1,1′-(Butane-1,4-di­yl)bis(1H-benzimidazol-3-ium) bis­[bis­(pyridine-2,6-dicarboxyl­ato-κ3O,N,O′)ferrate(III)] methanol disolvate

Hou, Z.-Y.; Zhu, D.-M.

doi:10.1107/S1600536805039152

1,1′-(Butane-1,4-diyl)bis(1H-benzimidazol-3-ium) bis[bis(pyridine-2,6-dicarboxylato-κ³O,N,O′)ferrate(III)] methanol disolvate

In the title complex, (C₁₈H₂₀N₄)[Fe(C₇O₄H₃N)₂]₂·2CH₄O, the Fe atom exists in an approximately octahedral geometry, chelated by two pyridine-2,6-dicarboxylate ligands. Extensive hydrogen bonding among the carboxylate groups, the 1,1′-(butane-1,4-diyl)bis-1H-benzimidazol-3-ium ion and solvent methanol molecules as well as π–π stacking are present in the structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039152/ng6243sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039152/ng6243Isup2.hkl Contains datablock I

CCDC reference: 296617

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Key indicators

Single-crystal X-ray study
T = 291 K
Mean (C-C) = 0.005 Å
R factor = 0.056
wR factor = 0.131
Data-to-parameter ratio = 13.8

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PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?

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   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
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Comment top

Proton transfer is one of the most important elementary processes in physics, chemistry and biochemistry, as it is the key process in important reactions such as auto ionization in water, acid–base neutralization reactions and enzyme catalysis (MacDonald et al., 2000). Extensive studies on the reaction of pyridine-2,6-dicarboxylic acid (H₂pdc) with lanthanides and transition metals in the presence of Lewis bases such as pyridine-2,6-diamine (pda), 1,10-phenanthroline (phen) and creatinine (creat) have led to the isolation of proton transfer ionic complexes [pdaH]₂[La₂(pdc)₄(H₂O)₄]·2H₂O, [pdaH]₂[Co(pdc)₂]·H₂O (Moghimi et al., 2002), (creatH)[Zn(pdc)(pdcH)]·4H₂O (Moghimi, Sharif et al., 2005) and [Zn(pdc)₂][Zn(phen)₂(H₂O)₂]·7H₂O (Moghimi, Sheshmani et al., 2005). On the other hand, the 1,1'-(butane-1,4-diyl)bis-1H-benzimidazole (bbbm) N-heterocycle as a flexible bidentate ligand affords adducts with some transition metal salts (Meng et al., 2003; Xiao et al., 2004). In this work, we selected H₂pdc as the proton donor and bbbm as the proton acceptor, and successfully prepared a new proton transfer Fe^III complex, (I).

Complex (I) consists of two mononuclear [Fe(pdc)₂]⁻ anions, one (H₂bbbm)²⁺ dication and two solvent methanol moleculars (Fig. 1). The central Fe atom is hexacoordinated by two pyridine N and four carboxylate O atoms from two deprotonated H₂pdc in an approximate octahedral geometry; the carboxyl group each coordinates in a monodentate fashion. The two ligands are almost perpendicular to each other.

Anions interact with the (H₂bbbm)²⁺ dication and solvent methanol molecules to produce a hydrogen-bonded layered structure by three types of hydrogen bond (N—H···O, O—H···O and C—H···O) (Table 1 and Fig. 2). The [Fe(pdc)₂]⁻ units are linked into layers, and the space between these layers is occupied by the (H₂bbbm)²⁺ cations. A face-to-face separation of 3.642 (2) A° between the N2-containing pyridine rings from two neighboring anions suggests the existence of π–π aromatic stacking interactions.

Experimental top

1,1'-(Butane-1,4-diyl)bis-1H-benzimidazole (bbbm) was prepared according to a literature method (Xie et al., 2000). A methanol solution (5 ml) of H₂pdc (16.7 mg, 0.1 mmol) was added dropwise to a methanol solution (5 ml) of Fe(ClO₄)₃·7H₂O (23.2 mg, 0.05 mmol) and bbbm (29.0 mg, 0.1 mmol) to give a clear solution. Light-green block-like crystals (55% yield) of (I) were obtained one week later. IR (KBr, cm⁻¹): 3081 (w), 1675 (s), 1452 (w), 1322 (s), 1167 (s), 1072 (s), 914 (m), 742 (s), 681 (m), 439 (w). Analysis calculated for C₄₈H₄₀Fe₂N₈O₁₈: C 51.08, H 3.57, N 9.93%; found: C 51.23, H 3.47, N 9.85%.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The molecular structure of the anion of (I), with 30% probability displacement ellipsoids.
	Fig. 2. A perspective view of the hydrogen-bonding interactions (dashed lines) in (I). For clarity, H atoms not involved in hydrogen bonding have been omitted.

1,1'-(Butane-1,4-diyl)bi-1H-benzimidazol-3-ium bis[bis(pyridine-2,6-dicarboxylato-κ³O,N,O')ferrate(III)] methanol disolvate top

Crystal data top

(C₁₈H₂₀N₄)[Fe(C₇H₃NO₄)₂]₂·2CH₄O	Z = 1
M_r = 1128.58	F(000) = 580
Triclinic, P1	D_x = 1.549 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.2751 (19) Å	Cell parameters from 779 reflections
b = 11.035 (2) Å	θ = 2.1–18.0°
c = 13.167 (3) Å	µ = 0.69 mm⁻¹
α = 106.50 (3)°	T = 291 K
β = 101.19 (3)°	Block, light-green
γ = 103.07 (3)°	0.20 × 0.18 × 0.17 mm
V = 1209.6 (6) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4764 independent reflections
Radiation source: sealed tube	3875 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
T_min = 0.875, T_max = 0.892	k = −13→13
8712 measured reflections	l = −16→16

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.06P)² + 0.88P] where P = (F_o² + 2F_c²)/3
4764 reflections	(Δ/σ)_max < 0.001
344 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.74 e Å⁻³

Crystal data top

(C₁₈H₂₀N₄)[Fe(C₇H₃NO₄)₂]₂·2CH₄O	γ = 103.07 (3)°
M_r = 1128.58	V = 1209.6 (6) Å³
Triclinic, P1	Z = 1
a = 9.2751 (19) Å	Mo Kα radiation
b = 11.035 (2) Å	µ = 0.69 mm⁻¹
c = 13.167 (3) Å	T = 291 K
α = 106.50 (3)°	0.20 × 0.18 × 0.17 mm
β = 101.19 (3)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4764 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3875 reflections with I > 2σ(I)
T_min = 0.875, T_max = 0.892	R_int = 0.046
8712 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.02	Δρ_max = 0.43 e Å⁻³
4764 reflections	Δρ_min = −0.74 e Å⁻³
344 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
C1	0.6926 (4)	1.0617 (3)	1.0015 (3)	0.0357 (7)
C2	0.7244 (4)	1.0636 (4)	1.1099 (3)	0.0413 (8)
H2	0.6968	1.1225	1.1632	0.050*
C3	0.7972 (4)	0.9767 (4)	1.1366 (3)	0.0442 (8)
H3	0.8200	0.9773	1.2088	0.053*
C4	0.8369 (4)	0.8886 (3)	1.0571 (3)	0.0380 (8)
H4	0.8852	0.8290	1.0746	0.046*
C5	0.8032 (3)	0.8914 (3)	0.9518 (2)	0.0311 (7)
C6	0.6193 (4)	1.1504 (3)	0.9533 (3)	0.0351 (7)
C7	0.8393 (4)	0.8089 (3)	0.8531 (3)	0.0340 (7)
C8	0.5383 (3)	0.8588 (3)	0.5293 (3)	0.0295 (6)
H9E	0.9205	0.7792	0.6721	0.035*
C9	0.5241 (4)	0.8296 (4)	0.4180 (3)	0.0422 (8)
H9	0.4370	0.7662	0.3664	0.051*
C10	0.6420 (5)	0.8965 (4)	0.3834 (3)	0.0486 (9)
H10	0.6336	0.8789	0.3087	0.058*
C11	0.7723 (4)	0.9900 (3)	0.4629 (3)	0.0355 (7)
H11	0.8521	1.0359	0.4423	0.043*
C12	0.7799 (3)	1.0128 (3)	0.5732 (2)	0.0284 (6)
C13	0.4284 (4)	0.7997 (3)	0.5859 (3)	0.0370 (7)
C14	0.9097 (4)	1.1072 (3)	0.6736 (3)	0.0359 (7)
C15	0.3360 (4)	0.5495 (3)	0.7372 (3)	0.0345 (7)
C16	0.4811 (4)	0.5538 (3)	0.7256 (3)	0.0394 (8)
H16A	0.5247	0.5991	0.6839	0.047*
C17	0.5572 (4)	0.4872 (4)	0.7792 (3)	0.0445 (8)
H17A	0.6554	0.4869	0.7732	0.053*
C18	0.4937 (4)	0.4200 (4)	0.8424 (3)	0.0483 (9)
H18A	0.5507	0.3773	0.8781	0.058*
C19	0.3489 (4)	0.4155 (3)	0.8533 (3)	0.0430 (8)
H19A	0.3050	0.3695	0.8944	0.052*
C20	0.2711 (4)	0.4834 (3)	0.7994 (3)	0.0353 (7)
C21	0.1078 (4)	0.5786 (3)	0.7354 (3)	0.0367 (7)
H21A	0.0217	0.6076	0.7215	0.044*
C22	0.0148 (4)	0.4522 (3)	0.8512 (3)	0.0380 (7)
H22A	0.0059	0.3598	0.8401	0.046*
H22B	−0.0853	0.4572	0.8173	0.046*
C23	0.0597 (4)	0.5286 (3)	0.9734 (3)	0.0389 (8)
H23B	0.0673	0.6209	0.9851	0.047*
H23A	0.1599	0.5240	1.0078	0.047*
C24	0.8961 (5)	0.6846 (4)	0.5266 (3)	0.0521 (9)
H24A	0.8356	0.7248	0.4864	0.078*
H24B	0.8290	0.6152	0.5409	0.078*
H24C	0.9590	0.6484	0.4839	0.078*
Fe1	0.68843 (5)	0.98165 (4)	0.76879 (4)	0.03254 (15)
N1	0.7338 (3)	0.9765 (3)	0.9268 (2)	0.0324 (6)
N2	0.6650 (3)	0.9485 (3)	0.6026 (2)	0.0295 (5)
N3	0.2277 (3)	0.6065 (3)	0.6977 (2)	0.0362 (6)
H3E	0.2352	0.6476	0.6494	0.043*
N4	0.1276 (3)	0.5030 (3)	0.7961 (2)	0.0326 (6)
O1	0.6088 (3)	1.1228 (2)	0.84865 (17)	0.0325 (5)
O2	0.5797 (3)	1.2364 (3)	1.0107 (2)	0.0484 (6)
O3	0.7941 (3)	0.8350 (2)	0.76377 (19)	0.0396 (5)
O4	0.9037 (3)	0.7241 (3)	0.8583 (2)	0.0427 (6)
O5	0.4744 (3)	0.8502 (2)	0.69136 (18)	0.0373 (5)
O6	0.3070 (3)	0.7114 (3)	0.5324 (2)	0.0487 (6)
O7	0.8761 (3)	1.1106 (2)	0.76627 (18)	0.0402 (5)
O8	1.0268 (3)	1.1721 (3)	0.6645 (2)	0.0524 (7)
O9	0.9909 (3)	0.7808 (3)	0.6272 (2)	0.0538 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0356 (16)	0.0354 (17)	0.0342 (16)	0.0069 (13)	0.0108 (13)	0.0112 (13)
C2	0.0405 (18)	0.047 (2)	0.0323 (17)	0.0051 (15)	0.0128 (14)	0.0124 (15)
C3	0.0421 (19)	0.046 (2)	0.0418 (19)	0.0038 (16)	0.0053 (15)	0.0225 (16)
C4	0.0377 (17)	0.0422 (18)	0.0394 (18)	0.0030 (14)	0.0069 (14)	0.0312 (15)
C5	0.0270 (14)	0.0406 (17)	0.0292 (15)	0.0052 (12)	0.0069 (12)	0.0215 (13)
C6	0.0409 (17)	0.0252 (15)	0.0359 (17)	0.0071 (13)	0.0139 (14)	0.0054 (13)
C7	0.0325 (16)	0.0299 (16)	0.0455 (18)	0.0099 (13)	0.0134 (14)	0.0194 (14)
C8	0.0271 (15)	0.0298 (15)	0.0368 (16)	0.0109 (12)	0.0124 (13)	0.0148 (13)
C9	0.0419 (18)	0.0424 (19)	0.0368 (18)	0.0106 (15)	0.0060 (15)	0.0100 (15)
C10	0.052 (2)	0.050 (2)	0.041 (2)	0.0158 (18)	0.0129 (17)	0.0105 (17)
C11	0.0394 (18)	0.0413 (18)	0.0358 (17)	0.0131 (14)	0.0209 (14)	0.0204 (14)
C12	0.0281 (14)	0.0318 (15)	0.0275 (14)	0.0062 (12)	0.0096 (12)	0.0146 (12)
C13	0.0400 (18)	0.0363 (17)	0.0390 (18)	0.0075 (14)	0.0153 (15)	0.0196 (14)
C14	0.0384 (17)	0.0298 (16)	0.0393 (17)	0.0059 (13)	0.0082 (14)	0.0164 (14)
C15	0.0407 (17)	0.0247 (15)	0.0427 (18)	0.0114 (13)	0.0228 (15)	0.0098 (13)
C16	0.0347 (17)	0.0373 (17)	0.051 (2)	0.0066 (14)	0.0281 (15)	0.0152 (15)
C17	0.0294 (16)	0.050 (2)	0.053 (2)	0.0163 (15)	0.0170 (15)	0.0085 (17)
C18	0.046 (2)	0.042 (2)	0.057 (2)	0.0192 (17)	0.0059 (17)	0.0194 (17)
C19	0.0416 (19)	0.0343 (18)	0.050 (2)	0.0076 (15)	0.0097 (16)	0.0153 (16)
C20	0.0349 (16)	0.0340 (17)	0.0323 (16)	0.0074 (13)	0.0118 (13)	0.0052 (13)
C21	0.0406 (18)	0.0386 (18)	0.0379 (18)	0.0184 (15)	0.0153 (14)	0.0155 (14)
C22	0.0333 (16)	0.0394 (18)	0.0431 (18)	0.0065 (14)	0.0181 (14)	0.0155 (15)
C23	0.0432 (19)	0.0349 (17)	0.0452 (19)	0.0079 (14)	0.0203 (16)	0.0208 (15)
C24	0.058 (2)	0.052 (2)	0.046 (2)	0.0216 (19)	0.0177 (18)	0.0087 (18)
Fe1	0.0391 (3)	0.0327 (3)	0.0290 (2)	0.0134 (2)	0.00964 (19)	0.01289 (19)
N1	0.0345 (14)	0.0311 (13)	0.0332 (14)	0.0100 (11)	0.0082 (11)	0.0139 (11)
N2	0.0291 (13)	0.0312 (13)	0.0297 (13)	0.0107 (11)	0.0092 (10)	0.0105 (11)
N3	0.0447 (16)	0.0364 (14)	0.0395 (15)	0.0150 (12)	0.0219 (13)	0.0218 (12)
N4	0.0359 (14)	0.0328 (14)	0.0308 (13)	0.0076 (11)	0.0147 (11)	0.0117 (11)
O1	0.0391 (12)	0.0327 (11)	0.0290 (11)	0.0134 (9)	0.0096 (9)	0.0129 (9)
O2	0.0469 (14)	0.0433 (14)	0.0588 (16)	0.0215 (12)	0.0301 (13)	0.0064 (12)
O3	0.0539 (14)	0.0421 (13)	0.0340 (12)	0.0249 (11)	0.0228 (11)	0.0143 (10)
O4	0.0508 (14)	0.0512 (14)	0.0525 (15)	0.0354 (12)	0.0266 (12)	0.0331 (12)
O5	0.0384 (12)	0.0461 (13)	0.0326 (12)	0.0082 (10)	0.0175 (10)	0.0197 (10)
O6	0.0441 (14)	0.0465 (15)	0.0488 (15)	−0.0039 (12)	0.0109 (12)	0.0209 (12)
O7	0.0397 (12)	0.0463 (14)	0.0258 (11)	0.0047 (11)	0.0014 (9)	0.0105 (10)
O8	0.0377 (13)	0.0490 (15)	0.0522 (16)	−0.0105 (11)	0.0117 (12)	0.0091 (12)
O9	0.0549 (16)	0.0572 (17)	0.0532 (16)	0.0157 (13)	0.0312 (13)	0.0146 (13)

Geometric parameters (Å, º) top

C1—N1	1.335 (4)	C15—N3	1.395 (4)
C1—C2	1.393 (5)	C16—C17	1.368 (5)
C1—C6	1.520 (5)	C16—H16A	0.9300
C2—C3	1.375 (5)	C17—C18	1.390 (6)
C2—H2	0.9300	C17—H17A	0.9300
C3—C4	1.382 (5)	C18—C19	1.369 (5)
C3—H3	0.9300	C18—H18A	0.9300
C4—C5	1.372 (4)	C19—C20	1.390 (5)
C4—H4	0.9300	C19—H19A	0.9300
C5—N1	1.330 (4)	C20—N4	1.391 (4)
C5—C7	1.504 (5)	C21—N3	1.313 (4)
C6—O2	1.210 (4)	C21—N4	1.327 (4)
C6—O1	1.303 (4)	C21—H21A	0.9300
C7—O4	1.229 (4)	C22—N4	1.482 (4)
C7—O3	1.303 (4)	C22—C23	1.511 (5)
C8—N2	1.336 (4)	C22—H22A	0.9700
C8—C9	1.380 (5)	C22—H22B	0.9700
C8—C13	1.514 (4)	C23—C23ⁱ	1.534 (6)
C9—C10	1.403 (5)	C23—H23B	0.9700
C9—H9	0.9300	C23—H23A	0.9700
C10—C11	1.397 (5)	C24—O9	1.407 (5)
C10—H10	0.9300	C24—H24A	0.9600
C11—C12	1.386 (4)	C24—H24B	0.9600
C11—H11	0.9300	C24—H24C	0.9600
C12—N2	1.328 (4)	Fe1—O1	1.992 (2)
C12—C14	1.522 (5)	Fe1—O7	1.996 (3)
C13—O6	1.233 (4)	Fe1—O5	2.039 (3)
C13—O5	1.282 (4)	Fe1—N1	2.061 (3)
C14—O8	1.205 (4)	Fe1—O3	2.066 (2)
C14—O7	1.310 (4)	Fe1—N2	2.073 (3)
C15—C16	1.376 (4)	N3—H3E	0.8847
C15—C20	1.378 (5)	O9—H9E	0.9628

N1—C1—C2	119.4 (3)	C15—C20—C19	121.5 (3)
N1—C1—C6	112.1 (3)	C15—C20—N4	107.1 (3)
C2—C1—C6	128.4 (3)	C19—C20—N4	131.4 (3)
C3—C2—C1	118.8 (3)	N3—C21—N4	110.0 (3)
C3—C2—H2	120.6	N3—C21—H21A	125.0
C1—C2—H2	120.6	N4—C21—H21A	125.0
C2—C3—C4	120.5 (3)	N4—C22—C23	112.6 (3)
C2—C3—H3	119.8	N4—C22—H22A	109.1
C4—C3—H3	119.8	C23—C22—H22A	109.1
C5—C4—C3	118.2 (3)	N4—C22—H22B	109.1
C5—C4—H4	120.9	C23—C22—H22B	109.1
C3—C4—H4	120.9	H22A—C22—H22B	107.8
N1—C5—C4	120.9 (3)	C22—C23—C23ⁱ	110.6 (4)
N1—C5—C7	111.2 (3)	C22—C23—H23B	109.5
C4—C5—C7	127.8 (3)	C23ⁱ—C23—H23B	109.5
O2—C6—O1	126.9 (3)	C22—C23—H23A	109.5
O2—C6—C1	120.8 (3)	C23ⁱ—C23—H23A	109.5
O1—C6—C1	112.3 (3)	H23B—C23—H23A	108.1
O4—C7—O3	124.3 (3)	O9—C24—H24A	109.5
O4—C7—C5	121.9 (3)	O9—C24—H24B	109.5
O3—C7—C5	113.8 (3)	H24A—C24—H24B	109.5
N2—C8—C9	119.7 (3)	O9—C24—H24C	109.5
N2—C8—C13	111.3 (3)	H24A—C24—H24C	109.5
C9—C8—C13	129.0 (3)	H24B—C24—H24C	109.5
C8—C9—C10	119.4 (3)	O1—Fe1—O7	93.60 (10)
C8—C9—H9	120.3	O1—Fe1—O5	93.73 (10)
C10—C9—H9	120.3	O7—Fe1—O5	150.61 (9)
C11—C10—C9	118.9 (3)	O1—Fe1—N1	76.79 (10)
C11—C10—H10	120.5	O7—Fe1—N1	105.10 (10)
C9—C10—H10	120.5	O5—Fe1—N1	104.28 (10)
C12—C11—C10	118.5 (3)	O1—Fe1—O3	151.81 (9)
C12—C11—H11	120.8	O7—Fe1—O3	93.24 (10)
C10—C11—H11	120.8	O5—Fe1—O3	93.59 (10)
N2—C12—C11	120.7 (3)	N1—Fe1—O3	75.03 (10)
N2—C12—C14	111.2 (3)	O1—Fe1—N2	117.19 (10)
C11—C12—C14	128.0 (3)	O7—Fe1—N2	75.91 (10)
O6—C13—O5	125.1 (3)	O5—Fe1—N2	75.43 (10)
O6—C13—C8	121.2 (3)	N1—Fe1—N2	166.01 (10)
O5—C13—C8	113.7 (3)	O3—Fe1—N2	91.00 (10)
O8—C14—O7	126.0 (3)	C5—N1—C1	122.2 (3)
O8—C14—C12	121.6 (3)	C5—N1—Fe1	120.2 (2)
O7—C14—C12	112.4 (3)	C1—N1—Fe1	117.6 (2)
C16—C15—C20	122.5 (3)	C12—N2—C8	122.7 (3)
C16—C15—N3	131.9 (3)	C12—N2—Fe1	118.6 (2)
C20—C15—N3	105.6 (3)	C8—N2—Fe1	118.7 (2)
C17—C16—C15	115.7 (3)	C21—N3—C15	109.3 (3)
C17—C16—H16A	122.1	C21—N3—H3E	125.7
C15—C16—H16A	122.1	C15—N3—H3E	124.8
C16—C17—C18	122.7 (3)	C21—N4—C20	108.0 (3)
C16—C17—H17A	118.7	C21—N4—C22	124.6 (3)
C18—C17—H17A	118.7	C20—N4—C22	127.3 (3)
C19—C18—C17	121.4 (3)	C6—O1—Fe1	121.2 (2)
C19—C18—H18A	119.3	C7—O3—Fe1	119.7 (2)
C17—C18—H18A	119.3	C13—O5—Fe1	120.5 (2)
C18—C19—C20	116.3 (3)	C14—O7—Fe1	121.1 (2)
C18—C19—H19A	121.8	C24—O9—H9E	100.5
C20—C19—H19A	121.8

N1—C1—C2—C3	−0.2 (5)	C11—C12—N2—C8	0.7 (5)
C6—C1—C2—C3	−177.5 (3)	C14—C12—N2—C8	−179.2 (3)
C1—C2—C3—C4	−0.5 (5)	C11—C12—N2—Fe1	177.4 (2)
C2—C3—C4—C5	0.7 (5)	C14—C12—N2—Fe1	−2.4 (3)
C3—C4—C5—N1	−0.2 (5)	C9—C8—N2—C12	0.3 (5)
C3—C4—C5—C7	178.0 (3)	C13—C8—N2—C12	179.0 (3)
N1—C1—C6—O2	−177.6 (3)	C9—C8—N2—Fe1	−176.4 (2)
C2—C1—C6—O2	−0.2 (5)	C13—C8—N2—Fe1	2.3 (3)
N1—C1—C6—O1	1.5 (4)	O1—Fe1—N2—C12	92.2 (2)
C2—C1—C6—O1	178.9 (3)	O7—Fe1—N2—C12	5.4 (2)
N1—C5—C7—O4	179.9 (3)	O5—Fe1—N2—C12	178.9 (2)
C4—C5—C7—O4	1.6 (5)	N1—Fe1—N2—C12	−90.5 (5)
N1—C5—C7—O3	−1.0 (4)	O3—Fe1—N2—C12	−87.6 (2)
C4—C5—C7—O3	−179.3 (3)	O1—Fe1—N2—C8	−90.9 (2)
N2—C8—C9—C10	−1.1 (5)	O7—Fe1—N2—C8	−177.7 (2)
C13—C8—C9—C10	−179.5 (3)	O5—Fe1—N2—C8	−4.3 (2)
C8—C9—C10—C11	0.9 (5)	N1—Fe1—N2—C8	86.4 (5)
C9—C10—C11—C12	0.1 (5)	O3—Fe1—N2—C8	89.2 (2)
C10—C11—C12—N2	−0.9 (5)	N4—C21—N3—C15	−1.5 (4)
C10—C11—C12—C14	178.9 (3)	C16—C15—N3—C21	−177.1 (4)
N2—C8—C13—O6	−177.4 (3)	C20—C15—N3—C21	1.1 (4)
C9—C8—C13—O6	1.1 (5)	N3—C21—N4—C20	1.2 (4)
N2—C8—C13—O5	2.7 (4)	N3—C21—N4—C22	−179.7 (3)
C9—C8—C13—O5	−178.9 (3)	C15—C20—N4—C21	−0.5 (4)
N2—C12—C14—O8	177.8 (3)	C19—C20—N4—C21	178.1 (4)
C11—C12—C14—O8	−2.0 (5)	C15—C20—N4—C22	−179.5 (3)
N2—C12—C14—O7	−4.0 (4)	C19—C20—N4—C22	−0.9 (6)
C11—C12—C14—O7	176.2 (3)	C23—C22—N4—C21	−102.7 (4)
C20—C15—C16—C17	0.4 (5)	C23—C22—N4—C20	76.2 (4)
N3—C15—C16—C17	178.4 (4)	O2—C6—O1—Fe1	177.4 (3)
C15—C16—C17—C18	−0.5 (5)	C1—C6—O1—Fe1	−1.6 (4)
C16—C17—C18—C19	0.9 (6)	O7—Fe1—O1—C6	−103.8 (2)
C17—C18—C19—C20	−1.1 (6)	O5—Fe1—O1—C6	104.7 (2)
C16—C15—C20—C19	−0.7 (5)	N1—Fe1—O1—C6	0.9 (2)
N3—C15—C20—C19	−179.2 (3)	O3—Fe1—O1—C6	0.0 (4)
C16—C15—C20—N4	178.0 (3)	N2—Fe1—O1—C6	−179.7 (2)
N3—C15—C20—N4	−0.4 (4)	O4—C7—O3—Fe1	−179.6 (3)
C18—C19—C20—C15	1.0 (5)	C5—C7—O3—Fe1	1.3 (4)
C18—C19—C20—N4	−177.4 (3)	O1—Fe1—O3—C7	0.1 (4)
N4—C22—C23—C23ⁱ	−179.5 (3)	O7—Fe1—O3—C7	103.9 (2)
C4—C5—N1—C1	−0.6 (5)	O5—Fe1—O3—C7	−104.7 (2)
C7—C5—N1—C1	−179.0 (3)	N1—Fe1—O3—C7	−0.9 (2)
C4—C5—N1—Fe1	178.7 (2)	N2—Fe1—O3—C7	179.8 (2)
C7—C5—N1—Fe1	0.3 (3)	O6—C13—O5—Fe1	173.4 (3)
C2—C1—N1—C5	0.8 (5)	C8—C13—O5—Fe1	−6.6 (4)
C6—C1—N1—C5	178.5 (3)	O1—Fe1—O5—C13	123.2 (2)
C2—C1—N1—Fe1	−178.5 (2)	O7—Fe1—O5—C13	19.1 (4)
C6—C1—N1—Fe1	−0.8 (3)	N1—Fe1—O5—C13	−159.5 (2)
O1—Fe1—N1—C5	−179.3 (2)	O3—Fe1—O5—C13	−84.0 (3)
O7—Fe1—N1—C5	−89.1 (2)	N2—Fe1—O5—C13	6.1 (2)
O5—Fe1—N1—C5	90.2 (2)	O8—C14—O7—Fe1	−172.6 (3)
O3—Fe1—N1—C5	0.3 (2)	C12—C14—O7—Fe1	9.3 (4)
N2—Fe1—N1—C5	3.2 (6)	O1—Fe1—O7—C14	−125.4 (3)
O1—Fe1—N1—C1	0.1 (2)	O5—Fe1—O7—C14	−21.2 (4)
O7—Fe1—N1—C1	90.3 (2)	N1—Fe1—O7—C14	157.3 (2)
O5—Fe1—N1—C1	−90.5 (2)	O3—Fe1—O7—C14	82.0 (3)
O3—Fe1—N1—C1	179.6 (3)	N2—Fe1—O7—C14	−8.2 (2)
N2—Fe1—N1—C1	−177.5 (4)

Symmetry code: (i) −x, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3E···O6	0.88	2.03	2.879 (4)	161
O9—H9E···O3	0.96	1.91	2.843 (4)	161
C22—H22A···O7ⁱⁱ	0.97	2.55	3.460 (4)	157

Symmetry code: (ii) x−1, y−1, z.

Experimental details

Crystal data
Chemical formula	(C₁₈H₂₀N₄)[Fe(C₇H₃NO₄)₂]₂·2CH₄O
M_r	1128.58
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	9.2751 (19), 11.035 (2), 13.167 (3)
α, β, γ (°)	106.50 (3), 101.19 (3), 103.07 (3)
V (Å³)	1209.6 (6)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.69
Crystal size (mm)	0.20 × 0.18 × 0.17

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.875, 0.892
No. of measured, independent and observed [I > 2σ(I)] reflections	8712, 4764, 3875
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.131, 1.02
No. of reflections	4764
No. of parameters	344
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.74

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL.

Selected geometric parameters (Å, º) top

C1—N1	1.335 (4)	C20—N4	1.391 (4)
C5—N1	1.330 (4)	C21—N3	1.313 (4)
C6—O2	1.210 (4)	C21—N4	1.327 (4)
C6—O1	1.303 (4)	C22—N4	1.482 (4)
C7—O4	1.229 (4)	C24—O9	1.407 (5)
C7—O3	1.303 (4)	Fe1—O1	1.992 (2)
C8—N2	1.336 (4)	Fe1—O7	1.996 (3)
C12—N2	1.328 (4)	Fe1—O5	2.039 (3)
C13—O6	1.233 (4)	Fe1—N1	2.061 (3)
C13—O5	1.282 (4)	Fe1—O3	2.066 (2)
C14—O8	1.205 (4)	Fe1—N2	2.073 (3)
C14—O7	1.310 (4)	N3—H3E	0.8847
C15—N3	1.395 (4)

O1—Fe1—O7	93.60 (10)	N1—Fe1—O3	75.03 (10)
O1—Fe1—O5	93.73 (10)	O1—Fe1—N2	117.19 (10)
O7—Fe1—O5	150.61 (9)	O7—Fe1—N2	75.91 (10)
O1—Fe1—N1	76.79 (10)	O5—Fe1—N2	75.43 (10)
O7—Fe1—N1	105.10 (10)	N1—Fe1—N2	166.01 (10)
O5—Fe1—N1	104.28 (10)	O3—Fe1—N2	91.00 (10)
O1—Fe1—O3	151.81 (9)	C5—N1—C1	122.2 (3)
O7—Fe1—O3	93.24 (10)	C5—N1—Fe1	120.2 (2)
O5—Fe1—O3	93.59 (10)	C1—N1—Fe1	117.6 (2)