research papers
The crystal structure of the iron(II) spin-crossover compound [Fe(C10H8N6)2](ClO4)2 in the high-spin state has been solved from powder X-ray diffraction data using the DASH program and refined using Rietveld refinement. The thermal spin transition has been monitored by following the change in unit-cell parameters with temperature. The title compound has been found to undergo a crystallographic phase change, involving a doubling of the crystallographic a axis, on undergoing the spin transition.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768103027897/bm5003sup1.cif |
CCDC reference: 1149463
Computing details top
Program(s) used to solve structure: DASH; program(s) used to refine structure: GSAS.
(TRIAL_F5_publ) top
Crystal data top
C20Cl2FeN12O8 | β = 90.539 (7)° |
Mr = 663.05 | V = 1382.27 Å3 |
Monoclinic, P21 | Z = 2 |
a = 8.4484 (8) Å | ? radiation, λ = ? Å |
b = 8.4322 (8) Å | ?, ? × ? × ? mm |
c = 19.404 (2) Å |
Refinement top
Least-squares matrix: full | ? data points |
Rp = ? | 152 parameters |
Rwp = ? | 94 restraints |
Rexp = ? | (Δ/σ)max = 0.18 |
χ2 = 12.816 |
Crystal data top
C20Cl2FeN12O8 | β = 90.539 (7)° |
Mr = 663.05 | V = 1382.27 Å3 |
Monoclinic, P21 | Z = 2 |
a = 8.4484 (8) Å | ? radiation, λ = ? Å |
b = 8.4322 (8) Å | ?, ? × ? × ? mm |
c = 19.404 (2) Å |
Refinement top
Rp = ? | ? data points |
Rwp = ? | 152 parameters |
Rexp = ? | 94 restraints |
χ2 = 12.816 | (Δ/σ)max = 0.18 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | ||
Fe1 | 0.750 (4) | 0.339 (4) | 0.2453 (14) | 0.04712* | |
N1 | 0.524 (5) | 0.237 (7) | 0.212 (5) | 0.01593* | |
N2 | 0.486 (9) | 0.231 (7) | 0.143 (4) | 0.01593* | |
C1 | 0.413 (12) | 0.157 (8) | 0.247 (3) | 0.01593* | |
C2 | 0.300 (6) | 0.109 (6) | 0.200 (6) | 0.01593* | |
C3 | 0.346 (10) | 0.156 (8) | 0.136 (4) | 0.01593* | |
N3 | 0.765 (10) | 0.347 (7) | 0.1345 (15) | 0.01593* | |
C4 | 0.633 (8) | 0.275 (7) | 0.115 (4) | 0.01593* | |
C5 | 0.598 (7) | 0.257 (6) | 0.045 (5) | 0.01593* | |
N11 | 0.700 (11) | 0.312 (8) | −0.001 (2) | 0.01593* | |
C7 | 0.832 (9) | 0.387 (7) | 0.019 (3) | 0.01593* | |
C8 | 0.865 (7) | 0.403 (6) | 0.089 (4) | 0.01593* | |
N4 | 0.997 (15) | 0.440 (10) | 0.131 (7) | 0.01593* | |
N5 | 0.970 (9) | 0.429 (8) | 0.201 (9) | 0.01593* | |
C9 | 1.136 (18) | 0.511 (11) | 0.122 (5) | 0.01593* | |
C10 | 1.193 (6) | 0.556 (6) | 0.186 (10) | 0.01593* | |
N6 | 0.643 (8) | 0.565 (7) | 0.280 (7) | 0.01593* | |
N7 | 0.640 (8) | 0.602 (10) | 0.349 (5) | 0.01593* | |
C11 | 1.09 (2) | 0.497 (11) | 0.234 (3) | 0.01593* | |
C12 | 0.562 (10) | 0.680 (15) | 0.245 (3) | 0.01593* | |
C13 | 0.507 (6) | 0.786 (6) | 0.292 (7) | 0.01593* | |
C14 | 0.563 (10) | 0.741 (11) | 0.356 (4) | 0.01593* | |
N8 | 0.756 (13) | 0.34 (3) | 0.3557 (15) | 0.01593* | |
C15 | 0.682 (11) | 0.462 (13) | 0.386 (10) | 0.01593* | |
C16 | 0.658 (7) | 0.458 (13) | 0.456 (10) | 0.01593* | |
N17 | 0.720 (13) | 0.34 (2) | 0.4937 (16) | 0.01593* | |
C18 | 0.789 (10) | 0.215 (12) | 0.462 (10) | 0.01593* | |
C19 | 0.806 (7) | 0.218 (14) | 0.391 (10) | 0.01593* | |
N9 | 0.860 (9) | 0.083 (10) | 0.353 (6) | 0.01593* | |
N10 | 0.830 (6) | 0.104 (8) | 0.283 (7) | 0.01593* | |
C20 | 0.929 (8) | −0.059 (13) | 0.361 (4) | 0.01593* | |
C21 | 0.949 (6) | −0.125 (5) | 0.298 (7) | 0.01593* | |
C22 | 0.878 (10) | −0.028 (16) | 0.250 (3) | 0.01593* | |
Cl1 | 0.230 (3) | 0.357 (4) | 0.9154 (10) | 0.07909* | |
O1 | 0.383 (5) | 0.384 (11) | 0.890 (3) | 0.11897* | |
O2 | 0.117 (8) | 0.426 (10) | 0.870 (3) | 0.11897* | |
O3 | 0.217 (9) | 0.426 (7) | 0.9810 (18) | 0.11897* | |
O4 | 0.203 (11) | 0.196 (4) | 0.920 (4) | 0.11897* | |
Cl2 | 0.752 (3) | 0.836 (4) | 0.5701 (11) | 0.07909* | |
O5 | 0.595 (5) | 0.800 (10) | 0.551 (4) | 0.11897* | |
O6 | 0.756 (10) | 0.981 (8) | 0.605 (5) | 0.11897* | |
O7 | 0.811 (9) | 0.716 (10) | 0.613 (4) | 0.11897* | |
O8 | 0.844 (8) | 0.847 (12) | 0.511 (2) | 0.11897* | |
H131 | 0.4382 | 0.8798 | 0.2818 | 0.0191* | |
H31 | 0.2866 | 0.1380 | 0.0919 | 0.0191* | |
H21 | 0.2009 | 0.0497 | 0.2110 | 0.0191* | |
H121 | 0.5459 | 0.6855 | 0.1940 | 0.0191* | |
H141 | 0.5490 | 0.8010 | 0.4000 | 0.0191* | |
H51 | 0.4979 | 0.2036 | 0.0298 | 0.0191* | |
H11 | 0.4127 | 0.1361 | 0.2972 | 0.0191* | |
H71 | 0.9065 | 0.4313 | −0.0154 | 0.0191* | |
H161 | 0.5948 | 0.5431 | 0.4787 | 0.0191* | |
H91 | 1.1896 | 0.5286 | 0.0769 | 0.0191* | |
H111 | 1.1082 | 0.5031 | 0.2853 | 0.0191* | |
H181 | 0.8275 | 0.1220 | 0.4894 | 0.0191* | |
H101 | 1.2903 | 0.6204 | 0.1953 | 0.0191* | |
H221 | 0.8643 | −0.0511 | 0.1998 | 0.0191* | |
H201 | 0.9605 | −0.1081 | 0.4060 | 0.0191* | |
H211 | 1.0056 | −0.2266 | 0.2882 | 0.0191* |
Geometric parameters (Å, º) top
Fe1—N1 | 2.187 (15) | N6—N7 | 1.375 (13) |
Fe1—N3 | 2.155 (15) | N6—C12 | 1.358 (16) |
Fe1—N5 | 2.191 (15) | N7—N6 | 1.375 (13) |
Fe1—N6 | 2.221 (15) | N7—C13 | 2.199 (14) |
Fe1—N8 | 2.143 (15) | N7—C14 | 1.350 (16) |
Fe1—N10 | 2.213 (15) | N7—C15 | 1.431 (16) |
N1—Fe1 | 2.187 (15) | C11—N5 | 1.351 (16) |
N1—N2 | 1.371 (13) | C11—C9 | 2.205 (14) |
N1—C1 | 1.344 (16) | C11—C10 | 1.360 (14) |
N1—C2 | 2.191 (14) | C12—N6 | 1.358 (16) |
N1—C3 | 2.199 (15) | C12—C13 | 1.365 (14) |
N1—C4 | 2.13 (12) | C12—C14 | 2.208 (14) |
N2—N1 | 1.371 (13) | C13—N7 | 2.199 (14) |
N2—C1 | 2.196 (15) | C13—C12 | 1.365 (14) |
N2—C2 | 2.189 (14) | C13—C14 | 1.365 (14) |
N2—C3 | 1.346 (16) | C14—N7 | 1.350 (16) |
N2—C4 | 1.414 (16) | C14—C12 | 2.208 (14) |
N2—C5 | 2.15 (10) | C14—C13 | 1.365 (14) |
C1—N1 | 1.344 (16) | N8—Fe1 | 2.143 (15) |
C1—N2 | 2.196 (15) | N8—C15 | 1.327 (16) |
C1—C2 | 1.365 (14) | N8—C19 | 1.326 (16) |
C1—C3 | 2.205 (14) | C15—N7 | 1.431 (16) |
C2—N1 | 2.191 (14) | C15—N8 | 1.327 (16) |
C2—N2 | 2.189 (14) | C15—C16 | 1.376 (16) |
C2—C1 | 1.365 (14) | C16—C15 | 1.376 (16) |
C2—C3 | 1.362 (14) | C16—N17 | 1.344 (16) |
C3—N1 | 2.199 (15) | N17—C16 | 1.344 (16) |
C3—N2 | 1.346 (16) | N17—C18 | 1.345 (16) |
C3—C1 | 2.205 (14) | C18—N17 | 1.345 (16) |
C3—C2 | 1.362 (14) | C18—C19 | 1.381 (16) |
N3—Fe1 | 2.155 (15) | C19—N8 | 1.326 (16) |
N3—C4 | 1.326 (16) | C19—C18 | 1.381 (16) |
N3—C8 | 1.320 (16) | C19—N9 | 1.439 (16) |
N3—N4 | 2.11 (18) | N9—C19 | 1.439 (16) |
C4—N1 | 2.13 (12) | N9—N10 | 1.380 (13) |
C4—N2 | 1.414 (16) | N9—C20 | 1.345 (16) |
C4—N3 | 1.326 (16) | N9—C21 | 2.194 (14) |
C4—C5 | 1.392 (16) | N10—Fe1 | 2.213 (15) |
C5—N2 | 2.15 (10) | N10—N9 | 1.380 (13) |
C5—C4 | 1.392 (16) | N10—C21 | 2.195 (15) |
C5—N11 | 1.335 (16) | N10—C22 | 1.353 (16) |
N11—C5 | 1.335 (16) | C20—N9 | 1.345 (16) |
N11—C7 | 1.340 (16) | C20—C21 | 1.365 (14) |
C7—N11 | 1.340 (16) | C20—C22 | 2.211 (14) |
C7—C8 | 1.376 (16) | C21—N9 | 2.194 (14) |
C8—N3 | 1.320 (16) | C21—N10 | 2.195 (15) |
C8—C7 | 1.376 (16) | C21—C20 | 1.365 (14) |
C8—N4 | 1.412 (16) | C21—C22 | 1.367 (14) |
N4—N3 | 2.11 (18) | C22—N10 | 1.353 (16) |
N4—C8 | 1.412 (16) | C22—C20 | 2.211 (14) |
N4—N5 | 1.372 (13) | C22—C21 | 1.367 (14) |
N4—C9 | 1.335 (16) | Cl1—O1 | 1.403 (16) |
N4—C10 | 2.187 (15) | Cl1—O2 | 1.414 (16) |
N5—Fe1 | 2.191 (15) | Cl1—O3 | 1.404 (16) |
N5—N4 | 1.372 (13) | Cl1—O4 | 1.386 (16) |
N5—C9 | 2.191 (15) | O1—Cl1 | 1.403 (16) |
N5—C10 | 2.187 (15) | O2—Cl1 | 1.414 (16) |
N5—C11 | 1.351 (16) | O3—Cl1 | 1.404 (16) |
C9—N4 | 1.335 (16) | O4—Cl1 | 1.386 (16) |
C9—N5 | 2.191 (15) | Cl2—O5 | 1.397 (16) |
C9—C10 | 1.366 (14) | Cl2—O6 | 1.402 (16) |
C9—C11 | 2.205 (14) | Cl2—O7 | 1.401 (16) |
C10—N4 | 2.187 (15) | Cl2—O8 | 1.399 (16) |
C10—N5 | 2.187 (15) | O5—Cl2 | 1.397 (16) |
C10—C9 | 1.366 (14) | O6—Cl2 | 1.402 (16) |
C10—C11 | 1.360 (14) | O7—Cl2 | 1.401 (16) |
N6—Fe1 | 2.221 (15) | O8—Cl2 | 1.399 (16) |
N2—N1—C1 | 108.0 (4) | Fe1—N8—C15 | 117 (16) |
N1—N2—C3 | 108.1 (3) | Fe1—N8—C19 | 121 (16) |
N1—N2—C4 | 100 (8) | C15—N8—C19 | 121.1 (8) |
C3—N2—C4 | 149 (8) | N7—C15—N8 | 121 (19) |
N1—C1—C2 | 107.9 (8) | N7—C15—C16 | 119 (19) |
C1—C2—C3 | 108.0 (4) | N8—C15—C16 | 119.9 (4) |
N2—C3—C2 | 107.9 (8) | C15—C16—N17 | 119.4 (10) |
C4—N3—C8 | 120.8 (8) | C16—N17—C18 | 120.1 (4) |
N2—C4—N3 | 139 (7) | N17—C18—C19 | 119.3 (9) |
N2—C4—C5 | 100 (7) | N8—C19—C18 | 119.8 (4) |
N3—C4—C5 | 120.0 (4) | N8—C19—N9 | 117 (20) |
C4—C5—N11 | 119.2 (9) | C18—C19—N9 | 123 (20) |
C5—N11—C7 | 120.0 (4) | C19—N9—N10 | 111 (16) |
N11—C7—C8 | 120.1 (9) | C19—N9—C20 | 141 (16) |
N3—C8—C7 | 119.9 (4) | N10—N9—C20 | 108.0 (4) |
N3—C8—N4 | 101 (12) | N9—N10—C22 | 107.9 (4) |
C7—C8—N4 | 138 (12) | N9—C20—C21 | 108.1 (8) |
C8—N4—N5 | 115 (18) | C20—C21—C22 | 108.0 (4) |
C8—N4—C9 | 136 (18) | N10—C22—C21 | 107.6 (9) |
N5—N4—C9 | 108.1 (4) | O1—Cl1—O2 | 109.6 (3) |
N4—N5—C11 | 108.1 (4) | O1—Cl1—O3 | 109.5 (3) |
N4—C9—C10 | 108.1 (9) | O1—Cl1—O4 | 109.4 (3) |
C9—C10—C11 | 108.0 (4) | O2—Cl1—O3 | 109.6 (3) |
N7—N6—C12 | 107.9 (4) | O2—Cl1—O4 | 109.4 (3) |
N6—N7—C14 | 107.9 (4) | O3—Cl1—O4 | 109.4 (3) |
N6—N7—C15 | 108 (14) | O5—Cl2—O6 | 109.6 (3) |
C14—N7—C15 | 141 (14) | O5—Cl2—O7 | 109.5 (3) |
N5—C11—C10 | 107.5 (8) | O5—Cl2—O8 | 109.4 (3) |
N6—C12—C13 | 107.9 (8) | O6—Cl2—O7 | 109.4 (3) |
C12—C13—C14 | 107.9 (4) | O6—Cl2—O8 | 109.5 (3) |
N7—C14—C13 | 108.2 (8) | O7—Cl2—O8 | 109.5 (3) |
Experimental details
Crystal data | |
Chemical formula | C20Cl2FeN12O8 |
Mr | 663.05 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | ? |
a, b, c (Å) | 8.4484 (8), 8.4322 (8), 19.404 (2) |
β (°) | 90.539 (7) |
V (Å3) | 1382.27 |
Z | 2 |
Radiation type | ?, λ = ? Å |
Specimen shape, size (mm) | ?, ? × ? × ? |
Data collection | |
Diffractometer | ? |
Specimen mounting | ? |
Data collection mode | ? |
Scan method | ? |
2θ values (°) | 2θmin = ? 2θmax = ? 2θstep = ? |
Refinement | |
R factors and goodness of fit | Rp = ?, Rwp = ?, Rexp = ?, χ2 = 12.816 |
No. of data points | ? |
No. of parameters | 152 |
No. of restraints | 94 |
(Δ/σ)max | 0.18 |
Computer programs: DASH, GSAS.