated by two N [Mn—N₁ 1.991 (2) Å and Mn—N₂ 1.989 (2) Å] and two O atoms [Mn—O₁ 1.8793 (18) Å and Mn—O₂ 1.8944 (18) Å] from the salen ligand to form an equatorial plane with a maximum deviation of 0.0052 (10) Å from the least-squares plane, while the opposite axial positions are occupied by another two O atoms from the 4,5-dicarboxylatoimidazole [Mn—O₄ 2.1815 (19) Å] and the ligated aqua [Mn—O₃ 2.249 (2) Å]. The Mn site is surrounded in a distorted octahedral coordination sphere, with the trans angles ranging from 172.83 (9) to 178.04 (9)° and the other angles ranging from N₂—Mn—N₁ of 82.50 (9)° to O₂—Mn—O₁ of 94.69 (8)°. All the bond lengths and angles are comparable to those of the other six-coordinate Mn^III Schiff base complexes (Shyu et al., 1999; Watkinson et al., 1999; Oshio et al., 1995), while the Mn—O bonds of (I) are longer than those reported by Caudle et al. (1997), where Mn possesses a 4+ oxidation state, higher than that in (I).

The packing diagram of the title compound is presented in Fig. 2 and shows the intermolecular extensive hydrogen-bonding interactions, which contain N_imidazo······H—O_aqua [2.992 (3) Å] O_carboxy······H—O_aqua [2.880 (3) Å]- and N_imidazo······H—O_aqua [2.861 (3) Å]. These hydrogen bonds produce a one-dimensional polymeric structure.

S2. Experimental

To a solution of 0.268 g (1 mmol) of H₂salen in 40 ml of CH₂Cl₂/MeCN (v/v, 1:1), 0.165 g (1 mmol) of 4,5-dicarboxyimidazole was added and the resulting solution stirred. The reaction solution was refluxed for 18 h, accompanied by the addition of 0.245 g (1 mmol) of Mn(CH₃COO)₂·4H₂O. After filtration, the filtrate was allowed to stay for several days at room temperature to deposit dark-red crystals of (I), which were recrystallized from ethanol solution to attain the crystals suitable for X-ray diffraction.

S3. Refinement

H atoms were located and added to the structure-factor calculations but their positions were not refined except for those of the aqua molecule coordinated to Mn.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens, 1994); data reduction: SHELXTL XPREP (Siemens, 1994); program(s) used to solve structure: SHELXTL (Siemens, 1994); program(s) used to refine structure: SHELXTL (Siemens, 1994); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).

Figures

	Fig. 1. ORTEP diagram (SHELXTL; Bruker, 1998) of (I) showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level. H atoms have been omitted for clarity.
	Fig. 2. The packing diagram of the title compound.

Aqua(N,N'-disalicylideneethylenediamino-N,N'O,O')(4,5-imidazoledicarboxylato- O)manganese(III) monohydrate

Crystal data

[Mn(C5H3N2O4)(C16H14N2O2)(H2O)]·H2O	F(000) = 1056
Mr = 512.36	Dx = 1.532 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.009 Å	Cell parameters from 4856 reflections
b = 19.8634 (4) Å	θ = 1.6–25.0°
c = 16.2811 (3) Å	µ = 0.65 mm^−1
β = 101.422 (1)°	T = 293 K
V = 2221.93 (6) Å^3	Block, dark-red
Z = 4	0.76 × 0.54 × 0.34 mm

Data collection

Siemens SMART CCD diffractometer	3856 independent reflections
Radiation source: fine-focus sealed tube	3101 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −8→6
Tmin = 0.611, Tmax = 0.802	k = −23→17
7277 measured reflections	l = −19→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.130	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
3856 reflections	(Δ/σ)max = 0.001
327 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Mn	0.70172 (5)	0.140530 (19)	0.66060 (2)	0.03263 (16)
O1	0.4914 (3)	0.19651 (9)	0.61470 (12)	0.0434 (5)
O2	0.5865 (3)	0.10854 (10)	0.74902 (11)	0.0404 (4)
O3	0.5628 (4)	0.05662 (12)	0.57685 (16)	0.0579 (6)
O4	0.8303 (3)	0.22437 (10)	0.73898 (13)	0.0508 (5)
O5	1.1027 (3)	0.27560 (10)	0.72089 (14)	0.0527 (5)
O6	1.2978 (3)	0.37689 (12)	0.78152 (17)	0.0594 (6)
O7	1.2960 (3)	0.44854 (11)	0.88485 (15)	0.0608 (6)
O8	0.4549 (4)	0.22497 (13)	0.82464 (17)	0.0551 (6)
N1	0.8476 (3)	0.16515 (11)	0.57174 (13)	0.0377 (5)
N2	0.9318 (3)	0.08161 (11)	0.69864 (14)	0.0409 (5)
N3	0.7437 (3)	0.32662 (12)	0.83806 (14)	0.0404 (5)
H3A	0.6498	0.2982	0.8262	0.048*
N4	0.9135 (3)	0.41443 (12)	0.89485 (14)	0.0428 (5)
C1	0.4872 (4)	0.24580 (14)	0.55992 (17)	0.0383 (6)
C2	0.3291 (4)	0.29061 (15)	0.54791 (19)	0.0504 (7)
H2A	0.2334	0.2860	0.5798	0.061*
C3	0.3145 (6)	0.34166 (18)	0.4890 (2)	0.0649 (9)
H3B	0.2088	0.3708	0.4820	0.078*
C4	0.4528 (6)	0.35008 (18)	0.4407 (2)	0.0682 (10)
H4B	0.4395	0.3843	0.4010	0.082*
C5	0.6102 (5)	0.30794 (17)	0.45151 (19)	0.0583 (8)
H5A	0.7041	0.3140	0.4190	0.070*
C6	0.6325 (4)	0.25537 (14)	0.51120 (17)	0.0416 (6)
C7	0.8014 (4)	0.21302 (15)	0.51856 (17)	0.0431 (6)
H7A	0.8843	0.2210	0.4816	0.052*
C8	1.0222 (4)	0.12261 (16)	0.5725 (2)	0.0493 (7)
H8A	1.1202	0.1478	0.5509	0.059*
H8B	0.9876	0.0832	0.5376	0.059*
C9	1.0998 (4)	0.10187 (16)	0.6617 (2)	0.0508 (8)
H9A	1.1897	0.0645	0.6634	0.061*
H9B	1.1683	0.1391	0.6930	0.061*
C10	0.9354 (4)	0.02887 (15)	0.74407 (18)	0.0477 (7)
H10A	1.0448	0.0015	0.7500	0.057*
C11	0.7833 (5)	0.00860 (14)	0.78675 (18)	0.0487 (7)
C12	0.8058 (6)	−0.05244 (19)	0.8325 (2)	0.0719 (11)
H12A	0.9134	−0.0795	0.8310	0.086*
C13	0.6746 (8)	−0.0725 (2)	0.8783 (3)	0.0893 (14)
H13A	0.6903	−0.1133	0.9070	0.107*
C14	0.5163 (7)	−0.0314 (2)	0.8820 (2)	0.0784 (12)
H14A	0.4271	−0.0448	0.9141	0.094*
C15	0.4878 (5)	0.02932 (18)	0.83891 (19)	0.0588 (8)
H15A	0.3817	0.0563	0.8429	0.071*
C16	0.6195 (4)	0.04963 (14)	0.78943 (16)	0.0429 (7)
C17	0.9523 (4)	0.27048 (13)	0.75183 (16)	0.0370 (6)
C18	0.9150 (3)	0.32475 (12)	0.80983 (15)	0.0321 (5)
C19	0.7488 (4)	0.38066 (16)	0.88730 (19)	0.0475 (7)
H19A	0.6475	0.3931	0.9134	0.057*
C20	1.0192 (4)	0.37964 (13)	0.84560 (16)	0.0345 (6)
C21	1.2155 (4)	0.40446 (14)	0.83944 (19)	0.0434 (7)
H8C	0.506 (7)	0.191 (3)	0.804 (3)	0.100 (16)*
H6A	1.227 (7)	0.341 (2)	0.755 (3)	0.105 (16)*
H8D	0.370 (6)	0.232 (2)	0.785 (3)	0.076 (14)*
H3C	0.528 (6)	0.063 (2)	0.532 (3)	0.066 (12)*
H3D	0.563 (6)	0.016 (3)	0.586 (3)	0.094 (15)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn	0.0330 (2)	0.0276 (2)	0.0371 (3)	−0.00024 (15)	0.00621 (17)	−0.00084 (15)
O1	0.0383 (10)	0.0365 (11)	0.0570 (12)	0.0048 (8)	0.0134 (8)	0.0125 (9)
O2	0.0434 (10)	0.0349 (10)	0.0435 (10)	−0.0014 (8)	0.0104 (8)	0.0033 (8)
O3	0.0937 (17)	0.0298 (12)	0.0405 (13)	−0.0141 (11)	−0.0104 (11)	0.0012 (10)
O4	0.0557 (12)	0.0414 (12)	0.0575 (13)	−0.0156 (9)	0.0163 (10)	−0.0192 (9)
O5	0.0473 (11)	0.0487 (13)	0.0680 (14)	−0.0042 (9)	0.0258 (10)	−0.0179 (10)
O6	0.0435 (12)	0.0504 (13)	0.0907 (18)	−0.0103 (10)	0.0282 (12)	−0.0141 (12)
O7	0.0540 (12)	0.0450 (13)	0.0803 (16)	−0.0171 (10)	0.0060 (11)	−0.0129 (11)
O8	0.0491 (13)	0.0525 (15)	0.0671 (16)	−0.0037 (11)	0.0194 (13)	−0.0076 (12)
N1	0.0395 (12)	0.0325 (12)	0.0422 (12)	−0.0025 (10)	0.0104 (10)	−0.0067 (10)
N2	0.0393 (12)	0.0361 (13)	0.0438 (12)	0.0057 (10)	−0.0002 (10)	−0.0098 (10)
N3	0.0359 (11)	0.0429 (14)	0.0442 (12)	−0.0093 (10)	0.0124 (9)	−0.0106 (10)
N4	0.0461 (13)	0.0395 (13)	0.0428 (13)	−0.0027 (10)	0.0087 (10)	−0.0108 (10)
C1	0.0440 (14)	0.0325 (14)	0.0367 (14)	−0.0036 (11)	0.0037 (11)	−0.0019 (11)
C2	0.0507 (17)	0.0464 (17)	0.0516 (17)	0.0136 (14)	0.0040 (14)	0.0032 (14)
C3	0.078 (2)	0.053 (2)	0.058 (2)	0.0209 (18)	−0.0004 (18)	0.0124 (16)
C4	0.102 (3)	0.052 (2)	0.0470 (18)	0.014 (2)	0.0069 (19)	0.0193 (15)
C5	0.082 (2)	0.0528 (19)	0.0417 (16)	−0.0031 (18)	0.0165 (15)	0.0064 (14)
C6	0.0539 (16)	0.0339 (14)	0.0355 (14)	−0.0018 (12)	0.0059 (12)	−0.0030 (11)
C7	0.0488 (15)	0.0428 (16)	0.0406 (15)	−0.0095 (13)	0.0159 (12)	−0.0074 (12)
C8	0.0443 (16)	0.0486 (17)	0.0596 (19)	0.0000 (13)	0.0215 (14)	−0.0118 (14)
C9	0.0360 (15)	0.0480 (18)	0.067 (2)	0.0067 (12)	0.0077 (13)	−0.0141 (15)
C10	0.0499 (16)	0.0390 (16)	0.0471 (16)	0.0084 (13)	−0.0073 (13)	−0.0084 (13)
C11	0.0645 (18)	0.0350 (15)	0.0392 (15)	0.0003 (14)	−0.0077 (14)	−0.0011 (12)
C12	0.101 (3)	0.045 (2)	0.058 (2)	0.0057 (19)	−0.012 (2)	0.0091 (16)
C13	0.136 (4)	0.056 (2)	0.065 (2)	−0.013 (3)	−0.007 (3)	0.026 (2)
C14	0.103 (3)	0.074 (3)	0.055 (2)	−0.027 (2)	0.006 (2)	0.0225 (19)
C15	0.070 (2)	0.057 (2)	0.0473 (17)	−0.0172 (17)	0.0063 (15)	0.0080 (15)
C16	0.0541 (16)	0.0377 (15)	0.0318 (13)	−0.0138 (13)	−0.0040 (11)	0.0014 (11)
C17	0.0357 (14)	0.0339 (14)	0.0406 (14)	0.0014 (11)	0.0057 (11)	−0.0030 (11)
C18	0.0309 (12)	0.0311 (13)	0.0347 (12)	−0.0021 (10)	0.0076 (10)	−0.0005 (10)
C19	0.0453 (16)	0.0536 (18)	0.0483 (17)	−0.0025 (14)	0.0204 (13)	−0.0134 (14)
C20	0.0374 (13)	0.0289 (13)	0.0369 (14)	0.0006 (11)	0.0065 (11)	−0.0012 (10)
C21	0.0372 (14)	0.0327 (15)	0.0578 (17)	−0.0033 (12)	0.0036 (13)	0.0038 (13)

Geometric parameters (Å, º)

Mn—O1	1.8793 (18)	N4—C20	1.380 (3)
Mn—O2	1.8944 (18)	C1—C2	1.405 (4)
Mn—N2	1.989 (2)	C1—C6	1.422 (4)
Mn—N1	1.991 (2)	C2—C3	1.385 (4)
Mn—O4	2.1815 (19)	C3—C4	1.373 (6)
Mn—O3	2.249 (2)	C4—C5	1.368 (5)
O1—C1	1.321 (3)	C5—C6	1.414 (4)
O2—C16	1.340 (3)	C6—C7	1.437 (4)
O4—C17	1.242 (3)	C8—C9	1.505 (5)
O5—C17	1.259 (3)	C10—C11	1.440 (5)
O6—C21	1.318 (4)	C11—C16	1.416 (4)
O7—C21	1.211 (4)	C11—C12	1.415 (5)
N1—C7	1.284 (4)	C12—C13	1.354 (6)
N1—C8	1.485 (4)	C13—C14	1.389 (6)
N2—C10	1.280 (4)	C14—C15	1.389 (5)
N2—C9	1.480 (4)	C15—C16	1.399 (4)
N3—C19	1.336 (4)	C17—C18	1.490 (3)
N3—C18	1.369 (3)	C18—C20	1.376 (4)
N4—C19	1.320 (4)	C20—C21	1.484 (4)
O1—Mn—O2	94.69 (8)	C4—C5—C6	121.1 (3)
O1—Mn—N2	174.55 (9)	C5—C6—C1	119.2 (3)
O2—Mn—N2	90.42 (9)	C5—C6—C7	117.8 (3)
O1—Mn—N1	92.35 (9)	C1—C6—C7	122.9 (3)
O2—Mn—N1	172.83 (9)	N1—C7—C6	125.7 (3)
N2—Mn—N1	82.50 (9)	N1—C8—C9	107.6 (2)
O1—Mn—O4	88.95 (9)	N2—C9—C8	107.6 (2)
O2—Mn—O4	90.02 (8)	N2—C10—C11	125.2 (3)
N2—Mn—O4	92.95 (9)	C16—C11—C12	118.9 (3)
N1—Mn—O4	91.45 (8)	C16—C11—C10	122.4 (3)
O1—Mn—O3	89.20 (10)	C12—C11—C10	118.5 (3)
O2—Mn—O3	90.78 (9)	C13—C12—C11	121.7 (4)
N2—Mn—O3	88.84 (10)	C12—C13—C14	119.1 (4)
N1—Mn—O3	87.97 (9)	C13—C14—C15	121.7 (4)
O4—Mn—O3	178.04 (9)	C14—C15—C16	119.7 (4)
C1—O1—Mn	128.15 (17)	O2—C16—C15	117.7 (3)
C16—O2—Mn	127.45 (18)	O2—C16—C11	123.3 (2)
C17—O4—Mn	148.47 (18)	C15—C16—C11	118.9 (3)
C7—N1—C8	121.6 (2)	O4—C17—O5	126.5 (2)
C7—N1—Mn	125.1 (2)	O4—C17—C18	116.0 (2)
C8—N1—Mn	113.30 (18)	O5—C17—C18	117.5 (2)
C10—N2—C9	122.1 (2)	N3—C18—C20	105.3 (2)
C10—N2—Mn	125.7 (2)	N3—C18—C17	120.5 (2)
C9—N2—Mn	112.02 (18)	C20—C18—C17	134.2 (2)
C19—N3—C18	107.6 (2)	N4—C19—N3	112.6 (2)
C19—N4—C20	104.6 (2)	C18—C20—N4	110.0 (2)
O1—C1—C2	118.4 (2)	C18—C20—C21	131.0 (2)
O1—C1—C6	123.6 (2)	N4—C20—C21	119.0 (2)
C2—C1—C6	118.0 (3)	O7—C21—O6	121.3 (3)
C3—C2—C1	120.5 (3)	O7—C21—C20	121.7 (3)
C4—C3—C2	121.4 (3)	O6—C21—C20	117.0 (2)
C5—C4—C3	119.6 (3)