Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The title compound, [Fe(C12H8N3O2)2]ClO4·2C2H3N, contains FeIII in a distorted octa­hedral coordination environment, with the Fe—N(pyridine) bonds significantly longer than the Fe—N(amine) bonds. The crystal packing involves a bifurcated C—H...(O,O) contact that is also found in all other [M(C12H8N3O2)2] complexes reported previously.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106037310/bg3019sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106037310/bg3019Isup2.hkl
Contains datablock I

CCDC reference: 628494

Comment top

During our investigations of iron complexes with di(2-picolyl)amine, we have noticed an unusual reactivity of the –CH2– group attached to the picolyl unit. In the presence of air, this group can be oxidized into a carbonyl group. The storage of a reaction mixture containing Fe(ClO4)2·6H2O, di(2-picolyl)amine and Et3N in the presence of air therefore unintentionally resulted in the formation of the title compound, (I), [Fe(III)(bpca)2]ClO4·2MeCN, where bpca is bis(2-pyridylcarbonyl)aminate. We report here the crystal structure of this complex.

The ligand bpca is present in 68 crystal structures included in the Cambridge Structural Database (Version 5.27 of November 2005, with updates in January, May and August 2006; Allen, 2002), ten of which contain complexes of type M(bpca)2. Among these are several `pseudopolymorphs', crystal structures containing the same coordination complexes but different counter-ions or solvent molecules. Two main types can be discerned, viz. the neutral complexes with MII and the cationic complexes with MIII as central ion. Neutral complexes have been reported where MII is Cu with water as cocrystallized solvent (Marcos, Martinez-Mañez et al., 1989), Fe with water (Wocadlo et al., 1993), Fe without solvent (Kamiyama et al., 2002), Mn with water (Marcos, Folgado et al., 1990), Rh with water (Paul, Tyagi, Bilakhiya et al., 1999) and Ni without solvent (Kamiyama et al., 2002). In the reported cationic complexes, MIII is Rh with PF6 counter-ions (Paul, Tyagi, Bhadbhade et al., 1997), Fe with NO3 and water (Wocadlo et al., 1993), Co with ClO4 and MeOH (Rowland et al., 2002), and Co with ClO4 and water (Kajiwara et al., 2002). The structure reported here is a pseudopolymorph of the FeIII cationic complex reported by Wocadlo and co-workers, which crystallizes in spacegroup P1.

The iron(III) ion in the structure of (I) has a distorted octahedral coordination, similar to that found in the nitrate/water pseudopolymorph. The two bpca ligands coordinate the Fe ion in a meridional configuration. The average N,N bite angle in the four five-membered chelate rings is 81.9 (3)°. As a consequence of this small bite angle, the N(pyridine)—Fe—N(pyridine) angles in one ligand [average value 163.8 (6)°] have the largest deviation from the ideal octahedral value of 180°. The Fe—N(pyridine) bonds are, with an average value of 1.969 (8) Å, significantly longer than the Fe—N(amine) bonds, with an average value of 1.920 (8) Å (Table 1 and Fig. 1). This difference in bond lengths is found in all structures containing bpca ligands coordinating metal ions. The average difference between the MN(pyridine) and MN(amine) bonds is 0.07 Å.

The structure of (I) contains a number of short C—H···O contacts (Table 2), with C···O distances as small as 2.981 (3) Å, i.e. 0.24 Å shorter then the sum of their van der Waals radii (Bondi, 1964). Neighbouring molecules are linked by a bifurcated C—H···O,O contact linking a pyridine H atom at an ortho position to the two O atoms of the ligand. Since these contacts occur for both independent ligands, the molecules are linked into an infinite one-dimensional chain, running in the c direction (Fig. 2). Inversion centres are located between C—H···O,O-linked molecules. The ClO4 counter-ion is also involved in this chain through C—H····O contacts and provides an extra link between two neighbouring molecules. In the nitrate/water pseudopolymorph, the same packing motif is found; bifurcated C—H···O,O contacts link the molecules into infinite one-dimensional chains with inversion centres located between the neighbouring molecules. Here also the counter-ion provides an extra link between neighbouring molecules through C—H····O contacts. The other M(bpca)2 structures of which coordinates are included in the CSD display a great variety in packing, from one-dimensional chains to three-dimensional networks. However, all these structures display the bifurcated pyridine-ortho-H···O,O-urea motif for at least one bpca ligand, even in the presence of classical hydrogen-bond donors, such as MeOH and water.

Experimental top

[Fe(III)(bpca)2]ClO4·2CH3CN was obtained as orange crystals by slow evaporation of an acetonitrile solution containing Fe(ClO4)2·6H2O (0.1 mmol), di(2-picolyl)amine (0.2 mmol) and Et3N (0.2 mmol). The resulting crystals three hours were collected by filtration, washed with diethyl ether and dried in a vacuum two hours (yield 23%). Elemental analysis calculated for C28H22ClFeN8O8: C 48.75, H 3.21, N 16.24%; found: C 49.17, H 3.93, N 16.53%. Spectroscopic details are given in the CIF.

Refinement top

H atoms were introduced in calulated positions and treated as riding on their carrier atoms, with C—H = 0.95 Å for the aromatic H atoms and 0.98 Å for the acetonitril methyl H atoms. The methyl groups were allowed to rotate around the C—C bond during refinement. Uiso(H) values were set at 1.5Ueq(methyl C) or 1.2Ueq(aromatic C).

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Figures top
[Figure 1] Fig. 1. A view of the title compound, with the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. H atoms have been omitted.
[Figure 2] Fig. 2. The one-dimensional chain of C—H···O-linked Fe(bpca)2 complexes and perchlorate ions, viewed approximately perpendicular to the bc plane. Dashed lines indicate the C—H···O contacts. Symmetry codes are as in Table 2.
Bis[bis(2-pyridylcarbonyl)aminato]iron(III) perchlorate acetonitrile disolvate top
Crystal data top
[Fe(C12H8N3O2)2]ClO4·2C2H3NF(000) = 1412
Mr = 689.84Quoted _cell_measurement_* data items refer to the initial cell determination. The cell parameters as reported in _cell_* are based on the complete data set.
Monoclinic, P21/cDx = 1.580 Mg m3
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 12.800 (2) ÅCell parameters from 385 reflections
b = 16.565 (3) Åθ = 2.0–25.0°
c = 14.895 (2) ŵ = 0.68 mm1
β = 113.356 (16)°T = 150 K
V = 2899.4 (9) Å3Plate, orange
Z = 40.40 × 0.18 × 0.02 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
6607 independent reflections
Radiation source: Rotating Anode4867 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.080
Detector resolution: 18.4 pixels mm-1θmax = 27.4°, θmin = 1.7°
ϕ scans, and ω scans with κ offseth = 1616
Absorption correction: multi-scan
(MULABS in PLATON; Spek, 2003)
k = 2121
Tmin = 0.875, Tmax = 0.989l = 1919
70020 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0423P)2 + 1.4P]
where P = (Fo2 + 2Fc2)/3
6607 reflections(Δ/σ)max = 0.001
417 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.36 e Å3
Crystal data top
[Fe(C12H8N3O2)2]ClO4·2C2H3NV = 2899.4 (9) Å3
Mr = 689.84Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.800 (2) ŵ = 0.68 mm1
b = 16.565 (3) ÅT = 150 K
c = 14.895 (2) Å0.40 × 0.18 × 0.02 mm
β = 113.356 (16)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
6607 independent reflections
Absorption correction: multi-scan
(MULABS in PLATON; Spek, 2003)
4867 reflections with I > 2σ(I)
Tmin = 0.875, Tmax = 0.989Rint = 0.080
70020 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.095H-atom parameters constrained
S = 1.03Δρmax = 0.38 e Å3
6607 reflectionsΔρmin = 0.36 e Å3
417 parameters
Special details top

Experimental. IR (ν / cm−1): 3112 (w), 1718 (s), 1661 (m), 1604 (s), 1568 (m), 1471 (m), 1446 (m), 1321 (s), 1289 (s), 1257 (m), 1188 (m), 1160 (w), 1076 (s), 1051 (s), 820 (w), 763 (m), 700 (m), 657 (m), 620 (s), 552 (w), 493 (m).

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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 (Å2) top
xyzUiso*/Ueq
Fe10.39115 (2)0.18358 (2)0.15722 (2)0.0194 (1)
O10.55942 (13)0.23478 (10)0.01336 (11)0.0336 (5)
O20.42000 (14)0.09579 (10)0.08348 (11)0.0370 (6)
O30.38064 (13)0.13124 (10)0.41801 (10)0.0337 (5)
O40.23611 (14)0.26513 (10)0.32723 (11)0.0366 (5)
N10.50297 (14)0.27235 (10)0.19678 (11)0.0207 (5)
N20.43868 (14)0.17615 (10)0.05075 (12)0.0214 (5)
N30.28887 (14)0.09604 (10)0.08530 (11)0.0206 (5)
N40.50032 (14)0.10390 (10)0.24337 (12)0.0224 (5)
N50.34806 (14)0.19036 (10)0.26705 (11)0.0207 (5)
N60.26854 (14)0.26320 (10)0.10334 (11)0.0201 (5)
C110.53042 (18)0.32040 (13)0.27554 (14)0.0244 (6)
C120.60896 (19)0.38178 (14)0.29375 (16)0.0312 (7)
C130.6619 (2)0.39479 (14)0.23047 (17)0.0339 (8)
C140.63332 (19)0.34589 (14)0.14854 (16)0.0293 (7)
C150.55422 (17)0.28575 (13)0.13389 (14)0.0224 (6)
C160.51961 (18)0.22969 (13)0.04778 (14)0.0245 (6)
C210.21011 (17)0.05945 (13)0.10936 (15)0.0239 (6)
C220.14372 (18)0.00270 (13)0.05341 (16)0.0281 (7)
C230.1567 (2)0.02672 (14)0.02989 (17)0.0332 (7)
C240.23756 (19)0.01129 (14)0.05538 (16)0.0314 (7)
C250.30241 (18)0.07125 (13)0.00381 (14)0.0244 (6)
C260.39354 (18)0.11513 (13)0.01681 (15)0.0249 (6)
C310.57910 (19)0.06174 (13)0.22485 (16)0.0295 (7)
C320.6529 (2)0.00938 (15)0.29271 (18)0.0400 (8)
C330.6463 (2)0.00041 (15)0.38219 (18)0.0408 (8)
C340.5638 (2)0.04149 (14)0.40117 (16)0.0331 (8)
C350.49250 (18)0.09244 (13)0.33070 (15)0.0244 (6)
C360.40100 (18)0.13984 (12)0.34600 (14)0.0240 (6)
C410.22901 (18)0.29518 (13)0.01330 (14)0.0241 (6)
C420.14386 (19)0.35272 (13)0.01541 (15)0.0289 (7)
C430.09887 (19)0.37937 (13)0.04925 (16)0.0285 (7)
C440.13928 (18)0.34625 (13)0.14253 (15)0.0262 (7)
C450.22258 (17)0.28818 (12)0.16652 (14)0.0215 (6)
C460.26814 (18)0.24731 (13)0.26379 (14)0.0239 (6)
N70.7673 (2)0.16218 (18)0.1904 (2)0.0717 (11)
C510.9636 (2)0.2277 (2)0.2382 (2)0.0573 (11)
C520.8541 (2)0.19042 (16)0.2124 (2)0.0439 (9)
N80.9587 (3)0.30670 (18)0.4872 (3)0.0813 (15)
C610.7905 (3)0.2065 (2)0.4429 (3)0.0723 (14)
C620.8847 (3)0.2630 (2)0.4671 (2)0.0581 (12)
Cl10.93200 (5)0.01938 (3)0.69799 (4)0.0354 (2)
O50.8610 (2)0.05876 (17)0.61221 (16)0.0861 (10)
O60.8735 (2)0.04449 (13)0.72108 (16)0.0712 (9)
O71.02648 (17)0.01286 (12)0.68245 (17)0.0638 (8)
O80.9694 (2)0.07583 (13)0.77667 (16)0.0736 (9)
H110.494800.311800.319800.0290*
H120.626600.415000.349800.0370*
H130.716900.436400.242700.0410*
H140.667800.353800.103300.0350*
H210.199700.076600.166100.0290*
H220.089500.028600.072500.0340*
H230.110900.068800.069500.0400*
H240.247700.004000.112800.0380*
H310.584300.068100.163400.0350*
H320.707900.019700.277800.0480*
H330.697500.035400.430000.0490*
H340.556500.035100.461800.0400*
H410.260200.277900.031700.0290*
H420.116300.373900.079900.0350*
H430.041300.419600.030500.0340*
H440.109900.363400.188800.0310*
H51A1.017700.187900.233300.0860*
H51B0.990700.248100.305400.0860*
H51C0.957100.272600.193400.0860*
H61A0.817000.157000.481500.1080*
H61B0.761700.193300.373100.1080*
H61C0.729600.230900.457800.1080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0246 (2)0.0222 (2)0.0160 (1)0.0002 (1)0.0130 (1)0.0005 (1)
O10.0408 (9)0.0436 (10)0.0279 (8)0.0130 (8)0.0260 (7)0.0094 (7)
O20.0528 (10)0.0396 (10)0.0326 (9)0.0140 (8)0.0319 (8)0.0145 (7)
O30.0425 (9)0.0441 (10)0.0231 (8)0.0066 (8)0.0221 (7)0.0080 (7)
O40.0467 (10)0.0488 (10)0.0243 (8)0.0171 (8)0.0247 (7)0.0063 (7)
N10.0240 (9)0.0234 (9)0.0178 (8)0.0007 (7)0.0116 (7)0.0009 (7)
N20.0264 (9)0.0246 (9)0.0193 (8)0.0025 (7)0.0155 (7)0.0029 (7)
N30.0248 (9)0.0215 (9)0.0179 (8)0.0008 (7)0.0111 (7)0.0005 (7)
N40.0258 (9)0.0244 (9)0.0205 (8)0.0010 (7)0.0128 (7)0.0001 (7)
N50.0256 (9)0.0257 (9)0.0162 (8)0.0016 (7)0.0139 (7)0.0014 (7)
N60.0235 (9)0.0233 (9)0.0169 (8)0.0025 (7)0.0116 (7)0.0018 (7)
C110.0289 (11)0.0294 (11)0.0186 (10)0.0013 (10)0.0133 (9)0.0019 (9)
C120.0380 (13)0.0328 (13)0.0260 (11)0.0045 (11)0.0161 (10)0.0095 (10)
C130.0354 (13)0.0341 (13)0.0369 (13)0.0109 (11)0.0195 (11)0.0088 (10)
C140.0333 (13)0.0342 (12)0.0277 (11)0.0062 (10)0.0199 (10)0.0032 (9)
C150.0262 (11)0.0260 (11)0.0191 (10)0.0003 (9)0.0133 (8)0.0001 (8)
C160.0273 (11)0.0301 (12)0.0207 (10)0.0004 (9)0.0143 (9)0.0002 (9)
C210.0264 (11)0.0283 (12)0.0209 (10)0.0010 (9)0.0136 (9)0.0036 (9)
C220.0261 (11)0.0301 (12)0.0302 (11)0.0005 (10)0.0134 (9)0.0049 (9)
C230.0351 (13)0.0328 (13)0.0313 (12)0.0109 (10)0.0129 (10)0.0048 (10)
C240.0379 (13)0.0346 (13)0.0259 (11)0.0058 (11)0.0171 (10)0.0066 (10)
C250.0308 (12)0.0262 (11)0.0206 (10)0.0001 (9)0.0148 (9)0.0005 (8)
C260.0321 (12)0.0275 (11)0.0204 (10)0.0004 (9)0.0160 (9)0.0002 (8)
C310.0357 (13)0.0297 (12)0.0289 (11)0.0056 (10)0.0190 (10)0.0001 (9)
C320.0453 (15)0.0399 (14)0.0412 (14)0.0171 (12)0.0241 (12)0.0072 (11)
C330.0442 (14)0.0408 (15)0.0371 (13)0.0176 (12)0.0159 (12)0.0135 (11)
C340.0391 (14)0.0353 (13)0.0262 (12)0.0051 (11)0.0142 (10)0.0065 (10)
C350.0296 (12)0.0241 (11)0.0220 (10)0.0019 (9)0.0128 (9)0.0003 (8)
C360.0297 (12)0.0260 (11)0.0196 (10)0.0033 (9)0.0133 (9)0.0006 (8)
C410.0288 (11)0.0293 (11)0.0186 (10)0.0034 (9)0.0141 (9)0.0005 (8)
C420.0330 (12)0.0312 (12)0.0219 (11)0.0012 (10)0.0102 (9)0.0050 (9)
C430.0281 (12)0.0285 (12)0.0313 (12)0.0019 (10)0.0144 (10)0.0034 (9)
C440.0287 (12)0.0268 (11)0.0284 (11)0.0002 (9)0.0171 (10)0.0020 (9)
C450.0242 (11)0.0234 (10)0.0210 (10)0.0026 (9)0.0133 (8)0.0013 (8)
C460.0268 (11)0.0290 (12)0.0202 (10)0.0022 (9)0.0139 (9)0.0003 (8)
N70.0533 (17)0.0665 (18)0.102 (2)0.0047 (15)0.0380 (16)0.0003 (16)
C510.0514 (18)0.065 (2)0.0540 (18)0.0122 (15)0.0193 (15)0.0047 (15)
C520.0461 (16)0.0376 (15)0.0518 (16)0.0067 (13)0.0235 (13)0.0039 (12)
N80.101 (3)0.0474 (18)0.109 (3)0.0218 (17)0.056 (2)0.0099 (17)
C610.068 (2)0.087 (3)0.070 (2)0.021 (2)0.0360 (19)0.0186 (19)
C620.075 (2)0.051 (2)0.063 (2)0.0309 (18)0.0429 (19)0.0154 (16)
Cl10.0482 (4)0.0324 (3)0.0334 (3)0.0043 (3)0.0246 (3)0.0017 (2)
O50.0915 (18)0.106 (2)0.0501 (13)0.0353 (16)0.0167 (13)0.0236 (13)
O60.1130 (19)0.0557 (13)0.0851 (16)0.0362 (13)0.0819 (15)0.0200 (11)
O70.0595 (13)0.0497 (12)0.1026 (17)0.0045 (10)0.0539 (13)0.0079 (12)
O80.1106 (19)0.0544 (13)0.0598 (14)0.0181 (13)0.0382 (13)0.0268 (11)
Geometric parameters (Å, º) top
Fe1—N11.9722 (18)C24—C251.368 (3)
Fe1—N21.9145 (18)C25—C261.506 (3)
Fe1—N31.9627 (17)C31—C321.382 (3)
Fe1—N41.9798 (18)C32—C331.378 (4)
Fe1—N51.9257 (17)C33—C341.383 (4)
Fe1—N61.9617 (18)C34—C351.374 (3)
Cl1—O61.415 (2)C35—C361.501 (3)
Cl1—O71.422 (2)C41—C421.382 (3)
Cl1—O81.426 (2)C42—C431.376 (3)
Cl1—O51.401 (2)C43—C441.389 (3)
O1—C161.210 (3)C44—C451.374 (3)
O2—C261.213 (3)C45—C461.493 (3)
O3—C361.208 (3)C11—H110.9500
O4—C461.206 (3)C12—H120.9500
N1—C151.358 (3)C13—H130.9500
N1—C111.344 (3)C14—H140.9500
N2—C261.381 (3)C21—H210.9500
N2—C161.378 (3)C22—H220.9500
N3—C211.341 (3)C23—H230.9500
N3—C251.356 (3)C24—H240.9500
N4—C311.342 (3)C31—H310.9500
N4—C351.357 (3)C32—H320.9500
N5—C461.378 (3)C33—H330.9500
N5—C361.382 (3)C34—H340.9500
N6—C411.341 (2)C41—H410.9500
N6—C451.357 (3)C42—H420.9500
N7—C521.128 (4)C43—H430.9500
N8—C621.134 (5)C44—H440.9500
C11—C121.379 (3)C51—C521.438 (4)
C12—C131.379 (4)C51—H51A0.9800
C13—C141.388 (3)C51—H51B0.9800
C14—C151.375 (3)C51—H51C0.9800
C15—C161.501 (3)C61—C621.454 (5)
C21—C221.384 (3)C61—H61B0.9800
C22—C231.374 (3)C61—H61C0.9800
C23—C241.387 (4)C61—H61A0.9800
Cl1···H44i3.0400C11···O2v3.269 (3)
Cl1···H42ii2.9000C13···C21x3.566 (3)
O1···C36iii3.073 (3)C14···N73.427 (4)
O1···O22.846 (2)C15···N73.243 (4)
O1···C61iii3.413 (5)C15···O3iii3.392 (3)
O1···C11iii3.152 (3)C16···N73.237 (4)
O1···O3iii3.058 (2)C16···C36iii3.520 (3)
O2···O12.846 (2)C16···O3iii3.079 (3)
O2···C31iv3.356 (3)C21···O6vii3.119 (3)
O2···C32iv3.363 (3)C21···C13ii3.566 (3)
O2···C11iii3.269 (3)C22···C22xi3.382 (3)
O2···O4iii3.184 (3)C22···N8ii3.380 (4)
O3···O42.861 (2)C23···O8xii3.385 (3)
O3···C15v3.392 (3)C23···N8ii3.308 (4)
O3···O1v3.058 (2)C26···C313.550 (3)
O3···C41v3.074 (3)C26···O4iii3.111 (3)
O3···C16v3.079 (3)C31···O2iv3.356 (3)
O4···C51vi3.262 (3)C31···N73.133 (4)
O4···C41v2.981 (3)C31···C263.550 (3)
O4···O32.861 (2)C32···O2iv3.363 (3)
O4···C26v3.111 (3)C33···C42ii3.584 (3)
O4···O2v3.184 (3)C36···C16v3.520 (3)
O5···C613.370 (5)C36···O1v3.073 (3)
O6···C21vii3.119 (3)C41···O4iii2.981 (3)
O7···C44i3.277 (3)C41···O3iii3.074 (3)
O7···C42ii3.406 (3)C42···O7x3.406 (3)
O7···C43i3.338 (3)C42···C33x3.584 (3)
O7···C52viii3.397 (3)C43···C62xiii3.452 (4)
O8···C23ix3.385 (3)C43···O7xiii3.338 (3)
O8···C51v3.300 (4)C44···O7xiii3.277 (3)
O1···H11iii2.4100C46···C113.507 (3)
O1···H61Ciii2.4500C51···O8iii3.300 (4)
O1···H142.6300C51···O4xiv3.262 (3)
O2···H11iii2.5400C52···O7viii3.397 (3)
O2···H242.6500C61···O53.370 (5)
O3···H41v2.4700C61···O1v3.413 (5)
O3···H342.6200C62···C43i3.452 (4)
O4···H41v2.1200C21···H12ii3.0800
O4···H442.6200C21···H13ii2.8700
O4···H51Avi2.8800C22···H13ii3.0200
O5···H14v2.8200C22···H22xi2.8700
O5···H61A2.4300C22···H12ii3.0400
O6···H51Aviii2.7000C23···H22xi3.1000
O6···H13v2.8000C26···H312.9300
O6···H21vii2.2900C36···H213.0700
O6···H42ii2.5500C41···H33x2.9700
O7···H42ii2.6400C42···H51Bxiii3.1000
O7···H44i2.6800C42···H33x2.6700
O7···H43i2.8100C43···H33x2.8700
O8···H22vii2.7500C44···H51Cvi2.9800
O8···H44i2.8000C44···H32x2.8900
O8···H51Cv2.7800C46···H112.8900
N1···N22.555 (2)C52···H61B3.0600
N1···N42.879 (2)C52···H23iv3.0900
N1···N52.919 (3)H11···O2v2.5400
N1···N62.766 (3)H11···C462.8900
N1···C453.445 (3)H11···O1v2.4100
N1···C162.418 (3)H11···N52.6500
N2···C252.363 (3)H12···C21x3.0800
N2···C152.359 (3)H12···C22x3.0400
N2···N12.555 (2)H13···O6iii2.8000
N2···N32.547 (3)H13···C21x2.8700
N2···N42.914 (2)H13···C22x3.0200
N2···N62.965 (3)H14···O5iii2.8200
N2···C313.139 (3)H14···O12.6300
N2···C413.196 (3)H21···N52.6700
N3···N52.953 (2)H21···C363.0700
N3···C262.413 (3)H21···O6vii2.2900
N3···N22.547 (3)H22···C22xi2.8700
N3···N42.799 (2)H22···O8vii2.7500
N3···N62.804 (2)H22···C23xi3.1000
N4···N12.879 (2)H22···N8ii2.8600
N4···C362.418 (3)H23···N8ii2.7200
N4···N52.553 (3)H23···C52iv3.0900
N4···N32.799 (2)H24···N7iv2.8400
N4···N22.914 (2)H24···O22.6500
N5···N32.953 (2)H31···N72.7100
N5···C113.142 (3)H31···C262.9300
N5···C213.170 (3)H31···N22.6500
N5···N12.919 (3)H32···C44ii2.8900
N5···N42.553 (3)H33···C41ii2.9700
N5···N62.544 (2)H33···C42ii2.6700
N5···C452.354 (3)H33···C43ii2.8700
N5···C352.358 (3)H34···H34vii2.4600
N6···N22.965 (3)H34···O32.6200
N6···C462.406 (3)H41···O4iii2.1200
N6···N12.766 (3)H41···N22.7100
N6···N52.544 (2)H41···O3iii2.4700
N6···C113.449 (3)H42···O7x2.6400
N6···N32.804 (2)H42···Cl1x2.9000
N7···C313.133 (4)H42···O6x2.5500
N7···C143.427 (4)H43···O7xiii2.8100
N7···C163.237 (4)H44···Cl1xiii3.0400
N7···C153.243 (4)H44···H51Cvi2.4900
N8···C23x3.308 (4)H44···O8xiii2.8000
N8···C22x3.380 (4)H44···O42.6200
N2···H412.7100H44···O7xiii2.6800
N2···H312.6500H51A···O6viii2.7000
N5···H112.6500H51A···O4xiv2.8800
N5···H212.6700H51B···C42i3.1000
N7···H24iv2.8400H51C···H44xiv2.4900
N7···H61B2.8000H51C···O8iii2.7800
N7···H312.7100H51C···C44xiv2.9800
N8···H22x2.8600H61A···O52.4300
N8···H23x2.7200H61B···N72.8000
C11···C463.507 (3)H61B···C523.0600
C11···O1v3.152 (3)H61C···O1v2.4500
N1—Fe1—N282.19 (7)C34—C35—C36121.8 (2)
N1—Fe1—N3164.15 (7)N4—C35—C34122.6 (2)
N1—Fe1—N493.51 (7)N4—C35—C36115.53 (18)
N1—Fe1—N596.95 (7)O3—C36—C35121.94 (19)
N1—Fe1—N689.37 (7)O3—C36—N5128.4 (2)
N2—Fe1—N382.10 (7)N5—C36—C35109.66 (18)
N2—Fe1—N496.87 (8)N6—C41—C42121.4 (2)
N2—Fe1—N5178.24 (8)C41—C42—C43120.2 (2)
N2—Fe1—N699.77 (7)C42—C43—C44118.7 (2)
N3—Fe1—N490.45 (7)C43—C44—C45118.7 (2)
N3—Fe1—N598.81 (7)N6—C45—C46115.14 (18)
N3—Fe1—N691.21 (7)N6—C45—C44122.56 (18)
N4—Fe1—N581.64 (7)C44—C45—C46122.3 (2)
N4—Fe1—N6163.35 (7)N5—C46—C45110.10 (18)
N5—Fe1—N681.73 (7)O4—C46—N5128.16 (19)
O7—Cl1—O8110.49 (15)O4—C46—C45121.7 (2)
O5—Cl1—O7108.20 (15)C12—C11—H11119.00
O5—Cl1—O8109.23 (15)N1—C11—H11119.00
O5—Cl1—O6110.81 (15)C11—C12—H12120.00
O6—Cl1—O8109.16 (14)C13—C12—H12120.00
O6—Cl1—O7108.95 (14)C14—C13—H13121.00
C11—N1—C15118.34 (19)C12—C13—H13121.00
Fe1—N1—C15114.06 (13)C15—C14—H14121.00
Fe1—N1—C11127.59 (15)C13—C14—H14121.00
C16—N2—C26123.40 (18)N3—C21—H21119.00
Fe1—N2—C16118.37 (13)C22—C21—H21119.00
Fe1—N2—C26118.17 (15)C21—C22—H22120.00
C21—N3—C25118.60 (18)C23—C22—H22120.00
Fe1—N3—C21126.69 (14)C24—C23—H23120.00
Fe1—N3—C25114.71 (15)C22—C23—H23120.00
Fe1—N4—C31127.48 (14)C23—C24—H24121.00
Fe1—N4—C35114.41 (15)C25—C24—H24121.00
C31—N4—C35118.11 (18)N4—C31—H31119.00
Fe1—N5—C36118.59 (15)C32—C31—H31119.00
C36—N5—C46123.44 (18)C33—C32—H32120.00
Fe1—N5—C46117.94 (13)C31—C32—H32120.00
C41—N6—C45118.54 (18)C32—C33—H33121.00
Fe1—N6—C41126.76 (15)C34—C33—H33121.00
Fe1—N6—C45114.69 (13)C35—C34—H34121.00
N1—C11—C12121.8 (2)C33—C34—H34121.00
C11—C12—C13119.9 (2)N6—C41—H41119.00
C12—C13—C14118.7 (2)C42—C41—H41119.00
C13—C14—C15118.9 (2)C41—C42—H42120.00
C14—C15—C16122.2 (2)C43—C42—H42120.00
N1—C15—C14122.39 (19)C44—C43—H43121.00
N1—C15—C16115.38 (19)C42—C43—H43121.00
O1—C16—N2127.98 (19)C43—C44—H44121.00
N2—C16—C15109.99 (18)C45—C44—H44121.00
O1—C16—C15122.0 (2)N7—C52—C51178.5 (3)
N3—C21—C22121.5 (2)H51B—C51—H51C109.00
C21—C22—C23119.6 (2)H51A—C51—H51C109.00
C22—C23—C24119.1 (2)C52—C51—H51A110.00
C23—C24—C25118.8 (2)C52—C51—H51B110.00
N3—C25—C26114.88 (18)C52—C51—H51C109.00
N3—C25—C24122.4 (2)H51A—C51—H51B109.00
C24—C25—C26122.7 (2)N8—C62—C61179.1 (4)
O2—C26—C25122.0 (2)H61B—C61—H61C110.00
O2—C26—N2128.2 (2)C62—C61—H61A109.00
N2—C26—C25109.81 (18)C62—C61—H61B109.00
N4—C31—C32121.9 (2)C62—C61—H61C110.00
C31—C32—C33119.7 (2)H61A—C61—H61B109.00
C32—C33—C34118.9 (2)H61A—C61—H61C109.00
C33—C34—C35118.8 (2)
N2—Fe1—N1—C11179.45 (19)Fe1—N3—C21—C22179.06 (16)
N2—Fe1—N1—C151.18 (15)C25—N3—C21—C220.4 (3)
N4—Fe1—N1—C1184.09 (18)Fe1—N3—C25—C24179.46 (18)
N4—Fe1—N1—C1597.64 (15)Fe1—N3—C25—C260.1 (2)
N5—Fe1—N1—C112.10 (19)C21—N3—C25—C241.1 (3)
N5—Fe1—N1—C15179.64 (15)C21—N3—C25—C26179.37 (19)
N6—Fe1—N1—C1179.49 (18)Fe1—N4—C31—C32178.03 (18)
N6—Fe1—N1—C1598.77 (15)C35—N4—C31—C321.6 (3)
N1—Fe1—N2—C160.44 (16)Fe1—N4—C35—C34177.79 (18)
N1—Fe1—N2—C26176.84 (17)Fe1—N4—C35—C361.7 (2)
N3—Fe1—N2—C16177.44 (17)C31—N4—C35—C341.9 (3)
N3—Fe1—N2—C265.29 (16)C31—N4—C35—C36178.61 (19)
N4—Fe1—N2—C1693.06 (16)Fe1—N5—C36—O3174.57 (18)
N4—Fe1—N2—C2684.21 (16)Fe1—N5—C36—C354.6 (2)
N6—Fe1—N2—C1687.57 (16)C46—N5—C36—O37.5 (4)
N6—Fe1—N2—C2695.16 (16)C46—N5—C36—C35173.35 (19)
N2—Fe1—N3—C21177.92 (18)Fe1—N5—C46—O4174.1 (2)
N2—Fe1—N3—C252.64 (15)Fe1—N5—C46—C455.4 (2)
N4—Fe1—N3—C2185.21 (18)C36—N5—C46—O43.9 (4)
N4—Fe1—N3—C2594.24 (15)C36—N5—C46—C45176.57 (19)
N5—Fe1—N3—C213.60 (19)Fe1—N6—C41—C42178.21 (17)
N5—Fe1—N3—C25175.85 (15)C45—N6—C41—C420.4 (3)
N6—Fe1—N3—C2178.22 (18)Fe1—N6—C45—C44177.14 (17)
N6—Fe1—N3—C25102.33 (15)Fe1—N6—C45—C463.5 (2)
N1—Fe1—N4—C3182.51 (19)C41—N6—C45—C441.6 (3)
N1—Fe1—N4—C3597.16 (16)C41—N6—C45—C46177.71 (19)
N2—Fe1—N4—C310.05 (19)N1—C11—C12—C130.3 (4)
N2—Fe1—N4—C35179.70 (15)C11—C12—C13—C140.8 (4)
N3—Fe1—N4—C3182.14 (19)C12—C13—C14—C150.7 (4)
N3—Fe1—N4—C3598.20 (16)C13—C14—C15—N10.1 (4)
N5—Fe1—N4—C31179.03 (19)C13—C14—C15—C16179.3 (2)
N5—Fe1—N4—C350.63 (15)N1—C15—C16—O1179.5 (2)
N1—Fe1—N5—C3695.69 (16)N1—C15—C16—N21.3 (3)
N1—Fe1—N5—C4682.40 (16)C14—C15—C16—O10.2 (3)
N3—Fe1—N5—C3686.02 (16)C14—C15—C16—N2179.4 (2)
N3—Fe1—N5—C4695.89 (16)N3—C21—C22—C231.3 (3)
N4—Fe1—N5—C363.14 (15)C21—C22—C23—C240.9 (3)
N4—Fe1—N5—C46174.95 (17)C22—C23—C24—C250.4 (4)
N6—Fe1—N5—C36175.97 (16)C23—C24—C25—N31.4 (3)
N6—Fe1—N5—C465.94 (16)C23—C24—C25—C26179.0 (2)
N1—Fe1—N6—C4186.58 (18)N3—C25—C26—O2175.1 (2)
N1—Fe1—N6—C4592.07 (15)N3—C25—C26—N24.1 (3)
N2—Fe1—N6—C414.62 (19)C24—C25—C26—O25.3 (3)
N2—Fe1—N6—C45174.03 (15)C24—C25—C26—N2175.5 (2)
N3—Fe1—N6—C4177.58 (18)N4—C31—C32—C330.0 (4)
N3—Fe1—N6—C45103.77 (15)C31—C32—C33—C341.3 (4)
N5—Fe1—N6—C41176.30 (19)C32—C33—C34—C351.1 (4)
N5—Fe1—N6—C455.05 (15)C33—C34—C35—N40.6 (4)
Fe1—N1—C11—C12178.61 (17)C33—C34—C35—C36180.0 (2)
C15—N1—C11—C120.4 (3)N4—C35—C36—O3175.3 (2)
Fe1—N1—C15—C14179.03 (18)N4—C35—C36—N54.0 (3)
Fe1—N1—C15—C161.7 (2)C34—C35—C36—O35.2 (3)
C11—N1—C15—C140.6 (3)C34—C35—C36—N5175.5 (2)
C11—N1—C15—C16179.88 (19)N6—C41—C42—C431.0 (3)
Fe1—N2—C16—O1179.43 (19)C41—C42—C43—C441.2 (3)
Fe1—N2—C16—C150.3 (2)C42—C43—C44—C450.0 (3)
C26—N2—C16—O13.5 (4)C43—C44—C45—N61.4 (3)
C26—N2—C16—C15177.44 (19)C43—C44—C45—C46177.9 (2)
Fe1—N2—C26—O2172.65 (19)N6—C45—C46—O4178.5 (2)
Fe1—N2—C26—C256.4 (2)N6—C45—C46—N51.1 (3)
C16—N2—C26—O24.5 (4)C44—C45—C46—O42.2 (3)
C16—N2—C26—C25176.43 (19)C44—C45—C46—N5178.3 (2)
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+1, y1/2, z+1/2; (iii) x, y+1/2, z1/2; (iv) x+1, y, z; (v) x, y+1/2, z+1/2; (vi) x1, y, z; (vii) x+1, y, z+1; (viii) x+2, y, z+1; (ix) x+1, y, z+1; (x) x+1, y+1/2, z+1/2; (xi) x, y, z; (xii) x1, y, z1; (xiii) x1, y+1/2, z1/2; (xiv) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11···O1v0.952.413.152 (3)134
C11—H11···O2v0.952.543.269 (3)134
C21—H21···O6vii0.952.293.119 (3)146
C41—H41···O3iii0.952.473.074 (3)121
C41—H41···O4iii0.952.122.981 (3)150
C42—H42···O6x0.952.553.434 (3)156
C61—H61A···O50.982.433.370 (5)161
C61—H61C···O1v0.982.453.413 (5)168
Symmetry codes: (iii) x, y+1/2, z1/2; (v) x, y+1/2, z+1/2; (vii) x+1, y, z+1; (x) x+1, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Fe(C12H8N3O2)2]ClO4·2C2H3N
Mr689.84
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)12.800 (2), 16.565 (3), 14.895 (2)
β (°) 113.356 (16)
V3)2899.4 (9)
Z4
Radiation typeMo Kα
µ (mm1)0.68
Crystal size (mm)0.40 × 0.18 × 0.02
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(MULABS in PLATON; Spek, 2003)
Tmin, Tmax0.875, 0.989
No. of measured, independent and
observed [I > 2σ(I)] reflections
70020, 6607, 4867
Rint0.080
(sin θ/λ)max1)0.648
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.095, 1.03
No. of reflections6607
No. of parameters417
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.38, 0.36

Computer programs: COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997), DENZO, SHELXS86 (Sheldrick, 1985), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PLATON.

Selected bond lengths (Å) top
Fe1—N11.9722 (18)Fe1—N41.9798 (18)
Fe1—N21.9145 (18)Fe1—N51.9257 (17)
Fe1—N31.9627 (17)Fe1—N61.9617 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11···O1i0.952.413.152 (3)134
C11—H11···O2i0.952.543.269 (3)134
C21—H21···O6ii0.952.293.119 (3)146
C41—H41···O3iii0.952.473.074 (3)121
C41—H41···O4iii0.952.122.981 (3)150
C42—H42···O6iv0.952.553.434 (3)156
C61—H61A···O50.982.433.370 (5)161
C61—H61C···O1i0.982.453.413 (5)168
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x+1, y, z+1; (iii) x, y+1/2, z1/2; (iv) x+1, y+1/2, z+1/2.
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

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