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The title compound, (NH4)[Fe4S3(NO)7]·H2O, contains an Fe4S3 partial cubane core in which the apical iron is coordinated by one nitrosyl group and three S atoms above the plane of three Fe atoms. These three Fe atoms are in turn each coordinated by two S atoms and two nitrosyl groups. The axial O atoms hydrogen bond with the ammonium cation, creating a `tight' ion-pair, consistent with the solubility of the salt in diethyl ether.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 123 K
- Mean (O-N) = 0.003 Å
- R factor = 0.033
- wR factor = 0.088
- Data-to-parameter ratio = 11.8
checkCIF/PLATON results
No syntax errors found
Alert level C
CELLV02_ALERT_1_C The supplied cell volume s.u. differs from that
calculated from the cell parameter s.u.'s by > 2
Calculated cell volume su = 21.15
Cell volume su given = 19.00
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Fe1 - N2 = 5.66 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Fe4 - N5 = 5.56 su
PLAT352_ALERT_3_C Short N-H Bond (0.87A) N8 - H6 = 0.75 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor N8 - H6 ... ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4 .. O4 = 2.72 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3 .. O1 = 2.80 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4 .. S3 = 3.01 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6 .. O6 = 2.62 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6 .. S2 = 3.01 Ang.
PLAT482_ALERT_4_C Small D-H..A Angle Rep for N8 .. O1 = 99.00 Deg.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
13 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
6 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: COLLECT (Nonius, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).
Crystal data top
(NH4)[Fe4S3(NO)7]·H2O | Z = 2 |
Mr = 565.71 | F(000) = 556 |
Triclinic, P1 | Dx = 2.384 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4373 (1) Å | Cell parameters from 11004 reflections |
b = 9.9388 (1) Å | θ = 3.8–25° |
c = 10.1736 (2) Å | µ = 4.05 mm−1 |
α = 117.1273 (6)° | T = 123 K |
β = 101.3320 (7)° | Prismatic, black |
γ = 101.0689 (10)° | 0.12 × 0.1 × 0.08 mm |
V = 788.17 (2) Å3 | |
Data collection top
Nonius KappaCCD diffractometer | 2682 reflections with I > 2σ(I) |
CCD rotation images in φ and ω, thick slices scans | Rint = 0.034 |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | θmax = 25.1°, θmin = 3.8° |
Tmin = 0.638, Tmax = 0.715 | h = −11→11 |
11004 measured reflections | k = −11→11 |
2741 independent reflections | l = −12→12 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.033 | w = 1/[σ2(Fo2) + (0.0614P)2 + 0.3376P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.088 | (Δ/σ)max < 0.001 |
S = 1.13 | Δρmax = 0.65 e Å−3 |
2741 reflections | Δρmin = −1.12 e Å−3 |
232 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Fe1 | 0.50426 (4) | 0.74181 (4) | 0.44243 (4) | 0.01483 (14) | |
Fe2 | 0.28128 (4) | 0.54882 (4) | 0.16372 (4) | 0.01298 (13) | |
Fe3 | 0.12048 (4) | 0.72590 (4) | 0.31814 (4) | 0.01668 (14) | |
Fe4 | 0.19493 (4) | 0.38020 (4) | 0.29761 (4) | 0.01602 (14) | |
N1 | 0.4786 (2) | 0.8034 (2) | 0.6159 (2) | 0.0180 (4) | |
N2 | 0.6845 (2) | 0.8060 (3) | 0.4482 (2) | 0.0213 (5) | |
N3 | 0.0011 (2) | 0.7921 (3) | 0.2370 (3) | 0.0218 (5) | |
N4 | 0.1364 (3) | 0.7785 (3) | 0.5033 (3) | 0.0211 (5) | |
N5 | 0.1911 (2) | 0.4675 (3) | 0.4808 (3) | 0.0208 (5) | |
N6 | 0.1539 (3) | 0.1815 (3) | 0.1957 (3) | 0.0232 (5) | |
N7 | 0.3016 (2) | 0.4923 (3) | −0.0111 (3) | 0.0186 (5) | |
N8 | 0.2969 (4) | 0.8292 (4) | 0.9476 (4) | 0.0365 (6) | |
O1 | 0.4908 (3) | 0.8639 (2) | 0.7498 (2) | 0.0297 (5) | |
O2 | 0.8163 (2) | 0.8602 (3) | 0.4823 (3) | 0.0356 (5) | |
O3 | −0.0875 (2) | 0.8521 (2) | 0.2100 (3) | 0.0350 (5) | |
O4 | 0.1328 (3) | 0.8300 (3) | 0.6313 (2) | 0.0372 (5) | |
O5 | 0.1844 (3) | 0.5094 (3) | 0.6063 (2) | 0.0347 (5) | |
O6 | 0.1330 (3) | 0.0451 (3) | 0.1499 (3) | 0.0413 (5) | |
O7 | 0.3221 (3) | 0.4620 (3) | −0.1295 (3) | 0.0422 (6) | |
O8 | 0.6160 (3) | 0.8628 (3) | 1.0422 (3) | 0.0420 (6) | |
S1 | 0.43038 (7) | 0.47319 (7) | 0.29439 (7) | 0.01546 (16) | |
S2 | 0.35208 (7) | 0.81227 (7) | 0.30043 (7) | 0.01673 (17) | |
S3 | 0.04681 (7) | 0.45692 (7) | 0.15951 (7) | 0.01643 (17) | |
H1 | 0.630 (7) | 0.791 (8) | 0.980 (8) | 0.11 (2)* | |
H2 | 0.669 (7) | 0.883 (7) | 1.129 (8) | 0.093 (19)* | |
H3 | 0.391 (5) | 0.826 (5) | 0.976 (5) | 0.048 (11)* | |
H4 | 0.233 (8) | 0.763 (9) | 0.857 (9) | 0.12 (3)* | |
H5 | 0.291 (5) | 0.911 (6) | 0.933 (5) | 0.057 (13)* | |
H6 | 0.269 (8) | 0.839 (8) | 1.014 (8) | 0.11 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Fe1 | 0.0151 (2) | 0.0149 (2) | 0.0143 (2) | 0.00567 (16) | 0.00302 (15) | 0.00770 (16) |
Fe2 | 0.0149 (2) | 0.0140 (2) | 0.0129 (2) | 0.00611 (15) | 0.00429 (15) | 0.00866 (16) |
Fe3 | 0.0172 (2) | 0.0175 (2) | 0.0187 (2) | 0.00970 (16) | 0.00578 (16) | 0.01042 (17) |
Fe4 | 0.0175 (2) | 0.0172 (2) | 0.0194 (2) | 0.00722 (16) | 0.00655 (16) | 0.01327 (17) |
N1 | 0.0204 (11) | 0.0156 (10) | 0.0196 (11) | 0.0077 (8) | 0.0049 (8) | 0.0102 (9) |
N2 | 0.0221 (12) | 0.0172 (10) | 0.0226 (11) | 0.0073 (9) | 0.0065 (9) | 0.0086 (9) |
N3 | 0.0189 (11) | 0.0197 (11) | 0.0289 (12) | 0.0082 (9) | 0.0054 (9) | 0.0142 (10) |
N4 | 0.0213 (11) | 0.0208 (11) | 0.0233 (12) | 0.0112 (9) | 0.0074 (9) | 0.0112 (9) |
N5 | 0.0184 (11) | 0.0252 (12) | 0.0256 (12) | 0.0085 (9) | 0.0071 (9) | 0.0178 (10) |
N6 | 0.0217 (12) | 0.0203 (12) | 0.0299 (12) | 0.0044 (9) | 0.0076 (9) | 0.0161 (10) |
N7 | 0.0168 (11) | 0.0212 (11) | 0.0177 (11) | 0.0048 (9) | 0.0049 (8) | 0.0106 (9) |
N8 | 0.0343 (17) | 0.0350 (16) | 0.0316 (15) | 0.0031 (13) | 0.0104 (13) | 0.0136 (13) |
O1 | 0.0434 (13) | 0.0290 (11) | 0.0183 (10) | 0.0151 (10) | 0.0133 (9) | 0.0109 (8) |
O2 | 0.0186 (11) | 0.0346 (12) | 0.0431 (12) | 0.0042 (9) | 0.0102 (9) | 0.0135 (10) |
O3 | 0.0267 (11) | 0.0305 (11) | 0.0528 (13) | 0.0160 (9) | 0.0060 (9) | 0.0253 (10) |
O4 | 0.0482 (14) | 0.0452 (13) | 0.0232 (11) | 0.0251 (11) | 0.0160 (9) | 0.0159 (10) |
O5 | 0.0454 (14) | 0.0429 (13) | 0.0241 (11) | 0.0181 (11) | 0.0174 (9) | 0.0197 (10) |
O6 | 0.0504 (14) | 0.0195 (11) | 0.0558 (14) | 0.0113 (10) | 0.0189 (11) | 0.0199 (10) |
O7 | 0.0417 (14) | 0.0602 (16) | 0.0215 (11) | 0.0086 (12) | 0.0174 (10) | 0.0187 (11) |
O8 | 0.0574 (16) | 0.0440 (14) | 0.0293 (12) | 0.0363 (13) | 0.0101 (11) | 0.0163 (11) |
S1 | 0.0161 (3) | 0.0156 (3) | 0.0183 (3) | 0.0082 (2) | 0.0051 (2) | 0.0105 (3) |
S2 | 0.0190 (3) | 0.0144 (3) | 0.0196 (3) | 0.0061 (3) | 0.0048 (2) | 0.0111 (3) |
S3 | 0.0144 (3) | 0.0185 (3) | 0.0183 (3) | 0.0061 (2) | 0.0039 (2) | 0.0113 (3) |
Geometric parameters (Å, º) top
Fe1—N1 | 1.670 (2) | Fe4—N6 | 1.675 (2) |
Fe1—N2 | 1.677 (2) | Fe4—S1 | 2.2495 (7) |
Fe1—S1 | 2.2556 (7) | Fe4—S3 | 2.2636 (7) |
Fe1—S2 | 2.2657 (6) | N1—O1 | 1.180 (3) |
Fe1—Fe2 | 2.7005 (5) | N2—O2 | 1.167 (3) |
Fe2—N7 | 1.667 (2) | N3—O3 | 1.175 (3) |
Fe2—S2 | 2.2088 (7) | N4—O4 | 1.172 (3) |
Fe2—S3 | 2.2099 (7) | N5—O5 | 1.168 (3) |
Fe2—S1 | 2.2123 (7) | N6—O6 | 1.175 (3) |
Fe2—Fe3 | 2.7036 (5) | N7—O7 | 1.168 (3) |
Fe2—Fe4 | 2.7058 (5) | N8—H3 | 0.89 (5) |
Fe3—N3 | 1.673 (2) | N8—H4 | 0.85 (8) |
Fe3—N4 | 1.675 (2) | N8—H5 | 0.89 (5) |
Fe3—S2 | 2.2631 (7) | N8—H6 | 0.74 (7) |
Fe3—S3 | 2.2684 (7) | O8—H1 | 0.76 (7) |
Fe4—N5 | 1.671 (2) | O8—H2 | 0.83 (6) |
| | | |
N1—Fe1—N2 | 115.48 (10) | N3—Fe3—Fe2 | 122.60 (8) |
N1—Fe1—S1 | 112.26 (7) | N4—Fe3—Fe2 | 121.74 (7) |
N2—Fe1—S1 | 105.31 (7) | S2—Fe3—Fe2 | 51.891 (18) |
N1—Fe1—S2 | 110.15 (7) | S3—Fe3—Fe2 | 51.881 (18) |
N2—Fe1—S2 | 108.93 (8) | N5—Fe4—N6 | 119.04 (11) |
S1—Fe1—S2 | 103.99 (2) | N5—Fe4—S1 | 110.07 (8) |
N1—Fe1—Fe2 | 124.91 (8) | N6—Fe4—S1 | 103.53 (8) |
N2—Fe1—Fe2 | 119.60 (7) | N5—Fe4—S3 | 109.44 (7) |
S1—Fe1—Fe2 | 52.084 (17) | N6—Fe4—S3 | 109.68 (8) |
S2—Fe1—Fe2 | 51.920 (18) | S1—Fe4—S3 | 103.92 (2) |
N7—Fe2—S2 | 108.69 (8) | N5—Fe4—Fe2 | 122.55 (8) |
N7—Fe2—S3 | 115.11 (8) | N6—Fe4—Fe2 | 118.31 (8) |
S2—Fe2—S3 | 107.40 (3) | S1—Fe4—Fe2 | 52.043 (18) |
N7—Fe2—S1 | 110.97 (8) | S3—Fe4—Fe2 | 51.881 (18) |
S2—Fe2—S1 | 107.38 (2) | O1—N1—Fe1 | 166.7 (2) |
S3—Fe2—S1 | 106.98 (2) | O2—N2—Fe1 | 167.0 (2) |
N7—Fe2—Fe1 | 126.06 (7) | O3—N3—Fe3 | 165.9 (2) |
S2—Fe2—Fe1 | 53.846 (18) | O4—N4—Fe3 | 169.0 (2) |
S3—Fe2—Fe1 | 118.82 (2) | O5—N5—Fe4 | 171.5 (2) |
S1—Fe2—Fe1 | 53.547 (18) | O6—N6—Fe4 | 168.1 (2) |
N7—Fe2—Fe3 | 132.79 (7) | O7—N7—Fe2 | 175.8 (2) |
S2—Fe2—Fe3 | 53.724 (19) | H3—N8—H4 | 122 (5) |
S3—Fe2—Fe3 | 53.860 (19) | H3—N8—H5 | 115 (4) |
S1—Fe2—Fe3 | 116.09 (2) | H4—N8—H5 | 91 (5) |
Fe1—Fe2—Fe3 | 81.880 (14) | H3—N8—H6 | 105 (6) |
N7—Fe2—Fe4 | 131.85 (8) | H4—N8—H6 | 116 (7) |
S2—Fe2—Fe4 | 119.39 (2) | H5—N8—H6 | 108 (5) |
S3—Fe2—Fe4 | 53.692 (19) | H1—O8—H2 | 107 (6) |
S1—Fe2—Fe4 | 53.298 (19) | Fe2—S1—Fe4 | 74.66 (2) |
Fe1—Fe2—Fe4 | 83.901 (14) | Fe2—S1—Fe1 | 74.37 (2) |
Fe3—Fe2—Fe4 | 82.308 (14) | Fe4—S1—Fe1 | 106.68 (3) |
N3—Fe3—N4 | 115.66 (11) | Fe2—S2—Fe3 | 74.38 (2) |
N3—Fe3—S2 | 107.65 (8) | Fe2—S2—Fe1 | 74.23 (2) |
N4—Fe3—S2 | 110.12 (8) | Fe3—S2—Fe1 | 102.87 (3) |
N3—Fe3—S3 | 107.26 (8) | Fe2—S3—Fe4 | 74.43 (2) |
N4—Fe3—S3 | 111.78 (8) | Fe2—S3—Fe3 | 74.26 (2) |
S2—Fe3—S3 | 103.60 (2) | Fe4—S3—Fe3 | 103.53 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N8—H3···O8 | 0.89 (5) | 2.00 (5) | 2.879 (4) | 168 (4) |
N8—H4···O5 | 0.85 (8) | 2.51 (7) | 3.237 (4) | 144 (6) |
N8—H4···O4 | 0.85 (8) | 2.72 (7) | 3.290 (4) | 126 (6) |
N8—H3···O1 | 0.89 (5) | 2.80 (4) | 3.059 (4) | 99 (3) |
N8—H4···S3i | 0.85 (8) | 3.01 (7) | 3.470 (3) | 116 (6) |
N8—H5···O8ii | 0.89 (5) | 2.13 (5) | 2.961 (4) | 154 (4) |
O8—H2···O3iii | 0.83 (6) | 2.41 (6) | 3.026 (3) | 131 (5) |
O8—H1···S1iv | 0.76 (7) | 2.67 (7) | 3.390 (3) | 158 (6) |
N8—H6···O6v | 0.74 (7) | 2.62 (7) | 3.120 (4) | 126 (6) |
N8—H6···S2vi | 0.74 (7) | 3.01 (7) | 3.610 (3) | 139 (6) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+2, −z+2; (iii) x+1, y, z+1; (iv) −x+1, −y+1, −z+1; (v) x, y+1, z+1; (vi) x, y, z+1. |
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