9-Amino­acridinium bis­(pyridine-2,6-dicarboxyl­ato-κ3O2,N,O6)ferrate(III) tetra­hydrate

Mirzaei, M.; Eshtiagh-Hosseini, H.; Eydizadeh, E.; Yousefi, Z.; Molčanov, K.

doi:10.1107/S1600536812020247

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Pages m761-m762

doi:10.1107/S1600536812020247

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9-Aminoacridinium bis(pyridine-2,6-dicarboxylato-κ³O²,N,O⁶)ferrate(III) tetrahydrate

Masoud Mirzaei,^a ^* Hossein Eshtiagh-Hosseini,^a Ehsan Eydizadeh,^a Zakieh Yousefi ^a and Krešimir Molčanov ^b

^aDepartment of Chemistry, Ferdowsi University of Mashhad, 917791436 Mashhad, Iran, and ^bLaboratory of Chemical Crystallography and Biocrystallography, Department of Physical Chemistry, Rudjer Bošković Institute, Bijenička 54, HR-10000, Zagreb, Croatia
^*Correspondence e-mail: mirzaeesh@um.ac.ir

(Received 10 April 2012; accepted 5 May 2012; online 12 May 2012)

The asymmetric unit of the title compound, (C₁₃H₁₁N₂)[Fe(C₇H₃NO₄)₂]·4H₂O, contains a 9-aminoacridinium cation, one anionic complex and four uncoordinated water molecules. In the anionic complex, the Fe^III ion is six-coordinated by two almost perpendicular [dihedral angle = 88.78 (7)°] pyridine-2,6-dicarboxylate ligands in a distorted octahedral geometry. In the crystal, anions are connected into chains along [10-1] by weak C—H⋯O interactions, which create ten-membered hydrogen-bonded R₂²(10) rings. These chains are linked by three-membered water clusters. The final three-dimensional network is constructed by numerous intermolecular O—H⋯O and N—H⋯O interactions.

Related literature

For background to supramolecular chemistry, see: Lehn (2002 ). For functionalized materials, see: Moulton & Zaworotko (2001 ). For a brief reviews on the pyridinedicarboxylate family of ligands, see: Mirzaei et al. (2011 ); Axelrod et al. (2000 ). For the role of water clusters, see: Aghabozorg et al. (2010 ). For related structures: Aghabozorg et al. (2008 ); Eshtiagh-Hosseini et al. (2010a ,b , 2011a ,b ).

Experimental

Crystal data

(C₁₃H₁₁N₂)[Fe(C₇H₃NO₄)₂]·4H₂O
M_r = 653.36
Monoclinic, P 2₁ /n
a = 9.6130 (1) Å
b = 18.9256 (2) Å
c = 15.9563 (2) Å
β = 96.037 (1)°
V = 2886.86 (6) Å³
Z = 4
Cu Kα radiation
μ = 4.77 mm⁻¹
T = 293 K
0.2 × 0.15 × 0.1 mm

Data collection

Agilent Xcalibur Ruby Nova diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.602, T_max = 1
15252 measured reflections
5940 independent reflections
5140 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.178
S = 1.05
5940 reflections
430 parameters
14 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O3	0.86	2.42	3.038 (4)	130
N3—H3A⋯O11	0.86	2.30	3.008 (4)	139
N4—H4A⋯O12ⁱ	0.86	2.03	2.822 (5)	152
N4—H4B⋯O5ⁱⁱ	0.86	2.39	3.115 (4)	142
O9—H9A⋯O6	0.93 (4)	1.81 (5)	2.726 (4)	165 (5)
O9—H9B⋯O11ⁱⁱⁱ	0.92 (2)	1.85 (2)	2.766 (4)	170 (5)
O10—H10A⋯O9^iv	0.97 (5)	1.81 (5)	2.750 (5)	164 (5)
O10—H10B⋯O1	0.97 (5)	1.90 (5)	2.859 (5)	176 (11)
O11—H11A⋯O4	0.95 (4)	1.78 (4)	2.715 (4)	165 (3)
O11—H11B⋯O8^v	0.93 (4)	1.97 (2)	2.865 (4)	163 (4)
O12—H12A⋯O10^vi	0.96 (6)	1.96 (7)	2.827 (5)	149 (7)
O12—H12B⋯O8	0.95 (11)	2.06 (8)	2.874 (4)	142 (10)
C4—H4⋯O6^vii	0.93	2.41	3.334 (4)	171
C9—H9⋯O4^viii	0.93	2.33	3.257 (4)	171
C16—H16⋯O12^v	0.93	2.59	3.426 (6)	150
C17—H17⋯O2^ix	0.93	2.54	3.329 (5)	143
Symmetry codes: (i) -x, -y+2, -z; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) x+1, y, z; (iv) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) x-1, y, z; (vii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (viii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ix) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812020247/bq2350sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020247/bq2350Isup2.hkl

checkCIF report

Comment top

Supramolecular chemistry, the knowledge of weak intermolecular interactions, has been attracting attention of basic sciences researchers and crystallographers (Lehn, 2002).

The functionalized materials such as dicarboxylic acids, amines and amides are important in this area (Moulton & Zaworotko, 2001).

Since 2008, we have focused on polycarboxylic acid complexes with transition metal ions along with N–, O–, and S– donor ligands for better clarification of non-covalent and coordination interactions of these ligands in natural human system, food chemistry, medicine etc (Mirzaei et al., 2011a; Axelrod et al., 2000).

Among them, pyridine-2,6-dicarboxylic acid with two carboxylic groups and a heteroaromatic ring has capability of participating in intermolecular interactions. Also, H₂pydc and its mono- or doubly protonated form with high symmetry and four electron donating oxygen atoms and one nitrogen atom can be applied as a multidendate ligand in coordination compounds which can possess various coordination modes (Aghabozorg et al., 2008; Mirzaei et al., 2011). The most common coordination mode for (pydc)^2- is tridentate: two (pydc)^2- are coordinated to metal and induce octahedral coordination environment to the metal ion (Eshtiagh-Hosseini et al., 2010b). In this case, a counter ion is required for compensation of charge, for example, (Hbmmpa)[Fe(pydc)₂].(EtOH)_0.8(H₂O)_0.2 (bmmpa is short for 5-bromo-6-methyl-2-morpholinepyrimidine-4-amine, Eshtiagh-Hosseini et al., 2010a) and (H2-apym)[Fe(pydc)₂].3H₂O (2-apym is abbreviation of 2-aminopyrimidine, Eshtiagh-Hosseini et al. 2011a).

In continuation of our studies, we have synthesized and structurally characterized a new crystalline coordination compound, (H9-Acr)[Fe(pydc)₂].4H₂O.

Fe^III has been coordinated by two almost perpendicular tridentate ligands (dihedral angle 88.78 (7)° ) with distorted octahedral geometry; a protonated 9-Acr moiety is present as a cation (Fig. 1).

In crystalline network, anionic complexes are connected to each other by C—H···O (〈D—H···A: 170.93°) interactions which can create a supramolecular synthon with graph set R²₂(10) in [101] direction (Fig. 2). These chains are attached to each other by three membered water cluster (Fig.3). In spite of the most recently observation which π-π interactions created between acridine moieties (Eshtiagh-Hosseini et al., 2011b), no π–π interaction between H9-Acr moieties is observed. Instead, such an interaction can be observed between anionic and cationic parts as seen in Fig. 4 that may be important in the formation of the ultimate network.

Related literature top

For background to supramolecular chemistry, see: Lehn (2002). For functionalized materials, see: Moulton & Zaworotko (2001). For a brief reviews on the pyridinedicarboxylate family of ligands, see: Mirzaei et al. (2011); Axelrod et al. (2000). For the role of water clusters, see: Aghabozorg et al. (2010). For related structures: Aghabozorg et al. (2008); Eshtiagh-Hosseini et al. (2010a,b, 2011a,b).

Experimental top

To an aqeous solution (5 ml) of pydcH₂ (0.034 g, 0.2 mmol), 9-Acr (0.020 g, 0.1 mmol) in methanol (10 ml) solution was added dropwise following which a solution of FeCl₃.6H₂O (0.027 g, 0.1 mmol) in water (2 ml) was added and the resultant solution was heated and stirred for 3 hrs at 60 °C. Yellow crystals were obtained by slow evaporation of the solvent at room temperature after a week.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. An ORTEP view of the title compound with numbering non-hydrogen atoms with probability 50%.
	Fig. 2. A representation of 1-D chains formed by anionic complexes with considering related synthons.
	Fig. 3. The role of water clusters in connection of 1-D chains.
	Fig. 4. Packing diagram of the title compounds with considering π—π stacking between cationic and anionic parts (water molecules have been omitted; Cg1: N2, C, C9, C10, C11, C12 and Cg2: N3, C15, C20, C21, C22, C27).

9-Aminoacridinium bis(pyridine-2,6-dicarboxylato- κ³O²,N,O⁶)ferrate(III) tetrahydrate top

Crystal data top

(C₁₃H₁₁N₂)[Fe(C₇H₃NO₄)₂]·4H₂O	F(000) = 1348
M_r = 653.36	D_x = 1.503 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 7426 reflections
a = 9.6130 (1) Å	θ = 3.6–75.8°
b = 18.9256 (2) Å	µ = 4.77 mm⁻¹
c = 15.9563 (2) Å	T = 293 K
β = 96.037 (1)°	Prism, yellow
V = 2886.86 (6) Å³	0.2 × 0.15 × 0.1 mm
Z = 4

Data collection top

Agilent Xcalibur Ruby Nova diffractometer	5140 reflections with I > 2σ(I)
ω scans	R_int = 0.020
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	θ_max = 76.0°, θ_min = 3.6°
T_min = 0.602, T_max = 1	h = −11→12
15252 measured reflections	k = −23→20
5940 independent reflections	l = −19→17

Refinement top

Refinement on F²	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.1074P)² + 1.5769P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.059	(Δ/σ)_max = 0.001
wR(F²) = 0.178	Δρ_max = 0.86 e Å⁻³
S = 1.05	Δρ_min = −0.33 e Å⁻³
5940 reflections	Extinction correction: SHELXS97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
430 parameters	Extinction coefficient: 0.0010 (3)
14 restraints

Crystal data top

(C₁₃H₁₁N₂)[Fe(C₇H₃NO₄)₂]·4H₂O	V = 2886.86 (6) Å³
M_r = 653.36	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 9.6130 (1) Å	µ = 4.77 mm⁻¹
b = 18.9256 (2) Å	T = 293 K
c = 15.9563 (2) Å	0.2 × 0.15 × 0.1 mm
β = 96.037 (1)°

Data collection top

Agilent Xcalibur Ruby Nova diffractometer	5940 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	5140 reflections with I > 2σ(I)
T_min = 0.602, T_max = 1	R_int = 0.020
15252 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	14 restraints
wR(F²) = 0.178	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.86 e Å⁻³
5940 reflections	Δρ_min = −0.33 e Å⁻³
430 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Fe1	0.52343 (5)	0.88273 (2)	0.30488 (3)	0.04513 (18)
O1	0.6777 (3)	0.95237 (13)	0.33779 (15)	0.0614 (6)
O2	0.7959 (3)	1.01376 (15)	0.4417 (2)	0.0796 (8)
O3	0.3790 (2)	0.81178 (12)	0.33429 (13)	0.0532 (5)
O4	0.2764 (3)	0.75917 (14)	0.43703 (16)	0.0697 (7)
O5	0.6572 (2)	0.80542 (12)	0.27746 (13)	0.0535 (5)
O6	0.7560 (3)	0.74841 (14)	0.17669 (16)	0.0657 (6)
O7	0.3804 (3)	0.95880 (13)	0.26910 (15)	0.0611 (6)
O8	0.2689 (3)	1.01957 (14)	0.1621 (2)	0.0754 (8)
N1	0.5332 (2)	0.88765 (12)	0.43414 (15)	0.0417 (5)
N2	0.5108 (3)	0.88283 (12)	0.17512 (15)	0.0418 (5)
C1	0.6238 (3)	0.93173 (15)	0.47541 (18)	0.0451 (6)
C2	0.6292 (4)	0.93776 (18)	0.5628 (2)	0.0550 (7)
H2	0.6926	0.968	0.5925	0.066*
C3	0.5380 (4)	0.89773 (19)	0.6036 (2)	0.0592 (8)
H3	0.5386	0.9016	0.6618	0.071*
C4	0.4454 (4)	0.85176 (18)	0.55960 (19)	0.0530 (7)
H4	0.3846	0.8242	0.5874	0.064*
C5	0.4457 (3)	0.84784 (15)	0.47327 (18)	0.0430 (6)
C6	0.7092 (3)	0.97043 (16)	0.4157 (2)	0.0550 (7)
C7	0.3576 (3)	0.80208 (16)	0.41175 (19)	0.0479 (6)
C8	0.5914 (3)	0.83863 (15)	0.13740 (17)	0.0424 (6)
C9	0.5902 (3)	0.83856 (18)	0.0508 (2)	0.0534 (7)
H9	0.6478	0.8084	0.0241	0.064*
C10	0.5001 (4)	0.88496 (19)	0.0052 (2)	0.0594 (8)
H10	0.496	0.8858	−0.0533	0.071*
C11	0.4157 (3)	0.93029 (17)	0.0460 (2)	0.0536 (7)
H11	0.3546	0.9613	0.0156	0.064*
C12	0.4250 (3)	0.92806 (14)	0.13266 (19)	0.0443 (6)
C13	0.6774 (3)	0.79258 (16)	0.20043 (19)	0.0467 (6)
C14	0.3490 (3)	0.97350 (16)	0.1909 (2)	0.0529 (7)
N3	0.2278 (3)	0.76041 (19)	0.1687 (2)	0.0685 (8)
H3A	0.2451	0.7491	0.2209	0.082*
N4	0.1409 (4)	0.80668 (19)	−0.0810 (2)	0.0756 (9)
H4A	0.0776	0.8374	−0.097	0.091*
H4B	0.1847	0.7852	−0.1178	0.091*
C15	0.3006 (3)	0.72748 (18)	0.1104 (2)	0.0562 (7)
C16	0.4026 (4)	0.6782 (2)	0.1433 (3)	0.0755 (11)
H16	0.417	0.6688	0.2007	0.091*
C17	0.4812 (4)	0.6441 (2)	0.0865 (4)	0.0830 (14)
H17	0.5494	0.6115	0.106	0.1*
C18	0.4577 (4)	0.6589 (2)	0.0009 (3)	0.0800 (12)
H18	0.5114	0.6364	−0.0364	0.096*
C19	0.3580 (4)	0.7053 (2)	−0.0290 (3)	0.0686 (9)
H19	0.3424	0.7135	−0.0867	0.082*
C20	0.2791 (3)	0.74077 (17)	0.0250 (2)	0.0549 (7)
C21	0.1699 (3)	0.79300 (18)	−0.0026 (2)	0.0565 (8)
C22	0.0989 (3)	0.82788 (15)	0.05985 (19)	0.0468 (6)
C23	−0.0044 (4)	0.88057 (18)	0.0422 (3)	0.0637 (9)
H23	−0.0291	0.8932	−0.0138	0.076*
C24	−0.0686 (5)	0.9133 (2)	0.1019 (3)	0.0802 (12)
H24	−0.1351	0.948	0.0873	0.096*
C25	−0.0347 (4)	0.8947 (3)	0.1863 (3)	0.0823 (13)
H25	−0.0796	0.9171	0.2279	0.099*
C26	0.0625 (5)	0.8445 (3)	0.2084 (3)	0.0775 (11)
H26	0.0843	0.833	0.265	0.093*
C27	0.1307 (4)	0.8097 (2)	0.1468 (3)	0.0618 (8)
O9	0.8858 (3)	0.66602 (17)	0.30146 (19)	0.0750 (7)
H9A	0.841 (5)	0.687 (3)	0.253 (2)	0.115 (19)*
H9B	0.982 (2)	0.671 (3)	0.302 (3)	0.089 (15)*
O10	0.7306 (4)	1.03358 (19)	0.1934 (3)	0.0988 (11)
H10A	0.675 (6)	1.076 (2)	0.199 (4)	0.14 (2)*
H10B	0.710 (9)	1.008 (3)	0.243 (3)	0.21 (4)*
O11	0.1750 (3)	0.66734 (15)	0.31482 (18)	0.0691 (7)
H11A	0.210 (5)	0.693 (2)	0.364 (2)	0.097 (16)*
H11B	0.206 (4)	0.6226 (12)	0.331 (3)	0.069 (12)*
O12	0.0023 (3)	1.08479 (18)	0.1758 (2)	0.0844 (8)
H12A	−0.090 (5)	1.067 (7)	0.160 (5)	1.1 (4)*
H12B	0.063 (7)	1.052 (8)	0.153 (10)	0.53 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0566 (3)	0.0466 (3)	0.0345 (3)	−0.00371 (19)	0.01561 (18)	−0.00198 (16)
O1	0.0685 (14)	0.0605 (13)	0.0584 (13)	−0.0183 (11)	0.0217 (11)	0.0015 (11)
O2	0.0737 (16)	0.0708 (16)	0.094 (2)	−0.0321 (14)	0.0055 (14)	−0.0027 (15)
O3	0.0645 (13)	0.0585 (12)	0.0382 (10)	−0.0174 (10)	0.0122 (9)	−0.0063 (9)
O4	0.0761 (15)	0.0758 (16)	0.0608 (14)	−0.0338 (13)	0.0245 (12)	−0.0043 (12)
O5	0.0655 (13)	0.0558 (12)	0.0406 (11)	0.0111 (10)	0.0117 (9)	0.0035 (9)
O6	0.0697 (14)	0.0677 (15)	0.0609 (14)	0.0242 (12)	0.0130 (11)	−0.0066 (11)
O7	0.0762 (15)	0.0572 (13)	0.0532 (13)	0.0114 (11)	0.0221 (11)	−0.0085 (10)
O8	0.0786 (17)	0.0567 (14)	0.092 (2)	0.0225 (13)	0.0144 (14)	0.0045 (13)
N1	0.0460 (12)	0.0426 (12)	0.0380 (12)	−0.0022 (9)	0.0118 (9)	−0.0038 (9)
N2	0.0484 (12)	0.0404 (12)	0.0387 (12)	−0.0015 (9)	0.0141 (9)	0.0007 (9)
C1	0.0482 (14)	0.0424 (13)	0.0450 (14)	−0.0003 (11)	0.0061 (11)	−0.0074 (11)
C2	0.0610 (18)	0.0549 (17)	0.0475 (16)	0.0039 (14)	−0.0014 (13)	−0.0139 (13)
C3	0.076 (2)	0.0651 (19)	0.0362 (15)	0.0081 (17)	0.0064 (14)	−0.0077 (13)
C4	0.0615 (17)	0.0594 (17)	0.0407 (15)	0.0040 (14)	0.0176 (13)	0.0025 (13)
C5	0.0469 (14)	0.0454 (14)	0.0388 (13)	0.0007 (11)	0.0142 (11)	−0.0002 (11)
C6	0.0542 (16)	0.0437 (15)	0.068 (2)	−0.0072 (13)	0.0114 (14)	−0.0008 (14)
C7	0.0514 (15)	0.0509 (15)	0.0436 (14)	−0.0088 (12)	0.0151 (12)	−0.0008 (12)
C8	0.0453 (13)	0.0434 (13)	0.0403 (14)	−0.0019 (11)	0.0129 (11)	−0.0031 (11)
C9	0.0601 (17)	0.0583 (17)	0.0446 (15)	−0.0004 (14)	0.0188 (13)	−0.0067 (13)
C10	0.073 (2)	0.073 (2)	0.0336 (15)	−0.0046 (16)	0.0093 (13)	0.0006 (13)
C11	0.0574 (17)	0.0527 (16)	0.0499 (16)	−0.0040 (13)	0.0031 (13)	0.0082 (13)
C12	0.0476 (14)	0.0382 (13)	0.0482 (15)	−0.0040 (11)	0.0103 (11)	0.0031 (11)
C13	0.0494 (14)	0.0479 (15)	0.0442 (15)	0.0023 (12)	0.0110 (11)	−0.0021 (12)
C14	0.0572 (17)	0.0412 (14)	0.0623 (19)	0.0028 (13)	0.0159 (14)	−0.0011 (13)
N3	0.0682 (18)	0.083 (2)	0.0547 (16)	0.0035 (16)	0.0074 (13)	0.0079 (15)
N4	0.081 (2)	0.075 (2)	0.072 (2)	0.0226 (17)	0.0148 (16)	0.0112 (17)
C15	0.0481 (15)	0.0581 (17)	0.0643 (19)	−0.0061 (14)	0.0142 (14)	−0.0041 (15)
C16	0.073 (2)	0.083 (3)	0.068 (2)	−0.009 (2)	−0.0075 (19)	0.020 (2)
C17	0.0507 (19)	0.064 (2)	0.132 (4)	0.0162 (17)	−0.001 (2)	0.011 (2)
C18	0.066 (2)	0.078 (3)	0.100 (3)	0.000 (2)	0.028 (2)	−0.016 (2)
C19	0.074 (2)	0.070 (2)	0.063 (2)	−0.0053 (18)	0.0125 (17)	−0.0034 (17)
C20	0.0540 (16)	0.0473 (15)	0.0628 (19)	−0.0045 (13)	0.0028 (14)	0.0047 (13)
C21	0.0541 (16)	0.0565 (17)	0.0598 (19)	−0.0091 (14)	0.0106 (14)	−0.0034 (14)
C22	0.0412 (13)	0.0451 (14)	0.0540 (16)	−0.0046 (11)	0.0049 (11)	−0.0008 (12)
C23	0.0570 (18)	0.0532 (18)	0.082 (3)	0.0021 (14)	0.0099 (17)	−0.0086 (16)
C24	0.072 (2)	0.070 (2)	0.100 (3)	0.010 (2)	0.015 (2)	−0.007 (2)
C25	0.075 (3)	0.083 (3)	0.093 (3)	0.002 (2)	0.027 (2)	−0.021 (2)
C26	0.075 (2)	0.092 (3)	0.068 (2)	−0.006 (2)	0.0185 (19)	−0.009 (2)
C27	0.0504 (17)	0.0624 (19)	0.074 (2)	−0.0068 (15)	0.0104 (15)	−0.0053 (17)
O9	0.0724 (17)	0.0870 (19)	0.0651 (16)	−0.0028 (15)	0.0058 (13)	0.0152 (14)
O10	0.120 (3)	0.077 (2)	0.109 (3)	0.0106 (19)	0.056 (2)	0.0198 (19)
O11	0.0763 (16)	0.0622 (15)	0.0669 (16)	−0.0011 (13)	−0.0014 (13)	0.0011 (12)
O12	0.0805 (18)	0.0745 (18)	0.098 (2)	0.0113 (15)	0.0102 (16)	0.0118 (16)

Geometric parameters (Å, º) top

Fe1—O1	2.012 (2)	N3—C27	1.341 (5)
Fe1—O3	2.022 (2)	N3—C15	1.371 (5)
Fe1—O5	2.026 (2)	N3—H3A	0.86
Fe1—O7	2.031 (2)	N4—C21	1.280 (5)
Fe1—N1	2.057 (2)	N4—H4A	0.86
Fe1—N2	2.061 (2)	N4—H4B	0.86
O1—C6	1.294 (4)	C15—C20	1.379 (5)
O2—C6	1.211 (4)	C15—C16	1.414 (5)
O3—C7	1.287 (4)	C16—C17	1.397 (7)
O4—C7	1.224 (4)	C16—H16	0.93
O5—C13	1.288 (4)	C17—C18	1.389 (7)
O6—C13	1.214 (4)	C17—H17	0.93
O7—C14	1.283 (4)	C18—C19	1.350 (6)
O8—C14	1.221 (4)	C18—H18	0.93
N1—C1	1.329 (4)	C19—C20	1.381 (5)
N1—C5	1.333 (4)	C19—H19	0.93
N2—C12	1.324 (4)	C20—C21	1.475 (5)
N2—C8	1.327 (4)	C21—C22	1.428 (5)
C1—C2	1.394 (4)	C22—C23	1.415 (5)
C1—C6	1.511 (4)	C22—C27	1.431 (5)
C2—C3	1.374 (5)	C23—C24	1.340 (6)
C2—H2	0.93	C23—H23	0.93
C3—C4	1.382 (5)	C24—C25	1.398 (7)
C3—H3	0.93	C24—H24	0.93
C4—C5	1.380 (4)	C25—C26	1.353 (7)
C4—H4	0.93	C25—H25	0.93
C5—C7	1.502 (4)	C26—C27	1.402 (6)
C8—C9	1.380 (4)	C26—H26	0.93
C8—C13	1.510 (4)	O9—H9A	0.928 (19)
C9—C10	1.385 (5)	O9—H9B	0.924 (19)
C9—H9	0.93	O10—H10A	0.97 (2)
C10—C11	1.388 (5)	O10—H10B	0.96 (2)
C10—H10	0.93	O11—H11A	0.946 (19)
C11—C12	1.377 (4)	O11—H11B	0.926 (18)
C11—H11	0.93	O12—H12A	0.96 (2)
C12—C14	1.510 (4)	O12—H12B	0.96 (2)

O1—Fe1—O3	151.61 (9)	N2—C12—C11	120.3 (3)
O1—Fe1—O5	93.57 (10)	N2—C12—C14	111.6 (3)
O3—Fe1—O5	92.15 (10)	C11—C12—C14	128.0 (3)
O1—Fe1—O7	93.89 (12)	O6—C13—O5	126.1 (3)
O3—Fe1—O7	94.29 (10)	O6—C13—C8	120.3 (3)
O5—Fe1—O7	151.37 (9)	O5—C13—C8	113.6 (2)
O1—Fe1—N1	75.75 (9)	O8—C14—O7	126.5 (3)
O3—Fe1—N1	75.96 (9)	O8—C14—C12	120.2 (3)
O5—Fe1—N1	106.63 (9)	O7—C14—C12	113.3 (3)
O7—Fe1—N1	102.00 (9)	C27—N3—C15	122.1 (3)
O1—Fe1—N2	103.03 (9)	C27—N3—H3A	119
O3—Fe1—N2	105.34 (9)	C15—N3—H3A	119
O5—Fe1—N2	75.84 (9)	C21—N4—H4A	120
O7—Fe1—N2	75.54 (9)	C21—N4—H4B	120
N1—Fe1—N2	177.24 (9)	H4A—N4—H4B	120
C6—O1—Fe1	121.0 (2)	N3—C15—C20	123.6 (3)
C7—O3—Fe1	120.05 (19)	N3—C15—C16	115.5 (4)
C13—O5—Fe1	120.35 (19)	C20—C15—C16	120.9 (3)
C14—O7—Fe1	120.66 (19)	C17—C16—C15	117.7 (4)
C1—N1—C5	122.4 (3)	C17—C16—H16	121.2
C1—N1—Fe1	118.93 (19)	C15—C16—H16	121.2
C5—N1—Fe1	118.67 (19)	C18—C17—C16	120.1 (4)
C12—N2—C8	122.5 (3)	C18—C17—H17	119.9
C12—N2—Fe1	118.83 (19)	C16—C17—H17	119.9
C8—N2—Fe1	118.65 (19)	C19—C18—C17	121.0 (4)
N1—C1—C2	120.0 (3)	C19—C18—H18	119.5
N1—C1—C6	111.3 (3)	C17—C18—H18	119.5
C2—C1—C6	128.7 (3)	C18—C19—C20	120.8 (4)
C3—C2—C1	118.1 (3)	C18—C19—H19	119.6
C3—C2—H2	120.9	C20—C19—H19	119.6
C1—C2—H2	120.9	C15—C20—C19	119.5 (3)
C2—C3—C4	121.0 (3)	C15—C20—C21	116.4 (3)
C2—C3—H3	119.5	C19—C20—C21	124.1 (3)
C4—C3—H3	119.5	N4—C21—C22	121.2 (3)
C5—C4—C3	118.2 (3)	N4—C21—C20	120.2 (3)
C5—C4—H4	120.9	C22—C21—C20	118.6 (3)
C3—C4—H4	120.9	C23—C22—C21	124.3 (3)
N1—C5—C4	120.3 (3)	C23—C22—C27	115.9 (3)
N1—C5—C7	111.1 (2)	C21—C22—C27	119.8 (3)
C4—C5—C7	128.5 (3)	C24—C23—C22	123.3 (4)
O2—C6—O1	126.2 (3)	C24—C23—H23	118.3
O2—C6—C1	120.8 (3)	C22—C23—H23	118.3
O1—C6—C1	112.9 (3)	C23—C24—C25	119.4 (4)
O4—C7—O3	125.7 (3)	C23—C24—H24	120.3
O4—C7—C5	120.2 (3)	C25—C24—H24	120.3
O3—C7—C5	114.1 (2)	C26—C25—C24	120.8 (4)
N2—C8—C9	120.7 (3)	C26—C25—H25	119.6
N2—C8—C13	111.5 (2)	C24—C25—H25	119.6
C9—C8—C13	127.8 (3)	C25—C26—C27	120.5 (4)
C8—C9—C10	117.7 (3)	C25—C26—H26	119.8
C8—C9—H9	121.2	C27—C26—H26	119.8
C10—C9—H9	121.2	N3—C27—C26	120.5 (4)
C9—C10—C11	120.6 (3)	N3—C27—C22	119.4 (3)
C9—C10—H10	119.7	C26—C27—C22	120.0 (4)
C11—C10—H10	119.7	H9A—O9—H9B	110 (4)
C12—C11—C10	118.2 (3)	H10A—O10—H10B	100 (4)
C12—C11—H11	120.9	H11A—O11—H11B	99 (3)
C10—C11—H11	120.9	H12A—O12—H12B	105 (5)

O3—Fe1—O1—C6	−7.7 (4)	C4—C5—C7—O3	178.1 (3)
O5—Fe1—O1—C6	−108.9 (3)	C12—N2—C8—C9	0.7 (4)
O7—Fe1—O1—C6	98.8 (3)	Fe1—N2—C8—C9	−177.7 (2)
N1—Fe1—O1—C6	−2.6 (2)	C12—N2—C8—C13	−179.4 (2)
N2—Fe1—O1—C6	174.9 (2)	Fe1—N2—C8—C13	2.2 (3)
O1—Fe1—O3—C7	5.6 (4)	N2—C8—C9—C10	−1.3 (5)
O5—Fe1—O3—C7	107.1 (2)	C13—C8—C9—C10	178.8 (3)
O7—Fe1—O3—C7	−100.8 (2)	C8—C9—C10—C11	0.8 (5)
N1—Fe1—O3—C7	0.5 (2)	C9—C10—C11—C12	0.4 (5)
N2—Fe1—O3—C7	−177.0 (2)	C8—N2—C12—C11	0.6 (4)
O1—Fe1—O5—C13	−100.7 (2)	Fe1—N2—C12—C11	179.0 (2)
O3—Fe1—O5—C13	107.1 (2)	C8—N2—C12—C14	−178.3 (2)
O7—Fe1—O5—C13	4.1 (4)	Fe1—N2—C12—C14	0.1 (3)
N1—Fe1—O5—C13	−176.9 (2)	C10—C11—C12—N2	−1.1 (4)
N2—Fe1—O5—C13	1.8 (2)	C10—C11—C12—C14	177.5 (3)
O1—Fe1—O7—C14	101.3 (3)	Fe1—O5—C13—O6	179.0 (3)
O3—Fe1—O7—C14	−105.9 (2)	Fe1—O5—C13—C8	−1.2 (3)
O5—Fe1—O7—C14	−3.4 (4)	N2—C8—C13—O6	179.1 (3)
N1—Fe1—O7—C14	177.6 (2)	C9—C8—C13—O6	−1.0 (5)
N2—Fe1—O7—C14	−1.1 (2)	N2—C8—C13—O5	−0.7 (4)
O1—Fe1—N1—C1	2.2 (2)	C9—C8—C13—O5	179.2 (3)
O3—Fe1—N1—C1	179.7 (2)	Fe1—O7—C14—O8	−177.2 (3)
O5—Fe1—N1—C1	91.7 (2)	Fe1—O7—C14—C12	1.5 (4)
O7—Fe1—N1—C1	−88.8 (2)	N2—C12—C14—O8	177.8 (3)
O1—Fe1—N1—C5	−179.6 (2)	C11—C12—C14—O8	−1.0 (5)
O3—Fe1—N1—C5	−2.1 (2)	N2—C12—C14—O7	−1.0 (4)
O5—Fe1—N1—C5	−90.1 (2)	C11—C12—C14—O7	−179.8 (3)
O7—Fe1—N1—C5	89.4 (2)	C27—N3—C15—C20	−1.3 (5)
O1—Fe1—N2—C12	−90.2 (2)	C27—N3—C15—C16	178.2 (3)
O3—Fe1—N2—C12	91.0 (2)	N3—C15—C16—C17	−179.0 (4)
O5—Fe1—N2—C12	179.3 (2)	C20—C15—C16—C17	0.5 (6)
O7—Fe1—N2—C12	0.5 (2)	C15—C16—C17—C18	−0.2 (6)
O1—Fe1—N2—C8	88.2 (2)	C16—C17—C18—C19	−0.9 (7)
O3—Fe1—N2—C8	−90.5 (2)	C17—C18—C19—C20	1.7 (7)
O5—Fe1—N2—C8	−2.2 (2)	N3—C15—C20—C19	179.6 (3)
O7—Fe1—N2—C8	178.9 (2)	C16—C15—C20—C19	0.2 (5)
C5—N1—C1—C2	−0.3 (4)	N3—C15—C20—C21	−0.7 (5)
Fe1—N1—C1—C2	177.9 (2)	C16—C15—C20—C21	179.9 (3)
C5—N1—C1—C6	−179.7 (3)	C18—C19—C20—C15	−1.3 (6)
Fe1—N1—C1—C6	−1.5 (3)	C18—C19—C20—C21	179.0 (4)
N1—C1—C2—C3	−0.7 (5)	C15—C20—C21—N4	−178.0 (3)
C6—C1—C2—C3	178.6 (3)	C19—C20—C21—N4	1.7 (5)
C1—C2—C3—C4	1.2 (5)	C15—C20—C21—C22	2.5 (4)
C2—C3—C4—C5	−0.8 (5)	C19—C20—C21—C22	−177.8 (3)
C1—N1—C5—C4	0.7 (4)	N4—C21—C22—C23	−1.7 (5)
Fe1—N1—C5—C4	−177.5 (2)	C20—C21—C22—C23	177.9 (3)
C1—N1—C5—C7	−178.8 (3)	N4—C21—C22—C27	178.0 (3)
Fe1—N1—C5—C7	3.1 (3)	C20—C21—C22—C27	−2.4 (4)
C3—C4—C5—N1	−0.1 (5)	C21—C22—C23—C24	−179.1 (4)
C3—C4—C5—C7	179.3 (3)	C27—C22—C23—C24	1.1 (5)
Fe1—O1—C6—O2	−176.8 (3)	C22—C23—C24—C25	−0.8 (6)
Fe1—O1—C6—C1	2.5 (4)	C23—C24—C25—C26	0.4 (7)
N1—C1—C6—O2	178.8 (3)	C24—C25—C26—C27	−0.4 (7)
C2—C1—C6—O2	−0.5 (5)	C15—N3—C27—C26	−177.3 (4)
N1—C1—C6—O1	−0.6 (4)	C15—N3—C27—C22	1.4 (5)
C2—C1—C6—O1	−179.9 (3)	C25—C26—C27—N3	179.5 (4)
Fe1—O3—C7—O4	−177.6 (3)	C25—C26—C27—C22	0.8 (6)
Fe1—O3—C7—C5	0.9 (4)	C23—C22—C27—N3	−179.8 (3)
N1—C5—C7—O4	176.0 (3)	C21—C22—C27—N3	0.5 (5)
C4—C5—C7—O4	−3.4 (5)	C23—C22—C27—C26	−1.1 (5)
N1—C5—C7—O3	−2.5 (4)	C21—C22—C27—C26	179.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O3	0.86	2.42	3.038 (4)	130
N3—H3A···O11	0.86	2.30	3.008 (4)	139
N4—H4A···O12ⁱ	0.86	2.03	2.822 (5)	152
N4—H4B···O5ⁱⁱ	0.86	2.39	3.115 (4)	142
O9—H9A···O6	0.93 (4)	1.81 (5)	2.726 (4)	165 (5)
O9—H9B···O11ⁱⁱⁱ	0.92 (2)	1.85 (2)	2.766 (4)	170 (5)
O10—H10A···O9^iv	0.97 (5)	1.81 (5)	2.750 (5)	164 (5)
O10—H10B···O1	0.97 (5)	1.90 (5)	2.859 (5)	176 (11)
O11—H11A···O4	0.95 (4)	1.78 (4)	2.715 (4)	165 (3)
O11—H11B···O8^v	0.93 (4)	1.97 (2)	2.865 (4)	163 (4)
O12—H12A···O10^vi	0.96 (6)	1.96 (7)	2.827 (5)	149 (7)
O12—H12B···O8	0.95 (11)	2.06 (8)	2.874 (4)	142 (10)
C4—H4···O6^vii	0.93	2.41	3.334 (4)	171
C9—H9···O4^viii	0.93	2.33	3.257 (4)	171
C16—H16···O12^v	0.93	2.59	3.426 (6)	150
C17—H17···O2^ix	0.93	2.54	3.329 (5)	143

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

Experimental details

Crystal data
Chemical formula	(C₁₃H₁₁N₂)[Fe(C₇H₃NO₄)₂]·4H₂O
M_r	653.36
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.6130 (1), 18.9256 (2), 15.9563 (2)
β (°)	96.037 (1)
V (Å³)	2886.86 (6)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	4.77
Crystal size (mm)	0.2 × 0.15 × 0.1

Data collection
Diffractometer	Agilent Xcalibur Ruby Nova diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.602, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	15252, 5940, 5140
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.629

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.178, 1.05
No. of reflections	5940
No. of parameters	430
No. of restraints	14
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.33

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O3	0.86	2.42	3.038 (4)	130
N3—H3A···O11	0.86	2.30	3.008 (4)	139
N4—H4A···O12ⁱ	0.86	2.03	2.822 (5)	152
N4—H4B···O5ⁱⁱ	0.86	2.39	3.115 (4)	142
O9—H9A···O6	0.93 (4)	1.81 (5)	2.726 (4)	165 (5)
O9—H9B···O11ⁱⁱⁱ	0.92 (2)	1.85 (2)	2.766 (4)	170 (5)
O10—H10A···O9^iv	0.97 (5)	1.81 (5)	2.750 (5)	164 (5)
O10—H10B···O1	0.97 (5)	1.90 (5)	2.859 (5)	176 (11)
O11—H11A···O4	0.95 (4)	1.78 (4)	2.715 (4)	165 (3)
O11—H11B···O8^v	0.93 (4)	1.97 (2)	2.865 (4)	163 (4)
O12—H12A···O10^vi	0.96 (6)	1.96 (7)	2.827 (5)	149 (7)
O12—H12B···O8	0.95 (11)	2.06 (8)	2.874 (4)	142 (10)
C4—H4···O6^vii	0.93	2.41	3.334 (4)	171
C9—H9···O4^viii	0.93	2.33	3.257 (4)	171
C16—H16···O12^v	0.93	2.59	3.426 (6)	150
C17—H17···O2^ix	0.93	2.54	3.329 (5)	143

Acknowledgements

The authors wish to thank to the Ferdowsi University of Mashhad (grant No. 1506/.3) and the Ministry of Science, Education and Sports, Republic of Croatia (grant No. 098–1191344–2943) for financial support of this work.

References

Aghabozorg, H., Eshtiagh-Hosseini, H., Salimi, A. & Mirzaei, M. (2010). J. Iran. Chem. Soc. 7, 289–300. CrossRef CAS Google Scholar
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