cis-Dichloro­[tris­(2-benzimidazolylmethyl)amine]iron(III) chloride ethanol dihydrate: hydrogen bonding changing the arrangement of tapes built from π–π and C—H...π inter­actions

The title compound, [FeCl₂(C₂₄H₂₁N₇)]Cl·C₂H₅OH·2H₂O, comprises an [FeCl₂(C₂₄H₂₁N₇)]⁺ cation, a Cl⁻ anion, an ethanol mol­ecule and two water mol­ecules. The cations are linked by π–π and C—H...π inter­actions into one-dimensional tapes, and hydrogen bonding between the cations, Cl⁻ anions, and ethanol and water mol­ecules links these tapes into a three-dimensional network.

S1. Comment

Benzimidazole (Bzim) is an important chemical group in the design of antitumour agents (Arrowsmith et al., 2002; Hay et al., 2003), and its metal complexes have been reported as having the functions of the enzymes superoxide dismutase (SOD) (Nishida et al., 1991; Kwak et al.,1999; Liao et al., 2001; Qin et al., 2005) and nuclease (Liu et al., 2004). Because of our interest in these areas, we have prepared the title compound, (I), and determined its crystal structure.

Compound (I) consists of a cis-[Fe(TBA)Cl₂]⁺ cation [TBA is tris(2-benzimidazolylmethyl)amine], a Cl⁻ anion, an ethanol molecule and two water molecules (Fig. 1, Table 1). In the cation, the four N atoms from TBA and two mutually cis Cl⁻ anions coordinate to Fe³⁺. Three N atoms of the TBA ligand (N1, N2 and N4) and atom Cl1 form an equatorial plane, from which the Fe³⁺ ion is displaced by only 0.067 (1) Å, in the direction of Cl2. The two axial sites are occupied by atom Cl2 and atom N6 from the TBA. The Fe—N(Bzim) bond lengths [2.095 (2)–2.113 (2) Å] are much shorter than the Fe—N(amine group) bond length [2.330 (2) Å]. This is due to the fact that the benzimidazole groups are good σ donors and good π acceptors compared with the amine (Li et al., 2003).

The Fe—Cl2 bond [2.3299 (9) Å] is significantly longer than the Fe—Cl1 bond [2.2426 (9) Å], due to the different trans influences of the tertiary amine and the benzimidazole group (Horng & Lee, 1999). Three N atoms from three TBA ligands coordinate to Fe³⁺, with angles of 86.00 (9)° for N2—Fe1—N6 and 86.53 (9)° for N4—Fe1—N6, very similar to the values of 84.9 (1) and 86.1 (1)° in [Fe(TBA)Cl₂]Cl·3CH₃OH (Pascaly et al., 2000) and 86.9 (2) and 86.8 (2)° in [Fe(TBA)Cl₂]ClO₄ (Kwak et al., 1999). Two benzimidazole rings (N2/N3/C2–C8 and N4/N5/C10–C16) are almost coplanar [dihedral angle 9.6 (1)°], while the third (N6/N7/C18–C24) lies approximately orthogonal to them with dihedral angles of 88.4 (1) and 78.9 (1)°, respectively. Overall, therefore, the cation in (I) is structurally very similar to those in the related complexes [Fe(TBA)Cl₂]Cl·3CH₃OH and [Fe(TBA)Cl₂]ClO₄.

Although many crystal structures of TBA coordinated to transition metal ions have been reported, there has been little investigation of noncovalent interactions. Several types of noncovalent interaction organize the molecules of (I) into the supramolecular architecture shown in Figs. 2 and 3. Firstly, two cations interact in an anti-parallel tail-to-tail manner viaπ–π and C—H···π interactions, which form a loop through four neighbouring benzimidazole groups, linking the [Fe(TBA)Cl₂]⁺ cations into ladders which are then cross-linked to form tapes (Fig. 2). This is also observed in [Fe(TBA)Cl₂]Cl·3CH₃OH (Pascaly et al., 2000) and in [Fe(TBA)Cl₂]ClO₄ (Kwak et al., 1999), indicating the role of the cation in directing the packing within the crystals. The centroid–centroid distance [Cg1···Cg2ⁱ, symmetry code: (i) −x, 2 − y, 1 − z] associated with the π–π interaction between the six-membered ring (C19–C24; centroid Cg1) and the five-membered ring (N6/C18/N7/C20/C19; centroid Cg2) of the anti-parallel benzimidazoles is 3.704 (2) Å and the two rings have a perpendicular separation of 3.462 (2) Å. The C···Cg distances involved in the C—H···π interactions are 3.647 (4) Å [C5···Cg1ⁱⁱ; symmetry code: (ii) −1 + x, y, z] and 3.665 (4) Å [C21···Cg3ⁱ; Cg3 is the centroid of the ring C3–C8].

Secondly, R₆⁶(12) hydrogen-bonded rings [O1/Cl3/O2^iv/O1^v/Cl3^v/O2^vi; symmetry codes: (iv) −x, 1/2 + y, 3/2 − z; (v) −x, 2 − y, 2 − z; (vi) x, 3/2 − y, 1/2 + z] consisting of four water molecules and two Cl⁻ anions directly connect four and indirectly another two neighbouring cations through ethanol molecules via hydrogen bonds (Fig. 3), arranging neighbouring tapes perpendicular to each other and leading to the C—H···π interaction, with a C7···Cg4ⁱⁱⁱ [Cg4 is the centroid of the ring N4/C10/N5/C12/C11; symmetry code: (iii) −x, 1/2 + y, 3/2 − z] distance of 3.332 (4) Å between the tapes (Fig. 2).

As a result of the hydrogen-bonding and C—H···π interactions, compound (I) forms a three-dimensional supramolecular network. This structural motif is clearly different from those in [Fe(TBA)Cl₂]Cl·3CH₃OH and [Fe(TBA)Cl₂]ClO₄, where the different hydrogen-bonding patterns give tapes arranged in a head-to-head parallel manner via π–π interactions, rather than the C—H···π interaction (C7···Cg4) seen in (I) between the horizontal benzimidazoles of the tapes. Therefore, the R₆⁶(12) hydrogen-bonded rings, together with the hydrogen bonds involving ethanol molecules, change the arrangement of the tapes, resulting in C—H···π interactions between the cations of the tapes in (I).

S2. Experimental

All chemicals were of reagent grade, commercially available and used without further purification. The ligand tris(2-benzimidazolylmethyl)amine (TBA) was synthesized as follows. Nitrilotracetic acid (0.479 g, 2.50 mmol) and 1,2-diaminobenzene (0.812 g, 7.50 mmol) were dissolved in glycol (10 ml) and the mixture irradiated intermittently (15 × 1 min.) using a WP700 LG microwave oven with an output power of 350 W. The solution was cooled to room temperature, and when distilled water (ca 80 ml) was added a yellow precipitate formed immediately. This was filtered off, washed with distilled water and dried in air. IR data (KBr pellet, ν, cm⁻¹): 3000–3500 (w), 1624 (ms), 1591.2 (ms), 1436.9 (s), 1325 (ms), 1274.9 (s), 1220.9 (ms), 1116.7 (s), 1024.1 (ms), 968.2 (ms), 740.6 (s).

FeCl₃·6H₂O (0.0344 g, 0.125 mmol) was added to a solution of TBA (0.0514 g, 0.125 mmol) in absolute ethanol (10 ml) and the mixture was stirred for 1 h. The clear solution was left at room temperature and red needles of (I) were obtained by slow evaporation of the solvent over several days. IR data (KBr pellet, ν, cm⁻¹): 3446 (w), 1629.7 (w), 1593.1 (w), 1548.7 (w), 1471.6 (s), 1450.4 (s), 1390.6 (ms), 1325 (ms), 1274.9 (s), 1218.9 (ms), 1049.2 (s), 995.2 (w), 894.9 (ms), 756 (s). Elemental analysis, found: C 47.79, H 4.80, N 14.70%; calculated for C₂₆H₃₁Cl₃FeN₇O₃: C 47.91, H 4.79, N 15.05%.

S3. Refinement

Atoms C25, C26 and O3 of the solvent ethanol in (I) were found to be disordered and were modelled over two sets of positions using restraints on their anisotropic displacement parameters. The major and minor disorder components had refined occupancies of 0.638 (11) and 0.362 (11), respectively. The H atoms attached to C, N and O(alcohol) atoms of (I) were placed in geometrically idealized positions, with C—H = 0.93–0.97 Å, N—H = 0.86 Å and O—H = 0.82–0.85 Å and refined with U_iso(H) = 1.2U_eq(parent), except for the H atoms on the O and C(methyl) atoms of the ethanol, which were refined with U_iso(H) = 1.5U_eq(parent). The H atoms attached to O(water) atoms were located in a difference Fourier map and refined with a global U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXTL/PC.

Figures

	Fig. 1. A view of the structure of (I), with displacement ellipsoids drawn at the 25% probability level. The minor disorder components and the H atoms have been omitted for clarity. Hydrogen bonds are indicated by dotted lines.
	Fig. 2. The face-to-face π–π and edge-to-face C—H···π interactions (dotted lines) and the perpendicular arrangement of the tapes in (I). Fe atoms are shaded, N atoms have a central dot, Cl atoms are large and cross-hatched, C atoms are plain spheres and H atoms are small circles. The minor disorder components have been omitted for clarity. [Symmetry codes: (i) 3 + x, y, z; (ii) 3 − x, 2 − y, 1 − z; (iii) 2 + x, y, z; (iv) 2 − x, 2 − y, 1 − z; (v) 3 − x, −1/2 + y, 3/2 − z.]
	Fig. 3. A view of the hydrogen-bonding motif. Fe atoms are shaded, N atoms have a central dot, Cl atoms are large and cross-hatched, C atoms are plain spheres and H atoms are small circles. Dotted lines indicate hydrogen bonds. [Symmetry codes: (i) −x, −1/2 + y, 3/2 − z; (ii) −x, 1 − y, 1 − z; (iii) x, 3/2 − y, −1/2 + z; (iv) −1 − x, 1 − y, 1 − z; (v) 1 + x, y, z.]

cis-Dichloro[tris(2-benzimidazolylmethyl)amine]iron(III) chloride ethanol dihydrate

Crystal data

[FeCl2(C24H21N7)]Cl·C2H6O·2H2O	F(000) = 1348
Mr = 651.78	Dx = 1.457 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2889 reflections
a = 10.3541 (12) Å	θ = 2.4–23.2°
b = 13.5873 (15) Å	µ = 0.82 mm^−1
c = 21.746 (3) Å	T = 298 K
β = 103.791 (5)°	Needle, red
V = 2971.1 (6) Å^3	0.44 × 0.06 × 0.06 mm
Z = 4

Data collection

Bruker SMART 1K CCD area-detector diffractometer	5216 independent reflections
Radiation source: sealed tube	3851 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −12→12
Tmin = 0.715, Tmax = 0.953	k = −16→15
13948 measured reflections	l = −25→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: water H atoms from ΔF, others placed geometrically
wR(F^2) = 0.113	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0616P)^2] where P = (Fo^2 + 2Fc^2)/3
5216 reflections	(Δ/σ)max = 0.001
395 parameters	Δρmax = 0.45 e Å^−3
42 restraints	Δρmin = −0.27 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Fe1	0.04350 (4)	0.78744 (3)	0.69286 (2)	0.02969 (14)
Cl1	0.13300 (8)	0.91236 (6)	0.75622 (4)	0.0457 (2)
Cl2	−0.01003 (8)	0.69246 (6)	0.77248 (4)	0.0425 (2)
N1	−0.0395 (2)	0.66172 (17)	0.62146 (11)	0.0303 (6)
N2	−0.1589 (2)	0.81868 (17)	0.65803 (11)	0.0310 (6)
N3	−0.3619 (2)	0.77724 (19)	0.60591 (13)	0.0394 (7)
H3	−0.4266	0.7417	0.5853	0.047*
N4	0.2077 (2)	0.69665 (17)	0.69087 (12)	0.0337 (6)
N5	0.2905 (2)	0.5533 (2)	0.67106 (13)	0.0426 (7)
H5A	0.2932	0.4935	0.6584	0.051*
N6	0.0700 (2)	0.84907 (17)	0.60750 (11)	0.0323 (6)
N7	0.0833 (2)	0.82359 (19)	0.50866 (12)	0.0391 (6)
H7A	0.0765	0.7943	0.4730	0.047*
C1	−0.1811 (3)	0.6482 (2)	0.62324 (16)	0.0374 (7)
H1A	−0.1871	0.6084	0.6595	0.045*
H1B	−0.2298	0.6155	0.5851	0.045*
C2	−0.2358 (3)	0.7470 (2)	0.62845 (15)	0.0334 (7)
C3	−0.2399 (3)	0.9012 (2)	0.65456 (14)	0.0328 (7)
C4	−0.3692 (3)	0.8743 (2)	0.62206 (15)	0.0384 (8)
C5	−0.4716 (3)	0.9433 (3)	0.61094 (19)	0.0563 (10)
H5	−0.5580	0.9261	0.5904	0.068*
C6	−0.4392 (4)	1.0367 (3)	0.63196 (19)	0.0592 (11)
H6	−0.5052	1.0846	0.6247	0.071*
C7	−0.3119 (3)	1.0632 (3)	0.66293 (17)	0.0489 (9)
H7	−0.2947	1.1280	0.6762	0.059*
C8	−0.2097 (3)	0.9964 (2)	0.67537 (15)	0.0390 (8)
H8	−0.1240	1.0144	0.6965	0.047*
C9	0.0416 (3)	0.5726 (2)	0.64314 (16)	0.0390 (8)
H9A	0.0096	0.5391	0.6760	0.047*
H9B	0.0366	0.5275	0.6081	0.047*
C10	0.1808 (3)	0.6075 (2)	0.66788 (15)	0.0355 (7)
C11	0.3468 (3)	0.7012 (2)	0.71076 (15)	0.0366 (7)
C12	0.3988 (3)	0.6112 (2)	0.69853 (15)	0.0398 (8)
C13	0.5347 (3)	0.5914 (3)	0.71466 (18)	0.0553 (10)
H13	0.5691	0.5308	0.7066	0.066*
C14	0.6157 (3)	0.6670 (3)	0.74372 (18)	0.0571 (10)
H14	0.7071	0.6570	0.7561	0.068*
C15	0.5651 (3)	0.7573 (3)	0.75535 (19)	0.0606 (11)
H15	0.6235	0.8063	0.7747	0.073*
C16	0.4299 (3)	0.7781 (3)	0.73921 (17)	0.0479 (9)
H16	0.3966	0.8394	0.7466	0.058*
C17	−0.0275 (3)	0.6922 (2)	0.55757 (15)	0.0375 (7)
H17A	0.0193	0.6415	0.5400	0.045*
H17B	−0.1158	0.6986	0.5300	0.045*
C18	0.0445 (3)	0.7884 (2)	0.55869 (14)	0.0328 (7)
C19	0.1273 (3)	0.9325 (2)	0.58696 (15)	0.0349 (7)
C20	0.1365 (3)	0.9161 (2)	0.52471 (15)	0.0380 (8)
C21	0.1888 (3)	0.9862 (3)	0.49057 (17)	0.0489 (9)
H21	0.1968	0.9740	0.4496	0.059*
C22	0.2274 (3)	1.0728 (3)	0.52027 (19)	0.0546 (10)
H22	0.2634	1.1209	0.4989	0.066*
C23	0.2159 (3)	1.0917 (3)	0.58181 (19)	0.0500 (9)
H23	0.2418	1.1527	0.6000	0.060*
C24	0.1666 (3)	1.0220 (2)	0.61611 (17)	0.0416 (8)
H24	0.1588	1.0347	0.6571	0.036 (9)*
O1	0.0342 (3)	0.80686 (18)	0.90414 (11)	0.0637 (7)
H31	0.0417	0.7933	0.8668	0.101 (9)*
H32	0.0943	0.8481	0.9207	0.101 (9)*
O2	0.2315 (3)	0.37557 (18)	0.60241 (14)	0.0696 (8)
H33	0.1568	0.3482	0.6012	0.101 (9)*
H34	0.2274	0.4081	0.5688	0.101 (9)*
Cl3	0.19657 (9)	0.96337 (7)	0.99532 (5)	0.0565 (3)
O3A	0.4659 (15)	0.8517 (12)	1.0272 (5)	0.075 (4)	0.362 (11)
H3A	0.3883	0.8702	1.0188	0.113*	0.362 (11)
C25A	0.5154 (11)	0.8537 (11)	0.9713 (5)	0.083 (5)	0.362 (11)
H5AA	0.6007	0.8206	0.9791	0.100*	0.362 (11)
H5BA	0.5279	0.9213	0.9596	0.100*	0.362 (11)
C26A	0.420 (2)	0.8040 (16)	0.9191 (6)	0.138 (9)	0.362 (11)
H6AA	0.4411	0.7353	0.9189	0.207*	0.362 (11)
H6BA	0.4244	0.8330	0.8794	0.207*	0.362 (11)
H6CA	0.3313	0.8115	0.9251	0.207*	0.362 (11)
O3B	0.4321 (11)	0.8111 (8)	1.0250 (3)	0.097 (3)	0.638 (11)
H3B	0.3601	0.8359	1.0254	0.145*	0.638 (11)
C25B	0.4284 (11)	0.7743 (6)	0.9631 (4)	0.139 (5)	0.638 (11)
H5AB	0.3416	0.7463	0.9447	0.167*	0.638 (11)
H5BB	0.4945	0.7229	0.9656	0.167*	0.638 (11)
C26B	0.4557 (14)	0.8556 (10)	0.9227 (4)	0.166 (6)	0.638 (11)
H6AB	0.4659	0.9160	0.9462	0.249*	0.638 (11)
H6BB	0.3830	0.8617	0.8861	0.249*	0.638 (11)
H6CB	0.5360	0.8418	0.9095	0.249*	0.638 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0301 (2)	0.0300 (3)	0.0277 (2)	0.00028 (18)	0.00422 (19)	−0.00328 (19)
Cl1	0.0495 (5)	0.0419 (5)	0.0424 (5)	−0.0052 (4)	0.0046 (4)	−0.0134 (4)
Cl2	0.0477 (5)	0.0445 (5)	0.0358 (5)	−0.0012 (4)	0.0110 (4)	0.0039 (4)
N1	0.0325 (13)	0.0262 (13)	0.0313 (14)	−0.0017 (10)	0.0060 (11)	−0.0018 (11)
N2	0.0298 (13)	0.0310 (14)	0.0306 (14)	0.0015 (11)	0.0039 (11)	−0.0014 (11)
N3	0.0275 (13)	0.0433 (16)	0.0436 (16)	−0.0062 (11)	0.0014 (12)	−0.0034 (13)
N4	0.0313 (13)	0.0334 (15)	0.0338 (14)	0.0022 (11)	0.0025 (11)	−0.0020 (12)
N5	0.0427 (15)	0.0397 (16)	0.0437 (17)	0.0082 (13)	0.0071 (13)	−0.0025 (13)
N6	0.0342 (13)	0.0317 (14)	0.0307 (14)	−0.0013 (11)	0.0068 (12)	−0.0014 (12)
N7	0.0480 (16)	0.0411 (16)	0.0297 (14)	0.0003 (13)	0.0121 (13)	−0.0015 (13)
C1	0.0347 (16)	0.0340 (17)	0.0416 (19)	−0.0046 (14)	0.0054 (15)	−0.0027 (15)
C2	0.0294 (16)	0.0368 (17)	0.0336 (17)	−0.0039 (13)	0.0066 (14)	−0.0009 (14)
C3	0.0310 (16)	0.0402 (18)	0.0278 (17)	0.0008 (13)	0.0082 (14)	−0.0010 (14)
C4	0.0316 (16)	0.0409 (19)	0.0401 (19)	0.0025 (14)	0.0037 (14)	0.0002 (16)
C5	0.0317 (18)	0.066 (3)	0.066 (3)	0.0092 (17)	0.0032 (18)	0.000 (2)
C6	0.052 (2)	0.051 (2)	0.072 (3)	0.0198 (18)	0.009 (2)	−0.003 (2)
C7	0.053 (2)	0.046 (2)	0.048 (2)	0.0128 (17)	0.0108 (18)	−0.0080 (18)
C8	0.0412 (18)	0.0383 (18)	0.0359 (18)	0.0025 (14)	0.0057 (15)	−0.0053 (15)
C9	0.0390 (17)	0.0329 (17)	0.043 (2)	0.0026 (14)	0.0047 (15)	−0.0030 (15)
C10	0.0353 (16)	0.0396 (18)	0.0308 (17)	0.0066 (14)	0.0061 (14)	−0.0007 (15)
C11	0.0338 (16)	0.045 (2)	0.0307 (17)	−0.0008 (14)	0.0067 (14)	0.0016 (15)
C12	0.0362 (17)	0.048 (2)	0.0359 (19)	0.0056 (15)	0.0103 (15)	0.0007 (16)
C13	0.043 (2)	0.071 (3)	0.053 (2)	0.0129 (19)	0.0143 (18)	0.007 (2)
C14	0.0355 (19)	0.082 (3)	0.054 (2)	0.007 (2)	0.0107 (18)	0.010 (2)
C15	0.037 (2)	0.092 (3)	0.051 (2)	−0.017 (2)	0.0067 (18)	−0.006 (2)
C16	0.0435 (19)	0.052 (2)	0.049 (2)	−0.0045 (16)	0.0127 (17)	−0.0051 (18)
C17	0.0437 (18)	0.0340 (18)	0.0338 (18)	−0.0032 (14)	0.0075 (15)	−0.0062 (14)
C18	0.0323 (16)	0.0354 (17)	0.0288 (17)	0.0014 (13)	0.0038 (14)	−0.0008 (14)
C19	0.0292 (15)	0.0382 (18)	0.0358 (18)	0.0033 (13)	0.0050 (14)	0.0051 (15)
C20	0.0334 (16)	0.043 (2)	0.0366 (19)	0.0015 (14)	0.0069 (15)	0.0057 (16)
C21	0.049 (2)	0.053 (2)	0.045 (2)	0.0004 (17)	0.0117 (17)	0.0112 (18)
C22	0.044 (2)	0.053 (2)	0.067 (3)	−0.0007 (17)	0.0142 (19)	0.023 (2)
C23	0.0437 (19)	0.040 (2)	0.062 (3)	−0.0026 (16)	0.0047 (18)	0.0043 (18)
C24	0.0468 (19)	0.0324 (18)	0.045 (2)	−0.0041 (15)	0.0092 (16)	−0.0012 (16)
O1	0.0861 (19)	0.0650 (18)	0.0391 (15)	−0.0035 (15)	0.0130 (14)	−0.0005 (13)
O2	0.0766 (18)	0.0534 (17)	0.076 (2)	0.0006 (14)	0.0128 (16)	−0.0023 (15)
Cl3	0.0599 (6)	0.0524 (6)	0.0570 (6)	0.0064 (4)	0.0135 (5)	0.0058 (5)
O3A	0.067 (6)	0.072 (8)	0.080 (7)	0.015 (5)	0.005 (5)	0.018 (5)
C25A	0.082 (8)	0.098 (8)	0.067 (8)	−0.001 (6)	0.011 (6)	0.027 (6)
C26A	0.157 (12)	0.120 (11)	0.138 (12)	−0.023 (9)	0.034 (9)	−0.011 (9)
O3B	0.094 (6)	0.094 (6)	0.085 (5)	0.054 (5)	−0.013 (4)	−0.012 (4)
C25B	0.132 (7)	0.152 (8)	0.111 (8)	0.059 (6)	−0.016 (6)	−0.012 (7)
C26B	0.131 (8)	0.210 (11)	0.176 (10)	−0.022 (8)	0.074 (8)	−0.021 (8)

Geometric parameters (Å, º)

Fe1—Cl1	2.2426 (9)	C12—C13	1.393 (4)
Fe1—Cl2	2.3299 (9)	C13—C14	1.381 (5)
Fe1—N1	2.330 (2)	C13—H13	0.9301
Fe1—N2	2.095 (2)	C14—C15	1.381 (5)
Fe1—N4	2.110 (2)	C14—H14	0.9300
Fe1—N6	2.113 (2)	C15—C16	1.388 (5)
N1—C1	1.487 (4)	C15—H15	0.9301
N1—C9	1.485 (4)	C16—H16	0.9300
N1—C17	1.483 (4)	C17—C18	1.503 (4)
N2—C2	1.324 (4)	C17—H17A	0.9700
N2—C3	1.392 (4)	C17—H17B	0.9700
N3—C2	1.345 (4)	C19—C24	1.388 (4)
N3—C4	1.371 (4)	C19—C20	1.397 (4)
N3—H3	0.8600	C20—C21	1.395 (4)
N4—C10	1.314 (4)	C21—C22	1.355 (5)
N4—C11	1.403 (4)	C21—H21	0.9301
N5—C10	1.342 (4)	C22—C23	1.395 (5)
N5—C12	1.384 (4)	C22—H22	0.9301
N5—H5A	0.8601	C23—C24	1.376 (5)
N6—C18	1.320 (4)	C23—H23	0.9300
N6—C19	1.401 (4)	C24—H24	0.9301
N7—C18	1.335 (4)	O1—H31	0.8546
N7—C20	1.383 (4)	O1—H32	0.8510
N7—H7A	0.8599	O2—H33	0.8528
C1—C2	1.472 (4)	O2—H34	0.8467
C1—H1A	0.9700	O3A—C25A	1.4294 (11)
C1—H1B	0.9700	O3A—H3A	0.8200
C3—C8	1.381 (4)	C25A—C26A	1.4794 (11)
C3—C4	1.405 (4)	C25A—H5AA	0.9700
C4—C5	1.392 (4)	C25A—H5BA	0.9700
C5—C6	1.363 (5)	C26A—H6AA	0.9600
C5—H5	0.9300	C26A—H6BA	0.9600
C6—C7	1.378 (5)	C26A—H6CA	0.9600
C6—H6	0.9300	O3B—C25B	1.4296 (11)
C7—C8	1.371 (4)	O3B—H3B	0.8200
C7—H7	0.9300	C25B—C26B	1.4800 (11)
C8—H8	0.9300	C25B—H5AB	0.9700
C9—C10	1.491 (4)	C25B—H5BB	0.9700
C9—H9A	0.9700	C26B—H6AB	0.9600
C9—H9B	0.9699	C26B—H6BB	0.9600
C11—C12	1.387 (4)	C26B—H6CB	0.9600
C11—C16	1.401 (4)
Cg1···Cg2^i	3.704 (2)	C7-H7···Cg4^iii	3.332 (4)
C5-H5···Cg1^ii	3.647 (4)	C21-H21···Cg3^i	3.665 (4)
Cl1—Fe1—Cl2	95.70 (4)	H9A—C9—H9B	108.6
Cl1—Fe1—N1	175.43 (6)	N4—C10—N5	112.7 (3)
Cl1—Fe1—N2	107.46 (7)	N4—C10—C9	122.0 (3)
Cl1—Fe1—N4	103.77 (7)	N5—C10—C9	125.3 (3)
Cl1—Fe1—N6	96.81 (7)	C12—C11—C16	121.1 (3)
Cl2—Fe1—N1	88.51 (6)	C12—C11—N4	108.6 (3)
Cl2—Fe1—N2	89.21 (7)	C16—C11—N4	130.2 (3)
Cl2—Fe1—N4	91.56 (7)	N5—C12—C11	105.8 (3)
Cl2—Fe1—N6	167.44 (7)	N5—C12—C13	131.6 (3)
N1—Fe1—N2	74.30 (9)	C11—C12—C13	122.5 (3)
N1—Fe1—N4	74.26 (9)	C14—C13—C12	116.0 (4)
N1—Fe1—N6	79.03 (9)	C14—C13—H13	121.8
N2—Fe1—N4	148.52 (9)	C12—C13—H13	122.2
N2—Fe1—N6	86.00 (9)	C13—C14—C15	121.9 (3)
N4—Fe1—N6	86.53 (9)	C13—C14—H14	119.3
C1—N1—C9	112.1 (2)	C15—C14—H14	118.8
C1—N1—C17	111.2 (2)	C14—C15—C16	122.6 (4)
C9—N1—C17	111.0 (2)	C14—C15—H15	118.9
C17—N1—Fe1	108.65 (16)	C16—C15—H15	118.5
C9—N1—Fe1	107.20 (17)	C15—C16—C11	115.8 (3)
C1—N1—Fe1	106.42 (17)	C15—C16—H16	122.2
C2—N2—C3	106.3 (2)	C11—C16—H16	122.0
C2—N2—Fe1	117.43 (19)	N1—C17—C18	112.3 (2)
C3—N2—Fe1	136.14 (19)	N1—C17—H17A	109.4
C2—N3—C4	108.0 (2)	C18—C17—H17A	109.4
C2—N3—H3	125.9	N1—C17—H17B	109.0
C4—N3—H3	126.1	C18—C17—H17B	108.8
C10—N4—C11	105.5 (2)	H17A—C17—H17B	107.8
C10—N4—Fe1	116.59 (19)	N6—C18—N7	113.0 (3)
C11—N4—Fe1	137.8 (2)	N6—C18—C17	124.0 (3)
C10—N5—C12	107.4 (3)	N7—C18—C17	122.9 (3)
C10—N5—H5A	126.4	C24—C19—C20	120.1 (3)
C12—N5—H5A	126.2	C24—C19—N6	131.6 (3)
C18—N6—C19	105.5 (3)	C20—C19—N6	108.2 (3)
C18—N6—Fe1	114.59 (19)	N7—C20—C21	132.0 (3)
C19—N6—Fe1	139.0 (2)	N7—C20—C19	105.9 (3)
C18—N7—C20	107.4 (3)	C21—C20—C19	122.1 (3)
C18—N7—H7A	126.4	C22—C21—C20	116.6 (3)
C20—N7—H7A	126.2	C22—C21—H21	121.9
C2—C1—N1	106.8 (2)	C20—C21—H21	121.5
C2—C1—H1A	110.2	C21—C22—C23	122.3 (3)
N1—C1—H1A	110.2	C21—C22—H22	118.7
C2—C1—H1B	110.6	C23—C22—H22	119.0
N1—C1—H1B	110.5	C24—C23—C22	121.3 (3)
H1A—C1—H1B	108.6	C24—C23—H23	119.2
N2—C2—N3	111.8 (3)	C22—C23—H23	119.4
N2—C2—C1	120.7 (3)	C23—C24—C19	117.5 (3)
N3—C2—C1	127.5 (3)	C23—C24—H24	121.4
C8—C3—N2	130.6 (3)	C19—C24—H24	121.1
C8—C3—C4	121.5 (3)	H31—O1—H32	108.8
N2—C3—C4	107.9 (3)	H33—O2—H34	110.0
N3—C4—C5	133.6 (3)	O3A—C25A—C26A	109.48 (11)
N3—C4—C3	105.9 (3)	O3A—C25A—H5AA	109.8
C5—C4—C3	120.4 (3)	C26A—C25A—H5AA	109.8
C6—C5—C4	116.9 (3)	O3A—C25A—H5BA	109.8
C6—C5—H5	121.8	C26A—C25A—H5BA	109.8
C4—C5—H5	121.3	H5AA—C25A—H5BA	108.2
C5—C6—C7	122.5 (3)	C25B—O3B—H3B	109.5
C5—C6—H6	118.9	O3B—C25B—C26B	109.42 (11)
C7—C6—H6	118.6	O3B—C25B—H5AB	109.8
C8—C7—C6	121.8 (3)	C26B—C25B—H5AB	109.8
C8—C7—H7	119.0	O3B—C25B—H5BB	109.8
C6—C7—H7	119.3	C26B—C25B—H5BB	109.8
C7—C8—C3	116.9 (3)	H5AB—C25B—H5BB	108.2
C7—C8—H8	121.6	C25B—C26B—H6AB	109.5
C3—C8—H8	121.5	C25B—C26B—H6BB	109.5
N1—C9—C10	106.2 (2)	H6AB—C26B—H6BB	109.5
N1—C9—H9A	110.5	C25B—C26B—H6CB	109.5
C10—C9—H9A	110.7	H6AB—C26B—H6CB	109.5
N1—C9—H9B	110.3	H6BB—C26B—H6CB	109.5
C10—C9—H9B	110.5
N2—Fe1—N1—C17	89.45 (19)	N3—C4—C5—C6	−176.5 (4)
N4—Fe1—N1—C17	−88.91 (18)	C3—C4—C5—C6	1.1 (5)
N6—Fe1—N1—C17	0.55 (18)	C4—C5—C6—C7	−0.1 (6)
Cl2—Fe1—N1—C17	179.05 (17)	C5—C6—C7—C8	−1.0 (6)
N2—Fe1—N1—C9	−150.56 (19)	C6—C7—C8—C3	0.9 (5)
N4—Fe1—N1—C9	31.08 (18)	N2—C3—C8—C7	177.8 (3)
N6—Fe1—N1—C9	120.54 (19)	C4—C3—C8—C7	0.1 (5)
Cl2—Fe1—N1—C9	−60.96 (17)	C17—N1—C9—C10	81.0 (3)
N2—Fe1—N1—C1	−30.42 (18)	C1—N1—C9—C10	−154.0 (2)
N4—Fe1—N1—C1	151.22 (19)	Fe1—N1—C9—C10	−37.5 (3)
N6—Fe1—N1—C1	−119.32 (19)	C11—N4—C10—N5	0.0 (3)
Cl2—Fe1—N1—C1	59.18 (17)	Fe1—N4—C10—N5	−177.1 (2)
N4—Fe1—N2—C2	18.9 (3)	C11—N4—C10—C9	178.4 (3)
N6—Fe1—N2—C2	95.6 (2)	Fe1—N4—C10—C9	1.2 (4)
Cl1—Fe1—N2—C2	−168.5 (2)	C12—N5—C10—N4	0.1 (4)
Cl2—Fe1—N2—C2	−72.8 (2)	C12—N5—C10—C9	−178.1 (3)
N1—Fe1—N2—C2	15.9 (2)	N1—C9—C10—N4	26.9 (4)
N4—Fe1—N2—C3	−157.2 (3)	N1—C9—C10—N5	−155.0 (3)
N6—Fe1—N2—C3	−80.5 (3)	C10—N4—C11—C12	−0.2 (3)
Cl1—Fe1—N2—C3	15.4 (3)	Fe1—N4—C11—C12	176.0 (2)
Cl2—Fe1—N2—C3	111.1 (3)	C10—N4—C11—C16	−179.5 (3)
N1—Fe1—N2—C3	−160.2 (3)	Fe1—N4—C11—C16	−3.3 (5)
N2—Fe1—N4—C10	−21.1 (3)	C10—N5—C12—C11	−0.2 (4)
N6—Fe1—N4—C10	−97.6 (2)	C10—N5—C12—C13	177.9 (4)
Cl1—Fe1—N4—C10	166.2 (2)	C16—C11—C12—N5	179.6 (3)
Cl2—Fe1—N4—C10	70.0 (2)	N4—C11—C12—N5	0.3 (3)
N1—Fe1—N4—C10	−18.0 (2)	C16—C11—C12—C13	1.3 (5)
N2—Fe1—N4—C11	163.1 (3)	N4—C11—C12—C13	−178.1 (3)
N6—Fe1—N4—C11	86.5 (3)	N5—C12—C13—C14	−178.0 (3)
Cl1—Fe1—N4—C11	−9.6 (3)	C11—C12—C13—C14	−0.1 (5)
Cl2—Fe1—N4—C11	−105.9 (3)	C12—C13—C14—C15	−0.8 (6)
N1—Fe1—N4—C11	166.1 (3)	C13—C14—C15—C16	0.5 (6)
N2—Fe1—N6—C18	−82.0 (2)	C14—C15—C16—C11	0.7 (5)
N4—Fe1—N6—C18	67.4 (2)	C12—C11—C16—C15	−1.5 (5)
Cl1—Fe1—N6—C18	170.87 (19)	N4—C11—C16—C15	177.7 (3)
Cl2—Fe1—N6—C18	−14.2 (5)	C9—N1—C17—C18	−112.3 (3)
N1—Fe1—N6—C18	−7.23 (19)	C1—N1—C17—C18	122.1 (3)
N2—Fe1—N6—C19	111.2 (3)	Fe1—N1—C17—C18	5.3 (3)
N4—Fe1—N6—C19	−99.4 (3)	C19—N6—C18—N7	1.7 (3)
Cl1—Fe1—N6—C19	4.0 (3)	Fe1—N6—C18—N7	−169.37 (19)
Cl2—Fe1—N6—C19	179.0 (2)	C19—N6—C18—C17	−175.0 (3)
N1—Fe1—N6—C19	−174.1 (3)	Fe1—N6—C18—C17	13.9 (4)
C17—N1—C1—C2	−79.2 (3)	C20—N7—C18—N6	−1.3 (3)
C9—N1—C1—C2	155.9 (2)	C20—N7—C18—C17	175.4 (3)
Fe1—N1—C1—C2	39.0 (3)	N1—C17—C18—N6	−13.2 (4)
C3—N2—C2—N3	0.0 (3)	N1—C17—C18—N7	170.4 (3)
Fe1—N2—C2—N3	−177.23 (19)	C18—N6—C19—C24	175.5 (3)
C3—N2—C2—C1	180.0 (3)	Fe1—N6—C19—C24	−16.9 (5)
Fe1—N2—C2—C1	2.8 (4)	C18—N6—C19—C20	−1.4 (3)
C4—N3—C2—N2	−0.7 (4)	Fe1—N6—C19—C20	166.2 (2)
C4—N3—C2—C1	179.3 (3)	C18—N7—C20—C21	−178.4 (3)
N1—C1—C2—N2	−30.6 (4)	C18—N7—C20—C19	0.3 (3)
N1—C1—C2—N3	149.4 (3)	C24—C19—C20—N7	−176.7 (3)
C2—N2—C3—C8	−177.2 (3)	N6—C19—C20—N7	0.7 (3)
Fe1—N2—C3—C8	−0.8 (5)	C24—C19—C20—C21	2.2 (5)
C2—N2—C3—C4	0.7 (3)	N6—C19—C20—C21	179.5 (3)
Fe1—N2—C3—C4	177.1 (2)	N7—C20—C21—C22	176.9 (3)
C2—N3—C4—C5	178.9 (4)	C19—C20—C21—C22	−1.7 (5)
C2—N3—C4—C3	1.1 (3)	C20—C21—C22—C23	0.0 (5)
C8—C3—C4—N3	177.0 (3)	C21—C22—C23—C24	1.2 (5)
N2—C3—C4—N3	−1.1 (3)	C22—C23—C24—C19	−0.7 (5)
C8—C3—C4—C5	−1.1 (5)	C20—C19—C24—C23	−1.0 (4)
N2—C3—C4—C5	−179.3 (3)	N6—C19—C24—C23	−177.5 (3)

Symmetry codes: (i) −x, −y+2, −z+1; (ii) x−1, y, z; (iii) −x, y+1/2, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O3B^iv	0.86	1.86	2.701 (9)	165
N3—H3···O3A^iv	0.86	1.94	2.779 (16)	164
O3A—H3A···Cl3	0.82	2.31	3.104 (16)	164
O3B—H3B···Cl3	0.82	2.40	3.145 (8)	151
N5—H5A···O2	0.86	2.02	2.828 (4)	156
N7—H7A···O1^v	0.86	2.00	2.831 (4)	162
O1—H32···Cl3	0.85	2.32	3.113 (3)	155
O1—H31···Cl2	0.85	2.42	3.193 (3)	151
O2—H33···O1^vi	0.85	2.03	2.877 (4)	170
O2—H34···Cl3^v	0.85	2.34	3.153 (3)	162

Symmetry codes: (iv) x−1, −y+3/2, z−1/2; (v) x, −y+3/2, z−1/2; (vi) −x, y−1/2, −z+3/2.