The LIESST state of [Fe(pic)₃]Cl₂.EtOH – the superstructure under continuous irradiation

The superstructure recently discovered in [Fe(pic)₃]Cl₂.EtOH at temperatures inside the step region of the high-spin–low-spin transition curve sheds new light on the anomalous transition behaviour in spin crossover compounds. The structure of the metastable LIESST state of [Fe(pic)₃]Cl₂.EtOH at 10 K has been measured. The decay has been followed by X-ray diffraction using a CCD camera in order to detect reflections of the superstructure building up during the decay. No signal above the noise of the CCD camera was observed, so that even diffuse scattering could not be detected. This finding is in agreement with correlation lengths of pair correlations of molecules in the HS and LS states being very short, as was concluded earlier from the shape of the decay curves of the HS fraction by theoretical considerations [Romstedt et al. (1998). J. Phys. Chem. Solids, 59, 265–275]. The crystal structure inside the step at 118 K has also been studied under continuous irradiation. The temperature range of the superstructure and the degree of order could be changed by continuous irradiation with green laser light, indicating an increase of the lifetime of the HS excited state by several orders of magnitude compared with the temperature regions outside.

Computing details

Data collection: Enraf Nonius Software V5 for ev_fpic118, fepic100, fepic200, fpic118h; CrysAlis (Oxford Diffraction, 2002) for fpic10k, fpic11hs. Cell refinement: Enraf Nonius Software V5 for ev_fpic118, fepic100, fepic200, fpic118h; STADI4 (Stoe, 1995) for fpic10k, fpic11hs. Data reduction: Corinc (Dräger, 1971) for ev_fpic118, fepic100, fepic200, fpic118h; CrysAlis (Oxford Diffraction, 2002) for fpic10k, fpic11hs. For all compounds, program(s) used to solve structure: SIR92 (Altomare, 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

(ev_fpic118) 'tris(2-Picolylamine)-iron(ii) chloride ethanol solvate'

Crystal data

C18H24FeN6·C2H6O·2(Cl)	F(000) = 1040
Mr = 497.25	Dx = 1.392 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 10.8041 (9) Å	Cell parameters from 25 reflections
b = 21.6945 (14) Å	θ = 21.5–26.8°
c = 11.395 (4) Å	µ = 7.36 mm^−1
β = 117.33 (3)°	T = 118 K
V = 2372.7 (9) Å^3	Block, red
Z = 4	0.46 × 0.12 × 0.12 mm

Data collection

CAD4 Enraf Nonius diffractometer	3612 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.053
Graphite monochromator	θmax = 73.8°, θmin = 4.1°
Detector resolution: point detector pixels mm^-1	h = −11→13
θ/2ω scans	k = −27→0
5041 measured reflections	l = −14→0
4798 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.075	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.197	Calculated w = 1/[σ^2(Fo^2) + (0.1071P)^2 + 2.315P] where P = (Fo^2 + 2Fc^2)/3
S = 1.13	(Δ/σ)max < 0.001
4798 reflections	Δρmax = 1.36 e Å^−3
274 parameters	Δρmin = −1.43 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0008 (2)

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	0.02844 (7)	0.13394 (3)	0.80450 (7)	0.0227 (2)
Cl2	0.26469 (11)	0.27405 (6)	1.08044 (12)	0.0336 (3)
Cl1	−0.13622 (12)	0.06958 (6)	1.06252 (11)	0.0309 (3)
N6	−0.1439 (4)	0.18945 (18)	0.7646 (4)	0.0270 (9)
N4	0.2316 (5)	0.1009 (2)	0.8755 (5)	0.0338 (10)
N1	−0.0619 (4)	0.0509 (2)	0.8160 (4)	0.0299 (9)
H1A	−0.1048	0.0547	0.8726	0.036*
H1B	0.0110	0.0224	0.8396	0.036*
N5	0.0959 (4)	0.21908 (18)	0.7674 (4)	0.0231 (8)
H5A	0.1472	0.2338	0.8562	0.028*
H5B	0.1751	0.2215	0.7421	0.028*
N3	0.1005 (5)	0.1429 (3)	1.0074 (6)	0.0581 (18)
H3A	0.0379	0.1379	1.0234	0.070*
H3B	0.1224	0.1830	1.0147	0.070*
N2	−0.0502 (4)	0.10136 (19)	0.6105 (4)	0.0247 (8)
C2	−0.1391 (5)	0.0534 (2)	0.5792 (5)	0.0266 (10)
C15	−0.2561 (5)	0.2855 (2)	0.6706 (5)	0.0283 (10)
H15	−0.2559	0.3230	0.6277	0.034*
O32	0.3050 (5)	0.3907 (3)	0.9344 (6)	0.0660 (14)
H32	0.280 (2)	0.344 (4)	0.983 (4)	0.099*
C18	−0.2484 (5)	0.1780 (3)	0.7948 (5)	0.0322 (11)
H18	−0.2449	0.1409	0.8406	0.039*
C5	−0.0673 (5)	0.0941 (2)	0.3932 (5)	0.0314 (11)
H5	−0.0409	0.1092	0.3296	0.038*
C8	0.2991 (5)	0.0919 (2)	1.0067 (6)	0.0347 (12)
C13	−0.0256 (5)	0.2573 (2)	0.6800 (5)	0.0265 (10)
H13A	−0.0511	0.2483	0.5865	0.032*
H13B	−0.0010	0.3015	0.6964	0.032*
C11	0.4451 (7)	0.0848 (3)	0.8649 (7)	0.0464 (16)
H11	0.4935	0.0827	0.8134	0.056*
C3	−0.1947 (6)	0.0247 (2)	0.4579 (5)	0.0336 (11)
H3	−0.2574	−0.0088	0.4394	0.040*
C14	−0.1472 (5)	0.2438 (2)	0.7058 (5)	0.0238 (9)
C16	−0.3647 (5)	0.2716 (2)	0.6986 (5)	0.0311 (11)
H16	−0.4411	0.2991	0.6741	0.037*
C1	−0.1752 (5)	0.0327 (2)	0.6874 (5)	0.0310 (11)
H1AA	−0.2636	0.0522	0.6743	0.037*
H1BB	−0.1875	−0.0126	0.6839	0.037*
C9	0.4400 (6)	0.0791 (3)	1.0715 (6)	0.0402 (13)
H9	0.4854	0.0729	1.1644	0.048*
C6	−0.0150 (5)	0.1209 (2)	0.5168 (5)	0.0296 (10)
H6	0.0482	0.1544	0.5370	0.036*
C4	−0.1581 (6)	0.0453 (3)	0.3636 (5)	0.0366 (12)
H4	−0.1951	0.0261	0.2794	0.044*
C7	0.2103 (6)	0.0973 (4)	1.0748 (6)	0.0525 (19)
H7A	0.1680	0.0568	1.0747	0.063*
H7B	0.2682	0.1100	1.1678	0.063*
C12	0.3043 (6)	0.0974 (2)	0.8068 (7)	0.0385 (13)
H12	0.2567	0.1038	0.7141	0.046*
C17	−0.3598 (5)	0.2168 (2)	0.7633 (5)	0.0317 (11)
H17	−0.4320	0.2063	0.7853	0.038*
C31	0.4475 (7)	0.3928 (3)	0.9705 (7)	0.0524 (16)
H31A	0.4994	0.3955	1.0680	0.063*
H31B	0.4661	0.4312	0.9344	0.063*
C30	0.5044 (7)	0.3405 (4)	0.9271 (7)	0.061 (2)
H30A	0.4942	0.3024	0.9681	0.091*
H30B	0.6032	0.3478	0.9538	0.091*
H30C	0.4534	0.3367	0.8308	0.091*
C10	0.5143 (6)	0.0753 (3)	1.0008 (7)	0.0434 (14)
H10	0.6112	0.0663	1.0440	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0113 (3)	0.0267 (4)	0.0313 (4)	−0.0008 (3)	0.0108 (3)	−0.0062 (3)
Cl2	0.0172 (5)	0.0509 (8)	0.0349 (6)	−0.0059 (5)	0.0139 (5)	−0.0084 (5)
Cl1	0.0252 (6)	0.0421 (7)	0.0282 (5)	0.0137 (5)	0.0148 (5)	0.0027 (5)
N6	0.0109 (17)	0.025 (2)	0.040 (2)	0.0003 (15)	0.0079 (16)	0.0057 (17)
N4	0.037 (2)	0.026 (2)	0.052 (3)	−0.0109 (18)	0.033 (2)	−0.0114 (19)
N1	0.025 (2)	0.039 (2)	0.025 (2)	0.0149 (17)	0.0103 (17)	−0.0003 (16)
N5	0.0163 (17)	0.026 (2)	0.0297 (19)	−0.0017 (15)	0.0130 (15)	−0.0018 (15)
N3	0.027 (2)	0.087 (4)	0.074 (4)	−0.024 (3)	0.034 (3)	−0.050 (3)
N2	0.0191 (18)	0.036 (2)	0.0195 (18)	0.0080 (16)	0.0094 (15)	0.0008 (15)
C2	0.024 (2)	0.031 (2)	0.026 (2)	0.0091 (19)	0.0123 (19)	0.0045 (18)
C15	0.020 (2)	0.025 (2)	0.039 (3)	0.0015 (18)	0.012 (2)	0.0025 (19)
O32	0.047 (3)	0.070 (3)	0.089 (4)	0.010 (2)	0.038 (3)	0.014 (3)
C18	0.014 (2)	0.036 (3)	0.041 (3)	−0.0027 (19)	0.008 (2)	0.008 (2)
C5	0.035 (3)	0.035 (3)	0.023 (2)	0.007 (2)	0.013 (2)	0.0025 (19)
C8	0.030 (3)	0.034 (3)	0.047 (3)	−0.018 (2)	0.023 (2)	−0.020 (2)
C13	0.023 (2)	0.025 (2)	0.033 (2)	0.0016 (18)	0.015 (2)	0.0004 (18)
C11	0.055 (4)	0.025 (3)	0.084 (5)	0.004 (2)	0.053 (4)	0.004 (3)
C3	0.038 (3)	0.031 (3)	0.029 (2)	0.003 (2)	0.013 (2)	−0.002 (2)
C14	0.020 (2)	0.020 (2)	0.031 (2)	−0.0011 (17)	0.0111 (19)	0.0020 (17)
C16	0.019 (2)	0.028 (2)	0.044 (3)	0.0058 (19)	0.013 (2)	0.002 (2)
C1	0.031 (3)	0.034 (3)	0.028 (2)	0.001 (2)	0.013 (2)	−0.001 (2)
C9	0.032 (3)	0.035 (3)	0.056 (3)	−0.008 (2)	0.023 (3)	−0.010 (2)
C6	0.024 (2)	0.038 (3)	0.029 (2)	0.006 (2)	0.014 (2)	0.000 (2)
C4	0.050 (3)	0.038 (3)	0.020 (2)	0.006 (2)	0.015 (2)	−0.003 (2)
C7	0.028 (3)	0.103 (6)	0.029 (3)	−0.022 (3)	0.014 (2)	−0.024 (3)
C12	0.048 (3)	0.023 (3)	0.066 (4)	0.006 (2)	0.044 (3)	0.004 (2)
C17	0.017 (2)	0.036 (3)	0.044 (3)	−0.0025 (19)	0.015 (2)	0.006 (2)
C31	0.037 (3)	0.059 (4)	0.059 (4)	0.002 (3)	0.020 (3)	0.006 (3)
C30	0.048 (4)	0.091 (6)	0.045 (4)	0.027 (4)	0.023 (3)	0.013 (4)
C10	0.034 (3)	0.025 (3)	0.079 (4)	0.000 (2)	0.033 (3)	−0.003 (3)

Geometric parameters (Å, º)

Fe1—N3	2.082 (6)	C2—C1	1.522 (6)
Fe1—N1	2.082 (5)	C15—C16	1.384 (7)
Fe1—N6	2.085 (4)	C15—C14	1.389 (6)
Fe1—N4	2.087 (5)	O32—C31	1.400 (7)
Fe1—N2	2.094 (4)	C18—C17	1.375 (7)
Fe1—N5	2.099 (4)	C5—C4	1.377 (8)
N6—C18	1.346 (6)	C5—C6	1.382 (7)
N6—C14	1.347 (6)	C8—C9	1.382 (8)
N4—C12	1.341 (6)	C8—C7	1.489 (7)
N4—C8	1.344 (7)	C13—C14	1.501 (6)
N1—C1	1.468 (6)	C11—C12	1.378 (8)
N5—C13	1.484 (6)	C11—C10	1.392 (10)
N3—C7	1.462 (9)	C3—C4	1.378 (7)
N2—C2	1.348 (6)	C16—C17	1.387 (7)
N2—C6	1.355 (6)	C9—C10	1.376 (8)
C2—C3	1.377 (7)	C31—C30	1.480 (10)
N3—Fe1—N1	87.6 (2)	C6—N2—Fe1	127.0 (4)
N3—Fe1—N6	91.71 (19)	N2—C2—C3	123.0 (4)
N1—Fe1—N6	96.67 (15)	N2—C2—C1	115.4 (4)
N3—Fe1—N4	79.09 (19)	C3—C2—C1	121.6 (5)
N1—Fe1—N4	96.82 (16)	C16—C15—C14	119.1 (5)
N6—Fe1—N4	163.30 (16)	N6—C18—C17	123.8 (5)
N3—Fe1—N2	165.3 (2)	C4—C5—C6	118.9 (5)
N1—Fe1—N2	78.43 (16)	N4—C8—C9	121.7 (5)
N6—Fe1—N2	94.34 (16)	N4—C8—C7	114.7 (5)
N4—Fe1—N2	97.96 (16)	C9—C8—C7	123.6 (6)
N3—Fe1—N5	98.9 (2)	N5—C13—C14	110.1 (4)
N1—Fe1—N5	172.15 (15)	C12—C11—C10	118.3 (5)
N6—Fe1—N5	78.78 (15)	C2—C3—C4	119.1 (5)
N4—Fe1—N5	88.81 (15)	N6—C14—C15	122.7 (4)
N2—Fe1—N5	95.43 (16)	N6—C14—C13	116.2 (4)
C18—N6—C14	117.0 (4)	C15—C14—C13	121.1 (4)
C18—N6—Fe1	127.4 (3)	C15—C16—C17	118.6 (4)
C14—N6—Fe1	115.5 (3)	N1—C1—C2	108.9 (4)
C12—N4—C8	118.5 (5)	C10—C9—C8	119.7 (6)
C12—N4—Fe1	126.0 (4)	N2—C6—C5	122.8 (5)
C8—N4—Fe1	114.7 (3)	C5—C4—C3	119.1 (5)
C1—N1—Fe1	111.7 (3)	N3—C7—C8	109.9 (6)
C13—N5—Fe1	110.2 (3)	N4—C12—C11	122.9 (6)
C7—N3—Fe1	108.7 (3)	C18—C17—C16	118.7 (4)
C2—N2—C6	117.1 (4)	O32—C31—C30	116.5 (6)
C2—N2—Fe1	115.8 (3)	C9—C10—C11	118.9 (6)

(fepic100) 'tris(2-Picolylamine)-iron(ii) chloride ethanol solvate'

Crystal data

C18H24FeN6·C2H6O·2(Cl)	F(000) = 1040
Mr = 497.25	Dx = 1.408 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 10.7098 (17) Å	Cell parameters from 25 reflections
b = 21.5711 (13) Å	θ = 21.5–26.8°
c = 11.356 (4) Å	µ = 7.44 mm^−1
β = 116.62 (3)°	T = 100 K
V = 2345.5 (9) Å^3	Block, red
Z = 4	0.46 × 0.12 × 0.12 mm

Data collection

CAD4 Enraf Nonius diffractometer	4752 independent reflections
Radiation source: rotating anode	3699 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
Detector resolution: point detector pixels mm^-1	θmax = 74.0°, θmin = 4.1°
θ/2ω scans	h = −11→13
Absorption correction: ψ scan ?	k = −26→0
Tmin = 0.399, Tmax = 0.411	l = −14→0
4994 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.064	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.173	Calculated w = 1/[σ^2(Fo^2) + (0.1071P)^2 + 2.315P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
4752 reflections	Δρmax = 1.20 e Å^−3
274 parameters	Δρmin = −1.34 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0009 (2)

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	0.02566 (6)	0.13334 (3)	0.80177 (6)	0.01536 (19)
Cl2	0.26794 (10)	0.27443 (5)	1.08067 (10)	0.0233 (2)
Cl1	−0.13660 (10)	0.07046 (5)	1.06507 (10)	0.0209 (2)
N6	−0.1446 (3)	0.18489 (16)	0.7613 (3)	0.0193 (7)
N4	0.2194 (4)	0.10005 (16)	0.8678 (4)	0.0209 (7)
N1	−0.0579 (3)	0.05174 (16)	0.8199 (3)	0.0189 (7)
H1A	−0.1007	0.0556	0.8766	0.023*
H1B	0.0151	0.0233	0.8436	0.023*
N5	0.0973 (3)	0.21639 (16)	0.7700 (4)	0.0194 (7)
H5A	0.1486	0.2311	0.8588	0.023*
H5B	0.1765	0.2188	0.7447	0.023*
N3	0.0913 (4)	0.14741 (17)	0.9965 (4)	0.0223 (8)
H3A	0.0286	0.1424	1.0125	0.027*
H3B	0.1131	0.1875	1.0038	0.027*
N2	−0.0475 (3)	0.10278 (16)	0.6146 (3)	0.0184 (7)
C2	−0.1369 (4)	0.05401 (19)	0.5837 (4)	0.0181 (8)
C15	−0.2559 (4)	0.2827 (2)	0.6729 (4)	0.0220 (9)
H15	−0.2551	0.3209	0.6318	0.026*
O32	0.3055 (4)	0.3910 (2)	0.9324 (5)	0.0490 (11)
H32	0.2865 (14)	0.347 (3)	0.980 (3)	0.073*
C18	−0.2507 (4)	0.1727 (2)	0.7913 (4)	0.0223 (9)
H18	−0.2487	0.1348	0.8346	0.027*
C5	−0.0655 (4)	0.0971 (2)	0.3966 (4)	0.0232 (9)
H5	−0.0381	0.1125	0.3333	0.028*
C8	0.2899 (4)	0.09322 (19)	0.9997 (4)	0.0211 (8)
C13	−0.0221 (4)	0.2552 (2)	0.6820 (4)	0.0214 (9)
H13A	−0.0449	0.2465	0.5890	0.026*
H13B	0.0026	0.2996	0.6995	0.026*
C11	0.4336 (5)	0.0815 (2)	0.8548 (5)	0.0293 (10)
H11	0.4814	0.0776	0.8021	0.035*
C3	−0.1933 (5)	0.0263 (2)	0.4619 (4)	0.0240 (9)
H3	−0.2560	−0.0076	0.4439	0.029*
C14	−0.1461 (4)	0.24092 (19)	0.7060 (4)	0.0192 (8)
C16	−0.3655 (4)	0.2682 (2)	0.7001 (5)	0.0245 (9)
H16	−0.4421	0.2958	0.6767	0.029*
C1	−0.1709 (4)	0.0325 (2)	0.6919 (4)	0.0203 (8)
H1AA	−0.2605	0.0508	0.6800	0.024*
H1BB	−0.1803	−0.0132	0.6891	0.024*
C9	0.4314 (5)	0.0809 (2)	1.0631 (5)	0.0292 (10)
H9	0.4779	0.0767	1.1562	0.035*
C6	−0.0132 (4)	0.12332 (19)	0.5200 (4)	0.0195 (8)
H6	0.0495	0.1573	0.5398	0.023*
C4	−0.1586 (5)	0.0479 (2)	0.3654 (4)	0.0251 (9)
H4	−0.1973	0.0295	0.2804	0.030*
C7	0.2016 (4)	0.1015 (2)	1.0703 (4)	0.0233 (9)
H7A	0.1589	0.0615	1.0751	0.028*
H7B	0.2598	0.1164	1.1612	0.028*
C12	0.2915 (5)	0.0939 (2)	0.7968 (5)	0.0246 (9)
H12	0.2431	0.0983	0.7038	0.030*
C17	−0.3618 (4)	0.2122 (2)	0.7626 (4)	0.0228 (9)
H17	−0.4345	0.2014	0.7851	0.027*
C31	0.4488 (6)	0.3963 (3)	0.9675 (6)	0.0422 (13)
H31A	0.5007	0.4001	1.0645	0.051*
H31B	0.4643	0.4349	0.9287	0.051*
C30	0.5076 (6)	0.3428 (3)	0.9241 (6)	0.0438 (14)
H30A	0.4971	0.3046	0.9656	0.066*
H30B	0.6068	0.3502	0.9502	0.066*
H30C	0.4572	0.3386	0.8281	0.066*
C10	0.5047 (5)	0.0748 (2)	0.9898 (6)	0.0322 (11)
H10	0.6020	0.0661	1.0315	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0088 (3)	0.0154 (3)	0.0229 (3)	0.0001 (2)	0.0081 (2)	−0.0003 (2)
Cl2	0.0133 (4)	0.0248 (5)	0.0335 (5)	−0.0025 (4)	0.0120 (4)	−0.0050 (4)
Cl1	0.0170 (5)	0.0228 (5)	0.0265 (5)	0.0039 (4)	0.0129 (4)	0.0024 (4)
N6	0.0119 (16)	0.0197 (17)	0.0257 (18)	0.0011 (13)	0.0079 (14)	0.0025 (14)
N4	0.0175 (17)	0.0151 (16)	0.034 (2)	−0.0005 (13)	0.0152 (15)	−0.0007 (14)
N1	0.0140 (16)	0.0172 (17)	0.0268 (18)	0.0013 (13)	0.0105 (14)	−0.0005 (13)
N5	0.0135 (16)	0.0184 (17)	0.0268 (18)	−0.0010 (13)	0.0093 (14)	−0.0001 (14)
N3	0.0156 (17)	0.0239 (19)	0.033 (2)	−0.0001 (14)	0.0162 (15)	−0.0027 (15)
N2	0.0127 (15)	0.0210 (17)	0.0229 (17)	0.0030 (13)	0.0094 (14)	−0.0006 (14)
C2	0.0137 (18)	0.020 (2)	0.0207 (19)	0.0015 (15)	0.0074 (16)	0.0028 (15)
C15	0.019 (2)	0.017 (2)	0.030 (2)	0.0003 (16)	0.0099 (17)	0.0020 (16)
O32	0.037 (2)	0.040 (2)	0.074 (3)	0.0109 (18)	0.028 (2)	0.016 (2)
C18	0.0117 (19)	0.026 (2)	0.029 (2)	−0.0019 (16)	0.0087 (17)	0.0019 (17)
C5	0.024 (2)	0.026 (2)	0.022 (2)	0.0007 (18)	0.0123 (18)	0.0015 (16)
C8	0.019 (2)	0.0148 (19)	0.030 (2)	−0.0047 (15)	0.0113 (18)	−0.0044 (15)
C13	0.021 (2)	0.018 (2)	0.029 (2)	0.0018 (16)	0.0140 (18)	0.0012 (16)
C11	0.024 (2)	0.020 (2)	0.053 (3)	0.0011 (18)	0.026 (2)	0.000 (2)
C3	0.021 (2)	0.022 (2)	0.030 (2)	−0.0010 (17)	0.0115 (19)	−0.0019 (17)
C14	0.019 (2)	0.017 (2)	0.022 (2)	−0.0017 (15)	0.0095 (17)	0.0024 (15)
C16	0.015 (2)	0.022 (2)	0.035 (2)	0.0030 (16)	0.0105 (18)	−0.0003 (18)
C1	0.017 (2)	0.022 (2)	0.024 (2)	−0.0027 (16)	0.0106 (17)	−0.0008 (16)
C9	0.022 (2)	0.024 (2)	0.040 (3)	−0.0021 (18)	0.012 (2)	−0.0031 (19)
C6	0.0163 (19)	0.018 (2)	0.027 (2)	−0.0012 (15)	0.0125 (17)	0.0000 (16)
C4	0.022 (2)	0.028 (2)	0.022 (2)	0.0014 (18)	0.0069 (18)	−0.0008 (17)
C7	0.0151 (19)	0.032 (2)	0.020 (2)	0.0026 (17)	0.0048 (16)	−0.0014 (17)
C12	0.021 (2)	0.021 (2)	0.036 (2)	0.0016 (17)	0.0169 (19)	−0.0006 (17)
C17	0.0134 (19)	0.025 (2)	0.032 (2)	−0.0016 (16)	0.0121 (17)	0.0015 (17)
C31	0.030 (3)	0.040 (3)	0.055 (3)	−0.001 (2)	0.017 (3)	0.002 (3)
C30	0.036 (3)	0.056 (4)	0.040 (3)	0.020 (3)	0.018 (2)	0.011 (3)
C10	0.015 (2)	0.023 (2)	0.057 (3)	−0.0004 (17)	0.015 (2)	−0.004 (2)

Geometric parameters (Å, º)

Fe1—N4	1.997 (4)	C2—C1	1.504 (5)
Fe1—N6	2.006 (3)	C15—C16	1.378 (6)
Fe1—N2	2.019 (4)	C15—C14	1.392 (6)
Fe1—N3	2.021 (4)	O32—C31	1.406 (6)
Fe1—N1	2.026 (4)	C18—C17	1.378 (6)
Fe1—N5	2.044 (4)	C5—C6	1.377 (6)
N6—C18	1.350 (5)	C5—C4	1.390 (6)
N6—C14	1.359 (5)	C8—C9	1.381 (6)
N4—C12	1.349 (5)	C8—C7	1.500 (6)
N4—C8	1.350 (6)	C13—C14	1.503 (6)
N1—C1	1.475 (5)	C11—C10	1.381 (8)
N5—C13	1.479 (5)	C11—C12	1.387 (6)
N3—C7	1.480 (5)	C3—C4	1.386 (6)
N2—C6	1.355 (5)	C16—C17	1.393 (6)
N2—C2	1.358 (5)	C9—C10	1.384 (7)
C2—C3	1.373 (6)	C31—C30	1.500 (8)
N4—Fe1—N6	166.03 (15)	C2—N2—Fe1	114.9 (3)
N4—Fe1—N2	97.21 (15)	N2—C2—C3	122.6 (4)
N6—Fe1—N2	93.19 (14)	N2—C2—C1	115.4 (4)
N4—Fe1—N3	81.38 (15)	C3—C2—C1	122.0 (4)
N6—Fe1—N3	90.12 (15)	C16—C15—C14	119.6 (4)
N2—Fe1—N3	169.12 (15)	N6—C18—C17	123.7 (4)
N4—Fe1—N1	94.66 (14)	C6—C5—C4	119.4 (4)
N6—Fe1—N1	96.17 (14)	N4—C8—C9	122.5 (4)
N2—Fe1—N1	80.95 (14)	N4—C8—C7	114.0 (4)
N3—Fe1—N1	88.39 (15)	C9—C8—C7	123.4 (4)
N4—Fe1—N5	88.41 (14)	N5—C13—C14	109.2 (3)
N6—Fe1—N5	81.27 (14)	C10—C11—C12	119.3 (4)
N2—Fe1—N5	95.72 (15)	C2—C3—C4	119.8 (4)
N3—Fe1—N5	95.03 (15)	N6—C14—C15	122.3 (4)
N1—Fe1—N5	175.72 (14)	N6—C14—C13	115.9 (4)
C18—N6—C14	116.9 (4)	C15—C14—C13	121.8 (4)
C18—N6—Fe1	128.0 (3)	C15—C16—C17	118.6 (4)
C14—N6—Fe1	114.9 (3)	N1—C1—C2	109.0 (3)
C12—N4—C8	117.8 (4)	C8—C9—C10	119.4 (5)
C12—N4—Fe1	126.0 (3)	N2—C6—C5	122.8 (4)
C8—N4—Fe1	115.2 (3)	C3—C4—C5	118.2 (4)
C1—N1—Fe1	110.5 (3)	N3—C7—C8	108.2 (4)
C13—N5—Fe1	109.6 (3)	N4—C12—C11	122.4 (4)
C7—N3—Fe1	108.5 (3)	C18—C17—C16	118.8 (4)
C6—N2—C2	117.3 (4)	O32—C31—C30	114.2 (5)
C6—N2—Fe1	127.8 (3)	C11—C10—C9	118.6 (4)

(fepic200) 'tris(2-Picolylamine)-iron(ii) chloride ethanol solvate'

Crystal data

C18H24FeN6·C2H6O·2(Cl)	F(000) = 1040
Mr = 497.25	Dx = 1.353 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 10.9348 (7) Å	Cell parameters from 25 reflections
b = 21.9329 (16) Å	θ = 21.5–26.8°
c = 11.484 (5) Å	µ = 7.15 mm^−1
β = 117.59 (2)°	T = 200 K
V = 2441.0 (11) Å^3	Block, yellow
Z = 4	0.46 × 0.12 × 0.12 mm

Data collection

CAD4 Enraf Nonius diffractometer	3585 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.057
Graphite monochromator	θmax = 73.6°, θmin = 4.0°
Detector resolution: point detector pixels mm^-1	h = −12→13
θ/2ω scans	k = −27→0
5190 measured reflections	l = −14→0
4939 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.076	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.199	Calculated w = 1/[σ^2(Fo^2) + (0.1071P)^2 + 2.315P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
4939 reflections	Δρmax = 1.15 e Å^−3
274 parameters	Δρmin = −1.28 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0010 (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	0.02826 (7)	0.13452 (3)	0.80631 (7)	0.0252 (2)
Cl2	0.25376 (13)	0.27338 (6)	1.07564 (14)	0.0414 (3)
Cl1	−0.13745 (12)	0.06834 (6)	1.05956 (12)	0.0327 (3)
N6	−0.1474 (4)	0.19467 (19)	0.7692 (4)	0.0292 (9)
N4	0.2416 (4)	0.10346 (19)	0.8798 (5)	0.0333 (9)
N1	−0.0694 (4)	0.04893 (18)	0.8119 (4)	0.0286 (9)
H1A	−0.1122	0.0528	0.8686	0.034*
H1B	0.0036	0.0205	0.8356	0.034*
N5	0.0884 (4)	0.22268 (19)	0.7611 (4)	0.0317 (9)
H5A	0.1397	0.2374	0.8499	0.038*
H5B	0.1676	0.2251	0.7358	0.038*
N3	0.1093 (4)	0.1376 (2)	1.0195 (4)	0.0329 (9)
H3A	0.0466	0.1326	1.0354	0.039*
H3B	0.1311	0.1777	1.0268	0.039*
N2	−0.0571 (4)	0.09854 (19)	0.6039 (4)	0.0287 (9)
C2	−0.1430 (5)	0.0509 (2)	0.5757 (5)	0.0296 (10)
C15	−0.2613 (6)	0.2875 (3)	0.6678 (6)	0.0415 (13)
H15	−0.2627	0.3240	0.6226	0.050*
O32	0.3060 (7)	0.3868 (3)	0.9371 (8)	0.109 (3)
H32	0.279 (3)	0.340 (5)	0.985 (5)	0.163*
C18	−0.2509 (5)	0.1836 (2)	0.7985 (5)	0.0354 (11)
H18	−0.2467	0.1475	0.8460	0.042*
C5	−0.0731 (6)	0.0900 (3)	0.3890 (5)	0.0407 (13)
H5	−0.0475	0.1045	0.3254	0.049*
C8	0.3076 (5)	0.0909 (2)	1.0106 (6)	0.0333 (11)
C13	−0.0335 (6)	0.2599 (2)	0.6768 (6)	0.0389 (13)
H13A	−0.0616	0.2507	0.5834	0.047*
H13B	−0.0090	0.3036	0.6920	0.047*
C11	0.4551 (6)	0.0886 (3)	0.8723 (8)	0.0511 (17)
H11	0.5041	0.0886	0.8222	0.061*
C3	−0.1977 (6)	0.0212 (3)	0.4551 (5)	0.0400 (12)
H3	−0.2590	−0.0122	0.4378	0.048*
C14	−0.1520 (5)	0.2471 (2)	0.7054 (5)	0.0324 (11)
C16	−0.3675 (6)	0.2745 (3)	0.6961 (7)	0.0444 (14)
H16	−0.4436	0.3016	0.6696	0.053*
C1	−0.1786 (6)	0.0313 (3)	0.6830 (5)	0.0382 (12)
H1AA	−0.2665	0.0505	0.6683	0.046*
H1BB	−0.1909	−0.0135	0.6799	0.046*
C9	0.4465 (5)	0.0765 (3)	1.0741 (7)	0.0438 (14)
H9	0.4904	0.0675	1.1654	0.053*
C6	−0.0228 (6)	0.1174 (3)	0.5098 (5)	0.0355 (11)
H6	0.0386	0.1509	0.5287	0.043*
C4	−0.1620 (6)	0.0409 (3)	0.3613 (6)	0.0451 (14)
H4	−0.1979	0.0211	0.2784	0.054*
C7	0.2204 (5)	0.0921 (3)	1.0793 (5)	0.0372 (12)
H7A	0.1796	0.0513	1.0742	0.045*
H7B	0.2786	0.1022	1.1731	0.045*
C12	0.3165 (6)	0.1022 (3)	0.8145 (7)	0.0425 (13)
H12	0.2712	0.1112	0.7232	0.051*
C17	−0.3626 (5)	0.2215 (3)	0.7636 (6)	0.0410 (13)
H17	−0.4343	0.2117	0.7852	0.049*
C31	0.4467 (9)	0.3881 (4)	0.9739 (11)	0.086 (3)
H31A	0.4982	0.3884	1.0710	0.103*
H31B	0.4674	0.4269	0.9424	0.103*
C30	0.4979 (11)	0.3391 (6)	0.9270 (9)	0.111 (4)
H30A	0.4950	0.3012	0.9709	0.167*
H30B	0.5933	0.3478	0.9460	0.167*
H30C	0.4405	0.3348	0.8319	0.167*
C10	0.5213 (6)	0.0750 (3)	1.0049 (8)	0.0527 (17)
H10	0.6166	0.0649	1.0476	0.063*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0198 (4)	0.0244 (4)	0.0352 (4)	0.0008 (3)	0.0160 (3)	0.0006 (3)
Cl2	0.0346 (6)	0.0417 (7)	0.0565 (8)	−0.0068 (5)	0.0285 (6)	−0.0093 (6)
Cl1	0.0310 (6)	0.0343 (6)	0.0419 (6)	0.0047 (5)	0.0247 (5)	0.0029 (5)
N6	0.0238 (19)	0.026 (2)	0.040 (2)	0.0002 (16)	0.0165 (17)	0.0029 (17)
N4	0.025 (2)	0.029 (2)	0.050 (3)	−0.0007 (17)	0.0219 (19)	−0.0023 (19)
N1	0.029 (2)	0.026 (2)	0.037 (2)	0.0011 (16)	0.0202 (18)	−0.0008 (16)
N5	0.026 (2)	0.036 (2)	0.041 (2)	−0.0028 (17)	0.0222 (18)	−0.0011 (18)
N3	0.030 (2)	0.034 (2)	0.042 (2)	−0.0009 (18)	0.0223 (19)	−0.0030 (18)
N2	0.026 (2)	0.031 (2)	0.030 (2)	−0.0015 (17)	0.0141 (17)	−0.0004 (16)
C2	0.023 (2)	0.034 (3)	0.031 (2)	−0.0001 (19)	0.012 (2)	−0.0014 (19)
C15	0.037 (3)	0.032 (3)	0.060 (4)	0.008 (2)	0.026 (3)	0.011 (2)
O32	0.090 (5)	0.086 (5)	0.179 (8)	0.028 (4)	0.086 (5)	0.045 (5)
C18	0.027 (2)	0.035 (3)	0.047 (3)	−0.001 (2)	0.020 (2)	0.002 (2)
C5	0.048 (3)	0.046 (3)	0.035 (3)	0.002 (3)	0.025 (3)	0.004 (2)
C8	0.025 (2)	0.026 (2)	0.048 (3)	−0.0032 (19)	0.016 (2)	−0.008 (2)
C13	0.049 (3)	0.026 (3)	0.057 (3)	0.006 (2)	0.038 (3)	0.008 (2)
C11	0.041 (3)	0.032 (3)	0.099 (5)	0.000 (2)	0.049 (4)	−0.001 (3)
C3	0.035 (3)	0.042 (3)	0.040 (3)	−0.007 (2)	0.014 (2)	−0.008 (2)
C14	0.034 (3)	0.026 (2)	0.042 (3)	0.002 (2)	0.021 (2)	0.002 (2)
C16	0.033 (3)	0.033 (3)	0.072 (4)	0.012 (2)	0.029 (3)	0.008 (3)
C1	0.035 (3)	0.046 (3)	0.037 (3)	−0.011 (2)	0.019 (2)	−0.002 (2)
C9	0.025 (3)	0.036 (3)	0.061 (4)	0.000 (2)	0.013 (2)	−0.006 (3)
C6	0.036 (3)	0.039 (3)	0.037 (3)	0.000 (2)	0.022 (2)	0.002 (2)
C4	0.050 (3)	0.047 (3)	0.036 (3)	−0.001 (3)	0.018 (3)	−0.005 (2)
C7	0.031 (3)	0.039 (3)	0.035 (3)	0.002 (2)	0.011 (2)	−0.001 (2)
C12	0.037 (3)	0.041 (3)	0.065 (4)	0.005 (2)	0.036 (3)	0.005 (3)
C17	0.027 (2)	0.043 (3)	0.062 (4)	0.002 (2)	0.028 (3)	0.006 (3)
C31	0.072 (6)	0.077 (6)	0.115 (8)	0.006 (5)	0.049 (6)	0.009 (6)
C30	0.120 (8)	0.155 (11)	0.075 (6)	0.086 (8)	0.059 (6)	0.044 (6)
C10	0.024 (3)	0.037 (3)	0.093 (5)	0.001 (2)	0.024 (3)	−0.006 (3)

Geometric parameters (Å, º)

Fe1—N1	2.175 (4)	C2—C1	1.516 (7)
Fe1—N5	2.181 (4)	C15—C16	1.374 (8)
Fe1—N3	2.185 (4)	C15—C14	1.386 (7)
Fe1—N4	2.190 (4)	O32—C31	1.395 (10)
Fe1—N6	2.203 (4)	C18—C17	1.375 (7)
Fe1—N2	2.210 (4)	C5—C6	1.372 (8)
N6—C18	1.344 (6)	C5—C4	1.386 (8)
N6—C14	1.352 (6)	C8—C9	1.383 (7)
N4—C12	1.342 (6)	C8—C7	1.493 (7)
N4—C8	1.360 (7)	C13—C14	1.503 (7)
N1—C1	1.459 (6)	C11—C12	1.377 (8)
N5—C13	1.477 (7)	C11—C10	1.382 (10)
N3—C7	1.472 (6)	C3—C4	1.375 (8)
N2—C2	1.340 (6)	C16—C17	1.383 (8)
N2—C6	1.362 (6)	C9—C10	1.379 (9)
C2—C3	1.390 (7)	C31—C30	1.426 (13)
N1—Fe1—N5	168.06 (16)	C6—N2—Fe1	126.0 (4)
N1—Fe1—N3	86.73 (16)	N2—C2—C3	122.4 (5)
N5—Fe1—N3	103.24 (17)	N2—C2—C1	116.1 (4)
N1—Fe1—N4	99.79 (16)	C3—C2—C1	121.5 (5)
N5—Fe1—N4	89.01 (16)	C16—C15—C14	119.7 (5)
N3—Fe1—N4	76.76 (16)	N6—C18—C17	123.7 (5)
N1—Fe1—N6	97.27 (15)	C6—C5—C4	118.8 (5)
N5—Fe1—N6	75.81 (15)	N4—C8—C9	121.3 (5)
N3—Fe1—N6	93.62 (16)	N4—C8—C7	116.0 (4)
N4—Fe1—N6	159.82 (16)	C9—C8—C7	122.7 (5)
N1—Fe1—N2	75.46 (15)	N5—C13—C14	111.2 (4)
N5—Fe1—N2	95.36 (16)	C12—C11—C10	118.4 (6)
N3—Fe1—N2	160.68 (16)	C4—C3—C2	119.1 (5)
N4—Fe1—N2	98.64 (16)	N6—C14—C15	121.5 (5)
N6—Fe1—N2	95.99 (16)	N6—C14—C13	117.2 (4)
C18—N6—C14	117.7 (4)	C15—C14—C13	121.3 (5)
C18—N6—Fe1	127.1 (3)	C15—C16—C17	119.3 (5)
C14—N6—Fe1	115.1 (3)	N1—C1—C2	110.6 (4)
C12—N4—C8	117.6 (5)	C10—C9—C8	120.1 (6)
C12—N4—Fe1	127.4 (4)	N2—C6—C5	122.8 (5)
C8—N4—Fe1	114.5 (3)	C3—C4—C5	119.2 (5)
C1—N1—Fe1	112.4 (3)	N3—C7—C8	110.9 (4)
C13—N5—Fe1	111.4 (3)	N4—C12—C11	123.8 (6)
C7—N3—Fe1	108.7 (3)	C18—C17—C16	118.0 (5)
C2—N2—C6	117.7 (4)	O32—C31—C30	116.2 (10)
C2—N2—Fe1	116.1 (3)	C9—C10—C11	118.8 (5)

(fpic10k) tris(2-Picolylamine)-iron(ii) chloride ethanol solvate

Crystal data

C18H24FeN6·C2H6O·2(Cl)	F(000) = 1040
Mr = 497.25	Dx = 1.421 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.7322 (14) Å	Cell parameters from 60 reflections
b = 21.5055 (7) Å	θ = 30–40°
c = 11.323 (2) Å	µ = 0.90 mm^−1
β = 117.184 (17)°	T = 10 K
V = 2324.7 (5) Å^3	Block, red
Z = 4	0.4 × 0.3 × 0.2 mm

Data collection

CCD Oxford Diffraction diffractometer	5154 independent reflections
Radiation source: fine-focus rotating anode	4302 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.105
ϕ–scans	θmax = 27.9°, θmin = 3.9°
Absorption correction: multi-scan ?	h = −13→13
Tmin = 0.730, Tmax = 0.835	k = −26→27
20473 measured reflections	l = −14→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.060	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.130	Calculated w = 1/[σ^2(Fo^2) + (0.0401P)^2 + 5.8012P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.001
5154 reflections	Δρmax = 0.62 e Å^−3
274 parameters	Δρmin = −0.57 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0044 (8)

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	0.02410 (5)	0.13315 (2)	0.80247 (5)	0.00395 (14)
Cl2	0.26959 (8)	0.27370 (4)	1.08624 (8)	0.00741 (18)
Cl1	−0.14068 (8)	0.06988 (4)	1.06312 (8)	0.00677 (18)
N6	−0.1460 (3)	0.18464 (13)	0.7601 (3)	0.0061 (5)
N4	0.2172 (3)	0.09936 (12)	0.8709 (3)	0.0059 (5)
N1	−0.0586 (3)	0.05172 (13)	0.8208 (3)	0.0057 (5)
H1A	−0.1015	0.0556	0.8774	0.007*
H1B	0.0143	0.0233	0.8444	0.007*
N5	0.0966 (3)	0.21592 (13)	0.7730 (3)	0.0069 (6)
H5A	0.1479	0.2306	0.8618	0.008*
H5B	0.1758	0.2183	0.7477	0.008*
N3	0.0886 (3)	0.14735 (13)	0.9983 (3)	0.0066 (5)
H3A	0.0260	0.1424	1.0143	0.008*
H3B	0.1105	0.1875	1.0056	0.008*
N2	−0.0462 (3)	0.10272 (13)	0.6159 (3)	0.0052 (5)
C2	−0.1364 (3)	0.05417 (15)	0.5830 (3)	0.0062 (6)
C15	−0.2553 (3)	0.28348 (15)	0.6753 (3)	0.0080 (6)
H15	−0.2536	0.3222	0.6359	0.010*
O32	0.3013 (2)	0.39001 (12)	0.9307 (3)	0.0124 (5)
H32	0.2893 (8)	0.3609 (18)	0.962 (2)	0.019*
C18	−0.2523 (3)	0.17177 (15)	0.7898 (3)	0.0063 (6)
H18	−0.2513	0.1331	0.8310	0.008*
C5	−0.0631 (3)	0.09669 (15)	0.3965 (3)	0.0072 (6)
H5	−0.0352	0.1122	0.3337	0.009*
C8	0.2874 (3)	0.09266 (15)	1.0044 (3)	0.0065 (6)
C13	−0.0225 (3)	0.25513 (15)	0.6834 (3)	0.0069 (6)
H13A	−0.0456	0.2464	0.5898	0.008*
H13B	0.0028	0.2996	0.7013	0.008*
C11	0.4347 (3)	0.08196 (15)	0.8623 (3)	0.0088 (7)
H11	0.4836	0.0785	0.8107	0.011*
C3	−0.1923 (3)	0.02574 (15)	0.4601 (3)	0.0075 (7)
H3	−0.2551	−0.0082	0.4413	0.009*
C14	−0.1474 (3)	0.24112 (15)	0.7065 (3)	0.0060 (6)
C16	−0.3657 (3)	0.26896 (16)	0.7021 (3)	0.0082 (6)
H16	−0.4417	0.2969	0.6794	0.010*
C1	−0.1724 (3)	0.03229 (16)	0.6909 (3)	0.0070 (6)
H1AA	−0.2624	0.0508	0.6776	0.008*
H1BB	−0.1822	−0.0135	0.6878	0.008*
C9	0.4298 (3)	0.08029 (15)	1.0699 (3)	0.0082 (6)
H9	0.4756	0.0754	1.1637	0.010*
C6	−0.0119 (3)	0.12317 (15)	0.5212 (3)	0.0061 (6)
H6	0.0506	0.1574	0.5416	0.007*
C4	−0.1558 (3)	0.04726 (15)	0.3640 (3)	0.0080 (6)
H4	−0.1934	0.0286	0.2786	0.010*
C7	0.1982 (3)	0.10096 (16)	1.0740 (3)	0.0076 (6)
H7A	0.1546	0.0609	1.0776	0.009*
H7B	0.2562	0.1157	1.1660	0.009*
C12	0.2917 (3)	0.09409 (15)	0.8016 (3)	0.0066 (6)
H12	0.2443	0.0989	0.7079	0.008*
C17	−0.3620 (3)	0.21236 (16)	0.7630 (3)	0.0079 (6)
H17	−0.4341	0.2017	0.7860	0.009*
C31	0.4471 (4)	0.39605 (16)	0.9684 (4)	0.0124 (7)
H31A	0.4993	0.4001	1.0661	0.015*
H31B	0.4623	0.4346	0.9288	0.015*
C30	0.5053 (4)	0.34127 (17)	0.9248 (4)	0.0135 (7)
H30A	0.5000	0.3037	0.9711	0.020*
H30B	0.6033	0.3495	0.9465	0.020*
H30C	0.4504	0.3353	0.8288	0.020*
C10	0.5049 (3)	0.07500 (15)	0.9987 (4)	0.0092 (7)
H10	0.6027	0.0668	1.0424	0.011*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0041 (2)	0.0037 (2)	0.0039 (2)	−0.00008 (16)	0.00172 (18)	−0.00002 (17)
Cl2	0.0070 (4)	0.0068 (4)	0.0082 (4)	−0.0002 (3)	0.0033 (3)	−0.0004 (3)
Cl1	0.0073 (3)	0.0069 (4)	0.0067 (4)	0.0007 (3)	0.0037 (3)	0.0004 (3)
N6	0.0072 (13)	0.0068 (13)	0.0028 (13)	−0.0022 (10)	0.0009 (11)	−0.0008 (11)
N4	0.0060 (12)	0.0037 (13)	0.0077 (14)	−0.0005 (10)	0.0029 (11)	−0.0004 (10)
N1	0.0039 (12)	0.0072 (13)	0.0062 (14)	−0.0004 (10)	0.0023 (11)	−0.0024 (11)
N5	0.0062 (13)	0.0075 (13)	0.0072 (14)	−0.0001 (10)	0.0032 (11)	0.0004 (11)
N3	0.0055 (12)	0.0059 (13)	0.0105 (14)	−0.0012 (10)	0.0053 (11)	0.0011 (11)
N2	0.0050 (12)	0.0055 (13)	0.0041 (13)	0.0011 (10)	0.0012 (11)	0.0009 (11)
C2	0.0049 (14)	0.0069 (15)	0.0064 (16)	0.0018 (12)	0.0022 (13)	0.0008 (12)
C15	0.0079 (15)	0.0060 (15)	0.0073 (16)	−0.0001 (12)	0.0012 (13)	0.0004 (13)
O32	0.0095 (12)	0.0097 (12)	0.0193 (14)	0.0024 (9)	0.0077 (11)	0.0064 (11)
C18	0.0049 (14)	0.0077 (15)	0.0048 (15)	−0.0010 (12)	0.0009 (13)	−0.0009 (12)
C5	0.0059 (14)	0.0083 (16)	0.0075 (16)	0.0024 (12)	0.0032 (13)	0.0023 (13)
C8	0.0088 (15)	0.0027 (14)	0.0076 (16)	−0.0009 (12)	0.0032 (13)	0.0006 (12)
C13	0.0057 (14)	0.0072 (15)	0.0085 (16)	0.0011 (12)	0.0038 (13)	0.0008 (13)
C11	0.0114 (16)	0.0060 (15)	0.0123 (17)	0.0008 (12)	0.0081 (14)	−0.0006 (13)
C3	0.0062 (15)	0.0075 (16)	0.0080 (16)	0.0008 (12)	0.0026 (13)	0.0006 (13)
C14	0.0084 (15)	0.0058 (15)	0.0019 (15)	−0.0008 (12)	0.0007 (12)	0.0000 (12)
C16	0.0081 (15)	0.0093 (16)	0.0063 (16)	0.0029 (12)	0.0026 (13)	−0.0004 (13)
C1	0.0075 (15)	0.0076 (15)	0.0073 (16)	−0.0024 (12)	0.0046 (13)	−0.0016 (13)
C9	0.0081 (15)	0.0063 (16)	0.0074 (16)	0.0002 (12)	0.0011 (13)	0.0006 (13)
C6	0.0047 (14)	0.0062 (15)	0.0058 (16)	0.0001 (12)	0.0009 (12)	0.0007 (12)
C4	0.0090 (15)	0.0077 (16)	0.0062 (16)	0.0011 (12)	0.0027 (13)	0.0005 (13)
C7	0.0057 (14)	0.0098 (16)	0.0049 (15)	0.0006 (12)	0.0002 (13)	0.0002 (13)
C12	0.0103 (15)	0.0030 (14)	0.0079 (16)	−0.0017 (12)	0.0053 (13)	−0.0025 (12)
C17	0.0070 (15)	0.0096 (16)	0.0083 (16)	0.0001 (12)	0.0045 (13)	−0.0015 (13)
C31	0.0095 (16)	0.0115 (17)	0.0147 (18)	−0.0006 (13)	0.0042 (14)	0.0012 (14)
C30	0.0106 (16)	0.0175 (18)	0.0113 (17)	0.0065 (14)	0.0040 (14)	0.0027 (15)
C10	0.0058 (14)	0.0060 (16)	0.0135 (17)	0.0008 (12)	0.0024 (13)	0.0017 (13)

Geometric parameters (Å, º)

Fe1—N4	1.989 (3)	C2—C1	1.515 (4)
Fe1—N6	1.997 (3)	C15—C14	1.387 (4)
Fe1—N2	2.001 (3)	C15—C16	1.385 (5)
Fe1—N1	2.017 (3)	O32—C31	1.427 (4)
Fe1—N3	2.022 (3)	C18—C17	1.384 (4)
Fe1—N5	2.031 (3)	C5—C6	1.382 (5)
N6—C18	1.357 (4)	C5—C4	1.386 (5)
N6—C14	1.355 (4)	C8—C9	1.385 (4)
N4—C8	1.354 (4)	C8—C7	1.503 (4)
N4—C12	1.357 (4)	C13—C14	1.508 (4)
N1—C1	1.479 (4)	C11—C10	1.383 (5)
N5—C13	1.480 (4)	C11—C12	1.389 (5)
N3—C7	1.480 (4)	C3—C4	1.393 (4)
N2—C2	1.355 (4)	C16—C17	1.391 (5)
N2—C6	1.356 (4)	C9—C10	1.382 (5)
C2—C3	1.381 (5)	C31—C30	1.518 (5)
N4—Fe1—N6	166.30 (11)	C6—N2—Fe1	128.4 (2)
N4—Fe1—N2	96.60 (11)	N2—C2—C3	123.0 (3)
N6—Fe1—N2	93.74 (11)	N2—C2—C1	115.6 (3)
N4—Fe1—N1	94.13 (11)	C3—C2—C1	121.5 (3)
N6—Fe1—N1	96.25 (11)	C14—C15—C16	119.6 (3)
N2—Fe1—N1	81.56 (11)	N6—C18—C17	123.0 (3)
N4—Fe1—N3	81.60 (11)	C6—C5—C4	119.3 (3)
N6—Fe1—N3	89.85 (11)	N4—C8—C9	122.2 (3)
N2—Fe1—N3	169.25 (11)	N4—C8—C7	114.2 (3)
N1—Fe1—N3	87.97 (11)	C9—C8—C7	123.6 (3)
N4—Fe1—N5	88.56 (11)	N5—C13—C14	109.0 (3)
N6—Fe1—N5	81.46 (11)	C10—C11—C12	119.2 (3)
N2—Fe1—N5	95.79 (11)	C2—C3—C4	119.5 (3)
N1—Fe1—N5	176.41 (11)	N6—C14—C15	122.7 (3)
N3—Fe1—N5	94.76 (11)	N6—C14—C13	115.3 (3)
C18—N6—C14	117.1 (3)	C15—C14—C13	122.0 (3)
C18—N6—Fe1	127.4 (2)	C15—C16—C17	118.2 (3)
C14—N6—Fe1	115.2 (2)	N1—C1—C2	108.4 (3)
C8—N4—C12	117.6 (3)	C10—C9—C8	119.9 (3)
C8—N4—Fe1	115.0 (2)	N2—C6—C5	123.3 (3)
C12—N4—Fe1	126.1 (2)	C5—C4—C3	118.1 (3)
C1—N1—Fe1	110.2 (2)	N3—C7—C8	107.7 (3)
C13—N5—Fe1	109.64 (19)	N4—C12—C11	122.6 (3)
C7—N3—Fe1	108.5 (2)	C18—C17—C16	119.3 (3)
C2—N2—C6	116.8 (3)	O32—C31—C30	113.0 (3)
C2—N2—Fe1	114.8 (2)	C9—C10—C11	118.5 (3)

(fpic118h) 'tris(2-Picolylamine)-iron(ii) chloride ethanol solvate'

Crystal data

C18H24FeN6·C2H6O·2(Cl)	F(000) = 2080
Mr = 994.50	Dx = 1.392 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
a = 21.6080 (18) Å	Cell parameters from 25 reflections
b = 21.6945 (14) Å	θ = 21.5–26.8°
c = 11.395 (4) Å	µ = 7.36 mm^−1
β = 117.33 (3)°	T = 118 K
V = 4745.4 (17) Å^3	Block, red
Z = 4	0.46 × 0.12 × 0.12 mm

Data collection

CAD4 Enraf Nonius diffractometer	5558 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.062
Graphite monochromator	θmax = 73.8°, θmin = 3.1°
Detector resolution: point detector pixels mm^-1	h = −23→26
θ/2ω scans	k = −27→0
10076 measured reflections	l = −14→0
9586 independent 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)] = 0.085	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.254	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Calculated w = 1/[σ^2(Fo^2) + (0.1507P)^2] where P = (Fo^2 + 2Fc^2)/3
9586 reflections	(Δ/σ)max < 0.001
543 parameters	Δρmax = 1.78 e Å^−3
0 restraints	Δρmin = −1.58 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	0.23626 (5)	0.13797 (4)	0.20150 (9)	0.0173 (2)
Fe1A	0.26474 (5)	−0.12980 (4)	−0.18916 (10)	0.0191 (2)
Cl2	0.31489 (8)	0.07458 (7)	−0.06222 (15)	0.0248 (3)
Cl1	−0.11672 (8)	−0.23200 (7)	−0.41747 (16)	0.0268 (3)
Cl2A	0.17877 (8)	−0.06458 (7)	0.06276 (15)	0.0240 (3)
Cl1A	0.61866 (8)	0.21996 (7)	0.42182 (16)	0.0269 (3)
N4	0.1384 (3)	0.1049 (2)	0.1319 (6)	0.0253 (12)
N1	0.2772 (3)	0.0558 (2)	0.1841 (5)	0.0207 (10)
H1A	0.2427	0.0263	0.1535	0.025*
H1B	0.2941	0.0596	0.1237	0.025*
N5	0.2022 (3)	0.2214 (2)	0.2341 (5)	0.0219 (11)
H5A	0.1777	0.2418	0.1552	0.026*
H5B	0.1729	0.2154	0.2716	0.026*
N2A	0.2224 (3)	−0.0968 (2)	−0.3889 (5)	0.0222 (11)
N2	0.2727 (3)	0.1055 (2)	0.3898 (5)	0.0188 (10)
N6A	0.1790 (3)	−0.1901 (2)	−0.2254 (5)	0.0231 (11)
C12A	0.4073 (4)	−0.0960 (3)	−0.1837 (8)	0.0369 (18)
H12A	0.3837	−0.1031	−0.2763	0.044*
N1A	0.2149 (3)	−0.0456 (2)	−0.1845 (5)	0.0245 (11)
H1AA	0.1977	−0.0493	−0.1245	0.029*
H1AB	0.2474	−0.0145	−0.1561	0.029*
C6	0.2548 (3)	0.1252 (3)	0.4824 (6)	0.0252 (13)
H6	0.2247	0.1598	0.4633	0.030*
C15A	0.1232 (3)	−0.2855 (3)	−0.3228 (7)	0.0272 (14)
H15A	0.1239	−0.3228	−0.3658	0.033*
C5A	0.2117 (3)	−0.0916 (3)	−0.6091 (6)	0.0270 (14)
H5A2	0.2247	−0.1070	−0.6728	0.032*
C17	0.4298 (3)	0.2149 (3)	0.2441 (7)	0.0274 (14)
H17	0.4655	0.2037	0.2213	0.033*
N3A	0.3036 (3)	−0.1335 (3)	0.0218 (6)	0.0343 (14)
H3AA	0.2681	−0.1257	0.0429	0.041*
H3AB	0.3212	−0.1720	0.0526	0.041*
N5A	0.2979 (3)	−0.2165 (2)	−0.2308 (5)	0.0220 (11)
H5AA	0.3251	−0.2098	−0.2724	0.026*
H5AB	0.3246	−0.2369	−0.1529	0.026*
C4A	0.1647 (4)	−0.0442 (3)	−0.6400 (7)	0.0320 (15)
H4A	0.1450	−0.0261	−0.7254	0.038*
C18A	0.1258 (3)	−0.1797 (3)	−0.1958 (7)	0.0270 (14)
H18A	0.1270	−0.1430	−0.1494	0.032*
C16A	0.0688 (4)	−0.2727 (3)	−0.2948 (7)	0.0302 (15)
H16A	0.0308	−0.3006	−0.3206	0.036*
N6	0.3226 (3)	0.1891 (2)	0.2449 (5)	0.0219 (11)
N4A	0.3705 (3)	−0.0969 (2)	−0.1164 (6)	0.0295 (13)
C1	0.3334 (3)	0.0364 (3)	0.3116 (6)	0.0248 (13)
H1A2	0.3779	0.0554	0.3257	0.030*
H1B2	0.3387	−0.0090	0.3134	0.030*
C2	0.3153 (3)	0.0565 (3)	0.4192 (6)	0.0220 (13)
C13A	0.2375 (3)	−0.2553 (3)	−0.3160 (7)	0.0257 (14)
H13A	0.2506	−0.2994	−0.2999	0.031*
H13B	0.2235	−0.2463	−0.4100	0.031*
C14A	0.1770 (3)	−0.2429 (3)	−0.2873 (6)	0.0214 (13)
C8	0.1042 (3)	0.0970 (3)	0.0007 (7)	0.0259 (14)
C13	0.2633 (3)	0.2592 (3)	0.3242 (6)	0.0243 (13)
H13Z	0.2748	0.2503	0.4172	0.029*
H13X	0.2517	0.3036	0.3077	0.029*
C3A	0.1462 (4)	−0.0228 (3)	−0.5457 (7)	0.0283 (14)
H3A	0.1137	0.0099	−0.5652	0.034*
C15	0.3792 (3)	0.2856 (3)	0.3356 (7)	0.0262 (14)
H15	0.3795	0.3235	0.3776	0.031*
C10	−0.0027 (4)	0.0756 (3)	0.0065 (9)	0.0383 (18)
H10	−0.0507	0.0652	−0.0364	0.046*
C30A	0.0031 (5)	−0.1644 (5)	−0.5707 (9)	0.065 (3)
H30A	−0.0033	−0.2024	−0.5311	0.098*
H30B	0.0529	−0.1574	−0.5408	0.098*
H30C	−0.0209	−0.1681	−0.6672	0.098*
C2A	0.1762 (3)	−0.0505 (3)	−0.4224 (6)	0.0223 (12)
C9A	0.4745 (4)	−0.0756 (3)	0.0802 (9)	0.0378 (17)
H9A	0.4973	−0.0687	0.1729	0.045*
C16	0.4336 (3)	0.2706 (3)	0.3078 (7)	0.0284 (15)
H16	0.4722	0.2975	0.3316	0.034*
C4	0.3230 (4)	0.0466 (3)	0.6333 (6)	0.0285 (14)
H4	0.3406	0.0265	0.7165	0.034*
C17A	0.0703 (3)	−0.2189 (3)	−0.2285 (7)	0.0289 (15)
H17A	0.0341	−0.2092	−0.2063	0.035*
C14	0.3245 (3)	0.2447 (3)	0.3014 (6)	0.0218 (13)
C1A	0.1580 (4)	−0.0291 (3)	−0.3136 (6)	0.0269 (14)
H1AZ	0.1509	0.0161	−0.3190	0.032*
H1AX	0.1143	−0.0491	−0.3255	0.032*
C7A	0.3581 (4)	−0.0874 (4)	0.0824 (7)	0.0338 (16)
H7AA	0.3866	−0.0970	0.1773	0.041*
H7AB	0.3369	−0.0462	0.0754	0.041*
C10A	0.5121 (4)	−0.0749 (3)	0.0093 (9)	0.0394 (19)
H10A	0.5609	−0.0673	0.0530	0.047*
O32A	−0.0954 (4)	−0.1151 (3)	−0.5604 (9)	0.086 (3)
H32A	−0.1023	−0.1463	−0.5241	0.128*
C31	0.5261 (4)	0.1025 (4)	0.5289 (9)	0.0438 (19)
H31A	0.5156	0.0639	0.5625	0.053*
H31B	0.5009	0.1010	0.4312	0.053*
C18	0.3743 (3)	0.1764 (3)	0.2145 (7)	0.0268 (14)
H18	0.3723	0.1389	0.1701	0.032*
C11A	0.4785 (4)	−0.0852 (3)	−0.1243 (10)	0.045 (2)
H11A	0.5034	−0.0849	−0.1748	0.054*
C7	0.1478 (4)	0.1066 (3)	−0.0678 (7)	0.0307 (15)
H7A	0.1690	0.0670	−0.0736	0.037*
H7B	0.1183	0.1217	−0.1587	0.037*
C6A	0.2397 (3)	−0.1164 (3)	−0.4842 (6)	0.0252 (13)
H6A	0.2727	−0.1488	−0.4630	0.030*
C8A	0.4037 (4)	−0.0864 (3)	0.0153 (7)	0.0278 (14)
N3	0.2030 (3)	0.1520 (3)	0.0060 (6)	0.0302 (13)
H3A1	0.1858	0.1914	−0.0167	0.036*
H3B	0.2394	0.1472	−0.0139	0.036*
C9	0.0339 (4)	0.0822 (3)	−0.0641 (8)	0.0331 (16)
H9	0.0112	0.0767	−0.1572	0.040*
C11	0.0326 (4)	0.0846 (3)	0.1444 (8)	0.0371 (17)
H11	0.0089	0.0813	0.1965	0.044*
C3	0.3409 (3)	0.0267 (3)	0.5381 (6)	0.0263 (14)
H3	0.3711	−0.0077	0.5550	0.032*
O32	0.5982 (3)	0.1045 (3)	0.5686 (6)	0.0465 (14)
H32	0.6076	0.1366	0.5388	0.070*
C5	0.2788 (3)	0.0966 (3)	0.6046 (6)	0.0266 (14)
H5	0.2649	0.1112	0.6676	0.032*
C30	0.4990 (5)	0.1559 (4)	0.5755 (9)	0.051 (2)
H30Z	0.5278	0.1614	0.6708	0.077*
H30X	0.4507	0.1477	0.5569	0.077*
H30V	0.5007	0.1934	0.5291	0.077*
C12	0.1022 (4)	0.0984 (3)	0.2010 (8)	0.0316 (16)
H12	0.1263	0.1036	0.2941	0.038*
C31A	−0.0261 (5)	−0.1120 (4)	−0.5302 (11)	0.056 (2)
H31Z	0.0012	−0.1072	−0.4334	0.067*
H31X	−0.0191	−0.0742	−0.5713	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0092 (5)	0.0184 (4)	0.0256 (5)	−0.0003 (3)	0.0093 (4)	0.0004 (3)
Fe1A	0.0121 (5)	0.0180 (5)	0.0291 (5)	0.0004 (4)	0.0112 (4)	0.0016 (4)
Cl2	0.0225 (8)	0.0277 (7)	0.0289 (8)	−0.0052 (6)	0.0158 (6)	−0.0017 (6)
Cl1	0.0150 (7)	0.0324 (8)	0.0350 (8)	−0.0024 (6)	0.0132 (6)	−0.0052 (6)
Cl2A	0.0187 (7)	0.0287 (7)	0.0287 (8)	−0.0067 (6)	0.0144 (6)	−0.0033 (6)
Cl1A	0.0179 (7)	0.0293 (8)	0.0362 (8)	−0.0039 (6)	0.0145 (7)	−0.0059 (6)
N4	0.022 (3)	0.021 (3)	0.038 (3)	0.002 (2)	0.018 (3)	0.006 (2)
N1	0.015 (2)	0.024 (3)	0.024 (3)	−0.004 (2)	0.009 (2)	0.001 (2)
N5	0.015 (3)	0.020 (2)	0.034 (3)	0.0025 (19)	0.014 (2)	0.002 (2)
N2A	0.019 (3)	0.027 (3)	0.024 (3)	−0.003 (2)	0.013 (2)	0.000 (2)
N2	0.014 (2)	0.025 (3)	0.017 (2)	−0.0023 (19)	0.007 (2)	−0.0020 (18)
N6A	0.013 (3)	0.025 (3)	0.030 (3)	0.000 (2)	0.009 (2)	−0.004 (2)
C12A	0.048 (5)	0.028 (4)	0.059 (5)	−0.008 (3)	0.045 (4)	−0.006 (3)
N1A	0.022 (3)	0.025 (3)	0.027 (3)	−0.005 (2)	0.012 (2)	−0.002 (2)
C6	0.020 (3)	0.028 (3)	0.031 (3)	0.002 (2)	0.015 (3)	0.003 (3)
C15A	0.017 (3)	0.027 (3)	0.036 (4)	0.001 (3)	0.011 (3)	−0.002 (3)
C5A	0.022 (3)	0.035 (4)	0.021 (3)	−0.002 (3)	0.008 (3)	−0.001 (3)
C17	0.016 (3)	0.034 (4)	0.033 (4)	0.006 (3)	0.012 (3)	−0.004 (3)
N3A	0.022 (3)	0.037 (3)	0.053 (4)	0.011 (2)	0.025 (3)	0.018 (3)
N5A	0.018 (3)	0.026 (3)	0.025 (3)	0.001 (2)	0.013 (2)	0.002 (2)
C4A	0.035 (4)	0.036 (4)	0.024 (3)	0.000 (3)	0.014 (3)	0.006 (3)
C18A	0.012 (3)	0.037 (4)	0.033 (4)	0.002 (3)	0.011 (3)	−0.005 (3)
C16A	0.019 (3)	0.031 (4)	0.039 (4)	−0.004 (3)	0.012 (3)	0.002 (3)
N6	0.009 (2)	0.028 (3)	0.026 (3)	0.000 (2)	0.005 (2)	−0.003 (2)
N4A	0.031 (3)	0.017 (3)	0.052 (4)	0.003 (2)	0.030 (3)	0.002 (2)
C1	0.019 (3)	0.024 (3)	0.031 (3)	0.003 (2)	0.011 (3)	0.001 (2)
C2	0.017 (3)	0.025 (3)	0.026 (3)	−0.005 (2)	0.012 (3)	−0.003 (2)
C13A	0.026 (4)	0.024 (3)	0.032 (4)	−0.006 (3)	0.017 (3)	−0.003 (3)
C14A	0.019 (3)	0.022 (3)	0.024 (3)	0.000 (2)	0.010 (3)	−0.004 (2)
C8	0.015 (3)	0.019 (3)	0.041 (4)	0.006 (2)	0.010 (3)	0.009 (2)
C13	0.019 (3)	0.024 (3)	0.030 (3)	0.004 (2)	0.012 (3)	0.000 (2)
C3A	0.024 (3)	0.031 (3)	0.027 (3)	0.006 (3)	0.009 (3)	0.004 (3)
C15	0.021 (3)	0.024 (3)	0.032 (4)	−0.003 (3)	0.011 (3)	−0.001 (2)
C10	0.021 (3)	0.026 (4)	0.066 (5)	−0.004 (3)	0.018 (4)	−0.001 (3)
C30A	0.058 (6)	0.096 (8)	0.045 (5)	0.043 (6)	0.026 (5)	0.018 (5)
C2A	0.016 (3)	0.026 (3)	0.026 (3)	0.000 (2)	0.010 (3)	−0.002 (2)
C9A	0.026 (4)	0.031 (4)	0.056 (5)	0.007 (3)	0.018 (4)	0.006 (3)
C16	0.017 (3)	0.027 (3)	0.038 (4)	−0.008 (3)	0.010 (3)	−0.003 (3)
C4	0.030 (4)	0.034 (4)	0.018 (3)	−0.004 (3)	0.009 (3)	0.003 (2)
C17A	0.018 (3)	0.034 (4)	0.039 (4)	0.000 (3)	0.016 (3)	−0.004 (3)
C14	0.020 (3)	0.020 (3)	0.026 (3)	0.002 (2)	0.010 (3)	−0.002 (2)
C1A	0.026 (4)	0.031 (3)	0.027 (3)	0.011 (3)	0.015 (3)	0.005 (3)
C7A	0.020 (3)	0.053 (5)	0.026 (3)	0.011 (3)	0.008 (3)	0.009 (3)
C10A	0.029 (4)	0.025 (4)	0.073 (6)	0.001 (3)	0.031 (4)	0.004 (3)
O32A	0.073 (6)	0.055 (5)	0.151 (8)	0.015 (4)	0.070 (6)	0.026 (5)
C31	0.033 (4)	0.049 (5)	0.046 (5)	0.003 (4)	0.015 (4)	0.002 (4)
C18	0.016 (3)	0.032 (3)	0.028 (3)	0.001 (3)	0.006 (3)	−0.004 (3)
C11A	0.051 (5)	0.024 (4)	0.086 (7)	−0.007 (3)	0.054 (5)	−0.008 (4)
C7	0.024 (4)	0.041 (4)	0.024 (3)	0.004 (3)	0.008 (3)	0.003 (3)
C6A	0.018 (3)	0.030 (3)	0.028 (3)	−0.001 (3)	0.012 (3)	0.000 (3)
C8A	0.031 (4)	0.021 (3)	0.035 (4)	0.011 (3)	0.018 (3)	0.011 (2)
N3	0.025 (3)	0.034 (3)	0.040 (3)	0.004 (2)	0.022 (3)	0.012 (2)
C9	0.020 (3)	0.032 (4)	0.045 (4)	−0.001 (3)	0.013 (3)	0.004 (3)
C11	0.031 (4)	0.025 (3)	0.063 (5)	−0.001 (3)	0.028 (4)	0.000 (3)
C3	0.020 (3)	0.029 (3)	0.027 (3)	0.001 (3)	0.008 (3)	0.002 (3)
O32	0.035 (3)	0.044 (3)	0.066 (4)	0.013 (3)	0.027 (3)	0.016 (3)
C5	0.028 (4)	0.030 (3)	0.022 (3)	−0.003 (3)	0.012 (3)	−0.001 (2)
C30	0.040 (5)	0.073 (6)	0.045 (5)	0.024 (4)	0.022 (4)	0.014 (4)
C12	0.031 (4)	0.020 (3)	0.052 (5)	−0.008 (3)	0.027 (4)	−0.003 (3)
C31A	0.040 (5)	0.052 (5)	0.079 (7)	0.000 (4)	0.029 (5)	0.013 (5)

Geometric parameters (Å, º)

Fe1—N4	2.018 (5)	N3A—C7A	1.455 (9)
Fe1—N3	2.025 (6)	N5A—C13A	1.481 (8)
Fe1—N6	2.027 (5)	C4A—C3A	1.387 (9)
Fe1—N1	2.040 (5)	C18A—C17A	1.375 (9)
Fe1—N2	2.042 (5)	C16A—C17A	1.383 (9)
Fe1—N5	2.052 (5)	N6—C18	1.340 (8)
Fe1A—N1A	2.132 (5)	N6—C14	1.358 (7)
Fe1A—N5A	2.142 (5)	N4A—C8A	1.352 (9)
Fe1A—N6A	2.147 (5)	C1—C2	1.512 (8)
Fe1A—N2A	2.149 (5)	C2—C3	1.368 (9)
Fe1A—N3A	2.153 (6)	C13A—C14A	1.510 (8)
Fe1A—N4A	2.162 (6)	C8—C9	1.387 (9)
N4—C8	1.341 (9)	C8—C7	1.488 (9)
N4—C12	1.348 (8)	C13—C14	1.496 (8)
N1—C1	1.464 (8)	C3A—C2A	1.385 (9)
N5—C13	1.491 (8)	C15—C14	1.382 (9)
N2A—C2A	1.342 (8)	C15—C16	1.389 (9)
N2A—C6A	1.369 (8)	C10—C9	1.370 (11)
N2—C2	1.344 (8)	C10—C11	1.410 (12)
N2—C6	1.350 (8)	C30A—C31A	1.473 (13)
N6A—C14A	1.336 (7)	C2A—C1A	1.535 (8)
N6A—C18A	1.356 (8)	C9A—C8A	1.380 (10)
C12A—N4A	1.336 (8)	C9A—C10A	1.384 (11)
C12A—C11A	1.388 (11)	C4—C3	1.379 (9)
N1A—C1A	1.465 (8)	C4—C5	1.381 (9)
C6—C5	1.390 (9)	C7A—C8A	1.498 (9)
C15A—C16A	1.382 (9)	C10A—C11A	1.371 (12)
C15A—C14A	1.392 (9)	O32A—C31A	1.375 (10)
C5A—C4A	1.375 (10)	C31—O32	1.409 (9)
C5A—C6A	1.374 (9)	C31—C30	1.501 (11)
C17—C18	1.372 (9)	C7—N3	1.476 (9)
C17—C16	1.392 (9)	C11—C12	1.369 (9)
N4—Fe1—N3	80.9 (2)	C5A—C4A—C3A	119.6 (6)
N4—Fe1—N6	166.2 (2)	N6A—C18A—C17A	124.3 (6)
N3—Fe1—N6	90.5 (2)	C15A—C16A—C17A	119.1 (6)
N4—Fe1—N1	94.2 (2)	C18—N6—C14	117.2 (5)
N3—Fe1—N1	88.6 (2)	C18—N6—Fe1	127.4 (4)
N6—Fe1—N1	96.4 (2)	C14—N6—Fe1	115.2 (4)
N4—Fe1—N2	96.9 (2)	C12A—N4A—C8A	118.8 (7)
N3—Fe1—N2	168.1 (2)	C12A—N4A—Fe1A	126.0 (5)
N6—Fe1—N2	93.7 (2)	C8A—N4A—Fe1A	114.2 (4)
N1—Fe1—N2	79.9 (2)	N1—C1—C2	108.4 (5)
N4—Fe1—N5	89.2 (2)	N2—C2—C3	122.7 (6)
N3—Fe1—N5	95.2 (2)	N2—C2—C1	115.4 (5)
N6—Fe1—N5	80.8 (2)	C3—C2—C1	121.9 (6)
N1—Fe1—N5	175.2 (2)	N5A—C13A—C14A	110.3 (5)
N2—Fe1—N5	96.4 (2)	N6A—C14A—C15A	122.9 (6)
N1A—Fe1A—N5A	168.9 (2)	N6A—C14A—C13A	116.6 (5)
N1A—Fe1A—N6A	97.2 (2)	C15A—C14A—C13A	120.6 (5)
N5A—Fe1A—N6A	76.70 (19)	N4—C8—C9	122.1 (7)
N1A—Fe1A—N2A	76.5 (2)	N4—C8—C7	114.1 (6)
N5A—Fe1A—N2A	94.7 (2)	C9—C8—C7	123.8 (7)
N6A—Fe1A—N2A	95.1 (2)	N5—C13—C14	109.8 (5)
N1A—Fe1A—N3A	86.9 (2)	C2A—C3A—C4A	118.2 (6)
N5A—Fe1A—N3A	102.5 (2)	C14—C15—C16	119.2 (6)
N6A—Fe1A—N3A	93.0 (2)	C9—C10—C11	118.5 (7)
N2A—Fe1A—N3A	162.3 (2)	N2A—C2A—C3A	123.7 (6)
N1A—Fe1A—N4A	99.5 (2)	N2A—C2A—C1A	115.4 (5)
N5A—Fe1A—N4A	88.4 (2)	C3A—C2A—C1A	120.9 (6)
N6A—Fe1A—N4A	160.2 (2)	C8A—C9A—C10A	119.6 (8)
N2A—Fe1A—N4A	99.0 (2)	C15—C16—C17	118.0 (6)
N3A—Fe1A—N4A	77.4 (2)	C3—C4—C5	118.2 (6)
C8—N4—C12	117.8 (6)	C18A—C17A—C16A	118.0 (6)
C8—N4—Fe1	115.2 (4)	N6—C14—C15	122.7 (6)
C12—N4—Fe1	126.3 (5)	N6—C14—C13	115.7 (5)
C1—N1—Fe1	110.7 (4)	C15—C14—C13	121.7 (6)
C13—N5—Fe1	109.4 (4)	N1A—C1A—C2A	109.2 (5)
C2A—N2A—C6A	116.4 (6)	N3A—C7A—C8A	110.2 (6)
C2A—N2A—Fe1A	116.8 (4)	C11A—C10A—C9A	119.5 (7)
C6A—N2A—Fe1A	126.7 (4)	O32—C31—C30	114.6 (7)
C2—N2—C6	117.8 (5)	N6—C18—C17	123.4 (6)
C2—N2—Fe1	115.1 (4)	C10A—C11A—C12A	118.2 (7)
C6—N2—Fe1	126.9 (4)	N3—C7—C8	109.6 (6)
C14A—N6A—C18A	116.6 (5)	N2A—C6A—C5A	123.3 (6)
C14A—N6A—Fe1A	116.0 (4)	N4A—C8A—C9A	121.1 (7)
C18A—N6A—Fe1A	127.3 (4)	N4A—C8A—C7A	115.2 (6)
N4A—C12A—C11A	122.9 (8)	C9A—C8A—C7A	123.7 (7)
C1A—N1A—Fe1A	112.7 (4)	C7—N3—Fe1	108.2 (4)
N2—C6—C5	122.1 (6)	C10—C9—C8	119.8 (7)
C16A—C15A—C14A	119.1 (6)	C12—C11—C10	118.1 (7)
C4A—C5A—C6A	118.7 (6)	C2—C3—C4	119.9 (6)
C18—C17—C16	119.4 (6)	C4—C5—C6	119.2 (6)
C7A—N3A—Fe1A	108.7 (4)	N4—C12—C11	123.6 (7)
C13A—N5A—Fe1A	111.1 (4)	O32A—C31A—C30A	117.3 (9)

(fpic11hs) 'tris(2-Picolylamine)-iron(ii) chloride ethanol solvate'

Crystal data

C18H24FeN6·C2H6O·2(Cl)	F(000) = 1040
Mr = 497.25	Dx = 1.388 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.949 (3) Å	Cell parameters from 60 reflections
b = 21.825 (5) Å	θ = 30–40°
c = 11.370 (2) Å	µ = 0.88 mm^−1
β = 118.85 (2)°	T = 10 K
V = 2379.9 (10) Å^3	Block, yellow
Z = 4	0.4 × 0.3 × 0.2 mm

Data collection

CCD Oxford Diffraction diffractometer	5279 independent reflections
Radiation source: fine-focus rotating anode	4081 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.142
ϕ–scans	θmax = 27.8°, θmin = 3.8°
Absorption correction: multi-scan ?	h = −14→13
Tmin = 0.735, Tmax = 0.838	k = −27→27
19183 measured reflections	l = −14→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.139	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.308	Calculated w = 1/[σ^2(Fo^2) + (0.074P)^2 + 44.0563P] where P = (Fo^2 + 2Fc^2)/3
S = 1.18	(Δ/σ)max < 0.001
5279 reflections	Δρmax = 0.95 e Å^−3
274 parameters	Δρmin = −1.42 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0051 (17)

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	0.02784 (12)	0.13510 (5)	0.80841 (13)	0.0144 (4)
Cl2	0.2583 (2)	0.27291 (9)	1.0835 (2)	0.0176 (5)
Cl1	−0.1442 (2)	0.06714 (9)	1.0540 (2)	0.0165 (5)
N6	−0.1496 (7)	0.1952 (3)	0.7665 (7)	0.0169 (15)
N4	0.2453 (7)	0.1034 (3)	0.8899 (8)	0.0177 (15)
N1	−0.0713 (7)	0.0489 (3)	0.8111 (7)	0.0149 (14)
H1A	−0.1142	0.0527	0.8678	0.018*
H1B	0.0016	0.0204	0.8348	0.018*
N5	0.0889 (7)	0.2236 (3)	0.7640 (7)	0.0146 (14)
H5A	0.1402	0.2383	0.8528	0.018*
H5B	0.1681	0.2260	0.7387	0.018*
N3	0.1088 (7)	0.1378 (3)	1.0259 (8)	0.0177 (15)
H3A	0.0462	0.1329	1.0419	0.021*
H3B	0.1307	0.1780	1.0332	0.021*
N2	−0.0567 (7)	0.0996 (3)	0.6005 (7)	0.0146 (14)
C2	−0.1458 (8)	0.0510 (4)	0.5700 (9)	0.0136 (16)
C15	−0.2610 (8)	0.2909 (4)	0.6717 (9)	0.0156 (17)
H15	−0.2602	0.3286	0.6303	0.019*
O32	0.2989 (6)	0.3873 (3)	0.9360 (7)	0.0213 (14)
H32	0.279 (3)	0.354 (5)	0.965 (4)	0.032*
C18	−0.2517 (8)	0.1839 (4)	0.7987 (9)	0.0158 (17)
H18	−0.2470	0.1471	0.8454	0.019*
C5	−0.0673 (9)	0.0891 (4)	0.3862 (9)	0.0160 (17)
H5	−0.0402	0.1040	0.3237	0.019*
C8	0.3077 (8)	0.0897 (4)	1.0211 (8)	0.0137 (16)
C13	−0.0359 (8)	0.2606 (3)	0.6748 (8)	0.0104 (15)
H13A	−0.0665	0.2502	0.5799	0.012*
H13B	−0.0117	0.3047	0.6877	0.012*
C11	0.4613 (8)	0.0892 (4)	0.8879 (9)	0.0158 (17)
H11	0.5121	0.0895	0.8397	0.019*
C3	−0.1947 (8)	0.0197 (4)	0.4495 (9)	0.0174 (17)
H3	−0.2544	−0.0147	0.4312	0.021*
C14	−0.1546 (9)	0.2482 (4)	0.7060 (9)	0.0189 (18)
C16	−0.3675 (9)	0.2773 (4)	0.6992 (10)	0.0194 (18)
H16	−0.4438	0.3047	0.6722	0.023*
C1	−0.1830 (9)	0.0329 (4)	0.6757 (9)	0.0185 (18)
H1AA	−0.2702	0.0539	0.6586	0.022*
H1BB	−0.2000	−0.0118	0.6707	0.022*
C9	0.4487 (9)	0.0740 (4)	1.0904 (9)	0.0191 (18)
H9	0.4909	0.0633	1.1828	0.023*
C6	−0.0188 (8)	0.1172 (4)	0.5105 (8)	0.0134 (16)
H6	0.0444	0.1506	0.5323	0.016*
C4	−0.1557 (9)	0.0391 (4)	0.3544 (10)	0.0200 (18)
H4	−0.1888	0.0185	0.2709	0.024*
C7	0.2164 (8)	0.0899 (4)	1.0862 (9)	0.0165 (17)
H7A	0.1713	0.0494	1.0743	0.020*
H7B	0.2741	0.0976	1.1837	0.020*
C12	0.3191 (9)	0.1040 (4)	0.8237 (9)	0.0177 (17)
H12	0.2738	0.1147	0.7313	0.021*
C17	−0.3632 (9)	0.2236 (4)	0.7664 (10)	0.0206 (19)
H17	−0.4336	0.2142	0.7896	0.025*
C31	0.4464 (9)	0.3895 (4)	0.9810 (9)	0.0212 (19)
H31A	0.4975	0.3902	1.0804	0.025*
H31B	0.4682	0.4280	0.9488	0.025*
C30	0.4973 (10)	0.3359 (5)	0.9324 (11)	0.027 (2)
H30A	0.4939	0.2985	0.9785	0.041*
H30B	0.5934	0.3435	0.9518	0.041*
H30C	0.4375	0.3310	0.8354	0.041*
C10	0.5270 (8)	0.0741 (4)	1.0245 (9)	0.0188 (18)
H10	0.6233	0.0641	1.0710	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0112 (6)	0.0101 (6)	0.0201 (7)	0.0007 (4)	0.0062 (5)	0.0010 (5)
Cl2	0.0150 (9)	0.0145 (10)	0.0222 (11)	−0.0013 (7)	0.0081 (8)	−0.0011 (8)
Cl1	0.0144 (9)	0.0137 (9)	0.0213 (11)	−0.0002 (7)	0.0085 (8)	0.0004 (8)
N6	0.012 (3)	0.013 (3)	0.023 (4)	−0.004 (3)	0.006 (3)	−0.002 (3)
N4	0.015 (3)	0.009 (3)	0.024 (4)	0.001 (3)	0.005 (3)	−0.002 (3)
N1	0.008 (3)	0.011 (3)	0.023 (4)	0.003 (3)	0.005 (3)	0.002 (3)
N5	0.010 (3)	0.012 (3)	0.019 (4)	0.000 (3)	0.005 (3)	0.003 (3)
N3	0.012 (3)	0.010 (3)	0.030 (4)	−0.001 (3)	0.010 (3)	−0.002 (3)
N2	0.013 (3)	0.010 (3)	0.022 (4)	0.001 (3)	0.010 (3)	0.001 (3)
C2	0.011 (4)	0.006 (3)	0.019 (4)	0.002 (3)	0.003 (3)	−0.001 (3)
C15	0.012 (4)	0.009 (4)	0.022 (4)	0.002 (3)	0.005 (3)	0.003 (3)
O32	0.013 (3)	0.014 (3)	0.037 (4)	0.005 (2)	0.012 (3)	0.007 (3)
C18	0.017 (4)	0.010 (4)	0.018 (4)	−0.001 (3)	0.006 (3)	−0.002 (3)
C5	0.016 (4)	0.015 (4)	0.018 (4)	0.001 (3)	0.010 (3)	0.002 (3)
C8	0.007 (3)	0.014 (4)	0.017 (4)	0.002 (3)	0.004 (3)	−0.002 (3)
C13	0.013 (4)	0.006 (3)	0.012 (4)	0.003 (3)	0.006 (3)	0.003 (3)
C11	0.010 (4)	0.014 (4)	0.023 (4)	0.004 (3)	0.007 (3)	0.006 (3)
C3	0.012 (4)	0.018 (4)	0.019 (4)	0.006 (3)	0.005 (3)	0.003 (3)
C14	0.019 (4)	0.015 (4)	0.021 (5)	0.002 (3)	0.008 (4)	0.004 (3)
C16	0.013 (4)	0.011 (4)	0.034 (5)	−0.001 (3)	0.010 (4)	0.003 (4)
C1	0.017 (4)	0.013 (4)	0.024 (5)	−0.004 (3)	0.008 (4)	0.002 (3)
C9	0.019 (4)	0.008 (4)	0.025 (5)	0.000 (3)	0.007 (4)	0.002 (3)
C6	0.011 (4)	0.014 (4)	0.016 (4)	0.003 (3)	0.007 (3)	0.002 (3)
C4	0.018 (4)	0.014 (4)	0.026 (5)	0.001 (3)	0.009 (4)	0.001 (4)
C7	0.012 (4)	0.011 (4)	0.017 (4)	0.005 (3)	0.000 (3)	0.005 (3)
C12	0.019 (4)	0.014 (4)	0.022 (5)	0.001 (3)	0.012 (4)	0.000 (3)
C17	0.024 (4)	0.014 (4)	0.032 (5)	0.003 (3)	0.019 (4)	−0.001 (4)
C31	0.011 (4)	0.026 (5)	0.023 (5)	0.001 (3)	0.005 (4)	0.008 (4)
C30	0.016 (4)	0.025 (5)	0.037 (6)	0.006 (4)	0.009 (4)	0.003 (4)
C10	0.011 (4)	0.018 (4)	0.025 (5)	−0.003 (3)	0.007 (4)	−0.005 (4)

Geometric parameters (Å, º)

Fe1—N1	2.181 (7)	C2—C1	1.496 (12)
Fe1—N5	2.182 (7)	C15—C16	1.376 (12)
Fe1—N3	2.189 (8)	C15—C14	1.392 (11)
Fe1—N6	2.197 (7)	O32—C31	1.440 (10)
Fe1—N4	2.208 (7)	C18—C17	1.394 (12)
Fe1—N2	2.221 (7)	C5—C4	1.386 (12)
N6—C14	1.334 (11)	C5—C6	1.390 (12)
N6—C18	1.356 (11)	C8—C9	1.395 (11)
N4—C8	1.342 (11)	C8—C7	1.503 (11)
N4—C12	1.344 (11)	C13—C14	1.528 (11)
N1—C1	1.473 (11)	C11—C10	1.401 (13)
N5—C13	1.487 (10)	C11—C12	1.401 (11)
N3—C7	1.474 (10)	C3—C4	1.406 (12)
N2—C6	1.333 (10)	C16—C17	1.389 (12)
N2—C2	1.369 (10)	C9—C10	1.384 (12)
C2—C3	1.386 (12)	C31—C30	1.510 (13)
N1—Fe1—N5	167.9 (3)	C2—N2—Fe1	114.8 (5)
N1—Fe1—N3	86.6 (3)	N2—C2—C3	121.3 (8)
N5—Fe1—N3	103.6 (3)	N2—C2—C1	116.0 (7)
N1—Fe1—N6	97.1 (3)	C3—C2—C1	122.6 (7)
N5—Fe1—N6	76.0 (3)	C16—C15—C14	118.6 (8)
N3—Fe1—N6	93.6 (3)	N6—C18—C17	123.1 (8)
N1—Fe1—N4	99.6 (3)	C4—C5—C6	119.4 (8)
N5—Fe1—N4	89.2 (3)	N4—C8—C9	120.9 (8)
N3—Fe1—N4	76.6 (3)	N4—C8—C7	116.4 (7)
N6—Fe1—N4	159.9 (3)	C9—C8—C7	122.7 (8)
N1—Fe1—N2	76.1 (3)	N5—C13—C14	110.5 (6)
N5—Fe1—N2	94.5 (3)	C10—C11—C12	118.6 (8)
N3—Fe1—N2	161.1 (3)	C2—C3—C4	119.8 (8)
N6—Fe1—N2	96.1 (3)	N6—C14—C15	123.1 (8)
N4—Fe1—N2	98.5 (3)	N6—C14—C13	116.5 (7)
C14—N6—C18	117.6 (7)	C15—C14—C13	120.5 (7)
C14—N6—Fe1	116.2 (6)	C15—C16—C17	119.9 (8)
C18—N6—Fe1	126.2 (6)	N1—C1—C2	111.5 (7)
C8—N4—C12	120.3 (7)	C10—C9—C8	120.0 (8)
C8—N4—Fe1	113.8 (5)	N2—C6—C5	123.0 (8)
C12—N4—Fe1	125.5 (6)	C5—C4—C3	117.9 (9)
C1—N1—Fe1	110.9 (5)	N3—C7—C8	110.2 (7)
C13—N5—Fe1	110.8 (5)	N4—C12—C11	121.6 (8)
C7—N3—Fe1	107.7 (5)	C16—C17—C18	117.6 (8)
C6—N2—C2	118.5 (7)	O32—C31—C30	113.1 (8)
C6—N2—Fe1	126.3 (6)	C9—C10—C11	118.7 (8)