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The crystal structure of Na2Fe(CN)5(NO)·2D2O, disodium penta­cyano­nitro­syl­ferrate(III) bis­(dideuterium oxide), has been determined by X-ray diffraction at 11 and 293 K, and by neutron diffraction at 15 K. The accurate and extensive data sets lead to more precise determinations than are available from earlier work. The agreement in atomic positional and displacement parameters between the determinations at low temperature is very good.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100008763/br1292sup1.cif
Contains datablocks Irtx, Iltx, Iltn, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100008763/br1292Irtxsup2.hkl
Contains datablock Irtx

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100008763/br1292Iltxsup3.hkl
Contains datablock Iltx

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100008763/br1292Iltnsup4.hkl
Contains datablock Iltn

Computing details top

Data collection: local software for Irtx, Iltx; IPNS data acquisition software for Iltn. Cell refinement: local software for Irtx, Iltx; values from X-ray data used for Iltn. Data reduction: PROFIT (Streltsov & Zavodnik, 1989) for Irtx, Iltx; ANVRED (ref?) for Iltn. Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for Irtx, Iltx. Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for Irtx, Iltx; GSAS (ref?) for Iltn. Molecular graphics: SHELXTL (Sheldrick, 1983) for Irtx, Iltx; ORTEPIII (Burnett & Johnson, 1996) for Iltn. Software used to prepare material for publication: SHELXTL for Irtx, Iltx.

(Irtx) disodium pentacyanonitrosylferrate(III) bis(dideuterium oxide) top
Crystal data top
Na2Fe(CN)5NO·2D2ODx = 1.740 Mg m3
Mr = 301.97Melting point: not measured K
Orthorhombic, PnnmMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2 2nCell parameters from 14 reflections
a = 6.207 (3) Åθ = 18.6–20.1°
b = 11.915 (5) ŵ = 1.39 mm1
c = 15.583 (6) ÅT = 293 K
V = 1152.5 (9) Å3Prism, dark red-brown
Z = 40.62 × 0.47 × 0.41 mm
F(000) = 592
Data collection top
Huber 512 goniometer
diffractometer
1048 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tubeRint = 0.022
None monochromatorθmax = 25.1°, θmin = 2.2°
ω/2θ scansh = 77
Absorption correction: gaussian
(XTAL3.4; Hall et al., 1995)
k = 1414
Tmin = 0.539, Tmax = 0.608l = 1818
7566 measured reflections3 standard reflections every 100 reflections
1067 independent reflections intensity decay: 1%
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)] = 0.019 w = 1/[σ2(Fo2) + (0.024P)2 + 0.3324P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.051(Δ/σ)max < 0.001
S = 1.23Δρmax = 0.23 e Å3
1067 reflectionsΔρmin = 0.28 e Å3
95 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.134 (4)
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
Fe10.49960 (3)0.279527 (19)1/20.01590 (14)
Na11/200.24487 (5)0.0282 (2)
Na2000.37797 (6)0.0338 (2)
O10.8776 (3)0.40583 (13)1/20.0491 (4)
O20.1742 (2)0.12298 (11)0.26842 (8)0.0447 (3)
N10.7207 (2)0.35789 (12)1/20.0227 (3)
N20.1065 (3)0.12264 (15)1/20.0378 (4)
N30.6671 (2)0.12081 (10)0.35881 (8)0.0364 (3)
N40.2496 (2)0.40418 (11)0.35727 (8)0.0399 (3)
C10.2527 (3)0.18139 (15)1/20.0232 (4)
C20.60727 (19)0.17954 (10)0.41187 (8)0.0229 (3)
C30.34422 (19)0.36084 (10)0.41117 (8)0.0236 (3)
D10.192 (5)0.187 (2)0.2853 (18)0.097 (10)*
D20.082 (5)0.128 (2)0.2365 (19)0.096 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.01572 (19)0.01722 (19)0.01476 (19)0.00100 (8)00
Na10.0291 (4)0.0324 (4)0.0231 (4)0.0062 (3)00
Na20.0316 (5)0.0378 (5)0.0320 (5)0.0021 (3)00
O10.0308 (8)0.0434 (9)0.0733 (12)0.0172 (7)00
O20.0443 (7)0.0456 (7)0.0443 (7)0.0040 (5)0.0078 (5)0.0039 (5)
N10.0207 (8)0.0215 (7)0.0258 (7)0.0014 (6)00
N20.0337 (10)0.0381 (10)0.0417 (10)0.0142 (8)00
N30.0358 (7)0.0414 (7)0.0320 (6)0.0051 (5)0.0002 (5)0.0130 (5)
N40.0395 (7)0.0510 (8)0.0292 (6)0.0100 (6)0.0033 (6)0.0105 (6)
C10.0251 (9)0.0249 (9)0.0196 (8)0.0012 (8)00
C20.0212 (6)0.0256 (6)0.0218 (6)0.0003 (5)0.0018 (5)0.0011 (5)
C30.0231 (6)0.0274 (6)0.0205 (6)0.0013 (5)0.0024 (5)0.0009 (5)
Geometric parameters (Å, º) top
Fe1—N11.660 (2)Fe1—C2iii1.937 (1)
Fe1—C11.928 (2)Fe1—C3iii1.9456 (13)
Fe1—C21.937 (1)Na1—N4iv2.4975 (14)
Fe1—C31.946 (1)Na1—N3v2.5100 (15)
Na1—O22.524 (2)Na1—O2v2.5241 (15)
Na1—N32.510 (2)Na1—Na2vi3.7328 (15)
Na1—N4i2.498 (1)Na1—Na23.7328 (15)
Na2—O22.496 (2)Na2—N2vii2.4876 (15)
Na2—N22.488 (2)Na2—O2viii2.4961 (15)
Na2—N3ii2.536 (2)Na2—N3v2.5360 (15)
O1—N11.129 (2)Na2—Na1ii3.7328 (15)
O2—D10.81 (3)Na2—Na2vii3.803 (2)
O2—D20.76 (3)N2—Na2vii2.4876 (15)
N2—C11.146 (3)N3—Na2vi2.5360 (15)
N3—C21.145 (2)N4—Na1ix2.4975 (14)
N4—C31.148 (2)
N1—Fe1—C1176.89 (7)N2—Na2—N2vii80.28 (7)
N1—Fe1—C293.48 (6)N2—Na2—O2viii169.33 (5)
N1—Fe1—C397.45 (6)N2vii—Na2—O2viii93.61 (5)
C1—Fe1—C284.33 (6)N2—Na2—O293.61 (5)
C1—Fe1—C384.72 (6)N2vii—Na2—O2169.33 (5)
C2—Fe1—C2iii90.31 (8)O2viii—Na2—O293.70 (8)
C2—Fe1—C388.45 (6)N2—Na2—N3ii88.45 (6)
C2—Fe1—C3iii169.05 (5)N2vii—Na2—N3ii101.94 (6)
C3—Fe1—C3iii90.71 (8)O2viii—Na2—N3ii84.24 (5)
D1—O2—D2104 (3)O2—Na2—N3ii86.52 (5)
N2—C1—Fe1179.7 (2)N2—Na2—N3v101.94 (6)
N3—C2—Fe1178.6 (1)N2vii—Na2—N3v88.45 (6)
N4—C3—Fe1176.9 (1)O2viii—Na2—N3v86.52 (5)
O1—N1—Fe1176.2 (2)O2—Na2—N3v84.24 (5)
N1—Fe1—C2iii93.48 (6)N3ii—Na2—N3v166.48 (7)
C1—Fe1—C2iii84.33 (6)N2—Na2—Na1ii130.21 (5)
N1—Fe1—C3iii97.45 (6)N2vii—Na2—Na1ii101.77 (4)
C1—Fe1—C3iii84.72 (6)O2viii—Na2—Na1ii42.25 (3)
C2iii—Fe1—C3169.05 (5)O2—Na2—Na1ii88.86 (5)
C2iii—Fe1—C3iii88.45 (6)N3ii—Na2—Na1ii42.02 (3)
N4iv—Na1—N4i100.81 (7)N3v—Na2—Na1ii127.74 (4)
N4iv—Na1—N3165.77 (4)N2—Na2—Na1101.77 (4)
N4i—Na1—N386.12 (5)N2vii—Na2—Na1130.21 (5)
N4iv—Na1—N3v86.12 (5)O2viii—Na2—Na188.86 (5)
N4i—Na1—N3v165.77 (4)O2—Na2—Na142.25 (3)
N3—Na1—N3v89.96 (7)N3ii—Na2—Na1127.74 (4)
N4iv—Na1—O282.01 (5)N3v—Na2—Na142.02 (3)
N4i—Na1—O2108.92 (5)Na1ii—Na2—Na1112.49 (5)
N3—Na1—O283.99 (5)N2—Na2—Na2vii40.14 (4)
N3v—Na1—O284.21 (5)N2vii—Na2—Na2vii40.14 (4)
N4iv—Na1—O2v108.92 (5)O2viii—Na2—Na2vii133.15 (4)
N4i—Na1—O2v82.01 (5)O2—Na2—Na2vii133.15 (4)
N3—Na1—O2v84.21 (5)N3ii—Na2—Na2vii96.76 (3)
N3v—Na1—O2v83.99 (5)N3v—Na2—Na2vii96.76 (3)
O2—Na1—O2v163.28 (7)Na1ii—Na2—Na2vii123.75 (2)
N4iv—Na1—Na2vi150.45 (3)Na1—Na2—Na2vii123.75 (2)
N4i—Na1—Na2vi80.70 (4)Na2—O2—Na196.07 (5)
N3—Na1—Na2vi42.56 (3)Na2—O2—D1113 (2)
N3v—Na1—Na2vi87.16 (4)Na1—O2—D1119 (2)
O2—Na1—Na2vi125.82 (5)Na2—O2—D299 (2)
O2v—Na1—Na2vi41.68 (3)Na1—O2—D2123 (2)
N4iv—Na1—Na280.70 (4)C1—N2—Na2124.69 (7)
N4i—Na1—Na2150.45 (3)C1—N2—Na2vii124.69 (7)
N3—Na1—Na287.16 (4)Na2—N2—Na2vii99.72 (7)
N3v—Na1—Na242.56 (3)C2—N3—Na1136.66 (11)
O2—Na1—Na241.68 (3)C2—N3—Na2vi121.74 (10)
O2v—Na1—Na2125.82 (5)Na1—N3—Na2vi95.42 (5)
Na2vi—Na1—Na2112.49 (5)C3—N4—Na1ix171.73 (11)
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x1, y, z; (iii) x, y, z+1; (iv) x+1/2, y1/2, z+1/2; (v) x+1, y, z; (vi) x+1, y, z; (vii) x, y, z+1; (viii) x, y, z; (ix) x+1/2, y+1/2, z+1/2.
(Iltx) disodium pentacyanonitrosylferrate(III) bis(dideuterium oxide) top
Crystal data top
Na2Fe(CN)5NO·2D2ODx = 1.780 Mg m3
Mr = 301.97Melting point: not measured K
Orthorhombic, PnnmMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2 2nCell parameters from 8 reflections
a = 6.124 (2) Åθ = 34.5–34.5°
b = 11.837 (5) ŵ = 1.42 mm1
c = 15.547 (6) ÅT = 11 K
V = 1127.0 (7) Å3Prism, dark red-brown
Z = 40.38 × 0.32 × 0.29 mm
F(000) = 592
Data collection top
Huber 512 goniometer
diffractometer
5342 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tubeRint = 0.028
None monochromatorθmax = 50.1°, θmin = 2.2°
ω/2θ scansh = 1212
Absorption correction: gaussian
(XTAL3.4; Hall et al., 1995)
k = 2525
Tmin = 0.641, Tmax = 0.705l = 3333
44955 measured reflections3 standard reflections every 100 reflections
6020 independent reflections intensity decay: 1%
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)] = 0.020 w = 1/[σ2(Fo2) + (0.023P)2 + 0.2957P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.054(Δ/σ)max = 0.002
S = 1.08Δρmax = 0.98 e Å3
6020 reflectionsΔρmin = 1.07 e Å3
95 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0096 (6)
Special details top

Experimental. The correction for the absorption by the Be shield was performed by PROFIT (Streltsov & Zavodnik, 1989).

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
Fe10.500791 (12)0.280406 (6)1/20.00324 (2)
Na11/200.245992 (17)0.00649 (4)
Na2000.378142 (18)0.00712 (4)
O10.88845 (8)0.40507 (4)1/20.01010 (6)
O20.17170 (6)0.12253 (3)0.26872 (2)0.00956 (4)
N10.72761 (7)0.35799 (4)1/20.00550 (5)
N20.09861 (9)0.12392 (4)1/20.00859 (6)
N30.66704 (6)0.11951 (3)0.35800 (2)0.00868 (4)
N40.25023 (6)0.40559 (3)0.35539 (2)0.00944 (5)
C10.24954 (9)0.18302 (4)1/20.00629 (6)
C20.60734 (6)0.17961 (3)0.41208 (2)0.00631 (4)
C30.34600 (6)0.36209 (3)0.41082 (2)0.00647 (4)
D10.180 (2)0.1871 (11)0.2860 (9)0.028 (3)*
D20.067 (2)0.1251 (12)0.2343 (9)0.033 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.00376 (2)0.00314 (2)0.00281 (2)0.00007 (2)00
Na10.00717 (9)0.00675 (8)0.00556 (8)0.00082 (7)00
Na20.00758 (9)0.00724 (8)0.00653 (8)0.00047 (7)00
O10.00714 (14)0.00948 (14)0.01369 (16)0.00352 (11)00
O20.01005 (11)0.00910 (9)0.00953 (10)0.00055 (8)0.00120 (8)0.00060 (8)
N10.00570 (13)0.00509 (12)0.00571 (12)0.00035 (10)00
N20.00811 (15)0.00843 (14)0.00923 (14)0.00269 (12)00
N30.00936 (11)0.00908 (10)0.00760 (10)0.00131 (8)0.00026 (8)0.00294 (8)
N40.00994 (12)0.01124 (11)0.00715 (10)0.00196 (9)0.00136 (8)0.00239 (8)
C10.00650 (15)0.00627 (14)0.00611 (13)0.00100 (11)00
C20.00701 (11)0.00636 (10)0.00556 (9)0.00050 (8)0.00009 (8)0.00097 (8)
C30.00723 (11)0.00682 (10)0.00537 (10)0.00080 (8)0.00038 (8)0.00079 (8)
Geometric parameters (Å, º) top
Fe1—N11.6652 (6)Fe1—C2iii1.9281 (6)
Fe1—C11.9226 (7)Fe1—C3iii1.9380 (6)
Fe1—C21.9281 (6)Na1—N3iv2.4658 (7)
Fe1—C31.9380 (6)Na1—N4v2.4661 (7)
Na1—O22.5042 (7)Na1—O2iv2.5042 (7)
Na1—N32.4658 (7)Na1—Na2vi3.687 (1)
Na1—N4i2.4661 (7)Na1—Na23.687 (1)
Na2—O22.4705 (7)Na2—O2vii2.4705 (7)
Na2—N22.4710 (8)Na2—N2viii2.4710 (8)
Na2—N3ii2.5014 (7)Na2—N3iv2.5014 (7)
O1—N11.1317 (7)Na2—Na1ii3.687 (1)
O2—D10.81 (1)Na2—Na2viii3.789 (2)
O2—D20.83 (2)N2—Na2viii2.4710 (8)
N2—C11.1591 (8)N3—Na2vi2.5014 (7)
N3—C21.1604 (6)N4—Na1ix2.4661 (7)
N4—C31.1627 (6)
N1—Fe1—C1176.63 (2)Na2vi—Na1—Na2112.28 (3)
N1—Fe1—C293.38 (2)O2vii—Na2—O292.96 (3)
N1—Fe1—C397.63 (3)O2vii—Na2—N2168.67 (2)
C1—Fe1—C284.25 (3)O2—Na2—N294.32 (3)
C1—Fe1—C384.70 (3)O2vii—Na2—N2viii94.32 (3)
C2—Fe1—C2iii90.29 (4)O2—Na2—N2viii168.67 (2)
C2—Fe1—C388.12 (3)N2—Na2—N2viii79.88 (4)
C2—Fe1—C3iii168.94 (2)O2vii—Na2—N3iv85.91 (2)
C3—Fe1—C3iii91.35 (3)O2—Na2—N3iv84.20 (2)
D1—O2—D2103 (1)N2—Na2—N3iv103.44 (2)
N2—C1—Fe1179.72 (5)N2viii—Na2—N3iv87.68 (2)
N3—C2—Fe1178.35 (4)O2vii—Na2—N3ii84.20 (2)
N4—C3—Fe1176.36 (4)O2—Na2—N3ii85.91 (2)
O1—N1—Fe1176.03 (5)N2—Na2—N3ii87.68 (2)
N1—Fe1—C2iii93.38 (2)N2viii—Na2—N3ii103.44 (2)
C1—Fe1—C2iii84.25 (3)N3iv—Na2—N3ii165.62 (2)
C2iii—Fe1—C290.29 (4)O2vii—Na2—Na1ii42.515 (14)
N1—Fe1—C3iii97.63 (3)O2—Na2—Na1ii88.27 (2)
C1—Fe1—C3iii84.70 (3)N2—Na2—Na1ii129.060 (17)
C2iii—Fe1—C3iii88.12 (3)N2viii—Na2—Na1ii102.96 (2)
C2—Fe1—C3iii168.94 (2)N3iv—Na2—Na1ii127.38 (2)
C2iii—Fe1—C3168.94 (2)N3ii—Na2—Na1ii41.70 (2)
N3iv—Na1—N390.14 (3)O2vii—Na2—Na188.27 (2)
N3iv—Na1—N4v86.19 (3)O2—Na2—Na142.52 (1)
N3—Na1—N4v165.73 (1)N2—Na2—Na1102.96 (2)
N3iv—Na1—N4i165.73 (1)N2viii—Na2—Na1129.06 (2)
N3—Na1—N4i86.19 (3)N3iv—Na2—Na141.70 (2)
N4v—Na1—N4i100.54 (3)N3ii—Na2—Na1127.38 (2)
N3iv—Na1—O2iv84.32 (2)Na1ii—Na2—Na1112.28 (3)
N3—Na1—O2iv84.24 (2)O2vii—Na2—Na2viii133.52 (2)
N4v—Na1—O2iv109.06 (3)O2—Na2—Na2viii133.52 (2)
N4i—Na1—O2iv81.59 (3)N2—Na2—Na2viii39.94 (2)
N3iv—Na1—O284.24 (2)N2viii—Na2—Na2viii39.94 (2)
N3—Na1—O284.32 (2)N3iv—Na2—Na2viii97.19 (1)
N4v—Na1—O281.59 (3)N3ii—Na2—Na2viii97.19 (1)
N4i—Na1—O2109.06 (3)Na1ii—Na2—Na2viii123.86 (1)
O2iv—Na1—O2163.77 (2)Na1—Na2—Na2viii123.86 (1)
N3iv—Na1—Na2vi87.19 (2)Na2—O2—Na195.67 (2)
N3—Na1—Na2vi42.44 (1)Na2—O2—D1110.7 (10)
N4v—Na1—Na2vi150.70 (1)Na1—O2—D1122.6 (10)
N4i—Na1—Na2vi80.80 (3)Na2—O2—D297.9 (10)
O2iv—Na1—Na2vi41.81 (2)Na1—O2—D2123.1 (10)
O2—Na1—Na2vi126.02 (2)C1—N2—Na2123.58 (2)
N3iv—Na1—Na242.44 (1)C1—N2—Na2viii123.58 (2)
N3—Na1—Na287.19 (2)Na2—N2—Na2viii100.12 (4)
N4v—Na1—Na280.80 (3)C2—N3—Na1137.11 (4)
N4i—Na1—Na2150.71 (1)C2—N3—Na2vi120.85 (3)
O2iv—Na1—Na2126.02 (2)Na1—N3—Na2vi95.86 (2)
O2—Na1—Na241.81 (2)C3—N4—Na1ix171.08 (3)
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x1, y, z; (iii) x, y, z+1; (iv) x+1, y, z; (v) x+1/2, y1/2, z+1/2; (vi) x+1, y, z; (vii) x, y, z; (viii) x, y, z+1; (ix) x+1/2, y+1/2, z+1/2.
(Iltn) disodium pentacyanonitrosylferrate(III) bis(dideuterium oxide) top
Crystal data top
Na2Fe(CN)5NO·1.45D2O·0.55H2ODx = 1.774 Mg m3
Mr = 300.87Melting point: not measured K
Orthorhombic, PnnmPulsed neutron radiation, λ = 0.7-4.2 Å
Hall symbol: -P 2 2nCell parameters from 8 reflections
a = 6.124 (2) Åθ = 34.5–34.5°
b = 11.837 (5) ŵ = 0.06 +0.0029 (λ) cm-1 mm1
c = 15.547 (6) ÅT = 11 K
V = 1127.0 (7) Å3Prism, dark red-brown
Z = 43.0 × 2.0 × 1.0 mm
Data collection top
IPNS Single Crystal Diffractometer6343 reflections with I > 3σ(I)
Laue time of flight scansRint = not applicable to TOF Laue technique
Absorption correction: gaussian
(ANVRED; ref?)
h = 113
Tmin = 0.879, Tmax = 0.940k = 2626
8305 measured reflectionsl = 734
8305 independent reflections
Refinement top
Refinement on FHydrogen site location: difference Fourier map
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.058Weighting scheme based on measured s.u.'s (2Fo/σFo2)2
wR(F2) = 0.051(Δ/σ)max = 0.04
S = 3.75Δρmax = 0.56 e Å3
6343 reflectionsΔρmin = 0.51 e Å3
131 parametersExtinction correction: secondary Type I
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 8.4 (1) × 10-5
Secondary atom site location: difference Fourier map
Special details top

Experimental. The sample was mounted on the Single Crystal Diffractometer (SCD) at the Intense Pulsed Neutron Source (IPNS) at Argonne National Laboratory and cooled to 15 K with a Displex closed-cycle helium refrigerator. One histogram of data was collected to check for crystal quality and to determine the initial orientation matrix using an auto-indexing routine. Twenty-five time-of-flight histograms were collected with different chi and phi settings and covered approximately two octants of data (+/-h, +k, +l). Bragg reflections in each histogram were integrated and corrected for the Lorentz factor, the incident spectrum, and the detector efficiency.13 A wavelength-dependent spherical absorption correction was applied but symmetry related reflections were not averaged because of the wavelength dependence of extinction.

Refinement. The two H/D positions were modeled by putting both an H and a D atom on the same site. The occupancies were constrained to be fully occupied and allowed to refine. As noted by Figgis et al. (J. Am. Chem. Soc. 1998, 120, 8715-8723), the zero point motion of H should be a factor of 20.5 greater than that for D. Therefore, the isotropic displacement parameters of the H atoms were allowed to vary, while those of D were constrained to be 1/20.5 of the H-atom displacement parameters. The occupancies on the H/D positions refined to 72% H on both sites. All atoms were refined isotropically. The large value for S relative to the X-ray structure determinations (3.75 vs ~1) arises because of the inclusion of many weak or unobserved reflections at high values of (sinθ)/λ.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Fe10.50072 (10)0.28033 (5)1/20.00348
Na11/200.24608 (11)0.00718
Na2000.37830 (11)0.00755
O10.88842 (18)0.40463 (10)1/20.01003
O20.17127 (13)0.12264 (7)0.26864 (5)0.00951
N10.72780 (10)0.35789 (5)1/20.00551
N20.09869 (11)0.12397 (6)1/20.00885
N30.66723 (8)0.11947 (4)0.35808 (3)0.00888
N40.25050 (8)0.40551 (4)0.35527 (3)0.00991
C10.24923 (15)0.18302 (8)1/20.00681
C20.60718 (11)0.17967 (6)0.41219 (4)0.00646
C30.34569 (10)0.36206 (5)0.41079 (4)0.0067
D10.1885 (3)0.19915 (13)0.28574 (13)0.028250.719 (3)
D20.0625 (3)0.12385 (15)0.22471 (11)0.025750.730 (3)
H10.1885 (3)0.19915 (13)0.28574 (13)0.039970.281 (3)
H20.0625 (3)0.12385 (15)0.22471 (11)0.036420.270 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.00398 (19)0.0036 (2)0.0028 (2)0.00022 (19)00
Na10.0078 (6)0.0075 (6)0.0062 (6)0.0007 (6)00
Na20.0081 (6)0.0081 (6)0.0065 (6)0.0010 (6)00
O10.0070 (4)0.0098 (4)0.0133 (5)0.0036 (4)00
O20.0099 (3)0.0089 (3)0.0097 (3)0.0001 (3)0.0014 (3)0.0007 (3)
N10.0048 (2)0.0052 (2)0.0065 (3)0.00084 (19)00
N20.0082 (2)0.0087 (3)0.0096 (3)0.0034 (2)00
N30.00948 (18)0.00953 (19)0.00764 (19)0.00118 (17)0.00106 (17)0.00373 (15)
N40.01017 (18)0.0118 (2)0.00779 (19)0.00204 (17)0.00160 (18)0.00265 (16)
C10.0066 (3)0.0071 (3)0.0068 (4)0.0018 (3)00
C20.0075 (2)0.0066 (2)0.0053 (2)0.0002 (2)0.0002 (2)0.00160 (19)
C30.0069 (2)0.0071 (2)0.0061 (3)0.0008 (2)0.0007 (2)0.00103 (19)
D10.0353 (10)0.0136 (7)0.0359 (11)0.0007 (7)0.0033 (9)0.0052 (7)
D20.0250 (8)0.0307 (9)0.0216 (9)0.0024 (7)0.0092 (7)0.0037 (7)
H10.0499 (14)0.0192 (10)0.0508 (16)0.0009 (10)0.0047 (12)0.0073 (9)
H20.0353 (11)0.0434 (13)0.0305 (12)0.0034 (10)0.0131 (9)0.0052 (9)
Geometric parameters (Å, º) top
Fe1—N11.666 (1)Na2—N22.470 (2)
Fe1—C11.923 (1)Na2—N3ii2.5003 (8)
Fe1—C21.9258 (9)O1—N11.129 (1)
Fe1—C31.9393 (9)O2—D10.950 (2)
Na1—O22.507 (1)O2—D20.954 (2)
Na1—N32.4660 (2)N2—C11.157 (1)
Na1—N4i2.467 (1)N3—C21.1621 (8)
Na2—O22.473 (2)N4—C31.1616 (8)
N1—Fe1—C1176.64 (5)C2—Fe1—C3iii168.93 (4)
N1—Fe1—C293.35 (4)C3—Fe1—C3iii91.31 (5)
N1—Fe1—C397.68 (4)D1—O2—D2105.3 (2)
C1—Fe1—C284.29 (4)N2—C1—Fe1179.623 (1)
C1—Fe1—C384.65 (4)N3—C2—Fe1178.44 (6)
C2—Fe1—C2iii90.30 (6)N4—C3—Fe1176.34 (6)
C2—Fe1—C388.13 (4)O1—N1—Fe1175.92 (8)
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x1, y, z; (iii) x, y, z+1.
Selected bond lengths and angles (Å, °) for Na2Fe(CN)5(NO).2D2O at 293 K (X-ray), 11 K (X-ray) and 15 K (neutron) top
293 K (X-ray)11 K (X-ray)15 K (neutron)
Fe1-N11.660 (2)1.6652 (6)1.666 (1)
Fe1-C11.928 (2)1.9226 (7)1.923 (1)
Fe1-C21.937 (1)1.9281 (6)1.9258 (9)
Fe1-C31.946 (1)1.9380 (6)1.9393 (9)
Na1-O22.524 (2)2.5042 (7)2.507 (1)
Na1-N32.510 (2)2.4658 (7)2.4660 (2)
Na1-N4i2.498 (1)2.4661 (7)2.467 (1)
Na2-O22.496 (2)2.4705 (7)2.473 (2)
Na2-N22.488 (2)2.4710 (8)2.470 (2)
Na2-N3ii2.536 (2)2.5014 (7)2.5003 (8)
O1-N11.129 (2)1.1317 (7)1.129 (1)
O2-D10.81 (3)0.81 (1)0.950 (2)
O2-D20.76 (3)0.83 (2)0.954 (2)
N2-C11.146 (3)1.1591 (8)1.157 (1)
N3-C21.145 (2)1.1604 (6)1.1621 (8)
N4-C31.148 (2)1.1627 (6)1.1616 (8)
N1-Fe1-C1176.89 (7)176.63 (2)176.64 (5)
N1-Fe1-C293.48 (6)93.38 (2)93.35 (4)
N1-Fe1-C397.45 (6)97.63 (3)97.68 (4)
C1-Fe1-C284.33 (6)84.25 (3)84.29 (4)
C1-Fe1-C384.72 (6)84.70 (3)84.65 (4)
C2-Fe1-C388.45 (6)88.12 (3)88.13 (4)
C2-Fe1-C3iii169.05 (5)168.94 (2)168.93 (4)
C3-Fe1-C3iii90.71 (8)91.35 (3)91.31 (5)
D1-O2-D2104 (3)103 (1)105.3 (2)
N2-C1-Fe1179.7 (2)179.72 (5)179.623 (1)
N3-C2-Fe1178.6 (1)178.35 (4)178.44 (6)
N4-C3-Fe1176.9 (1)176.36 (4)176.34 (6)
O1-N1-Fe1176.2 (2)176.03 (5)175.92 (8)
%T {σymcodesfn (i) ${σcript{1οver 2}}+x,{σcript {1οver 2}}-y,{σcript{1οver 2}}-z$; (ii) $x-1,y,z$; (iii) $x,y,1-z$.πar}
 

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