Rare examples of base pairing via a protonated pyridine N atom in two salts of N²,N⁶-bis­(1,3-dimethyl­imidazolin-2-yl­idene)pyridine-2,6-diamine

The title compounds, namely 2,6-bis­[(1,3-dimethyl­imidazolin-2-yl­idene)amino]pyridinium perchlorate, C₁₅H₂₄N₇⁺·ClO₄⁻, (I), and bis­{2,6-bis­[(1,3-dimethyl­imidazolin-2-yl­idene)­amino]­pyridinium} μ-oxido-bis­[trichloridoiron(III)], (C₁₅H₂₄N₇)₂[Fe₂Cl₆O], (II), are structurally unusual examples of the organization of mol­ecular units via base pairing. The cations in salts (I) and (II) are derived from the bis­guanidine N²,N⁶-bis­(1,3-dimethyl­imidazolin-2-yl­idene)pyridine-2,6-diamine, which associates in centrosymmetric pairs via two N—H...N hydrogen-bond inter­actions. N—H...N bridges are formed between the protonated pyridine N atom and one of the nonprotonated guanidine N atoms, with N...H distances of 2.01 (1)–2.10 (1) Å. Compound (I) contains two crystallographically independent cations and anions per asymmetric unit. One of the perchlorate anions is disordered, while the [Fe₂Cl₆O]²⁻ anion lies on an inversion centre.

S1. Comment

The development of discrete dimeric, trimeric and other higher-order ensembles is a significant field of research with possible applications in materials chemistry and nanotechnology. Furthermore, base pairs must be considered as playing a salient role in such critical areas as genetic coding, biological information storage and protein synthesis (Sessler et al., 2007). During synthesis of biomimetic complexes using iron and manganese salts, as well as ligands containing two guanidine (gua) N-donor functions and one pyridine N atom [N²,N⁶-bis(1,3-dimethylimidazolidin-2-ylidene)pyridine-2,6-diamine; Herres-Pawlis et al., 2005; Neuba et al., 2008], we synthesized the title compounds, (I) and (II), with an interesting base-pair arrangement in the crystal structure.

The C_gua–N formal single bonds in (I), with a mean bond length of 1.340 (4) Å, have the same length as the double bonds C5═N3 and C11═N5 [average 1.327 (4) Å]. In (II), the corresponding C_gua—N and C═N bonds have average lengths of 1.343 (3) and 1.323 (3) Å, respectively. Thus, the guanidyl double bonds in (I) and (II) are clearly delocalized over the three C—N bonds.

Similar delocalization of the guanidyl double bonds is known from the protonated form of bis(tetramethylguanidino)biphenyl (Pruszynski et al., 1992), but with a protonated N_gua atom instead. 2-Cyanoguanidine with C–N bonds in the range 1.3327–1.3441 Å (Hirshfeld & Hope, 1980) also shows delocalization, but this is due to the cyano groups attached to the imine N atom. Localized C═N bond lengths in nonprotonated bisguanidine ligands range from 1.276 Å in N,N'-bis(dipiperidin-1-ylmethylene)propane-1,3-diamine (Herres et al., 2004) to 1.302 Å in 2',2'-(2,2'-dithiodiphenylene)bis(1,1,3,3-tetramethylguanidine) (Neuba et al., 2007b). C_gua—N single bond lengths vary from 1.362 Å in N,N'-bis(1,3-dimethylimidazolindin-2-ylidene)-2,2'-dithiodianiline (Neuba et al., 2007a) to 1.407 Å in N,N'-bis(dipiperidin-1-ylmethylene)propane-1,3-diamine (Herres et al., 2004).

Furthermore, the C_gua—N_gua bond lengths in (I) and (II) are similar to the N_gua—C_py and C_py—N_py distances. The pyridine ring and both guanidine units lie in a plane, showing that the guanidine delocalization is extended over the pyridine ring. In consequence, the protonation occurs at the N_py atom and not the N_gua atom, which indicates that the basicity of the N_py atom is increased compared with that of the N_gua atom. Normally, the N_gua position is found to be more basic. In this special case, the protonation leads to a pyridinium species, which is stabilized by mesomeric effects from both guanidyl units.

The exocyclic N—C_gua—N angles show, for both structures, the same significant differences of 5.5–11.2° within each pair, but the angle sum at the C_gua atom in both (I) and (II) is 360°. Other geometric parameters of C═N, C_gua—N, N_gua—C_py and C_py—N_py for (I) and (II) are nearly identical (see Tables 1 and 3).

The crystal packing for both compounds (Figs. 1–4) is dominated by pairs of intermolecular hydrogen-bond interactions between the protonated pyridine atom N4 and the nonprotonated guanidine atom N5_gua of a centrosymmetrically related neighbouring molecule, stabilizing the structure with N_gua···H interactions of 2.007 (11) and 2.037 (11) Å in (I) and 2.096 (10) Å in (II). Additionally, these dimers form weak C—H···O and C—H···Cl bridges to the respective anions in (I) and (II). Thus the packing pattern of (II) shows infinite –dimer–anion–dimer– chains along [010]. For geometric details see Tables 2 and 4.

Similarly generated dimers incorporating N_py⁺–H and C═N functions are reported for 2-hydroxy(5-{[4- (2-pyridinylamino)sulfonyl]phenyl}azo)benzoic acid–N,N-dimethylformamide–water (1/0.5/n) (van der Sluis & Spek, 1990), 2-(nitroamino)pyridine (Angelova et al., 1998) and ethyl 3-[4,5-dimethoxy-2-(4-methyl-2- pyridylsulphamoyl)phenyl]propionate (Eliopoulos et al., 1983). The hydrogen-bond lengths in these structures range from 1.839 to 1.950 Å.

Similar dimers formed via N—H···N hydrogen bonds are reported for 2-(4-bromophenyl)-1,2-dihydropyrimido[1,2-a]benzimidazol-4(3H)-one and 4-(4-methylphenyl)-3,4-dihydropyrimido[1,2-a]benzimidazol-2(1H)-one (Low, Cobo, Insuasty et al., 2002). Here, the hydrogen bonds are formed between an aliphatic N—H and a C═N group with N···H distances from 1.98 to 2.30 Å. Similar geometries are observed in 2,2-dimethyl-1,2,3,4-tetrahydrobenzimidazo[3,2-a]pyrimid-4-one, with a hydrogen-bond length of 2.18 Å (Bird et al., 1991), and 2-phenyl-5-p-tolyl-1,5,6,10b-tetrahydropyrazolo[1,5-c]quinazoline, 5-(4-bromophenyl)-2-phenyl-1,5,6,10b-tetrahydropyrazolo[1,5-c]quinazoline and 2-(4-chlorophenyl)-5-phenyl-1,5,6,10b- tetrahydropyrazolo[1,5-c]quinazoline, with an average N···H distance of 2.23 Å (Low, Cobo, Nogueras et al., 2002).

Related literature

For related literature, see: Angelova et al. (1998); Bird et al. (1991); Eliopoulos et al. (1983); Herres et al. (2004); Herres-Pawlis, Neuba, Seewald, Seshadri, Egold, Flörke & Henkel (2005); Hirshfeld & Hope (1980); Low, Cobo, Insuasty et al. (2002); Low, Cobo, Nogueras et al. (2002); Neuba et al. (2007a, 2007b, 2008); Pruszynski et al. (1992); Sessler et al. (2007); van der Sluis & Spek (1990).

S2. Experimental

The synthesis of N²,N⁶-bis(1,3-dimethylimidazolidin-2-ylidene)pyridine-2,6-diamine is described in the literature (Herres-Pawlis et al., 2005). For the preparation of (I), a solution of Mn(ClO₄)₂.6H₂O (362 mg, 1 mmol) in MeCN (quantity?) was treated at room temperature with N²,N⁶-bis(1,3-dimethylimidazolidin-2-ylidene)pyridine-2,6-diamine (331 mg, 1.1 mmol). The clear solution was stirred for one hour, and diffusion of Et₂O gave colourless crystals suitable for X-ray diffraction after three days. IR (KBr, ν, cm^-1): 3486 (s), 2949 (w), 2871 (w), 1617 (m), 1585 (vs, C═N), 1536 (vs, C═ N), 1448 (s), 1417 (m), 1382 (s), 1294 (m), 1240 (w), 1166 (m), 960 (m), 838 (s), 557 (m). For the preparation of (II), a solution of FeCl₂ (127 mg, 1 mmol) in CH₂Cl₂ (quantity?) was treated at room temperature with N²,N⁶-bis(1,3-dimethylimidazolidin-2-ylidene)pyridine-2,6-diamine (331 mg, 1.1 mmol) to yield a yellow solution. After 30 min at reflux, the solution was filtered and allowed to stand in air. After 2 days, red crystals suitable for X-ray diffraction were obtained. IR (KBr, ν, cm^-1): 3423 (m), 2935 (w), 2875 (w), 1629 (m), 1596 (vs, C═N), 1562 (s, C═N), 1520 (vs), 1479 (s), 1446 (m), 1390 (s), 1361 (s), 1295 (m) 1250 (s), 1165 (s), 1049 (m), 960 (m), 877 (w), 785 (w), 673 (m), 569 (w).

S3. Refinement

N_py-bound H atoms were refined with N—H distance restraints of 0.88 (1) Å. All other H atoms were refined at idealized positions riding on their parent C atoms with U_iso(H) parameters of 1.2U_eq(C) or 1.5U_eq(CH₃). All CH₃ H atoms were allowed to rotate but not to tip. The disordered perchlorate anions of (I) were refined with an isotropic split model for O-atom positions O11/O12, O51/O52 and O61/O62, each with a site occupation factor of 0.5.

Computing details

For both compounds, data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular structure of (II). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. The crystal packing of (I), viewed along [100], with hydrogen bonds indicated as dashed lines. H atoms not involved in hydrogen bonds have been omitted. Only one orientation of each disordered perchlorate anion is shown.
	Fig. 4. The crystal packing of (II), viewed along [100], with hydrogen bonds indicated as dashed lines. H atoms not involved in hydrogen bonds have been omitted.

(I) 2,6-bis(1,3-dimethylimidazolin-2-ylideneamino)pyridinium perchlorate

Crystal data

C15H24N7^+·ClO4^−	Z = 4
Mr = 401.86	F(000) = 848
Triclinic, P1	Dx = 1.435 Mg m^−3 Dm = 0 Mg m^−3 Dm measured by not measured
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.4399 (11) Å	Cell parameters from 1687 reflections
b = 12.0367 (13) Å	θ = 2.4–21.8°
c = 16.6200 (18) Å	µ = 0.24 mm^−1
α = 95.979 (2)°	T = 120 K
β = 93.739 (2)°	Prism, colourless
γ = 115.549 (2)°	0.35 × 0.20 × 0.18 mm
V = 1859.9 (3) Å^3

Data collection

Bruker SMART APEX diffractometer	8994 independent reflections
Radiation source: sealed tube	3686 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.093
ϕ and ω scans	θmax = 28.1°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −13→13
Tmin = 0.920, Tmax = 0.960	k = −15→15
18737 measured reflections	l = −21→21

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)] = 0.064	Hydrogen site location: difference Fourier map
wR(F^2) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 0.83	w = 1/[σ^2(Fo^2) + (0.0481P)^2] where P = (Fo^2 + 2Fc^2)/3
8994 reflections	(Δ/σ)max < 0.001
499 parameters	Δρmax = 0.73 e Å^−3
9 restraints	Δρmin = −0.45 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.

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.4193 (3)	0.7986 (3)	0.30531 (18)	0.0298 (7)
N2	0.2195 (3)	0.7556 (3)	0.22891 (18)	0.0361 (8)
N3	0.1938 (3)	0.6525 (3)	0.34145 (17)	0.0257 (7)
N4	0.1482 (3)	0.5201 (3)	0.43559 (17)	0.0233 (7)
H4	0.085 (3)	0.547 (3)	0.448 (2)	0.031 (7)*
N5	0.0428 (3)	0.3750 (3)	0.51835 (18)	0.0265 (7)
N7	0.1384 (3)	0.2929 (3)	0.61883 (18)	0.0306 (8)
N6	−0.0726 (3)	0.1735 (2)	0.55170 (18)	0.0279 (7)
C1	0.5115 (4)	0.8253 (3)	0.3806 (2)	0.0355 (10)
H10D	0.4550	0.7809	0.4218	0.053*
H10E	0.5563	0.9150	0.3997	0.053*
H10F	0.5859	0.7979	0.3712	0.053*
C2	0.4649 (4)	0.8748 (3)	0.2406 (2)	0.0352 (10)
H10I	0.5195	0.8457	0.2046	0.042*
H10J	0.5249	0.9633	0.2634	0.042*
C3	0.3254 (4)	0.8573 (3)	0.1949 (2)	0.0394 (10)
H10G	0.3111	0.9335	0.2049	0.047*
H10H	0.3223	0.8350	0.1355	0.047*
C4	0.0690 (4)	0.6979 (4)	0.1986 (2)	0.0385 (10)
H10A	0.0161	0.6350	0.2323	0.058*
H10B	0.0550	0.6582	0.1421	0.058*
H10C	0.0336	0.7614	0.2008	0.058*
C5	0.2768 (4)	0.7299 (3)	0.2956 (2)	0.0264 (8)
C6	0.2329 (4)	0.5754 (3)	0.3792 (2)	0.0230 (8)
C7	0.3394 (4)	0.5383 (3)	0.3625 (2)	0.0257 (8)
H10K	0.4050	0.5766	0.3254	0.031*
C8	0.3470 (4)	0.4450 (3)	0.4009 (2)	0.0298 (9)
H10L	0.4193	0.4197	0.3897	0.036*
C9	0.2543 (4)	0.3870 (3)	0.4548 (2)	0.0295 (9)
H10M	0.2609	0.3215	0.4793	0.035*
C10	0.1504 (4)	0.4263 (3)	0.4730 (2)	0.0240 (8)
C11	0.0397 (4)	0.2857 (3)	0.5609 (2)	0.0241 (8)
C12	−0.2082 (4)	0.1369 (3)	0.5029 (2)	0.0355 (10)
H11D	−0.2056	0.2073	0.4771	0.053*
H11E	−0.2850	0.1116	0.5379	0.053*
H11F	−0.2258	0.0669	0.4608	0.053*
C13	−0.0588 (4)	0.1033 (3)	0.6152 (2)	0.0304 (9)
H11I	−0.0864	0.0155	0.5928	0.036*
H11J	−0.1176	0.1060	0.6591	0.036*
C14	0.1006 (4)	0.1726 (3)	0.6458 (2)	0.0361 (10)
H11G	0.1182	0.1810	0.7058	0.043*
H11H	0.1544	0.1304	0.6207	0.043*
C15	0.2695 (4)	0.4028 (3)	0.6505 (3)	0.0434 (11)
H11A	0.3502	0.3961	0.6273	0.065*
H11B	0.2845	0.4100	0.7100	0.065*
H11C	0.2624	0.4768	0.6355	0.065*
N1B	0.8872 (3)	0.8037 (2)	0.79216 (17)	0.0256 (7)
N2B	1.0488 (3)	0.7664 (3)	0.73194 (19)	0.0370 (8)
N3B	0.9617 (3)	0.6540 (3)	0.83672 (17)	0.0241 (7)
N4B	0.8704 (3)	0.5182 (2)	0.92639 (17)	0.0210 (7)
H4B	0.9621 (14)	0.547 (3)	0.9457 (19)	0.031 (7)*
N5B	0.8266 (3)	0.3693 (2)	1.00946 (17)	0.0247 (7)
N6B	0.7360 (3)	0.1658 (2)	1.04175 (17)	0.0248 (7)
N7B	0.6413 (3)	0.2831 (2)	1.09544 (17)	0.0252 (7)
C1B	0.8148 (4)	0.8241 (3)	0.8596 (2)	0.0302 (9)
H20D	0.8269	0.7798	0.9035	0.045*
H20E	0.7127	0.7931	0.8410	0.045*
H20F	0.8559	0.9134	0.8798	0.045*
C2B	0.9248 (4)	0.8871 (3)	0.7314 (2)	0.0326 (9)
H20I	0.9636	0.9750	0.7571	0.039*
H20J	0.8408	0.8677	0.6914	0.039*
C3B	1.0391 (4)	0.8621 (3)	0.6907 (2)	0.0341 (9)
H20G	1.0093	0.8329	0.6316	0.041*
H20H	1.1317	0.9377	0.6988	0.041*
C4B	1.1335 (4)	0.7043 (3)	0.7069 (2)	0.0370 (10)
H20A	1.1239	0.6412	0.7420	0.056*
H20B	1.2341	0.7652	0.7115	0.056*
H20C	1.1003	0.6641	0.6502	0.056*
C5B	0.9615 (4)	0.7355 (3)	0.7895 (2)	0.0240 (8)
C6B	0.8430 (4)	0.5760 (3)	0.8656 (2)	0.0223 (8)
C7B	0.7009 (4)	0.5381 (3)	0.8373 (2)	0.0239 (8)
H20K	0.6752	0.5774	0.7968	0.029*
C8B	0.5974 (4)	0.4427 (3)	0.8687 (2)	0.0268 (8)
H20L	0.4999	0.4174	0.8492	0.032*
C9B	0.6288 (4)	0.3821 (3)	0.9271 (2)	0.0242 (8)
H20M	0.5549	0.3148	0.9464	0.029*
C10B	0.7720 (4)	0.4219 (3)	0.9572 (2)	0.0218 (8)
C11B	0.7369 (3)	0.2783 (3)	1.0469 (2)	0.0222 (8)
C12B	0.8414 (4)	0.1344 (3)	1.0064 (2)	0.0283 (9)
H21A	0.9021	0.2019	0.9780	0.043*
H21B	0.7928	0.0573	0.9676	0.043*
H21C	0.9007	0.1226	1.0497	0.043*
C13B	0.6481 (4)	0.0937 (3)	1.0995 (2)	0.0260 (8)
H21G	0.7075	0.0960	1.1492	0.031*
H21H	0.5885	0.0060	1.0748	0.031*
C14B	0.5561 (4)	0.1615 (3)	1.1184 (2)	0.0284 (9)
H21I	0.4610	0.1192	1.0853	0.034*
H21J	0.5433	0.1679	1.1769	0.034*
C15B	0.6087 (4)	0.3876 (3)	1.1160 (2)	0.0341 (9)
H21D	0.6852	0.4635	1.1023	0.051*
H21E	0.6013	0.3984	1.1745	0.051*
H21F	0.5178	0.3716	1.0851	0.051*
Cl1	0.52136 (11)	0.80821 (9)	0.61828 (6)	0.0374 (3)
O11	0.5772 (7)	0.8296 (7)	0.7004 (4)	0.066 (2)*	0.50
O12	0.5313 (6)	0.7574 (5)	0.6928 (3)	0.0422 (15)*	0.50
O2	0.4741 (4)	0.9008 (3)	0.6159 (3)	0.0993 (14)
O3	0.4058 (3)	0.6962 (3)	0.5771 (2)	0.0839 (11)
O4	0.6386 (3)	0.8309 (3)	0.57352 (17)	0.0496 (8)
Cl2	0.21733 (10)	0.18930 (9)	0.90326 (6)	0.0367 (3)
O51	0.2283 (6)	0.3116 (5)	0.9423 (3)	0.0447 (14)*	0.50
O61	0.2643 (6)	0.2127 (6)	0.8281 (3)	0.0483 (15)*	0.50
O52	0.2469 (8)	0.3025 (7)	0.8784 (5)	0.092 (2)*	0.50
O62	0.2388 (7)	0.1222 (6)	0.8275 (4)	0.0695 (19)*	0.50
O7	0.0740 (3)	0.1098 (3)	0.90689 (19)	0.0625 (9)
O8	0.3122 (3)	0.1735 (3)	0.96106 (17)	0.0539 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0260 (18)	0.0259 (17)	0.0300 (18)	0.0035 (14)	0.0028 (14)	0.0084 (14)
N2	0.0310 (19)	0.048 (2)	0.0316 (19)	0.0152 (16)	0.0068 (16)	0.0220 (16)
N3	0.0244 (17)	0.0303 (17)	0.0242 (17)	0.0120 (14)	0.0044 (14)	0.0111 (14)
N4	0.0192 (16)	0.0247 (17)	0.0298 (18)	0.0120 (14)	0.0034 (14)	0.0093 (14)
N5	0.0186 (16)	0.0253 (17)	0.0370 (19)	0.0076 (13)	0.0063 (14)	0.0180 (15)
N7	0.0242 (17)	0.0237 (17)	0.044 (2)	0.0080 (14)	0.0000 (15)	0.0178 (15)
N6	0.0234 (17)	0.0218 (16)	0.0332 (18)	0.0041 (14)	−0.0009 (14)	0.0109 (14)
C1	0.027 (2)	0.029 (2)	0.043 (2)	0.0063 (17)	−0.0011 (19)	0.0036 (19)
C2	0.038 (2)	0.026 (2)	0.037 (2)	0.0090 (18)	0.011 (2)	0.0096 (18)
C3	0.055 (3)	0.032 (2)	0.034 (2)	0.018 (2)	0.010 (2)	0.0157 (19)
C4	0.035 (2)	0.048 (3)	0.037 (2)	0.022 (2)	−0.0036 (19)	0.011 (2)
C5	0.031 (2)	0.024 (2)	0.027 (2)	0.0140 (18)	0.0071 (18)	0.0049 (17)
C6	0.0223 (19)	0.0204 (19)	0.0203 (19)	0.0038 (16)	0.0026 (16)	0.0034 (15)
C7	0.024 (2)	0.0217 (19)	0.031 (2)	0.0086 (16)	0.0091 (17)	0.0049 (16)
C8	0.025 (2)	0.026 (2)	0.041 (2)	0.0134 (17)	0.0079 (18)	0.0062 (18)
C9	0.029 (2)	0.026 (2)	0.040 (2)	0.0148 (17)	0.0073 (18)	0.0118 (18)
C10	0.024 (2)	0.0179 (19)	0.029 (2)	0.0072 (16)	−0.0006 (17)	0.0071 (16)
C11	0.024 (2)	0.026 (2)	0.026 (2)	0.0133 (17)	0.0032 (16)	0.0085 (17)
C12	0.029 (2)	0.034 (2)	0.037 (2)	0.0078 (18)	−0.0021 (19)	0.0062 (19)
C13	0.030 (2)	0.024 (2)	0.036 (2)	0.0095 (17)	0.0052 (18)	0.0137 (17)
C14	0.032 (2)	0.035 (2)	0.046 (3)	0.0155 (19)	0.0022 (19)	0.022 (2)
C15	0.027 (2)	0.034 (2)	0.061 (3)	0.0069 (19)	−0.010 (2)	0.012 (2)
N1B	0.0298 (17)	0.0235 (16)	0.0265 (17)	0.0122 (14)	0.0070 (14)	0.0120 (14)
N2B	0.042 (2)	0.045 (2)	0.042 (2)	0.0288 (17)	0.0232 (17)	0.0309 (17)
N3B	0.0242 (17)	0.0257 (16)	0.0265 (17)	0.0127 (14)	0.0061 (14)	0.0113 (14)
N4B	0.0163 (16)	0.0226 (16)	0.0233 (16)	0.0066 (14)	0.0035 (14)	0.0088 (13)
N5B	0.0218 (16)	0.0221 (16)	0.0316 (18)	0.0082 (13)	0.0088 (14)	0.0134 (14)
N6B	0.0253 (17)	0.0211 (16)	0.0304 (18)	0.0105 (13)	0.0075 (14)	0.0097 (14)
N7B	0.0245 (17)	0.0221 (16)	0.0307 (18)	0.0098 (13)	0.0111 (14)	0.0077 (13)
C1B	0.031 (2)	0.022 (2)	0.038 (2)	0.0117 (17)	0.0042 (18)	0.0028 (17)
C2B	0.036 (2)	0.030 (2)	0.034 (2)	0.0123 (18)	0.0063 (19)	0.0211 (18)
C3B	0.038 (2)	0.033 (2)	0.029 (2)	0.0110 (18)	0.0073 (19)	0.0152 (18)
C4B	0.030 (2)	0.043 (2)	0.040 (2)	0.0158 (19)	0.0107 (19)	0.013 (2)
C5B	0.022 (2)	0.0221 (19)	0.024 (2)	0.0068 (16)	−0.0023 (16)	0.0056 (16)
C6B	0.027 (2)	0.0223 (19)	0.0199 (19)	0.0124 (16)	0.0037 (16)	0.0070 (16)
C7B	0.029 (2)	0.025 (2)	0.0222 (19)	0.0154 (17)	−0.0008 (16)	0.0094 (16)
C8B	0.023 (2)	0.025 (2)	0.031 (2)	0.0103 (17)	−0.0006 (17)	0.0039 (17)
C9B	0.0218 (19)	0.0180 (18)	0.030 (2)	0.0053 (15)	0.0041 (16)	0.0047 (16)
C10B	0.0213 (19)	0.0197 (19)	0.026 (2)	0.0088 (16)	0.0079 (16)	0.0070 (16)
C11B	0.0194 (19)	0.023 (2)	0.0207 (19)	0.0061 (16)	−0.0003 (16)	0.0034 (16)
C12B	0.032 (2)	0.026 (2)	0.032 (2)	0.0162 (17)	0.0061 (18)	0.0073 (17)
C13B	0.029 (2)	0.024 (2)	0.026 (2)	0.0101 (16)	0.0037 (17)	0.0114 (16)
C14B	0.023 (2)	0.027 (2)	0.029 (2)	0.0035 (16)	0.0084 (17)	0.0129 (17)
C15B	0.036 (2)	0.029 (2)	0.041 (2)	0.0167 (18)	0.0125 (19)	0.0054 (18)
Cl1	0.0386 (6)	0.0389 (6)	0.0413 (6)	0.0247 (5)	−0.0010 (5)	0.0031 (5)
O2	0.102 (3)	0.077 (3)	0.147 (4)	0.077 (2)	−0.014 (3)	−0.013 (2)
O3	0.057 (2)	0.043 (2)	0.122 (3)	−0.0012 (16)	0.001 (2)	−0.003 (2)
O4	0.0403 (17)	0.064 (2)	0.0505 (19)	0.0247 (15)	0.0160 (15)	0.0192 (16)
Cl2	0.0254 (5)	0.0384 (6)	0.0451 (6)	0.0108 (4)	0.0054 (5)	0.0156 (5)
O7	0.0199 (15)	0.062 (2)	0.089 (2)	−0.0001 (14)	0.0080 (16)	0.0232 (19)
O8	0.0368 (17)	0.065 (2)	0.053 (2)	0.0153 (15)	−0.0072 (15)	0.0211 (16)

Geometric parameters (Å, º)

N1—C5	1.342 (4)	N3B—C5B	1.319 (4)
N1—C1	1.445 (4)	N3B—C6B	1.348 (4)
N1—C2	1.455 (4)	N4B—C10B	1.352 (4)
N2—C5	1.352 (4)	N4B—C6B	1.366 (4)
N2—C4	1.445 (4)	N4B—H4B	0.888 (10)
N2—C3	1.449 (4)	N5B—C11B	1.341 (4)
N3—C5	1.318 (4)	N5B—C10B	1.357 (4)
N3—C6	1.355 (4)	N6B—C11B	1.344 (4)
N4—C10	1.352 (4)	N6B—C12B	1.448 (4)
N4—C6	1.354 (4)	N6B—C13B	1.455 (4)
N4—H4	0.881 (10)	N7B—C11B	1.340 (4)
N5—C11	1.337 (4)	N7B—C15B	1.452 (4)
N5—C10	1.350 (4)	N7B—C14B	1.455 (4)
N7—C11	1.331 (4)	C1B—H20D	0.9800
N7—C15	1.449 (4)	C1B—H20E	0.9800
N7—C14	1.456 (4)	C1B—H20F	0.9800
N6—C11	1.338 (4)	C2B—C3B	1.530 (5)
N6—C12	1.447 (4)	C2B—H20I	0.9900
N6—C13	1.456 (4)	C2B—H20J	0.9900
C1—H10D	0.9800	C3B—H20G	0.9900
C1—H10E	0.9800	C3B—H20H	0.9900
C1—H10F	0.9800	C4B—H20A	0.9800
C2—C3	1.517 (5)	C4B—H20B	0.9800
C2—H10I	0.9900	C4B—H20C	0.9800
C2—H10J	0.9900	C6B—C7B	1.383 (4)
C3—H10G	0.9900	C7B—C8B	1.373 (4)
C3—H10H	0.9900	C7B—H20K	0.9500
C4—H10A	0.9800	C8B—C9B	1.377 (5)
C4—H10B	0.9800	C8B—H20L	0.9500
C4—H10C	0.9800	C9B—C10B	1.397 (4)
C6—C7	1.398 (4)	C9B—H20M	0.9500
C7—C8	1.377 (5)	C12B—H21A	0.9800
C7—H10K	0.9500	C12B—H21B	0.9800
C8—C9	1.373 (5)	C12B—H21C	0.9800
C8—H10L	0.9500	C13B—C14B	1.532 (4)
C9—C10	1.395 (4)	C13B—H21G	0.9900
C9—H10M	0.9500	C13B—H21H	0.9900
C12—H11D	0.9800	C14B—H21I	0.9900
C12—H11E	0.9800	C14B—H21J	0.9900
C12—H11F	0.9800	C15B—H21D	0.9800
C13—C14	1.525 (5)	C15B—H21E	0.9800
C13—H11I	0.9900	C15B—H21F	0.9800
C13—H11J	0.9900	Cl1—O11	1.400 (6)
C14—H11G	0.9900	Cl1—O2	1.403 (3)
C14—H11H	0.9900	Cl1—O4	1.414 (3)
C15—H11A	0.9800	Cl1—O3	1.428 (3)
C15—H11B	0.9800	Cl1—O12	1.454 (5)
C15—H11C	0.9800	Cl2—O52	1.376 (7)
N1B—C5B	1.350 (4)	Cl2—O61	1.384 (5)
N1B—C1B	1.449 (4)	Cl2—O7	1.395 (3)
N1B—C2B	1.451 (4)	Cl2—O8	1.420 (3)
N2B—C5B	1.334 (4)	Cl2—O51	1.499 (5)
N2B—C3B	1.436 (4)	Cl2—O62	1.507 (6)
N2B—C4B	1.438 (4)
C5—N1—C1	124.8 (3)	C11B—N6B—C12B	124.9 (3)
C5—N1—C2	111.4 (3)	C11B—N6B—C13B	110.5 (3)
C1—N1—C2	121.3 (3)	C12B—N6B—C13B	121.5 (3)
C5—N2—C4	124.9 (3)	C11B—N7B—C15B	127.0 (3)
C5—N2—C3	111.9 (3)	C11B—N7B—C14B	110.9 (3)
C4—N2—C3	123.0 (3)	C15B—N7B—C14B	121.7 (3)
C5—N3—C6	122.4 (3)	N1B—C1B—H20D	109.5
C10—N4—C6	126.0 (3)	N1B—C1B—H20E	109.5
C10—N4—H4	118 (2)	H20D—C1B—H20E	109.5
C6—N4—H4	116 (2)	N1B—C1B—H20F	109.5
C11—N5—C10	119.5 (3)	H20D—C1B—H20F	109.5
C11—N7—C15	126.0 (3)	H20E—C1B—H20F	109.5
C11—N7—C14	111.0 (3)	N1B—C2B—C3B	103.5 (3)
C15—N7—C14	123.0 (3)	N1B—C2B—H20I	111.1
C11—N6—C12	125.8 (3)	C3B—C2B—H20I	111.1
C11—N6—C13	110.6 (3)	N1B—C2B—H20J	111.1
C12—N6—C13	121.3 (3)	C3B—C2B—H20J	111.1
N1—C1—H10D	109.5	H20I—C2B—H20J	109.0
N1—C1—H10E	109.5	N2B—C3B—C2B	103.2 (3)
H10D—C1—H10E	109.5	N2B—C3B—H20G	111.1
N1—C1—H10F	109.5	C2B—C3B—H20G	111.1
H10D—C1—H10F	109.5	N2B—C3B—H20H	111.1
H10E—C1—H10F	109.5	C2B—C3B—H20H	111.1
N1—C2—C3	103.6 (3)	H20G—C3B—H20H	109.1
N1—C2—H10I	111.0	N2B—C4B—H20A	109.5
C3—C2—H10I	111.0	N2B—C4B—H20B	109.5
N1—C2—H10J	111.0	H20A—C4B—H20B	109.5
C3—C2—H10J	111.0	N2B—C4B—H20C	109.5
H10I—C2—H10J	109.0	H20A—C4B—H20C	109.5
N2—C3—C2	102.7 (3)	H20B—C4B—H20C	109.5
N2—C3—H10G	111.2	N3B—C5B—N2B	120.9 (3)
C2—C3—H10G	111.2	N3B—C5B—N1B	129.1 (3)
N2—C3—H10H	111.2	N2B—C5B—N1B	109.9 (3)
C2—C3—H10H	111.2	N3B—C6B—N4B	113.5 (3)
H10G—C3—H10H	109.1	N3B—C6B—C7B	129.4 (3)
N2—C4—H10A	109.5	N4B—C6B—C7B	116.8 (3)
N2—C4—H10B	109.5	C8B—C7B—C6B	119.0 (3)
H10A—C4—H10B	109.5	C8B—C7B—H20K	120.5
N2—C4—H10C	109.5	C6B—C7B—H20K	120.5
H10A—C4—H10C	109.5	C7B—C8B—C9B	122.8 (3)
H10B—C4—H10C	109.5	C7B—C8B—H20L	118.6
N3—C5—N1	130.3 (3)	C9B—C8B—H20L	118.6
N3—C5—N2	120.5 (3)	C8B—C9B—C10B	118.4 (3)
N1—C5—N2	109.1 (3)	C8B—C9B—H20M	120.8
N4—C6—N3	114.2 (3)	C10B—C9B—H20M	120.8
N4—C6—C7	116.9 (3)	N4B—C10B—N5B	115.0 (3)
N3—C6—C7	128.6 (3)	N4B—C10B—C9B	117.0 (3)
C8—C7—C6	118.5 (3)	N5B—C10B—C9B	127.7 (3)
C8—C7—H10K	120.8	N7B—C11B—N5B	127.9 (3)
C6—C7—H10K	120.8	N7B—C11B—N6B	109.9 (3)
C9—C8—C7	122.7 (3)	N5B—C11B—N6B	122.2 (3)
C9—C8—H10L	118.7	N6B—C12B—H21A	109.5
C7—C8—H10L	118.7	N6B—C12B—H21B	109.5
C8—C9—C10	118.7 (3)	H21A—C12B—H21B	109.5
C8—C9—H10M	120.6	N6B—C12B—H21C	109.5
C10—C9—H10M	120.6	H21A—C12B—H21C	109.5
N5—C10—N4	115.0 (3)	H21B—C12B—H21C	109.5
N5—C10—C9	127.7 (3)	N6B—C13B—C14B	102.0 (3)
N4—C10—C9	117.0 (3)	N6B—C13B—H21G	111.4
N7—C11—N5	127.7 (3)	C14B—C13B—H21G	111.4
N7—C11—N6	109.9 (3)	N6B—C13B—H21H	111.4
N5—C11—N6	122.3 (3)	C14B—C13B—H21H	111.4
N6—C12—H11D	109.5	H21G—C13B—H21H	109.2
N6—C12—H11E	109.5	N7B—C14B—C13B	101.8 (3)
H11D—C12—H11E	109.5	N7B—C14B—H21I	111.4
N6—C12—H11F	109.5	C13B—C14B—H21I	111.4
H11D—C12—H11F	109.5	N7B—C14B—H21J	111.4
H11E—C12—H11F	109.5	C13B—C14B—H21J	111.4
N6—C13—C14	102.0 (3)	H21I—C14B—H21J	109.3
N6—C13—H11I	111.4	N7B—C15B—H21D	109.5
C14—C13—H11I	111.4	N7B—C15B—H21E	109.5
N6—C13—H11J	111.4	H21D—C15B—H21E	109.5
C14—C13—H11J	111.4	N7B—C15B—H21F	109.5
H11I—C13—H11J	109.2	H21D—C15B—H21F	109.5
N7—C14—C13	101.8 (3)	H21E—C15B—H21F	109.5
N7—C14—H11G	111.4	O11—Cl1—O2	101.5 (3)
C13—C14—H11G	111.4	O11—Cl1—O4	105.7 (3)
N7—C14—H11H	111.4	O2—Cl1—O4	111.7 (2)
C13—C14—H11H	111.4	O11—Cl1—O3	125.7 (3)
H11G—C14—H11H	109.3	O2—Cl1—O3	105.6 (2)
N7—C15—H11A	109.5	O4—Cl1—O3	106.4 (2)
N7—C15—H11B	109.5	O2—Cl1—O12	121.6 (3)
H11A—C15—H11B	109.5	O4—Cl1—O12	113.7 (2)
N7—C15—H11C	109.5	O3—Cl1—O12	94.8 (3)
H11A—C15—H11C	109.5	O52—Cl2—O7	117.1 (3)
H11B—C15—H11C	109.5	O61—Cl2—O7	119.3 (3)
C5B—N1B—C1B	126.0 (3)	O52—Cl2—O8	122.3 (4)
C5B—N1B—C2B	110.9 (3)	O61—Cl2—O8	115.7 (3)
C1B—N1B—C2B	120.4 (3)	O7—Cl2—O8	112.83 (18)
C5B—N2B—C3B	112.4 (3)	O61—Cl2—O51	104.1 (3)
C5B—N2B—C4B	125.0 (3)	O7—Cl2—O51	101.8 (2)
C3B—N2B—C4B	122.3 (3)	O8—Cl2—O51	99.4 (3)
C5B—N3B—C6B	122.7 (3)	O52—Cl2—O62	100.0 (4)
C10B—N4B—C6B	125.9 (3)	O7—Cl2—O62	98.5 (3)
C10B—N4B—H4B	119 (2)	O8—Cl2—O62	99.3 (3)
C6B—N4B—H4B	115 (2)	O51—Cl2—O62	144.4 (3)
C11B—N5B—C10B	119.1 (3)
C5—N1—C2—C3	8.0 (4)	C5B—N1B—C2B—C3B	−1.3 (4)
C1—N1—C2—C3	−154.7 (3)	C1B—N1B—C2B—C3B	161.4 (3)
C5—N2—C3—C2	11.0 (4)	C5B—N2B—C3B—C2B	−1.2 (4)
C4—N2—C3—C2	−174.4 (3)	C4B—N2B—C3B—C2B	173.1 (3)
N1—C2—C3—N2	−10.8 (4)	N1B—C2B—C3B—N2B	1.4 (4)
C6—N3—C5—N1	−38.5 (5)	C6B—N3B—C5B—N2B	−147.1 (3)
C6—N3—C5—N2	145.3 (3)	C6B—N3B—C5B—N1B	37.0 (5)
C1—N1—C5—N3	−15.9 (6)	C3B—N2B—C5B—N3B	−176.2 (3)
C2—N1—C5—N3	−177.9 (3)	C4B—N2B—C5B—N3B	9.7 (5)
C1—N1—C5—N2	160.6 (3)	C3B—N2B—C5B—N1B	0.4 (4)
C2—N1—C5—N2	−1.4 (4)	C4B—N2B—C5B—N1B	−173.7 (3)
C4—N2—C5—N3	−4.1 (5)	C1B—N1B—C5B—N3B	15.3 (6)
C3—N2—C5—N3	170.4 (3)	C2B—N1B—C5B—N3B	176.9 (3)
C4—N2—C5—N1	179.0 (3)	C1B—N1B—C5B—N2B	−160.9 (3)
C3—N2—C5—N1	−6.5 (4)	C2B—N1B—C5B—N2B	0.6 (4)
C10—N4—C6—N3	169.6 (3)	C5B—N3B—C6B—N4B	−166.9 (3)
C10—N4—C6—C7	−5.0 (5)	C5B—N3B—C6B—C7B	20.3 (5)
C5—N3—C6—N4	168.0 (3)	C10B—N4B—C6B—N3B	−168.9 (3)
C5—N3—C6—C7	−18.1 (5)	C10B—N4B—C6B—C7B	4.8 (5)
N4—C6—C7—C8	3.1 (5)	N3B—C6B—C7B—C8B	169.9 (3)
N3—C6—C7—C8	−170.7 (3)	N4B—C6B—C7B—C8B	−2.7 (5)
C6—C7—C8—C9	0.0 (5)	C6B—C7B—C8B—C9B	−0.4 (5)
C7—C8—C9—C10	−1.6 (5)	C7B—C8B—C9B—C10B	1.8 (5)
C11—N5—C10—N4	−176.7 (3)	C6B—N4B—C10B—N5B	171.5 (3)
C11—N5—C10—C9	9.3 (5)	C6B—N4B—C10B—C9B	−3.4 (5)
C6—N4—C10—N5	−171.1 (3)	C11B—N5B—C10B—N4B	175.9 (3)
C6—N4—C10—C9	3.5 (5)	C11B—N5B—C10B—C9B	−9.9 (5)
C8—C9—C10—N5	173.8 (3)	C8B—C9B—C10B—N4B	0.0 (5)
C8—C9—C10—N4	0.0 (5)	C8B—C9B—C10B—N5B	−174.2 (3)
C15—N7—C11—N5	2.7 (6)	C15B—N7B—C11B—N5B	2.7 (6)
C14—N7—C11—N5	−175.3 (3)	C14B—N7B—C11B—N5B	175.1 (3)
C15—N7—C11—N6	−174.8 (3)	C15B—N7B—C11B—N6B	−179.4 (3)
C14—N7—C11—N6	7.2 (4)	C14B—N7B—C11B—N6B	−7.0 (4)
C10—N5—C11—N7	59.1 (5)	C10B—N5B—C11B—N7B	−58.2 (5)
C10—N5—C11—N6	−123.7 (4)	C10B—N5B—C11B—N6B	124.1 (3)
C12—N6—C11—N7	170.9 (3)	C12B—N6B—C11B—N7B	−168.8 (3)
C13—N6—C11—N7	8.0 (4)	C13B—N6B—C11B—N7B	−8.5 (4)
C12—N6—C11—N5	−6.8 (5)	C12B—N6B—C11B—N5B	9.2 (5)
C13—N6—C11—N5	−169.6 (3)	C13B—N6B—C11B—N5B	169.6 (3)
C11—N6—C13—C14	−18.6 (4)	C11B—N6B—C13B—C14B	19.0 (4)
C12—N6—C13—C14	177.6 (3)	C12B—N6B—C13B—C14B	−179.8 (3)
C11—N7—C14—C13	−18.1 (4)	C11B—N7B—C14B—C13B	18.2 (4)
C15—N7—C14—C13	163.8 (3)	C15B—N7B—C14B—C13B	−169.0 (3)
N6—C13—C14—N7	20.9 (4)	N6B—C13B—C14B—N7B	−21.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N5^i	0.88 (1)	2.01 (1)	2.885 (4)	175 (3)
N4B—H4B···N5B^ii	0.89 (1)	2.04 (1)	2.922 (4)	174 (3)
C1—H10E···O2^iii	0.98	2.41	3.229 (5)	141
C2—H10J···O2^iii	0.99	2.45	3.219 (5)	134
C1B—H20F···O7^iv	0.98	2.44	3.301 (4)	146

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

(II) bis{2,6-bis[(1,3-dimethylimidazolin-2-ylidene)amino]pyridinium} µ-oxido-bis[trichloridoiron(III)]

Crystal data

(C15H24N7)2[Fe2Cl6O]	F(000) = 976
Mr = 945.22	Dx = 1.503 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1781 reflections
a = 10.5673 (8) Å	θ = 2.2–28.3°
b = 10.9286 (8) Å	µ = 1.12 mm^−1
c = 18.3329 (14) Å	T = 120 K
β = 99.438 (2)°	Prism, red
V = 2088.5 (3) Å^3	0.43 × 0.25 × 0.20 mm
Z = 2

Data collection

Bruker SMART APEX diffractometer	5142 independent reflections
Radiation source: sealed tube	3929 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
ϕ and ω scans	θmax = 28.2°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −14→14
Tmin = 0.644, Tmax = 0.807	k = −14→14
20962 measured reflections	l = −24→24

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)] = 0.045	Hydrogen site location: difference Fourier map
wR(F^2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0646P)^2] where P = (Fo^2 + 2Fc^2)/3
5142 reflections	(Δ/σ)max < 0.001
249 parameters	Δρmax = 0.96 e Å^−3
1 restraint	Δρmin = −0.72 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.

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 (Ų)

	x	y	z	Uiso*/Ueq
Fe1	0.10796 (3)	−0.07833 (3)	0.456159 (17)	0.02885 (11)
Cl1	0.13940 (7)	−0.27077 (6)	0.49480 (4)	0.0526 (2)
Cl2	0.03929 (7)	−0.07802 (7)	0.33459 (3)	0.04969 (19)
Cl3	0.29055 (6)	0.02168 (6)	0.48206 (4)	0.04693 (18)
O1	0.0000	0.0000	0.5000	0.0813 (11)
N1	0.31587 (19)	0.70020 (19)	0.76065 (11)	0.0363 (5)
N2	0.5183 (2)	0.6560 (2)	0.80379 (10)	0.0383 (5)
N3	0.44032 (17)	0.58018 (17)	0.68759 (10)	0.0279 (4)
N4	0.38268 (16)	0.49413 (16)	0.57400 (9)	0.0216 (4)
H4	0.4539 (16)	0.528 (2)	0.5661 (15)	0.046 (8)*
N5	0.37760 (16)	0.39960 (16)	0.46291 (9)	0.0248 (4)
N6	0.38638 (16)	0.23645 (16)	0.38284 (10)	0.0264 (4)
N7	0.20585 (17)	0.33867 (18)	0.36675 (10)	0.0317 (4)
C1	0.2135 (2)	0.7462 (2)	0.70542 (15)	0.0410 (6)
H1A	0.2229	0.7133	0.6569	0.061*
H1B	0.2176	0.8357	0.7041	0.061*
H1C	0.1307	0.7208	0.7178	0.061*
C2	0.3481 (3)	0.7679 (3)	0.83068 (14)	0.0481 (7)
H2A	0.2794	0.7599	0.8612	0.058*
H2B	0.3629	0.8557	0.8218	0.058*
C3	0.4701 (3)	0.7055 (3)	0.86695 (13)	0.0465 (7)
H3A	0.5311	0.7648	0.8943	0.056*
H3B	0.4521	0.6400	0.9011	0.056*
C4	0.6344 (3)	0.5822 (2)	0.81291 (14)	0.0436 (6)
H4A	0.6558	0.5625	0.7642	0.065*
H4B	0.6203	0.5062	0.8389	0.065*
H4C	0.7052	0.6280	0.8418	0.065*
C5	0.4204 (2)	0.6408 (2)	0.74617 (11)	0.0291 (5)
C6	0.34876 (19)	0.51945 (19)	0.64142 (11)	0.0228 (4)
C7	0.2344 (2)	0.4686 (2)	0.65571 (11)	0.0259 (4)
H7A	0.2035	0.4869	0.7003	0.031*
C8	0.1669 (2)	0.3912 (2)	0.60412 (12)	0.0271 (5)
H8A	0.0896	0.3559	0.6144	0.033*
C9	0.20649 (19)	0.36267 (19)	0.53832 (11)	0.0251 (4)
H9A	0.1591	0.3068	0.5047	0.030*
C10	0.31875 (19)	0.41802 (18)	0.52187 (11)	0.0226 (4)
C11	0.32300 (18)	0.32753 (19)	0.40762 (10)	0.0225 (4)
C12	0.5111 (2)	0.1920 (2)	0.41635 (13)	0.0316 (5)
H12A	0.5457	0.2446	0.4582	0.047*
H12B	0.5691	0.1934	0.3797	0.047*
H12C	0.5033	0.1081	0.4338	0.047*
C13	0.3120 (2)	0.1764 (2)	0.31942 (11)	0.0299 (5)
H13A	0.3047	0.0874	0.3282	0.036*
H13B	0.3507	0.1892	0.2744	0.036*
C14	0.1808 (2)	0.2396 (2)	0.31276 (13)	0.0332 (5)
H14A	0.1528	0.2719	0.2623	0.040*
H14B	0.1146	0.1829	0.3254	0.040*
C15	0.1156 (2)	0.4368 (2)	0.37111 (14)	0.0352 (5)
H15A	0.1578	0.5023	0.4026	0.053*
H15B	0.0425	0.4056	0.3923	0.053*
H15C	0.0851	0.4689	0.3214	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.02239 (17)	0.0393 (2)	0.02508 (18)	0.00218 (13)	0.00447 (12)	−0.00348 (13)
Cl1	0.0575 (4)	0.0451 (4)	0.0497 (4)	−0.0166 (3)	−0.0072 (3)	0.0111 (3)
Cl2	0.0573 (4)	0.0568 (4)	0.0293 (3)	−0.0050 (3)	−0.0098 (3)	−0.0033 (3)
Cl3	0.0424 (4)	0.0499 (4)	0.0435 (4)	−0.0162 (3)	−0.0076 (3)	0.0106 (3)
O1	0.0544 (19)	0.124 (3)	0.072 (2)	0.0340 (19)	0.0291 (17)	−0.024 (2)
N1	0.0397 (11)	0.0408 (11)	0.0305 (10)	−0.0076 (9)	0.0119 (9)	−0.0133 (9)
N2	0.0440 (12)	0.0483 (13)	0.0215 (9)	−0.0148 (10)	0.0020 (8)	−0.0084 (9)
N3	0.0267 (9)	0.0375 (11)	0.0187 (8)	−0.0052 (8)	0.0011 (7)	−0.0055 (7)
N4	0.0185 (8)	0.0273 (9)	0.0187 (8)	−0.0021 (7)	0.0017 (7)	−0.0030 (7)
N5	0.0189 (8)	0.0340 (10)	0.0209 (9)	−0.0017 (7)	0.0011 (7)	−0.0071 (7)
N6	0.0253 (9)	0.0272 (9)	0.0251 (9)	0.0007 (7)	−0.0003 (7)	−0.0051 (7)
N7	0.0246 (9)	0.0387 (11)	0.0286 (9)	0.0040 (8)	−0.0056 (7)	−0.0117 (8)
C1	0.0397 (14)	0.0380 (14)	0.0490 (15)	−0.0007 (11)	0.0184 (12)	−0.0062 (11)
C2	0.0663 (18)	0.0471 (16)	0.0368 (14)	−0.0173 (14)	0.0257 (13)	−0.0188 (12)
C3	0.0649 (18)	0.0504 (16)	0.0252 (12)	−0.0228 (14)	0.0105 (12)	−0.0124 (11)
C4	0.0431 (15)	0.0523 (17)	0.0308 (13)	−0.0112 (12)	−0.0073 (11)	0.0044 (11)
C5	0.0326 (11)	0.0339 (12)	0.0216 (10)	−0.0128 (9)	0.0070 (9)	−0.0025 (9)
C6	0.0242 (10)	0.0260 (11)	0.0171 (9)	0.0016 (8)	−0.0004 (8)	−0.0003 (8)
C7	0.0273 (11)	0.0302 (11)	0.0205 (10)	−0.0006 (9)	0.0047 (8)	0.0011 (8)
C8	0.0224 (10)	0.0316 (12)	0.0273 (11)	−0.0013 (9)	0.0036 (8)	0.0041 (9)
C9	0.0224 (10)	0.0273 (11)	0.0243 (10)	−0.0042 (8)	−0.0002 (8)	−0.0020 (8)
C10	0.0197 (10)	0.0268 (11)	0.0200 (9)	0.0038 (8)	−0.0006 (8)	−0.0014 (8)
C11	0.0211 (10)	0.0262 (11)	0.0196 (9)	−0.0018 (8)	0.0014 (8)	−0.0015 (8)
C12	0.0270 (11)	0.0317 (12)	0.0355 (12)	0.0053 (9)	0.0031 (9)	−0.0017 (10)
C13	0.0368 (12)	0.0291 (12)	0.0229 (10)	−0.0028 (9)	0.0017 (9)	−0.0053 (9)
C14	0.0357 (13)	0.0319 (12)	0.0283 (11)	−0.0036 (10)	−0.0056 (9)	−0.0073 (9)
C15	0.0293 (12)	0.0378 (13)	0.0346 (13)	0.0081 (10)	−0.0066 (10)	−0.0043 (10)

Geometric parameters (Å, º)

Fe1—O1	1.7266 (3)	C2—C3	1.512 (4)
Fe1—Cl3	2.2005 (7)	C2—H2A	0.9900
Fe1—Cl1	2.2267 (8)	C2—H2B	0.9900
Fe1—Cl2	2.2278 (7)	C3—H3A	0.9900
O1—Fe1^i	1.7266 (3)	C3—H3B	0.9900
N1—C5	1.345 (3)	C4—H4A	0.9800
N1—C1	1.445 (3)	C4—H4B	0.9800
N1—C2	1.472 (3)	C4—H4C	0.9800
N2—C5	1.362 (3)	C6—C7	1.394 (3)
N2—C3	1.444 (3)	C7—C8	1.377 (3)
N2—C4	1.455 (3)	C7—H7A	0.9500
N3—C5	1.308 (3)	C8—C9	1.376 (3)
N3—C6	1.351 (3)	C8—H8A	0.9500
N4—C10	1.360 (3)	C9—C10	1.408 (3)
N4—C6	1.370 (2)	C9—H9A	0.9500
N4—H4	0.871 (10)	C12—H12A	0.9800
N5—C11	1.337 (2)	C12—H12B	0.9800
N5—C10	1.348 (3)	C12—H12C	0.9800
N6—C11	1.321 (3)	C13—C14	1.536 (3)
N6—C12	1.444 (3)	C13—H13A	0.9900
N6—C13	1.449 (3)	C13—H13B	0.9900
N7—C11	1.343 (3)	C14—H14A	0.9900
N7—C15	1.446 (3)	C14—H14B	0.9900
N7—C14	1.461 (3)	C15—H15A	0.9800
C1—H1A	0.9800	C15—H15B	0.9800
C1—H1B	0.9800	C15—H15C	0.9800
C1—H1C	0.9800
O1—Fe1—Cl3	106.03 (3)	H4B—C4—H4C	109.5
O1—Fe1—Cl1	113.31 (3)	N3—C5—N1	130.9 (2)
Cl3—Fe1—Cl1	108.71 (3)	N3—C5—N2	119.7 (2)
O1—Fe1—Cl2	109.46 (2)	N1—C5—N2	109.37 (19)
Cl3—Fe1—Cl2	110.20 (3)	N3—C6—N4	113.45 (17)
Cl1—Fe1—Cl2	109.08 (3)	N3—C6—C7	129.23 (18)
Fe1—O1—Fe1^i	180.0	N4—C6—C7	116.87 (18)
C5—N1—C1	125.05 (19)	C8—C7—C6	118.90 (19)
C5—N1—C2	109.5 (2)	C8—C7—H7A	120.6
C1—N1—C2	118.4 (2)	C6—C7—H7A	120.6
C5—N2—C3	110.2 (2)	C9—C8—C7	122.93 (19)
C5—N2—C4	122.7 (2)	C9—C8—H8A	118.5
C3—N2—C4	121.1 (2)	C7—C8—H8A	118.5
C5—N3—C6	124.65 (19)	C8—C9—C10	118.59 (19)
C10—N4—C6	125.73 (17)	C8—C9—H9A	120.7
C10—N4—H4	119.0 (19)	C10—C9—H9A	120.7
C6—N4—H4	115.2 (19)	N5—C10—N4	114.43 (17)
C11—N5—C10	119.83 (17)	N5—C10—C9	128.57 (19)
C11—N6—C12	125.86 (18)	N4—C10—C9	116.83 (18)
C11—N6—C13	112.24 (17)	N6—C11—N5	121.62 (18)
C12—N6—C13	121.74 (18)	N6—C11—N7	110.44 (17)
C11—N7—C15	126.33 (18)	N5—C11—N7	127.80 (19)
C11—N7—C14	111.01 (17)	N6—C12—H12A	109.5
C15—N7—C14	122.60 (18)	N6—C12—H12B	109.5
N1—C1—H1A	109.5	H12A—C12—H12B	109.5
N1—C1—H1B	109.5	N6—C12—H12C	109.5
H1A—C1—H1B	109.5	H12A—C12—H12C	109.5
N1—C1—H1C	109.5	H12B—C12—H12C	109.5
H1A—C1—H1C	109.5	N6—C13—C14	102.91 (17)
H1B—C1—H1C	109.5	N6—C13—H13A	111.2
N1—C2—C3	102.5 (2)	C14—C13—H13A	111.2
N1—C2—H2A	111.3	N6—C13—H13B	111.2
C3—C2—H2A	111.3	C14—C13—H13B	111.2
N1—C2—H2B	111.3	H13A—C13—H13B	109.1
C3—C2—H2B	111.3	N7—C14—C13	102.63 (17)
H2A—C2—H2B	109.2	N7—C14—H14A	111.2
N2—C3—C2	101.7 (2)	C13—C14—H14A	111.2
N2—C3—H3A	111.4	N7—C14—H14B	111.2
C2—C3—H3A	111.4	C13—C14—H14B	111.2
N2—C3—H3B	111.4	H14A—C14—H14B	109.2
C2—C3—H3B	111.4	N7—C15—H15A	109.5
H3A—C3—H3B	109.3	N7—C15—H15B	109.5
N2—C4—H4A	109.5	H15A—C15—H15B	109.5
N2—C4—H4B	109.5	N7—C15—H15C	109.5
H4A—C4—H4B	109.5	H15A—C15—H15C	109.5
N2—C4—H4C	109.5	H15B—C15—H15C	109.5
H4A—C4—H4C	109.5
C5—N1—C2—C3	−18.7 (3)	C7—C8—C9—C10	−2.1 (3)
C1—N1—C2—C3	−170.9 (2)	C11—N5—C10—N4	−179.22 (18)
C5—N2—C3—C2	−23.9 (3)	C11—N5—C10—C9	5.7 (3)
C4—N2—C3—C2	−177.3 (2)	C6—N4—C10—N5	−174.28 (19)
N1—C2—C3—N2	24.5 (2)	C6—N4—C10—C9	1.4 (3)
C6—N3—C5—N1	−30.1 (4)	C8—C9—C10—N5	176.8 (2)
C6—N3—C5—N2	153.4 (2)	C8—C9—C10—N4	1.8 (3)
C1—N1—C5—N3	−22.4 (4)	C12—N6—C11—N5	8.9 (3)
C2—N1—C5—N3	−172.3 (2)	C13—N6—C11—N5	−175.75 (19)
C1—N1—C5—N2	154.4 (2)	C12—N6—C11—N7	−175.1 (2)
C2—N1—C5—N2	4.4 (3)	C13—N6—C11—N7	0.2 (3)
C3—N2—C5—N3	−169.8 (2)	C10—N5—C11—N6	−127.9 (2)
C4—N2—C5—N3	−16.8 (3)	C10—N5—C11—N7	56.8 (3)
C3—N2—C5—N1	13.1 (3)	C15—N7—C11—N6	−171.7 (2)
C4—N2—C5—N1	166.0 (2)	C14—N7—C11—N6	5.6 (3)
C5—N3—C6—N4	162.0 (2)	C15—N7—C11—N5	4.0 (4)
C5—N3—C6—C7	−26.0 (4)	C14—N7—C11—N5	−178.7 (2)
C10—N4—C6—N3	168.84 (19)	C11—N6—C13—C14	−5.5 (2)
C10—N4—C6—C7	−4.2 (3)	C12—N6—C13—C14	170.1 (2)
N3—C6—C7—C8	−168.0 (2)	C11—N7—C14—C13	−8.6 (2)
N4—C6—C7—C8	3.8 (3)	C15—N7—C14—C13	168.8 (2)
C6—C7—C8—C9	−0.8 (3)	N6—C13—C14—N7	8.0 (2)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N5^ii	0.87 (1)	2.10 (1)	2.964 (2)	174 (3)
C1—H1A···Cl1^iii	0.98	2.96	3.816 (3)	146
C1—H1C···Cl2^iv	0.98	2.94	3.716 (3)	137
C12—H12C···Cl3^v	0.98	2.83	3.469 (2)	123

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