catena-Poly[[[aqua-(formato-κO)(1,10-phenanthroline-κN,N')manganese(II)]-μ-formato-κO:O'] monohydrate].

The title compound, {[Mn(HCOO)(2)(C(12)H(8)N(2))(H(2)O)]·H(2)O}(n), consists of polymeric chains of the complex [Mn(HCOO)(2)(phen)(H(2)O)](∞) (phen is 1,10-phenanthroline) with solvent water mol-ecules. The chains contain six-coordinate Mn(II) ions bridged by formate anions. They are further extended into a three-dimensional network via O-H⋯O hydrogen-bonding inter-actions and inter-chain π-π stacking inter-actions, with a centroid-centroid distance of 3.679 (4) Å.

Related literature

For the design and synthesis of coordination polymer complexes and their potential applications, see: Robin & Fromm (2006 ▶); Farrusseng et al. (2008 ▶); Chen et al. (2010 ▶). For the formate anion as a ligand, see: Yuan et al. (2008 ▶); Hagen et al. (2009 ▶); Hu et al. (2009 ▶); Paredes-Gaecía (2009 ▶). For a related structure, see: Janiak (2000 ▶).

Experimental

Crystal data

[Mn(HCO2)2(C12H8N2)(H2O)]·H2O

M = 361.21

Orthorhombic,

a = 19.260 (4) Å

b = 12.161 (2) Å

c = 6.5493 (13) Å

V = 1534.0 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.89 mm−1

T = 295 K

0.31 × 0.12 × 0.09 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.664, T max = 0.791

11493 measured reflections

2644 independent reflections

1921 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.111

S = 1.20

2644 reflections

209 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.70 e Å−3

Δρmin = −0.93 e Å−3

Absolute structure: Flack (1983 ▶), 1165 Friedel pairs

Flack parameter: 0.01 (4)

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); 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) global, I. DOI: 10.1107/S1600536811020575/fj2422sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811020575/fj2422Isup2.hkl

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

[Mn(HCO2)2(C12H8N2)(H2O)]·H2O	F(000) = 740
Mr = 361.21	Dx = 1.564 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 8376 reflections
a = 19.260 (4) Å	θ = 3.4–27.4°
b = 12.161 (2) Å	µ = 0.89 mm−1
c = 6.5493 (13) Å	T = 295 K
V = 1534.0 (5) Å3	Needle, yellow
Z = 4	0.31 × 0.12 × 0.09 mm

Rigaku R-AXIS RAPID diffractometer	2644 independent reflections
Radiation source: fine-focus sealed tube	1921 reflections with I > 2σ(I)
graphite	Rint = 0.047
ω scans	θmax = 25.0°, θmin = 3.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −22→22
Tmin = 0.664, Tmax = 0.791	k = −14→14
11493 measured reflections	l = −7→7

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.037	w = 1/[σ2(Fo2) + (0.0135P)2 + 2.7605P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.111	(Δ/σ)max < 0.001
S = 1.20	Δρmax = 0.70 e Å−3
2644 reflections	Δρmin = −0.93 e Å−3
209 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraint	Extinction coefficient: 0.0025 (6)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1165 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.01 (4)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2σ(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	0.57992 (4)	0.37155 (6)	0.67916 (16)	0.0454 (3)
N1	0.6768 (3)	0.3026 (4)	0.5202 (9)	0.0525 (13)
N2	0.6704 (2)	0.4167 (4)	0.8785 (8)	0.0470 (12)
C1	0.6796 (4)	0.2444 (5)	0.3480 (10)	0.068 (2)
H1A	0.6385	0.2277	0.2802	0.082*
C2	0.7429 (5)	0.2076 (6)	0.2658 (13)	0.087 (3)
H2A	0.7435	0.1662	0.1464	0.105*
C3	0.8034 (5)	0.2333 (7)	0.3629 (15)	0.091 (3)
H3A	0.8455	0.2099	0.3084	0.110*
C4	0.8027 (4)	0.2946 (6)	0.5440 (13)	0.073 (2)
C5	0.8643 (4)	0.3266 (7)	0.6559 (18)	0.093 (3)
H5A	0.9077	0.3074	0.6049	0.112*
C6	0.8603 (4)	0.3828 (8)	0.8299 (16)	0.096 (3)
H6A	0.9010	0.4006	0.8988	0.116*
C7	0.7958 (3)	0.4161 (6)	0.9127 (12)	0.067 (2)
C8	0.7882 (4)	0.4722 (7)	1.0989 (12)	0.079 (3)
H8A	0.8274	0.4906	1.1742	0.095*
C9	0.7246 (4)	0.4999 (5)	1.1701 (14)	0.0725 (19)
H9A	0.7197	0.5372	1.2932	0.087*
C10	0.6668 (4)	0.4714 (5)	1.0556 (11)	0.0600 (17)
H10A	0.6233	0.4913	1.1043	0.072*
C11	0.7335 (3)	0.3880 (5)	0.8082 (10)	0.0513 (16)
C12	0.7379 (3)	0.3280 (5)	0.6200 (10)	0.0553 (19)
C13	0.5493 (3)	0.5910 (5)	0.4494 (9)	0.0508 (15)
H13	0.5562	0.6662	0.4325	0.061*
O1	0.5939 (2)	0.5392 (3)	0.5480 (7)	0.0537 (11)
O2	0.4966 (2)	0.5501 (3)	0.3718 (7)	0.0599 (12)
C14	0.5604 (4)	0.1288 (6)	0.7827 (12)	0.071 (2)
H14	0.5642	0.1173	0.6428	0.086*
O3	0.5629 (3)	0.2210 (4)	0.8388 (7)	0.0747 (14)
O4	0.5534 (4)	0.0457 (4)	0.8904 (10)	0.112 (2)
O5	0.5090 (2)	0.3307 (3)	0.4372 (7)	0.0719 (14)
H5B	0.4990	0.3890	0.3784	0.108*
H5C	0.5014	0.2710	0.3749	0.108*
O6	0.4906 (3)	0.1479 (4)	0.2384 (9)	0.115 (2)
H6B	0.4780	0.0927	0.3042	0.173*
H6C	0.5237	0.1210	0.1706	0.173*

	U11	U22	U33	U12	U13	U23
Mn1	0.0384 (4)	0.0469 (4)	0.0509 (5)	0.0040 (4)	0.0029 (6)	−0.0014 (6)
N1	0.052 (3)	0.052 (3)	0.054 (3)	0.013 (2)	0.016 (3)	0.008 (3)
N2	0.039 (3)	0.053 (3)	0.049 (3)	0.005 (2)	0.002 (2)	0.004 (3)
C1	0.094 (6)	0.053 (4)	0.056 (4)	0.020 (4)	0.035 (4)	−0.002 (4)
C2	0.129 (8)	0.061 (4)	0.073 (5)	0.023 (5)	0.050 (6)	0.012 (4)
C3	0.096 (7)	0.075 (6)	0.103 (7)	0.043 (5)	0.049 (6)	0.036 (6)
C4	0.062 (5)	0.080 (5)	0.078 (5)	0.021 (4)	0.030 (4)	0.041 (4)
C5	0.039 (4)	0.129 (7)	0.112 (8)	0.019 (4)	0.019 (5)	0.063 (8)
C6	0.050 (5)	0.133 (9)	0.106 (8)	−0.001 (5)	−0.002 (5)	0.059 (7)
C7	0.043 (4)	0.078 (5)	0.078 (6)	−0.007 (4)	−0.011 (4)	0.040 (4)
C8	0.075 (5)	0.083 (5)	0.081 (6)	−0.026 (4)	−0.036 (4)	0.033 (4)
C9	0.082 (5)	0.069 (4)	0.066 (4)	−0.018 (4)	−0.029 (5)	0.013 (5)
C10	0.069 (5)	0.058 (4)	0.053 (4)	−0.001 (4)	−0.005 (4)	0.005 (3)
C11	0.045 (4)	0.057 (4)	0.051 (4)	0.005 (3)	0.003 (3)	0.023 (3)
C12	0.040 (4)	0.057 (4)	0.068 (5)	0.017 (3)	0.011 (3)	0.024 (3)
C13	0.047 (4)	0.047 (4)	0.058 (4)	0.000 (3)	−0.007 (3)	0.013 (3)
O1	0.047 (2)	0.049 (2)	0.065 (3)	−0.0018 (19)	−0.016 (2)	0.008 (2)
O2	0.050 (3)	0.052 (3)	0.078 (3)	0.004 (2)	−0.019 (2)	0.008 (2)
C14	0.090 (6)	0.048 (4)	0.076 (5)	0.019 (4)	0.024 (4)	0.015 (4)
O3	0.090 (4)	0.058 (3)	0.075 (4)	0.005 (3)	0.021 (3)	0.002 (3)
O4	0.164 (6)	0.056 (3)	0.117 (5)	0.008 (4)	0.023 (5)	0.024 (4)
O5	0.085 (4)	0.048 (3)	0.082 (3)	0.000 (2)	−0.032 (3)	0.001 (2)
O6	0.165 (6)	0.085 (4)	0.095 (5)	−0.030 (4)	0.028 (4)	−0.033 (3)

Mn1—O3	2.134 (5)	C6—H6A	0.9300
Mn1—O5	2.150 (4)	C7—C8	1.405 (11)
Mn1—O2i	2.161 (4)	C7—C11	1.422 (9)
Mn1—O1	2.228 (4)	C8—C9	1.353 (10)
Mn1—N2	2.246 (5)	C8—H8A	0.9300
Mn1—N1	2.295 (5)	C9—C10	1.385 (9)
N1—C1	1.333 (8)	C9—H9A	0.9300
N1—C12	1.382 (8)	C10—H10A	0.9300
N2—C10	1.339 (9)	C11—C12	1.435 (9)
N2—C11	1.346 (7)	C13—O2	1.240 (7)
C1—C2	1.406 (10)	C13—O1	1.245 (7)
C1—H1A	0.9300	C13—H13	0.9300
C2—C3	1.364 (11)	O2—Mn1ii	2.161 (4)
C2—H2A	0.9300	C14—O3	1.180 (8)
C3—C4	1.401 (12)	C14—O4	1.240 (8)
C3—H3A	0.9300	C14—H14	0.9300
C4—C12	1.403 (9)	O5—H5B	0.8290
C4—C5	1.448 (12)	O5—H5C	0.8460
C5—C6	1.331 (13)	O6—H6B	0.8339
C5—H5A	0.9300	O6—H6C	0.8420
C6—C7	1.414 (11)
O3—Mn1—O5	93.75 (19)	C4—C5—H5A	119.2
O3—Mn1—O2i	89.28 (17)	C5—C6—C7	121.8 (9)
O5—Mn1—O2i	95.71 (18)	C5—C6—H6A	119.1
O3—Mn1—O1	172.92 (19)	C7—C6—H6A	119.1
O5—Mn1—O1	90.21 (16)	C8—C7—C6	124.3 (8)
O2i—Mn1—O1	84.49 (17)	C8—C7—C11	116.5 (7)
O3—Mn1—N2	92.55 (19)	C6—C7—C11	119.1 (8)
O5—Mn1—N2	167.9 (2)	C9—C8—C7	121.0 (7)
O2i—Mn1—N2	94.70 (18)	C9—C8—H8A	119.5
O1—Mn1—N2	84.64 (16)	C7—C8—H8A	119.5
O3—Mn1—N1	91.92 (18)	C8—C9—C10	118.6 (8)
O5—Mn1—N1	95.6 (2)	C8—C9—H9A	120.7
O2i—Mn1—N1	168.5 (2)	C10—C9—H9A	120.7
O1—Mn1—N1	93.53 (17)	N2—C10—C9	123.5 (7)
N2—Mn1—N1	73.86 (18)	N2—C10—H10A	118.3
C1—N1—C12	119.0 (6)	C9—C10—H10A	118.3
C1—N1—Mn1	127.6 (5)	N2—C11—C7	122.3 (7)
C12—N1—Mn1	113.4 (4)	N2—C11—C12	118.6 (6)
C10—N2—C11	118.2 (6)	C7—C11—C12	119.0 (6)
C10—N2—Mn1	125.8 (4)	N1—C12—C4	121.7 (7)
C11—N2—Mn1	116.0 (4)	N1—C12—C11	118.0 (6)
N1—C1—C2	121.9 (8)	C4—C12—C11	120.3 (7)
N1—C1—H1A	119.1	O2—C13—O1	125.0 (6)
C2—C1—H1A	119.1	O2—C13—H13	117.5
C3—C2—C1	119.3 (8)	O1—C13—H13	117.5
C3—C2—H2A	120.3	C13—O1—Mn1	125.5 (4)
C1—C2—H2A	120.3	C13—O2—Mn1ii	128.4 (4)
C2—C3—C4	120.5 (8)	O3—C14—O4	127.0 (8)
C2—C3—H3A	119.7	O3—C14—H14	116.5
C4—C3—H3A	119.7	O4—C14—H14	116.5
C3—C4—C12	117.6 (8)	C14—O3—Mn1	131.9 (5)
C3—C4—C5	124.3 (8)	Mn1—O5—H5B	107.1
C12—C4—C5	118.1 (8)	Mn1—O5—H5C	131.6
C6—C5—C4	121.6 (8)	H5B—O5—H5C	118.0
C6—C5—H5A	119.2	H6B—O6—H6C	100.5

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O2	0.83	1.96	2.713 (5)	150
O5—H5C···O6	0.85	1.76	2.601 (6)	177
O6—H6B···O4iii	0.83	1.88	2.693 (8)	166
O6—H6C···O4iv	0.83	2.13	2.864 (9)	145

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5B⋯O2	0.83	1.96	2.713 (5)	150
O5—H5C⋯O6	0.85	1.76	2.601 (6)	177
O6—H6B⋯O4i	0.83	1.88	2.693 (8)	166
O6—H6C⋯O4ii	0.83	2.13	2.864 (9)	145

Symmetry codes: (i) ; (ii) .