Na₂Fe(CN)₅(NO)·2D₂O at 11 and 293 K by X-ray, and at 15 K by neutron diffraction

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.

Computing details

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)

Crystal data

Na2Fe(CN)5NO·2D2O	Dx = 1.740 Mg m^−3
Mr = 301.97	Melting point: not measured K
Orthorhombic, Pnnm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2 2n	Cell parameters from 14 reflections
a = 6.207 (3) Å	θ = 18.6–20.1°
b = 11.915 (5) Å	µ = 1.39 mm^−1
c = 15.583 (6) Å	T = 293 K
V = 1152.5 (9) Å^3	Prism, dark red-brown
Z = 4	0.62 × 0.47 × 0.41 mm
F(000) = 592

Data collection

Huber 512 goniometer diffractometer	1048 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.022
None monochromator	θmax = 25.1°, θmin = 2.2°
ω/2θ scans	h = −7→7
Absorption correction: gaussian (XTAL3.4; Hall et al., 1995)	k = −14→14
Tmin = 0.539, Tmax = 0.608	l = −18→18
7566 measured reflections	3 standard reflections every 100 reflections
1067 independent reflections	intensity decay: 1%

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)] = 0.019	w = 1/[σ^2(Fo^2) + (0.024P)^2 + 0.3324P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.051	(Δ/σ)max < 0.001
S = 1.23	Δρmax = 0.23 e Å^−3
1067 reflections	Δρmin = −0.28 e Å^−3
95 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.134 (4)

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	0.49960 (3)	0.279527 (19)	1/2	0.01590 (14)
Na1	1/2	0	0.24487 (5)	0.0282 (2)
Na2	0	0	0.37797 (6)	0.0338 (2)
O1	0.8776 (3)	0.40583 (13)	1/2	0.0491 (4)
O2	0.1742 (2)	0.12298 (11)	0.26842 (8)	0.0447 (3)
N1	0.7207 (2)	0.35789 (12)	1/2	0.0227 (3)
N2	0.1065 (3)	0.12264 (15)	1/2	0.0378 (4)
N3	0.6671 (2)	0.12081 (10)	0.35881 (8)	0.0364 (3)
N4	0.2496 (2)	0.40418 (11)	0.35727 (8)	0.0399 (3)
C1	0.2527 (3)	0.18139 (15)	1/2	0.0232 (4)
C2	0.60727 (19)	0.17954 (10)	0.41187 (8)	0.0229 (3)
C3	0.34422 (19)	0.36084 (10)	0.41117 (8)	0.0236 (3)
D1	0.192 (5)	0.187 (2)	0.2853 (18)	0.097 (10)*
D2	0.082 (5)	0.128 (2)	0.2365 (19)	0.096 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.01572 (19)	0.01722 (19)	0.01476 (19)	−0.00100 (8)	0	0
Na1	0.0291 (4)	0.0324 (4)	0.0231 (4)	−0.0062 (3)	0	0
Na2	0.0316 (5)	0.0378 (5)	0.0320 (5)	0.0021 (3)	0	0
O1	0.0308 (8)	0.0434 (9)	0.0733 (12)	−0.0172 (7)	0	0
O2	0.0443 (7)	0.0456 (7)	0.0443 (7)	0.0040 (5)	−0.0078 (5)	0.0039 (5)
N1	0.0207 (8)	0.0215 (7)	0.0258 (7)	−0.0014 (6)	0	0
N2	0.0337 (10)	0.0381 (10)	0.0417 (10)	−0.0142 (8)	0	0
N3	0.0358 (7)	0.0414 (7)	0.0320 (6)	0.0051 (5)	−0.0002 (5)	−0.0130 (5)
N4	0.0395 (7)	0.0510 (8)	0.0292 (6)	0.0100 (6)	−0.0033 (6)	0.0105 (6)
C1	0.0251 (9)	0.0249 (9)	0.0196 (8)	−0.0012 (8)	0	0
C2	0.0212 (6)	0.0256 (6)	0.0218 (6)	0.0003 (5)	−0.0018 (5)	−0.0011 (5)
C3	0.0231 (6)	0.0274 (6)	0.0205 (6)	0.0013 (5)	0.0024 (5)	0.0009 (5)

Geometric parameters (Å, º)

Fe1—N1	1.660 (2)	Fe1—C2^iii	1.937 (1)
Fe1—C1	1.928 (2)	Fe1—C3^iii	1.9456 (13)
Fe1—C2	1.937 (1)	Na1—N4^iv	2.4975 (14)
Fe1—C3	1.946 (1)	Na1—N3^v	2.5100 (15)
Na1—O2	2.524 (2)	Na1—O2^v	2.5241 (15)
Na1—N3	2.510 (2)	Na1—Na2^vi	3.7328 (15)
Na1—N4^i	2.498 (1)	Na1—Na2	3.7328 (15)
Na2—O2	2.496 (2)	Na2—N2^vii	2.4876 (15)
Na2—N2	2.488 (2)	Na2—O2^viii	2.4961 (15)
Na2—N3^ii	2.536 (2)	Na2—N3^v	2.5360 (15)
O1—N1	1.129 (2)	Na2—Na1^ii	3.7328 (15)
O2—D1	0.81 (3)	Na2—Na2^vii	3.803 (2)
O2—D2	0.76 (3)	N2—Na2^vii	2.4876 (15)
N2—C1	1.146 (3)	N3—Na2^vi	2.5360 (15)
N3—C2	1.145 (2)	N4—Na1^ix	2.4975 (14)
N4—C3	1.148 (2)
N1—Fe1—C1	176.89 (7)	N2—Na2—N2^vii	80.28 (7)
N1—Fe1—C2	93.48 (6)	N2—Na2—O2^viii	169.33 (5)
N1—Fe1—C3	97.45 (6)	N2^vii—Na2—O2^viii	93.61 (5)
C1—Fe1—C2	84.33 (6)	N2—Na2—O2	93.61 (5)
C1—Fe1—C3	84.72 (6)	N2^vii—Na2—O2	169.33 (5)
C2—Fe1—C2^iii	90.31 (8)	O2^viii—Na2—O2	93.70 (8)
C2—Fe1—C3	88.45 (6)	N2—Na2—N3^ii	88.45 (6)
C2—Fe1—C3^iii	169.05 (5)	N2^vii—Na2—N3^ii	101.94 (6)
C3—Fe1—C3^iii	90.71 (8)	O2^viii—Na2—N3^ii	84.24 (5)
D1—O2—D2	104 (3)	O2—Na2—N3^ii	86.52 (5)
N2—C1—Fe1	179.7 (2)	N2—Na2—N3^v	101.94 (6)
N3—C2—Fe1	178.6 (1)	N2^vii—Na2—N3^v	88.45 (6)
N4—C3—Fe1	176.9 (1)	O2^viii—Na2—N3^v	86.52 (5)
O1—N1—Fe1	176.2 (2)	O2—Na2—N3^v	84.24 (5)
N1—Fe1—C2^iii	93.48 (6)	N3^ii—Na2—N3^v	166.48 (7)
C1—Fe1—C2^iii	84.33 (6)	N2—Na2—Na1^ii	130.21 (5)
N1—Fe1—C3^iii	97.45 (6)	N2^vii—Na2—Na1^ii	101.77 (4)
C1—Fe1—C3^iii	84.72 (6)	O2^viii—Na2—Na1^ii	42.25 (3)
C2^iii—Fe1—C3	169.05 (5)	O2—Na2—Na1^ii	88.86 (5)
C2^iii—Fe1—C3^iii	88.45 (6)	N3^ii—Na2—Na1^ii	42.02 (3)
N4^iv—Na1—N4^i	100.81 (7)	N3^v—Na2—Na1^ii	127.74 (4)
N4^iv—Na1—N3	165.77 (4)	N2—Na2—Na1	101.77 (4)
N4^i—Na1—N3	86.12 (5)	N2^vii—Na2—Na1	130.21 (5)
N4^iv—Na1—N3^v	86.12 (5)	O2^viii—Na2—Na1	88.86 (5)
N4^i—Na1—N3^v	165.77 (4)	O2—Na2—Na1	42.25 (3)
N3—Na1—N3^v	89.96 (7)	N3^ii—Na2—Na1	127.74 (4)
N4^iv—Na1—O2	82.01 (5)	N3^v—Na2—Na1	42.02 (3)
N4^i—Na1—O2	108.92 (5)	Na1^ii—Na2—Na1	112.49 (5)
N3—Na1—O2	83.99 (5)	N2—Na2—Na2^vii	40.14 (4)
N3^v—Na1—O2	84.21 (5)	N2^vii—Na2—Na2^vii	40.14 (4)
N4^iv—Na1—O2^v	108.92 (5)	O2^viii—Na2—Na2^vii	133.15 (4)
N4^i—Na1—O2^v	82.01 (5)	O2—Na2—Na2^vii	133.15 (4)
N3—Na1—O2^v	84.21 (5)	N3^ii—Na2—Na2^vii	96.76 (3)
N3^v—Na1—O2^v	83.99 (5)	N3^v—Na2—Na2^vii	96.76 (3)
O2—Na1—O2^v	163.28 (7)	Na1^ii—Na2—Na2^vii	123.75 (2)
N4^iv—Na1—Na2^vi	150.45 (3)	Na1—Na2—Na2^vii	123.75 (2)
N4^i—Na1—Na2^vi	80.70 (4)	Na2—O2—Na1	96.07 (5)
N3—Na1—Na2^vi	42.56 (3)	Na2—O2—D1	113 (2)
N3^v—Na1—Na2^vi	87.16 (4)	Na1—O2—D1	119 (2)
O2—Na1—Na2^vi	125.82 (5)	Na2—O2—D2	99 (2)
O2^v—Na1—Na2^vi	41.68 (3)	Na1—O2—D2	123 (2)
N4^iv—Na1—Na2	80.70 (4)	C1—N2—Na2	124.69 (7)
N4^i—Na1—Na2	150.45 (3)	C1—N2—Na2^vii	124.69 (7)
N3—Na1—Na2	87.16 (4)	Na2—N2—Na2^vii	99.72 (7)
N3^v—Na1—Na2	42.56 (3)	C2—N3—Na1	136.66 (11)
O2—Na1—Na2	41.68 (3)	C2—N3—Na2^vi	121.74 (10)
O2^v—Na1—Na2	125.82 (5)	Na1—N3—Na2^vi	95.42 (5)
Na2^vi—Na1—Na2	112.49 (5)	C3—N4—Na1^ix	171.73 (11)

Symmetry codes: (i) x+1/2, −y+1/2, −z+1/2; (ii) x−1, y, z; (iii) x, y, −z+1; (iv) −x+1/2, y−1/2, −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)

Crystal data

Na2Fe(CN)5NO·2D2O	Dx = 1.780 Mg m^−3
Mr = 301.97	Melting point: not measured K
Orthorhombic, Pnnm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2 2n	Cell parameters from 8 reflections
a = 6.124 (2) Å	θ = 34.5–34.5°
b = 11.837 (5) Å	µ = 1.42 mm^−1
c = 15.547 (6) Å	T = 11 K
V = 1127.0 (7) Å^3	Prism, dark red-brown
Z = 4	0.38 × 0.32 × 0.29 mm
F(000) = 592

Data collection

Huber 512 goniometer diffractometer	5342 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.028
None monochromator	θmax = 50.1°, θmin = 2.2°
ω/2θ scans	h = −12→12
Absorption correction: gaussian (XTAL3.4; Hall et al., 1995)	k = −25→25
Tmin = 0.641, Tmax = 0.705	l = −33→33
44955 measured reflections	3 standard reflections every 100 reflections
6020 independent reflections	intensity decay: 1%

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)] = 0.020	w = 1/[σ^2(Fo^2) + (0.023P)^2 + 0.2957P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.054	(Δ/σ)max = 0.002
S = 1.08	Δρmax = 0.98 e Å^−3
6020 reflections	Δρmin = −1.07 e Å^−3
95 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0096 (6)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Fe1	0.500791 (12)	0.280406 (6)	1/2	0.00324 (2)
Na1	1/2	0	0.245992 (17)	0.00649 (4)
Na2	0	0	0.378142 (18)	0.00712 (4)
O1	0.88845 (8)	0.40507 (4)	1/2	0.01010 (6)
O2	0.17170 (6)	0.12253 (3)	0.26872 (2)	0.00956 (4)
N1	0.72761 (7)	0.35799 (4)	1/2	0.00550 (5)
N2	0.09861 (9)	0.12392 (4)	1/2	0.00859 (6)
N3	0.66704 (6)	0.11951 (3)	0.35800 (2)	0.00868 (4)
N4	0.25023 (6)	0.40559 (3)	0.35539 (2)	0.00944 (5)
C1	0.24954 (9)	0.18302 (4)	1/2	0.00629 (6)
C2	0.60734 (6)	0.17961 (3)	0.41208 (2)	0.00631 (4)
C3	0.34600 (6)	0.36209 (3)	0.41082 (2)	0.00647 (4)
D1	0.180 (2)	0.1871 (11)	0.2860 (9)	0.028 (3)*
D2	0.067 (2)	0.1251 (12)	0.2343 (9)	0.033 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.00376 (2)	0.00314 (2)	0.00281 (2)	−0.00007 (2)	0	0
Na1	0.00717 (9)	0.00675 (8)	0.00556 (8)	−0.00082 (7)	0	0
Na2	0.00758 (9)	0.00724 (8)	0.00653 (8)	0.00047 (7)	0	0
O1	0.00714 (14)	0.00948 (14)	0.01369 (16)	−0.00352 (11)	0	0
O2	0.01005 (11)	0.00910 (9)	0.00953 (10)	0.00055 (8)	−0.00120 (8)	0.00060 (8)
N1	0.00570 (13)	0.00509 (12)	0.00571 (12)	−0.00035 (10)	0	0
N2	0.00811 (15)	0.00843 (14)	0.00923 (14)	−0.00269 (12)	0	0
N3	0.00936 (11)	0.00908 (10)	0.00760 (10)	0.00131 (8)	0.00026 (8)	−0.00294 (8)
N4	0.00994 (12)	0.01124 (11)	0.00715 (10)	0.00196 (9)	−0.00136 (8)	0.00239 (8)
C1	0.00650 (15)	0.00627 (14)	0.00611 (13)	−0.00100 (11)	0	0
C2	0.00701 (11)	0.00636 (10)	0.00556 (9)	0.00050 (8)	0.00009 (8)	−0.00097 (8)
C3	0.00723 (11)	0.00682 (10)	0.00537 (10)	0.00080 (8)	−0.00038 (8)	0.00079 (8)

Geometric parameters (Å, º)

Fe1—N1	1.6652 (6)	Fe1—C2^iii	1.9281 (6)
Fe1—C1	1.9226 (7)	Fe1—C3^iii	1.9380 (6)
Fe1—C2	1.9281 (6)	Na1—N3^iv	2.4658 (7)
Fe1—C3	1.9380 (6)	Na1—N4^v	2.4661 (7)
Na1—O2	2.5042 (7)	Na1—O2^iv	2.5042 (7)
Na1—N3	2.4658 (7)	Na1—Na2^vi	3.687 (1)
Na1—N4^i	2.4661 (7)	Na1—Na2	3.687 (1)
Na2—O2	2.4705 (7)	Na2—O2^vii	2.4705 (7)
Na2—N2	2.4710 (8)	Na2—N2^viii	2.4710 (8)
Na2—N3^ii	2.5014 (7)	Na2—N3^iv	2.5014 (7)
O1—N1	1.1317 (7)	Na2—Na1^ii	3.687 (1)
O2—D1	0.81 (1)	Na2—Na2^viii	3.789 (2)
O2—D2	0.83 (2)	N2—Na2^viii	2.4710 (8)
N2—C1	1.1591 (8)	N3—Na2^vi	2.5014 (7)
N3—C2	1.1604 (6)	N4—Na1^ix	2.4661 (7)
N4—C3	1.1627 (6)
N1—Fe1—C1	176.63 (2)	Na2^vi—Na1—Na2	112.28 (3)
N1—Fe1—C2	93.38 (2)	O2^vii—Na2—O2	92.96 (3)
N1—Fe1—C3	97.63 (3)	O2^vii—Na2—N2	168.67 (2)
C1—Fe1—C2	84.25 (3)	O2—Na2—N2	94.32 (3)
C1—Fe1—C3	84.70 (3)	O2^vii—Na2—N2^viii	94.32 (3)
C2—Fe1—C2^iii	90.29 (4)	O2—Na2—N2^viii	168.67 (2)
C2—Fe1—C3	88.12 (3)	N2—Na2—N2^viii	79.88 (4)
C2—Fe1—C3^iii	168.94 (2)	O2^vii—Na2—N3^iv	85.91 (2)
C3—Fe1—C3^iii	91.35 (3)	O2—Na2—N3^iv	84.20 (2)
D1—O2—D2	103 (1)	N2—Na2—N3^iv	103.44 (2)
N2—C1—Fe1	179.72 (5)	N2^viii—Na2—N3^iv	87.68 (2)
N3—C2—Fe1	178.35 (4)	O2^vii—Na2—N3^ii	84.20 (2)
N4—C3—Fe1	176.36 (4)	O2—Na2—N3^ii	85.91 (2)
O1—N1—Fe1	176.03 (5)	N2—Na2—N3^ii	87.68 (2)
N1—Fe1—C2^iii	93.38 (2)	N2^viii—Na2—N3^ii	103.44 (2)
C1—Fe1—C2^iii	84.25 (3)	N3^iv—Na2—N3^ii	165.62 (2)
C2^iii—Fe1—C2	90.29 (4)	O2^vii—Na2—Na1^ii	42.515 (14)
N1—Fe1—C3^iii	97.63 (3)	O2—Na2—Na1^ii	88.27 (2)
C1—Fe1—C3^iii	84.70 (3)	N2—Na2—Na1^ii	129.060 (17)
C2^iii—Fe1—C3^iii	88.12 (3)	N2^viii—Na2—Na1^ii	102.96 (2)
C2—Fe1—C3^iii	168.94 (2)	N3^iv—Na2—Na1^ii	127.38 (2)
C2^iii—Fe1—C3	168.94 (2)	N3^ii—Na2—Na1^ii	41.70 (2)
N3^iv—Na1—N3	90.14 (3)	O2^vii—Na2—Na1	88.27 (2)
N3^iv—Na1—N4^v	86.19 (3)	O2—Na2—Na1	42.52 (1)
N3—Na1—N4^v	165.73 (1)	N2—Na2—Na1	102.96 (2)
N3^iv—Na1—N4^i	165.73 (1)	N2^viii—Na2—Na1	129.06 (2)
N3—Na1—N4^i	86.19 (3)	N3^iv—Na2—Na1	41.70 (2)
N4^v—Na1—N4^i	100.54 (3)	N3^ii—Na2—Na1	127.38 (2)
N3^iv—Na1—O2^iv	84.32 (2)	Na1^ii—Na2—Na1	112.28 (3)
N3—Na1—O2^iv	84.24 (2)	O2^vii—Na2—Na2^viii	133.52 (2)
N4^v—Na1—O2^iv	109.06 (3)	O2—Na2—Na2^viii	133.52 (2)
N4^i—Na1—O2^iv	81.59 (3)	N2—Na2—Na2^viii	39.94 (2)
N3^iv—Na1—O2	84.24 (2)	N2^viii—Na2—Na2^viii	39.94 (2)
N3—Na1—O2	84.32 (2)	N3^iv—Na2—Na2^viii	97.19 (1)
N4^v—Na1—O2	81.59 (3)	N3^ii—Na2—Na2^viii	97.19 (1)
N4^i—Na1—O2	109.06 (3)	Na1^ii—Na2—Na2^viii	123.86 (1)
O2^iv—Na1—O2	163.77 (2)	Na1—Na2—Na2^viii	123.86 (1)
N3^iv—Na1—Na2^vi	87.19 (2)	Na2—O2—Na1	95.67 (2)
N3—Na1—Na2^vi	42.44 (1)	Na2—O2—D1	110.7 (10)
N4^v—Na1—Na2^vi	150.70 (1)	Na1—O2—D1	122.6 (10)
N4^i—Na1—Na2^vi	80.80 (3)	Na2—O2—D2	97.9 (10)
O2^iv—Na1—Na2^vi	41.81 (2)	Na1—O2—D2	123.1 (10)
O2—Na1—Na2^vi	126.02 (2)	C1—N2—Na2	123.58 (2)
N3^iv—Na1—Na2	42.44 (1)	C1—N2—Na2^viii	123.58 (2)
N3—Na1—Na2	87.19 (2)	Na2—N2—Na2^viii	100.12 (4)
N4^v—Na1—Na2	80.80 (3)	C2—N3—Na1	137.11 (4)
N4^i—Na1—Na2	150.71 (1)	C2—N3—Na2^vi	120.85 (3)
O2^iv—Na1—Na2	126.02 (2)	Na1—N3—Na2^vi	95.86 (2)
O2—Na1—Na2	41.81 (2)	C3—N4—Na1^ix	171.08 (3)

Symmetry codes: (i) x+1/2, −y+1/2, −z+1/2; (ii) x−1, y, z; (iii) x, y, −z+1; (iv) −x+1, −y, z; (v) −x+1/2, y−1/2, −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)

Crystal data

Na2Fe(CN)5NO·1.45D2O·0.55H2O	Dx = 1.774 Mg m^−3
Mr = 300.87	Melting point: not measured K
Orthorhombic, Pnnm	Pulsed neutron radiation, λ = 0.7-4.2 Å
Hall symbol: -P 2 2n	Cell parameters from 8 reflections
a = 6.124 (2) Å	θ = 34.5–34.5°
b = 11.837 (5) Å	µ = 0.06 +0.0029 (λ) cm^-1 mm^−1
c = 15.547 (6) Å	T = 11 K
V = 1127.0 (7) Å^3	Prism, dark red-brown
Z = 4	3.0 × 2.0 × 1.0 mm

Data collection

IPNS Single Crystal Diffractometer	6343 reflections with I > 3σ(I)
Laue time of flight scans	Rint = not applicable to TOF Laue technique
Absorption correction: gaussian (ANVRED; ref?)	h = −1→13
Tmin = 0.879, Tmax = 0.940	k = −26→26
8305 measured reflections	l = −7→34
8305 independent reflections

Refinement

Refinement on F	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.058	Weighting scheme based on measured s.u.'s (2Fo/σFo^2)^2
wR(F^2) = 0.051	(Δ/σ)max = 0.04
S = 3.75	Δρmax = 0.56 e Å^−3
6343 reflections	Δρmin = −0.51 e Å^−3
131 parameters	Extinction correction: secondary Type I
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 8.4 (1) × 10^-5
Secondary atom site location: difference Fourier map

Special details

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 2^0.5 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 1/2^0.5 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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Fe1	0.50072 (10)	0.28033 (5)	1/2	0.00348
Na1	1/2	0	0.24608 (11)	0.00718
Na2	0	0	0.37830 (11)	0.00755
O1	0.88842 (18)	0.40463 (10)	1/2	0.01003
O2	0.17127 (13)	0.12264 (7)	0.26864 (5)	0.00951
N1	0.72780 (10)	0.35789 (5)	1/2	0.00551
N2	0.09869 (11)	0.12397 (6)	1/2	0.00885
N3	0.66723 (8)	0.11947 (4)	0.35808 (3)	0.00888
N4	0.25050 (8)	0.40551 (4)	0.35527 (3)	0.00991
C1	0.24923 (15)	0.18302 (8)	1/2	0.00681
C2	0.60718 (11)	0.17967 (6)	0.41219 (4)	0.00646
C3	0.34569 (10)	0.36206 (5)	0.41079 (4)	0.0067
D1	0.1885 (3)	0.19915 (13)	0.28574 (13)	0.02825	0.719 (3)
D2	0.0625 (3)	0.12385 (15)	0.22471 (11)	0.02575	0.730 (3)
H1	0.1885 (3)	0.19915 (13)	0.28574 (13)	0.03997	0.281 (3)
H2	0.0625 (3)	0.12385 (15)	0.22471 (11)	0.03642	0.270 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.00398 (19)	0.0036 (2)	0.0028 (2)	−0.00022 (19)	0	0
Na1	0.0078 (6)	0.0075 (6)	0.0062 (6)	−0.0007 (6)	0	0
Na2	0.0081 (6)	0.0081 (6)	0.0065 (6)	−0.0010 (6)	0	0
O1	0.0070 (4)	0.0098 (4)	0.0133 (5)	−0.0036 (4)	0	0
O2	0.0099 (3)	0.0089 (3)	0.0097 (3)	0.0001 (3)	−0.0014 (3)	0.0007 (3)
N1	0.0048 (2)	0.0052 (2)	0.0065 (3)	−0.00084 (19)	0	0
N2	0.0082 (2)	0.0087 (3)	0.0096 (3)	−0.0034 (2)	0	0
N3	0.00948 (18)	0.00953 (19)	0.00764 (19)	0.00118 (17)	0.00106 (17)	−0.00373 (15)
N4	0.01017 (18)	0.0118 (2)	0.00779 (19)	0.00204 (17)	−0.00160 (18)	0.00265 (16)
C1	0.0066 (3)	0.0071 (3)	0.0068 (4)	−0.0018 (3)	0	0
C2	0.0075 (2)	0.0066 (2)	0.0053 (2)	0.0002 (2)	0.0002 (2)	−0.00160 (19)
C3	0.0069 (2)	0.0071 (2)	0.0061 (3)	0.0008 (2)	−0.0007 (2)	0.00103 (19)
D1	0.0353 (10)	0.0136 (7)	0.0359 (11)	−0.0007 (7)	−0.0033 (9)	−0.0052 (7)
D2	0.0250 (8)	0.0307 (9)	0.0216 (9)	0.0024 (7)	−0.0092 (7)	0.0037 (7)
H1	0.0499 (14)	0.0192 (10)	0.0508 (16)	−0.0009 (10)	−0.0047 (12)	−0.0073 (9)
H2	0.0353 (11)	0.0434 (13)	0.0305 (12)	0.0034 (10)	−0.0131 (9)	0.0052 (9)

Geometric parameters (Å, º)

Fe1—N1	1.666 (1)	Na2—N2	2.470 (2)
Fe1—C1	1.923 (1)	Na2—N3^ii	2.5003 (8)
Fe1—C2	1.9258 (9)	O1—N1	1.129 (1)
Fe1—C3	1.9393 (9)	O2—D1	0.950 (2)
Na1—O2	2.507 (1)	O2—D2	0.954 (2)
Na1—N3	2.4660 (2)	N2—C1	1.157 (1)
Na1—N4^i	2.467 (1)	N3—C2	1.1621 (8)
Na2—O2	2.473 (2)	N4—C3	1.1616 (8)
N1—Fe1—C1	176.64 (5)	C2—Fe1—C3^iii	168.93 (4)
N1—Fe1—C2	93.35 (4)	C3—Fe1—C3^iii	91.31 (5)
N1—Fe1—C3	97.68 (4)	D1—O2—D2	105.3 (2)
C1—Fe1—C2	84.29 (4)	N2—C1—Fe1	179.623 (1)
C1—Fe1—C3	84.65 (4)	N3—C2—Fe1	178.44 (6)
C2—Fe1—C2^iii	90.30 (6)	N4—C3—Fe1	176.34 (6)
C2—Fe1—C3	88.13 (4)	O1—N1—Fe1	175.92 (8)

Symmetry codes: (i) x+1/2, −y+1/2, −z+1/2; (ii) x−1, y, z; (iii) x, y, −z+1.