Diaqua-bis-(2,2'-bi-1H-imidazole)-man-ganese(II) benzene-1,4-di-carboxyl-ate.

The asymmetric unit of the title compound, [Mn(C(6)H(6)N(4))(2)(H(2)O)(2)](C(8)H(4)O(4)), contains one-half each of the centrosymmetric cation and anion. The Mn(II) atom is coordinated by four N atoms [Mn-N = 2.2168 (14) and 2.2407 (14) Å] from two 2,2'-biimidazole ligands and two water mol-ecules [Mn-O = 2.2521 (14) Å] in a distorted octa-hedral geometry. Inter-molecular N-H⋯O and O-H⋯O hydrogen bonds consol-idate the crystal packing, which also exhibits π-π inter-actions between five-membered rings, with a centroid-centroid distance of 3.409 (2) Å.

Related literature

For related structures, see: Fortin & Beauchamp (2001 ▶); Sang et al. (2002 ▶); Atencio et al. (2004 ▶); Wang et al. (2007 ▶). For background to supra­molecular assemblies, see: Ramirez et al. (2002 ▶); Baca et al. (2003 ▶).

Experimental

Crystal data

[Mn(C6H6N4)2(H2O)2](C8H4O4)

M = 523.38

Monoclinic,

a = 8.2666 (10) Å

b = 10.9027 (13) Å

c = 12.6734 (16) Å

β = 93.986 (2)°

V = 1139.5 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.63 mm−1

T = 293 K

0.46 × 0.19 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.761, T max = 0.960

5689 measured reflections

2024 independent reflections

1712 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.075

S = 1.04

2024 reflections

167 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.17 e Å−3

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681202199X/cv5293sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681202199X/cv5293Isup2.hkl

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

[Mn(C6H6N4)2(H2O)2](C8H4O4)	F(000) = 538
Mr = 523.38	Dx = 1.525 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.2666 (10) Å	Cell parameters from 2178 reflections
b = 10.9027 (13) Å	θ = 3.0–26.9°
c = 12.6734 (16) Å	µ = 0.63 mm−1
β = 93.986 (2)°	T = 293 K
V = 1139.5 (2) Å3	Block, yellow
Z = 2	0.46 × 0.19 × 0.07 mm

Bruker SMART CCD area-detector diffractometer	2024 independent reflections
Radiation source: fine-focus sealed tube	1712 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
φ and ω scans	θmax = 25.1°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −6→9
Tmin = 0.761, Tmax = 0.960	k = −13→12
5689 measured reflections	l = −14→15

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)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.075	w = 1/[σ2(Fo2) + (0.0403P)2 + 0.2933P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
2024 reflections	Δρmax = 0.20 e Å−3
167 parameters	Δρmin = −0.17 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0048 (12)

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
Mn1	0.0000	0.5000	0.5000	0.02879 (15)
N1	0.24692 (16)	0.58566 (12)	0.51483 (10)	0.0273 (3)
N2	0.48208 (17)	0.58683 (13)	0.60838 (11)	0.0289 (3)
H2A	0.5580	0.5673	0.6552	0.035*
N3	0.12437 (17)	0.39115 (14)	0.62924 (11)	0.0316 (4)
N4	0.34624 (18)	0.37195 (14)	0.73441 (11)	0.0354 (4)
H4	0.4422	0.3851	0.7628	0.042*
O1	0.62726 (17)	0.39434 (14)	0.85633 (11)	0.0517 (4)
O2	0.72528 (16)	0.54524 (15)	0.76328 (11)	0.0501 (4)
O3	0.08176 (19)	0.36279 (14)	0.38200 (11)	0.0431 (4)
C1	0.3431 (2)	0.67589 (16)	0.47712 (14)	0.0322 (4)
H1	0.3136	0.7280	0.4210	0.039*
C2	0.4879 (2)	0.67729 (16)	0.53438 (14)	0.0335 (4)
H2	0.5744	0.7298	0.5250	0.040*
C3	0.3359 (2)	0.53425 (15)	0.59437 (13)	0.0248 (4)
C4	0.2721 (2)	0.43418 (15)	0.65354 (12)	0.0272 (4)
C5	0.2410 (2)	0.28425 (19)	0.76286 (16)	0.0432 (5)
H5	0.2592	0.2268	0.8166	0.052*
C6	0.1051 (2)	0.29636 (18)	0.69827 (15)	0.0403 (5)
H6	0.0128	0.2479	0.7003	0.048*
C7	0.7311 (2)	0.47488 (17)	0.84132 (14)	0.0342 (4)
C8	0.8711 (2)	0.48881 (15)	0.92349 (14)	0.0297 (4)
C9	0.8507 (2)	0.45947 (17)	1.02814 (14)	0.0337 (4)
H9	0.7504	0.4323	1.0476	0.040*
C10	0.9791 (2)	0.47042 (17)	1.10393 (14)	0.0345 (4)
H10	0.9643	0.4502	1.1739	0.041*
H3A	0.135 (3)	0.390 (3)	0.330 (2)	0.080*
H3B	0.104 (3)	0.292 (3)	0.391 (2)	0.080*

	U11	U22	U33	U12	U13	U23
Mn1	0.0234 (2)	0.0332 (2)	0.0286 (2)	−0.00110 (16)	−0.00624 (14)	0.00314 (16)
N1	0.0261 (8)	0.0281 (8)	0.0272 (7)	0.0002 (6)	−0.0017 (6)	0.0020 (6)
N2	0.0229 (8)	0.0310 (8)	0.0321 (8)	−0.0009 (6)	−0.0041 (6)	−0.0006 (6)
N3	0.0259 (8)	0.0362 (9)	0.0316 (8)	−0.0039 (7)	−0.0047 (6)	0.0066 (6)
N4	0.0290 (8)	0.0414 (9)	0.0342 (8)	−0.0042 (7)	−0.0085 (6)	0.0097 (7)
O1	0.0465 (9)	0.0514 (9)	0.0536 (9)	−0.0173 (7)	−0.0224 (7)	0.0128 (7)
O2	0.0357 (8)	0.0730 (10)	0.0397 (8)	−0.0108 (7)	−0.0124 (6)	0.0198 (7)
O3	0.0497 (9)	0.0394 (8)	0.0410 (8)	−0.0008 (7)	0.0093 (6)	−0.0038 (7)
C1	0.0342 (10)	0.0297 (10)	0.0327 (9)	0.0005 (8)	0.0015 (8)	0.0055 (8)
C2	0.0306 (10)	0.0300 (10)	0.0404 (10)	−0.0061 (8)	0.0045 (8)	0.0008 (8)
C3	0.0229 (9)	0.0249 (9)	0.0261 (8)	0.0011 (7)	−0.0007 (7)	−0.0022 (7)
C4	0.0260 (9)	0.0291 (9)	0.0261 (9)	0.0005 (7)	−0.0026 (7)	0.0014 (7)
C5	0.0409 (11)	0.0451 (12)	0.0426 (11)	−0.0073 (9)	−0.0056 (9)	0.0216 (9)
C6	0.0327 (10)	0.0434 (12)	0.0439 (11)	−0.0111 (9)	−0.0035 (8)	0.0144 (9)
C7	0.0289 (10)	0.0397 (11)	0.0331 (10)	−0.0006 (8)	−0.0055 (8)	−0.0006 (8)
C8	0.0299 (10)	0.0273 (9)	0.0308 (9)	0.0027 (7)	−0.0066 (7)	−0.0007 (7)
C9	0.0268 (10)	0.0384 (10)	0.0354 (10)	−0.0015 (8)	−0.0021 (7)	0.0008 (8)
C10	0.0354 (11)	0.0398 (11)	0.0274 (9)	−0.0008 (8)	−0.0026 (8)	0.0010 (8)

Mn1—N3	2.2168 (14)	O2—C7	1.250 (2)
Mn1—N3i	2.2168 (14)	O3—H3A	0.87 (3)
Mn1—N1	2.2407 (14)	O3—H3B	0.80 (3)
Mn1—N1i	2.2407 (14)	C1—C2	1.356 (2)
Mn1—O3	2.2521 (14)	C1—H1	0.9300
Mn1—O3i	2.2521 (14)	C2—H2	0.9300
N1—C3	1.330 (2)	C3—C4	1.444 (2)
N1—C1	1.372 (2)	C5—C6	1.350 (3)
N2—C3	1.338 (2)	C5—H5	0.9300
N2—C2	1.364 (2)	C6—H6	0.9300
N2—H2A	0.8600	C7—C8	1.510 (2)
N3—C4	1.324 (2)	C8—C10ii	1.383 (3)
N3—C6	1.370 (2)	C8—C9	1.386 (3)
N4—C4	1.341 (2)	C9—C10	1.386 (2)
N4—C5	1.358 (2)	C9—H9	0.9300
N4—H4	0.8600	C10—C8ii	1.383 (3)
O1—C7	1.252 (2)	C10—H10	0.9300
N3—Mn1—N3i	180.0	C2—C1—N1	109.46 (15)
N3—Mn1—N1	77.77 (5)	C2—C1—H1	125.3
N3i—Mn1—N1	102.23 (5)	N1—C1—H1	125.3
N3—Mn1—N1i	102.23 (5)	C1—C2—N2	106.73 (15)
N3i—Mn1—N1i	77.77 (5)	C1—C2—H2	126.6
N1—Mn1—N1i	180.00 (6)	N2—C2—H2	126.6
N3—Mn1—O3	89.42 (6)	N1—C3—N2	111.53 (15)
N3i—Mn1—O3	90.58 (6)	N1—C3—C4	120.62 (15)
N1—Mn1—O3	91.08 (5)	N2—C3—C4	127.86 (15)
N1i—Mn1—O3	88.92 (5)	N3—C4—N4	111.31 (15)
N3—Mn1—O3i	90.58 (6)	N3—C4—C3	120.73 (15)
N3i—Mn1—O3i	89.42 (6)	N4—C4—C3	127.95 (15)
N1—Mn1—O3i	88.92 (5)	C6—C5—N4	106.95 (16)
N1i—Mn1—O3i	91.08 (5)	C6—C5—H5	126.5
O3—Mn1—O3i	180.00 (5)	N4—C5—H5	126.5
C3—N1—C1	105.24 (14)	C5—C6—N3	109.40 (16)
C3—N1—Mn1	109.91 (11)	C5—C6—H6	125.3
C1—N1—Mn1	144.74 (11)	N3—C6—H6	125.3
C3—N2—C2	107.05 (14)	O2—C7—O1	124.18 (17)
C3—N2—H2A	126.5	O2—C7—C8	118.01 (17)
C2—N2—H2A	126.5	O1—C7—C8	117.81 (16)
C4—N3—C6	105.36 (14)	C10ii—C8—C9	119.03 (16)
C4—N3—Mn1	110.79 (11)	C10ii—C8—C7	121.06 (16)
C6—N3—Mn1	143.79 (12)	C9—C8—C7	119.91 (16)
C4—N4—C5	106.97 (15)	C8—C9—C10	120.33 (17)
C4—N4—H4	126.5	C8—C9—H9	119.8
C5—N4—H4	126.5	C10—C9—H9	119.8
Mn1—O3—H3A	117.7 (18)	C8ii—C10—C9	120.64 (17)
Mn1—O3—H3B	129 (2)	C8ii—C10—H10	119.7
H3A—O3—H3B	108 (3)	C9—C10—H10	119.7
N3—Mn1—N1—C3	−3.35 (11)	C1—N1—C3—C4	179.99 (15)
N3i—Mn1—N1—C3	176.65 (11)	Mn1—N1—C3—C4	2.77 (19)
N1i—Mn1—N1—C3	118.74 (12)	C2—N2—C3—N1	0.25 (19)
O3—Mn1—N1—C3	−92.52 (11)	C2—N2—C3—C4	−179.90 (17)
O3i—Mn1—N1—C3	87.48 (11)	C6—N3—C4—N4	−0.3 (2)
N3—Mn1—N1—C1	−178.7 (2)	Mn1—N3—C4—N4	177.63 (11)
N3i—Mn1—N1—C1	1.3 (2)	C6—N3—C4—C3	178.54 (16)
N1i—Mn1—N1—C1	−56.59 (18)	Mn1—N3—C4—C3	−3.5 (2)
O3—Mn1—N1—C1	92.1 (2)	C5—N4—C4—N3	0.4 (2)
O3i—Mn1—N1—C1	−87.9 (2)	C5—N4—C4—C3	−178.38 (18)
N3i—Mn1—N3—C4	−180 (81)	N1—C3—C4—N3	0.5 (3)
N1—Mn1—N3—C4	3.61 (11)	N2—C3—C4—N3	−179.33 (16)
N1i—Mn1—N3—C4	−176.39 (11)	N1—C3—C4—N4	179.15 (16)
O3—Mn1—N3—C4	94.84 (12)	N2—C3—C4—N4	−0.7 (3)
O3i—Mn1—N3—C4	−85.16 (12)	C4—N4—C5—C6	−0.3 (2)
N3i—Mn1—N3—C6	−3 (81)	N4—C5—C6—N3	0.1 (2)
N1—Mn1—N3—C6	−179.8 (2)	C4—N3—C6—C5	0.1 (2)
N1i—Mn1—N3—C6	0.2 (2)	Mn1—N3—C6—C5	−176.60 (16)
O3—Mn1—N3—C6	−88.5 (2)	O2—C7—C8—C10ii	−30.4 (3)
O3i—Mn1—N3—C6	91.5 (2)	O1—C7—C8—C10ii	150.38 (18)
C3—N1—C1—C2	0.00 (19)	O2—C7—C8—C9	150.21 (18)
Mn1—N1—C1—C2	175.45 (14)	O1—C7—C8—C9	−29.0 (3)
N1—C1—C2—N2	0.1 (2)	C10ii—C8—C9—C10	−0.3 (3)
C3—N2—C2—C1	−0.24 (19)	C7—C8—C9—C10	179.15 (17)
C1—N1—C3—N2	−0.15 (18)	C8—C9—C10—C8ii	0.3 (3)
Mn1—N1—C3—N2	−177.37 (11)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O1iii	0.80 (3)	2.09 (3)	2.850 (2)	159 (3)
O3—H3A···O2iv	0.87 (3)	1.85 (3)	2.711 (2)	170 (3)
N4—H4···O1	0.86	1.87	2.7101 (19)	165
N2—H2A···O2	0.86	1.89	2.7482 (19)	173

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯O1i	0.80 (3)	2.09 (3)	2.850 (2)	159 (3)
O3—H3A⋯O2ii	0.87 (3)	1.85 (3)	2.711 (2)	170 (3)
N4—H4⋯O1	0.86	1.87	2.7101 (19)	165
N2—H2A⋯O2	0.86	1.89	2.7482 (19)	173

Symmetry codes: (i) ; (ii) .