Tetra-aqua-bis-[3-(pyridin-4-yl)benzoato-κN]manganese(II).

In the title compound, [Mn(C(12)H(8)NO(2))(2)(H(2)O)(4)], the Mn(2+) ion lies on a twofold rotation axis and has a distorted N(2)O(4) octa-hedral coordination geometry formed by four water O atoms in the equatorial plane and two apical pyridyl N atoms. A three-dimensional network is formed in the crystal structure by multiple O-H⋯O hydrogen bonds between the coordin-ating water molecules and the free carboxylate groups.

Related literature

For pyrid­yl–multicarboxyl­ate–metal frameworks, see: Huang et al. (2007 ▶). For 3-pyridin-4-yl­benzo­ate compounds, see: Wu et al. (2011 ▶) For the isotypic Co complex, see: Wang & Li (2011 ▶).

Experimental

Crystal data

[Mn(C12H8NO2)2(H2O)4]

M = 523.39

Monoclinic,

a = 24.935 (3) Å

b = 7.1911 (6) Å

c = 13.9283 (16) Å

β = 112.199 (13)°

V = 2312.4 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.63 mm−1

T = 293 K

0.24 × 0.20 × 0.16 mm

Data collection

Siemens SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.875, T max = 0.913

4456 measured reflections

2035 independent reflections

1673 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.079

S = 1.05

2035 reflections

171 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.19 e Å−3

Δρmin = −0.20 e Å−3

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1994 ▶); data reduction: SAINT; 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812014602/bt5868sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014602/bt5868Isup2.hkl

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

[Mn(C12H8NO2)2(H2O)4]	F(000) = 1084
Mr = 523.39	Dx = 1.503 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1769 reflections
a = 24.935 (3) Å	θ = 3.0–27.6°
b = 7.1911 (6) Å	µ = 0.63 mm−1
c = 13.9283 (16) Å	T = 293 K
β = 112.199 (13)°	Needle, yellow
V = 2312.4 (4) Å3	0.24 × 0.20 × 0.16 mm
Z = 4

Siemens SMART CCD diffractometer	2035 independent reflections
Radiation source: fine-focus sealed tube	1673 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω scan	θmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −29→29
Tmin = 0.875, Tmax = 0.913	k = −5→8
4456 measured reflections	l = −16→16

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0389P)2] where P = (Fo2 + 2Fc2)/3
2035 reflections	(Δ/σ)max < 0.001
171 parameters	Δρmax = 0.19 e Å−3
0 restraints	Δρmin = −0.20 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
Mn1	0.0000	0.30640 (6)	0.7500	0.03055 (16)
O1	0.46120 (6)	0.2912 (2)	0.87784 (13)	0.0494 (4)
O2	0.40494 (7)	0.2263 (2)	0.96408 (12)	0.0557 (5)
O3	0.03234 (7)	0.5054 (2)	0.87792 (12)	0.0434 (4)
O4	−0.02832 (7)	0.0811 (2)	0.63641 (12)	0.0414 (4)
N1	0.08789 (7)	0.3200 (2)	0.73735 (13)	0.0343 (4)
C1	0.41251 (9)	0.2746 (3)	0.88379 (18)	0.0373 (5)
C2	0.35888 (8)	0.3161 (3)	0.78874 (16)	0.0307 (5)
C3	0.30485 (8)	0.3071 (3)	0.79533 (16)	0.0304 (4)
H3	0.3024	0.2747	0.8597	0.036*
C4	0.25382 (8)	0.3442 (3)	0.71007 (15)	0.0296 (5)
C5	0.25909 (9)	0.3921 (3)	0.61674 (16)	0.0372 (5)
H5	0.2253	0.4182	0.5574	0.045*
C6	0.31246 (9)	0.4019 (3)	0.60960 (16)	0.0422 (6)
H6	0.3151	0.4351	0.5455	0.051*
C7	0.36272 (9)	0.3639 (3)	0.69523 (17)	0.0372 (5)
H7	0.3995	0.3707	0.6895	0.045*
C8	0.19674 (8)	0.3344 (3)	0.71925 (15)	0.0294 (5)
C9	0.19034 (9)	0.3677 (3)	0.81302 (16)	0.0368 (5)
H9	0.2233	0.3967	0.8732	0.044*
C10	0.13683 (9)	0.3587 (3)	0.81876 (17)	0.0384 (5)
H10	0.1341	0.3812	0.8840	0.046*
C11	0.09364 (9)	0.2880 (3)	0.64725 (17)	0.0362 (5)
H11	0.0598	0.2597	0.5884	0.043*
C12	0.14589 (9)	0.2939 (3)	0.63492 (16)	0.0364 (5)
H12	0.1473	0.2703	0.5688	0.044*
H3A	0.0499 (10)	0.451 (3)	0.9365 (18)	0.055*
H4A	−0.0072 (10)	−0.013 (3)	0.6343 (18)	0.055*
H3B	0.0120 (11)	0.588 (3)	0.8818 (18)	0.055*
H4B	−0.0448 (10)	0.126 (3)	0.5770 (19)	0.055*

	U11	U22	U33	U12	U13	U23
Mn1	0.0213 (3)	0.0359 (3)	0.0354 (3)	0.000	0.0119 (2)	0.000
O1	0.0229 (8)	0.0438 (9)	0.0791 (12)	−0.0003 (7)	0.0165 (8)	0.0015 (8)
O2	0.0358 (9)	0.0824 (12)	0.0427 (9)	−0.0011 (8)	0.0076 (8)	0.0058 (9)
O3	0.0351 (10)	0.0453 (10)	0.0458 (10)	0.0083 (7)	0.0107 (8)	−0.0068 (8)
O4	0.0409 (10)	0.0388 (9)	0.0435 (9)	0.0052 (7)	0.0147 (8)	−0.0010 (7)
N1	0.0263 (9)	0.0370 (10)	0.0409 (10)	0.0025 (8)	0.0139 (8)	0.0045 (8)
C1	0.0272 (12)	0.0313 (11)	0.0493 (13)	−0.0015 (10)	0.0098 (10)	−0.0065 (10)
C2	0.0238 (11)	0.0273 (10)	0.0420 (12)	−0.0025 (9)	0.0136 (9)	−0.0063 (9)
C3	0.0271 (11)	0.0300 (10)	0.0365 (11)	−0.0015 (9)	0.0149 (9)	−0.0028 (9)
C4	0.0254 (11)	0.0277 (11)	0.0388 (11)	−0.0013 (9)	0.0157 (9)	−0.0013 (9)
C5	0.0293 (12)	0.0440 (12)	0.0368 (12)	−0.0019 (10)	0.0110 (10)	0.0020 (10)
C6	0.0404 (14)	0.0547 (14)	0.0383 (12)	−0.0023 (12)	0.0227 (11)	0.0028 (11)
C7	0.0294 (12)	0.0384 (12)	0.0508 (13)	−0.0050 (10)	0.0229 (11)	−0.0056 (10)
C8	0.0248 (11)	0.0276 (11)	0.0373 (11)	0.0021 (9)	0.0134 (9)	0.0050 (9)
C9	0.0255 (11)	0.0453 (12)	0.0387 (12)	−0.0006 (10)	0.0110 (10)	−0.0005 (10)
C10	0.0287 (12)	0.0524 (13)	0.0366 (11)	0.0023 (10)	0.0152 (10)	0.0000 (10)
C11	0.0241 (11)	0.0423 (12)	0.0398 (12)	0.0009 (10)	0.0094 (9)	0.0006 (10)
C12	0.0295 (12)	0.0443 (12)	0.0377 (11)	0.0001 (10)	0.0154 (10)	−0.0011 (10)

Mn1—O4	2.1867 (16)	C3—C4	1.400 (3)
Mn1—O4i	2.1867 (16)	C3—H3	0.9500
Mn1—O3	2.1878 (16)	C4—C5	1.398 (3)
Mn1—O3i	2.1878 (16)	C4—C8	1.478 (3)
Mn1—N1	2.2661 (16)	C5—C6	1.373 (3)
Mn1—N1i	2.2661 (16)	C5—H5	0.9500
O1—C1	1.253 (2)	C6—C7	1.392 (3)
O2—C1	1.252 (3)	C6—H6	0.9500
O3—H3A	0.86 (2)	C7—H7	0.9500
O3—H3B	0.80 (2)	C8—C9	1.395 (3)
O4—H4A	0.86 (3)	C8—C12	1.395 (3)
O4—H4B	0.84 (2)	C9—C10	1.368 (3)
N1—C11	1.336 (3)	C9—H9	0.9500
N1—C10	1.344 (3)	C10—H10	0.9500
C1—C2	1.514 (3)	C11—C12	1.378 (3)
C2—C7	1.385 (3)	C11—H11	0.9500
C2—C3	1.386 (3)	C12—H12	0.9500
O4—Mn1—O4i	84.40 (9)	C2—C3—C4	121.98 (18)
O4—Mn1—O3	173.04 (6)	C2—C3—H3	119.0
O4i—Mn1—O3	88.64 (6)	C4—C3—H3	119.0
O4—Mn1—O3i	88.64 (6)	C5—C4—C3	117.47 (18)
O4i—Mn1—O3i	173.04 (6)	C5—C4—C8	121.60 (18)
O3—Mn1—O3i	98.31 (10)	C3—C4—C8	120.92 (18)
O4—Mn1—N1	91.89 (6)	C6—C5—C4	120.93 (19)
O4i—Mn1—N1	91.76 (6)	C6—C5—H5	119.5
O3—Mn1—N1	88.02 (6)	C4—C5—H5	119.5
O3i—Mn1—N1	88.75 (6)	C5—C6—C7	120.74 (19)
O4—Mn1—N1i	91.76 (6)	C5—C6—H6	119.6
O4i—Mn1—N1i	91.89 (6)	C7—C6—H6	119.6
O3—Mn1—N1i	88.75 (6)	C2—C7—C6	119.66 (19)
O3i—Mn1—N1i	88.02 (6)	C2—C7—H7	120.2
N1—Mn1—N1i	175.06 (8)	C6—C7—H7	120.2
Mn1—O3—H3A	112.0 (16)	C9—C8—C12	115.78 (18)
Mn1—O3—H3B	119.7 (18)	C9—C8—C4	121.83 (18)
H3A—O3—H3B	113 (2)	C12—C8—C4	122.39 (18)
Mn1—O4—H4A	124.7 (16)	C10—C9—C8	120.39 (19)
Mn1—O4—H4B	109.7 (17)	C10—C9—H9	119.8
H4A—O4—H4B	110 (2)	C8—C9—H9	119.8
C11—N1—C10	116.28 (18)	N1—C10—C9	123.71 (19)
C11—N1—Mn1	121.06 (14)	N1—C10—H10	118.1
C10—N1—Mn1	122.66 (14)	C9—C10—H10	118.1
O2—C1—O1	124.2 (2)	N1—C11—C12	123.65 (19)
O2—C1—C2	117.03 (19)	N1—C11—H11	118.2
O1—C1—C2	118.8 (2)	C12—C11—H11	118.2
C7—C2—C3	119.22 (19)	C11—C12—C8	120.20 (19)
C7—C2—C1	121.28 (19)	C11—C12—H12	119.9
C3—C2—C1	119.50 (18)	C8—C12—H12	119.9

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2ii	0.86 (2)	1.91 (2)	2.732 (2)	160 (2)
O3—H3B···O1iii	0.80 (2)	1.92 (3)	2.715 (2)	175 (2)
O4—H4A···O1iv	0.86 (3)	1.86 (3)	2.728 (2)	176 (2)
O4—H4B···O2v	0.84 (2)	1.92 (2)	2.726 (2)	161 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O2i	0.86 (2)	1.91 (2)	2.732 (2)	160 (2)
O3—H3B⋯O1ii	0.80 (2)	1.92 (3)	2.715 (2)	175 (2)
O4—H4A⋯O1iii	0.86 (3)	1.86 (3)	2.728 (2)	176 (2)
O4—H4B⋯O2iv	0.84 (2)	1.92 (2)	2.726 (2)	161 (2)

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