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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0021889807040149/db5028sup1.cif
Contains datablocks hs_32k, hs_15k, ls_15k

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0021889807040149/db5028hs_32ksup2.hkl
Contains datablock hs_32k

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0021889807040149/db5028hs_15ksup3.hkl
Contains datablock hs_15k

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0021889807040149/db5028ls_15ksup4.hkl
Contains datablock ls_15k

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S0021889807040149/db5028sup5.pdf
Supplementary material

CCDC references: 671655; 671656; 671657

Computing details top

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 top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
[Figure 7]
[Figure 8]
[Figure 9]
[Figure 10]
[Figure 11]
[Figure 12]
[Figure 13]
(hs_32k) top
Crystal data top
C26H16FeN6S2F(000) = 1088
Mr = 532.42Dx = 1.571 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 18028 reflections
a = 13.1928 (4) Åθ = 3.5–34.8°
b = 9.9503 (3) ŵ = 0.89 mm1
c = 17.1498 (8) ÅT = 32 K
V = 2251.29 (14) Å3Block, purple
Z = 40.15 × 0.10 × 0.05 mm
Data collection top
Oxford Xcalibur CCD
diffractometer
4045 independent reflections
Radiation source: fine-focus sealed tube2423 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.055
ω scansθmax = 34.8°, θmin = 3.5°
Absorption correction: gaussian
Absorption correction were performed using CRYSALIS Oxford Diffraction (2004)
h = 020
Tmin = 0.90, Tmax = 0.95k = 015
18028 measured reflectionsl = 022
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 0.91 w = 1/[σ2(Fo2) + (0.0644P)2]
where P = (Fo2 + 2Fc2)/3
4045 reflections(Δ/σ)max < 0.001
191 parametersΔρmax = 1.14 e Å3
0 restraintsΔρmin = 0.41 e Å3
Crystal data top
C26H16FeN6S2V = 2251.29 (14) Å3
Mr = 532.42Z = 4
Orthorhombic, PbcnMo Kα radiation
a = 13.1928 (4) ŵ = 0.89 mm1
b = 9.9503 (3) ÅT = 32 K
c = 17.1498 (8) Å0.15 × 0.10 × 0.05 mm
Data collection top
Oxford Xcalibur CCD
diffractometer
4045 independent reflections
Absorption correction: gaussian
Absorption correction were performed using CRYSALIS Oxford Diffraction (2004)
2423 reflections with I > 2σ(I)
Tmin = 0.90, Tmax = 0.95Rint = 0.055
18028 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 0.91Δρmax = 1.14 e Å3
4045 reflectionsΔρmin = 0.41 e Å3
191 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Fe10.00000.17477 (3)0.25000.01199 (10)
N200.04161 (13)0.31625 (15)0.33376 (10)0.0175 (4)
C210.08609 (14)0.38685 (18)0.37576 (12)0.0149 (4)
S220.14811 (4)0.48490 (4)0.43526 (3)0.01700 (12)
N10.00196 (12)0.01594 (14)0.16020 (10)0.0139 (3)
N20.16106 (11)0.13292 (15)0.22730 (10)0.0126 (3)
C10.09108 (13)0.03007 (17)0.13894 (11)0.0128 (4)
C20.17808 (14)0.03191 (17)0.17541 (11)0.0131 (4)
C30.08241 (14)0.03712 (18)0.12497 (13)0.0166 (4)
C40.07546 (15)0.14000 (19)0.06945 (13)0.0193 (4)
C50.01788 (15)0.19010 (19)0.04988 (13)0.0179 (4)
C60.10573 (15)0.13383 (18)0.08458 (12)0.0156 (4)
C70.20599 (14)0.17839 (18)0.06693 (12)0.0154 (4)
C80.28803 (15)0.12095 (19)0.10118 (12)0.0158 (4)
C90.27634 (14)0.01291 (17)0.15613 (12)0.0140 (4)
C100.35881 (15)0.05122 (19)0.19223 (12)0.0158 (4)
C110.34114 (15)0.15284 (18)0.24475 (12)0.0165 (4)
C120.24110 (15)0.19048 (17)0.26060 (12)0.0147 (4)
H30.1482 (17)0.002 (2)0.1361 (15)0.021 (6)*
H40.1375 (19)0.175 (2)0.0470 (15)0.028 (7)*
H50.0269 (16)0.264 (3)0.0150 (14)0.024 (6)*
H70.2166 (16)0.251 (2)0.0307 (13)0.018 (6)*
H80.3567 (17)0.148 (2)0.0883 (13)0.019 (6)*
H100.4241 (18)0.027 (2)0.1783 (13)0.021 (6)*
H110.3978 (17)0.198 (2)0.2696 (12)0.012 (5)*
H120.2267 (15)0.258 (2)0.2974 (12)0.014 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.01190 (17)0.01127 (16)0.0128 (2)0.0000.00035 (15)0.000
N200.0180 (8)0.0162 (7)0.0182 (10)0.0011 (6)0.0008 (7)0.0005 (7)
C210.0156 (9)0.0147 (8)0.0144 (11)0.0013 (7)0.0011 (7)0.0028 (7)
S220.0194 (2)0.0156 (2)0.0160 (3)0.00136 (17)0.00189 (19)0.00020 (19)
N10.0143 (7)0.0126 (6)0.0148 (9)0.0001 (6)0.0008 (6)0.0002 (6)
N20.0147 (7)0.0105 (6)0.0124 (9)0.0006 (5)0.0011 (6)0.0011 (6)
C10.0156 (8)0.0099 (7)0.0128 (11)0.0005 (6)0.0005 (7)0.0012 (7)
C20.0150 (8)0.0122 (8)0.0121 (11)0.0003 (6)0.0003 (7)0.0030 (7)
C30.0144 (9)0.0151 (8)0.0202 (12)0.0006 (7)0.0004 (8)0.0022 (8)
C40.0187 (10)0.0173 (8)0.0218 (12)0.0027 (7)0.0025 (8)0.0037 (8)
C50.0224 (10)0.0149 (8)0.0163 (12)0.0012 (7)0.0001 (7)0.0052 (8)
C60.0202 (9)0.0109 (7)0.0157 (11)0.0003 (7)0.0014 (7)0.0012 (7)
C70.0181 (9)0.0139 (8)0.0142 (11)0.0020 (7)0.0035 (7)0.0001 (8)
C80.0177 (9)0.0154 (8)0.0142 (12)0.0019 (7)0.0029 (7)0.0006 (7)
C90.0176 (9)0.0121 (7)0.0122 (10)0.0012 (7)0.0010 (7)0.0028 (7)
C100.0143 (9)0.0162 (8)0.0167 (12)0.0020 (7)0.0008 (8)0.0036 (7)
C110.0184 (9)0.0154 (8)0.0155 (11)0.0020 (7)0.0036 (8)0.0031 (8)
C120.0170 (8)0.0121 (7)0.0150 (11)0.0003 (6)0.0001 (7)0.0008 (8)
Geometric parameters (Å, º) top
Fe1—N202.0848 (17)C3—H30.95 (2)
Fe1—N20i2.0848 (17)C4—C51.370 (3)
Fe1—N2i2.2000 (15)C4—H40.97 (2)
Fe1—N22.2000 (15)C5—C61.418 (3)
Fe1—N12.2068 (16)C5—H50.95 (2)
Fe1—N1i2.2068 (16)C6—C71.428 (3)
N20—C211.165 (3)C7—C81.358 (3)
C21—S221.632 (2)C7—H70.96 (2)
N1—C31.331 (2)C8—C91.438 (3)
N1—C11.360 (2)C8—H80.97 (2)
N2—C121.330 (2)C9—C101.405 (3)
N2—C21.361 (2)C10—C111.374 (3)
C1—C61.404 (3)C10—H100.93 (2)
C1—C21.445 (3)C11—C121.399 (3)
C2—C91.410 (3)C11—H110.97 (2)
C3—C41.401 (3)C12—H120.94 (2)
N20—Fe1—N20i95.06 (9)N1—C3—H3119.3 (14)
N20—Fe1—N2i105.08 (6)C4—C3—H3117.6 (14)
N20i—Fe1—N2i89.74 (6)C5—C4—C3119.41 (18)
N20—Fe1—N289.74 (6)C5—C4—H4122.1 (14)
N20i—Fe1—N2105.08 (6)C3—C4—H4118.5 (14)
N2i—Fe1—N2158.18 (8)C4—C5—C6119.22 (18)
N20—Fe1—N1165.35 (6)C4—C5—H5123.0 (13)
N20i—Fe1—N189.98 (6)C6—C5—H5117.7 (13)
N2i—Fe1—N188.66 (6)C1—C6—C5117.16 (18)
N2—Fe1—N175.66 (6)C1—C6—C7119.77 (18)
N20—Fe1—N1i89.98 (6)C5—C6—C7123.07 (18)
N20i—Fe1—N1i165.35 (6)C8—C7—C6121.08 (18)
N2i—Fe1—N1i75.66 (6)C8—C7—H7118.6 (13)
N2—Fe1—N1i88.66 (6)C6—C7—H7120.3 (13)
N1—Fe1—N1i88.53 (8)C7—C8—C9120.85 (18)
C21—N20—Fe1165.01 (16)C7—C8—H8122.1 (13)
N20—C21—S22179.5 (2)C9—C8—H8117.0 (13)
C3—N1—C1117.69 (16)C10—C9—C2117.70 (17)
C3—N1—Fe1127.62 (13)C10—C9—C8123.04 (17)
C1—N1—Fe1114.68 (12)C2—C9—C8119.26 (17)
C12—N2—C2117.89 (16)C11—C10—C9119.45 (18)
C12—N2—Fe1127.54 (13)C11—C10—H10121.2 (14)
C2—N2—Fe1114.50 (12)C9—C10—H10119.3 (14)
N1—C1—C6123.34 (17)C10—C11—C12118.98 (18)
N1—C1—C2117.20 (16)C10—C11—H11119.8 (13)
C6—C1—C2119.45 (17)C12—C11—H11121.2 (13)
N2—C2—C9122.58 (17)N2—C12—C11123.40 (18)
N2—C2—C1117.85 (16)N2—C12—H12115.8 (12)
C9—C2—C1119.57 (17)C11—C12—H12120.7 (13)
N1—C3—C4123.11 (18)
Symmetry code: (i) x, y, z+1/2.
(hs_15k) top
Crystal data top
C26H16FeN6S2F(000) = 1088
Mr = 532.42Dx = 1.573 Mg m3
Orthorhombic, PbcnSynchrotron radiation, λ = 0.71 Å
Hall symbol: -P 2n 2abCell parameters from 23123 reflections
a = 13.185 (1) Åθ = 3.9–45.5°
b = 9.948 (1) ŵ = 0.89 mm1
c = 17.135 (1) ÅT = 15 K
V = 2247.5 (5) Å3Block, purple
Z = 40.24 × 0.22 × 0.21 mm
Data collection top
KUMA KM6
diffractometer
7259 independent reflections
Radiation source: synchrotron5353 reflections with I > 2σ(I)
Si monochromatorRint = 0.021
phi scansθmax = 45.5°, θmin = 3.9°
Absorption correction: gaussian
Absorption correction were performed using CRYSALIS Oxford Diffraction (2004)
h = 026
Tmin = 0.809, Tmax = 0.827k = 019
23123 measured reflectionsl = 031
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.064Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.200H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.1359P)2 + 0.8177P]
where P = (Fo2 + 2Fc2)/3
7259 reflections(Δ/σ)max = 0.001
191 parametersΔρmax = 5.60 e Å3
0 restraintsΔρmin = 1.93 e Å3
Crystal data top
C26H16FeN6S2V = 2247.5 (5) Å3
Mr = 532.42Z = 4
Orthorhombic, PbcnSynchrotron radiation, λ = 0.71 Å
a = 13.185 (1) ŵ = 0.89 mm1
b = 9.948 (1) ÅT = 15 K
c = 17.135 (1) Å0.24 × 0.22 × 0.21 mm
Data collection top
KUMA KM6
diffractometer
7259 independent reflections
Absorption correction: gaussian
Absorption correction were performed using CRYSALIS Oxford Diffraction (2004)
5353 reflections with I > 2σ(I)
Tmin = 0.809, Tmax = 0.827Rint = 0.021
23123 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0640 restraints
wR(F2) = 0.200H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 5.60 e Å3
7259 reflectionsΔρmin = 1.93 e Å3
191 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Fe0.50000.17576 (3)0.25000.01252 (7)
N0.54159 (11)0.31708 (13)0.16616 (8)0.01732 (19)
C0.58648 (10)0.38766 (14)0.12380 (8)0.01546 (19)
S0.64840 (3)0.48547 (4)0.06459 (2)0.01692 (8)
N10.49823 (9)0.01611 (12)0.34018 (7)0.01384 (17)
N20.66122 (9)0.13359 (12)0.27274 (7)0.01388 (16)
C10.59118 (10)0.02973 (13)0.36080 (8)0.01366 (18)
C20.67808 (10)0.03233 (13)0.32461 (8)0.01347 (18)
C30.41777 (11)0.03666 (15)0.37523 (9)0.0163 (2)
C40.42469 (12)0.14032 (16)0.43086 (9)0.0184 (2)
C50.51841 (12)0.19038 (16)0.45028 (10)0.0175 (2)
C60.60559 (11)0.13361 (14)0.41545 (8)0.01470 (19)
C70.70644 (12)0.17905 (14)0.43319 (9)0.0161 (2)
C80.78828 (11)0.12137 (14)0.39845 (8)0.0159 (2)
C90.77627 (10)0.01273 (13)0.34373 (8)0.01442 (18)
C100.85929 (11)0.05143 (15)0.30762 (9)0.0162 (2)
C110.84118 (11)0.15326 (16)0.25476 (8)0.0160 (2)
C120.74111 (11)0.19118 (14)0.23913 (9)0.01548 (19)
H50.529 (3)0.266 (4)0.485 (2)0.030 (8)*
H70.709 (2)0.245 (3)0.4697 (18)0.022 (7)*
H80.858 (2)0.147 (3)0.4122 (19)0.021 (7)*
H100.928 (3)0.027 (3)0.322 (2)0.028 (8)*
H110.900 (2)0.197 (3)0.2332 (17)0.015 (6)*
H120.728 (3)0.256 (4)0.200 (2)0.031 (8)*
H30.356 (3)0.005 (4)0.365 (2)0.036 (9)*
H40.363 (3)0.175 (4)0.453 (2)0.033 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe0.01479 (11)0.01327 (11)0.00950 (12)0.0000.00030 (7)0.000
N0.0192 (4)0.0184 (5)0.0144 (5)0.0002 (4)0.0011 (4)0.0020 (3)
C0.0173 (5)0.0165 (4)0.0125 (5)0.0005 (4)0.0006 (4)0.0005 (3)
S0.02005 (15)0.01729 (14)0.01341 (15)0.00135 (10)0.00137 (10)0.00085 (9)
N10.0156 (4)0.0142 (4)0.0117 (4)0.0001 (3)0.0003 (3)0.0019 (3)
N20.0163 (4)0.0145 (4)0.0108 (4)0.0014 (3)0.0000 (3)0.0009 (3)
C10.0156 (4)0.0148 (4)0.0106 (4)0.0004 (3)0.0009 (3)0.0006 (3)
C20.0151 (4)0.0144 (4)0.0109 (4)0.0012 (3)0.0002 (3)0.0000 (3)
C30.0163 (4)0.0177 (5)0.0148 (5)0.0001 (4)0.0005 (4)0.0031 (4)
C40.0183 (5)0.0192 (5)0.0175 (6)0.0023 (4)0.0008 (4)0.0043 (4)
C50.0182 (5)0.0188 (5)0.0155 (5)0.0005 (4)0.0004 (4)0.0047 (4)
C60.0167 (4)0.0152 (4)0.0122 (4)0.0000 (4)0.0013 (4)0.0020 (3)
C70.0178 (5)0.0171 (5)0.0132 (5)0.0001 (4)0.0007 (4)0.0027 (3)
C80.0171 (5)0.0174 (5)0.0131 (5)0.0005 (4)0.0013 (4)0.0014 (3)
C90.0159 (4)0.0151 (4)0.0123 (5)0.0012 (3)0.0001 (3)0.0000 (3)
C100.0161 (4)0.0181 (5)0.0145 (5)0.0015 (4)0.0000 (4)0.0004 (4)
C110.0162 (4)0.0180 (5)0.0137 (5)0.0003 (4)0.0017 (4)0.0013 (4)
C120.0162 (5)0.0159 (4)0.0143 (5)0.0005 (4)0.0009 (4)0.0014 (3)
Geometric parameters (Å, º) top
Fe—Ni2.0835 (13)C3—H30.89 (4)
Fe—N2.0835 (13)C4—C51.373 (2)
Fe—N22.2014 (12)C4—H40.97 (4)
Fe—N2i2.2014 (12)C5—C61.413 (2)
Fe—N1i2.2160 (12)C5—H50.97 (4)
Fe—N12.2160 (12)C6—C71.437 (2)
N—C1.1706 (19)C7—C81.359 (2)
C—S1.6256 (14)C7—H70.91 (3)
N1—C31.3273 (18)C8—C91.4394 (19)
N1—C11.3546 (17)C8—H80.98 (3)
N2—C121.3301 (19)C9—C101.410 (2)
N2—C21.3616 (18)C10—C111.380 (2)
C1—C61.4074 (18)C10—H100.97 (4)
C1—C21.4417 (19)C11—C121.398 (2)
C2—C91.4088 (19)C11—H110.97 (3)
C3—C41.407 (2)C12—H120.95 (3)
Ni—Fe—N95.13 (8)N1—C3—H3120 (3)
Ni—Fe—N2105.11 (5)C4—C3—H3117 (3)
N—Fe—N289.80 (5)C5—C4—C3119.23 (14)
Ni—Fe—N2i89.80 (5)C5—C4—H4122 (2)
N—Fe—N2i105.11 (5)C3—C4—H4118 (2)
N2—Fe—N2i158.03 (6)C4—C5—C6118.99 (13)
Ni—Fe—N1i165.28 (5)C4—C5—H5124 (2)
N—Fe—N1i90.00 (5)C6—C5—H5117 (2)
N2—Fe—N1i88.66 (4)C1—C6—C5117.69 (13)
N2i—Fe—N1i75.53 (4)C1—C6—C7119.78 (13)
Ni—Fe—N190.00 (5)C5—C6—C7122.53 (13)
N—Fe—N1165.28 (5)C8—C7—C6120.60 (13)
N2—Fe—N175.53 (4)C8—C7—H7125 (2)
N2i—Fe—N188.66 (4)C6—C7—H7114 (2)
N1i—Fe—N188.44 (7)C7—C8—C9120.99 (13)
C—N—Fe164.88 (13)C7—C8—H8121.7 (19)
N—C—S179.68 (15)C9—C8—H8117.1 (19)
C3—N1—C1118.16 (12)C2—C9—C10117.86 (12)
C3—N1—Fe127.40 (9)C2—C9—C8119.44 (12)
C1—N1—Fe114.44 (9)C10—C9—C8122.71 (12)
C12—N2—C2118.16 (12)C11—C10—C9119.08 (13)
C12—N2—Fe127.29 (10)C11—C10—H10121 (2)
C2—N2—Fe114.46 (9)C9—C10—H10120 (2)
N1—C1—C6122.88 (12)C10—C11—C12119.15 (13)
N1—C1—C2117.55 (11)C10—C11—H11116.5 (18)
C6—C1—C2119.57 (12)C12—C11—H11124.3 (18)
N2—C2—C9122.50 (12)N2—C12—C11123.24 (13)
N2—C2—C1117.90 (12)N2—C12—H12117 (2)
C9—C2—C1119.60 (12)C11—C12—H12120 (2)
N1—C3—C4122.99 (13)
Symmetry code: (i) x+1, y, z+1/2.
(ls_15k) top
Crystal data top
C26H16FeN6S2F(000) = 1088
Mr = 532.42Dx = 1.618 Mg m3
Orthorhombic, PbcnSynchrotron radiation, λ = 0.71 Å
Hall symbol: -P 2n 2abCell parameters from 23007 reflections
a = 12.762 (1) Åθ = 4.0–45.3°
b = 10.024 (1) ŵ = 0.91 mm1
c = 17.090 (1) ÅT = 15 K
V = 2186.2 (3) Å3Block, purple
Z = 40.24 × 0.22 × 0.21 mm
Data collection top
KUMA KM6
diffractometer
7122 independent reflections
Radiation source: synchrotron5377 reflections with I > 2σ(I)
Si monochromatorRint = 0.019
phi scansθmax = 45.3°, θmin = 4.0°
Absorption correction: gaussian
Absorption correction were performed using CRYSALIS Oxford Diffraction (2004)
h = 025
Tmin = 0.808, Tmax = 0.830k = 020
23007 measured reflectionsl = 031
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.148H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.1061P)2 + 0.2257P]
where P = (Fo2 + 2Fc2)/3
7122 reflections(Δ/σ)max = 0.001
191 parametersΔρmax = 3.66 e Å3
0 restraintsΔρmin = 0.73 e Å3
Crystal data top
C26H16FeN6S2V = 2186.2 (3) Å3
Mr = 532.42Z = 4
Orthorhombic, PbcnSynchrotron radiation, λ = 0.71 Å
a = 12.762 (1) ŵ = 0.91 mm1
b = 10.024 (1) ÅT = 15 K
c = 17.090 (1) Å0.24 × 0.22 × 0.21 mm
Data collection top
KUMA KM6
diffractometer
7122 independent reflections
Absorption correction: gaussian
Absorption correction were performed using CRYSALIS Oxford Diffraction (2004)
5377 reflections with I > 2σ(I)
Tmin = 0.808, Tmax = 0.830Rint = 0.019
23007 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.148H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 3.66 e Å3
7122 reflectionsΔρmin = 0.73 e Å3
191 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Fe0.50000.14734 (2)0.25000.01108 (5)
N0.52856 (8)0.28326 (10)0.17235 (6)0.01507 (14)
C0.56909 (8)0.36224 (10)0.13155 (7)0.01454 (15)
S0.62638 (2)0.47174 (3)0.074878 (18)0.01562 (6)
N10.48795 (7)0.01028 (9)0.33294 (6)0.01242 (12)
N20.65193 (7)0.13266 (9)0.27546 (5)0.01219 (12)
C10.58258 (7)0.03021 (10)0.36135 (6)0.01236 (14)
C20.67223 (8)0.03504 (10)0.32915 (6)0.01224 (13)
C30.40256 (8)0.04384 (11)0.36486 (7)0.01521 (15)
C40.40741 (9)0.14209 (12)0.42327 (8)0.01728 (17)
C50.50314 (9)0.18715 (12)0.44977 (8)0.01656 (17)
C60.59481 (8)0.12900 (10)0.41889 (6)0.01369 (14)
C70.69873 (9)0.16625 (11)0.44212 (7)0.01562 (15)
C80.78465 (8)0.10668 (11)0.41029 (7)0.01526 (16)
C90.77361 (8)0.00208 (10)0.35304 (6)0.01330 (14)
C100.85878 (8)0.06613 (11)0.31868 (7)0.01574 (16)
C110.83805 (8)0.16439 (12)0.26436 (7)0.01582 (16)
C120.73406 (8)0.19607 (11)0.24471 (6)0.01400 (15)
H30.335 (2)0.018 (2)0.3497 (16)0.025 (6)*
H40.340 (2)0.173 (3)0.4401 (15)0.022 (6)*
H50.5100 (16)0.249 (3)0.4890 (15)0.018 (5)*
H70.7064 (18)0.240 (3)0.4812 (14)0.021 (5)*
H80.8557 (17)0.132 (2)0.4239 (13)0.011 (4)*
H100.926 (2)0.052 (3)0.3329 (16)0.028 (6)*
H110.8968 (19)0.205 (2)0.2409 (13)0.014 (5)*
H120.7199 (18)0.261 (2)0.2059 (14)0.018 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe0.01078 (8)0.01042 (8)0.01204 (9)0.0000.00013 (5)0.000
N0.0154 (3)0.0135 (3)0.0163 (4)0.0003 (2)0.0002 (3)0.0012 (2)
C0.0145 (3)0.0134 (3)0.0157 (4)0.0009 (3)0.0002 (3)0.0007 (3)
S0.01643 (10)0.01413 (10)0.01630 (12)0.00044 (7)0.00094 (8)0.00163 (7)
N10.0113 (3)0.0118 (3)0.0141 (3)0.0003 (2)0.0006 (2)0.0018 (2)
N20.0129 (3)0.0114 (3)0.0123 (3)0.0000 (2)0.0003 (2)0.0004 (2)
C10.0118 (3)0.0112 (3)0.0141 (4)0.0002 (2)0.0008 (3)0.0007 (2)
C20.0114 (3)0.0117 (3)0.0136 (4)0.0001 (2)0.0005 (2)0.0007 (2)
C30.0121 (3)0.0153 (3)0.0183 (4)0.0003 (3)0.0002 (3)0.0030 (3)
C40.0133 (3)0.0182 (4)0.0203 (5)0.0017 (3)0.0004 (3)0.0055 (3)
C50.0159 (3)0.0159 (4)0.0178 (4)0.0010 (3)0.0007 (3)0.0053 (3)
C60.0130 (3)0.0136 (3)0.0144 (4)0.0003 (3)0.0013 (3)0.0024 (3)
C70.0145 (3)0.0153 (4)0.0171 (4)0.0000 (3)0.0019 (3)0.0039 (3)
C80.0134 (3)0.0153 (4)0.0171 (4)0.0011 (3)0.0021 (3)0.0024 (3)
C90.0121 (3)0.0130 (3)0.0148 (4)0.0008 (2)0.0013 (3)0.0007 (3)
C100.0120 (3)0.0170 (4)0.0182 (4)0.0004 (3)0.0009 (3)0.0013 (3)
C110.0125 (3)0.0162 (4)0.0188 (4)0.0008 (3)0.0003 (3)0.0020 (3)
C120.0125 (3)0.0138 (3)0.0157 (4)0.0007 (3)0.0003 (3)0.0018 (3)
Geometric parameters (Å, º) top
Fe—Ni1.9365 (10)C3—H30.93 (3)
Fe—N1.9365 (10)C4—C51.3790 (16)
Fe—N1i1.9800 (9)C4—H40.96 (3)
Fe—N11.9800 (9)C5—C61.4096 (15)
Fe—N2i1.9926 (9)C5—H50.92 (3)
Fe—N21.9926 (9)C6—C71.4339 (15)
N—C1.1749 (15)C7—C81.3619 (16)
C—S1.6363 (11)C7—H71.00 (2)
N1—C31.3340 (14)C8—C91.4409 (15)
N1—C11.3635 (13)C8—H80.97 (2)
N2—C121.3337 (14)C9—C101.4120 (15)
N2—C21.3662 (14)C10—C111.3791 (16)
C1—C61.4043 (15)C10—H100.90 (3)
C1—C21.4282 (14)C11—C121.4053 (15)
C2—C91.4069 (14)C11—H110.94 (2)
C3—C41.4036 (16)C12—H120.94 (2)
Ni—Fe—N90.57 (6)N1—C3—H3121.7 (16)
Ni—Fe—N1i173.40 (4)C4—C3—H3115.6 (16)
N—Fe—N1i89.02 (4)C5—C4—C3120.16 (10)
Ni—Fe—N189.02 (4)C5—C4—H4126.1 (15)
N—Fe—N1173.40 (4)C3—C4—H4113.7 (15)
N1i—Fe—N192.13 (6)C4—C5—C6118.48 (10)
Ni—Fe—N2i91.05 (4)C4—C5—H5123.1 (13)
N—Fe—N2i94.90 (4)C6—C5—H5118.3 (13)
N1i—Fe—N2i82.42 (4)C1—C6—C5117.49 (9)
N1—Fe—N2i91.69 (4)C1—C6—C7118.70 (10)
Ni—Fe—N294.90 (4)C5—C6—C7123.80 (10)
N—Fe—N291.05 (4)C8—C7—C6121.32 (10)
N1i—Fe—N291.69 (4)C8—C7—H7120.7 (13)
N1—Fe—N282.42 (4)C6—C7—H7117.9 (13)
N2i—Fe—N2171.53 (5)C7—C8—C9120.77 (10)
C—N—Fe164.49 (9)C7—C8—H8123.0 (13)
N—C—S179.58 (11)C9—C8—H8116.3 (13)
C3—N1—C1117.19 (9)C2—C9—C10117.33 (10)
C3—N1—Fe129.67 (7)C2—C9—C8118.65 (9)
C1—N1—Fe113.12 (7)C10—C9—C8124.02 (9)
C12—N2—C2117.19 (9)C11—C10—C9118.56 (10)
C12—N2—Fe130.05 (7)C11—C10—H10118.5 (18)
C2—N2—Fe112.58 (7)C9—C10—H10122.8 (18)
N1—C1—C6123.90 (9)C10—C11—C12120.23 (10)
N1—C1—C2115.85 (9)C10—C11—H11116.2 (15)
C6—C1—C2120.26 (9)C12—C11—H11123.5 (15)
N2—C2—C9123.97 (9)N2—C12—C11122.71 (10)
N2—C2—C1115.78 (9)N2—C12—H12116.9 (14)
C9—C2—C1120.25 (9)C11—C12—H12120.2 (14)
N1—C3—C4122.69 (10)
Symmetry code: (i) x+1, y, z+1/2.

Experimental details

(hs_32k)(hs_15k)(ls_15k)
Crystal data
Chemical formulaC26H16FeN6S2C26H16FeN6S2C26H16FeN6S2
Mr532.42532.42532.42
Crystal system, space groupOrthorhombic, PbcnOrthorhombic, PbcnOrthorhombic, Pbcn
Temperature (K)321515
a, b, c (Å)13.1928 (4), 9.9503 (3), 17.1498 (8)13.185 (1), 9.948 (1), 17.135 (1)12.762 (1), 10.024 (1), 17.090 (1)
V3)2251.29 (14)2247.5 (5)2186.2 (3)
Z444
Radiation typeMo KαSynchrotron, λ = 0.71 ÅSynchrotron, λ = 0.71 Å
µ (mm1)0.890.890.91
Crystal size (mm)0.15 × 0.10 × 0.050.24 × 0.22 × 0.210.24 × 0.22 × 0.21
Data collection
DiffractometerOxford Xcalibur CCD
diffractometer
KUMA KM6
diffractometer
KUMA KM6
diffractometer
Absorption correctionGaussian
Absorption correction were performed using CRYSALIS Oxford Diffraction (2004)
Gaussian
Absorption correction were performed using CRYSALIS Oxford Diffraction (2004)
Gaussian
Absorption correction were performed using CRYSALIS Oxford Diffraction (2004)
Tmin, Tmax0.90, 0.950.809, 0.8270.808, 0.830
No. of measured, independent and
observed [I > 2σ(I)] reflections
18028, 4045, 2423 23123, 7259, 5353 23007, 7122, 5377
Rint0.0550.0210.019
(sin θ/λ)max1)0.8041.0041.001
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.108, 0.91 0.064, 0.200, 1.07 0.049, 0.148, 1.03
No. of reflections404572597122
No. of parameters191191191
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)1.14, 0.415.60, 1.933.66, 0.73

Computer programs: CRYSALIS Oxford Diffraction (2004), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997)', SHELXL97 (Sheldrick, 1997).

 

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