On the precision and accuracy of structural analysis of light-induced metastable states

Bragg diffraction data were collected on single crystals of the spin-crossover complex [Fe(phen)₂(NCS)₂] in its low-spin and light-induced metastable high-spin states. Experimental variables included the temperature (32 and 15 K), the X-ray source (sealed tube and synchrotron), and the time interval between laser light excitation of the sample (λ = 647 nm). From a comparison of the structural parameters refined, it is shown that photo-crystallographic measurements suffer significantly and systematically from bias if the probed sample contains residual ground-state species, resulting from an incomplete photo-conversion or a significant metastable- to ground-state relaxation. It follows that a 4% population of species in a different spin state affects the Fe—N bond lengths by more than three standard deviations, and the FeN₆ polyhedron volume by as much as seven standard deviations, while the mean atomic position misfit exceeds 0.005 Å.

Computing details

For all compounds, data collection: CRYSALIS Oxford Diffraction (2004); cell refinement: CRYSALIS Oxford Diffraction (2004); data reduction: CRYSALIS Oxford Diffraction (2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997)' for hs_32k; SHELXL97 (Sheldrick, 1997) for hs_15k, ls_15k.

Figures

(hs_32k)

Crystal data

C26H16FeN6S2	F(000) = 1088
Mr = 532.42	Dx = 1.571 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 18028 reflections
a = 13.1928 (4) Å	θ = 3.5–34.8°
b = 9.9503 (3) Å	µ = 0.89 mm^−1
c = 17.1498 (8) Å	T = 32 K
V = 2251.29 (14) Å^3	Block, purple
Z = 4	0.15 × 0.10 × 0.05 mm

Data collection

Oxford Xcalibur CCD diffractometer	4045 independent reflections
Radiation source: fine-focus sealed tube	2423 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
ω scans	θmax = 34.8°, θmin = 3.5°
Absorption correction: gaussian Absorption correction were performed using CRYSALIS Oxford Diffraction (2004)	h = 0→20
Tmin = 0.90, Tmax = 0.95	k = 0→15
18028 measured reflections	l = 0→22

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: inferred from neighbouring sites
wR(F^2) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 0.91	w = 1/[σ^2(Fo^2) + (0.0644P)^2] where P = (Fo^2 + 2Fc^2)/3
4045 reflections	(Δ/σ)max < 0.001
191 parameters	Δρmax = 1.14 e Å^−3
0 restraints	Δρmin = −0.41 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	0.0000	0.17477 (3)	0.2500	0.01199 (10)
N20	0.04161 (13)	0.31625 (15)	0.33376 (10)	0.0175 (4)
C21	0.08609 (14)	0.38685 (18)	0.37576 (12)	0.0149 (4)
S22	0.14811 (4)	0.48490 (4)	0.43526 (3)	0.01700 (12)
N1	−0.00196 (12)	0.01594 (14)	0.16020 (10)	0.0139 (3)
N2	0.16106 (11)	0.13292 (15)	0.22730 (10)	0.0126 (3)
C1	0.09108 (13)	−0.03007 (17)	0.13894 (11)	0.0128 (4)
C2	0.17808 (14)	0.03191 (17)	0.17541 (11)	0.0131 (4)
C3	−0.08241 (14)	−0.03712 (18)	0.12497 (13)	0.0166 (4)
C4	−0.07546 (15)	−0.14000 (19)	0.06945 (13)	0.0193 (4)
C5	0.01788 (15)	−0.19010 (19)	0.04988 (13)	0.0179 (4)
C6	0.10573 (15)	−0.13383 (18)	0.08458 (12)	0.0156 (4)
C7	0.20599 (14)	−0.17839 (18)	0.06693 (12)	0.0154 (4)
C8	0.28803 (15)	−0.12095 (19)	0.10118 (12)	0.0158 (4)
C9	0.27634 (14)	−0.01291 (17)	0.15613 (12)	0.0140 (4)
C10	0.35881 (15)	0.05122 (19)	0.19223 (12)	0.0158 (4)
C11	0.34114 (15)	0.15284 (18)	0.24475 (12)	0.0165 (4)
C12	0.24110 (15)	0.19048 (17)	0.26060 (12)	0.0147 (4)
H3	−0.1482 (17)	−0.002 (2)	0.1361 (15)	0.021 (6)*
H4	−0.1375 (19)	−0.175 (2)	0.0470 (15)	0.028 (7)*
H5	0.0269 (16)	−0.264 (3)	0.0150 (14)	0.024 (6)*
H7	0.2166 (16)	−0.251 (2)	0.0307 (13)	0.018 (6)*
H8	0.3567 (17)	−0.148 (2)	0.0883 (13)	0.019 (6)*
H10	0.4241 (18)	0.027 (2)	0.1783 (13)	0.021 (6)*
H11	0.3978 (17)	0.198 (2)	0.2696 (12)	0.012 (5)*
H12	0.2267 (15)	0.258 (2)	0.2974 (12)	0.014 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.01190 (17)	0.01127 (16)	0.0128 (2)	0.000	−0.00035 (15)	0.000
N20	0.0180 (8)	0.0162 (7)	0.0182 (10)	0.0011 (6)	0.0008 (7)	0.0005 (7)
C21	0.0156 (9)	0.0147 (8)	0.0144 (11)	0.0013 (7)	0.0011 (7)	0.0028 (7)
S22	0.0194 (2)	0.0156 (2)	0.0160 (3)	−0.00136 (17)	−0.00189 (19)	−0.00020 (19)
N1	0.0143 (7)	0.0126 (6)	0.0148 (9)	−0.0001 (6)	0.0008 (6)	−0.0002 (6)
N2	0.0147 (7)	0.0105 (6)	0.0124 (9)	0.0006 (5)	0.0011 (6)	0.0011 (6)
C1	0.0156 (8)	0.0099 (7)	0.0128 (11)	0.0005 (6)	0.0005 (7)	0.0012 (7)
C2	0.0150 (8)	0.0122 (8)	0.0121 (11)	−0.0003 (6)	0.0003 (7)	0.0030 (7)
C3	0.0144 (9)	0.0151 (8)	0.0202 (12)	0.0006 (7)	−0.0004 (8)	−0.0022 (8)
C4	0.0187 (10)	0.0173 (8)	0.0218 (12)	−0.0027 (7)	−0.0025 (8)	−0.0037 (8)
C5	0.0224 (10)	0.0149 (8)	0.0163 (12)	−0.0012 (7)	−0.0001 (7)	−0.0052 (8)
C6	0.0202 (9)	0.0109 (7)	0.0157 (11)	0.0003 (7)	0.0014 (7)	0.0012 (7)
C7	0.0181 (9)	0.0139 (8)	0.0142 (11)	0.0020 (7)	0.0035 (7)	−0.0001 (8)
C8	0.0177 (9)	0.0154 (8)	0.0142 (12)	0.0019 (7)	0.0029 (7)	0.0006 (7)
C9	0.0176 (9)	0.0121 (7)	0.0122 (10)	0.0012 (7)	0.0010 (7)	0.0028 (7)
C10	0.0143 (9)	0.0162 (8)	0.0167 (12)	0.0020 (7)	0.0008 (8)	0.0036 (7)
C11	0.0184 (9)	0.0154 (8)	0.0155 (11)	−0.0020 (7)	−0.0036 (8)	0.0031 (8)
C12	0.0170 (8)	0.0121 (7)	0.0150 (11)	0.0003 (6)	0.0001 (7)	−0.0008 (8)

Geometric parameters (Å, º)

Fe1—N20	2.0848 (17)	C3—H3	0.95 (2)
Fe1—N20^i	2.0848 (17)	C4—C5	1.370 (3)
Fe1—N2^i	2.2000 (15)	C4—H4	0.97 (2)
Fe1—N2	2.2000 (15)	C5—C6	1.418 (3)
Fe1—N1	2.2068 (16)	C5—H5	0.95 (2)
Fe1—N1^i	2.2068 (16)	C6—C7	1.428 (3)
N20—C21	1.165 (3)	C7—C8	1.358 (3)
C21—S22	1.632 (2)	C7—H7	0.96 (2)
N1—C3	1.331 (2)	C8—C9	1.438 (3)
N1—C1	1.360 (2)	C8—H8	0.97 (2)
N2—C12	1.330 (2)	C9—C10	1.405 (3)
N2—C2	1.361 (2)	C10—C11	1.374 (3)
C1—C6	1.404 (3)	C10—H10	0.93 (2)
C1—C2	1.445 (3)	C11—C12	1.399 (3)
C2—C9	1.410 (3)	C11—H11	0.97 (2)
C3—C4	1.401 (3)	C12—H12	0.94 (2)
N20—Fe1—N20^i	95.06 (9)	N1—C3—H3	119.3 (14)
N20—Fe1—N2^i	105.08 (6)	C4—C3—H3	117.6 (14)
N20^i—Fe1—N2^i	89.74 (6)	C5—C4—C3	119.41 (18)
N20—Fe1—N2	89.74 (6)	C5—C4—H4	122.1 (14)
N20^i—Fe1—N2	105.08 (6)	C3—C4—H4	118.5 (14)
N2^i—Fe1—N2	158.18 (8)	C4—C5—C6	119.22 (18)
N20—Fe1—N1	165.35 (6)	C4—C5—H5	123.0 (13)
N20^i—Fe1—N1	89.98 (6)	C6—C5—H5	117.7 (13)
N2^i—Fe1—N1	88.66 (6)	C1—C6—C5	117.16 (18)
N2—Fe1—N1	75.66 (6)	C1—C6—C7	119.77 (18)
N20—Fe1—N1^i	89.98 (6)	C5—C6—C7	123.07 (18)
N20^i—Fe1—N1^i	165.35 (6)	C8—C7—C6	121.08 (18)
N2^i—Fe1—N1^i	75.66 (6)	C8—C7—H7	118.6 (13)
N2—Fe1—N1^i	88.66 (6)	C6—C7—H7	120.3 (13)
N1—Fe1—N1^i	88.53 (8)	C7—C8—C9	120.85 (18)
C21—N20—Fe1	165.01 (16)	C7—C8—H8	122.1 (13)
N20—C21—S22	179.5 (2)	C9—C8—H8	117.0 (13)
C3—N1—C1	117.69 (16)	C10—C9—C2	117.70 (17)
C3—N1—Fe1	127.62 (13)	C10—C9—C8	123.04 (17)
C1—N1—Fe1	114.68 (12)	C2—C9—C8	119.26 (17)
C12—N2—C2	117.89 (16)	C11—C10—C9	119.45 (18)
C12—N2—Fe1	127.54 (13)	C11—C10—H10	121.2 (14)
C2—N2—Fe1	114.50 (12)	C9—C10—H10	119.3 (14)
N1—C1—C6	123.34 (17)	C10—C11—C12	118.98 (18)
N1—C1—C2	117.20 (16)	C10—C11—H11	119.8 (13)
C6—C1—C2	119.45 (17)	C12—C11—H11	121.2 (13)
N2—C2—C9	122.58 (17)	N2—C12—C11	123.40 (18)
N2—C2—C1	117.85 (16)	N2—C12—H12	115.8 (12)
C9—C2—C1	119.57 (17)	C11—C12—H12	120.7 (13)
N1—C3—C4	123.11 (18)

Symmetry code: (i) −x, y, −z+1/2.

(hs_15k)

Crystal data

C26H16FeN6S2	F(000) = 1088
Mr = 532.42	Dx = 1.573 Mg m^−3
Orthorhombic, Pbcn	Synchrotron radiation, λ = 0.71 Å
Hall symbol: -P 2n 2ab	Cell parameters from 23123 reflections
a = 13.185 (1) Å	θ = 3.9–45.5°
b = 9.948 (1) Å	µ = 0.89 mm^−1
c = 17.135 (1) Å	T = 15 K
V = 2247.5 (5) Å^3	Block, purple
Z = 4	0.24 × 0.22 × 0.21 mm

Data collection

KUMA KM6 diffractometer	7259 independent reflections
Radiation source: synchrotron	5353 reflections with I > 2σ(I)
Si monochromator	Rint = 0.021
phi scans	θmax = 45.5°, θmin = 3.9°
Absorption correction: gaussian Absorption correction were performed using CRYSALIS Oxford Diffraction (2004)	h = 0→26
Tmin = 0.809, Tmax = 0.827	k = 0→19
23123 measured reflections	l = 0→31

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: inferred from neighbouring sites
wR(F^2) = 0.200	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.1359P)^2 + 0.8177P] where P = (Fo^2 + 2Fc^2)/3
7259 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 5.60 e Å^−3
0 restraints	Δρmin = −1.93 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
Fe	0.5000	0.17576 (3)	0.2500	0.01252 (7)
N	0.54159 (11)	0.31708 (13)	0.16616 (8)	0.01732 (19)
C	0.58648 (10)	0.38766 (14)	0.12380 (8)	0.01546 (19)
S	0.64840 (3)	0.48547 (4)	0.06459 (2)	0.01692 (8)
N1	0.49823 (9)	0.01611 (12)	0.34018 (7)	0.01384 (17)
N2	0.66122 (9)	0.13359 (12)	0.27274 (7)	0.01388 (16)
C1	0.59118 (10)	−0.02973 (13)	0.36080 (8)	0.01366 (18)
C2	0.67808 (10)	0.03233 (13)	0.32461 (8)	0.01347 (18)
C3	0.41777 (11)	−0.03666 (15)	0.37523 (9)	0.0163 (2)
C4	0.42469 (12)	−0.14032 (16)	0.43086 (9)	0.0184 (2)
C5	0.51841 (12)	−0.19038 (16)	0.45028 (10)	0.0175 (2)
C6	0.60559 (11)	−0.13361 (14)	0.41545 (8)	0.01470 (19)
C7	0.70644 (12)	−0.17905 (14)	0.43319 (9)	0.0161 (2)
C8	0.78828 (11)	−0.12137 (14)	0.39845 (8)	0.0159 (2)
C9	0.77627 (10)	−0.01273 (13)	0.34373 (8)	0.01442 (18)
C10	0.85929 (11)	0.05143 (15)	0.30762 (9)	0.0162 (2)
C11	0.84118 (11)	0.15326 (16)	0.25476 (8)	0.0160 (2)
C12	0.74111 (11)	0.19118 (14)	0.23913 (9)	0.01548 (19)
H5	0.529 (3)	−0.266 (4)	0.485 (2)	0.030 (8)*
H7	0.709 (2)	−0.245 (3)	0.4697 (18)	0.022 (7)*
H8	0.858 (2)	−0.147 (3)	0.4122 (19)	0.021 (7)*
H10	0.928 (3)	0.027 (3)	0.322 (2)	0.028 (8)*
H11	0.900 (2)	0.197 (3)	0.2332 (17)	0.015 (6)*
H12	0.728 (3)	0.256 (4)	0.200 (2)	0.031 (8)*
H3	0.356 (3)	−0.005 (4)	0.365 (2)	0.036 (9)*
H4	0.363 (3)	−0.175 (4)	0.453 (2)	0.033 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe	0.01479 (11)	0.01327 (11)	0.00950 (12)	0.000	0.00030 (7)	0.000
N	0.0192 (4)	0.0184 (5)	0.0144 (5)	0.0002 (4)	0.0011 (4)	0.0020 (3)
C	0.0173 (5)	0.0165 (4)	0.0125 (5)	0.0005 (4)	0.0006 (4)	0.0005 (3)
S	0.02005 (15)	0.01729 (14)	0.01341 (15)	−0.00135 (10)	0.00137 (10)	0.00085 (9)
N1	0.0156 (4)	0.0142 (4)	0.0117 (4)	−0.0001 (3)	0.0003 (3)	0.0019 (3)
N2	0.0163 (4)	0.0145 (4)	0.0108 (4)	0.0014 (3)	0.0000 (3)	0.0009 (3)
C1	0.0156 (4)	0.0148 (4)	0.0106 (4)	0.0004 (3)	−0.0009 (3)	0.0006 (3)
C2	0.0151 (4)	0.0144 (4)	0.0109 (4)	0.0012 (3)	−0.0002 (3)	0.0000 (3)
C3	0.0163 (4)	0.0177 (5)	0.0148 (5)	0.0001 (4)	0.0005 (4)	0.0031 (4)
C4	0.0183 (5)	0.0192 (5)	0.0175 (6)	−0.0023 (4)	0.0008 (4)	0.0043 (4)
C5	0.0182 (5)	0.0188 (5)	0.0155 (5)	−0.0005 (4)	−0.0004 (4)	0.0047 (4)
C6	0.0167 (4)	0.0152 (4)	0.0122 (4)	0.0000 (4)	−0.0013 (4)	0.0020 (3)
C7	0.0178 (5)	0.0171 (5)	0.0132 (5)	0.0001 (4)	−0.0007 (4)	0.0027 (3)
C8	0.0171 (5)	0.0174 (5)	0.0131 (5)	0.0005 (4)	−0.0013 (4)	0.0014 (3)
C9	0.0159 (4)	0.0151 (4)	0.0123 (5)	0.0012 (3)	−0.0001 (3)	0.0000 (3)
C10	0.0161 (4)	0.0181 (5)	0.0145 (5)	0.0015 (4)	0.0000 (4)	0.0004 (4)
C11	0.0162 (4)	0.0180 (5)	0.0137 (5)	0.0003 (4)	0.0017 (4)	0.0013 (4)
C12	0.0162 (5)	0.0159 (4)	0.0143 (5)	−0.0005 (4)	0.0009 (4)	0.0014 (3)

Geometric parameters (Å, º)

Fe—N^i	2.0835 (13)	C3—H3	0.89 (4)
Fe—N	2.0835 (13)	C4—C5	1.373 (2)
Fe—N2	2.2014 (12)	C4—H4	0.97 (4)
Fe—N2^i	2.2014 (12)	C5—C6	1.413 (2)
Fe—N1^i	2.2160 (12)	C5—H5	0.97 (4)
Fe—N1	2.2160 (12)	C6—C7	1.437 (2)
N—C	1.1706 (19)	C7—C8	1.359 (2)
C—S	1.6256 (14)	C7—H7	0.91 (3)
N1—C3	1.3273 (18)	C8—C9	1.4394 (19)
N1—C1	1.3546 (17)	C8—H8	0.98 (3)
N2—C12	1.3301 (19)	C9—C10	1.410 (2)
N2—C2	1.3616 (18)	C10—C11	1.380 (2)
C1—C6	1.4074 (18)	C10—H10	0.97 (4)
C1—C2	1.4417 (19)	C11—C12	1.398 (2)
C2—C9	1.4088 (19)	C11—H11	0.97 (3)
C3—C4	1.407 (2)	C12—H12	0.95 (3)
N^i—Fe—N	95.13 (8)	N1—C3—H3	120 (3)
N^i—Fe—N2	105.11 (5)	C4—C3—H3	117 (3)
N—Fe—N2	89.80 (5)	C5—C4—C3	119.23 (14)
N^i—Fe—N2^i	89.80 (5)	C5—C4—H4	122 (2)
N—Fe—N2^i	105.11 (5)	C3—C4—H4	118 (2)
N2—Fe—N2^i	158.03 (6)	C4—C5—C6	118.99 (13)
N^i—Fe—N1^i	165.28 (5)	C4—C5—H5	124 (2)
N—Fe—N1^i	90.00 (5)	C6—C5—H5	117 (2)
N2—Fe—N1^i	88.66 (4)	C1—C6—C5	117.69 (13)
N2^i—Fe—N1^i	75.53 (4)	C1—C6—C7	119.78 (13)
N^i—Fe—N1	90.00 (5)	C5—C6—C7	122.53 (13)
N—Fe—N1	165.28 (5)	C8—C7—C6	120.60 (13)
N2—Fe—N1	75.53 (4)	C8—C7—H7	125 (2)
N2^i—Fe—N1	88.66 (4)	C6—C7—H7	114 (2)
N1^i—Fe—N1	88.44 (7)	C7—C8—C9	120.99 (13)
C—N—Fe	164.88 (13)	C7—C8—H8	121.7 (19)
N—C—S	179.68 (15)	C9—C8—H8	117.1 (19)
C3—N1—C1	118.16 (12)	C2—C9—C10	117.86 (12)
C3—N1—Fe	127.40 (9)	C2—C9—C8	119.44 (12)
C1—N1—Fe	114.44 (9)	C10—C9—C8	122.71 (12)
C12—N2—C2	118.16 (12)	C11—C10—C9	119.08 (13)
C12—N2—Fe	127.29 (10)	C11—C10—H10	121 (2)
C2—N2—Fe	114.46 (9)	C9—C10—H10	120 (2)
N1—C1—C6	122.88 (12)	C10—C11—C12	119.15 (13)
N1—C1—C2	117.55 (11)	C10—C11—H11	116.5 (18)
C6—C1—C2	119.57 (12)	C12—C11—H11	124.3 (18)
N2—C2—C9	122.50 (12)	N2—C12—C11	123.24 (13)
N2—C2—C1	117.90 (12)	N2—C12—H12	117 (2)
C9—C2—C1	119.60 (12)	C11—C12—H12	120 (2)
N1—C3—C4	122.99 (13)

Symmetry code: (i) −x+1, y, −z+1/2.

(ls_15k)

Crystal data

C26H16FeN6S2	F(000) = 1088
Mr = 532.42	Dx = 1.618 Mg m^−3
Orthorhombic, Pbcn	Synchrotron radiation, λ = 0.71 Å
Hall symbol: -P 2n 2ab	Cell parameters from 23007 reflections
a = 12.762 (1) Å	θ = 4.0–45.3°
b = 10.024 (1) Å	µ = 0.91 mm^−1
c = 17.090 (1) Å	T = 15 K
V = 2186.2 (3) Å^3	Block, purple
Z = 4	0.24 × 0.22 × 0.21 mm

Data collection

KUMA KM6 diffractometer	7122 independent reflections
Radiation source: synchrotron	5377 reflections with I > 2σ(I)
Si monochromator	Rint = 0.019
phi scans	θmax = 45.3°, θmin = 4.0°
Absorption correction: gaussian Absorption correction were performed using CRYSALIS Oxford Diffraction (2004)	h = 0→25
Tmin = 0.808, Tmax = 0.830	k = 0→20
23007 measured reflections	l = 0→31

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.1061P)^2 + 0.2257P] where P = (Fo^2 + 2Fc^2)/3
7122 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 3.66 e Å^−3
0 restraints	Δρmin = −0.73 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
Fe	0.5000	0.14734 (2)	0.2500	0.01108 (5)
N	0.52856 (8)	0.28326 (10)	0.17235 (6)	0.01507 (14)
C	0.56909 (8)	0.36224 (10)	0.13155 (7)	0.01454 (15)
S	0.62638 (2)	0.47174 (3)	0.074878 (18)	0.01562 (6)
N1	0.48795 (7)	0.01028 (9)	0.33294 (6)	0.01242 (12)
N2	0.65193 (7)	0.13266 (9)	0.27546 (5)	0.01219 (12)
C1	0.58258 (7)	−0.03021 (10)	0.36135 (6)	0.01236 (14)
C2	0.67223 (8)	0.03504 (10)	0.32915 (6)	0.01224 (13)
C3	0.40256 (8)	−0.04384 (11)	0.36486 (7)	0.01521 (15)
C4	0.40741 (9)	−0.14209 (12)	0.42327 (8)	0.01728 (17)
C5	0.50314 (9)	−0.18715 (12)	0.44977 (8)	0.01656 (17)
C6	0.59481 (8)	−0.12900 (10)	0.41889 (6)	0.01369 (14)
C7	0.69873 (9)	−0.16625 (11)	0.44212 (7)	0.01562 (15)
C8	0.78465 (8)	−0.10668 (11)	0.41029 (7)	0.01526 (16)
C9	0.77361 (8)	−0.00208 (10)	0.35304 (6)	0.01330 (14)
C10	0.85878 (8)	0.06613 (11)	0.31868 (7)	0.01574 (16)
C11	0.83805 (8)	0.16439 (12)	0.26436 (7)	0.01582 (16)
C12	0.73406 (8)	0.19607 (11)	0.24471 (6)	0.01400 (15)
H3	0.335 (2)	−0.018 (2)	0.3497 (16)	0.025 (6)*
H4	0.340 (2)	−0.173 (3)	0.4401 (15)	0.022 (6)*
H5	0.5100 (16)	−0.249 (3)	0.4890 (15)	0.018 (5)*
H7	0.7064 (18)	−0.240 (3)	0.4812 (14)	0.021 (5)*
H8	0.8557 (17)	−0.132 (2)	0.4239 (13)	0.011 (4)*
H10	0.926 (2)	0.052 (3)	0.3329 (16)	0.028 (6)*
H11	0.8968 (19)	0.205 (2)	0.2409 (13)	0.014 (5)*
H12	0.7199 (18)	0.261 (2)	0.2059 (14)	0.018 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe	0.01078 (8)	0.01042 (8)	0.01204 (9)	0.000	−0.00013 (5)	0.000
N	0.0154 (3)	0.0135 (3)	0.0163 (4)	0.0003 (2)	0.0002 (3)	0.0012 (2)
C	0.0145 (3)	0.0134 (3)	0.0157 (4)	0.0009 (3)	−0.0002 (3)	0.0007 (3)
S	0.01643 (10)	0.01413 (10)	0.01630 (12)	−0.00044 (7)	0.00094 (8)	0.00163 (7)
N1	0.0113 (3)	0.0118 (3)	0.0141 (3)	−0.0003 (2)	−0.0006 (2)	0.0018 (2)
N2	0.0129 (3)	0.0114 (3)	0.0123 (3)	0.0000 (2)	−0.0003 (2)	0.0004 (2)
C1	0.0118 (3)	0.0112 (3)	0.0141 (4)	−0.0002 (2)	−0.0008 (3)	0.0007 (2)
C2	0.0114 (3)	0.0117 (3)	0.0136 (4)	−0.0001 (2)	−0.0005 (2)	0.0007 (2)
C3	0.0121 (3)	0.0153 (3)	0.0183 (4)	−0.0003 (3)	−0.0002 (3)	0.0030 (3)
C4	0.0133 (3)	0.0182 (4)	0.0203 (5)	−0.0017 (3)	0.0004 (3)	0.0055 (3)
C5	0.0159 (3)	0.0159 (4)	0.0178 (4)	−0.0010 (3)	−0.0007 (3)	0.0053 (3)
C6	0.0130 (3)	0.0136 (3)	0.0144 (4)	0.0003 (3)	−0.0013 (3)	0.0024 (3)
C7	0.0145 (3)	0.0153 (4)	0.0171 (4)	0.0000 (3)	−0.0019 (3)	0.0039 (3)
C8	0.0134 (3)	0.0153 (4)	0.0171 (4)	0.0011 (3)	−0.0021 (3)	0.0024 (3)
C9	0.0121 (3)	0.0130 (3)	0.0148 (4)	0.0008 (2)	−0.0013 (3)	0.0007 (3)
C10	0.0120 (3)	0.0170 (4)	0.0182 (4)	−0.0004 (3)	−0.0009 (3)	0.0013 (3)
C11	0.0125 (3)	0.0162 (4)	0.0188 (4)	−0.0008 (3)	0.0003 (3)	0.0020 (3)
C12	0.0125 (3)	0.0138 (3)	0.0157 (4)	−0.0007 (3)	−0.0003 (3)	0.0018 (3)

Geometric parameters (Å, º)

Fe—N^i	1.9365 (10)	C3—H3	0.93 (3)
Fe—N	1.9365 (10)	C4—C5	1.3790 (16)
Fe—N1^i	1.9800 (9)	C4—H4	0.96 (3)
Fe—N1	1.9800 (9)	C5—C6	1.4096 (15)
Fe—N2^i	1.9926 (9)	C5—H5	0.92 (3)
Fe—N2	1.9926 (9)	C6—C7	1.4339 (15)
N—C	1.1749 (15)	C7—C8	1.3619 (16)
C—S	1.6363 (11)	C7—H7	1.00 (2)
N1—C3	1.3340 (14)	C8—C9	1.4409 (15)
N1—C1	1.3635 (13)	C8—H8	0.97 (2)
N2—C12	1.3337 (14)	C9—C10	1.4120 (15)
N2—C2	1.3662 (14)	C10—C11	1.3791 (16)
C1—C6	1.4043 (15)	C10—H10	0.90 (3)
C1—C2	1.4282 (14)	C11—C12	1.4053 (15)
C2—C9	1.4069 (14)	C11—H11	0.94 (2)
C3—C4	1.4036 (16)	C12—H12	0.94 (2)
N^i—Fe—N	90.57 (6)	N1—C3—H3	121.7 (16)
N^i—Fe—N1^i	173.40 (4)	C4—C3—H3	115.6 (16)
N—Fe—N1^i	89.02 (4)	C5—C4—C3	120.16 (10)
N^i—Fe—N1	89.02 (4)	C5—C4—H4	126.1 (15)
N—Fe—N1	173.40 (4)	C3—C4—H4	113.7 (15)
N1^i—Fe—N1	92.13 (6)	C4—C5—C6	118.48 (10)
N^i—Fe—N2^i	91.05 (4)	C4—C5—H5	123.1 (13)
N—Fe—N2^i	94.90 (4)	C6—C5—H5	118.3 (13)
N1^i—Fe—N2^i	82.42 (4)	C1—C6—C5	117.49 (9)
N1—Fe—N2^i	91.69 (4)	C1—C6—C7	118.70 (10)
N^i—Fe—N2	94.90 (4)	C5—C6—C7	123.80 (10)
N—Fe—N2	91.05 (4)	C8—C7—C6	121.32 (10)
N1^i—Fe—N2	91.69 (4)	C8—C7—H7	120.7 (13)
N1—Fe—N2	82.42 (4)	C6—C7—H7	117.9 (13)
N2^i—Fe—N2	171.53 (5)	C7—C8—C9	120.77 (10)
C—N—Fe	164.49 (9)	C7—C8—H8	123.0 (13)
N—C—S	179.58 (11)	C9—C8—H8	116.3 (13)
C3—N1—C1	117.19 (9)	C2—C9—C10	117.33 (10)
C3—N1—Fe	129.67 (7)	C2—C9—C8	118.65 (9)
C1—N1—Fe	113.12 (7)	C10—C9—C8	124.02 (9)
C12—N2—C2	117.19 (9)	C11—C10—C9	118.56 (10)
C12—N2—Fe	130.05 (7)	C11—C10—H10	118.5 (18)
C2—N2—Fe	112.58 (7)	C9—C10—H10	122.8 (18)
N1—C1—C6	123.90 (9)	C10—C11—C12	120.23 (10)
N1—C1—C2	115.85 (9)	C10—C11—H11	116.2 (15)
C6—C1—C2	120.26 (9)	C12—C11—H11	123.5 (15)
N2—C2—C9	123.97 (9)	N2—C12—C11	122.71 (10)
N2—C2—C1	115.78 (9)	N2—C12—H12	116.9 (14)
C9—C2—C1	120.25 (9)	C11—C12—H12	120.2 (14)
N1—C3—C4	122.69 (10)

Symmetry code: (i) −x+1, y, −z+1/2.