Temperature- and pressure-dependent structural study of {Fe(pmd)₂[Ag(CN)₂]₂}_n spin-crossover compound by neutron Laue diffraction

The effect of pressure (up to 0.17 GPa) on the spin-crossover compound {Fe(pmd)₂[Ag(CN)₂]₂}_n [orthorhombic isomer (II), pmd = pyrimidine] has been investigated by temperature- and pressure-dependent neutron Laue diffraction and magnetometry. The cooperative high-spin ↔ low-spin transition, centred at ca 180 K at ambient pressure, is shifted to higher temperatures as pressure is applied, showing a moderate sensitivity of the compound to pressure, since the spin transition is displaced by ca 140 K GPa⁻¹. The space-group symmetry (orthorhombic Pccn) remains unchanged over the pressure–temperature (P–T) range studied. The main structural consequence of the high-spin to low-spin transition is the contraction of the distorted octahedral [FeN₆] chromophores, being more marked in the axial positions (occupied by the pmd units), than in the equatorial positions (occupied by four [Ag(CN)₂]⁻ bridging ligands).

Computing details

For all compounds, cell refinement: NEWLAUEGEN (J. Campbell et al., 1998); data reduction: ARGONNE-BOXES(C. Wilkinson et al.,1988)& LAUENORM (J. W. Campbell et al.,1986; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

(fepmd1)

Crystal data

C12H8Ag2FeN8	Z = 4
Mr = 535.83	F(000) = 584
Orthorhombic, Pccn	Dx = 2.219 Mg m^−3
Hall symbol: -P 2ab 2ac	Neutron radiation, λ = 0.90-3.00 Å
a = 14.895 (3) Å	µ = 0.08 mm^−1
b = 8.106 (3) Å	T = 150 K
c = 13.285 (3) Å	Prism, orange-yellow
V = 1604.0 (8) Å^3	1.0 × 0.6 × 0.5 mm

Data collection

ILL-VIVALDI Laue single xtal diffractometer	Rint = 0.197
Radiation source: ILL neutron source	θmax = 36.5°, θmin = 4.0°
7581 measured reflections	h = −12→20
1543 independent reflections	k = −10→10
1236 reflections with I > 2σ(I)	l = −17→15

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)] = 0.083	Hydrogen site location: difference Fourier map
wR(F^2) = 0.149	All H-atom parameters refined
S = 1.24	w = 1/[σ^2(Fo^2) + (0.0554P)^2] where P = (Fo^2 + 2Fc^2)/3
1543 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 0.86 e Å^−3
0 restraints	Δρmin = −0.88 e Å^−3

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
C1	0.6287 (2)	0.5259 (4)	0.9526 (2)	0.0236 (7)
C2	0.58924 (18)	0.4495 (4)	0.87013 (19)	0.0211 (6)
C3	0.58671 (16)	0.3118 (4)	1.05253 (18)	0.0167 (6)
C4	0.54938 (17)	0.2976 (4)	0.88628 (18)	0.0173 (6)
C5	0.32911 (16)	0.0733 (4)	0.87685 (18)	0.0170 (6)
C6	0.38886 (16)	0.0845 (3)	1.18864 (18)	0.0170 (6)
Ag1	0.29509 (17)	0.0881 (4)	1.3042 (2)	0.0169 (7)
Fe1	0.5000	0.0000	1.0000	0.0093 (6)
N1	0.54892 (13)	0.2265 (2)	0.97754 (14)	0.0140 (4)
N2	0.62570 (14)	0.4583 (3)	1.04394 (15)	0.0213 (5)
N3	0.43592 (11)	0.0670 (3)	1.11982 (12)	0.0153 (4)
N4	0.39526 (10)	0.0526 (3)	0.92123 (13)	0.0147 (4)
H1	0.6612 (5)	0.6447 (11)	0.9459 (5)	0.0508 (19)
H2	0.5904 (5)	0.5047 (9)	0.7960 (5)	0.0442 (18)
H3	0.5857 (5)	0.2556 (8)	1.1264 (4)	0.0356 (16)
H4	0.5169 (5)	0.2308 (8)	0.8255 (4)	0.0350 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0283 (14)	0.0241 (19)	0.0182 (14)	−0.0075 (13)	−0.0007 (11)	0.0009 (12)
C2	0.0294 (13)	0.0198 (17)	0.0141 (13)	−0.0049 (12)	0.0009 (9)	0.0051 (12)
C3	0.0182 (11)	0.0202 (17)	0.0117 (11)	−0.0050 (11)	0.0001 (8)	−0.0009 (10)
C4	0.0199 (11)	0.0205 (16)	0.0115 (11)	−0.0017 (11)	−0.0002 (9)	0.0020 (10)
C5	0.0139 (11)	0.0239 (17)	0.0133 (11)	−0.0002 (11)	−0.0042 (8)	0.0000 (10)
C6	0.0156 (11)	0.0245 (17)	0.0109 (11)	−0.0004 (11)	0.0061 (8)	0.0000 (10)
Ag1	0.0143 (12)	0.0216 (19)	0.0150 (12)	0.0040 (11)	0.0082 (9)	0.0018 (11)
Fe1	0.0074 (12)	0.0144 (18)	0.0060 (13)	0.0007 (8)	0.0009 (7)	−0.0008 (8)
N1	0.0135 (8)	0.0176 (11)	0.0109 (7)	−0.0004 (7)	0.0002 (7)	−0.0003 (7)
N2	0.0253 (9)	0.0217 (12)	0.0170 (10)	−0.0080 (9)	−0.0010 (7)	−0.0020 (8)
N3	0.0135 (8)	0.0216 (12)	0.0108 (8)	0.0018 (8)	0.0040 (6)	−0.0008 (7)
N4	0.0114 (7)	0.0201 (11)	0.0126 (8)	0.0003 (8)	−0.0026 (6)	0.0013 (8)
H1	0.064 (4)	0.049 (5)	0.039 (4)	−0.024 (4)	−0.002 (3)	0.006 (3)
H2	0.065 (4)	0.047 (5)	0.021 (3)	−0.008 (3)	−0.001 (3)	0.012 (3)
H3	0.054 (4)	0.037 (4)	0.016 (3)	−0.015 (3)	−0.002 (2)	0.003 (2)
H4	0.045 (3)	0.040 (4)	0.020 (3)	−0.013 (3)	−0.010 (2)	0.002 (2)

Geometric parameters (Å, º)

C1—N2	1.332 (4)	C6—N3	1.161 (3)
C1—C2	1.389 (4)	C6—Ag1	2.075 (3)
C1—H1	1.081 (9)	Ag1—C5^ii	2.090 (3)
C2—C4	1.384 (4)	Ag1—N2^iii	2.563 (3)
C2—H2	1.081 (7)	Ag1—Ag1^iv	2.949 (6)
C3—N2	1.327 (4)	Fe1—N4^v	1.9263 (16)
C3—N1	1.337 (3)	Fe1—N4	1.9263 (16)
C3—H3	1.082 (6)	Fe1—N3^v	1.9339 (17)
C4—N1	1.342 (3)	Fe1—N3	1.9339 (17)
C4—H4	1.086 (6)	Fe1—N1	1.998 (2)
C5—N4	1.161 (3)	Fe1—N1^v	1.998 (2)
C5—Ag1^i	2.090 (3)	N2—Ag1^vi	2.563 (4)
N2—C1—C2	121.4 (3)	N4—Fe1—N3^v	90.84 (7)
N2—C1—H1	117.2 (5)	N4^v—Fe1—N3	90.84 (7)
C2—C1—H1	121.4 (5)	N4—Fe1—N3	89.16 (7)
C4—C2—C1	117.1 (3)	N3^v—Fe1—N3	180.0
C4—C2—H2	121.1 (5)	N4^v—Fe1—N1	89.38 (8)
C1—C2—H2	121.8 (5)	N4—Fe1—N1	90.62 (8)
N2—C3—N1	125.7 (2)	N3^v—Fe1—N1	87.43 (9)
N2—C3—H3	117.4 (4)	N3—Fe1—N1	92.57 (9)
N1—C3—H3	116.9 (4)	N4^v—Fe1—N1^v	90.62 (8)
N1—C4—C2	121.6 (2)	N4—Fe1—N1^v	89.38 (8)
N1—C4—H4	117.1 (4)	N3^v—Fe1—N1^v	92.57 (9)
C2—C4—H4	121.3 (4)	N3—Fe1—N1^v	87.43 (9)
N4—C5—Ag1^i	174.0 (3)	N1—Fe1—N1^v	180.0
N3—C6—Ag1	172.1 (2)	C3—N1—C4	116.7 (2)
C6—Ag1—C5^ii	159.47 (18)	C3—N1—Fe1	121.16 (17)
C6—Ag1—N2^iii	105.47 (13)	C4—N1—Fe1	122.08 (18)
C5^ii—Ag1—N2^iii	91.16 (13)	C3—N2—C1	117.5 (2)
C6—Ag1—Ag1^iv	108.60 (15)	C3—N2—Ag1^vi	120.06 (17)
C5^ii—Ag1—Ag1^iv	69.38 (13)	C1—N2—Ag1^vi	122.2 (2)
N2^iii—Ag1—Ag1^iv	125.10 (10)	C6—N3—Fe1	168.7 (2)
N4^v—Fe1—N4	180.0	C5—N4—Fe1	174.7 (2)
N4^v—Fe1—N3^v	89.16 (7)

Symmetry codes: (i) −x+1/2, y, z−1/2; (ii) −x+1/2, y, z+1/2; (iii) −x+1, y−1/2, −z+5/2; (iv) −x+1/2, −y+1/2, z; (v) −x+1, −y, −z+2; (vi) −x+1, y+1/2, −z+5/2.

(fepmd2)

Crystal data

C12H8Ag2FeN8	Z = 4
Mr = 535.83	F(000) = 584
Orthorhombic, Pccn	Dx = 2.214 Mg m^−3
Hall symbol: -P 2ab 2ac	Neutron radiation, λ = 0.90-3.00 Å
a = 14.895 (3) Å	µ = 0.08 mm^−1
b = 8.122 (3) Å	T = 187 K
c = 13.288 (3) Å	Prism, orange-yellow
V = 1607.5 (8) Å^3	1.0 × 0.6 × 0.5 mm

Data collection

ILL-VIVALDI Laue single xtal diffractometer	Rint = 0.321
Radiation source: ILL neutron source	θmax = 33.4°, θmin = 4.0°
5504 measured reflections	h = −11→18
1210 independent reflections	k = −9→9
943 reflections with I > 2σ(I)	l = −16→14

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)] = 0.166	Hydrogen site location: difference Fourier map
wR(F^2) = 0.281	All H-atom parameters refined
S = 1.35	w = 1/[σ^2(Fo^2) + (0.P)^2 + 81.4399P] where P = (Fo^2 + 2Fc^2)/3
1210 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 0.90 e Å^−3
0 restraints	Δρmin = −0.99 e Å^−3

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
N3	0.6051 (3)	0.0535 (8)	0.0788 (4)	0.0191 (12)
N4	0.5645 (3)	0.0687 (8)	−0.1195 (3)	0.0206 (12)
N2	0.3744 (4)	0.4577 (8)	−0.0440 (4)	0.0257 (13)
N1	0.4508 (4)	0.2253 (8)	0.0221 (4)	0.0199 (12)
C1	0.6111 (5)	0.0859 (11)	−0.1884 (5)	0.0236 (18)
Ag1	0.7051 (5)	0.0867 (12)	−0.3038 (5)	0.023 (2)
C2	0.6701 (4)	0.0727 (11)	0.1235 (5)	0.0206 (17)
C5	0.4107 (5)	0.4508 (11)	0.1288 (5)	0.0251 (18)
C3	0.4130 (4)	0.3123 (10)	−0.0526 (5)	0.0173 (16)
Fe1	0.5000	0.0000	0.0000	0.015 (2)
C6	0.4503 (5)	0.2987 (11)	0.1134 (5)	0.0218 (17)
C4	0.3707 (7)	0.5234 (12)	0.0472 (6)	0.031 (2)
H5	0.4082 (16)	0.505 (3)	0.2026 (12)	0.058 (6)
H3	0.4147 (13)	0.2541 (18)	−0.1261 (11)	0.034 (4)
H6	0.4838 (13)	0.234 (2)	0.1740 (13)	0.043 (5)
H4	0.3383 (15)	0.645 (3)	0.0523 (16)	0.064 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N3	0.015 (2)	0.027 (3)	0.015 (2)	−0.004 (2)	−0.0018 (18)	−0.001 (2)
N4	0.019 (2)	0.028 (4)	0.015 (2)	0.001 (2)	0.0045 (19)	0.003 (2)
N2	0.035 (3)	0.021 (3)	0.021 (3)	0.006 (3)	−0.002 (2)	0.002 (2)
N1	0.017 (3)	0.029 (4)	0.0138 (19)	0.003 (2)	−0.0008 (19)	−0.001 (2)
C1	0.023 (3)	0.033 (5)	0.014 (3)	0.000 (3)	0.005 (3)	0.005 (3)
Ag1	0.013 (3)	0.037 (6)	0.018 (3)	−0.004 (3)	0.011 (3)	−0.004 (4)
C2	0.018 (3)	0.024 (5)	0.020 (3)	0.000 (3)	−0.004 (3)	0.003 (3)
C5	0.037 (4)	0.018 (5)	0.020 (4)	0.007 (4)	0.001 (3)	−0.003 (3)
C3	0.024 (3)	0.013 (4)	0.016 (3)	0.007 (3)	−0.004 (2)	−0.001 (3)
Fe1	0.010 (4)	0.026 (6)	0.008 (3)	0.002 (2)	0.000 (2)	0.000 (2)
C6	0.030 (4)	0.022 (5)	0.014 (3)	−0.003 (3)	0.003 (3)	−0.003 (3)
C4	0.042 (5)	0.029 (6)	0.023 (4)	0.010 (4)	0.001 (4)	−0.001 (3)
H5	0.079 (14)	0.078 (18)	0.016 (8)	0.017 (11)	0.002 (8)	−0.004 (8)
H3	0.072 (12)	0.015 (9)	0.014 (7)	0.011 (7)	0.008 (6)	−0.001 (5)
H6	0.046 (9)	0.052 (14)	0.030 (9)	0.007 (8)	−0.016 (7)	−0.006 (7)
H4	0.072 (13)	0.056 (15)	0.063 (12)	0.055 (13)	0.009 (10)	0.005 (10)

Geometric parameters (Å, º)

N3—C2	1.148 (8)	Ag1—N2^iii	2.568 (9)
N3—Fe1	1.932 (5)	Ag1—Ag1^iv	2.970 (18)
N4—C1	1.157 (8)	C2—Ag1^v	2.097 (10)
N4—Fe1	1.939 (4)	C5—C4	1.371 (12)
N2—C3	1.318 (10)	C5—C6	1.384 (12)
N2—C4	1.325 (12)	C5—H5	1.073 (19)
N2—Ag1^i	2.568 (9)	C3—H3	1.085 (15)
N1—C3	1.344 (9)	Fe1—N3^vi	1.932 (5)
N1—C6	1.351 (9)	Fe1—N4^vi	1.939 (4)
N1—Fe1	1.992 (6)	Fe1—N1^vi	1.992 (6)
C1—Ag1	2.077 (9)	C6—H6	1.083 (19)
Ag1—C2^ii	2.097 (10)	C4—H4	1.10 (2)
C2—N3—Fe1	174.4 (6)	N3^vi—Fe1—N3	180.0 (3)
C1—N4—Fe1	168.6 (6)	N3^vi—Fe1—N4^vi	88.7 (2)
C3—N2—C4	117.3 (7)	N3—Fe1—N4^vi	91.3 (2)
C3—N2—Ag1^i	119.9 (5)	N3^vi—Fe1—N4	91.3 (2)
C4—N2—Ag1^i	122.4 (6)	N3—Fe1—N4	88.7 (2)
C3—N1—C6	115.4 (6)	N4^vi—Fe1—N4	180.0 (4)
C3—N1—Fe1	121.9 (5)	N3^vi—Fe1—N1	89.4 (2)
C6—N1—Fe1	122.7 (5)	N3—Fe1—N1	90.6 (2)
N4—C1—Ag1	171.5 (7)	N4^vi—Fe1—N1	87.8 (2)
C1—Ag1—C2^ii	159.6 (5)	N4—Fe1—N1	92.2 (2)
C1—Ag1—N2^iii	105.6 (4)	N3^vi—Fe1—N1^vi	90.6 (2)
C2^ii—Ag1—N2^iii	91.4 (4)	N3—Fe1—N1^vi	89.4 (2)
C1—Ag1—Ag1^iv	107.8 (4)	N4^vi—Fe1—N1^vi	92.2 (2)
C2^ii—Ag1—Ag1^iv	69.5 (4)	N4—Fe1—N1^vi	87.8 (2)
N2^iii—Ag1—Ag1^iv	124.9 (3)	N1—Fe1—N1^vi	180.0 (3)
N3—C2—Ag1^v	173.8 (7)	N1—C6—C5	122.0 (7)
C4—C5—C6	116.8 (7)	N1—C6—H6	116.9 (12)
C4—C5—H5	122.2 (14)	C5—C6—H6	121.1 (12)
C6—C5—H5	120.9 (14)	N2—C4—C5	122.2 (9)
N2—C3—N1	126.2 (6)	N2—C4—H4	115.9 (14)
N2—C3—H3	118.7 (10)	C5—C4—H4	121.8 (14)
N1—C3—H3	115.2 (10)

Symmetry codes: (i) −x+1, y+1/2, −z−1/2; (ii) −x+3/2, y, z−1/2; (iii) −x+1, y−1/2, −z−1/2; (iv) −x+3/2, −y+1/2, z; (v) −x+3/2, y, z+1/2; (vi) −x+1, −y, −z.

(fepmd3)

Crystal data

C12H8Ag2FeN8	Z = 4
Mr = 535.83	F(000) = 584
Orthorhombic, Pccn	Dx = 2.010 Mg m^−3
Hall symbol: -P 2ab 2ac	Neutron radiation, λ = 0.95-2.50 Å
a = 15.782 (3) Å	µ = 0.09 mm^−1
b = 8.424 (3) Å	T = 210 K
c = 13.320 (3) Å	Prism, orange-yellow
V = 1770.9 (8) Å^3	1.0 × 0.6 × 0.5 mm

Data collection

ILL-VIVALDI Laue single xtal diffractometer	Rint = 0.259
Radiation source: ILL neutron source	θmax = 29.3°, θmin = 4.0°
2295 measured reflections	h = −17→7
686 independent reflections	k = −8→7
510 reflections with I > 2σ(I)	l = −14→13

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)] = 0.158	Hydrogen site location: difference Fourier map
wR(F^2) = 0.261	All H-atom parameters refined
S = 1.39	w = 1/[σ^2(Fo^2) + (0.0838P)^2] where P = (Fo^2 + 2Fc^2)/3
686 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.66 e Å^−3
0 restraints	Δρmin = −0.75 e Å^−3

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. Restrains used in the refinement EADP C4 H4 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
C1	0.6281 (10)	0.538 (2)	0.9512 (11)	0.046 (4)
C2	0.5878 (9)	0.468 (2)	0.8682 (10)	0.040 (4)
C3	0.5949 (7)	0.3249 (19)	1.0486 (9)	0.033 (3)
C4	0.5498 (11)	0.321 (2)	0.8856 (10)	0.043 (3)
C5	0.3257 (8)	0.0732 (17)	0.8752 (8)	0.036 (3)
C6	0.3852 (7)	0.0778 (19)	1.1965 (8)	0.032 (3)
Ag1	0.2901 (7)	0.0853 (18)	1.3049 (8)	0.029 (4)
Fe1	0.5000	0.0000	1.0000	0.031 (4)
N1	0.5521 (7)	0.2460 (11)	0.9760 (6)	0.036 (3)
N2	0.6296 (6)	0.4686 (14)	1.0395 (7)	0.040 (3)
N3	0.4350 (6)	0.0713 (14)	1.1341 (6)	0.038 (3)
N4	0.3908 (6)	0.0611 (16)	0.9142 (6)	0.041 (3)
H1	0.660 (3)	0.658 (5)	0.944 (3)	0.090 (12)
H2	0.583 (2)	0.530 (4)	0.794 (3)	0.079 (10)
H3	0.5944 (16)	0.259 (4)	1.123 (2)	0.058 (9)
H4	0.515 (2)	0.258 (3)	0.830 (2)	0.043 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.049 (9)	0.051 (12)	0.038 (9)	−0.009 (9)	−0.006 (7)	−0.005 (9)
C2	0.040 (8)	0.050 (12)	0.029 (8)	0.002 (7)	−0.012 (6)	0.005 (7)
C3	0.039 (7)	0.048 (11)	0.012 (7)	−0.016 (8)	−0.010 (5)	0.000 (8)
C4	0.057 (8)	0.041 (10)	0.032 (6)	0.003 (7)	−0.003 (7)	0.018 (7)
C5	0.016 (6)	0.056 (11)	0.036 (7)	0.002 (7)	−0.013 (5)	−0.006 (7)
C6	0.028 (7)	0.048 (11)	0.019 (6)	0.005 (6)	0.013 (5)	0.002 (6)
Ag1	0.017 (6)	0.037 (12)	0.033 (7)	0.000 (7)	0.011 (5)	0.018 (6)
Fe1	0.041 (9)	0.035 (13)	0.015 (7)	0.009 (6)	−0.005 (5)	−0.005 (4)
N1	0.039 (6)	0.053 (8)	0.017 (4)	−0.002 (5)	0.001 (5)	0.005 (4)
N2	0.031 (5)	0.053 (8)	0.036 (6)	−0.008 (5)	0.007 (4)	−0.007 (5)
N3	0.030 (5)	0.061 (8)	0.023 (5)	−0.004 (6)	0.007 (4)	0.000 (4)
N4	0.037 (6)	0.051 (8)	0.036 (6)	0.006 (6)	−0.001 (5)	0.006 (6)
H1	0.12 (3)	0.05 (3)	0.10 (3)	−0.04 (3)	0.01 (2)	0.00 (2)
H2	0.10 (3)	0.07 (3)	0.07 (2)	−0.013 (19)	0.000 (19)	0.007 (18)
H3	0.033 (16)	0.08 (3)	0.06 (2)	−0.024 (14)	−0.007 (13)	0.003 (16)
H4	0.057 (8)	0.041 (10)	0.032 (6)	0.003 (7)	−0.003 (7)	0.018 (7)

Geometric parameters (Å, º)

C1—N2	1.31 (2)	C6—N3	1.146 (12)
C1—C2	1.40 (2)	C6—Ag1	2.083 (15)
C1—H1	1.14 (5)	Ag1—C5^ii	2.056 (17)
C2—C4	1.40 (2)	Ag1—N2^iii	2.621 (15)
C2—H2	1.12 (5)	Ag1—Ag1^iv	3.05 (3)
C3—N2	1.334 (17)	Fe1—N4	2.130 (10)
C3—N1	1.353 (17)	Fe1—N4^v	2.130 (10)
C3—H3	1.13 (4)	Fe1—N3	2.145 (9)
C4—N1	1.359 (16)	Fe1—N3^v	2.145 (9)
C4—H4	1.06 (5)	Fe1—N1^v	2.252 (10)
C5—N4	1.157 (14)	Fe1—N1	2.252 (10)
C5—Ag1^i	2.056 (17)	N2—Ag1^vi	2.621 (15)
N2—C1—C2	122.1 (16)	N4^v—Fe1—N3	90.4 (3)
N2—C1—H1	117 (2)	N4—Fe1—N3^v	90.4 (3)
C2—C1—H1	120 (2)	N4^v—Fe1—N3^v	89.6 (3)
C1—C2—C4	115.6 (15)	N3—Fe1—N3^v	180.000 (2)
C1—C2—H2	122 (2)	N4—Fe1—N1^v	90.2 (4)
C4—C2—H2	122 (2)	N4^v—Fe1—N1^v	89.8 (4)
N2—C3—N1	125.8 (12)	N3—Fe1—N1^v	88.0 (4)
N2—C3—H3	121.8 (17)	N3^v—Fe1—N1^v	92.0 (4)
N1—C3—H3	112.3 (18)	N4—Fe1—N1	89.8 (4)
N1—C4—C2	123.1 (15)	N4^v—Fe1—N1	90.2 (4)
N1—C4—H4	113.9 (18)	N3—Fe1—N1	92.0 (4)
C2—C4—H4	123.0 (16)	N3^v—Fe1—N1	88.0 (4)
N4—C5—Ag1^i	177.7 (14)	N1^v—Fe1—N1	180.0000 (10)
N3—C6—Ag1	177.0 (11)	C3—N1—C4	114.8 (13)
C5^ii—Ag1—C6	162.7 (8)	C3—N1—Fe1	122.2 (9)
C5^ii—Ag1—N2^iii	92.9 (6)	C4—N1—Fe1	122.8 (10)
C6—Ag1—N2^iii	100.9 (6)	C1—N2—C3	118.4 (12)
C5^ii—Ag1—Ag1^iv	71.1 (6)	C1—N2—Ag1^vi	123.5 (11)
C6—Ag1—Ag1^iv	109.1 (7)	C3—N2—Ag1^vi	117.8 (8)
N2^iii—Ag1—Ag1^iv	122.8 (5)	C6—N3—Fe1	161.1 (11)
N4—Fe1—N4^v	180.000 (3)	C5—N4—Fe1	168.9 (12)
N4—Fe1—N3	89.6 (3)

Symmetry codes: (i) −x+1/2, y, z−1/2; (ii) −x+1/2, y, z+1/2; (iii) −x+1, y−1/2, −z+5/2; (iv) −x+1/2, −y+1/2, z; (v) −x+1, −y, −z+2; (vi) −x+1, y+1/2, −z+5/2.

(fepmd4)

Crystal data

C12H8Ag2FeN8	Z = 4
Mr = 535.83	F(000) = 584
Orthorhombic, Pccn	Dx = 2.056 Mg m^−3
Hall symbol: -P 2ab 2ac	Neutron radiation, λ = 0.90-3.00 Å
a = 15.782 (3) Å	µ = 0.09 mm^−1
b = 8.235 (3) Å	T = 240 K
c = 13.319 (3) Å	Prism, orange-yellow
V = 1731.0 (8) Å^3	1.0 × 0.6 × 0.5 mm

Data collection

ILL-VIVALDI Laue single xtal diffractometer	Rint = 0.267
Radiation source: ILL neutron source	θmax = 29.3°, θmin = 4.0°
3616 measured reflections	h = −17→11
788 independent reflections	k = −8→8
641 reflections with I > 2σ(I)	l = −14→13

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)] = 0.128	Hydrogen site location: difference Fourier map
wR(F^2) = 0.207	All H-atom parameters refined
S = 1.28	w = 1/[σ^2(Fo^2) + (0.0724P)^2 + 8.3726P] where P = (Fo^2 + 2Fc^2)/3
788 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 0.62 e Å^−3
0 restraints	Δρmin = −0.58 e Å^−3

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
C1	0.6297 (6)	0.5398 (14)	0.9508 (7)	0.045 (2)
C2	0.5869 (6)	0.4671 (12)	0.8703 (7)	0.041 (2)
C3	0.5932 (5)	0.3246 (11)	1.0485 (6)	0.034 (2)
C4	0.5496 (5)	0.3200 (12)	0.8861 (7)	0.041 (2)
C5	0.3268 (5)	0.0757 (10)	0.8742 (5)	0.0335 (19)
C6	0.3858 (4)	0.0805 (11)	1.1973 (5)	0.032 (2)
Ag1	0.2915 (4)	0.0843 (11)	1.3041 (6)	0.034 (2)
Fe1	0.5000	0.0000	1.0000	0.022 (2)
N1	0.5530 (4)	0.2461 (7)	0.9759 (4)	0.0312 (15)
N2	0.6307 (4)	0.4688 (9)	1.0403 (5)	0.0429 (17)
N3	0.4359 (3)	0.0709 (8)	1.1342 (4)	0.0364 (16)
N4	0.3907 (3)	0.0604 (8)	0.9147 (4)	0.0352 (15)
H1	0.6609 (16)	0.655 (3)	0.9432 (16)	0.084 (7)
H2	0.5845 (15)	0.528 (3)	0.793 (2)	0.088 (7)
H3	0.5947 (13)	0.265 (2)	1.1221 (14)	0.070 (6)
H4	0.5157 (14)	0.258 (2)	0.8279 (15)	0.060 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.059 (6)	0.030 (6)	0.047 (6)	−0.010 (5)	0.000 (4)	0.004 (5)
C2	0.064 (6)	0.023 (5)	0.035 (6)	−0.010 (4)	−0.004 (4)	0.008 (4)
C3	0.042 (4)	0.040 (6)	0.020 (5)	−0.012 (4)	−0.010 (3)	0.002 (5)
C4	0.053 (5)	0.039 (6)	0.032 (5)	0.002 (5)	−0.002 (4)	0.000 (5)
C5	0.030 (4)	0.038 (6)	0.033 (4)	0.002 (4)	−0.010 (3)	0.001 (4)
C6	0.030 (4)	0.043 (6)	0.024 (4)	0.007 (3)	0.010 (3)	0.000 (3)
Ag1	0.025 (4)	0.041 (7)	0.036 (5)	0.005 (4)	0.008 (3)	0.009 (4)
Fe1	0.021 (5)	0.031 (7)	0.015 (4)	0.000 (3)	0.002 (2)	0.005 (3)
N1	0.036 (3)	0.037 (4)	0.021 (3)	−0.007 (3)	−0.003 (2)	0.005 (2)
N2	0.050 (4)	0.039 (4)	0.039 (4)	−0.014 (3)	−0.003 (3)	−0.006 (3)
N3	0.031 (3)	0.050 (5)	0.027 (3)	0.001 (3)	0.009 (2)	−0.003 (3)
N4	0.034 (3)	0.040 (4)	0.032 (3)	0.000 (3)	−0.004 (3)	0.004 (3)
H1	0.131 (19)	0.064 (17)	0.058 (14)	−0.040 (16)	0.015 (11)	−0.006 (11)
H2	0.108 (17)	0.077 (16)	0.079 (17)	−0.015 (12)	−0.005 (13)	0.036 (14)
H3	0.105 (16)	0.079 (16)	0.025 (10)	−0.025 (11)	−0.016 (8)	0.021 (9)
H4	0.113 (15)	0.029 (12)	0.038 (11)	−0.014 (9)	−0.029 (10)	0.018 (8)

Geometric parameters (Å, º)

C1—N2	1.328 (13)	C6—N3	1.157 (8)
C1—C2	1.402 (13)	C6—Ag1	2.059 (10)
C1—H1	1.07 (3)	Ag1—C5^ii	2.088 (10)
C2—C4	1.364 (14)	Ag1—N2^iii	2.590 (10)
C2—H2	1.15 (3)	Ag1—Ag1^iv	3.026 (18)
C3—N1	1.325 (10)	Fe1—N4^v	2.125 (6)
C3—N2	1.331 (10)	Fe1—N4	2.125 (6)
C3—H3	1.10 (2)	Fe1—N3^v	2.135 (5)
C4—N1	1.342 (11)	Fe1—N3	2.135 (5)
C4—H4	1.07 (3)	Fe1—N1^v	2.216 (5)
C5—N4	1.150 (9)	Fe1—N1	2.216 (5)
C5—Ag1^i	2.088 (10)	N2—Ag1^vi	2.590 (10)
N2—C1—C2	120.3 (10)	N4—Fe1—N3^v	90.07 (19)
N2—C1—H1	117.9 (15)	N4^v—Fe1—N3	90.07 (19)
C2—C1—H1	121.7 (15)	N4—Fe1—N3	89.93 (19)
C4—C2—C1	118.0 (9)	N3^v—Fe1—N3	180.0000 (10)
C4—C2—H2	120.9 (15)	N4^v—Fe1—N1^v	90.9 (2)
C1—C2—H2	121.2 (15)	N4—Fe1—N1^v	89.1 (2)
N1—C3—N2	126.1 (7)	N3^v—Fe1—N1^v	92.9 (2)
N1—C3—H3	116.4 (12)	N3—Fe1—N1^v	87.1 (2)
N2—C3—H3	117.6 (12)	N4^v—Fe1—N1	89.1 (2)
N1—C4—C2	121.5 (9)	N4—Fe1—N1	90.9 (2)
N1—C4—H4	116.7 (12)	N3^v—Fe1—N1	87.1 (2)
C2—C4—H4	121.7 (11)	N3—Fe1—N1	92.9 (2)
N4—C5—Ag1^i	175.3 (8)	N1^v—Fe1—N1	180.0000 (10)
N3—C6—Ag1	175.7 (8)	C3—N1—C4	116.6 (7)
C6—Ag1—C5^ii	162.6 (5)	C3—N1—Fe1	121.4 (5)
C6—Ag1—N2^iii	101.8 (4)	C4—N1—Fe1	121.9 (6)
C5^ii—Ag1—N2^iii	93.1 (4)	C1—N2—C3	117.4 (8)
C6—Ag1—Ag1^iv	109.1 (4)	C1—N2—Ag1^vi	124.2 (7)
C5^ii—Ag1—Ag1^iv	69.1 (3)	C3—N2—Ag1^vi	118.3 (5)
N2^iii—Ag1—Ag1^iv	122.5 (3)	C6—N3—Fe1	161.9 (6)
N4^v—Fe1—N4	180.0000 (10)	C5—N4—Fe1	171.2 (7)
N4^v—Fe1—N3^v	89.93 (19)

Symmetry codes: (i) −x+1/2, y, z−1/2; (ii) −x+1/2, y, z+1/2; (iii) −x+1, y−1/2, −z+5/2; (iv) −x+1/2, −y+1/2, z; (v) −x+1, −y, −z+2; (vi) −x+1, y+1/2, −z+5/2.

(fepmd5)

Crystal data

C12H8Ag2FeN8	Z = 4
Mr = 535.83	F(000) = 584
Orthorhombic, Pccn	Dx = 2.048 Mg m^−3
Hall symbol: -P 2ab 2ac	Neutron radiation, λ = 0.90-3.00 Å
a = 15.780 (3) Å	µ = 0.08 mm^−1
b = 8.250 (3) Å	T = 260 K
c = 13.350 (3) Å	Prism, orange-yellow
V = 1738.0 (8) Å^3	1.0 × 0.6 × 0.5 mm

Data collection

ILL-VIVALDI Laue single xtal diffractometer	Rint = 0.185
Radiation source: ILL neutron source	θmax = 30.0°, θmin = 3.1°
5945 measured reflections	h = −11→19
1291 independent reflections	k = −10→8
978 reflections with I > 2σ(I)	l = −14→16

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)] = 0.079	Hydrogen site location: difference Fourier map
wR(F^2) = 0.155	All H-atom parameters refined
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0716P)^2] where P = (Fo^2 + 2Fc^2)/3
1291 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 0.51 e Å^−3
0 restraints	Δρmin = −0.56 e Å^−3

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
C1	0.6286 (3)	0.5387 (5)	0.9507 (3)	0.0471 (9)
C2	0.5875 (2)	0.4688 (5)	0.8702 (3)	0.0480 (10)
C3	0.59351 (19)	0.3249 (4)	1.0487 (2)	0.0374 (8)
C4	0.5498 (2)	0.3205 (4)	0.8869 (3)	0.0384 (8)
C5	0.32727 (16)	0.0750 (4)	0.8729 (2)	0.0356 (8)
C6	0.38492 (18)	0.0786 (4)	1.1965 (2)	0.0358 (8)
Ag1	0.29081 (19)	0.0830 (4)	1.3049 (3)	0.0372 (9)
Fe1	0.5000	0.0000	1.0000	0.0231 (8)
N1	0.55374 (14)	0.2462 (3)	0.97579 (19)	0.0322 (6)
N2	0.63144 (17)	0.4672 (3)	1.0406 (2)	0.0452 (7)
N3	0.43561 (13)	0.0713 (3)	1.13422 (17)	0.0375 (6)
N4	0.39103 (12)	0.0615 (3)	0.91522 (17)	0.0353 (6)
H1	0.6603 (6)	0.6569 (12)	0.9466 (8)	0.085 (3)
H2	0.5851 (7)	0.5267 (12)	0.7998 (9)	0.085 (3)
H3	0.5952 (6)	0.2641 (10)	1.1219 (6)	0.070 (3)
H4	0.5149 (6)	0.2582 (9)	0.8289 (7)	0.067 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.057 (2)	0.042 (2)	0.042 (2)	−0.0141 (18)	0.0019 (16)	0.0039 (19)
C2	0.058 (2)	0.048 (2)	0.038 (2)	−0.0088 (17)	0.0010 (16)	0.0085 (19)
C3	0.0419 (16)	0.043 (2)	0.028 (2)	−0.0089 (15)	−0.0037 (13)	0.0024 (16)
C4	0.0452 (17)	0.041 (2)	0.0287 (18)	−0.0040 (15)	−0.0033 (14)	0.0037 (16)
C5	0.0246 (14)	0.051 (2)	0.0317 (18)	0.0005 (14)	−0.0081 (11)	0.0043 (15)
C6	0.0302 (14)	0.045 (2)	0.0322 (19)	0.0034 (14)	0.0110 (12)	−0.0023 (14)
Ag1	0.0292 (15)	0.044 (2)	0.039 (2)	0.0074 (15)	0.0145 (14)	0.0045 (17)
Fe1	0.0148 (13)	0.035 (2)	0.020 (2)	−0.0013 (10)	0.0016 (8)	0.0005 (11)
N1	0.0310 (11)	0.0395 (16)	0.0261 (11)	−0.0050 (8)	−0.0015 (10)	0.0005 (10)
N2	0.0512 (15)	0.0466 (16)	0.0377 (17)	−0.0155 (12)	−0.0040 (11)	−0.0013 (12)
N3	0.0326 (11)	0.0504 (17)	0.0295 (13)	0.0019 (11)	0.0114 (9)	−0.0019 (11)
N4	0.0230 (10)	0.0483 (15)	0.0345 (13)	0.0021 (10)	−0.0084 (9)	0.0038 (11)
H1	0.102 (6)	0.066 (6)	0.086 (7)	−0.039 (6)	−0.001 (5)	0.009 (5)
H2	0.115 (8)	0.079 (7)	0.062 (7)	−0.011 (5)	0.001 (5)	0.022 (5)
H3	0.109 (7)	0.071 (6)	0.030 (4)	−0.031 (5)	−0.014 (4)	0.017 (4)
H4	0.088 (5)	0.062 (6)	0.050 (5)	−0.024 (4)	−0.026 (4)	0.004 (4)

Geometric parameters (Å, º)

C1—N2	1.338 (5)	C6—N3	1.156 (4)
C1—C2	1.382 (6)	C6—Ag1	2.073 (4)
C1—H1	1.097 (10)	Ag1—C5^ii	2.074 (4)
C2—C4	1.378 (6)	Ag1—N2^iii	2.583 (4)
C2—H2	1.055 (13)	Ag1—Ag1^iv	3.042 (7)
C3—N2	1.323 (4)	Fe1—N4^v	2.120 (2)
C3—N1	1.328 (4)	Fe1—N4	2.120 (2)
C3—H3	1.098 (9)	Fe1—N3^v	2.142 (2)
C4—N1	1.337 (4)	Fe1—N3	2.142 (2)
C4—H4	1.080 (9)	Fe1—N1	2.225 (2)
C5—N4	1.159 (3)	Fe1—N1^v	2.225 (2)
C5—Ag1^i	2.074 (4)	N2—Ag1^vi	2.583 (4)
N2—C1—C2	121.9 (4)	N4—Fe1—N3^v	90.22 (9)
N2—C1—H1	115.0 (7)	N4^v—Fe1—N3	90.22 (9)
C2—C1—H1	123.1 (7)	N4—Fe1—N3	89.78 (9)
C4—C2—C1	116.6 (4)	N3^v—Fe1—N3	180.0000 (10)
C4—C2—H2	122.0 (7)	N4^v—Fe1—N1	89.25 (9)
C1—C2—H2	121.4 (7)	N4—Fe1—N1	90.75 (9)
N2—C3—N1	126.0 (3)	N3^v—Fe1—N1	87.04 (10)
N2—C3—H3	117.9 (5)	N3—Fe1—N1	92.96 (10)
N1—C3—H3	116.1 (5)	N4^v—Fe1—N1^v	90.75 (9)
N1—C4—C2	122.0 (3)	N4—Fe1—N1^v	89.25 (9)
N1—C4—H4	116.2 (5)	N3^v—Fe1—N1^v	92.96 (10)
C2—C4—H4	121.8 (5)	N3—Fe1—N1^v	87.04 (10)
N4—C5—Ag1^i	175.0 (3)	N1—Fe1—N1^v	180.0
N3—C6—Ag1	177.3 (3)	C3—N1—C4	116.7 (3)
C6—Ag1—C5^ii	161.5 (2)	C3—N1—Fe1	121.3 (2)
C6—Ag1—N2^iii	102.16 (15)	C4—N1—Fe1	122.0 (2)
C5^ii—Ag1—N2^iii	93.74 (16)	C3—N2—C1	116.8 (3)
C6—Ag1—Ag1^iv	108.60 (17)	C3—N2—Ag1^vi	118.5 (2)
C5^ii—Ag1—Ag1^iv	69.41 (15)	C1—N2—Ag1^vi	124.7 (3)
N2^iii—Ag1—Ag1^iv	122.41 (12)	C6—N3—Fe1	160.9 (2)
N4^v—Fe1—N4	180.0	C5—N4—Fe1	170.8 (3)
N4^v—Fe1—N3^v	89.78 (9)

Symmetry codes: (i) −x+1/2, y, z−1/2; (ii) −x+1/2, y, z+1/2; (iii) −x+1, y−1/2, −z+5/2; (iv) −x+1/2, −y+1/2, z; (v) −x+1, −y, −z+2; (vi) −x+1, y+1/2, −z+5/2.

(fepmd6)

Crystal data

C12H8Ag2FeN8	Z = 4
Mr = 535.83	F(000) = 584
Orthorhombic, Pccn	Dx = 2.214 Mg m^−3
Hall symbol: -P 2ab 2ac	Neutron radiation, λ = 0.90-3.00 Å
a = 14.895 (3) Å	µ = 0.09 mm^−1
b = 8.125 (3) Å	T = 200 K
c = 13.286 (3) Å	Prism, orange-yellow
V = 1607.9 (8) Å^3	1.0 × 0.6 × 0.5 mm

Data collection

ILL-VIVALDI Laue single xtal diffractometer	Rint = 0.366
Radiation source: ILL neutron source	θmax = 30.9°, θmin = 4.0°
4785 measured reflections	h = −11→17
991 independent reflections	k = −9→9
735 reflections with I > 2σ(I)	l = −15→14

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)] = 0.172	Hydrogen site location: difference Fourier map
wR(F^2) = 0.337	All H-atom parameters refined
S = 1.36	w = 1/[σ^2(Fo^2) + (0.1301P)^2 + 25.1243P] where P = (Fo^2 + 2Fc^2)/3
991 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 1.05 e Å^−3
0 restraints	Δρmin = −0.88 e Å^−3

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
N3	0.6048 (4)	0.0531 (11)	0.0781 (5)	0.0229 (18)
N4	0.5640 (4)	0.0670 (10)	−0.1198 (4)	0.0234 (18)
N2	0.3751 (5)	0.4576 (12)	−0.0434 (5)	0.030 (2)
N1	0.4508 (5)	0.2259 (10)	0.0222 (5)	0.0226 (19)
C1	0.6111 (6)	0.0859 (13)	−0.1884 (7)	0.024 (2)
Ag1	0.7059 (7)	0.0869 (15)	−0.3036 (7)	0.025 (3)
C2	0.6704 (6)	0.0729 (14)	0.1241 (6)	0.024 (2)
C5	0.4107 (7)	0.4509 (15)	0.1293 (8)	0.029 (3)
C3	0.4125 (6)	0.3112 (14)	−0.0531 (6)	0.021 (2)
Fe1	0.5000	0.0000	0.0000	0.016 (3)
C6	0.4513 (6)	0.2986 (15)	0.1133 (7)	0.025 (3)
C4	0.3704 (9)	0.5225 (18)	0.0466 (8)	0.037 (3)
H5	0.4070 (17)	0.503 (3)	0.2006 (16)	0.049 (7)
H3	0.4167 (14)	0.257 (2)	−0.1281 (14)	0.035 (6)
H6	0.4848 (16)	0.236 (2)	0.1755 (16)	0.040 (6)
H4	0.3363 (18)	0.641 (4)	0.0529 (16)	0.067 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N3	0.017 (3)	0.032 (5)	0.020 (4)	0.002 (3)	−0.003 (3)	−0.003 (3)
N4	0.024 (3)	0.032 (5)	0.014 (3)	−0.005 (3)	0.006 (3)	0.005 (3)
N2	0.040 (4)	0.038 (5)	0.013 (4)	0.012 (4)	−0.002 (3)	0.007 (3)
N1	0.026 (4)	0.032 (5)	0.010 (3)	0.002 (3)	0.000 (3)	−0.001 (3)
C1	0.028 (5)	0.033 (7)	0.012 (4)	−0.002 (4)	0.008 (4)	0.008 (4)
Ag1	0.022 (5)	0.039 (9)	0.014 (5)	−0.002 (5)	0.006 (4)	−0.006 (5)
C2	0.025 (5)	0.033 (7)	0.013 (4)	0.011 (4)	−0.001 (4)	0.005 (4)
C5	0.045 (6)	0.024 (7)	0.018 (6)	0.007 (5)	0.000 (4)	−0.005 (5)
C3	0.030 (5)	0.020 (7)	0.015 (6)	0.011 (5)	−0.001 (4)	0.001 (4)
Fe1	0.015 (5)	0.015 (8)	0.017 (5)	0.008 (4)	−0.005 (3)	0.000 (3)
C6	0.030 (5)	0.031 (7)	0.014 (5)	0.007 (5)	−0.001 (4)	−0.007 (5)
C4	0.051 (8)	0.044 (9)	0.016 (6)	0.006 (6)	−0.007 (5)	−0.001 (5)
H5	0.068 (15)	0.06 (2)	0.019 (12)	0.014 (12)	0.010 (9)	−0.005 (10)
H3	0.061 (14)	0.038 (15)	0.007 (10)	0.012 (10)	−0.004 (8)	0.003 (7)
H6	0.071 (15)	0.019 (15)	0.031 (13)	0.022 (10)	−0.013 (10)	0.003 (8)
H4	0.080 (17)	0.09 (2)	0.035 (13)	0.057 (18)	0.002 (11)	−0.023 (12)

Geometric parameters (Å, º)

N3—C2	1.165 (11)	Ag1—N2^iii	2.587 (12)
N3—Fe1	1.923 (6)	Ag1—Ag1^iv	2.96 (2)
N4—C1	1.160 (11)	C2—Ag1^v	2.080 (13)
N4—Fe1	1.934 (6)	C5—C4	1.381 (16)
N2—C4	1.309 (16)	C5—C6	1.393 (16)
N2—C3	1.320 (14)	C5—H5	1.04 (3)
N2—Ag1^i	2.587 (12)	C3—H3	1.09 (2)
N1—C3	1.344 (12)	Fe1—N3^vi	1.923 (6)
N1—C6	1.347 (12)	Fe1—N4^vi	1.934 (6)
N1—Fe1	1.998 (8)	Fe1—N1^vi	1.998 (8)
C1—Ag1	2.083 (12)	C6—H6	1.09 (2)
Ag1—C2^ii	2.080 (13)	C4—H4	1.09 (4)
C2—N3—Fe1	174.7 (8)	N3—Fe1—N3^vi	180.0 (4)
C1—N4—Fe1	169.1 (8)	N3—Fe1—N4	88.9 (3)
C4—N2—C3	118.4 (9)	N3^vi—Fe1—N4	91.1 (3)
C4—N2—Ag1^i	121.9 (9)	N3—Fe1—N4^vi	91.1 (3)
C3—N2—Ag1^i	119.1 (6)	N3^vi—Fe1—N4^vi	88.9 (3)
C3—N1—C6	116.4 (9)	N4—Fe1—N4^vi	180.0 (6)
C3—N1—Fe1	121.3 (6)	N3—Fe1—N1	90.7 (3)
C6—N1—Fe1	122.3 (7)	N3^vi—Fe1—N1	89.3 (3)
N4—C1—Ag1	171.0 (9)	N4—Fe1—N1	92.5 (3)
C2^ii—Ag1—C1	160.0 (6)	N4^vi—Fe1—N1	87.5 (3)
C2^ii—Ag1—N2^iii	91.6 (4)	N3—Fe1—N1^vi	89.3 (3)
C1—Ag1—N2^iii	105.1 (5)	N3^vi—Fe1—N1^vi	90.7 (3)
C2^ii—Ag1—Ag1^iv	69.9 (5)	N4—Fe1—N1^vi	87.5 (3)
C1—Ag1—Ag1^iv	107.7 (5)	N4^vi—Fe1—N1^vi	92.5 (3)
N2^iii—Ag1—Ag1^iv	124.8 (4)	N1—Fe1—N1^vi	180.0 (5)
N3—C2—Ag1^v	173.5 (9)	N1—C6—C5	121.6 (9)
C4—C5—C6	116.2 (10)	N1—C6—H6	118.5 (14)
C4—C5—H5	121.9 (17)	C5—C6—H6	119.9 (13)
C6—C5—H5	121.7 (16)	N2—C4—C5	122.2 (13)
N2—C3—N1	124.9 (8)	N2—C4—H4	116.8 (16)
N2—C3—H3	118.6 (13)	C5—C4—H4	120.8 (16)
N1—C3—H3	116.5 (14)

Symmetry codes: (i) −x+1, y+1/2, −z−1/2; (ii) −x+3/2, y, z−1/2; (iii) −x+1, y−1/2, −z−1/2; (iv) −x+3/2, −y+1/2, z; (v) −x+3/2, y, z+1/2; (vi) −x+1, −y, −z.

(fepmd7)

Crystal data

C12H8Ag2FeN8	Z = 4
Mr = 535.83	F(000) = 584
Orthorhombic, Pccn	Dx = 2.055 Mg m^−3
Hall symbol: -P 2ab 2ac	Neutron radiation, λ = 0.90-3.00 Å
a = 15.782 (3) Å	µ = 0.09 mm^−1
b = 8.235 (3) Å	T = 250 K
c = 13.325 (3) Å	Prism, orange-yellow
V = 1731.8 (8) Å^3	1.0 × 0.6 × 0.5 mm

Data collection

ILL-VIVALDI Laue single xtal diffractometer	Rint = 0.378
Radiation source: ILL neutron source	θmax = 31.1°, θmin = 4.3°
2764 measured reflections	h = −17→10
661 independent reflections	k = −8→8
600 reflections with I > 2σ(I)	l = −14→13

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)] = 0.192	Hydrogen site location: difference Fourier map
wR(F^2) = 0.346	All H-atom parameters refined
S = 1.54	w = 1/[σ^2(Fo^2) + (0.0553P)^2 + 130.1284P] where P = (Fo^2 + 2Fc^2)/3
661 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 0.79 e Å^−3
0 restraints	Δρmin = −0.75 e Å^−3

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
C1	0.6307 (15)	0.545 (3)	0.9491 (15)	0.048 (5)
C2	0.5871 (11)	0.470 (2)	0.8693 (15)	0.037 (5)
C3	0.5949 (10)	0.325 (2)	1.0500 (11)	0.037 (5)
C4	0.5489 (12)	0.320 (3)	0.8849 (15)	0.041 (5)
C5	0.3278 (10)	0.077 (2)	0.8743 (11)	0.034 (4)
C6	0.3878 (10)	0.083 (2)	1.1957 (10)	0.031 (4)
Ag1	0.2901 (11)	0.087 (2)	1.3045 (11)	0.031 (5)
Fe1	0.5000	0.0000	1.0000	0.019 (5)
N1	0.5525 (8)	0.2448 (13)	0.9752 (9)	0.026 (3)
N2	0.6311 (9)	0.4681 (17)	1.0401 (9)	0.041 (4)
N3	0.4369 (7)	0.0673 (17)	1.1340 (8)	0.035 (3)
N4	0.3907 (8)	0.0590 (17)	0.9138 (8)	0.035 (3)
H1	0.660 (3)	0.650 (8)	0.946 (3)	0.089 (18)
H2	0.593 (3)	0.521 (6)	0.794 (4)	0.083 (14)
H3	0.592 (2)	0.264 (5)	1.123 (3)	0.059 (11)
H4	0.518 (3)	0.261 (4)	0.828 (3)	0.049 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.062 (14)	0.046 (13)	0.037 (12)	−0.017 (12)	0.001 (10)	0.005 (12)
C2	0.041 (11)	0.029 (11)	0.040 (13)	−0.009 (9)	−0.002 (8)	0.018 (8)
C3	0.042 (10)	0.056 (13)	0.013 (10)	−0.029 (10)	−0.015 (6)	0.010 (8)
C4	0.033 (10)	0.059 (15)	0.030 (10)	0.020 (10)	0.005 (8)	0.016 (11)
C5	0.021 (8)	0.042 (12)	0.037 (9)	0.011 (8)	−0.018 (7)	−0.002 (8)
C6	0.037 (9)	0.035 (11)	0.020 (8)	0.003 (8)	0.002 (7)	−0.002 (7)
Ag1	0.030 (9)	0.040 (14)	0.024 (8)	0.007 (8)	0.004 (7)	0.009 (8)
Fe1	0.032 (11)	0.019 (13)	0.006 (8)	−0.004 (6)	0.006 (5)	−0.002 (5)
N1	0.025 (6)	0.030 (7)	0.024 (5)	−0.009 (5)	0.000 (5)	−0.001 (5)
N2	0.048 (8)	0.042 (9)	0.032 (8)	−0.013 (7)	0.005 (6)	−0.011 (6)
N3	0.025 (6)	0.055 (9)	0.024 (7)	−0.005 (7)	0.021 (5)	−0.007 (5)
N4	0.030 (7)	0.042 (8)	0.032 (7)	0.001 (7)	−0.008 (5)	0.013 (6)
H1	0.12 (4)	0.10 (4)	0.04 (3)	−0.07 (4)	0.02 (2)	0.00 (3)
H2	0.09 (3)	0.10 (4)	0.06 (3)	−0.01 (3)	0.01 (2)	0.01 (3)
H3	0.06 (3)	0.08 (3)	0.03 (2)	−0.01 (2)	−0.020 (16)	0.013 (19)
H4	0.09 (3)	0.012 (19)	0.04 (2)	−0.019 (18)	−0.02 (2)	0.016 (15)

Geometric parameters (Å, º)

C1—N2	1.37 (3)	C6—N3	1.137 (18)
C1—C2	1.41 (3)	C6—Ag1	2.12 (2)
C1—H1	0.98 (8)	Ag1—C5^ii	2.08 (2)
C2—C4	1.39 (3)	Ag1—N2^iii	2.61 (2)
C2—H2	1.09 (6)	Ag1—Ag1^iv	2.97 (4)
C3—N2	1.32 (2)	Fe1—N3^v	2.119 (10)
C3—N1	1.37 (2)	Fe1—N3	2.119 (10)
C3—H3	1.10 (4)	Fe1—N4^v	2.128 (11)
C4—N1	1.35 (2)	Fe1—N4	2.128 (11)
C4—H4	1.02 (6)	Fe1—N1^v	2.205 (11)
C5—N4	1.135 (18)	Fe1—N1	2.205 (11)
C5—Ag1^i	2.08 (2)	N2—Ag1^vi	2.61 (2)
N2—C1—C2	118 (2)	N3—Fe1—N4^v	89.2 (4)
N2—C1—H1	116 (3)	N3^v—Fe1—N4	89.2 (4)
C2—C1—H1	126 (3)	N3—Fe1—N4	90.8 (4)
C4—C2—C1	119.1 (18)	N4^v—Fe1—N4	180.000 (2)
C4—C2—H2	121 (3)	N3^v—Fe1—N1^v	93.6 (5)
C1—C2—H2	119 (3)	N3—Fe1—N1^v	86.4 (5)
N2—C3—N1	124.7 (14)	N4^v—Fe1—N1^v	90.8 (5)
N2—C3—H3	121 (2)	N4—Fe1—N1^v	89.2 (5)
N1—C3—H3	114 (2)	N3^v—Fe1—N1	86.4 (5)
N1—C4—C2	121 (2)	N3—Fe1—N1	93.6 (5)
N1—C4—H4	118 (3)	N4^v—Fe1—N1	89.2 (5)
C2—C4—H4	121 (2)	N4—Fe1—N1	90.8 (5)
N4—C5—Ag1^i	174.4 (17)	N1^v—Fe1—N1	180.0000 (10)
N3—C6—Ag1	173.5 (16)	C4—N1—C3	116.6 (16)
C5^ii—Ag1—C6	163.1 (10)	C4—N1—Fe1	122.3 (14)
C5^ii—Ag1—N2^iii	93.3 (8)	C3—N1—Fe1	121.0 (10)
C6—Ag1—N2^iii	101.0 (8)	C3—N2—C1	120.1 (17)
C5^ii—Ag1—Ag1^iv	69.7 (8)	C3—N2—Ag1^vi	117.6 (11)
C6—Ag1—Ag1^iv	109.0 (9)	C1—N2—Ag1^vi	122.2 (15)
N2^iii—Ag1—Ag1^iv	122.9 (6)	C6—N3—Fe1	163.5 (12)
N3^v—Fe1—N3	180.000 (3)	C5—N4—Fe1	172.1 (13)
N3^v—Fe1—N4^v	90.8 (4)

Symmetry codes: (i) −x+1/2, y, z−1/2; (ii) −x+1/2, y, z+1/2; (iii) −x+1, y−1/2, −z+5/2; (iv) −x+1/2, −y+1/2, z; (v) −x+1, −y, −z+2; (vi) −x+1, y+1/2, −z+5/2.

(fepmd8)

Crystal data

C12H8Ag2FeN8	Z = 4
Mr = 535.83	F(000) = 584
Orthorhombic, Pccn	Dx = 2.045 Mg m^−3
Hall symbol: -P 2ab 2ac	Neutron radiation, λ = 0.90-3.00 Å
a = 15.782 (3) Å	µ = 0.09 mm^−1
b = 8.262 (3) Å	T = 280 K
c = 13.350 (3) Å	Prism, orange-yellow
V = 1740.7 (8) Å^3	1.0 × 0.6 × 0.5 mm

Data collection

ILL-VIVALDI Laue single xtal diffractometer	Rint = 0.300
Radiation source: ILL neutron source	θmax = 28.6°, θmin = 3.9°
3564 measured reflections	h = −17→11
797 independent reflections	k = −8→8
674 reflections with I > 2σ(I)	l = −14→13

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)] = 0.169	Hydrogen site location: difference Fourier map
wR(F^2) = 0.259	All H-atom parameters refined
S = 1.51	w = 1/[σ^2(Fo^2) + (0.0661P)^2 + 21.984P] where P = (Fo^2 + 2Fc^2)/3
797 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 0.70 e Å^−3
0 restraints	Δρmin = −0.57 e Å^−3

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
C1	0.6308 (9)	0.5371 (17)	0.9510 (9)	0.055 (3)
C2	0.5872 (7)	0.4672 (15)	0.8704 (9)	0.049 (3)
C3	0.5940 (6)	0.3236 (14)	1.0490 (7)	0.041 (3)
C4	0.5495 (7)	0.3195 (15)	0.8862 (8)	0.045 (3)
C5	0.3278 (6)	0.0762 (13)	0.8728 (6)	0.041 (3)
C6	0.3858 (6)	0.0792 (13)	1.1962 (6)	0.036 (2)
Ag1	0.2906 (6)	0.0842 (14)	1.3043 (7)	0.041 (3)
Fe1	0.5000	0.0000	1.0000	0.026 (3)
N1	0.5530 (5)	0.2461 (8)	0.9762 (5)	0.0345 (18)
N2	0.6312 (5)	0.4680 (10)	1.0409 (6)	0.049 (2)
N3	0.4353 (4)	0.0700 (10)	1.1338 (5)	0.042 (2)
N4	0.3909 (4)	0.0606 (10)	0.9147 (5)	0.0411 (19)
H1	0.661 (2)	0.656 (4)	0.944 (2)	0.100 (10)
H2	0.589 (2)	0.527 (4)	0.796 (2)	0.103 (10)
H3	0.5930 (16)	0.265 (3)	1.1205 (19)	0.074 (8)
H4	0.5158 (18)	0.259 (3)	0.8274 (19)	0.067 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.069 (8)	0.042 (7)	0.053 (8)	−0.021 (7)	0.002 (6)	0.008 (7)
C2	0.057 (7)	0.050 (8)	0.041 (7)	−0.013 (6)	−0.002 (5)	0.011 (5)
C3	0.046 (6)	0.051 (8)	0.027 (6)	−0.021 (6)	−0.004 (4)	0.000 (6)
C4	0.048 (6)	0.052 (8)	0.034 (6)	−0.002 (6)	−0.004 (5)	0.007 (6)
C5	0.030 (5)	0.053 (7)	0.039 (5)	0.004 (5)	−0.011 (4)	0.003 (5)
C6	0.035 (5)	0.043 (7)	0.031 (5)	0.004 (4)	0.011 (4)	−0.004 (4)
Ag1	0.029 (5)	0.053 (8)	0.042 (6)	0.005 (5)	0.011 (4)	0.009 (5)
Fe1	0.026 (6)	0.040 (8)	0.014 (5)	−0.003 (4)	−0.002 (3)	0.003 (3)
N1	0.037 (4)	0.041 (5)	0.025 (3)	−0.008 (3)	−0.001 (3)	0.003 (3)
N2	0.055 (5)	0.049 (5)	0.042 (5)	−0.014 (4)	−0.001 (4)	−0.004 (4)
N3	0.036 (4)	0.057 (6)	0.033 (4)	0.005 (4)	0.013 (3)	−0.004 (3)
N4	0.031 (4)	0.051 (5)	0.041 (4)	0.000 (4)	−0.007 (3)	0.004 (4)
H1	0.13 (3)	0.11 (2)	0.064 (17)	−0.07 (2)	0.005 (14)	0.016 (15)
H2	0.13 (3)	0.11 (2)	0.07 (2)	−0.027 (18)	0.000 (17)	0.033 (17)
H3	0.083 (19)	0.09 (2)	0.047 (14)	−0.031 (14)	−0.014 (11)	0.020 (13)
H4	0.110 (19)	0.043 (16)	0.048 (14)	−0.007 (12)	−0.033 (13)	0.017 (10)

Geometric parameters (Å, º)

C1—N2	1.329 (16)	C6—N3	1.145 (10)
C1—C2	1.401 (17)	C6—Ag1	2.083 (13)
C1—H1	1.10 (4)	Ag1—C5^ii	2.082 (13)
C2—C4	1.375 (17)	Ag1—N2^iii	2.592 (12)
C2—H2	1.11 (3)	Ag1—Ag1^iv	3.02 (2)
C3—N1	1.332 (12)	Fe1—N4	2.124 (7)
C3—N2	1.333 (13)	Fe1—N4^v	2.124 (7)
C3—H3	1.07 (3)	Fe1—N3	2.138 (6)
C4—N1	1.346 (13)	Fe1—N3^v	2.138 (6)
C4—H4	1.07 (3)	Fe1—N1^v	2.222 (6)
C5—N4	1.150 (11)	Fe1—N1	2.222 (7)
C5—Ag1^i	2.082 (13)	N2—Ag1^vi	2.592 (12)
N2—C1—C2	121.2 (12)	N4^v—Fe1—N3	90.2 (2)
N2—C1—H1	117.3 (19)	N4—Fe1—N3^v	90.2 (2)
C2—C1—H1	121.3 (18)	N4^v—Fe1—N3^v	89.8 (2)
C4—C2—C1	117.4 (11)	N3—Fe1—N3^v	180.0000 (10)
C4—C2—H2	122.8 (19)	N4—Fe1—N1^v	89.3 (3)
C1—C2—H2	119 (2)	N4^v—Fe1—N1^v	90.7 (3)
N1—C3—N2	125.8 (9)	N3—Fe1—N1^v	87.0 (3)
N1—C3—H3	115.3 (16)	N3^v—Fe1—N1^v	93.0 (3)
N2—C3—H3	118.8 (15)	N4—Fe1—N1	90.7 (3)
N1—C4—C2	121.3 (10)	N4^v—Fe1—N1	89.3 (3)
N1—C4—H4	117.6 (15)	N3—Fe1—N1	93.0 (3)
C2—C4—H4	121.1 (14)	N3^v—Fe1—N1	87.0 (3)
N4—C5—Ag1^i	174.3 (9)	N1^v—Fe1—N1	180.0000 (10)
N3—C6—Ag1	176.0 (9)	C3—N1—C4	117.0 (9)
C5^ii—Ag1—C6	162.0 (7)	C3—N1—Fe1	121.2 (7)
C5^ii—Ag1—N2^iii	93.7 (5)	C4—N1—Fe1	121.6 (7)
C6—Ag1—N2^iii	101.6 (5)	C1—N2—C3	117.1 (10)
C5^ii—Ag1—Ag1^iv	69.4 (5)	C1—N2—Ag1^vi	124.3 (8)
C6—Ag1—Ag1^iv	108.9 (5)	C3—N2—Ag1^vi	118.4 (6)
N2^iii—Ag1—Ag1^iv	122.5 (4)	C6—N3—Fe1	162.2 (7)
N4—Fe1—N4^v	180.000 (2)	C5—N4—Fe1	171.8 (8)
N4—Fe1—N3	89.8 (2)

Symmetry codes: (i) −x+1/2, y, z−1/2; (ii) −x+1/2, y, z+1/2; (iii) −x+1, y−1/2, −z+5/2; (iv) −x+1/2, −y+1/2, z; (v) −x+1, −y, −z+2; (vi) −x+1, y+1/2, −z+5/2.

(fepmd9)

Crystal data

C12H8Ag2FeN8	Z = 4
Mr = 535.83	F(000) = 584
Orthorhombic, Pccn	Dx = 2.060 Mg m^−3
Hall symbol: -P 2ab 2ac	Neutron radiation, λ = 1.10-2.50 Å
a = 15.782 (3) Å	µ = 0.09 mm^−1
b = 8.229 (3) Å	T = 250 K
c = 13.304 (3) Å	Prism, orange-yellow
V = 1727.8 (8) Å^3	1.0 × 0.6 × 0.5 mm

Data collection

ILL-VIVALDI Laue single xtal diffractometer	Rint = 0.242
Radiation source: ILL neutron source	θmax = 30.0°, θmin = 3.5°
2910 measured reflections	h = −17→10
772 independent reflections	k = −8→8
618 reflections with I > 2σ(I)	l = −14→12

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)] = 0.155	Hydrogen site location: difference Fourier map
wR(F^2) = 0.194	All H-atom parameters refined
S = 1.45	w = 1/[σ^2(Fo^2) + (0.016P)^2 + 13.6689P] where P = (Fo^2 + 2Fc^2)/3
772 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 0.59 e Å^−3
0 restraints	Δρmin = −0.68 e Å^−3

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
C1	0.6292 (9)	0.5383 (17)	0.9501 (9)	0.055 (3)
C2	0.5870 (7)	0.4697 (14)	0.8692 (9)	0.045 (3)
C3	0.5938 (6)	0.3268 (13)	1.0481 (7)	0.039 (3)
C4	0.5497 (7)	0.3208 (16)	0.8862 (7)	0.046 (3)
C5	0.3275 (6)	0.0737 (13)	0.8739 (6)	0.042 (3)
C6	0.3859 (6)	0.0801 (13)	1.1955 (6)	0.036 (2)
Ag1	0.2907 (6)	0.0847 (14)	1.3034 (7)	0.038 (3)
Fe1	0.5000	0.0000	1.0000	0.029 (3)
N1	0.5529 (5)	0.2465 (8)	0.9760 (5)	0.0340 (18)
N2	0.6304 (6)	0.4701 (10)	1.0393 (5)	0.047 (2)
N3	0.4354 (4)	0.0681 (10)	1.1341 (5)	0.044 (2)
N4	0.3906 (5)	0.0606 (10)	0.9141 (4)	0.043 (2)
H1	0.6617 (19)	0.657 (4)	0.9412 (19)	0.100 (10)
H2	0.5879 (17)	0.522 (3)	0.798 (2)	0.087 (8)
H3	0.5932 (14)	0.263 (3)	1.1249 (15)	0.065 (7)
H4	0.5128 (17)	0.257 (2)	0.8273 (18)	0.063 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.076 (9)	0.045 (8)	0.043 (7)	−0.005 (7)	0.001 (6)	0.001 (7)
C2	0.050 (7)	0.030 (8)	0.054 (8)	−0.010 (6)	−0.008 (6)	0.005 (6)
C3	0.052 (6)	0.044 (8)	0.021 (6)	−0.018 (6)	−0.003 (4)	0.011 (5)
C4	0.048 (7)	0.060 (9)	0.029 (6)	0.007 (7)	−0.006 (5)	0.007 (6)
C5	0.040 (5)	0.046 (7)	0.040 (5)	0.011 (6)	−0.017 (4)	−0.008 (5)
C6	0.038 (5)	0.045 (7)	0.025 (5)	−0.007 (5)	0.014 (4)	−0.008 (4)
Ag1	0.034 (6)	0.045 (8)	0.036 (6)	0.003 (6)	0.007 (4)	0.009 (5)
Fe1	0.034 (6)	0.034 (9)	0.019 (5)	−0.001 (4)	0.001 (3)	0.000 (3)
N1	0.038 (4)	0.042 (5)	0.022 (3)	−0.008 (3)	−0.002 (3)	0.002 (3)
N2	0.057 (5)	0.047 (6)	0.037 (5)	−0.016 (4)	0.006 (4)	−0.005 (4)
N3	0.036 (4)	0.063 (6)	0.032 (4)	0.007 (4)	0.011 (3)	−0.006 (3)
N4	0.039 (4)	0.057 (6)	0.033 (4)	0.002 (4)	−0.006 (3)	0.008 (4)
H1	0.14 (3)	0.10 (2)	0.061 (17)	−0.06 (2)	0.013 (14)	0.015 (15)
H2	0.091 (19)	0.10 (2)	0.065 (17)	−0.011 (15)	0.001 (14)	−0.001 (16)
H3	0.077 (17)	0.084 (19)	0.034 (12)	−0.035 (12)	−0.019 (10)	0.014 (11)
H4	0.11 (2)	0.033 (17)	0.044 (13)	0.010 (12)	−0.021 (12)	0.001 (10)

Geometric parameters (Å, º)

C1—N2	1.313 (15)	C6—N3	1.136 (9)
C1—C2	1.385 (15)	C6—Ag1	2.078 (12)
C1—H1	1.11 (4)	Ag1—C5^ii	2.089 (13)
C2—C4	1.379 (15)	Ag1—N2^iii	2.611 (12)
C2—H2	1.04 (4)	Ag1—Ag1^iv	3.01 (2)
C3—N2	1.318 (12)	Fe1—N3^v	2.129 (6)
C3—N1	1.331 (12)	Fe1—N3	2.129 (6)
C3—H3	1.15 (2)	Fe1—N4^v	2.130 (7)
C4—N1	1.343 (11)	Fe1—N4	2.130 (7)
C4—H4	1.11 (3)	Fe1—N1	2.217 (7)
C5—N4	1.136 (10)	Fe1—N1^v	2.217 (7)
C5—Ag1^i	2.089 (13)	N2—Ag1^vi	2.611 (12)
N2—C1—C2	122.4 (12)	N3—Fe1—N4^v	90.0 (2)
N2—C1—H1	117.7 (17)	N3^v—Fe1—N4	90.0 (2)
C2—C1—H1	119.9 (16)	N3—Fe1—N4	90.0 (2)
C4—C2—C1	116.0 (11)	N4^v—Fe1—N4	180.0000 (10)
C4—C2—H2	121.7 (18)	N3^v—Fe1—N1	86.6 (3)
C1—C2—H2	122.1 (18)	N3—Fe1—N1	93.4 (3)
N2—C3—N1	126.3 (8)	N4^v—Fe1—N1	89.2 (3)
N2—C3—H3	119.5 (13)	N4—Fe1—N1	90.8 (3)
N1—C3—H3	114.1 (14)	N3^v—Fe1—N1^v	93.4 (3)
N1—C4—C2	122.3 (11)	N3—Fe1—N1^v	86.6 (3)
N1—C4—H4	115.6 (15)	N4^v—Fe1—N1^v	90.8 (3)
C2—C4—H4	122.1 (13)	N4—Fe1—N1^v	89.2 (3)
N4—C5—Ag1^i	176.7 (10)	N1—Fe1—N1^v	180.0000 (10)
N3—C6—Ag1	175.3 (9)	C3—N1—C4	115.7 (9)
C6—Ag1—C5^ii	162.6 (6)	C3—N1—Fe1	122.2 (6)
C6—Ag1—N2^iii	101.7 (5)	C4—N1—Fe1	122.0 (7)
C5^ii—Ag1—N2^iii	92.9 (4)	C1—N2—C3	117.1 (9)
C6—Ag1—Ag1^iv	109.0 (5)	C1—N2—Ag1^vi	125.2 (8)
C5^ii—Ag1—Ag1^iv	70.0 (5)	C3—N2—Ag1^vi	117.5 (6)
N2^iii—Ag1—Ag1^iv	122.0 (4)	C6—N3—Fe1	162.8 (8)
N3^v—Fe1—N3	180.000 (2)	C5—N4—Fe1	170.4 (9)
N3^v—Fe1—N4^v	90.0 (2)

Symmetry codes: (i) −x+1/2, y, z−1/2; (ii) −x+1/2, y, z+1/2; (iii) −x+1, y−1/2, −z+5/2; (iv) −x+1/2, −y+1/2, z; (v) −x+1, −y, −z+2; (vi) −x+1, y+1/2, −z+5/2.

(fepmd10)

Crystal data

C12H8Ag2FeN8	Z = 4
Mr = 535.83	F(000) = 584
Orthorhombic, Pccn	Dx = 2.077 Mg m^−3
Hall symbol: -P 2ab 2ac	Neutron radiation, λ = 0.90-3.00 Å
a = 15.780 (3) Å	µ = 0.08 mm^−1
b = 8.200 (3) Å	T = 220 K
c = 13.240 (3) Å	Prism, orange-yellow
V = 1713.2 (8) Å^3	1.0 × 0.6 × 0.5 mm

Data collection

ILL-VIVALDI Laue single xtal diffractometer	Rint = 0.357
Radiation source: ILL neutron source	θmax = 24.5°, θmin = 3.2°
3553 measured reflections	h = −7→18
973 independent reflections	k = −8→9
743 reflections with I > 2σ(I)	l = −15→14

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)] = 0.167	Hydrogen site location: difference Fourier map
wR(F^2) = 0.307	All H-atom parameters refined
S = 1.40	w = 1/[σ^2(Fo^2) + (0.0516P)^2 + 58.4407P] where P = (Fo^2 + 2Fc^2)/3
973 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 0.69 e Å^−3
0 restraints	Δρmin = −0.82 e Å^−3

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
C1	0.6289 (8)	0.5408 (17)	0.9490 (9)	0.044 (3)
C2	0.5862 (7)	0.4690 (16)	0.8683 (8)	0.040 (3)
C3	0.5952 (6)	0.3251 (15)	1.0484 (7)	0.033 (3)
C4	0.5486 (7)	0.3201 (17)	0.8839 (8)	0.039 (3)
C5	0.3272 (6)	0.0750 (13)	0.8738 (7)	0.032 (2)
C6	0.3866 (6)	0.0818 (14)	1.1971 (6)	0.031 (2)
Ag1	0.2919 (6)	0.0837 (16)	1.3055 (7)	0.034 (3)
Fe1	0.5000	0.0000	1.0000	0.024 (3)
N1	0.5520 (5)	0.2464 (9)	0.9761 (5)	0.0309 (18)
N2	0.6309 (5)	0.4692 (11)	1.0406 (6)	0.039 (2)
N3	0.4365 (4)	0.0707 (11)	1.1344 (5)	0.0347 (19)
N4	0.3906 (4)	0.0607 (11)	0.9153 (5)	0.0344 (19)
H1	0.6606 (18)	0.655 (4)	0.9430 (19)	0.075 (9)
H2	0.584 (2)	0.527 (4)	0.794 (2)	0.085 (9)
H3	0.5943 (15)	0.264 (3)	1.1198 (18)	0.050 (6)
H4	0.5158 (18)	0.258 (3)	0.8284 (19)	0.053 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.053 (7)	0.037 (7)	0.044 (7)	−0.009 (7)	0.003 (5)	0.006 (6)
C2	0.045 (6)	0.045 (8)	0.030 (6)	−0.006 (5)	−0.003 (4)	0.007 (5)
C3	0.027 (5)	0.043 (8)	0.027 (6)	−0.017 (5)	−0.007 (4)	−0.002 (5)
C4	0.040 (6)	0.055 (8)	0.023 (5)	0.008 (6)	0.000 (4)	0.010 (6)
C5	0.027 (5)	0.040 (7)	0.031 (5)	0.013 (5)	−0.011 (4)	−0.001 (5)
C6	0.032 (5)	0.040 (7)	0.022 (4)	0.010 (4)	0.006 (4)	−0.001 (4)
Ag1	0.026 (5)	0.045 (8)	0.030 (5)	0.012 (5)	0.012 (4)	0.010 (5)
Fe1	0.020 (5)	0.041 (9)	0.010 (5)	0.002 (4)	0.001 (3)	−0.001 (3)
N1	0.025 (4)	0.046 (5)	0.022 (3)	−0.006 (3)	−0.004 (3)	0.003 (3)
N2	0.043 (5)	0.043 (5)	0.029 (4)	−0.007 (4)	−0.001 (3)	−0.001 (3)
N3	0.030 (4)	0.049 (5)	0.025 (4)	−0.002 (4)	0.009 (3)	−0.006 (3)
N4	0.029 (4)	0.045 (5)	0.030 (4)	0.009 (4)	−0.005 (3)	0.001 (4)
H1	0.089 (19)	0.08 (2)	0.060 (15)	−0.057 (18)	0.017 (13)	−0.004 (13)
H2	0.11 (2)	0.08 (2)	0.07 (2)	−0.026 (17)	−0.006 (16)	0.027 (16)
H3	0.068 (15)	0.043 (14)	0.039 (12)	−0.009 (10)	0.000 (10)	−0.002 (10)
H4	0.084 (17)	0.028 (15)	0.046 (14)	−0.020 (11)	−0.009 (12)	0.009 (10)

Geometric parameters (Å, º)

C1—N2	1.348 (16)	C6—N3	1.148 (11)
C1—C2	1.394 (17)	C6—Ag1	2.073 (12)
C1—H1	1.07 (3)	Ag1—C5^ii	2.086 (13)
C2—C4	1.373 (18)	Ag1—N2^iii	2.553 (12)
C2—H2	1.10 (3)	Ag1—Ag1^iv	3.03 (2)
C3—N2	1.313 (14)	Fe1—N4^v	2.118 (7)
C3—N1	1.340 (12)	Fe1—N4	2.118 (7)
C3—H3	1.07 (3)	Fe1—N3	2.123 (6)
C4—N1	1.363 (13)	Fe1—N3^v	2.123 (6)
C4—H4	1.03 (3)	Fe1—N1	2.204 (7)
C5—N4	1.148 (11)	Fe1—N1^v	2.204 (7)
C5—Ag1^i	2.086 (13)	N2—Ag1^vi	2.553 (12)
N2—C1—C2	121.1 (12)	N4—Fe1—N3	89.7 (3)
N2—C1—H1	116.1 (19)	N4^v—Fe1—N3^v	89.7 (3)
C2—C1—H1	122.8 (19)	N4—Fe1—N3^v	90.3 (3)
C4—C2—C1	118.0 (11)	N3—Fe1—N3^v	180.0000 (10)
C4—C2—H2	120 (2)	N4^v—Fe1—N1	89.3 (3)
C1—C2—H2	122 (2)	N4—Fe1—N1	90.7 (3)
N2—C3—N1	126.6 (9)	N3—Fe1—N1	92.6 (3)
N2—C3—H3	119.7 (14)	N3^v—Fe1—N1	87.4 (3)
N1—C3—H3	113.5 (15)	N4^v—Fe1—N1^v	90.7 (3)
N1—C4—C2	120.8 (11)	N4—Fe1—N1^v	89.3 (3)
N1—C4—H4	116.0 (16)	N3—Fe1—N1^v	87.4 (3)
C2—C4—H4	123.2 (15)	N3^v—Fe1—N1^v	92.6 (3)
N4—C5—Ag1^i	175.1 (10)	N1—Fe1—N1^v	180.0000 (10)
N3—C6—Ag1	175.1 (10)	C3—N1—C4	116.5 (10)
C6—Ag1—C5^ii	161.7 (7)	C3—N1—Fe1	121.9 (7)
C6—Ag1—N2^iii	101.9 (5)	C4—N1—Fe1	121.4 (7)
C5^ii—Ag1—N2^iii	94.1 (5)	C3—N2—C1	116.9 (10)
C6—Ag1—Ag1^iv	108.8 (6)	C3—N2—Ag1^vi	118.3 (7)
C5^ii—Ag1—Ag1^iv	68.8 (5)	C1—N2—Ag1^vi	124.7 (8)
N2^iii—Ag1—Ag1^iv	122.6 (4)	C6—N3—Fe1	162.1 (8)
N4^v—Fe1—N4	180.000 (2)	C5—N4—Fe1	171.2 (9)
N4^v—Fe1—N3	90.3 (3)

Symmetry codes: (i) −x+1/2, y, z−1/2; (ii) −x+1/2, y, z+1/2; (iii) −x+1, y−1/2, −z+5/2; (iv) −x+1/2, −y+1/2, z; (v) −x+1, −y, −z+2; (vi) −x+1, y+1/2, −z+5/2.

(fepmd11)

Crystal data

C12H8Ag2FeN8	Z = 4
Mr = 535.83	F(000) = 584
Orthorhombic, Pccn	Dx = 2.062 Mg m^−3
Hall symbol: -P 2ab 2ac	Neutron radiation, λ = 0.90-3.00 Å
a = 15.7820 (15) Å	µ = 0.08 mm^−1
b = 8.2250 (15) Å	T = 260 K
c = 13.2980 (15) Å	Prism, orange-yellow
V = 1726.2 (4) Å^3	1.0 × 0.6 × 0.5 mm

Data collection

ILL-VIVALDI Laue single xtal diffractometer	Rint = 0.221
Radiation source: ILL neutron source	θmax = 27.7°, θmin = 3.6°
5638 measured reflections	h = −11→18
1069 independent reflections	k = −9→9
885 reflections with I > 2σ(I)	l = −15→14

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)] = 0.100	Hydrogen site location: difference Fourier map
wR(F^2) = 0.161	All H-atom parameters refined
S = 1.29	w = 1/[σ^2(Fo^2) + (0.0558P)^2 + 4.1743P] where P = (Fo^2 + 2Fc^2)/3
1069 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 0.60 e Å^−3
0 restraints	Δρmin = −0.57 e Å^−3

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
C1	0.6287 (3)	0.5402 (7)	0.9506 (4)	0.0488 (12)
C2	0.5870 (3)	0.4695 (7)	0.8701 (4)	0.0464 (13)
C3	0.5938 (3)	0.3241 (6)	1.0486 (3)	0.0373 (11)
C4	0.5493 (3)	0.3207 (6)	0.8867 (3)	0.0389 (11)
C5	0.3273 (2)	0.0757 (6)	0.8735 (3)	0.0351 (10)
C6	0.3856 (2)	0.0790 (6)	1.1968 (3)	0.0338 (10)
Ag1	0.2911 (2)	0.0851 (6)	1.3053 (3)	0.0371 (12)
Fe1	0.5000	0.0000	1.0000	0.0236 (11)
N1	0.55311 (19)	0.2470 (3)	0.9755 (2)	0.0312 (8)
N2	0.6316 (2)	0.4678 (5)	1.0403 (3)	0.0448 (9)
N3	0.43573 (17)	0.0711 (4)	1.1348 (2)	0.0371 (8)
N4	0.39087 (16)	0.0608 (4)	0.9150 (2)	0.0361 (8)
H1	0.6601 (9)	0.6579 (16)	0.9446 (9)	0.084 (4)
H2	0.5852 (9)	0.5243 (16)	0.7971 (10)	0.084 (4)
H3	0.5949 (7)	0.2650 (14)	1.1198 (8)	0.069 (3)
H4	0.5152 (8)	0.2584 (13)	0.8278 (9)	0.070 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.063 (3)	0.038 (3)	0.045 (3)	−0.015 (3)	0.005 (2)	0.005 (3)
C2	0.063 (3)	0.039 (3)	0.038 (3)	−0.008 (2)	−0.001 (2)	0.008 (2)
C3	0.046 (2)	0.036 (3)	0.030 (3)	−0.011 (2)	−0.0039 (16)	0.001 (2)
C4	0.048 (2)	0.040 (3)	0.029 (2)	−0.005 (2)	−0.0021 (18)	0.006 (2)
C5	0.0248 (19)	0.046 (3)	0.034 (2)	0.0003 (18)	−0.0078 (15)	0.0035 (19)
C6	0.0341 (19)	0.037 (3)	0.030 (2)	0.0044 (18)	0.0092 (16)	−0.0002 (18)
Ag1	0.031 (2)	0.041 (3)	0.040 (3)	0.005 (2)	0.0146 (18)	0.008 (2)
Fe1	0.021 (2)	0.030 (3)	0.019 (2)	−0.0012 (13)	−0.0007 (11)	0.0000 (13)
N1	0.0352 (15)	0.031 (2)	0.0271 (14)	−0.0049 (11)	−0.0023 (13)	0.0012 (12)
N2	0.055 (2)	0.041 (2)	0.038 (2)	−0.0115 (16)	−0.0017 (15)	−0.0018 (16)
N3	0.0369 (15)	0.045 (2)	0.0297 (16)	0.0026 (15)	0.0115 (12)	−0.0018 (14)
N4	0.0275 (14)	0.046 (2)	0.0352 (17)	0.0017 (14)	−0.0055 (12)	0.0034 (15)
H1	0.122 (9)	0.058 (8)	0.073 (8)	−0.041 (8)	−0.008 (6)	0.016 (6)
H2	0.133 (11)	0.073 (9)	0.047 (7)	−0.019 (7)	−0.004 (6)	0.021 (6)
H3	0.108 (8)	0.071 (8)	0.028 (5)	−0.032 (6)	−0.012 (5)	0.008 (5)
H4	0.091 (7)	0.068 (8)	0.051 (7)	−0.011 (5)	−0.024 (5)	0.003 (5)

Geometric parameters (Å, º)

C1—N2	1.335 (7)	C6—N3	1.145 (5)
C1—C2	1.384 (7)	C6—Ag1	2.075 (5)
C1—H1	1.091 (15)	Ag1—C5^ii	2.079 (5)
C2—C4	1.379 (7)	Ag1—N2^iii	2.576 (5)
C2—H2	1.071 (14)	Ag1—Ag1^iv	3.006 (9)
C3—N1	1.326 (5)	Fe1—N4^v	2.120 (3)
C3—N2	1.328 (6)	Fe1—N4	2.120 (3)
C3—H3	1.065 (12)	Fe1—N3^v	2.141 (3)
C4—N1	1.328 (5)	Fe1—N3	2.141 (3)
C4—H4	1.080 (13)	Fe1—N1	2.221 (3)
C5—N4	1.152 (4)	Fe1—N1^v	2.221 (3)
C5—Ag1^i	2.079 (5)	N2—Ag1^vi	2.576 (5)
N2—C1—C2	121.3 (5)	N4—Fe1—N3^v	90.16 (11)
N2—C1—H1	116.4 (8)	N4^v—Fe1—N3	90.16 (11)
C2—C1—H1	122.2 (8)	N4—Fe1—N3	89.84 (11)
C4—C2—C1	117.0 (5)	N3^v—Fe1—N3	180.0000 (10)
C4—C2—H2	120.4 (8)	N4^v—Fe1—N1	89.28 (12)
C1—C2—H2	122.5 (8)	N4—Fe1—N1	90.72 (12)
N1—C3—N2	125.6 (4)	N3^v—Fe1—N1	87.02 (12)
N1—C3—H3	116.2 (7)	N3—Fe1—N1	92.98 (12)
N2—C3—H3	118.2 (7)	N4^v—Fe1—N1^v	90.72 (12)
N1—C4—C2	121.8 (4)	N4—Fe1—N1^v	89.28 (12)
N1—C4—H4	116.8 (7)	N3^v—Fe1—N1^v	92.98 (12)
C2—C4—H4	121.4 (7)	N3—Fe1—N1^v	87.02 (12)
N4—C5—Ag1^i	175.1 (4)	N1—Fe1—N1^v	180.0
N3—C6—Ag1	177.2 (4)	C3—N1—C4	117.0 (4)
C6—Ag1—C5^ii	161.5 (3)	C3—N1—Fe1	120.8 (3)
C6—Ag1—N2^iii	101.8 (2)	C4—N1—Fe1	122.0 (3)
C5^ii—Ag1—N2^iii	93.7 (2)	C3—N2—C1	117.1 (4)
C6—Ag1—Ag1^iv	109.4 (2)	C3—N2—Ag1^vi	118.7 (3)
C5^ii—Ag1—Ag1^iv	69.24 (19)	C1—N2—Ag1^vi	124.2 (3)
N2^iii—Ag1—Ag1^iv	122.86 (16)	C6—N3—Fe1	161.1 (3)
N4^v—Fe1—N4	180.0000 (10)	C5—N4—Fe1	171.3 (3)
N4^v—Fe1—N3^v	89.84 (11)

Symmetry codes: (i) −x+1/2, y, z−1/2; (ii) −x+1/2, y, z+1/2; (iii) −x+1, y−1/2, −z+5/2; (iv) −x+1/2, −y+1/2, z; (v) −x+1, −y, −z+2; (vi) −x+1, y+1/2, −z+5/2.

(fepmd12)

Crystal data

C12H8Ag2FeN8	Z = 4
Mr = 535.83	F(000) = 584
Orthorhombic, Pccn	Dx = 2.054 Mg m^−3
Hall symbol: -P 2ab 2ac	Neutron radiation, λ = 0.95-2.50 Å
a = 15.782 (3) Å	µ = 0.09 mm^−1
b = 8.242 (3) Å	T = 280 K
c = 13.320 (3) Å	Prism, orange-yellow
V = 1732.6 (8) Å^3	1.0 × 0.6 × 0.5 mm

Data collection

ILL-VIVALDI Laue single xtal diffractometer	Rint = 0.352
Radiation source: ILL neutron source	θmax = 29.3°, θmin = 4.0°
3459 measured reflections	h = −17→11
782 independent reflections	k = −8→8
641 reflections with I > 2σ(I)	l = −14→13

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)] = 0.172	Hydrogen site location: difference Fourier map
wR(F^2) = 0.293	All H-atom parameters refined
S = 1.42	w = 1/[σ^2(Fo^2) + (0.0311P)^2 + 71.9321P] where P = (Fo^2 + 2Fc^2)/3
782 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 0.73 e Å^−3
0 restraints	Δρmin = −0.58 e Å^−3

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
C1	0.6283 (10)	0.537 (2)	0.9494 (11)	0.052 (4)
C2	0.5866 (9)	0.4672 (18)	0.8697 (10)	0.045 (3)
C3	0.5949 (7)	0.3248 (16)	1.0484 (8)	0.037 (3)
C4	0.5492 (8)	0.3209 (19)	0.8862 (10)	0.045 (3)
C5	0.3269 (8)	0.0766 (17)	0.8740 (8)	0.043 (3)
C6	0.3858 (7)	0.0805 (16)	1.1963 (8)	0.037 (3)
Fe1	0.5000	0.0000	1.0000	0.029 (3)
N1	0.5523 (6)	0.2463 (10)	0.9759 (7)	0.036 (2)
N2	0.6307 (6)	0.4686 (12)	1.0403 (7)	0.045 (3)
N3	0.4362 (5)	0.0694 (13)	1.1344 (6)	0.041 (2)
N4	0.3902 (6)	0.0605 (13)	0.9146 (6)	0.042 (2)
Ag1	0.2901 (8)	0.0861 (18)	1.3047 (9)	0.039 (4)
H1	0.661 (3)	0.655 (5)	0.944 (2)	0.104 (14)
H3	0.5933 (19)	0.263 (4)	1.122 (2)	0.071 (9)
H2	0.589 (2)	0.525 (5)	0.794 (3)	0.085 (10)
H4	0.514 (2)	0.255 (3)	0.829 (2)	0.066 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.063 (9)	0.046 (9)	0.047 (9)	−0.003 (8)	0.003 (7)	0.005 (8)
C2	0.058 (8)	0.041 (8)	0.036 (8)	−0.014 (7)	−0.003 (6)	0.005 (6)
C3	0.044 (7)	0.050 (9)	0.016 (6)	−0.021 (7)	−0.009 (5)	0.007 (6)
C4	0.044 (7)	0.054 (10)	0.038 (8)	0.002 (7)	−0.008 (6)	0.010 (7)
C5	0.031 (6)	0.055 (9)	0.044 (6)	0.004 (6)	−0.020 (6)	−0.002 (6)
C6	0.039 (6)	0.045 (8)	0.027 (6)	0.002 (6)	0.009 (5)	−0.002 (5)
Fe1	0.039 (8)	0.035 (9)	0.014 (6)	−0.001 (5)	0.005 (4)	0.005 (4)
N1	0.035 (5)	0.043 (6)	0.028 (4)	−0.005 (4)	−0.004 (4)	0.001 (3)
N2	0.047 (6)	0.045 (6)	0.043 (6)	−0.018 (5)	0.002 (4)	−0.009 (5)
N3	0.033 (5)	0.065 (7)	0.026 (5)	0.001 (5)	0.011 (4)	−0.005 (4)
N4	0.039 (5)	0.050 (6)	0.038 (5)	0.005 (5)	−0.006 (4)	0.000 (5)
Ag1	0.029 (6)	0.055 (11)	0.032 (7)	0.006 (6)	0.011 (5)	0.017 (6)
H1	0.17 (4)	0.09 (3)	0.06 (2)	−0.07 (3)	0.03 (2)	0.005 (17)
H3	0.09 (2)	0.08 (2)	0.046 (18)	−0.041 (17)	−0.015 (13)	0.022 (14)
H2	0.08 (2)	0.10 (3)	0.08 (2)	−0.008 (17)	−0.001 (18)	0.03 (2)
H4	0.13 (3)	0.04 (2)	0.033 (16)	0.003 (15)	−0.029 (15)	−0.004 (11)

Geometric parameters (Å, º)

C1—N2	1.34 (2)	C6—N3	1.150 (13)
C1—C2	1.37 (2)	C6—Ag1	2.088 (15)
C1—H1	1.11 (5)	Fe1—N3	2.132 (8)
C2—C4	1.36 (2)	Fe1—N3^ii	2.132 (8)
C2—H2	1.12 (4)	Fe1—N4	2.132 (9)
C3—N2	1.318 (16)	Fe1—N4^ii	2.132 (9)
C3—N1	1.343 (15)	Fe1—N1^ii	2.214 (9)
C3—H3	1.10 (3)	Fe1—N1	2.214 (9)
C4—N1	1.346 (16)	N2—Ag1^iii	2.601 (15)
C4—H4	1.09 (4)	Ag1—C5^iv	2.067 (16)
C5—N4	1.144 (14)	Ag1—N2^v	2.601 (14)
C5—Ag1^i	2.067 (16)	Ag1—Ag1^vi	2.98 (3)
N2—C1—C2	122.6 (15)	N4—Fe1—N1^ii	89.4 (4)
N2—C1—H1	114 (2)	N4^ii—Fe1—N1^ii	90.6 (4)
C2—C1—H1	123 (2)	N3—Fe1—N1	92.9 (4)
C4—C2—C1	116.9 (13)	N3^ii—Fe1—N1	87.1 (4)
C4—C2—H2	123 (2)	N4—Fe1—N1	90.6 (4)
C1—C2—H2	120 (2)	N4^ii—Fe1—N1	89.4 (4)
N2—C3—N1	126.2 (10)	N1^ii—Fe1—N1	180.0000 (10)
N2—C3—H3	119.7 (17)	C3—N1—C4	115.8 (11)
N1—C3—H3	113.9 (18)	C3—N1—Fe1	121.7 (8)
N1—C4—C2	122.3 (13)	C4—N1—Fe1	122.3 (9)
N1—C4—H4	114 (2)	C3—N2—C1	116.1 (12)
C2—C4—H4	123.2 (18)	C3—N2—Ag1^iii	118.4 (8)
N4—C5—Ag1^i	175.1 (13)	C1—N2—Ag1^iii	125.3 (10)
N3—C6—Ag1	176.0 (12)	C6—N3—Fe1	161.9 (9)
N3—Fe1—N3^ii	180.000 (2)	C5—N4—Fe1	171.6 (11)
N3—Fe1—N4	90.1 (3)	C5^iv—Ag1—C6	162.5 (8)
N3^ii—Fe1—N4	89.9 (3)	C5^iv—Ag1—N2^v	93.4 (6)
N3—Fe1—N4^ii	89.9 (3)	C6—Ag1—N2^v	101.1 (6)
N3^ii—Fe1—N4^ii	90.1 (3)	C5^iv—Ag1—Ag1^vi	69.8 (6)
N4—Fe1—N4^ii	180.000 (2)	C6—Ag1—Ag1^vi	109.1 (7)
N3—Fe1—N1^ii	87.1 (4)	N2^v—Ag1—Ag1^vi	122.8 (5)
N3^ii—Fe1—N1^ii	92.9 (4)

Symmetry codes: (i) −x+1/2, y, z−1/2; (ii) −x+1, −y, −z+2; (iii) −x+1, y+1/2, −z+5/2; (iv) −x+1/2, y, z+1/2; (v) −x+1, y−1/2, −z+5/2; (vi) −x+1/2, −y+1/2, z.

(fepmd13)

Crystal data

C12H8Ag2FeN8	Z = 4
Mr = 535.83	F(000) = 584
Orthorhombic, Pccn	Dx = 2.055 Mg m^−3
Hall symbol: -P 2ab 2ac	Neutron radiation, λ = 0.90-3.00 Å
a = 15.7820 (15) Å	µ = 0.08 mm^−1
b = 8.2430 (15) Å	T = 290 K
c = 13.3100 (15) Å	Prism, orange-yellow
V = 1731.5 (4) Å^3	1.0 × 0.6 × 0.5 mm

Data collection

ILL-VIVALDI Laue single xtal diffractometer	Rint = 0.227
Radiation source: ILL neutron source	θmax = 31.5°, θmin = 4.0°
5485 measured reflections	h = −11→18
1068 independent reflections	k = −9→9
860 reflections with I > 2σ(I)	l = −15→14

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)] = 0.114	Hydrogen site location: difference Fourier map
wR(F^2) = 0.168	All H-atom parameters refined
S = 1.30	w = 1/[σ^2(Fo^2) + (0.0625P)^2 + 3.3037P] where P = (Fo^2 + 2Fc^2)/3
1068 reflections	(Δ/σ)max < 0.001
142 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.54 e Å^−3

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
C1	0.3857 (2)	0.0795 (6)	0.1965 (3)	0.0371 (11)
C2	0.5935 (3)	0.3244 (6)	0.0485 (3)	0.0400 (12)
C3	0.5496 (3)	0.3203 (7)	−0.1137 (3)	0.0426 (12)
C4	0.5869 (3)	0.4685 (7)	−0.1296 (4)	0.0515 (14)
C5	0.3274 (2)	0.0760 (6)	−0.1265 (3)	0.0390 (11)
C6	0.6289 (4)	0.5389 (8)	−0.0496 (4)	0.0512 (13)
Ag1	0.2915 (3)	0.0844 (6)	0.3051 (3)	0.0395 (13)
Fe1	0.5000	0.0000	0.0000	0.0241 (12)
N1	0.39086 (17)	0.0610 (5)	−0.0850 (2)	0.0385 (9)
N2	0.43564 (18)	0.0710 (5)	0.1347 (2)	0.0402 (9)
N3	0.6314 (2)	0.4675 (5)	0.0405 (3)	0.0483 (10)
N4	0.5532 (2)	0.2458 (4)	−0.0243 (2)	0.0342 (8)
H2	0.5953 (8)	0.2643 (15)	0.1200 (8)	0.078 (4)
H3	0.5138 (8)	0.2582 (14)	−0.1714 (9)	0.071 (3)
H4	0.5851 (10)	0.5259 (18)	−0.2041 (11)	0.096 (4)
H6	0.6611 (10)	0.6551 (18)	−0.0562 (10)	0.096 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.039 (2)	0.042 (3)	0.031 (2)	0.004 (2)	0.0100 (17)	−0.0007 (19)
C2	0.048 (2)	0.044 (3)	0.028 (3)	−0.014 (2)	−0.0028 (17)	0.001 (2)
C3	0.054 (3)	0.044 (3)	0.030 (2)	−0.004 (2)	−0.0025 (19)	0.005 (2)
C4	0.070 (3)	0.047 (4)	0.038 (3)	−0.013 (2)	0.003 (2)	0.011 (3)
C5	0.030 (2)	0.053 (3)	0.035 (2)	0.001 (2)	−0.0090 (16)	0.005 (2)
C6	0.067 (3)	0.037 (3)	0.050 (3)	−0.014 (3)	0.002 (2)	0.008 (3)
Ag1	0.035 (2)	0.044 (4)	0.040 (3)	0.008 (2)	0.0155 (18)	0.008 (2)
Fe1	0.021 (2)	0.031 (4)	0.020 (2)	−0.0012 (14)	−0.0003 (12)	−0.0017 (14)
N1	0.0286 (15)	0.050 (2)	0.0374 (19)	0.0018 (15)	−0.0084 (13)	0.0016 (16)
N2	0.0390 (15)	0.051 (3)	0.0307 (17)	0.0029 (16)	0.0131 (13)	−0.0024 (15)
N3	0.062 (2)	0.042 (2)	0.041 (2)	−0.0142 (18)	−0.0026 (16)	−0.0008 (17)
N4	0.0389 (16)	0.035 (2)	0.0288 (15)	−0.0049 (13)	−0.0002 (14)	0.0024 (13)
H2	0.130 (10)	0.071 (9)	0.034 (6)	−0.035 (7)	−0.022 (5)	0.015 (5)
H3	0.104 (8)	0.062 (9)	0.048 (7)	−0.018 (6)	−0.021 (6)	0.007 (5)
H4	0.147 (12)	0.077 (10)	0.065 (9)	−0.027 (8)	−0.008 (7)	0.028 (7)
H6	0.132 (11)	0.074 (10)	0.082 (9)	−0.049 (9)	−0.001 (7)	0.012 (7)

Geometric parameters (Å, º)

C1—N2	1.142 (5)	C6—N3	1.336 (8)
C1—Ag1	2.074 (5)	C6—H6	1.088 (17)
C2—N3	1.327 (6)	Ag1—C5^ii	2.088 (5)
C2—N4	1.329 (6)	Ag1—N3^iii	2.576 (6)
C2—H2	1.073 (13)	Ag1—Ag1^iv	3.028 (10)
C3—N4	1.339 (6)	Fe1—N1^v	2.121 (3)
C3—C4	1.372 (8)	Fe1—N1	2.121 (3)
C3—H3	1.082 (14)	Fe1—N2^v	2.142 (3)
C4—C6	1.381 (8)	Fe1—N2	2.142 (3)
C4—H4	1.100 (16)	Fe1—N4	2.217 (3)
C5—N1	1.150 (5)	Fe1—N4^v	2.217 (3)
C5—Ag1^i	2.088 (5)	N3—Ag1^vi	2.576 (6)
N2—C1—Ag1	176.8 (4)	N1—Fe1—N2^v	90.21 (12)
N3—C2—N4	126.2 (4)	N1^v—Fe1—N2	90.21 (12)
N3—C2—H2	118.1 (7)	N1—Fe1—N2	89.79 (12)
N4—C2—H2	115.8 (7)	N2^v—Fe1—N2	180.00 (15)
N4—C3—C4	121.8 (4)	N1^v—Fe1—N4	89.27 (13)
N4—C3—H3	115.8 (7)	N1—Fe1—N4	90.73 (13)
C4—C3—H3	122.4 (7)	N2^v—Fe1—N4	87.01 (13)
C3—C4—C6	117.4 (5)	N2—Fe1—N4	92.99 (13)
C3—C4—H4	120.7 (9)	N1^v—Fe1—N4^v	90.73 (13)
C6—C4—H4	121.8 (9)	N1—Fe1—N4^v	89.27 (13)
N1—C5—Ag1^i	174.8 (4)	N2^v—Fe1—N4^v	92.99 (13)
N3—C6—C4	121.4 (6)	N2—Fe1—N4^v	87.01 (13)
N3—C6—H6	116.4 (9)	N4—Fe1—N4^v	180.0 (2)
C4—C6—H6	122.2 (9)	C5—N1—Fe1	171.3 (4)
C1—Ag1—C5^ii	161.5 (3)	C1—N2—Fe1	161.4 (4)
C1—Ag1—N3^iii	102.1 (2)	C2—N3—C6	116.8 (4)
C5^ii—Ag1—N3^iii	93.7 (2)	C2—N3—Ag1^vi	118.7 (3)
C1—Ag1—Ag1^iv	109.1 (2)	C6—N3—Ag1^vi	124.5 (4)
C5^ii—Ag1—Ag1^iv	69.0 (2)	C2—N4—C3	116.4 (4)
N3^iii—Ag1—Ag1^iv	122.78 (17)	C2—N4—Fe1	121.3 (3)
N1^v—Fe1—N1	180.0 (3)	C3—N4—Fe1	122.2 (3)
N1^v—Fe1—N2^v	89.79 (12)

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