Ammonium hepta­nitro­syl­tri­thio­tetraferrate monohydrate

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.

Key indicators

• Single-crystal X-ray study
• T = 123 K
• Mean [sigma](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

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Computing details

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).

(I)

Crystal data

(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) Å^3

Data collection

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

Refinement on F^2	0 restraints
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.033	w = 1/[σ^2(Fo^2) + (0.0614P)^2 + 0.3376P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···S3^i	0.85 (8)	3.01 (7)	3.470 (3)	116 (6)
N8—H5···O8^ii	0.89 (5)	2.13 (5)	2.961 (4)	154 (4)
O8—H2···O3^iii	0.83 (6)	2.41 (6)	3.026 (3)	131 (5)
O8—H1···S1^iv	0.76 (7)	2.67 (7)	3.390 (3)	158 (6)
N8—H6···O6^v	0.74 (7)	2.62 (7)	3.120 (4)	126 (6)
N8—H6···S2^vi	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.