Crystal structure of bis-(acetato-κO)di-aqua-(2,2'-bi-pyridine-κ(2) N,N')manganese(II).

In the title monomeric manganese(II) complex, [Mn(CH3COO)2(C10H8N2)(H2O)2], the metal ion is coordinated by a bidentate 2,2'-bi-pyridine (bpy) ligand, two water mol-ecules and two axial acetate anions, resulting in a highly distorted octa-hedral environment. The aqua ligands are stabilized by the formation of strong intra-molecular hydrogen bonds with the uncoordinated acetate O atoms, giving rise to pseudo-bridging arrangement of the terminal acetate groups. In the crystal, the mol-ecules form [010] zigzag chains via O-H⋯O hydrogen bonds involving the aqua ligands and acetate O atoms. Further, the water and bpy ligands are trans to each other, and are arranged in an off-set fashion showing inter-molecular π-π stacking between nearly parallel bi-py rings, the centroid-centroid separations being 3.8147 (12) and 3.9305 (13) Å.

Related literature

For complexes with the same ligands as the title complex, see: Chen et al. (1995 ▶); Carballo et al. (2001 ▶); Hu et al. (2011 ▶); Ye et al. (1998 ▶); Zhao et al. (2009 ▶). For ionic radii, see: Shannon (1976 ▶).

Experimental

Crystal data

[Mn(C2H3O2)2(C10H8N2)(n class="Chemical">H2O)2]

M = 365.24

Monoclinic,

a = 12.8494 (8) Å

b = 8.1434 (5) Å

c = 15.5918 (10) Å

β = 98.926 (2)°

V = 1611.73 (18) Å3

Z = 4

Mo Kα radiation

μ = 0.85 mm−1

T = 296 K

0.30 × 0.25 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.775, T max = 0.873

11092 measured reflections

2820 independent reflections

2469 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.076

S = 1.06

2820 reflections

226 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.26 e Å−3

Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAIn class="Chemical">NT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814017814/gw2147sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814017814/gw2147Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814017814/gw2147Isup3.cdx

Click here for additional data file.

ORTEP . DOI: 10.1107/S1600536814017814/gw2147fig1.tif

ORTEP of the mol­ecule with atoms represented as 30% probability ellipsoids.

Click here for additional data file.

b . DOI: 10.1107/S1600536814017814/gw2147fig2.tif

Mol­ecular packing of complex 1 viewed along b axis.

CCDC reference: 1006361

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Mn(C2H3O2)2(C10H8N2)(H2O)2]	F(000) = 756
Mr = 365.24	Dx = 1.505 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.8494 (8) Å	Cell parameters from 6258 reflections
b = 8.1434 (5) Å	θ = 2.2–28.2°
c = 15.5918 (10) Å	µ = 0.85 mm−1
β = 98.926 (2)°	T = 296 K
V = 1611.73 (18) Å3	Rectangular, brown
Z = 4	0.30 × 0.25 × 0.16 mm

Bruker APEXII CCD diffractometer	2469 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.023
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θmax = 25.0°, θmin = 1.9°
Tmin = 0.775, Tmax = 0.873	h = −15→15
11092 measured reflections	k = −9→8
2820 independent reflections	l = −18→18

Refinement on F2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.029	w = 1/[σ2(Fo2) + (0.0349P)2 + 0.7672P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.076	(Δ/σ)max = 0.001
S = 1.06	Δρmax = 0.26 e Å−3
2820 reflections	Δρmin = −0.21 e Å−3
226 parameters

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.

	x	y	z	Uiso*/Ueq
C1	0.40953 (16)	0.3913 (3)	1.13971 (13)	0.0389 (5)
H1	0.3553	0.4152	1.1709	0.047*
C2	0.51018 (17)	0.4448 (3)	1.17221 (15)	0.0476 (6)
H2	0.5238	0.5018	1.2244	0.057*
C3	0.58959 (17)	0.4107 (3)	1.12467 (15)	0.0501 (6)
H3	0.6579	0.4469	1.1439	0.060*
C4	0.56718 (15)	0.3231 (3)	1.04872 (14)	0.0428 (5)
H4	0.6203	0.2987	1.0165	0.051*
C5	0.46481 (14)	0.2714 (2)	1.02057 (13)	0.0316 (4)
C6	0.43430 (14)	0.1760 (3)	0.93939 (12)	0.0327 (4)
C7	0.50731 (16)	0.1105 (3)	0.89147 (14)	0.0437 (6)
H7	0.5791	0.1244	0.9102	0.052*
C8	0.47254 (19)	0.0249 (3)	0.81621 (15)	0.0506 (6)
H8	0.5206	−0.0184	0.7835	0.061*
C9	0.36604 (19)	0.0042 (3)	0.78996 (14)	0.0500 (6)
H9	0.3408	−0.0529	0.7393	0.060*
C10	0.29791 (17)	0.0702 (3)	0.84067 (13)	0.0434 (5)
H10	0.2260	0.0555	0.8233	0.052*
C11	0.11250 (15)	0.5562 (3)	0.92173 (12)	0.0327 (5)
C12	0.11895 (19)	0.7383 (3)	0.90939 (18)	0.0539 (6)
H12A	0.0999	0.7643	0.8489	0.081*
H12B	0.1896	0.7748	0.9293	0.081*
H12C	0.0715	0.7924	0.9421	0.081*
C13	0.18311 (15)	−0.0662 (3)	1.12096 (13)	0.0358 (5)
C14	0.21073 (19)	−0.2375 (3)	1.15213 (17)	0.0507 (6)
H14A	0.2282	−0.3022	1.1049	0.076*
H14B	0.1516	−0.2858	1.1736	0.076*
H14C	0.2700	−0.2340	1.1979	0.076*
Mn1	0.21987 (2)	0.23631 (4)	1.00781 (2)	0.03042 (11)
N1	0.38666 (12)	0.3072 (2)	1.06586 (10)	0.0314 (4)
N2	0.32980 (12)	0.1546 (2)	0.91379 (10)	0.0341 (4)
O1	0.19541 (10)	0.48188 (18)	0.95383 (9)	0.0409 (4)
O2	0.08066 (12)	0.1747 (2)	0.91193 (12)	0.0501 (4)
O3	0.14983 (11)	0.3191 (2)	1.11986 (10)	0.0396 (4)
O4	0.23998 (10)	0.00016 (18)	1.07180 (9)	0.0399 (3)
O5	0.02567 (10)	0.48655 (18)	0.89735 (10)	0.0411 (4)
O6	0.10520 (12)	0.0026 (2)	1.14539 (12)	0.0529 (4)
H2X	0.056 (2)	0.276 (4)	0.9014 (17)	0.063 (9)*
H1X	0.034 (2)	0.109 (4)	0.9040 (18)	0.070 (10)*
H4X	0.096 (2)	0.392 (4)	1.1099 (17)	0.074 (9)*
H3X	0.131 (2)	0.230 (4)	1.1320 (17)	0.054 (9)*

	U11	U22	U33	U12	U13	U23
C1	0.0341 (11)	0.0412 (13)	0.0416 (11)	−0.0004 (9)	0.0067 (9)	0.0019 (10)
C2	0.0427 (13)	0.0515 (15)	0.0458 (12)	−0.0095 (11)	−0.0023 (10)	−0.0010 (11)
C3	0.0290 (11)	0.0636 (17)	0.0547 (14)	−0.0136 (11)	−0.0033 (10)	0.0107 (12)
C4	0.0204 (9)	0.0604 (15)	0.0478 (13)	−0.0004 (10)	0.0065 (9)	0.0129 (11)
C5	0.0212 (9)	0.0355 (12)	0.0385 (11)	0.0021 (8)	0.0056 (8)	0.0123 (9)
C6	0.0247 (9)	0.0384 (12)	0.0359 (10)	0.0054 (9)	0.0074 (8)	0.0114 (9)
C7	0.0297 (11)	0.0552 (15)	0.0485 (12)	0.0116 (10)	0.0135 (9)	0.0120 (11)
C8	0.0550 (14)	0.0572 (16)	0.0443 (13)	0.0194 (12)	0.0231 (11)	0.0063 (11)
C9	0.0593 (15)	0.0561 (16)	0.0358 (11)	0.0080 (12)	0.0115 (10)	0.0001 (11)
C10	0.0378 (11)	0.0534 (15)	0.0383 (11)	−0.0008 (11)	0.0039 (9)	0.0017 (10)
C11	0.0308 (11)	0.0349 (12)	0.0335 (10)	0.0036 (9)	0.0088 (8)	0.0018 (9)
C12	0.0463 (14)	0.0355 (14)	0.0749 (17)	0.0024 (10)	−0.0067 (12)	0.0028 (12)
C13	0.0258 (10)	0.0354 (12)	0.0454 (12)	−0.0028 (9)	0.0029 (9)	0.0009 (9)
C14	0.0516 (14)	0.0412 (14)	0.0615 (15)	0.0047 (11)	0.0155 (12)	0.0103 (11)
Mn1	0.01912 (16)	0.03294 (19)	0.03953 (19)	0.00163 (12)	0.00552 (12)	0.00237 (13)
N1	0.0227 (8)	0.0343 (10)	0.0371 (9)	0.0002 (7)	0.0048 (7)	0.0050 (7)
N2	0.0268 (8)	0.0405 (11)	0.0355 (9)	0.0034 (7)	0.0065 (7)	0.0054 (8)
O1	0.0266 (7)	0.0363 (9)	0.0582 (9)	0.0029 (6)	0.0015 (6)	0.0088 (7)
O2	0.0291 (8)	0.0373 (10)	0.0783 (12)	−0.0018 (8)	−0.0089 (8)	−0.0034 (9)
O3	0.0303 (8)	0.0364 (10)	0.0546 (9)	0.0052 (8)	0.0140 (7)	0.0024 (8)
O4	0.0316 (7)	0.0356 (8)	0.0548 (9)	0.0042 (6)	0.0143 (6)	0.0086 (7)
O5	0.0268 (7)	0.0379 (9)	0.0571 (9)	0.0032 (6)	0.0024 (6)	0.0031 (7)
O6	0.0374 (8)	0.0409 (10)	0.0865 (12)	0.0016 (7)	0.0284 (8)	0.0067 (8)

C1—N1	1.333 (3)	C11—O1	1.260 (2)
C1—C2	1.384 (3)	C11—C12	1.499 (3)
C1—H1	0.9300	C12—H12A	0.9600
C2—C3	1.379 (3)	C12—H12B	0.9600
C2—H2	0.9300	C12—H12C	0.9600
C3—C4	1.374 (3)	C13—O6	1.257 (2)
C3—H3	0.9300	C13—O4	1.260 (2)
C4—C5	1.386 (3)	C13—C14	1.501 (3)
C4—H4	0.9300	C14—H14A	0.9600
C5—N1	1.346 (2)	C14—H14B	0.9600
C5—C6	1.485 (3)	C14—H14C	0.9600
C6—N2	1.351 (2)	Mn1—O4	2.1634 (15)
C6—C7	1.393 (3)	Mn1—O1	2.1736 (15)
C7—C8	1.378 (3)	Mn1—O3	2.1918 (15)
C7—H7	0.9300	Mn1—O2	2.2038 (16)
C8—C9	1.376 (3)	Mn1—N1	2.2679 (15)
C8—H8	0.9300	Mn1—N2	2.2869 (16)
C9—C10	1.377 (3)	O2—H2X	0.89 (3)
C9—H9	0.9300	O2—H1X	0.79 (3)
C10—N2	1.340 (3)	O3—H4X	0.91 (3)
C10—H10	0.9300	O3—H3X	0.80 (3)
C11—O5	1.257 (2)
N1—C1—C2	123.1 (2)	O6—C13—O4	123.9 (2)
N1—C1—H1	118.4	O6—C13—C14	118.38 (19)
C2—C1—H1	118.4	O4—C13—C14	117.72 (19)
C3—C2—C1	117.9 (2)	C13—C14—H14A	109.5
C3—C2—H2	121.1	C13—C14—H14B	109.5
C1—C2—H2	121.1	H14A—C14—H14B	109.5
C4—C3—C2	119.60 (19)	C13—C14—H14C	109.5
C4—C3—H3	120.2	H14A—C14—H14C	109.5
C2—C3—H3	120.2	H14B—C14—H14C	109.5
C3—C4—C5	119.5 (2)	O4—Mn1—O1	174.99 (5)
C3—C4—H4	120.3	O4—Mn1—O3	86.57 (6)
C5—C4—H4	120.3	O1—Mn1—O3	88.46 (6)
N1—C5—C4	121.1 (2)	O4—Mn1—O2	97.86 (7)
N1—C5—C6	116.15 (16)	O1—Mn1—O2	83.88 (6)
C4—C5—C6	122.74 (18)	O3—Mn1—O2	102.72 (6)
N2—C6—C7	120.87 (19)	O4—Mn1—N1	90.26 (6)
N2—C6—C5	115.98 (16)	O1—Mn1—N1	89.49 (6)
C7—C6—C5	123.15 (18)	O3—Mn1—N1	94.76 (6)
C8—C7—C6	119.6 (2)	O2—Mn1—N1	161.08 (6)
C8—C7—H7	120.2	O4—Mn1—N2	89.74 (6)
C6—C7—H7	120.2	O1—Mn1—N2	94.94 (6)
C9—C8—C7	119.4 (2)	O3—Mn1—N2	166.23 (6)
C9—C8—H8	120.3	O2—Mn1—N2	90.92 (6)
C7—C8—H8	120.3	N1—Mn1—N2	71.97 (6)
C8—C9—C10	118.2 (2)	C1—N1—C5	118.82 (17)
C8—C9—H9	120.9	C1—N1—Mn1	122.94 (13)
C10—C9—H9	120.9	C5—N1—Mn1	118.11 (13)
N2—C10—C9	123.5 (2)	C10—N2—C6	118.44 (17)
N2—C10—H10	118.3	C10—N2—Mn1	123.85 (13)
C9—C10—H10	118.3	C6—N2—Mn1	117.22 (13)
O5—C11—O1	124.03 (19)	C11—O1—Mn1	131.20 (13)
O5—C11—C12	118.15 (18)	Mn1—O2—H2X	98.4 (17)
O1—C11—C12	117.79 (19)	Mn1—O2—H1X	140 (2)
C11—C12—H12A	109.5	H2X—O2—H1X	111 (3)
C11—C12—H12B	109.5	Mn1—O3—H4X	117.6 (17)
H12A—C12—H12B	109.5	Mn1—O3—H3X	94.8 (19)
C11—C12—H12C	109.5	H4X—O3—H3X	113 (3)
H12A—C12—H12C	109.5	C13—O4—Mn1	128.52 (13)
H12B—C12—H12C	109.5
N1—C1—C2—C3	1.0 (4)	C2—C1—N1—Mn1	−175.33 (17)
C1—C2—C3—C4	−1.4 (4)	C4—C5—N1—C1	−1.2 (3)
C2—C3—C4—C5	0.6 (4)	C6—C5—N1—C1	179.38 (18)
C3—C4—C5—N1	0.8 (3)	C4—C5—N1—Mn1	174.66 (15)
C3—C4—C5—C6	−179.9 (2)	C6—C5—N1—Mn1	−4.7 (2)
N1—C5—C6—N2	8.5 (3)	C9—C10—N2—C6	−0.1 (3)
C4—C5—C6—N2	−170.84 (19)	C9—C10—N2—Mn1	−171.77 (17)
N1—C5—C6—C7	−171.14 (19)	C7—C6—N2—C10	−0.7 (3)
C4—C5—C6—C7	9.5 (3)	C5—C6—N2—C10	179.61 (19)
N2—C6—C7—C8	1.1 (3)	C7—C6—N2—Mn1	171.52 (16)
C5—C6—C7—C8	−179.3 (2)	C5—C6—N2—Mn1	−8.2 (2)
C6—C7—C8—C9	−0.6 (4)	O5—C11—O1—Mn1	−16.3 (3)
C7—C8—C9—C10	−0.2 (4)	C12—C11—O1—Mn1	165.72 (16)
C8—C9—C10—N2	0.5 (4)	O6—C13—O4—Mn1	−4.4 (3)
C2—C1—N1—C5	0.3 (3)	C14—C13—O4—Mn1	175.79 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1X···O6i	0.80 (3)	2.05 (3)	2.815 (2)	161 (3)
O2—H2X···O5	0.89 (3)	1.76 (3)	2.636 (2)	169 (2)
O3—H3X···O6	0.80 (3)	1.90 (3)	2.684 (2)	168 (3)
O3—H4X···O5ii	0.91 (3)	1.84 (3)	2.734 (2)	169 (3)

Table 1

Selected bond lengths (Å)

Mn1—O4	2.1634 (15)
Mn1—O1	2.1736 (15)
Mn1—O3	2.1918 (15)
Mn1—O2	2.2038 (16)
Mn1—N1	2.2679 (15)
Mn1—N2	2.2869 (16)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1X⋯O6i	0.80 (3)	2.05 (3)	2.815 (2)	161 (3)
O2—H2X⋯O5	0.89 (3)	1.76 (3)	2.636 (2)	169 (2)
O3—H3X⋯O6	0.80 (3)	1.90 (3)	2.684 (2)	168 (3)
O3—H4X⋯O5ii	0.91 (3)	1.84 (3)	2.734 (2)	169 (3)

Symmetry codes: (i) ; (ii) .