Poly[(μ₆-naphthalene-1,4-dicarboxyl­ato-κ⁶ O ¹:O ^1′:O ^1′:O ⁴:O ^4′:O ^4′)iron(II)]

Abstract

In the title compound, [Fe(C₁₂H₆O₄)]_n, the Fe^II atom is coordinated by six O atoms from six symmetrically equivalent naphthalene-1,4-dicarboxyl­ate ligands in a strongly distorted octa­hedral geometry. These octa­hedra are connected via common edges into chains that elongate along the a axis, with Fe⋯Fe distances of 2.9712 (4) and 2.9724 (4) Å. The chains are linked via the naphthalene-1,4-dicarboxyl­ate ligands into a three-dimensional coordination network.

Related literature

For isotypical structures with Mn^II and Co^II, see: Maji et al. (2005 ▶).

Experimental

Crystal data

• [Fe(C₁₂H₆O₄)]

• M _r = 270.02

• Monoclinic,

• a = 4.7863 (4) Å

• b = 14.8940 (9) Å

• c = 13.4705 (10) Å

• β = 91.098 (9)°

• V = 960.10 (12) ų

• Z = 4

• Mo Kα radiation

• μ = 1.57 mm⁻¹

• T = 170 (2) K

• 0.30 × 0.04 × 0.04 mm

Data collection

• Stoe IPDS-1 diffractometer

• Absorption correction: none

• 13722 measured reflections

• 2256 independent reflections

• 1816 reflections with I > 2σ(I)

• R _int = 0.026

Refinement

• R[F ² > 2σ(F ²)] = 0.030

• wR(F ²) = 0.087

• S = 1.06

• 2256 reflections

• 155 parameters

• H-atom parameters constrained

• Δρ_max = 0.40 e Å⁻³

• Δρ_min = −0.46 e Å⁻³

Data collection: IPDS (Stoe & Cie, 1998 ▶); cell refinement: IPDS; data reduction: IPDS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

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

Table 1. Selected bond lengths (Å).

Fe1—O3i	2.0557 (11)
Fe1—O2ii	2.0604 (11)
Fe1—O1	2.1533 (13)
Fe1—O4iii	2.1550 (13)
Fe1—O4iv	2.1867 (11)
Fe1—O1v	2.1908 (11)
Fe1—Fe1vi	2.9712 (4)
Fe1—Fe1v	2.9724 (4)

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

supplementary crystallographic information

Comment

The structure determination of the title compound was performed as a part of a project on the synthesis of new metal–organic frameworks. In this project we have reacted iron(II) sulfate with naphthalene-1,4-dicarboxylic acid in potassium hydroxide and water, which leads to the formation of a naphthalene-1,4-dicarboxylate iron(II) coordination polymer.

The title compound is isostructural to the manganese(II) and cobalt(II) complexes of naphthalene-1,4-dicarboxylate (Maji et al., 2005). In the title compound, the Fe^II atom is surrounded by six O atoms from six crystallographically equivalent naphthalene-1,4-dicarboxylate ligands in a distorted octahedral coordination environment (Fig. 1 and Table 1). The Fe atoms are linked by O atoms of the carboxylate groups in a µ₃-O:O':O' mode into chains, which elongate along the a axis (Fig. 2). Within these chains the Fe coordination octahedra are connected via common edges. These chains are connected by the naphthalene-1,4-dicarboxylate ligands into a three-dimensional network.

Experimental

A mixture of FeSO₄.7H₂O (0.139 g, 0.5 mmol), naphthalene-1,4-dicarboxylic acid (0.108 g, 0.5 mmol), KOH (0.112 g, 1 mmol) and water (5 ml) was transfered into a glass tube and heated to 423 K for 4 d. On cooling, yellow needle crystals of the title compound were obtained.

Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.95 Å and with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The structure of the title compound, together with symmetry-related atoms to complete the Fe coordination. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x+1/2, -y+1/2, z-1/2; (ii) x-1, y, z; (iii) x-1/2, -y+1/2, z-1/2; (iv) -x+1/2, y+1/2, -z+3/2; (v) -x+1, -y+1, -z+1.]

Fig. 2.

A view of the chains formed by the Fe coordination octahedra.

Fig. 3.

Three-dimensional structure of the title compound viewed along the a axis.

Crystal data

[Fe(C12H6O4)]	F(000) = 544
Mr = 270.02	Dx = 1.868 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8000 reflections
a = 4.7863 (4) Å	θ = 9–26°
b = 14.8940 (9) Å	µ = 1.57 mm−1
c = 13.4705 (10) Å	T = 170 K
β = 91.098 (9)°	Needle, yellow
V = 960.10 (12) Å3	0.30 × 0.04 × 0.04 mm
Z = 4

Data collection

Stoe IPDS-1 diffractometer	1816 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.026
graphite	θmax = 28.0°, θmin = 2.7°
φ scans	h = −6→6
13722 measured reflections	k = −19→19
2256 independent reflections	l = −17→17

Refinement

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)] = 0.030	H-atom parameters constrained
wR(F2) = 0.087	w = 1/[σ2(Fo2) + (0.0535P)2 + 0.4222P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.002
2256 reflections	Δρmax = 0.40 e Å−3
155 parameters	Δρmin = −0.46 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: 0.012 (3)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Fe1	0.24998 (4)	0.440859 (14)	0.501167 (14)	0.00529 (13)
O1	0.6268 (3)	0.44515 (7)	0.59098 (9)	0.0071 (2)
O2	1.0178 (2)	0.36165 (8)	0.59405 (9)	0.0095 (2)
O3	−0.0120 (2)	0.13335 (8)	0.90581 (9)	0.0099 (2)
O4	0.3838 (3)	0.05263 (7)	0.90583 (9)	0.0067 (2)
C1	0.6451 (3)	0.31639 (10)	0.69582 (11)	0.0077 (3)
C2	0.6838 (4)	0.22537 (11)	0.68337 (12)	0.0097 (3)
H2	0.8026	0.2044	0.6326	0.012*
C3	0.5492 (4)	0.16326 (11)	0.74501 (12)	0.0097 (3)
H3	0.5782	0.1008	0.7353	0.012*
C4	0.3761 (3)	0.19163 (10)	0.81920 (11)	0.0074 (3)
C5	0.1863 (4)	0.31859 (12)	0.91907 (13)	0.0165 (4)
H5	0.0869	0.2776	0.9593	0.020*
C6	0.1788 (5)	0.40864 (12)	0.94029 (14)	0.0233 (5)
H6	0.0777	0.4292	0.9959	0.028*
C7	0.3198 (5)	0.47108 (12)	0.88038 (13)	0.0199 (4)
H7	0.3155	0.5332	0.8963	0.024*
C8	0.4628 (4)	0.44215 (10)	0.79915 (13)	0.0135 (4)
H8	0.5519	0.4848	0.7579	0.016*
C9	0.4798 (3)	0.34898 (10)	0.77570 (11)	0.0081 (3)
C10	0.3413 (3)	0.28589 (11)	0.83760 (11)	0.0084 (3)
C11	0.7751 (3)	0.37880 (10)	0.62232 (11)	0.0067 (3)
C12	0.2371 (3)	0.12168 (10)	0.88160 (11)	0.0067 (3)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Fe1	0.00470 (18)	0.00449 (16)	0.00679 (17)	0.00009 (8)	0.00311 (10)	0.00003 (7)
O1	0.0072 (6)	0.0065 (5)	0.0076 (5)	0.0000 (4)	0.0012 (4)	0.0020 (4)
O2	0.0071 (6)	0.0088 (5)	0.0129 (5)	0.0000 (4)	0.0048 (4)	0.0036 (4)
O3	0.0063 (6)	0.0095 (5)	0.0139 (5)	−0.0002 (4)	0.0036 (4)	0.0044 (4)
O4	0.0071 (6)	0.0056 (5)	0.0074 (5)	−0.0002 (4)	0.0009 (4)	0.0023 (4)
C1	0.0069 (7)	0.0085 (7)	0.0078 (7)	−0.0012 (6)	0.0011 (6)	0.0027 (5)
C2	0.0103 (8)	0.0096 (7)	0.0094 (7)	0.0010 (6)	0.0048 (6)	0.0017 (5)
C3	0.0116 (8)	0.0071 (7)	0.0104 (7)	0.0008 (5)	0.0032 (6)	0.0020 (6)
C4	0.0068 (8)	0.0071 (7)	0.0082 (6)	−0.0004 (5)	0.0009 (5)	0.0029 (5)
C5	0.0230 (10)	0.0120 (8)	0.0150 (8)	0.0004 (7)	0.0117 (7)	0.0020 (6)
C6	0.0367 (12)	0.0128 (9)	0.0210 (9)	0.0038 (8)	0.0183 (8)	−0.0011 (7)
C7	0.0338 (11)	0.0089 (8)	0.0173 (8)	0.0011 (7)	0.0100 (8)	−0.0005 (6)
C8	0.0207 (10)	0.0077 (8)	0.0122 (7)	−0.0020 (6)	0.0050 (7)	0.0011 (6)
C9	0.0084 (8)	0.0075 (7)	0.0083 (7)	−0.0003 (5)	0.0017 (6)	0.0017 (5)
C10	0.0091 (8)	0.0081 (7)	0.0080 (7)	0.0004 (5)	0.0025 (6)	0.0016 (5)
C11	0.0074 (8)	0.0066 (7)	0.0061 (6)	−0.0018 (5)	0.0012 (5)	0.0000 (5)
C12	0.0076 (8)	0.0070 (7)	0.0056 (6)	−0.0011 (5)	0.0015 (5)	0.0004 (5)

Geometric parameters (Å, °)

Fe1—O3i	2.0557 (11)	C2—H2	0.9500
Fe1—O2ii	2.0604 (11)	C3—C4	1.377 (2)
Fe1—O1	2.1533 (13)	C3—H3	0.9500
Fe1—O4iii	2.1550 (13)	C4—C10	1.436 (2)
Fe1—O4iv	2.1867 (11)	C4—C12	1.502 (2)
Fe1—O1v	2.1908 (11)	C5—C6	1.372 (3)
Fe1—Fe1vi	2.9712 (4)	C5—C10	1.422 (2)
Fe1—Fe1v	2.9724 (4)	C5—H5	0.9500
O1—C11	1.2835 (19)	C6—C7	1.411 (3)
O2—C11	1.256 (2)	C6—H6	0.9500
O3—C12	1.254 (2)	C7—C8	1.371 (2)
O4—C12	1.2839 (19)	C7—H7	0.9500
C1—C2	1.379 (2)	C8—C9	1.426 (2)
C1—C9	1.433 (2)	C8—H8	0.9500
C1—C11	1.502 (2)	C9—C10	1.428 (2)
C2—C3	1.407 (2)
O3i—Fe1—O2ii	112.54 (5)	C2—C1—C9	120.12 (14)
O3i—Fe1—O1	84.19 (5)	C2—C1—C11	118.04 (13)
O2ii—Fe1—O1	97.55 (5)	C9—C1—C11	121.82 (14)
O3i—Fe1—O4iii	96.08 (5)	C1—C2—C3	120.69 (15)
O2ii—Fe1—O4iii	86.89 (5)	C1—C2—H2	119.7
O1—Fe1—O4iii	175.08 (4)	C3—C2—H2	119.7
O3i—Fe1—O4iv	159.92 (5)	C4—C3—C2	121.01 (15)
O2ii—Fe1—O4iv	85.45 (4)	C4—C3—H3	119.5
O1—Fe1—O4iv	84.65 (4)	C2—C3—H3	119.5
O4iii—Fe1—O4iv	93.64 (4)	C3—C4—C10	119.93 (14)
O3i—Fe1—O1v	84.50 (4)	C3—C4—C12	118.20 (14)
O2ii—Fe1—O1v	160.39 (5)	C10—C4—C12	121.83 (13)
O1—Fe1—O1v	93.65 (4)	C6—C5—C10	120.77 (16)
O4iii—Fe1—O1v	81.50 (4)	C6—C5—H5	119.6
O4iv—Fe1—O1v	79.61 (5)	C10—C5—H5	119.6
O3i—Fe1—Fe1vi	140.19 (4)	C5—C6—C7	120.69 (16)
O2ii—Fe1—Fe1vi	84.39 (3)	C5—C6—H6	119.7
O1—Fe1—Fe1vi	130.85 (3)	C7—C6—H6	119.7
O4iii—Fe1—Fe1vi	47.26 (3)	C8—C7—C6	120.04 (16)
O4iv—Fe1—Fe1vi	46.37 (3)	C8—C7—H7	120.0
O1v—Fe1—Fe1vi	76.12 (3)	C6—C7—H7	120.0
O3i—Fe1—Fe1v	81.72 (3)	C7—C8—C9	120.93 (15)
O2ii—Fe1—Fe1v	142.14 (4)	C7—C8—H8	119.5
O1—Fe1—Fe1v	47.35 (3)	C9—C8—H8	119.5
O4iii—Fe1—Fe1v	127.79 (3)	C8—C9—C10	118.82 (14)
O4iv—Fe1—Fe1v	78.44 (3)	C8—C9—C1	122.06 (14)
O1v—Fe1—Fe1v	46.30 (3)	C10—C9—C1	119.01 (14)
Fe1vi—Fe1—Fe1v	107.275 (14)	C5—C10—C9	118.68 (14)
C11—O1—Fe1	127.88 (10)	C5—C10—C4	122.14 (14)
C11—O1—Fe1v	129.03 (11)	C9—C10—C4	119.07 (13)
Fe1—O1—Fe1v	86.35 (4)	O2—C11—O1	124.47 (14)
C11—O2—Fe1vii	125.49 (10)	O2—C11—C1	118.13 (14)
C12—O3—Fe1viii	128.98 (10)	O1—C11—C1	117.38 (14)
C12—O4—Fe1ix	123.36 (10)	O3—C12—O4	124.25 (14)
C12—O4—Fe1x	126.21 (10)	O3—C12—C4	118.88 (14)
Fe1ix—O4—Fe1x	86.36 (4)	O4—C12—C4	116.87 (14)

Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) x−1, y, z; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1/2, y+1/2, −z+3/2; (v) −x+1, −y+1, −z+1; (vi) −x, −y+1, −z+1; (vii) x+1, y, z; (viii) x−1/2, −y+1/2, z+1/2; (ix) x+1/2, −y+1/2, z+1/2; (x) −x+1/2, y−1/2, −z+3/2.