catena-Poly[[[diaqua-(1,3-benzimidazole-κN)manganese(II)]-μ-benzene-1,3-di-carboxyl-ato-κO,O:O] dihydrate].

In the polymeric title complex, {[Mn(C(8)H(4)O(4))(C(7)H(6)N(2))(H(2)O)(2)]·2H(2)O}(n), the Mn(II) cation is coordinated by two benzene-dicarboxyl-ate anions, one benzimidazole ligand and two water mol-ecules in a distorted MnNO(5) octa-hedral geometry. In the crystal, each benzene-dicarboxyl-ate anion bridges adjacent Mn(II) cations through the terminal carboxyl-ate groups, forming a polymeric complex chain along the a axis. One Mn-O(carboxyl-ate) bond is much longer than the others. In the crystal, π-π stacking is observed between nearly parallel [dihedral angle = 4.32 (6)°] benzimidazole aromatic ring systems of adjacent mol-ecules, the centroid-centroid distance between the imidazole and benzene rings being 3.5421 (11) Å. Extensive inter-molecular O-H⋯O and N-H⋯O hydrogen bonding is present in the crystal structure. The two lattice water mol-ecules are located on twofold rotation axes.

Related literature

For background to π–π stacking, see: Deisenhofer & Michel (1989 ▶). For a related structure, see: Hu et al. (2006 ▶). For a longer Mn—O bond length in complex with a seven-coordinate MnII atom, see: Liu et al. (2005 ▶).

Experimental

Crystal data

[Mn(C8H4O4)(C7H6N2)(H2O)2]·2H2O

M = 409.25

Orthorhombic,

a = 18.9148 (12) Å

b = 23.7112 (16) Å

c = 7.8701 (4) Å

V = 3529.7 (4) Å3

Z = 8

Mo Kα radiation

μ = 0.79 mm−1

T = 292 K

0.24 × 0.20 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.786, T max = 0.880

20574 measured reflections

4043 independent reflections

3261 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.091

S = 1.04

4043 reflections

236 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.26 e Å−3

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, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811008555/xu5169sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811008555/xu5169Isup2.hkl

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

[Mn(C8H4O4)(C7H6N2)(H2O)2]·2H2O	F(000) = 1688
Mr = 409.25	Dx = 1.540 Mg m−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 8868 reflections
a = 18.9148 (12) Å	θ = 3.0–25.0°
b = 23.7112 (16) Å	µ = 0.79 mm−1
c = 7.8701 (4) Å	T = 292 K
V = 3529.7 (4) Å3	Prism, yellow
Z = 8	0.24 × 0.20 × 0.18 mm

Rigaku R-AXIS RAPID IP diffractometer	4043 independent reflections
Radiation source: fine-focus sealed tube	3261 reflections with I > 2σ(I)
graphite	Rint = 0.029
ω scans	θmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −24→20
Tmin = 0.786, Tmax = 0.880	k = −30→30
20574 measured reflections	l = −10→7

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0428P)2 + 2.5725P] where P = (Fo2 + 2Fc2)/3
4043 reflections	(Δ/σ)max = 0.002
236 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

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.

	x	y	z	Uiso*/Ueq
Mn	0.714708 (13)	0.679735 (11)	0.66543 (3)	0.01758 (9)
N1	0.63968 (9)	0.50825 (7)	0.6050 (2)	0.0300 (4)
H1	0.6084	0.4848	0.5691	0.036*
N3	0.69188 (8)	0.59024 (6)	0.66113 (19)	0.0227 (3)
O1	0.37986 (7)	0.73206 (5)	0.33053 (17)	0.0255 (3)
O2	0.32557 (7)	0.81586 (6)	0.33551 (17)	0.0278 (3)
O3	0.60704 (7)	0.71200 (6)	0.64217 (17)	0.0283 (3)
O4	0.67794 (7)	0.78568 (7)	0.65720 (16)	0.0305 (3)
O5	0.71498 (6)	0.68148 (5)	0.94037 (17)	0.0232 (3)
H5A	0.7534	0.6897	1.0001	0.035*
H5B	0.6793	0.6937	1.0010	0.035*
O6	0.71830 (6)	0.69029 (5)	0.39202 (17)	0.0234 (3)
H6A	0.7572	0.6963	0.3418	0.035*
H6B	0.6861	0.7025	0.3247	0.035*
O7	0.5000	0.66207 (9)	0.2500	0.0384 (5)
H7A	0.4605	0.6869	0.2419	0.058*
O8	0.5000	0.64354 (8)	0.7500	0.0321 (4)
H8A	0.5364	0.6685	0.7171	0.048*
O9	0.45942 (9)	0.57472 (7)	0.4780 (2)	0.0496 (4)
H9A	0.4713	0.5996	0.3886	0.074*
H9B	0.4773	0.5905	0.5737	0.074*
C2	0.63681 (10)	0.56472 (8)	0.5930 (2)	0.0277 (4)
H2	0.5996	0.5839	0.5417	0.033*
C4	0.79996 (10)	0.54864 (8)	0.8052 (2)	0.0270 (4)
H4	0.8220	0.5827	0.8297	0.032*
C5	0.83029 (11)	0.49747 (9)	0.8501 (3)	0.0333 (5)
H5	0.8739	0.4972	0.9049	0.040*
C6	0.79648 (12)	0.44598 (9)	0.8146 (3)	0.0357 (5)
H6	0.8180	0.4125	0.8482	0.043*
C7	0.73256 (12)	0.44362 (8)	0.7318 (3)	0.0340 (5)
H7	0.7106	0.4094	0.7077	0.041*
C8	0.70224 (11)	0.49489 (8)	0.6857 (2)	0.0264 (4)
C9	0.73497 (10)	0.54671 (7)	0.7219 (2)	0.0229 (4)
C10	0.37791 (9)	0.78435 (8)	0.3620 (2)	0.0215 (4)
C11	0.44298 (9)	0.81128 (7)	0.4375 (2)	0.0202 (3)
C12	0.49726 (9)	0.77770 (7)	0.5012 (2)	0.0203 (3)
H12	0.4924	0.7387	0.5003	0.024*
C13	0.55886 (9)	0.80183 (8)	0.5661 (2)	0.0217 (4)
C14	0.56567 (10)	0.86047 (8)	0.5684 (2)	0.0275 (4)
H14	0.6069	0.8770	0.6095	0.033*
C15	0.51092 (11)	0.89410 (8)	0.5092 (3)	0.0315 (4)
H15	0.5152	0.9331	0.5134	0.038*
C16	0.44988 (10)	0.86999 (8)	0.4437 (2)	0.0255 (4)
H16	0.4135	0.8929	0.4038	0.031*
C17	0.61786 (9)	0.76481 (8)	0.6275 (2)	0.0242 (4)

	U11	U22	U33	U12	U13	U23
Mn	0.01342 (14)	0.02063 (14)	0.01869 (15)	0.00030 (9)	0.00052 (9)	0.00094 (10)
N1	0.0311 (9)	0.0279 (8)	0.0310 (9)	−0.0081 (7)	0.0018 (7)	−0.0039 (7)
N3	0.0232 (7)	0.0235 (8)	0.0215 (8)	0.0005 (6)	0.0010 (6)	−0.0007 (6)
O1	0.0192 (6)	0.0291 (7)	0.0282 (7)	−0.0034 (5)	−0.0031 (5)	−0.0002 (5)
O2	0.0157 (6)	0.0364 (7)	0.0313 (8)	0.0021 (5)	−0.0017 (5)	0.0056 (6)
O3	0.0188 (6)	0.0350 (7)	0.0310 (7)	0.0057 (5)	0.0008 (5)	0.0066 (6)
O4	0.0143 (6)	0.0546 (9)	0.0226 (7)	−0.0021 (6)	−0.0021 (5)	0.0012 (6)
O5	0.0179 (6)	0.0317 (7)	0.0201 (6)	−0.0003 (5)	0.0006 (5)	−0.0032 (5)
O6	0.0184 (6)	0.0324 (7)	0.0195 (6)	0.0012 (5)	0.0016 (5)	0.0048 (5)
O7	0.0381 (12)	0.0359 (11)	0.0413 (13)	0.000	0.0073 (10)	0.000
O8	0.0264 (10)	0.0320 (10)	0.0379 (12)	0.000	0.0047 (9)	0.000
O9	0.0577 (11)	0.0495 (10)	0.0417 (10)	−0.0234 (8)	−0.0079 (8)	0.0003 (8)
C2	0.0271 (10)	0.0297 (10)	0.0264 (10)	−0.0010 (8)	0.0011 (8)	−0.0030 (8)
C4	0.0273 (10)	0.0285 (9)	0.0253 (10)	−0.0021 (7)	0.0028 (7)	0.0022 (7)
C5	0.0318 (11)	0.0394 (11)	0.0288 (11)	0.0076 (9)	0.0014 (8)	0.0056 (8)
C6	0.0468 (13)	0.0282 (10)	0.0321 (11)	0.0115 (9)	0.0113 (9)	0.0069 (8)
C7	0.0491 (13)	0.0219 (9)	0.0310 (11)	−0.0005 (8)	0.0116 (9)	0.0003 (8)
C8	0.0317 (10)	0.0250 (9)	0.0224 (9)	−0.0036 (7)	0.0070 (8)	−0.0010 (7)
C9	0.0271 (9)	0.0219 (8)	0.0195 (9)	0.0004 (7)	0.0056 (7)	0.0010 (7)
C10	0.0156 (8)	0.0308 (9)	0.0179 (8)	−0.0014 (6)	0.0015 (6)	0.0033 (7)
C11	0.0149 (8)	0.0288 (9)	0.0170 (8)	0.0004 (6)	0.0012 (6)	0.0001 (7)
C12	0.0172 (8)	0.0259 (8)	0.0178 (8)	0.0003 (6)	0.0022 (6)	−0.0008 (7)
C13	0.0171 (8)	0.0309 (9)	0.0171 (8)	0.0006 (7)	0.0009 (7)	−0.0002 (7)
C14	0.0213 (9)	0.0345 (10)	0.0267 (10)	−0.0058 (7)	−0.0030 (7)	−0.0035 (8)
C15	0.0311 (11)	0.0261 (9)	0.0373 (12)	−0.0019 (8)	−0.0034 (9)	−0.0019 (8)
C16	0.0214 (9)	0.0287 (9)	0.0265 (9)	0.0047 (7)	−0.0011 (7)	0.0008 (7)
C17	0.0164 (8)	0.0396 (11)	0.0165 (8)	0.0035 (7)	0.0023 (6)	0.0003 (7)

Mn—N3	2.1657 (15)	C2—H2	0.9300
Mn—O2i	2.0995 (13)	C4—C5	1.388 (3)
Mn—O3	2.1832 (13)	C4—C9	1.394 (3)
Mn—O4	2.6075 (16)	C4—H4	0.9300
Mn—O5	2.1642 (14)	C5—C6	1.406 (3)
Mn—O6	2.1674 (14)	C5—H5	0.9300
N1—C2	1.343 (2)	C6—C7	1.375 (3)
N1—C8	1.380 (3)	C6—H6	0.9300
N1—H1	0.8600	C7—C8	1.392 (3)
N3—C2	1.319 (2)	C7—H7	0.9300
N3—C9	1.400 (2)	C8—C9	1.405 (3)
O1—C10	1.265 (2)	C10—C11	1.509 (2)
O2—C10	1.258 (2)	C11—C12	1.393 (2)
O3—C17	1.274 (2)	C11—C16	1.399 (3)
O4—C17	1.261 (2)	C12—C13	1.395 (2)
O5—H5A	0.8866	C12—H12	0.9300
O5—H5B	0.8758	C13—C14	1.396 (3)
O6—H6A	0.8469	C13—C17	1.500 (2)
O6—H6B	0.8576	C14—C15	1.388 (3)
O7—H7A	0.9532	C14—H14	0.9300
O8—H8A	0.9437	C15—C16	1.388 (3)
O9—H9A	0.9455	C15—H15	0.9300
O9—H9B	0.9065	C16—H16	0.9300
O2i—Mn—O5	90.01 (5)	C7—C6—H6	119.0
O2i—Mn—N3	104.35 (6)	C5—C6—H6	119.0
O5—Mn—N3	92.00 (5)	C6—C7—C8	116.76 (19)
O2i—Mn—O6	87.68 (5)	C6—C7—H7	121.6
O5—Mn—O6	172.03 (5)	C8—C7—H7	121.6
N3—Mn—O6	95.96 (5)	N1—C8—C7	132.35 (19)
O2i—Mn—O3	156.06 (5)	N1—C8—C9	105.70 (16)
O5—Mn—O3	94.55 (5)	C7—C8—C9	121.95 (19)
N3—Mn—O3	98.98 (6)	C4—C9—N3	130.56 (17)
O6—Mn—O3	84.58 (5)	C4—C9—C8	120.85 (17)
C2—N1—C8	107.21 (16)	N3—C9—C8	108.60 (16)
C2—N1—H1	126.4	O2—C10—O1	124.95 (16)
C8—N1—H1	126.4	O2—C10—C11	117.13 (16)
C2—N3—C9	105.11 (15)	O1—C10—C11	117.92 (15)
C2—N3—Mn	127.84 (13)	C12—C11—C16	119.20 (16)
C9—N3—Mn	126.95 (12)	C12—C11—C10	120.08 (15)
C10—O2—Mnii	144.73 (12)	C16—C11—C10	120.72 (16)
C17—O3—Mn	101.66 (11)	C11—C12—C13	120.86 (16)
Mn—O5—H5A	122.4	C11—C12—H12	119.6
Mn—O5—H5B	123.3	C13—C12—H12	119.6
H5A—O5—H5B	105.7	C12—C13—C14	119.34 (16)
Mn—O6—H6A	120.7	C12—C13—C17	119.96 (16)
Mn—O6—H6B	129.0	C14—C13—C17	120.67 (16)
H6A—O6—H6B	105.8	C15—C14—C13	119.94 (17)
H9A—O9—H9B	105.8	C15—C14—H14	120.0
N3—C2—N1	113.38 (18)	C13—C14—H14	120.0
N3—C2—H2	123.3	C14—C15—C16	120.60 (18)
N1—C2—H2	123.3	C14—C15—H15	119.7
C5—C4—C9	117.11 (18)	C16—C15—H15	119.7
C5—C4—H4	121.4	C15—C16—C11	120.02 (17)
C9—C4—H4	121.4	C15—C16—H16	120.0
C4—C5—C6	121.4 (2)	C11—C16—H16	120.0
C4—C5—H5	119.3	O4—C17—O3	120.89 (17)
C6—C5—H5	119.3	O4—C17—C13	120.04 (17)
C7—C6—C5	121.98 (19)	O3—C17—C13	119.01 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O9iii	0.86	1.94	2.795 (2)	171
O5—H5A···O4iv	0.89	1.89	2.7605 (18)	168
O5—H5B···O1v	0.88	1.96	2.8120 (18)	164
O6—H6A···O4vi	0.85	1.95	2.7553 (18)	159
O6—H6B···O1vii	0.86	1.88	2.7379 (18)	176
O7—H7A···O1	0.95	1.99	2.8844 (18)	155
O8—H8A···O3	0.94	1.79	2.7303 (18)	176
O9—H9A···O7	0.94	1.92	2.846 (2)	167
O9—H9B···O8	0.91	1.92	2.799 (2)	162

Table 1

Selected bond lengths (Å)

Mn—N3	2.1657 (15)
Mn—O2i	2.0995 (13)
Mn—O3	2.1832 (13)
Mn—O4	2.6075 (16)
Mn—O5	2.1642 (14)
Mn—O6	2.1674 (14)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O9ii	0.86	1.94	2.795 (2)	171
O5—H5A⋯O4iii	0.89	1.89	2.7605 (18)	168
O5—H5B⋯O1iv	0.88	1.96	2.8120 (18)	164
O6—H6A⋯O4v	0.85	1.95	2.7553 (18)	159
O6—H6B⋯O1vi	0.86	1.88	2.7379 (18)	176
O7—H7A⋯O1	0.95	1.99	2.8844 (18)	155
O8—H8A⋯O3	0.94	1.79	2.7303 (18)	176
O9—H9A⋯O7	0.94	1.92	2.846 (2)	167
O9—H9B⋯O8	0.91	1.92	2.799 (2)	162

Symmetry codes: (ii) ; (iii) ; (iv) ; (v) ; (vi) .