Diaqua­[5,5′-dicarb­oxy-2,2′-(propane-1,3-di­yl)bis­(1H-imidazole-4-carboxyl­ato)]manganese(II)

Abstract

The complex mol­ecule of the title compound, [Mn(C₁₃H₁₀N₄O₈)(H₂O)₂] or [Mn(H₄pbidc)(H₂O)₂] (H₆pbidc = 2,2′-(propane-1,3-di­yl)bis­(1H-imidazole-4,5-dicarb­oxy­lic acid), has 2 symmetry with the twofold rotation axis running through the Mn²⁺ cation and the central C atom of the propanediyl unit. The cation is six-coordinated by two N atoms and two O atoms from one H₄pbidc²⁻ anion and two water O atoms in a considerably distorted octa­hedral coordination. In the crystal, adjacent mol­ecules are linked through O—H⋯O and N—H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For background to complexes based on 1H-imidazole-4,5-dicarb­oxy­lic acid, see: Ghosh et al. (2009 ▶); Liu et al. (2008 ▶); Sun & Yang (2007 ▶).

Experimental

Crystal data

• [Mn(C₁₃H₁₀N₄O₈)(H₂O)₂]

• M _r = 441.22

• Monoclinic,

• a = 15.620 (3) Å

• b = 8.5310 (17) Å

• c = 12.739 (3) Å

• β = 97.07 (3)°

• V = 1684.7 (6) ų

• Z = 4

• Mo Kα radiation

• μ = 0.85 mm⁻¹

• T = 293 K

• 0.23 × 0.21 × 0.18 mm

Data collection

• Rigaku Saturn diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2006 ▶) T _min = 0.828, T _max = 0.862

• 3426 measured reflections

• 1464 independent reflections

• 1265 reflections with I > 2σ(I)

• R _int = 0.026

Refinement

• R[F ² > 2σ(F ²)] = 0.037

• wR(F ²) = 0.090

• S = 1.09

• 1464 reflections

• 128 parameters

• H-atom parameters constrained

• Δρ_max = 0.47 e Å⁻³

• Δρ_min = −0.45 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2006 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Mn1—O5	2.107 (2)
Mn1—N1	2.237 (2)
Mn1—O1	2.3236 (19)

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H2W⋯O4i	0.85	1.94	2.780 (3)	168
O5—H1W⋯O3ii	0.85	1.93	2.780 (3)	174
N2—H2A⋯O4iii	0.86	1.97	2.785 (3)	159
O3—H3⋯O2	0.85	1.68	2.527 (3)	178

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

Up to date, a large number of metal-organic frameworks derived from 1H-imidazole-4,5-dicarboxylic acid (H₃idc) have been synthesized since it is a good linker and can be successively deprotonated to generate H₂idc^-, Hidc^2- and idc^3- anions (Ghosh et al., 2009; Liu et al., 2008; Sun & Yang, 2007). Compared with H₃idc, 2,2'-(1,3-propanediyl)bis-1H-imidazole-4,5-dicarboxylic acid (H₆pbidc) can provide a greater tunability of structural frameworks because of the presence of the propanediyl spacer. However, complexes derived from this ligand have been scarcely reported. In this work, through the reaction of H₆pbidc with MnSO₄, we obtained the title complex [Mn(H₄pbidc) (H₂O)₂], (I).

As shown in Figure 1, the Mn²⁺ cation in (I) is hexacoordinated and features a distorted octahedral coordination geometry. N1, O1, N1A, O1A atoms from the tetradentate H₄pbidc^2- group coordinate to the cation in a chelating fashion and O5, O5A atoms from water molecules complete the coordination polyhedron. The entire complex molecule has symmetry 2. The bond angles around the Mn²⁺ cation significantly deviate from 90 or 180° (see supplementary material). Intramolecular O—H···O hydrogen bonds between the carboxyl/carboxylate groups stabilize the molecular configuration whereas O—H···O and N—H···O hydrogen bonds between the water molecules and carboxylate O atoms and between imidazole groups and carboxylate O atoms of adjacent molecules consolidate the crystal packing.

Experimental

A mixture of MnSO₄ (0.05 mmol), 2,2'-(1,3-propanediyl)bis-1H-imidazole-4,5-dicarboxylic (0.05 mmol), methanol (2 ml) and water (2 ml) was placed in a 25 ml Teflon-lined stainless steel vessel and heated at 433 K for 72 h, then cooled to room temperature. Light yellow crystals with good quality were obtained from the filtrate and dried in air.

Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.97 Å, N—H = 0.86 Å and O—H = 0.85 Å, and with U_iso(H) = 1.2 U_eq(C,N,O).

Figures

Fig. 1.

View of the title complex, showing the labelling of the atoms which are displayed with their displacement ellipsoids at the 30% probability level. [Symmetry code A: -x, y, -z + 1/2.]

Crystal data

[Mn(C13H10N4O8)(H2O)2]	F(000) = 900
Mr = 441.22	Dx = 1.740 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2738 reflections
a = 15.620 (3) Å	θ = 2.6–27.9°
b = 8.5310 (17) Å	µ = 0.85 mm−1
c = 12.739 (3) Å	T = 293 K
β = 97.07 (3)°	Prism, light yellow
V = 1684.7 (6) Å3	0.23 × 0.21 × 0.18 mm
Z = 4

Data collection

Rigaku Saturn diffractometer	1464 independent reflections
Radiation source: fine-focus sealed tube	1265 reflections with I > 2σ(I)
graphite	Rint = 0.026
Detector resolution: 28.5714 pixels mm-1	θmax = 25.0°, θmin = 2.6°
ω scans	h = −17→18
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2006)	k = −10→8
Tmin = 0.828, Tmax = 0.862	l = −15→12
3426 measured reflections

Refinement

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0405P)2 + 1.7694P] where P = (Fo2 + 2Fc2)/3
1464 reflections	(Δ/σ)max < 0.001
128 parameters	Δρmax = 0.47 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
Mn1	0.0000	0.22580 (7)	0.2500	0.0249 (2)
N1	0.08997 (14)	0.4109 (3)	0.32272 (18)	0.0273 (5)
N2	0.16454 (14)	0.5985 (3)	0.40995 (19)	0.0308 (6)
H2A	0.1767	0.6876	0.4397	0.037*
O1	0.13833 (12)	0.1209 (2)	0.26815 (16)	0.0336 (5)
O2	0.27378 (12)	0.1518 (2)	0.34234 (17)	0.0382 (5)
O3	0.35729 (12)	0.3642 (2)	0.44866 (16)	0.0336 (5)
H3	0.3281	0.2937	0.4133	0.040*
O4	0.34141 (12)	0.6152 (2)	0.48617 (17)	0.0370 (5)
O5	0.00284 (13)	0.1299 (3)	0.09807 (16)	0.0466 (6)
H1W	−0.0390	0.1314	0.0487	0.056*
H2W	0.0460	0.1216	0.0637	0.056*
C1	0.19523 (18)	0.2024 (3)	0.3170 (2)	0.0278 (6)
C2	0.17401 (16)	0.3615 (3)	0.3491 (2)	0.0242 (6)
C3	0.22101 (16)	0.4777 (3)	0.4038 (2)	0.0258 (6)
C4	0.31248 (17)	0.4881 (3)	0.4495 (2)	0.0269 (6)
C5	0.08645 (17)	0.5546 (3)	0.3616 (2)	0.0297 (7)
C6	0.00932 (19)	0.6586 (4)	0.3507 (3)	0.0462 (9)
H6A	0.0130	0.7285	0.4111	0.055*
H6B	−0.0420	0.5947	0.3516	0.055*
C7	0.0000	0.7559 (5)	0.2500	0.0562 (15)
H7A	−0.0509	0.8214	0.2480	0.067*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Mn1	0.0183 (3)	0.0268 (3)	0.0276 (3)	0.000	−0.0048 (2)	0.000
N1	0.0177 (11)	0.0278 (12)	0.0344 (13)	0.0007 (9)	−0.0048 (10)	−0.0048 (10)
N2	0.0222 (12)	0.0279 (12)	0.0396 (14)	−0.0003 (10)	−0.0068 (11)	−0.0085 (10)
O1	0.0237 (11)	0.0333 (11)	0.0416 (12)	0.0003 (9)	−0.0051 (9)	−0.0114 (9)
O2	0.0227 (11)	0.0373 (12)	0.0515 (13)	0.0084 (9)	−0.0078 (10)	−0.0074 (10)
O3	0.0208 (10)	0.0361 (12)	0.0408 (11)	−0.0011 (9)	−0.0094 (9)	−0.0059 (9)
O4	0.0236 (10)	0.0357 (12)	0.0490 (13)	−0.0055 (9)	−0.0062 (10)	−0.0099 (10)
O5	0.0241 (11)	0.0804 (17)	0.0328 (12)	0.0111 (11)	−0.0070 (10)	−0.0179 (11)
C1	0.0238 (15)	0.0319 (15)	0.0268 (14)	0.0015 (12)	−0.0008 (12)	−0.0008 (12)
C2	0.0174 (13)	0.0281 (14)	0.0262 (14)	0.0001 (11)	−0.0008 (12)	0.0002 (11)
C3	0.0191 (14)	0.0291 (14)	0.0278 (14)	−0.0010 (11)	−0.0028 (11)	−0.0012 (12)
C4	0.0206 (14)	0.0331 (16)	0.0261 (14)	−0.0018 (12)	−0.0002 (12)	0.0023 (12)
C5	0.0189 (14)	0.0298 (15)	0.0381 (16)	0.0004 (12)	−0.0054 (13)	−0.0094 (13)
C6	0.0235 (16)	0.0419 (18)	0.069 (2)	0.0065 (14)	−0.0091 (16)	−0.0271 (17)
C7	0.029 (2)	0.023 (2)	0.109 (5)	0.000	−0.020 (3)	0.000

Geometric parameters (Å, °)

Mn1—O5	2.107 (2)	O3—H3	0.8500
Mn1—O5i	2.107 (2)	O4—C4	1.243 (3)
Mn1—N1	2.237 (2)	O5—H1W	0.8501
Mn1—N1i	2.237 (2)	O5—H2W	0.8500
Mn1—O1	2.3236 (19)	C1—C2	1.467 (4)
Mn1—O1i	2.3236 (19)	C2—C3	1.371 (4)
N1—C5	1.326 (3)	C3—C4	1.478 (4)
N1—C2	1.380 (3)	C5—C6	1.489 (4)
N2—C5	1.350 (3)	C6—C7	1.520 (4)
N2—C3	1.365 (3)	C6—H6A	0.9700
N2—H2A	0.8600	C6—H6B	0.9700
O1—C1	1.235 (3)	C7—C6i	1.520 (4)
O2—C1	1.303 (3)	C7—H7A	0.9700
O3—C4	1.269 (3)
O5—Mn1—O5i	134.29 (13)	H1W—O5—H2W	101.9
O5—Mn1—N1	124.84 (9)	O1—C1—O2	122.4 (3)
O5i—Mn1—N1	88.68 (8)	O1—C1—C2	119.2 (2)
O5—Mn1—N1i	88.68 (8)	O2—C1—C2	118.4 (2)
O5i—Mn1—N1i	124.84 (9)	C3—C2—N1	109.7 (2)
N1—Mn1—N1i	90.22 (11)	C3—C2—C1	133.2 (2)
O5—Mn1—O1	79.48 (8)	N1—C2—C1	117.1 (2)
O5i—Mn1—O1	83.31 (8)	N2—C3—C2	105.4 (2)
N1—Mn1—O1	72.64 (7)	N2—C3—C4	122.2 (2)
N1i—Mn1—O1	147.34 (8)	C2—C3—C4	132.4 (2)
O5—Mn1—O1i	83.31 (8)	O4—C4—O3	123.7 (2)
O5i—Mn1—O1i	79.48 (8)	O4—C4—C3	119.3 (2)
N1—Mn1—O1i	147.34 (8)	O3—C4—C3	117.0 (2)
N1i—Mn1—O1i	72.64 (7)	N1—C5—N2	110.5 (2)
O1—Mn1—O1i	134.71 (10)	N1—C5—C6	125.9 (2)
C5—N1—C2	105.8 (2)	N2—C5—C6	123.5 (2)
C5—N1—Mn1	138.97 (18)	C5—C6—C7	113.4 (3)
C2—N1—Mn1	114.56 (17)	C5—C6—H6A	108.9
C5—N2—C3	108.6 (2)	C7—C6—H6A	108.9
C5—N2—H2A	125.7	C5—C6—H6B	108.9
C3—N2—H2A	125.7	C7—C6—H6B	108.9
C1—O1—Mn1	115.86 (17)	H6A—C6—H6B	107.7
C4—O3—H3	109.4	C6i—C7—C6	113.7 (3)
Mn1—O5—H1W	124.9	C6i—C7—H7A	107.4
Mn1—O5—H2W	127.8	C6—C7—H7A	109.3
O5—Mn1—N1—C5	121.0 (3)	O2—C1—C2—C3	−0.1 (5)
O5i—Mn1—N1—C5	−92.4 (3)	O1—C1—C2—N1	0.3 (4)
N1i—Mn1—N1—C5	32.5 (3)	O2—C1—C2—N1	−178.9 (2)
O1—Mn1—N1—C5	−175.8 (3)	C5—N2—C3—C2	0.6 (3)
O1i—Mn1—N1—C5	−24.3 (4)	C5—N2—C3—C4	−179.9 (2)
O5—Mn1—N1—C2	−69.7 (2)	N1—C2—C3—N2	−0.2 (3)
O5i—Mn1—N1—C2	76.92 (19)	C1—C2—C3—N2	−179.0 (3)
N1i—Mn1—N1—C2	−158.2 (2)	N1—C2—C3—C4	−179.5 (3)
O1—Mn1—N1—C2	−6.49 (17)	C1—C2—C3—C4	1.6 (5)
O1i—Mn1—N1—C2	144.92 (17)	N2—C3—C4—O4	−6.9 (4)
O5—Mn1—O1—C1	138.8 (2)	C2—C3—C4—O4	172.4 (3)
O5i—Mn1—O1—C1	−83.7 (2)	N2—C3—C4—O3	173.2 (3)
N1—Mn1—O1—C1	7.01 (19)	C2—C3—C4—O3	−7.5 (4)
N1i—Mn1—O1—C1	68.3 (3)	C2—N1—C5—N2	0.8 (3)
O1i—Mn1—O1—C1	−151.7 (2)	Mn1—N1—C5—N2	170.6 (2)
Mn1—O1—C1—O2	172.9 (2)	C2—N1—C5—C6	178.2 (3)
Mn1—O1—C1—C2	−6.3 (3)	Mn1—N1—C5—C6	−11.9 (5)
C5—N1—C2—C3	−0.4 (3)	C3—N2—C5—N1	−0.9 (3)
Mn1—N1—C2—C3	−173.07 (18)	C3—N2—C5—C6	−178.5 (3)
C5—N1—C2—C1	178.7 (2)	N1—C5—C6—C7	−87.0 (4)
Mn1—N1—C2—C1	6.0 (3)	N2—C5—C6—C7	90.1 (4)
O1—C1—C2—C3	179.1 (3)	C5—C6—C7—C6i	60.5 (2)

Symmetry codes: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H2W···O4ii	0.85	1.94	2.780 (3)	168
O5—H1W···O3iii	0.85	1.93	2.780 (3)	174
N2—H2A···O4iv	0.86	1.97	2.785 (3)	159
O3—H3···O2	0.85	1.68	2.527 (3)	178

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