Strong hydrogen bonds in the ionic pair (1,3-diisopropyl-4,5-dimethyl-4-imidazolin-2-yl­idene)ammonium trichloro­(1,3-diisopropyl-4,5-dimethyl-4-imidazolin-2-ylideneamine)­iron(II)

The title compound, (C₁₁H₂₂N₃)[FeCl₃(C₁₁H₂₁N₃)], is one of the rare examples where an isolated ionic pair of the type [A]ⁿ⁺[EMX₃]^n- (E is any non-metal, M is any transition metal and X is any halogen) could be structurally characterized. Two short N-H...Cl contacts between the two ammonium H atoms and two of the three Cl atoms of the counter-anion generate a six-membered ring. The third Cl atom is involved in a weaker intra­molecular hydrogen bond to the neutral 1,3-diisopropyl-4,5-dimethyl-4-imidazolin-2-yl­idene­amine ligand.

S1. Comment

Over the past decade, the coordination chemistry of phosphoraneiminate ligands, R₃PN⁻, has developed into a broad area of research which has produced a large number of structurally diverse main group element and transition metal complexes (Dehnicke & Strähle, 1989; Dehnicke & Weller, 1997; Dehnicke et al., 1999; Dehnicke & Greiner, 2003). Based on the striking similarity between electron-rich organophosphanes and nucleophilic carbenes of the imidazolin-2-ylidene type, formal replacement of phosphane by an imidazolin-2-ylidene moiety in phosphoraneimides gives imidazolin-2-imides. The ability of an imidazolium ring to stabilize a positive charge in a more effective manner than a phosphonium group should increase the negative charge on the N atom, and thus lead to the formation of ligands with enhanced basicity and electron-donating capacity. Recently, we have published (Tamm et al., 2004, 2006) examples of titanium complexes bearing imidazolin-2-iminate ligands which proved to be very active and long-lived catalysts for ethylene polymerization. Due to the capability of phosphoraneimides and imidazolin-2-imides to act as 2σ,4π-electron donors, these anionic ligands can be regarded as monodentate analogues of cyclopentadienyls, C₅R₅⁻, and this relationship has been described as a pseudo-isolobal phenomenon (Diefenbach & Bickelhaupt, 1999). In that respect, monomeric bis(imidazolin-2-iminato) transition metal complexes can be regarded as metallocene analogues, and therefore, we intended to synthesize the complex bis(imidazolin-2-imine)iron(II) chloride, (I), which could be converted into the corresponding bis(imidazolin-2-iminato)iron(II), (II), by the loss of two equivalents of HCl. Surprisingly, the reaction of two equivalents of 1,3-diisopropyl-4,5-dimethylimidazolin-2-imine with FeCl₂ did not result in the formation of the expected bis(imidazolin-2-imine)iron(II) chloride, but instead furnished the title HCl adduct, [ImNH₂]⁺[(ImNH)Fe^IICl₃]⁻, (III).

As the most prominent feature in the solid state structure of (III), one strong N4—H2···Cl1 hydrogen bond [3.173 (2) Å] and one weaker N4—H3···Cl2 hydrogen bond [3.379 (2) Å] connect the cation and the anion to form an ionic pair (Fig. 1 and Table 2). No other short intramolecular contacts are observed. This hydrogen-bonding type is unique within complexes of the formula [A]ⁿ⁺[EMX₃]ⁿ⁻ (E is any non-metal, M is any transition metal, X is any halogen) or zwitterionic salts such as [(1-methylpiperazin-1-ium-N⁴)Co^IICl₃] or [(1,4-dimethylpiperazin-1-ium-N⁴)Zn^IICl₃]. The latter salt exhibits a linear assembly in the crystal structure (Clemente et al., 2002), whereas the cobalt complex forms layer-structured hydrogen bonds (Clemente et al., 1999). All other such compounds build up a three-dimensional network of hydrogen bonds, for example in bis(N,N-dimethyl-N'-(3-chlorophenyl)guanidinium)tetrachlorocopper(II) (Davydov et al., 1992) or bis(1,1-dimethylguanidinium)tetrachlorocopper(II) (Fernandez et al., 1997).

The Fe^II ion of (III) is tetrahedrally coordinated by three Cl atoms and the imidazolin-2-imine N atom bearing one H atom (Fig. 1). The tetrahedral coordination is rather distorted (Table 1), as can be seen by the Cl3—Fe—N1 angle of 95.58 (6)°, with a deviation of about 14° from the ideal tetrahedral value of 109.5°. The Fe—Cl mean distance [2.3084 (6) Å] fits exactly to the value of 2.314 (2) Å found for 21 mononuclear [FeCl₄]²⁻ tetrahedral complexes found in the Cambridge Structural Database (CSD, Version 5.26; Allen, 2002). Comparable complexes having a 3Cl+1 N ligand set are not currently known (0 hits in the CSD). Effects responsible for such a conspicuous deviation are packing effects and a possible Jahn–Teller effect, as well as strong hydrogen bonds (Weller & Petz, 1994). In addition, the third contact, a non-classical agostic contact (N1—H1)···Cl3 [3.229 (2) Å], has to be considered.

S2. Experimental

The title compound was prepared by the reaction of 1,3-diisopropyl-4,5-dimethylimidazolin-2-imine (0.185 g, 0.947 mmol) with FeCl₂ (0.060 g, 0.473 mmol) in tetrahydrofuran (20 ml). After stirring the reaction mixture for 10 h at ambient temperature, the product was precipitated with an excess of n-hexane, filtered and washed several times with n-hexane. Prolonged drying in vacuo afforded 0.165 g of the title compound as a yellow solid (yield 63%). Elemental analysis revealed a formulation of a 1:1 mixture of the tetrachloro- and corresponding tetrabromocobaltate compound; calculated for [ImNH₂]⁺[(ImNH)Fe^IICl₃]⁻: C 23.10, H 3.02, N 11.97%; found: C 23.15, H 3.01, N 11.98%. Crystals of (III) could be obtained selectively from a tetrahydrofuran–n-hexane solution (Ratio?) as clear yellow prisms.

S3. Refinement

The final difference Fourier map shows no striking features. All H atoms could be located in the difference Fourier maps and were allowed to refine freely.

Computing details

Data collection: KappaCCD Control Software (Nonius, 2001); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1998); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Figures

Fig. 1. A perspective view of compound (III), showing the atom-numbering scheme. Displacement ellipsoids are at drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.

(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)ammonium trichloro(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylideneamine)iron(II)

Crystal data

(C11H22N3)[FeCl3(C11H21N3)]	F(000) = 1176
Mr = 553.82	Dx = 1.296 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2997 reflections
a = 9.6108 (1) Å	θ = 2.2–25.3°
b = 9.6349 (1) Å	µ = 0.84 mm^−1
c = 30.6453 (3) Å	T = 173 K
V = 2837.73 (5) Å^3	Prism, yellow
Z = 4	0.60 × 0.51 × 0.46 mm

Data collection

Nonius KappaCCD area-detector diffractometer	5193 independent reflections
Radiation source: Nonius FR 591 rotating anode	4875 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
Detector resolution: 18 pixels mm^-1	θmax = 25.3°, θmin = 2.2°
ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	k = −11→11
Tmin = 0.582, Tmax = 0.677	l = −36→36
56451 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.025	All H-atom parameters refined
wR(F^2) = 0.055	Weighting scheme based on measured s.u.'s w = 1/[σ^2(Fo^2) + (Fo^2) + (0.0251P)^2 + 0.7647P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
5193 reflections	Δρmax = 0.37 e Å^−3
461 parameters	Δρmin = −0.24 e Å^−3
0 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.001 (11)

Special details

Experimental. Diffractometer operator E. Herdtweck scanspeed 2 x 20 s per film repetition 1 dx 40 1046 films measured in 9 data sets set 1: phi-scan with delta_phi = 1.0 set 2 to 9: omega-scans with delta_omega = 1.0

The crystal was fixed in a capillary with perfluorinated ether and transferred to the diffractometer. Preliminary examination and data collection were carried out on a κ-CCD device with an Oxford Cryosystems cooling system at the window of a rotating anode. Data collection were performed at 173 K. A total of 56451 reflections were integrated. Raw data were corrected for Lorentz, polarization, and, arising from the scaling procedure, for latent decay and absorption effects. After merging all independent intensities were used during the refinements. The structure was solved by a combination of direct methods and difference-Fourier syntheses. All non-hydrogen atoms were refined with anisotropic displacement parameters. The final difference-Fourier map shows no striking features. All hydrogen atoms could be located in the difference-Fourier maps and were allowed to refine freely.

Refinement. Refinement on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R_factor_obs 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 (Ų)

	x	y	z	Uiso*/Ueq
Fe	0.17932 (3)	0.97093 (3)	0.15259 (1)	0.0264 (1)
Cl1	0.21812 (5)	1.20443 (5)	0.16480 (2)	0.0376 (2)
Cl2	−0.05120 (5)	0.93926 (5)	0.13433 (2)	0.0350 (2)
Cl3	0.27628 (6)	0.84129 (6)	0.20819 (2)	0.0381 (2)
N1	0.3071 (2)	0.8963 (2)	0.10469 (6)	0.0353 (6)
N2	0.29119 (18)	1.00230 (18)	0.03467 (5)	0.0300 (5)
N3	0.44378 (19)	0.83443 (18)	0.04189 (6)	0.0292 (5)
C1	0.3450 (2)	0.9091 (2)	0.06401 (7)	0.0275 (6)
C2	0.3606 (2)	0.9861 (2)	−0.00573 (7)	0.0325 (7)
C3	0.4546 (2)	0.8851 (2)	−0.00104 (7)	0.0341 (7)
C4	0.1885 (2)	1.1084 (2)	0.04723 (8)	0.0342 (7)
C5	0.2488 (4)	1.2544 (3)	0.04627 (13)	0.0556 (11)
C6	0.0545 (3)	1.0968 (4)	0.02169 (12)	0.0562 (10)
C7	0.3255 (3)	1.0669 (3)	−0.04594 (8)	0.0430 (8)
C8	0.5585 (3)	0.8284 (4)	−0.03275 (9)	0.0506 (10)
C9	0.5280 (2)	0.7206 (2)	0.06041 (8)	0.0317 (7)
C10	0.6305 (3)	0.7740 (3)	0.09460 (11)	0.0500 (10)
C11	0.4389 (3)	0.6008 (3)	0.07618 (10)	0.0445 (9)
N4	−0.1046 (2)	1.2738 (2)	0.16283 (8)	0.0383 (8)
N5	−0.17198 (16)	1.49892 (15)	0.18825 (5)	0.0234 (5)
N6	−0.33790 (16)	1.35024 (16)	0.17362 (5)	0.0230 (5)
C12	−0.1987 (2)	1.3682 (2)	0.17522 (7)	0.0244 (6)
C13	−0.3002 (2)	1.56582 (19)	0.19573 (6)	0.0228 (6)
C14	−0.40125 (19)	1.4752 (2)	0.18703 (6)	0.0220 (6)
C15	−0.0331 (2)	1.5625 (2)	0.19501 (7)	0.0270 (7)
C16	0.0493 (2)	1.5688 (2)	0.15301 (9)	0.0328 (7)
C17	0.0445 (3)	1.4940 (3)	0.23244 (8)	0.0374 (8)
C18	−0.3085 (3)	1.7114 (2)	0.21256 (8)	0.0304 (7)
C19	−0.5549 (2)	1.4874 (2)	0.19133 (8)	0.0295 (7)
C20	−0.4137 (2)	1.2210 (2)	0.16214 (7)	0.0276 (7)
C21	−0.3921 (3)	1.1820 (3)	0.11483 (8)	0.0367 (8)
C22	−0.3828 (3)	1.1038 (2)	0.19357 (9)	0.0348 (8)
H1	0.350 (3)	0.844 (3)	0.1169 (8)	0.037 (8)*
H41	0.166 (2)	1.093 (2)	0.0775 (7)	0.026 (5)*
H51	0.333 (4)	1.258 (4)	0.0585 (12)	0.081 (11)*
H52	0.179 (3)	1.317 (3)	0.0595 (9)	0.053 (8)*
H53	0.249 (4)	1.285 (4)	0.0146 (13)	0.103 (14)*
H61	0.016 (3)	1.004 (3)	0.0245 (9)	0.063 (9)*
H62	0.068 (4)	1.133 (4)	−0.0092 (12)	0.092 (12)*
H63	−0.009 (3)	1.154 (3)	0.0394 (10)	0.073 (10)*
H71	0.317 (3)	1.163 (3)	−0.0399 (8)	0.050 (7)*
H72	0.233 (3)	1.042 (3)	−0.0583 (9)	0.061 (8)*
H73	0.407 (4)	1.056 (4)	−0.0696 (11)	0.105 (13)*
H81	0.657 (3)	0.825 (3)	−0.0174 (9)	0.066 (9)*
H82	0.564 (3)	0.891 (3)	−0.0571 (10)	0.061 (8)*
H83	0.524 (3)	0.736 (4)	−0.0416 (11)	0.080 (11)*
H91	0.584 (2)	0.688 (2)	0.0353 (7)	0.029 (6)*
H101	0.688 (4)	0.848 (4)	0.0769 (11)	0.084 (11)*
H102	0.693 (3)	0.693 (3)	0.1032 (8)	0.056 (8)*
H103	0.578 (3)	0.805 (3)	0.1179 (9)	0.052 (8)*
H111	0.387 (3)	0.568 (3)	0.0516 (9)	0.058 (9)*
H112	0.366 (3)	0.625 (3)	0.0998 (9)	0.055 (8)*
H113	0.499 (3)	0.526 (3)	0.0862 (8)	0.048 (7)*
H2	−0.025 (3)	1.287 (3)	0.1695 (8)	0.038 (7)*
H3	−0.129 (2)	1.200 (2)	0.1603 (7)	0.028 (7)*
H151	−0.052 (2)	1.651 (2)	0.2035 (6)	0.018 (5)*
H161	0.002 (3)	1.607 (3)	0.1295 (9)	0.057 (9)*
H162	0.072 (2)	1.480 (3)	0.1428 (7)	0.033 (6)*
H163	0.131 (3)	1.619 (3)	0.1563 (9)	0.055 (8)*
H171	−0.014 (3)	1.497 (3)	0.2562 (8)	0.039 (7)*
H172	0.117 (3)	1.553 (3)	0.2378 (7)	0.039 (7)*
H173	0.073 (3)	1.399 (3)	0.2254 (8)	0.047 (7)*
H181	−0.262 (3)	1.774 (3)	0.1950 (8)	0.039 (7)*
H182	−0.274 (2)	1.712 (2)	0.2410 (8)	0.027 (6)*
H183	−0.408 (3)	1.739 (2)	0.2120 (7)	0.037 (6)*
H191	−0.609 (2)	1.461 (2)	0.1636 (8)	0.040 (6)*
H192	−0.578 (2)	1.581 (3)	0.1961 (7)	0.029 (6)*
H193	−0.589 (2)	1.431 (2)	0.2151 (7)	0.035 (6)*
H201	−0.509 (2)	1.245 (2)	0.1646 (7)	0.034 (6)*
H211	−0.412 (3)	1.266 (3)	0.0956 (9)	0.055 (8)*
H212	−0.450 (3)	1.109 (3)	0.1077 (8)	0.043 (7)*
H213	−0.299 (3)	1.152 (3)	0.1069 (8)	0.050 (8)*
H221	−0.384 (3)	1.137 (3)	0.2230 (9)	0.055 (8)*
H222	−0.291 (3)	1.066 (3)	0.1895 (8)	0.044 (7)*
H223	−0.455 (3)	1.038 (3)	0.1911 (8)	0.046 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe	0.0196 (1)	0.0259 (1)	0.0337 (2)	0.0012 (1)	0.0005 (1)	−0.0078 (1)
Cl1	0.0189 (2)	0.0280 (3)	0.0660 (4)	−0.0005 (2)	−0.0024 (2)	−0.0158 (3)
Cl2	0.0205 (2)	0.0300 (3)	0.0544 (3)	−0.0020 (2)	−0.0031 (2)	−0.0076 (2)
Cl3	0.0414 (3)	0.0360 (3)	0.0370 (3)	0.0094 (3)	−0.0054 (2)	−0.0043 (2)
N1	0.0363 (12)	0.0363 (10)	0.0332 (11)	0.0167 (10)	0.0026 (9)	0.0019 (8)
N2	0.0300 (9)	0.0290 (10)	0.0311 (9)	0.0067 (8)	−0.0014 (7)	−0.0009 (7)
N3	0.0292 (9)	0.0309 (10)	0.0276 (9)	0.0074 (8)	0.0022 (8)	0.0003 (8)
C1	0.0249 (11)	0.0267 (10)	0.0309 (11)	0.0033 (9)	−0.0008 (9)	−0.0039 (9)
C2	0.0328 (12)	0.0343 (12)	0.0304 (11)	0.0001 (10)	−0.0016 (9)	0.0008 (9)
C3	0.0342 (12)	0.0403 (13)	0.0278 (12)	0.0011 (11)	0.0006 (10)	−0.0008 (10)
C4	0.0316 (13)	0.0289 (11)	0.0421 (13)	0.0081 (10)	−0.0023 (11)	−0.0013 (10)
C5	0.054 (2)	0.0318 (14)	0.081 (2)	0.0043 (13)	−0.0018 (17)	−0.0048 (15)
C6	0.0357 (15)	0.0550 (19)	0.078 (2)	0.0145 (14)	−0.0110 (15)	−0.0081 (17)
C7	0.0508 (16)	0.0401 (15)	0.0380 (13)	0.0008 (13)	−0.0061 (13)	0.0057 (11)
C8	0.0605 (18)	0.0570 (19)	0.0342 (15)	0.0180 (16)	0.0147 (13)	0.0058 (14)
C9	0.0301 (12)	0.0312 (12)	0.0339 (12)	0.0112 (10)	0.0007 (10)	−0.0033 (10)
C10	0.0445 (16)	0.0513 (17)	0.0542 (18)	0.0172 (14)	−0.0168 (14)	−0.0086 (14)
C11	0.0442 (15)	0.0353 (14)	0.0540 (18)	0.0098 (12)	0.0100 (14)	0.0066 (13)
N4	0.0153 (10)	0.0206 (11)	0.0789 (17)	−0.0001 (8)	−0.0042 (10)	−0.0145 (10)
N5	0.0172 (8)	0.0194 (8)	0.0336 (9)	−0.0009 (7)	−0.0025 (7)	−0.0034 (7)
N6	0.0152 (8)	0.0161 (8)	0.0378 (10)	0.0007 (7)	−0.0017 (7)	−0.0030 (7)
C12	0.0165 (10)	0.0214 (10)	0.0353 (11)	−0.0010 (8)	−0.0028 (8)	−0.0011 (8)
C13	0.0221 (11)	0.0194 (10)	0.0268 (10)	0.0027 (8)	−0.0018 (8)	−0.0003 (8)
C14	0.0209 (10)	0.0196 (9)	0.0256 (10)	0.0035 (8)	−0.0011 (8)	0.0028 (8)
C15	0.0227 (11)	0.0195 (11)	0.0388 (12)	−0.0043 (9)	−0.0025 (9)	−0.0047 (9)
C16	0.0306 (12)	0.0285 (12)	0.0393 (13)	−0.0077 (10)	0.0007 (11)	−0.0006 (11)
C17	0.0258 (12)	0.0508 (17)	0.0356 (13)	−0.0080 (12)	−0.0067 (10)	−0.0040 (12)
C18	0.0313 (13)	0.0221 (11)	0.0378 (13)	0.0003 (10)	0.0017 (11)	−0.0053 (10)
C19	0.0220 (10)	0.0241 (12)	0.0425 (14)	0.0026 (9)	0.0035 (10)	−0.0023 (10)
C20	0.0152 (10)	0.0198 (10)	0.0478 (14)	−0.0014 (8)	−0.0024 (9)	−0.0017 (9)
C21	0.0376 (14)	0.0264 (13)	0.0462 (14)	−0.0078 (11)	−0.0105 (12)	−0.0033 (11)
C22	0.0324 (13)	0.0258 (12)	0.0462 (15)	−0.0070 (11)	0.0007 (11)	0.0026 (11)

Geometric parameters (Å, º)

Fe—Cl1	2.3109 (6)	C8—H83	0.99 (4)
Fe—Cl2	2.3053 (6)	C8—H82	0.96 (3)
Fe—Cl3	2.3091 (7)	C8—H81	1.06 (3)
Fe—N1	2.0445 (19)	C9—H91	0.99 (2)
N1—C1	1.305 (3)	C10—H102	1.02 (3)
N2—C1	1.372 (3)	C10—H101	1.05 (4)
N2—C2	1.415 (3)	C10—H103	0.92 (3)
N2—C4	1.472 (3)	C11—H111	0.96 (3)
N3—C1	1.371 (3)	C11—H113	0.97 (3)
N3—C3	1.407 (3)	C11—H112	1.03 (3)
N3—C9	1.477 (3)	C13—C18	1.497 (3)
N4—C12	1.338 (3)	C13—C14	1.333 (3)
N5—C13	1.410 (2)	C14—C19	1.487 (3)
N5—C12	1.346 (2)	C15—C16	1.512 (3)
N5—C15	1.483 (2)	C15—C17	1.519 (3)
N6—C14	1.410 (2)	C20—C22	1.514 (3)
N6—C20	1.485 (2)	C20—C21	1.512 (3)
N6—C12	1.350 (2)	C15—H151	0.910 (19)
N1—H1	0.75 (3)	C16—H161	0.93 (3)
N4—H2	0.80 (3)	C16—H162	0.94 (3)
N4—H3	0.753 (19)	C16—H163	0.93 (3)
C2—C3	1.336 (3)	C17—H171	0.92 (3)
C2—C7	1.496 (3)	C17—H172	0.91 (3)
C3—C8	1.497 (4)	C17—H173	0.98 (3)
C4—C5	1.522 (4)	C18—H181	0.92 (3)
C4—C6	1.511 (4)	C18—H182	0.93 (2)
C9—C11	1.516 (4)	C18—H183	0.99 (3)
C9—C10	1.527 (4)	C19—H191	1.03 (2)
C4—H41	0.96 (2)	C19—H192	0.94 (3)
C5—H52	0.99 (3)	C19—H193	0.97 (2)
C5—H51	0.89 (4)	C20—H201	0.948 (19)
C5—H53	1.01 (4)	C21—H211	1.02 (3)
C6—H62	1.02 (4)	C21—H212	0.92 (3)
C6—H63	0.99 (3)	C21—H213	0.97 (3)
C6—H61	0.97 (3)	C22—H221	0.96 (3)
C7—H72	1.00 (3)	C22—H222	0.96 (3)
C7—H73	1.07 (4)	C22—H223	0.94 (3)
C7—H71	0.95 (3)
Cl1—Fe—Cl2	108.86 (2)	C9—C10—H101	102.3 (19)
Cl1—Fe—Cl3	110.00 (2)	C9—C10—H102	107.4 (15)
Cl1—Fe—N1	111.21 (6)	C9—C10—H103	106.7 (18)
Cl2—Fe—Cl3	119.69 (2)	H102—C10—H103	112 (2)
Cl2—Fe—N1	110.88 (6)	H101—C10—H103	118 (3)
Cl3—Fe—N1	95.58 (6)	H101—C10—H102	110 (3)
Fe—N1—C1	145.14 (16)	C9—C11—H112	115.7 (16)
C1—N2—C2	108.88 (16)	C9—C11—H113	109.2 (17)
C1—N2—C4	122.40 (17)	H111—C11—H113	108 (2)
C2—N2—C4	128.42 (17)	H112—C11—H113	110 (2)
C1—N3—C3	109.36 (17)	H111—C11—H112	106 (2)
C1—N3—C9	125.42 (18)	C9—C11—H111	107.2 (18)
C3—N3—C9	125.21 (18)	N5—C12—N6	108.65 (16)
C13—N5—C15	125.12 (15)	N4—C12—N5	126.26 (18)
C12—N5—C13	108.02 (15)	N4—C12—N6	124.93 (18)
C12—N5—C15	126.84 (16)	N5—C13—C18	122.09 (18)
C14—N6—C20	124.97 (15)	N5—C13—C14	107.75 (16)
C12—N6—C14	107.93 (15)	C14—C13—C18	130.1 (2)
C12—N6—C20	127.04 (16)	N6—C14—C13	107.63 (16)
Fe—N1—H1	102 (2)	N6—C14—C19	121.46 (16)
C1—N1—H1	113 (2)	C13—C14—C19	130.84 (18)
H2—N4—H3	118 (3)	C16—C15—C17	113.76 (18)
C12—N4—H3	117.5 (15)	N5—C15—C16	111.65 (17)
C12—N4—H2	118 (2)	N5—C15—C17	111.58 (18)
N1—C1—N3	128.05 (19)	N6—C20—C21	111.61 (18)
N2—C1—N3	106.29 (17)	N6—C20—C22	112.25 (17)
N1—C1—N2	125.65 (18)	C21—C20—C22	113.44 (19)
C3—C2—C7	128.3 (2)	N5—C15—H151	104.3 (12)
N2—C2—C7	123.85 (18)	C16—C15—H151	108.1 (12)
N2—C2—C3	107.77 (18)	C17—C15—H151	106.8 (12)
N3—C3—C8	122.0 (2)	C15—C16—H161	114.8 (18)
C2—C3—C8	130.4 (2)	C15—C16—H162	111.7 (14)
N3—C3—C2	107.66 (18)	C15—C16—H163	111.8 (17)
N2—C4—C5	112.4 (2)	H161—C16—H162	103 (2)
N2—C4—C6	112.6 (2)	H161—C16—H163	107 (2)
C5—C4—C6	112.5 (2)	H162—C16—H163	108 (2)
N3—C9—C10	111.53 (18)	C15—C17—H171	106.5 (17)
N3—C9—C11	112.23 (18)	C15—C17—H172	103.9 (16)
C10—C9—C11	113.7 (2)	C15—C17—H173	112.2 (15)
C6—C4—H41	107.2 (12)	H171—C17—H172	108 (2)
N2—C4—H41	107.2 (12)	H171—C17—H173	112 (2)
C5—C4—H41	104.3 (12)	H172—C17—H173	114 (2)
C4—C5—H53	107 (2)	C13—C18—H181	112.7 (17)
H51—C5—H52	115 (3)	C13—C18—H182	108.0 (12)
H51—C5—H53	113 (3)	C13—C18—H183	107.2 (12)
H52—C5—H53	103 (3)	H181—C18—H182	112 (2)
C4—C5—H51	112 (2)	H181—C18—H183	106 (2)
C4—C5—H52	107.3 (17)	H182—C18—H183	110.9 (18)
C4—C6—H62	110 (2)	C14—C19—H191	114.2 (12)
C4—C6—H61	110.3 (17)	C14—C19—H192	108.9 (12)
C4—C6—H63	101.6 (17)	C14—C19—H193	111.1 (12)
H61—C6—H62	117 (3)	H191—C19—H192	104.3 (17)
H61—C6—H63	103 (2)	H191—C19—H193	108.2 (17)
H62—C6—H63	114 (3)	H192—C19—H193	110.0 (18)
C2—C7—H71	111.5 (15)	N6—C20—H201	104.5 (12)
C2—C7—H73	110 (2)	C21—C20—H201	105.6 (13)
H71—C7—H72	104 (2)	C22—C20—H201	108.7 (12)
H72—C7—H73	112 (3)	C20—C21—H211	109.4 (16)
H71—C7—H73	107 (3)	C20—C21—H212	109.5 (16)
C2—C7—H72	112.9 (17)	C20—C21—H213	116.1 (15)
C3—C8—H82	108.2 (18)	H211—C21—H212	111 (2)
C3—C8—H81	108.7 (15)	H211—C21—H213	105 (2)
H81—C8—H83	113 (2)	H212—C21—H213	106 (2)
C3—C8—H83	106.5 (18)	C20—C22—H221	110.4 (17)
H81—C8—H82	108 (2)	C20—C22—H222	112.3 (16)
H82—C8—H83	112 (3)	C20—C22—H223	107.8 (17)
N3—C9—H91	103.6 (12)	H221—C22—H222	105 (2)
C10—C9—H91	106.8 (12)	H221—C22—H223	107 (2)
C11—C9—H91	108.3 (11)	H222—C22—H223	114 (2)
Cl1—Fe—N1—C1	−58.4 (3)	C15—N5—C12—N4	−5.2 (3)
Cl2—Fe—N1—C1	62.9 (3)	C12—N5—C13—C18	177.23 (19)
Cl3—Fe—N1—C1	−172.4 (3)	C15—N5—C12—N6	179.16 (17)
Cl2—Fe—N1—H1	−122 (2)	C12—N5—C13—C14	−0.2 (2)
Cl3—Fe—N1—H1	3 (2)	C13—N5—C12—N6	0.8 (2)
Cl1—Fe—N1—H1	117 (2)	C15—N5—C13—C14	−178.61 (17)
Fe—N1—C1—N2	−1.2 (4)	C13—N5—C12—N4	176.4 (2)
Fe—N1—C1—N3	179.10 (18)	C13—N5—C15—C17	112.7 (2)
C4—N2—C1—N1	4.7 (3)	C12—N5—C15—C17	−65.4 (3)
C2—N2—C1—N3	−1.3 (2)	C13—N5—C15—C16	−118.75 (19)
C1—N2—C2—C7	177.6 (2)	C15—N5—C13—C18	−1.2 (3)
C4—N2—C1—N3	−175.48 (17)	C12—N5—C15—C16	63.1 (2)
C1—N2—C2—C3	0.0 (2)	C12—N6—C14—C13	0.9 (2)
C1—N2—C4—C5	110.2 (3)	C20—N6—C12—N5	−178.12 (17)
C1—N2—C4—C6	−121.4 (2)	C14—N6—C20—C21	116.5 (2)
C2—N2—C4—C5	−62.8 (3)	C20—N6—C14—C19	0.7 (3)
C2—N2—C4—C6	65.6 (3)	C12—N6—C20—C21	−66.9 (3)
C2—N2—C1—N1	178.9 (2)	C12—N6—C20—C22	61.7 (3)
C4—N2—C2—C3	173.76 (18)	C14—N6—C12—N4	−176.7 (2)
C4—N2—C2—C7	−8.7 (3)	C14—N6—C12—N5	−1.0 (2)
C3—N3—C1—N1	−178.2 (2)	C20—N6—C12—N4	6.2 (3)
C1—N3—C3—C2	−2.1 (2)	C12—N6—C14—C19	−176.50 (19)
C1—N3—C3—C8	177.3 (2)	C20—N6—C14—C13	178.08 (17)
C9—N3—C3—C2	179.13 (18)	C14—N6—C20—C22	−114.9 (2)
C9—N3—C3—C8	−1.5 (3)	C7—C2—C3—N3	−176.2 (2)
C1—N3—C9—C10	−68.2 (3)	C7—C2—C3—C8	4.5 (4)
C1—N3—C9—C11	60.8 (3)	N2—C2—C3—N3	1.2 (2)
C3—N3—C9—C10	110.4 (2)	N2—C2—C3—C8	−178.1 (2)
C3—N3—C9—C11	−120.7 (2)	N5—C13—C14—N6	−0.4 (2)
C9—N3—C1—N2	−179.16 (17)	C18—C13—C14—N6	−177.58 (19)
C3—N3—C1—N2	2.1 (2)	C18—C13—C14—C19	−0.5 (4)
C9—N3—C1—N1	0.6 (3)	N5—C13—C14—C19	176.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H2···Cl1	0.80 (3)	2.47 (3)	3.173 (2)	147 (3)
N4—H3···Cl2	0.753 (19)	2.739 (19)	3.379 (2)	144.2 (19)
N1—H1···Cl3	0.75 (3)	2.89 (2)	3.229 (2)	111 (2)