Bis[4-(4-pyridyl)pyridinium] (4-carboxy­pyridine-2,6-dicarboxyl­ato-κ3O2,N,O6)(pyridine-2,4,6-tricarboxyl­ato-κ3O2,N,O6)ferrate(III) trihydrate

Zhao, L.; Dong, Y.-R.; Xie, H.-Z.

doi:10.1107/S1600536809010514

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Pages m450-m451

doi:10.1107/S1600536809010514

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Bis[4-(4-pyridyl)pyridinium] (4-carboxypyridine-2,6-dicarboxylato-κ³O²,N,O⁶)(pyridine-2,4,6-tricarboxylato-κ³O²,N,O⁶)ferrate(III) trihydrate

Li Zhao,^a You-Ren Dong ^a and Hong-Zhen Xie ^a ^*

^aState Key Laboratory Base of Novel Functional Materials and Preparation Science, Faculty of Materials Science and Chemical Engineering, Institute of Solid Materials Chemistry, Ningbo University, Zhejiang 315211, People's Republic of China
^*Correspondence e-mail: zhengyueqing@nbu.edu.cn

(Received 16 March 2009; accepted 23 March 2009; online 28 March 2009)

In the title salt, (C₁₀H₉N₂)₂[Fe(C₈H₂NO₆)(C₈H₃NO₆)]·3H₂O, the Fe^III atom is O,N,O′-chelated by dianionic and trianionic ligands in a slightly distorted octahedral coordination geometry. The cations and ferrate anions are linked into a layered structure; the layers are connected through the uncoordinated water molecules into a hydrogen-bonded three-dimensional supramolecular structure. One of the uncoordinated water molecules is disordered around an inversion centre and was refined with half-occupancy for each position.

Related literature

For the design and synthesis of coordination polymer complexes and their potential applications, see: Kaneko et al. (2007 ); Li et al. (2008 ); Lin et al. (2009 ). For the H₃ptc ligand, see: Ghosh & Bharadwaj (2006 ); Lin et al. (2007 ); Syper et al. (1980 ).

Experimental

Crystal data

(C₁₀H₉N₂)₂[Fe(C₈H₂NO₆)(C₈H₃NO₆)]·3H₂O
M_r = 841.50
Triclinic, $[P \overline 1]$
a = 10.568 (2) Å
b = 12.386 (3) Å
c = 14.344 (3) Å
α = 77.13 (3)°
β = 79.82 (3)°
γ = 76.15 (3)°
V = 1761.9 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 293 K
0.35 × 0.24 × 0.17 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.860, T_max = 0.913
17019 measured reflections
7934 independent reflections
5458 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.138
S = 1.06
7934 reflections
526 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Fe—O6	2.008 (2)
Fe—O7	2.012 (2)
Fe—O1	2.018 (2)
Fe—O12	2.026 (2)
Fe—N2	2.056 (2)
Fe—N1	2.058 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O9ⁱ	0.82	1.64	2.454 (3)	172
N3—H3A⋯N5ⁱⁱ	0.86	1.93	2.741 (4)	158
N6—H6A⋯N4ⁱⁱⁱ	0.86	1.84	2.694 (4)	170
O13A—H13A⋯O7^iv	0.90	1.90	2.766 (4)	161
O13B—H13B⋯O4	0.78	2.17	2.821 (4)	142
O14—H14A⋯O11	0.85	2.16	2.973 (4)	160
O14—H14B⋯O5^v	0.85	1.95	2.788 (4)	169
O15—H15A⋯O10	0.85	1.97	2.801 (3)	166
O15—H15B⋯O1^vi	0.85	2.10	2.877 (3)	152
Symmetry codes: (i) x-1, y, z+1; (ii) -x+2, -y+1, -z+2; (iii) -x+1, -y+1, -z+1; (iv) -x, -y+1, -z+2; (v) x+1, y, z; (vi) -x+2, -y+1, -z+1.

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: SHELXL97; software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809010514/ng2562sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809010514/ng2562Isup2.hkl

checkCIF report

Comment top

Great interest has been focused on the rapidly expanding field of supramolecular chemistry and crystal engineering of the coordination polymers in reacent years because of their intriguing network topoloies as well as their potential application as functional materials in many areas such as separations and catalysis, gas storage, and magnetism (Kaneko et al., 2007; Li et al., 2008; Lin et al., 2009). Pyridine-2,4,6-tricarboxylic acid (H₃ptc) is a good building block for constructing supramolecular complex, which can link 3 d, 4f and 3 d-4f metal ions. However, plenty of researches have focused on the supramolecular chemistry and coordination polymers which only include single carboxylic acid ligands, whereas the studies and syntheses about the mixed-ligand compounds which contain two or two more ligands seem comparatively limited (Ghosh & Bharadwaj, 2006; Lin et al., 2007). In this paper, we report the crystal structure of the title compound prepared from FeCl₂.6H₂O, H₃ptc and 4,4'-bipyridine (4,4'-bpy).

The structure of title compound consists of [Fe(Hptc)(ptc)]^2- anions, Hbpy+ cations and lattice water molecules. In the anion, Hptc^2- and ptc^3- ligands are bound to one Fe(III) ion through pyridine N and deprotonated carboxylate O atoms at 2- and 6-positions, leading to a distorted octahedral geometry around the metal. The carboxylic groups at the 4-position of ptc ligands are uncoordinated. [Fe(Hptc)(ptc)]^2- anion is connected into two-dimensional layers through H-bonding interactions (Talbe 2). In the cationic part, the Hbpy⁺ ligands are not coordinated to metal ions. They are connected by N—H···N hydrogen-bonding and π-π stacking interactions to form another two-dimensional layers. The layers are futher linked into three-dimensional supramolecular structure by the intermolecular hydrogen bond interaction.

Related literature top

For the design and synthesis of coordination polymer complexes and their potential applications, see: Kaneko et al. (2007); Li et al. (2008); Lin et al. (2009). For the H₃ptc ligand, see: Ghosh & Bharadwaj (2006); Lin et al. (2007); Syper et al. (1980).

Experimental top

Pyridine-2,4,6-tricarboxylic acid (H₃ptc) was synthesized by oxidization of pyridine-2,4,6-trimethyl with potassium permanganate according to a literature (Syper et al., 1980).A mixture of H₃ptc (0.110 g, 0.05 mmol), FeCl₂.6H₂O (0.126 g, 0.10 mmol), 4,4'-bpy (0.156 g, 0.10 mmol), 16 ml H₂O and seven drops of triethylamine were loaded into a 23 ml Teflon-lined stainless autoclave, which was heated up to 120 °C, at which temperature the reactor was held for 3 days, and then cooled to room temperature. The reaction yielded brown block crystals of (I) in a yield of 10.32% based on FeCl₂.6H₂O. IR spectroscopic analysis (KBr, υ/cm^-1): 3535(m), 3436(m), 1674(s), 1612(m), 1573(w), 1492(m), 1330(s), 1195(s), 1076(w), 1043(m), 1006(m), 931(w), 813(s), 779(w), 748(m), 771(w), 678(w).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); 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: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Aview of the complex molecule of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 45% probability level. (Lattice water molecules and hydrogen atoms are all delected)
	Fig. 2. The two-dimensional layers constructed with [Fe(Hptc)(ptc)]^2- by hydrogen bonds.
	Fig. 3. The two-dimensional layers constructed with Hbpy⁺ by hydrogen bonds and π-π stacking.

Bis[4-(4-pyridyl)pyridinium] (4-carboxypyridine-2,6-dicarboxylato- κ³O²,N,O⁶)(pyridine-2,4,6-tricarboxylato- κ³O²,N,O⁶)ferrate(III) trihydrate top

Crystal data top

(C₁₀H₉N₂)₂[Fe(C₈H₂NO₆)(C₈H₃NO₆)]·3H₂O	Z = 2
M_r = 841.50	F(000) = 866
Triclinic, P1	D_x = 1.586 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.568 (2) Å	Cell parameters from 17019 reflections
b = 12.386 (3) Å	θ = 3.2–27.5°
c = 14.344 (3) Å	µ = 0.51 mm⁻¹
α = 77.13 (3)°	T = 293 K
β = 79.82 (3)°	Block, brown
γ = 76.15 (3)°	0.35 × 0.24 × 0.17 mm
V = 1761.9 (6) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	7934 independent reflections
Radiation source: fine-focus sealed tube	5458 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 0 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −13→13
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −15→16
T_min = 0.860, T_max = 0.913	l = −17→18
17019 measured reflections

Refinement top

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.138	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0677P)² + 0.2949P] where P = (F_o² + 2F_c²)/3
7934 reflections	(Δ/σ)_max = 0.018
526 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

(C₁₀H₉N₂)₂[Fe(C₈H₂NO₆)(C₈H₃NO₆)]·3H₂O	γ = 76.15 (3)°
M_r = 841.50	V = 1761.9 (6) Å³
Triclinic, P1	Z = 2
a = 10.568 (2) Å	Mo Kα radiation
b = 12.386 (3) Å	µ = 0.51 mm⁻¹
c = 14.344 (3) Å	T = 293 K
α = 77.13 (3)°	0.35 × 0.24 × 0.17 mm
β = 79.82 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	7934 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	5458 reflections with I > 2σ(I)
T_min = 0.860, T_max = 0.913	R_int = 0.040
17019 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.138	H-atom parameters constrained
S = 1.06	Δρ_max = 0.41 e Å⁻³
7934 reflections	Δρ_min = −0.41 e Å⁻³
526 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Fe	0.48489 (4)	0.50845 (4)	0.74947 (3)	0.02949 (13)
N1	0.3459 (2)	0.51476 (19)	0.86945 (15)	0.0271 (5)
N2	0.6260 (2)	0.52164 (19)	0.63117 (14)	0.0253 (5)
C1	0.3767 (3)	0.4481 (2)	0.95274 (18)	0.0272 (6)
C2	0.2896 (3)	0.4545 (2)	1.03624 (18)	0.0299 (6)
H2	0.3096	0.4081	1.0945	0.036*
C3	0.1708 (3)	0.5328 (2)	1.03055 (18)	0.0300 (6)
C4	0.1416 (3)	0.6013 (2)	0.94256 (19)	0.0310 (6)
H4	0.0624	0.6535	0.9381	0.037*
C5	0.2338 (3)	0.5894 (2)	0.86208 (18)	0.0286 (6)
C6	0.5121 (3)	0.3728 (2)	0.94093 (19)	0.0308 (6)
O1	0.57272 (18)	0.39221 (17)	0.85399 (13)	0.0358 (5)
O2	0.5550 (2)	0.30376 (19)	1.00811 (15)	0.0450 (5)
C7	0.0695 (3)	0.5450 (3)	1.1186 (2)	0.0335 (6)
O3	0.1080 (2)	0.4852 (2)	1.19749 (14)	0.0525 (6)
H3	0.0457	0.4873	1.2407	0.079*
O4	−0.0370 (2)	0.6083 (2)	1.10993 (15)	0.0529 (6)
C8	0.2268 (3)	0.6545 (2)	0.75967 (19)	0.0311 (6)
O5	0.1333 (2)	0.73086 (19)	0.73936 (14)	0.0436 (5)
O6	0.32849 (19)	0.62091 (18)	0.70084 (12)	0.0352 (5)
C9	0.6408 (2)	0.4532 (2)	0.56858 (18)	0.0266 (6)
C10	0.7329 (3)	0.4614 (2)	0.48723 (18)	0.0294 (6)
H10	0.7429	0.4149	0.4426	0.035*
C11	0.8105 (3)	0.5417 (2)	0.47426 (18)	0.0299 (6)
C12	0.7941 (3)	0.6101 (2)	0.54191 (18)	0.0301 (6)
H12	0.8464	0.6629	0.5345	0.036*
C13	0.6987 (2)	0.5981 (2)	0.62030 (18)	0.0271 (6)
C14	0.5477 (3)	0.3726 (2)	0.60007 (19)	0.0317 (6)
O7	0.47146 (19)	0.38846 (18)	0.67958 (14)	0.0379 (5)
O8	0.5477 (2)	0.3013 (2)	0.55424 (17)	0.0524 (6)
C15	0.9150 (3)	0.5546 (3)	0.38788 (19)	0.0356 (7)
O9	0.9347 (2)	0.4803 (2)	0.33614 (16)	0.0558 (7)
O10	0.9727 (2)	0.6326 (2)	0.37478 (17)	0.0595 (7)
C16	0.6609 (3)	0.6649 (2)	0.70080 (19)	0.0305 (6)
O11	0.7138 (2)	0.74272 (19)	0.69996 (15)	0.0441 (5)
O12	0.56886 (19)	0.63358 (17)	0.76424 (13)	0.0360 (5)
N3	0.9300 (3)	0.0772 (3)	0.6608 (2)	0.0529 (8)
H3A	0.9740	0.0865	0.7025	0.079*
C17	0.8781 (4)	−0.0123 (4)	0.6781 (2)	0.0579 (10)
H17	0.8887	−0.0644	0.7354	0.069*
C18	0.8083 (4)	−0.0307 (3)	0.6131 (2)	0.0556 (10)
H18	0.7717	−0.0945	0.6263	0.067*
C19	0.7928 (3)	0.0467 (3)	0.5278 (2)	0.0373 (7)
C20	0.8491 (3)	0.1404 (3)	0.5113 (2)	0.0422 (7)
H20	0.8415	0.1932	0.4542	0.051*
C21	0.9160 (3)	0.1548 (3)	0.5797 (3)	0.0512 (9)
H21	0.9519	0.2187	0.5697	0.061*
N4	0.5820 (3)	−0.0089 (3)	0.3213 (2)	0.0502 (7)
C22	0.7179 (3)	0.0271 (3)	0.4566 (2)	0.0380 (7)
C23	0.6505 (3)	0.1171 (3)	0.3962 (2)	0.0430 (7)
H23	0.6490	0.1913	0.4003	0.052*
C24	0.5854 (3)	0.0946 (3)	0.3297 (2)	0.0476 (8)
H24	0.5414	0.1555	0.2886	0.057*
C25	0.6459 (5)	−0.0947 (4)	0.3793 (3)	0.0829 (15)
H25	0.6458	−0.1680	0.3735	0.100*
C26	0.7133 (5)	−0.0797 (3)	0.4485 (3)	0.0783 (15)
H26	0.7552	−0.1423	0.4893	0.094*
N5	0.9437 (3)	0.9490 (3)	1.1818 (2)	0.0495 (7)
C27	0.8663 (3)	1.0491 (3)	1.1540 (2)	0.0491 (9)
H27	0.8631	1.1076	1.1858	0.059*
C28	0.7908 (3)	1.0700 (3)	1.0802 (2)	0.0443 (8)
H28	0.7390	1.1414	1.0619	0.053*
C29	0.7940 (3)	0.9821 (2)	1.0337 (2)	0.0320 (6)
C30	0.8776 (3)	0.8807 (3)	1.0597 (2)	0.0418 (7)
H30	0.8854	0.8217	1.0273	0.050*
C31	0.9503 (3)	0.8665 (3)	1.1342 (3)	0.0509 (9)
H31	1.0059	0.7969	1.1518	0.061*
N6	0.5522 (3)	1.0162 (2)	0.81949 (19)	0.0445 (7)
H6A	0.5044	1.0219	0.7753	0.067*
C32	0.7079 (3)	0.9959 (3)	0.9582 (2)	0.0324 (6)
C33	0.6801 (3)	1.0959 (3)	0.8931 (2)	0.0403 (7)
H33	0.7144	1.1574	0.8958	0.048*
C34	0.6010 (3)	1.1043 (3)	0.8238 (2)	0.0452 (8)
H34	0.5817	1.1718	0.7799	0.054*
C35	0.5763 (3)	0.9191 (3)	0.8826 (2)	0.0433 (8)
H35	0.5400	0.8592	0.8786	0.052*
C36	0.6533 (3)	0.9062 (3)	0.9529 (2)	0.0394 (7)
H36	0.6690	0.8383	0.9967	0.047*
O14	0.8797 (3)	0.7658 (3)	0.8387 (2)	0.0770 (9)
H14A	0.8215	0.7521	0.8116	0.116*
H14B	0.9524	0.7531	0.8024	0.116*
O15	1.1872 (2)	0.7054 (2)	0.25415 (18)	0.0571 (7)
H15A	1.1225	0.6765	0.2841	0.086*
H15B	1.2405	0.6626	0.2191	0.086*
O13A	−0.299 (4)	0.735 (3)	1.201 (2)	0.087 (5)	0.50
O13B	−0.293 (4)	0.719 (3)	1.174 (2)	0.087 (5)	0.50
H13A	−0.3480	0.6982	1.2502	0.131*
H13B	−0.2432	0.6654	1.1609	0.131*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe	0.0310 (2)	0.0340 (2)	0.0201 (2)	−0.00864 (17)	0.00912 (14)	−0.00606 (16)
N1	0.0288 (12)	0.0288 (12)	0.0202 (10)	−0.0050 (10)	0.0050 (8)	−0.0047 (9)
N2	0.0270 (11)	0.0293 (12)	0.0175 (10)	−0.0071 (9)	0.0045 (8)	−0.0043 (9)
C1	0.0317 (14)	0.0284 (15)	0.0196 (12)	−0.0071 (11)	0.0038 (10)	−0.0052 (11)
C2	0.0357 (15)	0.0335 (16)	0.0178 (12)	−0.0097 (12)	0.0040 (10)	−0.0026 (11)
C3	0.0340 (15)	0.0350 (16)	0.0213 (13)	−0.0107 (12)	0.0070 (10)	−0.0106 (12)
C4	0.0275 (14)	0.0339 (16)	0.0296 (14)	−0.0021 (12)	0.0021 (11)	−0.0111 (12)
C5	0.0312 (14)	0.0297 (15)	0.0228 (13)	−0.0055 (12)	0.0025 (10)	−0.0061 (11)
C6	0.0355 (15)	0.0304 (16)	0.0254 (13)	−0.0082 (12)	0.0027 (11)	−0.0066 (12)
O1	0.0309 (10)	0.0404 (12)	0.0280 (10)	−0.0012 (9)	0.0100 (8)	−0.0074 (9)
O2	0.0454 (13)	0.0424 (13)	0.0325 (11)	0.0073 (10)	0.0005 (9)	0.0016 (10)
C7	0.0355 (16)	0.0363 (17)	0.0270 (14)	−0.0091 (13)	0.0094 (11)	−0.0113 (12)
O3	0.0432 (13)	0.0707 (17)	0.0273 (11)	−0.0002 (12)	0.0159 (9)	−0.0045 (11)
O4	0.0406 (13)	0.0621 (16)	0.0411 (12)	0.0063 (12)	0.0118 (10)	−0.0107 (12)
C8	0.0367 (16)	0.0336 (16)	0.0223 (13)	−0.0077 (13)	−0.0017 (11)	−0.0050 (12)
O5	0.0447 (13)	0.0442 (14)	0.0337 (11)	0.0016 (11)	−0.0047 (9)	−0.0022 (10)
O6	0.0388 (11)	0.0427 (12)	0.0196 (9)	−0.0065 (9)	0.0032 (8)	−0.0046 (8)
C9	0.0289 (14)	0.0282 (15)	0.0208 (12)	−0.0066 (11)	0.0033 (10)	−0.0054 (11)
C10	0.0287 (14)	0.0369 (16)	0.0207 (12)	−0.0055 (12)	0.0031 (10)	−0.0078 (11)
C11	0.0278 (14)	0.0339 (16)	0.0225 (13)	−0.0061 (12)	0.0054 (10)	−0.0013 (11)
C12	0.0326 (15)	0.0305 (15)	0.0251 (13)	−0.0118 (12)	0.0032 (11)	−0.0009 (11)
C13	0.0278 (14)	0.0290 (15)	0.0219 (13)	−0.0071 (11)	0.0015 (10)	−0.0016 (11)
C14	0.0342 (15)	0.0342 (16)	0.0267 (14)	−0.0121 (13)	0.0047 (11)	−0.0070 (12)
O7	0.0385 (11)	0.0427 (13)	0.0330 (10)	−0.0194 (10)	0.0127 (8)	−0.0104 (9)
O8	0.0595 (15)	0.0541 (15)	0.0543 (14)	−0.0294 (12)	0.0149 (11)	−0.0308 (12)
C15	0.0340 (15)	0.0437 (18)	0.0253 (14)	−0.0104 (14)	0.0064 (11)	−0.0043 (13)
O9	0.0602 (15)	0.0702 (17)	0.0390 (13)	−0.0285 (13)	0.0272 (11)	−0.0246 (12)
O10	0.0616 (15)	0.0712 (18)	0.0495 (14)	−0.0384 (14)	0.0268 (12)	−0.0193 (13)
C16	0.0352 (15)	0.0272 (15)	0.0279 (14)	−0.0060 (12)	−0.0013 (11)	−0.0056 (12)
O11	0.0546 (14)	0.0407 (13)	0.0431 (12)	−0.0207 (11)	0.0018 (10)	−0.0153 (10)
O12	0.0451 (12)	0.0380 (12)	0.0260 (10)	−0.0130 (10)	0.0076 (8)	−0.0131 (9)
N3	0.0578 (18)	0.066 (2)	0.0462 (17)	−0.0192 (16)	−0.0176 (14)	−0.0182 (16)
C17	0.072 (3)	0.068 (3)	0.0364 (18)	−0.023 (2)	−0.0220 (17)	0.0058 (17)
C18	0.074 (3)	0.053 (2)	0.0473 (19)	−0.034 (2)	−0.0233 (17)	0.0104 (17)
C19	0.0395 (17)	0.0368 (18)	0.0388 (16)	−0.0089 (14)	−0.0146 (13)	−0.0047 (13)
C20	0.054 (2)	0.0351 (18)	0.0424 (17)	−0.0150 (15)	−0.0144 (14)	−0.0053 (14)
C21	0.055 (2)	0.053 (2)	0.056 (2)	−0.0212 (18)	−0.0125 (16)	−0.0168 (18)
N4	0.0571 (18)	0.0484 (18)	0.0533 (17)	−0.0110 (14)	−0.0291 (14)	−0.0092 (14)
C22	0.0448 (17)	0.0364 (18)	0.0375 (16)	−0.0154 (14)	−0.0135 (13)	−0.0028 (13)
C23	0.055 (2)	0.0358 (18)	0.0409 (17)	−0.0031 (15)	−0.0181 (14)	−0.0100 (14)
C24	0.049 (2)	0.044 (2)	0.0485 (19)	0.0038 (16)	−0.0258 (15)	−0.0067 (16)
C25	0.127 (4)	0.038 (2)	0.106 (4)	−0.024 (2)	−0.078 (3)	−0.004 (2)
C26	0.121 (4)	0.032 (2)	0.100 (3)	−0.018 (2)	−0.085 (3)	0.007 (2)
N5	0.0512 (17)	0.056 (2)	0.0476 (16)	−0.0099 (15)	−0.0234 (13)	−0.0100 (14)
C27	0.053 (2)	0.052 (2)	0.050 (2)	−0.0059 (17)	−0.0173 (16)	−0.0223 (17)
C28	0.0459 (18)	0.0380 (19)	0.053 (2)	−0.0032 (15)	−0.0188 (15)	−0.0139 (16)
C29	0.0312 (15)	0.0330 (16)	0.0317 (14)	−0.0065 (12)	−0.0058 (11)	−0.0047 (12)
C30	0.0453 (18)	0.0384 (18)	0.0449 (18)	−0.0040 (14)	−0.0157 (14)	−0.0119 (15)
C31	0.054 (2)	0.041 (2)	0.061 (2)	−0.0005 (16)	−0.0284 (17)	−0.0111 (17)
N6	0.0439 (15)	0.0547 (18)	0.0402 (14)	−0.0101 (13)	−0.0208 (12)	−0.0078 (13)
C32	0.0330 (15)	0.0345 (17)	0.0311 (14)	−0.0061 (12)	−0.0064 (11)	−0.0082 (12)
C33	0.0451 (18)	0.0387 (18)	0.0398 (17)	−0.0109 (14)	−0.0113 (13)	−0.0063 (14)
C34	0.051 (2)	0.044 (2)	0.0418 (18)	−0.0082 (16)	−0.0191 (14)	−0.0015 (15)
C35	0.0421 (18)	0.046 (2)	0.0494 (19)	−0.0134 (15)	−0.0148 (14)	−0.0123 (16)
C36	0.0435 (18)	0.0368 (18)	0.0397 (16)	−0.0118 (14)	−0.0124 (13)	−0.0018 (14)
O14	0.0659 (18)	0.091 (2)	0.0760 (19)	−0.0138 (17)	−0.0019 (15)	−0.0274 (18)
O15	0.0461 (14)	0.0489 (15)	0.0652 (15)	−0.0081 (12)	0.0163 (11)	−0.0084 (12)
O13A	0.075 (4)	0.063 (8)	0.101 (15)	−0.016 (5)	0.050 (8)	−0.016 (6)
O13B	0.075 (4)	0.063 (8)	0.101 (15)	−0.016 (5)	0.050 (8)	−0.016 (6)

Geometric parameters (Å, º) top

Fe—O6	2.008 (2)	C18—H18	0.9300
Fe—O7	2.012 (2)	C19—C20	1.384 (4)
Fe—O1	2.018 (2)	C19—C22	1.488 (4)
Fe—O12	2.026 (2)	C20—C21	1.371 (4)
Fe—N2	2.056 (2)	C20—H20	0.9300
Fe—N1	2.058 (2)	C21—H21	0.9300
N1—C5	1.321 (3)	N4—C25	1.318 (5)
N1—C1	1.336 (3)	N4—C24	1.323 (4)
N2—C13	1.324 (3)	C22—C26	1.367 (5)
N2—C9	1.332 (3)	C22—C23	1.381 (4)
C1—C2	1.380 (3)	C23—C24	1.380 (4)
C1—C6	1.514 (4)	C23—H23	0.9300
C2—C3	1.393 (4)	C24—H24	0.9300
C2—H2	0.9300	C25—C26	1.386 (5)
C3—C4	1.394 (4)	C25—H25	0.9300
C3—C7	1.515 (3)	C26—H26	0.9300
C4—C5	1.383 (3)	N5—C27	1.332 (4)
C4—H4	0.9300	N5—C31	1.332 (4)
C5—C8	1.515 (4)	C27—C28	1.379 (4)
C6—O2	1.212 (3)	C27—H27	0.9300
C6—O1	1.296 (3)	C28—C29	1.389 (4)
C7—O4	1.216 (4)	C28—H28	0.9300
C7—O3	1.281 (4)	C29—C30	1.369 (4)
O3—H3	0.8200	C29—C32	1.491 (4)
C8—O5	1.220 (3)	C30—C31	1.380 (4)
C8—O6	1.289 (3)	C30—H30	0.9300
C9—C10	1.383 (3)	C31—H31	0.9300
C9—C14	1.510 (4)	N6—C34	1.331 (4)
C10—C11	1.397 (4)	N6—C35	1.334 (4)
C10—H10	0.9300	N6—H6A	0.8600
C11—C12	1.388 (4)	C32—C33	1.379 (4)
C11—C15	1.514 (3)	C32—C36	1.390 (4)
C12—C13	1.378 (3)	C33—C34	1.379 (4)
C12—H12	0.9300	C33—H33	0.9300
C13—C16	1.510 (4)	C34—H34	0.9300
C14—O8	1.213 (3)	C35—C36	1.364 (4)
C14—O7	1.299 (3)	C35—H35	0.9300
C15—O10	1.225 (4)	C36—H36	0.9300
C15—O9	1.265 (4)	O14—H14A	0.8499
C16—O11	1.221 (3)	O14—H14B	0.8508
C16—O12	1.279 (3)	O15—H15A	0.8517
N3—C17	1.309 (5)	O15—H15B	0.8520
N3—C21	1.339 (5)	O13A—H13A	0.9035
N3—H3A	0.8600	O13A—H13B	1.1256
C17—C18	1.372 (5)	O13B—H13A	1.1455
C17—H17	0.9300	O13B—H13B	0.7764
C18—C19	1.383 (4)

O6—Fe—O7	95.18 (9)	C16—O12—Fe	120.48 (17)
O6—Fe—O1	151.77 (7)	C17—N3—C21	121.4 (3)
O7—Fe—O1	92.17 (9)	C17—N3—H3A	119.3
O6—Fe—O12	91.68 (9)	C21—N3—H3A	119.3
O7—Fe—O12	151.67 (8)	N3—C17—C18	121.1 (3)
O1—Fe—O12	94.66 (9)	N3—C17—H17	119.5
O6—Fe—N2	102.03 (9)	C18—C17—H17	119.5
O7—Fe—N2	75.81 (8)	C17—C18—C19	119.5 (3)
O1—Fe—N2	106.20 (8)	C17—C18—H18	120.3
O12—Fe—N2	75.88 (8)	C19—C18—H18	120.3
O6—Fe—N1	75.78 (9)	C18—C19—C20	118.3 (3)
O7—Fe—N1	110.98 (8)	C18—C19—C22	119.9 (3)
O1—Fe—N1	76.14 (8)	C20—C19—C22	121.9 (3)
O12—Fe—N1	97.35 (8)	C21—C20—C19	119.5 (3)
N2—Fe—N1	172.91 (9)	C21—C20—H20	120.2
C5—N1—C1	122.9 (2)	C19—C20—H20	120.2
C5—N1—Fe	118.62 (18)	N3—C21—C20	120.3 (3)
C1—N1—Fe	118.31 (18)	N3—C21—H21	119.9
C13—N2—C9	122.6 (2)	C20—C21—H21	119.9
C13—N2—Fe	118.47 (16)	C25—N4—C24	117.7 (3)
C9—N2—Fe	118.94 (17)	C26—C22—C23	117.7 (3)
N1—C1—C2	120.3 (2)	C26—C22—C19	121.5 (3)
N1—C1—C6	111.8 (2)	C23—C22—C19	120.8 (3)
C2—C1—C6	127.9 (3)	C24—C23—C22	118.6 (3)
C1—C2—C3	118.0 (2)	C24—C23—H23	120.7
C1—C2—H2	121.0	C22—C23—H23	120.7
C3—C2—H2	121.0	N4—C24—C23	123.6 (3)
C2—C3—C4	120.4 (2)	N4—C24—H24	118.2
C2—C3—C7	121.4 (3)	C23—C24—H24	118.2
C4—C3—C7	118.2 (3)	N4—C25—C26	122.5 (4)
C5—C4—C3	118.1 (3)	N4—C25—H25	118.8
C5—C4—H4	120.9	C26—C25—H25	118.8
C3—C4—H4	120.9	C22—C26—C25	119.9 (4)
N1—C5—C4	120.3 (2)	C22—C26—H26	120.1
N1—C5—C8	111.4 (2)	C25—C26—H26	120.1
C4—C5—C8	128.3 (3)	C27—N5—C31	118.0 (3)
O2—C6—O1	126.0 (3)	N5—C27—C28	123.1 (3)
O2—C6—C1	121.2 (2)	N5—C27—H27	118.4
O1—C6—C1	112.7 (2)	C28—C27—H27	118.4
C6—O1—Fe	120.88 (18)	C27—C28—C29	118.4 (3)
O4—C7—O3	126.2 (2)	C27—C28—H28	120.8
O4—C7—C3	119.8 (3)	C29—C28—H28	120.8
O3—C7—C3	114.1 (3)	C30—C29—C28	118.4 (3)
C7—O3—H3	109.5	C30—C29—C32	120.1 (3)
O5—C8—O6	126.1 (3)	C28—C29—C32	121.5 (3)
O5—C8—C5	121.1 (2)	C29—C30—C31	119.6 (3)
O6—C8—C5	112.8 (2)	C29—C30—H30	120.2
C8—O6—Fe	120.84 (18)	C31—C30—H30	120.2
N2—C9—C10	120.4 (2)	N5—C31—C30	122.4 (3)
N2—C9—C14	111.4 (2)	N5—C31—H31	118.8
C10—C9—C14	128.2 (2)	C30—C31—H31	118.8
C9—C10—C11	117.9 (2)	C34—N6—C35	121.2 (3)
C9—C10—H10	121.0	C34—N6—H6A	119.4
C11—C10—H10	121.0	C35—N6—H6A	119.4
C12—C11—C10	120.1 (2)	C33—C32—C36	118.6 (3)
C12—C11—C15	118.8 (2)	C33—C32—C29	121.7 (3)
C10—C11—C15	121.1 (2)	C36—C32—C29	119.7 (3)
C13—C12—C11	118.6 (2)	C34—C33—C32	119.7 (3)
C13—C12—H12	120.7	C34—C33—H33	120.2
C11—C12—H12	120.7	C32—C33—H33	120.2
N2—C13—C12	120.4 (2)	N6—C34—C33	120.2 (3)
N2—C13—C16	111.8 (2)	N6—C34—H34	119.9
C12—C13—C16	127.8 (2)	C33—C34—H34	119.9
O8—C14—O7	125.4 (3)	N6—C35—C36	121.1 (3)
O8—C14—C9	121.8 (2)	N6—C35—H35	119.4
O7—C14—C9	112.8 (2)	C36—C35—H35	119.4
C14—O7—Fe	121.07 (17)	C35—C36—C32	119.2 (3)
O10—C15—O9	126.3 (3)	C35—C36—H36	120.4
O10—C15—C11	118.9 (3)	C32—C36—H36	120.4
O9—C15—C11	114.8 (3)	H14A—O14—H14B	107.2
O11—C16—O12	126.0 (2)	H15A—O15—H15B	112.8
O11—C16—C13	120.6 (2)	H13A—O13A—H13B	103.2
O12—C16—C13	113.4 (2)	H13A—O13B—H13B	110.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O9ⁱ	0.82	1.64	2.454 (3)	172
N3—H3A···N5ⁱⁱ	0.86	1.93	2.741 (4)	158
N6—H6A···N4ⁱⁱⁱ	0.86	1.84	2.694 (4)	170
O13A—H13A···O7^iv	0.90	1.90	2.766 (4)	161
O13B—H13B···O4	0.78	2.17	2.821 (4)	142
O14—H14A···O11	0.85	2.16	2.973 (4)	160
O14—H14B···O5^v	0.85	1.95	2.788 (4)	169
O15—H15A···O10	0.85	1.97	2.801 (3)	166
O15—H15B···O1^vi	0.85	2.10	2.877 (3)	152

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

Experimental details

Crystal data
Chemical formula	(C₁₀H₉N₂)₂[Fe(C₈H₂NO₆)(C₈H₃NO₆)]·3H₂O
M_r	841.50
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	10.568 (2), 12.386 (3), 14.344 (3)
α, β, γ (°)	77.13 (3), 79.82 (3), 76.15 (3)
V (Å³)	1761.9 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.51
Crystal size (mm)	0.35 × 0.24 × 0.17

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.860, 0.913
No. of measured, independent and observed [I > 2σ(I)] reflections	17019, 7934, 5458
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.138, 1.06
No. of reflections	7934
No. of parameters	526
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.41

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Fe—O6	2.008 (2)	Fe—O12	2.026 (2)
Fe—O7	2.012 (2)	Fe—N2	2.056 (2)
Fe—O1	2.018 (2)	Fe—N1	2.058 (2)

O6—Fe—O7	95.18 (9)	O1—Fe—N2	106.20 (8)
O6—Fe—O1	151.77 (7)	O12—Fe—N2	75.88 (8)
O7—Fe—O1	92.17 (9)	O6—Fe—N1	75.78 (9)
O6—Fe—O12	91.68 (9)	O7—Fe—N1	110.98 (8)
O7—Fe—O12	151.67 (8)	O1—Fe—N1	76.14 (8)
O1—Fe—O12	94.66 (9)	O12—Fe—N1	97.35 (8)
O6—Fe—N2	102.03 (9)	N2—Fe—N1	172.91 (9)
O7—Fe—N2	75.81 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O9ⁱ	0.82	1.64	2.454 (3)	172
N3—H3A···N5ⁱⁱ	0.86	1.93	2.741 (4)	158
N6—H6A···N4ⁱⁱⁱ	0.86	1.84	2.694 (4)	170
O13A—H13A···O7^iv	0.90	1.90	2.766 (4)	161
O13B—H13B···O4	0.78	2.17	2.821 (4)	142
O14—H14A···O11	0.85	2.16	2.973 (4)	160
O14—H14B···O5^v	0.85	1.95	2.788 (4)	169
O15—H15A···O10	0.85	1.97	2.801 (3)	166
O15—H15B···O1^vi	0.85	2.10	2.877 (3)	152

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

Acknowledgements

This project was sponsored by the K. C. Wong Magna Fund of Ningbo University and supported by the Expert Project of Key Basic Research of the Ministry of Science and Technology of China (grant No. 2003CCA00800), the Zhejiang Provincial Natural Science Foundation (grant No. Z203067) and the Ningbo Municipal Natural Science Foundation (grant No. 2006 A610061).

References

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