Crystal structures of two (5,5,7,12,12,14-hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­deca­ne)iron(III) com­plexes

Reported in this contribution are the synthesis and crystal structures of two new Fe^III com­plexes of 5,5,7,12,12,14-hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane (HMC), namely, di­chlorido­(5,5,7,12,12,14-hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­deca­ne)iron(III) chloride, [FeCl₂(C₁₆H₃₆N₄)]Cl or cis-[FeCl₂(rac-HMC)]Cl (1), and di­chlorido­(5,5,7,12,12,14-hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­deca­ne)iron(III) tetra­chloridoferrate, [FeCl₂(C₁₆H₃₆N₄)][FeCl₄] or trans-[FeCl₂(meso-HMC)][FeCl₄] (2). Single-crystal X-ray diffraction studies revealed that both 1 and 2 adopt a pseudo-octa­hedral geometry, where the macrocycles adopt folded and planar geometries, respectively. The chloride ligands in 1 are cis to each other, while those in 2 have a trans configuration. The relevant bond angles in 1 deviate substanti­ally from an ideal octa­hedral coordination geometry, with the angles between the cis substituents varying from 81.55 (5) to 107.56 (4)°, and those between the trans-ligating atoms varying from 157.76 (8) to 170.88 (3)°. In contrast, 2 adopts a less strained configuration, in which the N—Fe—N angles vary from 84.61 (8) to 95.39 (8)° and the N—Fe—Cl angles vary from 86.02 (5) to 93.98 (5)°.

Computing details

For both structures, data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXM (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015) and SHELXLE (Hübschle et al., 2011); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Dichlorido(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)iron(III) chloride (1)

Crystal data

[FeCl2(C16H36N4)]Cl	Dx = 1.461 Mg m^−3
Mr = 446.69	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Fdd2	Cell parameters from 9904 reflections
a = 34.5658 (16) Å	θ = 2.8–34.4°
b = 9.3832 (4) Å	µ = 1.14 mm^−1
c = 12.5209 (6) Å	T = 150 K
V = 4061.0 (3) Å^3	Plate, yellow
Z = 8	0.18 × 0.17 × 0.05 mm
F(000) = 1896

Data collection

Bruker D8 Quest CMOS diffractometer	4166 independent reflections
Radiation source: sealed tube X-ray source	3897 reflections with I > 2σ(I)
Triumph curved graphite crystal monochromator	Rint = 0.042
Detector resolution: 10.4167 pixels mm^-1	θmax = 34.4°, θmin = 2.8°
ω and phi scans	h = −54→54
Absorption correction: multi-scan (Krause et al., 2015)	k = −14→14
Tmin = 0.595, Tmax = 0.747	l = −17→19
17097 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.064	w = 1/[σ^2(Fo^2) + (0.0327P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.030
4166 reflections	Δρmax = 0.86 e Å^−3
120 parameters	Δρmin = −0.58 e Å^−3
2 restraints	Absolute structure: Refined as an inversion twin
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.004 (13)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component inversion twin

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

	x	y	z	Uiso*/Ueq
Fe1	0.000000	0.500000	0.47177 (2)	0.01024 (7)
Cl1	0.04066 (2)	0.59399 (4)	0.59972 (4)	0.01780 (8)
N1	−0.01980 (4)	0.71984 (15)	0.43765 (12)	0.0120 (2)
H1	−0.0100 (7)	0.760 (3)	0.493 (2)	0.014*
N2	0.04360 (3)	0.55678 (13)	0.35009 (12)	0.0113 (2)
H2	0.0352 (7)	0.533 (3)	0.2897 (19)	0.014*
C1	0.00232 (4)	0.76806 (17)	0.34277 (15)	0.0139 (3)
H1A	0.002287	0.873496	0.339879	0.017*
H1AB	−0.010308	0.732065	0.277130	0.017*
C2	0.04357 (4)	0.71467 (16)	0.34726 (16)	0.0141 (3)
H2A	0.057976	0.748405	0.283775	0.017*
H2AB	0.056538	0.752492	0.411806	0.017*
C3	0.08320 (5)	0.49628 (15)	0.36508 (14)	0.0130 (3)
H3	0.091517	0.515461	0.440218	0.016*
C4	0.08278 (4)	0.33465 (16)	0.34788 (15)	0.0145 (3)
H4A	0.070712	0.315941	0.277559	0.017*
H4AB	0.109969	0.302072	0.343351	0.017*
C5	0.06217 (5)	0.24162 (15)	0.43060 (14)	0.0129 (3)
C6	0.11327 (5)	0.5615 (2)	0.28966 (16)	0.0193 (3)
H6A	0.105473	0.544654	0.215473	0.029*
H6B	0.138525	0.517310	0.302598	0.029*
H6C	0.115042	0.664296	0.302647	0.029*
C7	0.07963 (5)	0.25789 (19)	0.54183 (17)	0.0183 (3)
H7A	0.107197	0.233676	0.539414	0.027*
H7B	0.066338	0.193831	0.591581	0.027*
H7C	0.076579	0.356608	0.565959	0.027*
C8	0.06705 (5)	0.08418 (18)	0.39781 (15)	0.0175 (3)
H8A	0.059364	0.072337	0.322999	0.026*
H8B	0.050716	0.024097	0.443246	0.026*
H8C	0.094184	0.056091	0.406353	0.026*
Cl2	0.000000	0.500000	0.11978 (5)	0.02101 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.01000 (12)	0.01121 (12)	0.00952 (13)	0.00018 (11)	0.000	0.000
Cl1	0.01758 (16)	0.02242 (18)	0.01340 (16)	−0.00021 (13)	−0.00299 (14)	−0.00439 (15)
N1	0.0112 (5)	0.0134 (5)	0.0114 (6)	0.0009 (4)	−0.0002 (4)	−0.0011 (4)
N2	0.0108 (5)	0.0115 (5)	0.0116 (5)	0.0001 (4)	−0.0005 (5)	0.0003 (5)
C1	0.0136 (6)	0.0120 (6)	0.0161 (8)	0.0018 (4)	0.0020 (6)	0.0024 (5)
C2	0.0130 (6)	0.0112 (6)	0.0180 (7)	−0.0008 (5)	0.0010 (6)	0.0013 (5)
C3	0.0101 (6)	0.0151 (6)	0.0138 (7)	0.0003 (5)	0.0006 (5)	0.0018 (5)
C4	0.0126 (6)	0.0150 (6)	0.0159 (7)	0.0020 (5)	0.0030 (6)	0.0006 (6)
C5	0.0115 (6)	0.0134 (6)	0.0137 (7)	0.0028 (5)	0.0006 (5)	0.0014 (5)
C6	0.0142 (7)	0.0194 (7)	0.0244 (8)	0.0010 (6)	0.0057 (6)	0.0051 (6)
C7	0.0181 (7)	0.0202 (7)	0.0165 (7)	0.0021 (6)	−0.0042 (7)	0.0018 (6)
C8	0.0175 (7)	0.0140 (6)	0.0210 (8)	0.0050 (6)	0.0017 (6)	0.0008 (6)
Cl2	0.0267 (3)	0.0226 (3)	0.0137 (3)	−0.0070 (2)	0.000	0.000

Geometric parameters (Å, º)

Fe1—N2	2.2081 (14)	C3—C4	1.532 (2)
Fe1—N2^i	2.2081 (14)	C3—C6	1.532 (2)
Fe1—N1	2.2149 (14)	C3—H3	1.0000
Fe1—N1^i	2.2150 (14)	C4—C5	1.530 (2)
Fe1—Cl1	2.3065 (5)	C4—H4A	0.9900
Fe1—Cl1^i	2.3066 (5)	C4—H4AB	0.9900
N1—C1	1.483 (2)	C5—C7	1.526 (3)
N1—C5^i	1.511 (2)	C5—C8	1.543 (2)
N1—H1	0.86 (2)	C6—H6A	0.9800
N2—C2	1.4819 (19)	C6—H6B	0.9800
N2—C3	1.494 (2)	C6—H6C	0.9800
N2—H2	0.84 (2)	C7—H7A	0.9800
C1—C2	1.512 (2)	C7—H7B	0.9800
C1—H1A	0.9900	C7—H7C	0.9800
C1—H1AB	0.9900	C8—H8A	0.9800
C2—H2A	0.9900	C8—H8B	0.9800
C2—H2AB	0.9900	C8—H8C	0.9800
N2—Fe1—N2^i	92.75 (7)	H2A—C2—H2AB	108.2
N2—Fe1—N1	81.55 (5)	N2—C3—C4	110.47 (12)
N2^i—Fe1—N1	83.15 (5)	N2—C3—C6	113.11 (13)
N2—Fe1—N1^i	83.15 (5)	C4—C3—C6	108.39 (14)
N2^i—Fe1—N1^i	81.55 (5)	N2—C3—H3	108.2
N1—Fe1—N1^i	157.76 (8)	C4—C3—H3	108.2
N2—Fe1—Cl1	88.35 (4)	C6—C3—H3	108.2
N2^i—Fe1—Cl1	170.88 (3)	C5—C4—C3	118.29 (14)
N1—Fe1—Cl1	88.06 (4)	C5—C4—H4A	107.7
N1^i—Fe1—Cl1	107.56 (4)	C3—C4—H4A	107.7
N2—Fe1—Cl1^i	170.88 (3)	C5—C4—H4AB	107.7
N2^i—Fe1—Cl1^i	88.34 (4)	C3—C4—H4AB	107.7
N1—Fe1—Cl1^i	107.56 (4)	H4A—C4—H4AB	107.1
N1^i—Fe1—Cl1^i	88.06 (4)	N1^i—C5—C7	107.84 (14)
Cl1—Fe1—Cl1^i	92.01 (2)	N1^i—C5—C4	110.74 (12)
C1—N1—C5^i	112.32 (13)	C7—C5—C4	112.12 (14)
C1—N1—Fe1	106.22 (9)	N1^i—C5—C8	110.54 (13)
C5^i—N1—Fe1	122.25 (10)	C7—C5—C8	107.19 (13)
C1—N1—H1	108.0 (17)	C4—C5—C8	108.37 (14)
C5^i—N1—H1	109.0 (16)	C3—C6—H6A	109.5
Fe1—N1—H1	97.5 (17)	C3—C6—H6B	109.5
C2—N2—C3	112.55 (11)	H6A—C6—H6B	109.5
C2—N2—Fe1	104.91 (10)	C3—C6—H6C	109.5
C3—N2—Fe1	116.56 (10)	H6A—C6—H6C	109.5
C2—N2—H2	104.3 (17)	H6B—C6—H6C	109.5
C3—N2—H2	109.0 (16)	C5—C7—H7A	109.5
Fe1—N2—H2	108.8 (17)	C5—C7—H7B	109.5
N1—C1—C2	110.80 (14)	H7A—C7—H7B	109.5
N1—C1—H1A	109.5	C5—C7—H7C	109.5
C2—C1—H1A	109.5	H7A—C7—H7C	109.5
N1—C1—H1AB	109.5	H7B—C7—H7C	109.5
C2—C1—H1AB	109.5	C5—C8—H8A	109.5
H1A—C1—H1AB	108.1	C5—C8—H8B	109.5
N2—C2—C1	109.43 (12)	H8A—C8—H8B	109.5
N2—C2—H2A	109.8	C5—C8—H8C	109.5
C1—C2—H2A	109.8	H8A—C8—H8C	109.5
N2—C2—H2AB	109.8	H8B—C8—H8C	109.5
C1—C2—H2AB	109.8
C5^i—N1—C1—C2	−174.18 (13)	C2—N2—C3—C6	−48.38 (19)
Fe1—N1—C1—C2	−38.12 (15)	Fe1—N2—C3—C6	−169.64 (11)
C3—N2—C2—C1	−174.53 (14)	N2—C3—C4—C5	−69.37 (19)
Fe1—N2—C2—C1	−46.83 (16)	C6—C3—C4—C5	166.19 (14)
N1—C1—C2—N2	59.91 (19)	C3—C4—C5—N1^i	60.64 (19)
C2—N2—C3—C4	−170.07 (15)	C3—C4—C5—C7	−59.86 (18)
Fe1—N2—C3—C4	68.67 (15)	C3—C4—C5—C8	−177.95 (14)

Symmetry code: (i) −x, −y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2^ii	0.86 (2)	2.78 (2)	3.5467 (15)	150 (2)
N2—H2···Cl2	0.84 (2)	2.47 (2)	3.2971 (16)	168 (2)

Symmetry code: (ii) x, y+1/2, z+1/2.

Dichlorido(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)iron(III) tetrachloridoferrate (2)

Crystal data

[FeCl2(C16H36N4)][FeCl4]	F(000) = 1256
Mr = 608.89	Dx = 1.593 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 6.5569 (2) Å	Cell parameters from 9909 reflections
b = 19.1663 (5) Å	θ = 3.2–80.2°
c = 20.2946 (5) Å	µ = 15.06 mm^−1
β = 95.3558 (15)°	T = 150 K
V = 2539.32 (12) Å^3	Plate, orange
Z = 4	0.18 × 0.09 × 0.05 mm

Data collection

Bruker AXS D8 Quest CMOS diffractometer	5481 independent reflections
Radiation source: I-mu-S microsource X-ray tube	4930 reflections with I > 2σ(I)
Laterally graded multilayer (Goebel) mirror monochromator	Rint = 0.044
Detector resolution: 7.4074 pixels mm^-1	θmax = 81.3°, θmin = 3.2°
ω and phi scans	h = −8→6
Absorption correction: multi-scan (Krause et al., 2015)	k = −24→24
Tmin = 0.426, Tmax = 0.754	l = −25→25
26483 measured reflections

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)] = 0.032	Hydrogen site location: mixed
wR(F^2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0331P)^2 + 2.0722P] where P = (Fo^2 + 2Fc^2)/3
5481 reflections	(Δ/σ)max = 0.001
274 parameters	Δρmax = 0.76 e Å^−3
6 restraints	Δρmin = −0.57 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	−0.0492 (4)	1.11813 (12)	0.10684 (11)	0.0232 (5)
C2	−0.1633 (5)	1.18787 (14)	0.10898 (14)	0.0346 (6)
H2A	−0.084339	1.224426	0.089129	0.052*
H2B	−0.180296	1.200042	0.155047	0.052*
H2C	−0.298274	1.183688	0.084114	0.052*
C3	0.1555 (4)	1.12327 (14)	0.14890 (12)	0.0297 (5)
H3A	0.231959	1.079690	0.145364	0.045*
H3B	0.131237	1.131251	0.195216	0.045*
H3C	0.234986	1.162156	0.133134	0.045*
C4	−0.1897 (4)	1.06314 (13)	0.13413 (11)	0.0243 (5)
H4A	−0.215710	1.077966	0.179321	0.029*
H4AB	−0.322629	1.065052	0.106727	0.029*
C5	−0.1231 (4)	0.98678 (13)	0.13820 (11)	0.0206 (4)
H5	0.027068	0.984812	0.152253	0.025*
C6	−0.2370 (4)	0.94789 (14)	0.18902 (12)	0.0280 (5)
H6A	−0.384013	0.947843	0.174889	0.042*
H6B	−0.212902	0.971097	0.232071	0.042*
H6C	−0.187189	0.899710	0.192790	0.042*
C7	−0.1294 (4)	0.87858 (12)	0.06771 (12)	0.0240 (5)
H7A	−0.238405	0.853989	0.089144	0.029*
H7AB	0.004589	0.865893	0.091186	0.029*
C8	−0.1358 (4)	0.85781 (13)	−0.00432 (12)	0.0270 (5)
H8A	−0.107160	0.807318	−0.008034	0.032*
H8AB	−0.273230	0.867329	−0.026998	0.032*
C9	0.3590 (3)	0.38600 (12)	0.09872 (11)	0.0206 (4)
C10	0.1558 (4)	0.35671 (15)	0.11853 (13)	0.0303 (5)
H10A	0.060053	0.395164	0.123661	0.045*
H10B	0.180228	0.331459	0.160515	0.045*
H10C	0.097286	0.324785	0.084078	0.045*
C11	0.5122 (4)	0.32617 (13)	0.09735 (12)	0.0265 (5)
H11A	0.453000	0.288955	0.068458	0.040*
H11B	0.543601	0.307893	0.142246	0.040*
H11C	0.638195	0.343238	0.080461	0.040*
C12	0.4309 (3)	0.44094 (12)	0.15058 (11)	0.0213 (4)
H12A	0.320651	0.476148	0.151269	0.026*
H12B	0.442905	0.417652	0.194316	0.026*
C13	0.6305 (3)	0.48006 (12)	0.14432 (11)	0.0201 (4)
H13	0.734764	0.446424	0.130329	0.024*
C14	0.7096 (4)	0.51152 (14)	0.21111 (12)	0.0288 (5)
H14A	0.841309	0.534543	0.207154	0.043*
H14B	0.727466	0.474415	0.244372	0.043*
H14C	0.610562	0.545765	0.224616	0.043*
C15	0.7680 (3)	0.58345 (12)	0.08705 (11)	0.0212 (4)
H15A	0.896328	0.556868	0.084148	0.025*
H15B	0.785607	0.613909	0.126568	0.025*
C16	0.7210 (4)	0.62701 (12)	0.02542 (11)	0.0223 (5)
H16A	0.600184	0.656944	0.030186	0.027*
H16B	0.838984	0.657466	0.018423	0.027*
N1	−0.0211 (3)	1.10117 (10)	0.03540 (9)	0.0197 (4)
H1	−0.139 (3)	1.1114 (15)	0.0134 (13)	0.024*
N2	−0.1609 (3)	0.95519 (10)	0.07070 (9)	0.0190 (4)
H2	−0.288 (3)	0.9627 (15)	0.0562 (14)	0.023*
N3	0.3209 (3)	0.42067 (10)	0.03155 (9)	0.0173 (4)
H3	0.209 (3)	0.4443 (13)	0.0335 (14)	0.021*
N4	0.5940 (3)	0.53475 (10)	0.09237 (9)	0.0177 (4)
H4	0.490 (3)	0.5576 (14)	0.1050 (13)	0.021*
Cl1	0.30936 (8)	0.97775 (3)	0.06127 (3)	0.02332 (12)
Cl2	0.21952 (7)	0.56951 (3)	0.00283 (3)	0.02014 (11)
Cl3	0.69585 (11)	0.74121 (4)	0.20082 (4)	0.04673 (19)
Cl4	0.24204 (10)	0.63793 (3)	0.18618 (3)	0.03526 (15)
Cl5	0.21825 (11)	0.82224 (4)	0.22565 (3)	0.03874 (16)
Cl6	0.32760 (14)	0.76773 (4)	0.06291 (3)	0.0490 (2)
Fe1	0.000000	1.000000	0.000000	0.01496 (11)
Fe2	0.500000	0.500000	0.000000	0.01370 (11)
Fe3	0.36770 (6)	0.74286 (2)	0.16940 (2)	0.02616 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0344 (12)	0.0204 (11)	0.0146 (10)	0.0022 (9)	0.0018 (9)	−0.0005 (8)
C2	0.0530 (16)	0.0228 (12)	0.0283 (13)	0.0080 (12)	0.0056 (12)	−0.0043 (10)
C3	0.0409 (14)	0.0287 (13)	0.0180 (11)	−0.0060 (11)	−0.0047 (10)	−0.0043 (9)
C4	0.0296 (12)	0.0266 (12)	0.0174 (10)	0.0034 (10)	0.0063 (9)	−0.0015 (9)
C5	0.0239 (11)	0.0277 (12)	0.0108 (10)	−0.0008 (9)	0.0047 (8)	0.0011 (8)
C6	0.0313 (13)	0.0356 (14)	0.0184 (11)	−0.0014 (10)	0.0089 (9)	0.0056 (10)
C7	0.0313 (12)	0.0203 (11)	0.0212 (11)	−0.0023 (9)	0.0067 (9)	0.0041 (9)
C8	0.0381 (13)	0.0198 (11)	0.0238 (12)	−0.0056 (10)	0.0062 (10)	0.0003 (9)
C9	0.0213 (10)	0.0222 (11)	0.0184 (10)	0.0005 (9)	0.0025 (8)	0.0027 (9)
C10	0.0259 (12)	0.0367 (14)	0.0287 (13)	−0.0046 (10)	0.0046 (10)	0.0078 (11)
C11	0.0288 (12)	0.0243 (12)	0.0254 (12)	0.0061 (10)	−0.0021 (9)	0.0045 (10)
C12	0.0228 (11)	0.0261 (12)	0.0153 (10)	0.0044 (9)	0.0043 (8)	0.0019 (9)
C13	0.0210 (10)	0.0251 (11)	0.0138 (10)	0.0031 (9)	−0.0007 (8)	0.0006 (8)
C14	0.0345 (13)	0.0357 (14)	0.0149 (11)	−0.0001 (11)	−0.0038 (9)	−0.0021 (10)
C15	0.0202 (10)	0.0251 (11)	0.0179 (10)	−0.0042 (9)	−0.0003 (8)	−0.0060 (9)
C16	0.0238 (11)	0.0214 (11)	0.0213 (11)	−0.0031 (9)	0.0002 (9)	−0.0034 (9)
N1	0.0242 (9)	0.0196 (9)	0.0152 (9)	−0.0020 (7)	0.0015 (7)	−0.0014 (7)
N2	0.0217 (9)	0.0208 (9)	0.0142 (8)	0.0013 (7)	0.0009 (7)	0.0010 (7)
N3	0.0171 (8)	0.0190 (9)	0.0157 (8)	0.0023 (7)	0.0010 (7)	−0.0007 (7)
N4	0.0155 (8)	0.0233 (9)	0.0143 (8)	0.0010 (7)	0.0019 (7)	−0.0018 (7)
Cl1	0.0195 (2)	0.0293 (3)	0.0212 (3)	−0.0001 (2)	0.00196 (19)	0.0017 (2)
Cl2	0.0168 (2)	0.0231 (3)	0.0207 (2)	0.00348 (19)	0.00231 (18)	−0.00202 (19)
Cl3	0.0322 (3)	0.0408 (4)	0.0658 (5)	−0.0008 (3)	−0.0029 (3)	0.0069 (3)
Cl4	0.0390 (3)	0.0292 (3)	0.0374 (3)	−0.0048 (3)	0.0027 (3)	−0.0016 (3)
Cl5	0.0463 (4)	0.0376 (4)	0.0310 (3)	0.0097 (3)	−0.0030 (3)	−0.0129 (3)
Cl6	0.0767 (5)	0.0465 (4)	0.0243 (3)	0.0307 (4)	0.0080 (3)	0.0056 (3)
Fe1	0.0176 (2)	0.0156 (2)	0.0120 (2)	−0.00026 (17)	0.00293 (17)	0.00091 (17)
Fe2	0.0128 (2)	0.0169 (2)	0.0114 (2)	0.00094 (17)	0.00103 (16)	−0.00157 (16)
Fe3	0.0322 (2)	0.0237 (2)	0.0223 (2)	0.00353 (15)	0.00095 (15)	0.00045 (14)

Geometric parameters (Å, º)

C1—N1	1.514 (3)	C11—H11A	0.9800
C1—C3	1.525 (3)	C11—H11B	0.9800
C1—C2	1.535 (3)	C11—H11C	0.9800
C1—C4	1.536 (3)	C12—C13	1.524 (3)
C2—H2A	0.9800	C12—H12A	0.9900
C2—H2B	0.9800	C12—H12B	0.9900
C2—H2C	0.9800	C13—N4	1.490 (3)
C3—H3A	0.9800	C13—C14	1.529 (3)
C3—H3B	0.9800	C13—H13	1.0000
C3—H3C	0.9800	C14—H14A	0.9800
C4—C5	1.527 (3)	C14—H14B	0.9800
C4—H4A	0.9900	C14—H14C	0.9800
C4—H4AB	0.9900	C15—N4	1.486 (3)
C5—N2	1.497 (3)	C15—C16	1.512 (3)
C5—C6	1.523 (3)	C15—H15A	0.9900
C5—H5	1.0000	C15—H15B	0.9900
C6—H6A	0.9800	C16—N3^ii	1.479 (3)
C6—H6B	0.9800	C16—H16A	0.9900
C6—H6C	0.9800	C16—H16B	0.9900
C7—N2	1.485 (3)	Fe1—N1	2.0768 (19)
C7—C8	1.512 (3)	N1—H1	0.880 (19)
C7—H7A	0.9900	Fe1—N2	2.0477 (19)
C7—H7AB	0.9900	N2—H2	0.872 (19)
C8—N1^i	1.481 (3)	Fe2—N3	2.0595 (19)
C8—H8A	0.9900	N3—H3	0.864 (19)
C8—H8AB	0.9900	Fe2—N4	2.0301 (18)
C9—N3	1.516 (3)	N4—H4	0.869 (19)
C9—C11	1.526 (3)	Fe1—Cl1	2.3177 (5)
C9—C12	1.532 (3)	Fe2—Cl2	2.2760 (5)
C9—C10	1.534 (3)	Fe3—Cl3	2.1866 (8)
C10—H10A	0.9800	Fe3—Cl4	2.2117 (8)
C10—H10B	0.9800	Fe3—Cl5	2.1879 (7)
C10—H10C	0.9800	Fe3—Cl6	2.2048 (8)
N1—C1—C3	111.7 (2)	C13—C14—H14A	109.5
N1—C1—C2	108.51 (19)	C13—C14—H14B	109.5
C3—C1—C2	109.5 (2)	H14A—C14—H14B	109.5
N1—C1—C4	109.19 (18)	C13—C14—H14C	109.5
C3—C1—C4	111.62 (19)	H14A—C14—H14C	109.5
C2—C1—C4	106.1 (2)	H14B—C14—H14C	109.5
C1—C2—H2A	109.5	N4—C15—C16	107.96 (17)
C1—C2—H2B	109.5	N4—C15—H15A	110.1
H2A—C2—H2B	109.5	C16—C15—H15A	110.1
C1—C2—H2C	109.5	N4—C15—H15B	110.1
H2A—C2—H2C	109.5	C16—C15—H15B	110.1
H2B—C2—H2C	109.5	H15A—C15—H15B	108.4
C1—C3—H3A	109.5	N3^ii—C16—C15	108.31 (18)
C1—C3—H3B	109.5	N3^ii—C16—H16A	110.0
H3A—C3—H3B	109.5	C15—C16—H16A	110.0
C1—C3—H3C	109.5	N3^ii—C16—H16B	110.0
H3A—C3—H3C	109.5	C15—C16—H16B	110.0
H3B—C3—H3C	109.5	H16A—C16—H16B	108.4
C5—C4—C1	119.9 (2)	C8^i—N1—C1	116.44 (18)
C5—C4—H4A	107.3	C8^i—N1—Fe1	106.08 (14)
C1—C4—H4A	107.3	C1—N1—Fe1	123.35 (14)
C5—C4—H4AB	107.3	C8^i—N1—H1	106.2 (19)
C1—C4—H4AB	107.3	C1—N1—H1	104.9 (19)
H4A—C4—H4AB	106.9	Fe1—N1—H1	96.7 (19)
N2—C5—C6	111.8 (2)	C7—N2—C5	115.19 (18)
N2—C5—C4	108.42 (18)	C7—N2—Fe1	107.65 (14)
C6—C5—C4	110.5 (2)	C5—N2—Fe1	114.80 (14)
N2—C5—H5	108.7	C7—N2—H2	106.4 (19)
C6—C5—H5	108.7	C5—N2—H2	108.2 (19)
C4—C5—H5	108.7	Fe1—N2—H2	103.6 (19)
C5—C6—H6A	109.5	C16^ii—N3—C9	115.78 (18)
C5—C6—H6B	109.5	C16^ii—N3—Fe2	106.42 (14)
H6A—C6—H6B	109.5	C9—N3—Fe2	123.52 (13)
C5—C6—H6C	109.5	C16^ii—N3—H3	105.3 (18)
H6A—C6—H6C	109.5	C9—N3—H3	104.9 (19)
H6B—C6—H6C	109.5	Fe2—N3—H3	97.9 (18)
N2—C7—C8	107.97 (18)	C15—N4—C13	114.79 (17)
N2—C7—H7A	110.1	C15—N4—Fe2	107.94 (13)
C8—C7—H7A	110.1	C13—N4—Fe2	115.95 (14)
N2—C7—H7AB	110.1	C15—N4—H4	109.5 (18)
C8—C7—H7AB	110.1	C13—N4—H4	103.0 (19)
H7A—C7—H7AB	108.4	Fe2—N4—H4	105.0 (18)
N1^i—C8—C7	108.32 (19)	N2^i—Fe1—N2	180.0
N1^i—C8—H8A	110.0	N2^i—Fe1—N1^i	95.39 (8)
C7—C8—H8A	110.0	N2—Fe1—N1^i	84.61 (8)
N1^i—C8—H8AB	110.0	N2^i—Fe1—N1	84.61 (8)
C7—C8—H8AB	110.0	N2—Fe1—N1	95.39 (8)
H8A—C8—H8AB	108.4	N1^i—Fe1—N1	180.0
N3—C9—C11	111.50 (19)	N2^i—Fe1—Cl1	88.32 (5)
N3—C9—C12	109.32 (18)	N2—Fe1—Cl1	91.68 (5)
C11—C9—C12	111.59 (19)	N1^i—Fe1—Cl1	86.02 (5)
N3—C9—C10	108.78 (18)	N1—Fe1—Cl1	93.98 (5)
C11—C9—C10	108.6 (2)	N2^i—Fe1—Cl1^i	91.68 (5)
C12—C9—C10	106.90 (19)	N2—Fe1—Cl1^i	88.32 (5)
C9—C10—H10A	109.5	N1^i—Fe1—Cl1^i	93.98 (5)
C9—C10—H10B	109.5	N1—Fe1—Cl1^i	86.02 (5)
H10A—C10—H10B	109.5	Cl1—Fe1—Cl1^i	180.0
C9—C10—H10C	109.5	N4—Fe2—N4^ii	180.0
H10A—C10—H10C	109.5	N4—Fe2—N3	95.04 (7)
H10B—C10—H10C	109.5	N4^ii—Fe2—N3	84.97 (7)
C9—C11—H11A	109.5	N4—Fe2—N3^ii	84.96 (7)
C9—C11—H11B	109.5	N4^ii—Fe2—N3^ii	95.03 (7)
H11A—C11—H11B	109.5	N3—Fe2—N3^ii	180.0
C9—C11—H11C	109.5	N4—Fe2—Cl2	87.76 (5)
H11A—C11—H11C	109.5	N4^ii—Fe2—Cl2	92.23 (5)
H11B—C11—H11C	109.5	N3—Fe2—Cl2	86.49 (5)
C13—C12—C9	119.51 (19)	N3^ii—Fe2—Cl2	93.51 (5)
C13—C12—H12A	107.4	N4—Fe2—Cl2^ii	92.23 (5)
C9—C12—H12A	107.4	N4^ii—Fe2—Cl2^ii	87.77 (5)
C13—C12—H12B	107.4	N3—Fe2—Cl2^ii	93.51 (5)
C9—C12—H12B	107.4	N3^ii—Fe2—Cl2^ii	86.49 (5)
H12A—C12—H12B	107.0	Cl2—Fe2—Cl2^ii	180.0
N4—C13—C12	108.82 (17)	Cl3—Fe3—Cl5	109.53 (3)
N4—C13—C14	111.64 (19)	Cl3—Fe3—Cl6	108.24 (4)
C12—C13—C14	110.04 (19)	Cl5—Fe3—Cl6	110.05 (3)
N4—C13—H13	108.8	Cl3—Fe3—Cl4	108.22 (3)
C12—C13—H13	108.8	Cl5—Fe3—Cl4	111.14 (3)
C14—C13—H13	108.8	Cl6—Fe3—Cl4	109.60 (3)
N1—C1—C4—C5	62.5 (3)	C8—C7—N2—C5	−169.80 (19)
C3—C1—C4—C5	−61.5 (3)	C8—C7—N2—Fe1	−40.3 (2)
C2—C1—C4—C5	179.3 (2)	C6—C5—N2—C7	−50.4 (3)
C1—C4—C5—N2	−79.0 (2)	C4—C5—N2—C7	−172.44 (19)
C1—C4—C5—C6	158.1 (2)	C6—C5—N2—Fe1	−176.30 (15)
N2—C7—C8—N1^i	56.4 (3)	C4—C5—N2—Fe1	61.7 (2)
N3—C9—C12—C13	−62.2 (3)	C11—C9—N3—C16^ii	47.7 (3)
C11—C9—C12—C13	61.6 (3)	C12—C9—N3—C16^ii	171.61 (18)
C10—C9—C12—C13	−179.8 (2)	C10—C9—N3—C16^ii	−72.0 (2)
C9—C12—C13—N4	77.3 (2)	C11—C9—N3—Fe2	−86.4 (2)
C9—C12—C13—C14	−160.0 (2)	C12—C9—N3—Fe2	37.5 (2)
N4—C15—C16—N3^ii	−55.2 (2)	C10—C9—N3—Fe2	153.86 (16)
C3—C1—N1—C8^i	−46.7 (3)	C16—C15—N4—C13	170.47 (18)
C2—C1—N1—C8^i	74.1 (3)	C16—C15—N4—Fe2	39.5 (2)
C4—C1—N1—C8^i	−170.6 (2)	C12—C13—N4—C15	172.13 (18)
C3—C1—N1—Fe1	87.5 (2)	C14—C13—N4—C15	50.5 (3)
C2—C1—N1—Fe1	−151.62 (17)	C12—C13—N4—Fe2	−60.9 (2)
C4—C1—N1—Fe1	−36.4 (2)	C14—C13—N4—Fe2	177.49 (15)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl6^i	0.88 (2)	2.99 (2)	3.686 (2)	138 (2)
N2—H2···Cl1^iii	0.87 (2)	2.66 (2)	3.487 (2)	158 (2)
N3—H3···Cl2^iv	0.86 (2)	2.85 (2)	3.5519 (19)	139 (2)
N4—H4···Cl4	0.87 (2)	2.87 (2)	3.699 (2)	160 (2)

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