Download citation
Download citation
link to html
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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768103027897/bm5003sup1.cif
Contains datablock TRIAL_F5_publ

CCDC reference: 1149463

Computing details top

Program(s) used to solve structure: DASH; program(s) used to refine structure: GSAS.

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
(TRIAL_F5_publ) top
Crystal data top
C20Cl2FeN12O8β = 90.539 (7)°
Mr = 663.05V = 1382.27 Å3
Monoclinic, P21Z = 2
a = 8.4484 (8) Å? radiation, λ = ? Å
b = 8.4322 (8) Å?, ? × ? × ? mm
c = 19.404 (2) Å
Data collection top
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
C20Cl2FeN12O8β = 90.539 (7)°
Mr = 663.05V = 1382.27 Å3
Monoclinic, P21Z = 2
a = 8.4484 (8) Å? radiation, λ = ? Å
b = 8.4322 (8) Å?, ? × ? × ? mm
c = 19.404 (2) Å
Data collection top
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
xyzUiso*/Ueq
Fe10.750 (4)0.339 (4)0.2453 (14)0.04712*
N10.524 (5)0.237 (7)0.212 (5)0.01593*
N20.486 (9)0.231 (7)0.143 (4)0.01593*
C10.413 (12)0.157 (8)0.247 (3)0.01593*
C20.300 (6)0.109 (6)0.200 (6)0.01593*
C30.346 (10)0.156 (8)0.136 (4)0.01593*
N30.765 (10)0.347 (7)0.1345 (15)0.01593*
C40.633 (8)0.275 (7)0.115 (4)0.01593*
C50.598 (7)0.257 (6)0.045 (5)0.01593*
N110.700 (11)0.312 (8)0.001 (2)0.01593*
C70.832 (9)0.387 (7)0.019 (3)0.01593*
C80.865 (7)0.403 (6)0.089 (4)0.01593*
N40.997 (15)0.440 (10)0.131 (7)0.01593*
N50.970 (9)0.429 (8)0.201 (9)0.01593*
C91.136 (18)0.511 (11)0.122 (5)0.01593*
C101.193 (6)0.556 (6)0.186 (10)0.01593*
N60.643 (8)0.565 (7)0.280 (7)0.01593*
N70.640 (8)0.602 (10)0.349 (5)0.01593*
C111.09 (2)0.497 (11)0.234 (3)0.01593*
C120.562 (10)0.680 (15)0.245 (3)0.01593*
C130.507 (6)0.786 (6)0.292 (7)0.01593*
C140.563 (10)0.741 (11)0.356 (4)0.01593*
N80.756 (13)0.34 (3)0.3557 (15)0.01593*
C150.682 (11)0.462 (13)0.386 (10)0.01593*
C160.658 (7)0.458 (13)0.456 (10)0.01593*
N170.720 (13)0.34 (2)0.4937 (16)0.01593*
C180.789 (10)0.215 (12)0.462 (10)0.01593*
C190.806 (7)0.218 (14)0.391 (10)0.01593*
N90.860 (9)0.083 (10)0.353 (6)0.01593*
N100.830 (6)0.104 (8)0.283 (7)0.01593*
C200.929 (8)0.059 (13)0.361 (4)0.01593*
C210.949 (6)0.125 (5)0.298 (7)0.01593*
C220.878 (10)0.028 (16)0.250 (3)0.01593*
Cl10.230 (3)0.357 (4)0.9154 (10)0.07909*
O10.383 (5)0.384 (11)0.890 (3)0.11897*
O20.117 (8)0.426 (10)0.870 (3)0.11897*
O30.217 (9)0.426 (7)0.9810 (18)0.11897*
O40.203 (11)0.196 (4)0.920 (4)0.11897*
Cl20.752 (3)0.836 (4)0.5701 (11)0.07909*
O50.595 (5)0.800 (10)0.551 (4)0.11897*
O60.756 (10)0.981 (8)0.605 (5)0.11897*
O70.811 (9)0.716 (10)0.613 (4)0.11897*
O80.844 (8)0.847 (12)0.511 (2)0.11897*
H1310.43820.87980.28180.0191*
H310.28660.13800.09190.0191*
H210.20090.04970.21100.0191*
H1210.54590.68550.19400.0191*
H1410.54900.80100.40000.0191*
H510.49790.20360.02980.0191*
H110.41270.13610.29720.0191*
H710.90650.43130.01540.0191*
H1610.59480.54310.47870.0191*
H911.18960.52860.07690.0191*
H1111.10820.50310.28530.0191*
H1810.82750.12200.48940.0191*
H1011.29030.62040.19530.0191*
H2210.86430.05110.19980.0191*
H2010.96050.10810.40600.0191*
H2111.00560.22660.28820.0191*
Geometric parameters (Å, º) top
Fe1—N12.187 (15)N6—N71.375 (13)
Fe1—N32.155 (15)N6—C121.358 (16)
Fe1—N52.191 (15)N7—N61.375 (13)
Fe1—N62.221 (15)N7—C132.199 (14)
Fe1—N82.143 (15)N7—C141.350 (16)
Fe1—N102.213 (15)N7—C151.431 (16)
N1—Fe12.187 (15)C11—N51.351 (16)
N1—N21.371 (13)C11—C92.205 (14)
N1—C11.344 (16)C11—C101.360 (14)
N1—C22.191 (14)C12—N61.358 (16)
N1—C32.199 (15)C12—C131.365 (14)
N1—C42.13 (12)C12—C142.208 (14)
N2—N11.371 (13)C13—N72.199 (14)
N2—C12.196 (15)C13—C121.365 (14)
N2—C22.189 (14)C13—C141.365 (14)
N2—C31.346 (16)C14—N71.350 (16)
N2—C41.414 (16)C14—C122.208 (14)
N2—C52.15 (10)C14—C131.365 (14)
C1—N11.344 (16)N8—Fe12.143 (15)
C1—N22.196 (15)N8—C151.327 (16)
C1—C21.365 (14)N8—C191.326 (16)
C1—C32.205 (14)C15—N71.431 (16)
C2—N12.191 (14)C15—N81.327 (16)
C2—N22.189 (14)C15—C161.376 (16)
C2—C11.365 (14)C16—C151.376 (16)
C2—C31.362 (14)C16—N171.344 (16)
C3—N12.199 (15)N17—C161.344 (16)
C3—N21.346 (16)N17—C181.345 (16)
C3—C12.205 (14)C18—N171.345 (16)
C3—C21.362 (14)C18—C191.381 (16)
N3—Fe12.155 (15)C19—N81.326 (16)
N3—C41.326 (16)C19—C181.381 (16)
N3—C81.320 (16)C19—N91.439 (16)
N3—N42.11 (18)N9—C191.439 (16)
C4—N12.13 (12)N9—N101.380 (13)
C4—N21.414 (16)N9—C201.345 (16)
C4—N31.326 (16)N9—C212.194 (14)
C4—C51.392 (16)N10—Fe12.213 (15)
C5—N22.15 (10)N10—N91.380 (13)
C5—C41.392 (16)N10—C212.195 (15)
C5—N111.335 (16)N10—C221.353 (16)
N11—C51.335 (16)C20—N91.345 (16)
N11—C71.340 (16)C20—C211.365 (14)
C7—N111.340 (16)C20—C222.211 (14)
C7—C81.376 (16)C21—N92.194 (14)
C8—N31.320 (16)C21—N102.195 (15)
C8—C71.376 (16)C21—C201.365 (14)
C8—N41.412 (16)C21—C221.367 (14)
N4—N32.11 (18)C22—N101.353 (16)
N4—C81.412 (16)C22—C202.211 (14)
N4—N51.372 (13)C22—C211.367 (14)
N4—C91.335 (16)Cl1—O11.403 (16)
N4—C102.187 (15)Cl1—O21.414 (16)
N5—Fe12.191 (15)Cl1—O31.404 (16)
N5—N41.372 (13)Cl1—O41.386 (16)
N5—C92.191 (15)O1—Cl11.403 (16)
N5—C102.187 (15)O2—Cl11.414 (16)
N5—C111.351 (16)O3—Cl11.404 (16)
C9—N41.335 (16)O4—Cl11.386 (16)
C9—N52.191 (15)Cl2—O51.397 (16)
C9—C101.366 (14)Cl2—O61.402 (16)
C9—C112.205 (14)Cl2—O71.401 (16)
C10—N42.187 (15)Cl2—O81.399 (16)
C10—N52.187 (15)O5—Cl21.397 (16)
C10—C91.366 (14)O6—Cl21.402 (16)
C10—C111.360 (14)O7—Cl21.401 (16)
N6—Fe12.221 (15)O8—Cl21.399 (16)
N2—N1—C1108.0 (4)Fe1—N8—C15117 (16)
N1—N2—C3108.1 (3)Fe1—N8—C19121 (16)
N1—N2—C4100 (8)C15—N8—C19121.1 (8)
C3—N2—C4149 (8)N7—C15—N8121 (19)
N1—C1—C2107.9 (8)N7—C15—C16119 (19)
C1—C2—C3108.0 (4)N8—C15—C16119.9 (4)
N2—C3—C2107.9 (8)C15—C16—N17119.4 (10)
C4—N3—C8120.8 (8)C16—N17—C18120.1 (4)
N2—C4—N3139 (7)N17—C18—C19119.3 (9)
N2—C4—C5100 (7)N8—C19—C18119.8 (4)
N3—C4—C5120.0 (4)N8—C19—N9117 (20)
C4—C5—N11119.2 (9)C18—C19—N9123 (20)
C5—N11—C7120.0 (4)C19—N9—N10111 (16)
N11—C7—C8120.1 (9)C19—N9—C20141 (16)
N3—C8—C7119.9 (4)N10—N9—C20108.0 (4)
N3—C8—N4101 (12)N9—N10—C22107.9 (4)
C7—C8—N4138 (12)N9—C20—C21108.1 (8)
C8—N4—N5115 (18)C20—C21—C22108.0 (4)
C8—N4—C9136 (18)N10—C22—C21107.6 (9)
N5—N4—C9108.1 (4)O1—Cl1—O2109.6 (3)
N4—N5—C11108.1 (4)O1—Cl1—O3109.5 (3)
N4—C9—C10108.1 (9)O1—Cl1—O4109.4 (3)
C9—C10—C11108.0 (4)O2—Cl1—O3109.6 (3)
N7—N6—C12107.9 (4)O2—Cl1—O4109.4 (3)
N6—N7—C14107.9 (4)O3—Cl1—O4109.4 (3)
N6—N7—C15108 (14)O5—Cl2—O6109.6 (3)
C14—N7—C15141 (14)O5—Cl2—O7109.5 (3)
N5—C11—C10107.5 (8)O5—Cl2—O8109.4 (3)
N6—C12—C13107.9 (8)O6—Cl2—O7109.4 (3)
C12—C13—C14107.9 (4)O6—Cl2—O8109.5 (3)
N7—C14—C13108.2 (8)O7—Cl2—O8109.5 (3)

Experimental details

Crystal data
Chemical formulaC20Cl2FeN12O8
Mr663.05
Crystal system, space groupMonoclinic, P21
Temperature (K)?
a, b, c (Å)8.4484 (8), 8.4322 (8), 19.404 (2)
β (°) 90.539 (7)
V3)1382.27
Z2
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 fitRp = ?, Rwp = ?, Rexp = ?, χ2 = 12.816
No. of data points?
No. of parameters152
No. of restraints94
(Δ/σ)max0.18

Computer programs: DASH, GSAS.

 

Follow Acta Cryst. B
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds