Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The new compound [Fe(H2cit)(H2O)]n (NICS-2) is the first neutral ferrous citrate carboxylate that has been synthesized up to now. The iron citrate coordination polymer was hydrothermally synthesized and the structure was solved using single-crystal X-ray diffraction. It crystallizes in an orthorhombic space group P212121 (No. 19), with a = 5.9470 (4), b = 10.4021 (5), c = 13.5773 (7) Å, V = 839.91 (8) Å3, Z = 4. Its structure consists of one-dimensional chains of corner-sharing FeIIO6 octahedra that are additionally cross-linked with citrate ligands. Chains are additionally stabilized into a pseudo-three-dimensional structure by hydrogen bonds. The measurement of magnetic properties revealed that the magnetic moment is almost constant above 100 K (μeff = 5.1 µB), but decreases rapidly below this temperature most probably due to the appearance of weak antiferromagnetic interactions between Fe atoms. Additionally, analysis of Mossbauer spectra confirmed the presence of divalent Fe atoms in the structure. Thermogravimetrical and X-ray high-temperature diffraction analyses showed the thermal stability of the material up to 548 K.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052519213023713/bp5057sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052519213023713/bp5057Isup2.hkl
Contains datablock I

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2052519213023713/bp5057sup3.pdf
Additional supporting information

CCDC reference: 969685

Experimental top

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Results and discussion top

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3, DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXL2013, WinGX (Faruggia, 2012).

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
(I) top
Crystal data top
C6H8FeO8Dx = 2.088 Mg m3
Mr = 263.97Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 4978 reflections
a = 5.9470 (4) Åθ = 3.0–30.3°
b = 10.4021 (5) ŵ = 1.82 mm1
c = 13.5773 (7) ÅT = 293 K
V = 839.91 (8) Å3Prism, colourless
Z = 40.35 × 0.18 × 0.17 mm
F(000) = 536
Data collection top
SuperNova, Dual, Cu at zero, Atlas
diffractometer
2321 independent reflections
Radiation source: SuperNova (Mo) X-ray2193 reflections with I > 2σ(I)
Detector resolution: 10.4933 pixels mm-1Rint = 0.065
/w scansθmax = 30.4°, θmin = 3.0°
Absorption correction: multi-scan
CrysAlis PRO, (Agilent, 2011)
h = 78
Tmin = 0.568, Tmax = 0.747k = 1114
8571 measured reflectionsl = 1818
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullOnly H-atom displacement parameters refined
R[F2 > 2σ(F2)] = 0.036 w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.102(Δ/σ)max = 0.001
S = 0.81Δρmax = 0.81 e Å3
2321 reflectionsΔρmin = 0.71 e Å3
156 parametersAbsolute structure: Flack x determined using 843 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61).
4 restraintsAbsolute structure parameter: 0.009 (12)
Crystal data top
C6H8FeO8V = 839.91 (8) Å3
Mr = 263.97Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.9470 (4) ŵ = 1.82 mm1
b = 10.4021 (5) ÅT = 293 K
c = 13.5773 (7) Å0.35 × 0.18 × 0.17 mm
Data collection top
SuperNova, Dual, Cu at zero, Atlas
diffractometer
2321 independent reflections
Absorption correction: multi-scan
CrysAlis PRO, (Agilent, 2011)
2193 reflections with I > 2σ(I)
Tmin = 0.568, Tmax = 0.747Rint = 0.065
8571 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.036Only H-atom displacement parameters refined
wR(F2) = 0.102Δρmax = 0.81 e Å3
S = 0.81Δρmin = 0.71 e Å3
2321 reflectionsAbsolute structure: Flack x determined using 843 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61).
156 parametersAbsolute structure parameter: 0.009 (12)
4 restraints
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
xyzUiso*/Ueq
Fe10.41542 (7)0.33217 (4)0.94876 (3)0.01198 (16)
O10.5451 (4)0.4980 (2)0.88421 (18)0.0145 (5)
O20.0928 (4)0.3672 (3)0.8894 (2)0.0210 (5)
O30.2836 (4)0.1695 (2)1.02115 (17)0.0140 (5)
O40.5276 (4)0.2360 (2)0.81842 (17)0.0161 (5)
O50.6089 (5)0.2249 (2)0.65950 (18)0.0192 (5)
O60.9071 (7)0.6263 (3)1.0001 (2)0.0301 (7)
O70.8753 (6)0.8057 (3)0.9114 (2)0.0310 (7)
O80.3431 (5)0.4322 (3)1.0811 (2)0.0251 (6)
C10.7611 (5)0.4767 (3)0.8414 (2)0.0102 (5)
C20.1067 (5)0.3860 (3)0.9094 (2)0.0114 (6)
C30.7328 (7)0.4119 (3)0.7408 (2)0.0154 (6)
H3A0.65050.47000.69810.025 (12)*
H3B0.88070.39990.71220.040 (16)*
C40.6125 (6)0.2829 (3)0.7410 (2)0.0132 (6)
C50.8875 (6)0.6041 (3)0.8271 (2)0.0138 (6)
H5A1.04170.58530.80890.019 (11)*
H5B0.81930.65050.77280.040 (15)*
C60.8888 (6)0.6902 (3)0.9169 (3)0.0162 (6)
H10.487 (7)0.563 (3)0.858 (3)0.012 (11)*
H60.906 (10)0.681 (5)1.044 (3)0.050 (19)*
H8A0.223 (6)0.403 (4)1.106 (3)0.018 (11)*
H8B0.349 (10)0.512 (3)1.086 (4)0.038 (16)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0107 (2)0.0113 (3)0.0138 (2)0.00036 (16)0.00133 (15)0.00232 (17)
O10.0114 (11)0.0103 (11)0.0217 (11)0.0026 (9)0.0035 (8)0.0059 (9)
O20.0113 (11)0.0262 (13)0.0255 (12)0.0015 (10)0.0010 (10)0.0061 (10)
O30.0160 (11)0.0101 (11)0.0161 (10)0.0005 (9)0.0001 (8)0.0041 (9)
O40.0205 (13)0.0144 (11)0.0136 (11)0.0034 (9)0.0008 (8)0.0000 (9)
O50.0258 (14)0.0148 (11)0.0171 (11)0.0053 (11)0.0023 (11)0.0039 (9)
O60.057 (2)0.0171 (13)0.0166 (12)0.0058 (15)0.0058 (13)0.0034 (10)
O70.044 (2)0.0113 (12)0.0374 (16)0.0022 (12)0.0046 (15)0.0029 (11)
O80.0328 (15)0.0147 (13)0.0277 (14)0.0032 (11)0.0091 (11)0.0032 (11)
C10.0098 (13)0.0082 (13)0.0127 (12)0.0008 (11)0.0005 (10)0.0009 (10)
C20.0126 (14)0.0072 (13)0.0144 (12)0.0005 (11)0.0008 (11)0.0005 (11)
C30.0222 (18)0.0134 (15)0.0107 (12)0.0036 (13)0.0000 (12)0.0005 (11)
C40.0121 (15)0.0121 (13)0.0155 (13)0.0008 (11)0.0018 (12)0.0003 (11)
C50.0177 (16)0.0102 (14)0.0136 (12)0.0044 (12)0.0009 (12)0.0004 (11)
C60.0127 (14)0.0158 (15)0.0201 (14)0.0031 (12)0.0017 (12)0.0033 (12)
Geometric parameters (Å, º) top
Fe1—O12.083 (2)O5—C41.261 (4)
Fe1—O32.108 (2)O6—C61.316 (5)
Fe1—O22.113 (3)O7—C61.207 (5)
Fe1—O82.120 (3)C1—C31.533 (4)
Fe1—O42.139 (2)C1—C51.536 (4)
Fe1—O3i2.227 (2)C1—C2iii1.536 (4)
O1—C11.427 (4)C2—O3ii1.284 (4)
O2—C21.233 (4)C2—C1iv1.536 (4)
O3—C2i1.284 (4)C3—C41.521 (5)
O3—Fe1ii2.227 (2)C5—C61.512 (5)
O4—C41.264 (4)
O1—Fe1—O3177.01 (10)Fe1—O3—Fe1ii117.23 (11)
O1—Fe1—O291.88 (10)C4—O4—Fe1129.2 (2)
O3—Fe1—O288.78 (10)O1—C1—C3109.4 (3)
O1—Fe1—O891.45 (10)O1—C1—C5111.0 (2)
O3—Fe1—O885.60 (10)C3—C1—C5108.7 (3)
O2—Fe1—O893.11 (12)O1—C1—C2iii108.1 (2)
O1—Fe1—O485.62 (9)C3—C1—C2iii108.8 (2)
O3—Fe1—O497.26 (9)C5—C1—C2iii110.8 (3)
O2—Fe1—O492.78 (11)O2—C2—O3ii125.4 (3)
O8—Fe1—O4173.51 (12)O2—C2—C1iv117.2 (3)
O1—Fe1—O3i73.72 (9)O3ii—C2—C1iv117.2 (3)
O3—Fe1—O3i105.88 (7)C4—C3—C1116.0 (3)
O2—Fe1—O3i164.58 (10)O5—C4—O4122.6 (3)
O8—Fe1—O3i92.74 (11)O5—C4—C3115.4 (3)
O4—Fe1—O3i80.88 (10)O4—C4—C3122.0 (3)
C1—O1—Fe1112.12 (18)C6—C5—C1114.3 (3)
C2—O2—Fe1144.8 (2)O7—C6—O6124.1 (3)
C2i—O3—Fe1121.0 (2)O7—C6—C5122.7 (3)
C2i—O3—Fe1ii111.2 (2)O6—C6—C5113.2 (3)
Symmetry codes: (i) x+1/2, y+1/2, z+2; (ii) x1/2, y+1/2, z+2; (iii) x+1, y, z; (iv) x1, y, z.

Experimental details

Crystal data
Chemical formulaC6H8FeO8
Mr263.97
Crystal system, space groupOrthorhombic, P212121
Temperature (K)293
a, b, c (Å)5.9470 (4), 10.4021 (5), 13.5773 (7)
V3)839.91 (8)
Z4
Radiation typeMo Kα
µ (mm1)1.82
Crystal size (mm)0.35 × 0.18 × 0.17
Data collection
DiffractometerSuperNova, Dual, Cu at zero, Atlas
diffractometer
Absorption correctionMulti-scan
CrysAlis PRO, (Agilent, 2011)
Tmin, Tmax0.568, 0.747
No. of measured, independent and
observed [I > 2σ(I)] reflections
8571, 2321, 2193
Rint0.065
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.102, 0.81
No. of reflections2321
No. of parameters156
No. of restraints4
H-atom treatmentOnly H-atom displacement parameters refined
Δρmax, Δρmin (e Å3)0.81, 0.71
Absolute structureFlack x determined using 843 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61).
Absolute structure parameter0.009 (12)

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2008), ORTEP-3, DIAMOND (Brandenburg, 2009), SHELXL2013, WinGX (Faruggia, 2012).

 

Subscribe to Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. B
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds