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The title compounds, tris(1,10-phenanthroline-
2N,
N')iron(II) bis(2,4,5-tricarboxybenzoate) monohydrate, [Fe(C
12H
8N
2)
3](C
10H
5O
8)
2·H
2O, (I), and tris(2,2'-bipyridine-
2N,
N')iron(II) 2,5-dicarboxybenzene-1,4-dicarboxylate-benzene-1,2,4,5-tetracarboxylic acid-water (1/1/2), [Fe(C
10H
8N
2)
3](C
10H
4O
8)·C
10H
6O
8·2H
2O, (II), were obtained during an attempt to synthesize a mixed-ligand complex of Fe
II with an N-containing ligand and benzene-1,2,4,5-tetracarboxylic acid
via a solvothermal reaction. In both mononuclear complexes, each Fe
II metal ion is six-coordinated in a distorted octahedral manner by six N atoms from three chelating 1,10-phenanthroline or 2,2'-bipyridine ligands. In compound (I), the Fe
II atom lies on a twofold axis in the space group
C2/
c, whereas (II) crystallizes in the space group
P2
1/
n. In both compounds, the uncoordinated carboxylate anions and water molecules are linked by typical O-H
O hydrogen bonds, generating extensive three-dimensional hydrogen-bond networks which surround the cations.
Supporting information
CCDC references: 778937; 825888
1,10-Phenanthroline (0.2 mmol), benzene-1,2,4,5-tetracarboxylic acid (0.1 mmol), FeSO4.7H2O (0.1 mmol) and water (2 ml) were mixed and placed in a
thick Pyrex tube, which was sealed and heated to 388 K for 72 h, whereupon red
block-shaped crystals of (I) suitable for X-ray diffraction were obtained.
Analysis, found: C 58.66, H 3.43, N 9.01%; calculated for
C56H36FeN6O17: C 59.96, H 3.21, N 9.50%. Red block-shaped crystals of
(II) were obtained by a similar procedure, using 2,2'-bipyridine instead of
1,10-phenanthroline. Analysis, found: C 55.14, H 3.91, N 7.48%; calculated for
C50H38FeN6O18: C 56.25, H 3.56, N 7.87%.
H atoms bonded to C and O atoms were positioned geometrically and allowed to
ride on their parent atoms, with C—H = 0.93 Å and Uiso(H) =
1.2Ueq(C), and O—H = 0.82 Å and Uiso(H) =
1.5Ueq(O). The H atoms of the water molecules were either located in
difference Fourier maps or placed in calculated positions so as to form a
reasonable hydrogen-bond network. Initially, their positions were refined with
tight restraints on the O—H and H···H distances [0.82 (1) and 1.35 (1) Å,
respectively] in order to ensure a reasonable geometry. They were then
constrained to ride on their parent O atoms, with Uiso(H) =
1.5Ueq(O).
For both compounds, data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
(I) Tris(1,10-phenanthroline-
κ2N,
N')iron(II)
bis(2,4,5-tricarboxybenzoate) monohydrate
top
Crystal data top
[Fe(C12H8N2)3](C10H5O8)2·H2O | F(000) = 2304 |
Mr = 1120.76 | Dx = 1.563 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C2yc | Cell parameters from 9791 reflections |
a = 24.151 (5) Å | θ = 3.2–27.5° |
b = 14.088 (3) Å | µ = 0.41 mm−1 |
c = 15.651 (3) Å | T = 223 K |
β = 116.54 (3)° | Block, red |
V = 4764 (2) Å3 | 0.46 × 0.22 × 0.20 mm |
Z = 4 | |
Data collection top
Rigaku Mercury CCD area-detector diffractometer | 4190 independent reflections |
Radiation source: fine-focus sealed tube | 3613 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 25.0°, θmin = 3.2° |
ω scans | h = −21→28 |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | k = −15→16 |
Tmin = 0.836, Tmax = 0.923 | l = −18→18 |
11666 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0436P)2 + 3.7531P] where P = (Fo2 + 2Fc2)/3 |
4190 reflections | (Δ/σ)max < 0.001 |
366 parameters | Δρmax = 0.31 e Å−3 |
1 restraint | Δρmin = −0.37 e Å−3 |
Crystal data top
[Fe(C12H8N2)3](C10H5O8)2·H2O | V = 4764 (2) Å3 |
Mr = 1120.76 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.151 (5) Å | µ = 0.41 mm−1 |
b = 14.088 (3) Å | T = 223 K |
c = 15.651 (3) Å | 0.46 × 0.22 × 0.20 mm |
β = 116.54 (3)° | |
Data collection top
Rigaku Mercury CCD area-detector diffractometer | 4190 independent reflections |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 3613 reflections with I > 2σ(I) |
Tmin = 0.836, Tmax = 0.923 | Rint = 0.041 |
11666 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 1 restraint |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.31 e Å−3 |
4190 reflections | Δρmin = −0.37 e Å−3 |
366 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. |
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 (Å2) top | x | y | z | Uiso*/Ueq | |
Fe1 | 0.0000 | 0.18738 (3) | 0.2500 | 0.02212 (16) | |
N1 | −0.02446 (10) | 0.28252 (14) | 0.31913 (15) | 0.0237 (5) | |
N2 | 0.07970 (10) | 0.19321 (14) | 0.36566 (15) | 0.0244 (5) | |
N3 | 0.02734 (10) | 0.08130 (14) | 0.19453 (15) | 0.0235 (5) | |
C1 | −0.07746 (13) | 0.32961 (18) | 0.2930 (2) | 0.0294 (6) | |
H1A | −0.1079 | 0.3239 | 0.2303 | 0.035* | |
C2 | −0.08935 (14) | 0.3872 (2) | 0.3556 (2) | 0.0344 (7) | |
H2A | −0.1271 | 0.4185 | 0.3345 | 0.041* | |
C3 | −0.04528 (13) | 0.39742 (19) | 0.4482 (2) | 0.0313 (7) | |
H3A | −0.0531 | 0.4351 | 0.4905 | 0.038* | |
C4 | 0.01164 (13) | 0.35064 (18) | 0.47892 (19) | 0.0271 (6) | |
C5 | 0.06205 (14) | 0.35795 (19) | 0.5730 (2) | 0.0321 (7) | |
H5A | 0.0569 | 0.3927 | 0.6194 | 0.039* | |
C6 | 0.11662 (14) | 0.31552 (19) | 0.5952 (2) | 0.0318 (7) | |
H6A | 0.1489 | 0.3232 | 0.6561 | 0.038* | |
C7 | 0.12632 (13) | 0.25864 (19) | 0.52691 (19) | 0.0278 (6) | |
C8 | 0.18198 (13) | 0.21333 (19) | 0.5447 (2) | 0.0334 (7) | |
H8A | 0.2160 | 0.2182 | 0.6042 | 0.040* | |
C9 | 0.18567 (13) | 0.1619 (2) | 0.4734 (2) | 0.0347 (7) | |
H9A | 0.2228 | 0.1332 | 0.4836 | 0.042* | |
C10 | 0.13391 (12) | 0.15226 (19) | 0.3854 (2) | 0.0297 (6) | |
H10A | 0.1373 | 0.1158 | 0.3384 | 0.036* | |
C11 | 0.07670 (12) | 0.24697 (17) | 0.43607 (18) | 0.0238 (6) | |
C12 | 0.01991 (12) | 0.29464 (17) | 0.41157 (18) | 0.0229 (6) | |
C13 | 0.01415 (15) | −0.17877 (19) | 0.2214 (2) | 0.0393 (8) | |
H13A | 0.0235 | −0.2363 | 0.2017 | 0.047* | |
C14 | 0.02996 (13) | −0.09186 (19) | 0.1904 (2) | 0.0304 (6) | |
C15 | 0.05964 (15) | −0.0862 (2) | 0.1315 (2) | 0.0386 (8) | |
H15A | 0.0706 | −0.1413 | 0.1100 | 0.046* | |
C16 | 0.07249 (15) | 0.0006 (2) | 0.1057 (2) | 0.0389 (7) | |
H16A | 0.0923 | 0.0048 | 0.0668 | 0.047* | |
C17 | 0.05571 (13) | 0.08285 (19) | 0.13819 (19) | 0.0291 (6) | |
H17A | 0.0647 | 0.1414 | 0.1198 | 0.035* | |
C18 | 0.01500 (12) | −0.00580 (18) | 0.22019 (18) | 0.0245 (6) | |
C19 | 0.34024 (12) | 0.26772 (18) | 0.07340 (19) | 0.0252 (6) | |
C20 | 0.35245 (13) | 0.17643 (18) | 0.0525 (2) | 0.0299 (6) | |
H20A | 0.3750 | 0.1696 | 0.0178 | 0.036* | |
C21 | 0.33296 (12) | 0.09545 (18) | 0.08056 (19) | 0.0255 (6) | |
C22 | 0.29900 (12) | 0.10456 (18) | 0.13234 (18) | 0.0233 (6) | |
C23 | 0.28616 (12) | 0.19515 (17) | 0.15374 (18) | 0.0240 (6) | |
H23A | 0.2631 | 0.2011 | 0.1877 | 0.029* | |
C24 | 0.30636 (12) | 0.27782 (17) | 0.12667 (18) | 0.0225 (6) | |
C25 | 0.36870 (15) | 0.3430 (2) | 0.0349 (2) | 0.0359 (7) | |
C26 | 0.35310 (14) | 0.00205 (19) | 0.0565 (2) | 0.0311 (7) | |
C27 | 0.27979 (12) | 0.01653 (19) | 0.16563 (18) | 0.0268 (6) | |
C28 | 0.28801 (13) | 0.36947 (18) | 0.1580 (2) | 0.0284 (6) | |
O1 | 0.35933 (11) | 0.43281 (13) | 0.04296 (17) | 0.0497 (6) | |
H1 | 0.3372 | 0.4389 | 0.0698 | 0.075* | |
O1W | 0.5000 | 0.0805 (3) | 0.2500 | 0.0922 (16) | |
H1W | 0.526 (2) | 0.043 (3) | 0.289 (3) | 0.13 (2)* | |
O2 | 0.39998 (13) | 0.31844 (15) | −0.0036 (2) | 0.0620 (8) | |
O3 | 0.40358 (9) | −0.03143 (14) | 0.10578 (16) | 0.0406 (5) | |
O4 | 0.31610 (10) | −0.03704 (13) | −0.02634 (14) | 0.0377 (5) | |
H4 | 0.2857 | −0.0031 | −0.0544 | 0.056* | |
O5 | 0.29198 (9) | −0.06166 (12) | 0.14631 (14) | 0.0331 (5) | |
O6 | 0.25118 (11) | 0.03190 (13) | 0.21869 (15) | 0.0446 (6) | |
H6 | 0.2421 | −0.0190 | 0.2344 | 0.067* | |
O7 | 0.27058 (11) | 0.36543 (14) | 0.22097 (16) | 0.0476 (6) | |
O8 | 0.28975 (9) | 0.44736 (12) | 0.11732 (14) | 0.0348 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Fe1 | 0.0262 (3) | 0.0201 (3) | 0.0229 (3) | 0.000 | 0.0135 (2) | 0.000 |
N1 | 0.0270 (12) | 0.0177 (11) | 0.0274 (12) | −0.0018 (9) | 0.0131 (10) | 0.0018 (9) |
N2 | 0.0303 (13) | 0.0189 (11) | 0.0276 (12) | 0.0004 (10) | 0.0162 (10) | 0.0018 (10) |
N3 | 0.0277 (12) | 0.0209 (11) | 0.0243 (12) | −0.0026 (9) | 0.0137 (10) | 0.0017 (9) |
C1 | 0.0303 (15) | 0.0268 (14) | 0.0306 (15) | 0.0044 (12) | 0.0133 (13) | 0.0033 (13) |
C2 | 0.0360 (17) | 0.0287 (15) | 0.0444 (18) | 0.0047 (13) | 0.0231 (15) | −0.0009 (14) |
C3 | 0.0432 (18) | 0.0219 (14) | 0.0410 (17) | −0.0017 (13) | 0.0298 (15) | −0.0031 (13) |
C4 | 0.0364 (16) | 0.0204 (13) | 0.0311 (15) | −0.0064 (12) | 0.0210 (13) | −0.0013 (12) |
C5 | 0.0476 (19) | 0.0256 (15) | 0.0308 (16) | −0.0077 (14) | 0.0244 (14) | −0.0031 (13) |
C6 | 0.0418 (18) | 0.0295 (15) | 0.0213 (14) | −0.0080 (14) | 0.0115 (13) | −0.0002 (12) |
C7 | 0.0333 (16) | 0.0244 (14) | 0.0270 (14) | −0.0056 (12) | 0.0145 (13) | 0.0045 (12) |
C8 | 0.0301 (16) | 0.0328 (16) | 0.0289 (16) | −0.0025 (13) | 0.0056 (13) | 0.0047 (13) |
C9 | 0.0285 (16) | 0.0339 (16) | 0.0390 (17) | 0.0036 (13) | 0.0127 (14) | 0.0042 (14) |
C10 | 0.0306 (16) | 0.0271 (14) | 0.0329 (16) | 0.0044 (13) | 0.0155 (13) | 0.0010 (13) |
C11 | 0.0310 (15) | 0.0192 (13) | 0.0240 (14) | −0.0039 (12) | 0.0149 (12) | 0.0030 (11) |
C12 | 0.0289 (15) | 0.0181 (13) | 0.0238 (14) | −0.0026 (11) | 0.0136 (12) | 0.0015 (11) |
C13 | 0.058 (2) | 0.0214 (14) | 0.0504 (19) | 0.0031 (14) | 0.0347 (17) | −0.0002 (14) |
C14 | 0.0366 (16) | 0.0261 (14) | 0.0350 (16) | 0.0002 (13) | 0.0220 (14) | −0.0029 (13) |
C15 | 0.054 (2) | 0.0277 (15) | 0.0480 (19) | 0.0031 (14) | 0.0348 (17) | −0.0041 (14) |
C16 | 0.053 (2) | 0.0356 (17) | 0.0446 (18) | 0.0041 (15) | 0.0371 (17) | −0.0001 (15) |
C17 | 0.0373 (16) | 0.0266 (14) | 0.0328 (15) | −0.0029 (12) | 0.0242 (14) | 0.0001 (12) |
C18 | 0.0281 (15) | 0.0239 (14) | 0.0250 (14) | −0.0009 (11) | 0.0150 (12) | −0.0004 (12) |
C19 | 0.0289 (15) | 0.0213 (13) | 0.0296 (15) | 0.0002 (11) | 0.0169 (13) | 0.0016 (12) |
C20 | 0.0366 (16) | 0.0284 (15) | 0.0349 (16) | 0.0005 (13) | 0.0252 (14) | 0.0010 (13) |
C21 | 0.0294 (15) | 0.0230 (14) | 0.0271 (14) | 0.0002 (12) | 0.0154 (13) | −0.0012 (12) |
C22 | 0.0263 (14) | 0.0212 (13) | 0.0241 (14) | −0.0002 (11) | 0.0129 (12) | 0.0012 (11) |
C23 | 0.0266 (14) | 0.0270 (14) | 0.0207 (13) | 0.0018 (12) | 0.0126 (12) | 0.0011 (11) |
C24 | 0.0252 (14) | 0.0219 (13) | 0.0204 (13) | 0.0003 (11) | 0.0104 (12) | −0.0006 (11) |
C25 | 0.0498 (19) | 0.0249 (15) | 0.0443 (18) | −0.0016 (14) | 0.0311 (16) | 0.0030 (14) |
C26 | 0.0390 (18) | 0.0241 (14) | 0.0406 (17) | 0.0020 (14) | 0.0270 (15) | 0.0048 (14) |
C27 | 0.0263 (15) | 0.0295 (15) | 0.0239 (14) | −0.0019 (12) | 0.0106 (12) | 0.0017 (12) |
C28 | 0.0315 (16) | 0.0246 (15) | 0.0308 (15) | −0.0002 (12) | 0.0156 (13) | −0.0034 (12) |
O1 | 0.0760 (17) | 0.0237 (11) | 0.0799 (17) | −0.0007 (11) | 0.0621 (15) | 0.0039 (11) |
O1W | 0.085 (3) | 0.047 (2) | 0.094 (4) | 0.000 | −0.005 (3) | 0.000 |
O2 | 0.100 (2) | 0.0355 (12) | 0.098 (2) | −0.0021 (13) | 0.0866 (19) | 0.0022 (13) |
O3 | 0.0365 (13) | 0.0333 (11) | 0.0522 (13) | 0.0092 (10) | 0.0200 (11) | −0.0001 (10) |
O4 | 0.0485 (13) | 0.0277 (11) | 0.0397 (12) | 0.0090 (10) | 0.0223 (11) | −0.0047 (10) |
O5 | 0.0433 (12) | 0.0218 (10) | 0.0401 (12) | −0.0003 (9) | 0.0238 (10) | −0.0008 (9) |
O6 | 0.0737 (16) | 0.0272 (11) | 0.0603 (14) | −0.0010 (11) | 0.0544 (13) | 0.0041 (10) |
O7 | 0.0844 (17) | 0.0289 (11) | 0.0587 (14) | 0.0056 (11) | 0.0580 (14) | −0.0014 (10) |
O8 | 0.0481 (13) | 0.0198 (10) | 0.0459 (12) | 0.0036 (9) | 0.0295 (11) | 0.0024 (9) |
Geometric parameters (Å, º) top
Fe1—N1 | 1.972 (2) | C13—H13A | 0.9300 |
Fe1—N2 | 1.968 (2) | C14—C15 | 1.400 (4) |
Fe1—N3 | 1.984 (2) | C14—C18 | 1.403 (4) |
Fe1—N2i | 1.968 (2) | C15—C16 | 1.365 (4) |
Fe1—N1i | 1.972 (2) | C15—H15A | 0.9300 |
Fe1—N3i | 1.984 (2) | C16—C17 | 1.396 (4) |
N1—C1 | 1.333 (3) | C16—H16A | 0.9300 |
N1—C12 | 1.373 (3) | C17—H17A | 0.9300 |
N2—C10 | 1.335 (3) | C18—C18i | 1.414 (5) |
N2—C11 | 1.366 (3) | C19—C20 | 1.391 (4) |
N3—C17 | 1.337 (3) | C19—C24 | 1.412 (4) |
N3—C18 | 1.365 (3) | C19—C25 | 1.526 (4) |
C1—C2 | 1.398 (4) | C20—C21 | 1.379 (4) |
C1—H1A | 0.9300 | C20—H20A | 0.9300 |
C2—C3 | 1.370 (4) | C21—C22 | 1.393 (4) |
C2—H2A | 0.9300 | C21—C26 | 1.508 (4) |
C3—C4 | 1.402 (4) | C22—C23 | 1.389 (3) |
C3—H3A | 0.9300 | C22—C27 | 1.497 (4) |
C4—C12 | 1.401 (4) | C23—C24 | 1.399 (3) |
C4—C5 | 1.435 (4) | C23—H23A | 0.9300 |
C6—C5 | 1.344 (4) | C24—C28 | 1.516 (3) |
C6—C7 | 1.436 (4) | C25—O2 | 1.209 (3) |
C6—H6A | 0.9300 | C25—O1 | 1.301 (3) |
C5—H5A | 0.9300 | C26—O3 | 1.210 (3) |
C7—C8 | 1.399 (4) | C26—O4 | 1.322 (3) |
C7—C11 | 1.401 (4) | C27—O5 | 1.213 (3) |
C8—C9 | 1.367 (4) | C27—O6 | 1.314 (3) |
C8—H8A | 0.9300 | C28—O7 | 1.234 (3) |
C9—C10 | 1.392 (4) | C28—O8 | 1.279 (3) |
C9—H9A | 0.9300 | O1—H1 | 0.8200 |
C10—H10A | 0.9300 | O1W—H1W | 0.84 (3) |
C11—C12 | 1.418 (4) | O4—H4 | 0.8200 |
C13—C13i | 1.348 (6) | O6—H6 | 0.8200 |
C13—C14 | 1.430 (4) | | |
| | | |
N2—Fe1—N2i | 175.22 (12) | C7—C11—C12 | 120.3 (2) |
N2—Fe1—N1i | 93.83 (9) | N1—C12—C4 | 123.8 (2) |
N2—Fe1—N1 | 82.91 (9) | N1—C12—C11 | 115.6 (2) |
N2—Fe1—N3i | 90.51 (9) | C4—C12—C11 | 120.6 (2) |
N3i—Fe1—N3 | 82.24 (12) | C13i—C13—C14 | 121.12 (16) |
N2i—Fe1—N1i | 82.91 (9) | C13i—C13—H13A | 119.4 |
N2i—Fe1—N1 | 93.83 (9) | C14—C13—H13A | 119.4 |
N1i—Fe1—N1 | 94.34 (12) | C15—C14—C18 | 116.9 (2) |
N2i—Fe1—N3i | 93.09 (9) | C15—C14—C13 | 124.4 (3) |
N1i—Fe1—N3i | 172.85 (8) | C18—C14—C13 | 118.7 (2) |
N1—Fe1—N3i | 91.84 (8) | C16—C15—C14 | 119.8 (3) |
N2—Fe1—N3 | 93.09 (9) | C16—C15—H15A | 120.1 |
N2i—Fe1—N3 | 90.51 (9) | C14—C15—H15A | 120.1 |
N1i—Fe1—N3 | 91.84 (8) | C15—C16—C17 | 119.6 (3) |
N1—Fe1—N3 | 172.85 (8) | C15—C16—H16A | 120.2 |
C1—N1—C12 | 116.8 (2) | C17—C16—H16A | 120.2 |
C1—N1—Fe1 | 130.68 (19) | N3—C17—C16 | 122.9 (2) |
C12—N1—Fe1 | 112.26 (17) | N3—C17—H17A | 118.5 |
C10—N2—C11 | 117.0 (2) | C16—C17—H17A | 118.5 |
C10—N2—Fe1 | 130.53 (19) | N3—C18—C14 | 123.8 (2) |
C11—N2—Fe1 | 112.50 (17) | N3—C18—C18i | 115.97 (14) |
C17—N3—C18 | 116.9 (2) | C14—C18—C18i | 120.21 (15) |
C17—N3—Fe1 | 130.18 (18) | C20—C19—C24 | 118.1 (2) |
C18—N3—Fe1 | 112.91 (17) | C20—C19—C25 | 111.7 (2) |
N1—C1—C2 | 122.9 (3) | C24—C19—C25 | 130.1 (2) |
N1—C1—H1A | 118.5 | C21—C20—C19 | 123.5 (2) |
C2—C1—H1A | 118.5 | C21—C20—H20A | 118.2 |
C3—C2—C1 | 119.8 (3) | C19—C20—H20A | 118.2 |
C3—C2—H2A | 120.1 | C20—C21—C22 | 118.9 (2) |
C1—C2—H2A | 120.1 | C20—C21—C26 | 116.6 (2) |
C2—C3—C4 | 119.5 (3) | C22—C21—C26 | 124.4 (2) |
C2—C3—H3A | 120.2 | C23—C22—C21 | 118.5 (2) |
C4—C3—H3A | 120.2 | C23—C22—C27 | 122.7 (2) |
C12—C4—C3 | 117.1 (2) | C21—C22—C27 | 118.7 (2) |
C12—C4—C5 | 118.1 (3) | C22—C23—C24 | 123.1 (2) |
C3—C4—C5 | 124.8 (3) | C22—C23—H23A | 118.4 |
C5—C6—C7 | 121.6 (3) | C24—C23—H23A | 118.4 |
C5—C6—H6A | 119.2 | C23—C24—C19 | 117.8 (2) |
C7—C6—H6A | 119.2 | C23—C24—C28 | 114.8 (2) |
C6—C5—C4 | 121.2 (3) | C19—C24—C28 | 127.4 (2) |
C6—C5—H5A | 119.4 | O2—C25—O1 | 120.1 (3) |
C4—C5—H5A | 119.4 | O2—C25—C19 | 119.3 (3) |
C8—C7—C11 | 117.3 (3) | O1—C25—C19 | 120.6 (3) |
C8—C7—C6 | 124.6 (3) | O3—C26—O4 | 120.7 (3) |
C11—C7—C6 | 118.1 (3) | O3—C26—C21 | 121.8 (3) |
C9—C8—C7 | 119.1 (3) | O4—C26—C21 | 117.2 (2) |
C9—C8—H8A | 120.4 | O5—C27—O6 | 124.2 (2) |
C7—C8—H8A | 120.4 | O5—C27—C22 | 121.2 (2) |
C8—C9—C10 | 120.1 (3) | O6—C27—C22 | 114.6 (2) |
C8—C9—H9A | 119.9 | O7—C28—O8 | 122.4 (2) |
C10—C9—H9A | 119.9 | O7—C28—C24 | 118.2 (2) |
N2—C10—C9 | 122.8 (3) | O8—C28—C24 | 119.3 (2) |
N2—C10—H10A | 118.6 | C25—O1—H1 | 109.5 |
C9—C10—H10A | 118.6 | C26—O4—H4 | 109.5 |
N2—C11—C7 | 123.7 (2) | C27—O6—H6 | 109.5 |
N2—C11—C12 | 116.0 (2) | | |
Symmetry code: (i) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O8ii | 0.82 | 1.82 | 2.628 (3) | 170 |
O6—H6···O7iii | 0.82 | 1.85 | 2.667 (3) | 174 |
O1—H1···O8 | 0.82 | 1.62 | 2.443 (3) | 176 |
O1W—H1W···O3iv | 0.84 (3) | 2.05 (3) | 2.882 (3) | 171 (5) |
Symmetry codes: (ii) −x+1/2, −y+1/2, −z; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x+1, y, −z+1/2. |
(II) tris(2,2'-bipyridine-
κ2N,
N')iron(II)
2,5-dicarboxybenzene-1,4-dicarboxylate–benzene-1,2,4,5-tetracarboxylic
acid–water (1/1/2)
top
Crystal data top
[Fe(C10H8N2)3](C10H4O8)·C10H6O8·2H2O | F(000) = 2200 |
Mr = 1066.71 | Dx = 1.567 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 19949 reflections |
a = 13.767 (3) Å | θ = 3.0–27.5° |
b = 13.911 (3) Å | µ = 0.42 mm−1 |
c = 24.202 (5) Å | T = 223 K |
β = 102.68 (3)° | Block, red |
V = 4521.7 (16) Å3 | 0.40 × 0.35 × 0.10 mm |
Z = 4 | |
Data collection top
Rigaku Mercury CCD area-detector diffractometer | 7925 independent reflections |
Radiation source: fine-focus sealed tube | 6272 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.074 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 25.0°, θmin = 3.0° |
ω scans | h = −14→16 |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | k = −16→16 |
Tmin = 0.849, Tmax = 0.959 | l = −26→28 |
22163 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.093 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.160 | H-atom parameters constrained |
S = 1.23 | w = 1/[σ2(Fo2) + (0.0284P)2 + 7.0361P] where P = (Fo2 + 2Fc2)/3 |
7925 reflections | (Δ/σ)max < 0.001 |
676 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
Crystal data top
[Fe(C10H8N2)3](C10H4O8)·C10H6O8·2H2O | V = 4521.7 (16) Å3 |
Mr = 1066.71 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.767 (3) Å | µ = 0.42 mm−1 |
b = 13.911 (3) Å | T = 223 K |
c = 24.202 (5) Å | 0.40 × 0.35 × 0.10 mm |
β = 102.68 (3)° | |
Data collection top
Rigaku Mercury CCD area-detector diffractometer | 7925 independent reflections |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 6272 reflections with I > 2σ(I) |
Tmin = 0.849, Tmax = 0.959 | Rint = 0.074 |
22163 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.093 | 0 restraints |
wR(F2) = 0.160 | H-atom parameters constrained |
S = 1.23 | Δρmax = 0.43 e Å−3 |
7925 reflections | Δρmin = −0.33 e Å−3 |
676 parameters | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 (Å2) top | x | y | z | Uiso*/Ueq | |
Fe1 | 0.90033 (5) | 0.67650 (5) | 0.23293 (3) | 0.0288 (2) | |
N1 | 1.0281 (3) | 0.6191 (3) | 0.27004 (18) | 0.0328 (10) | |
N2 | 0.8860 (3) | 0.5532 (3) | 0.19218 (18) | 0.0332 (10) | |
N3 | 0.8288 (3) | 0.6213 (3) | 0.28746 (17) | 0.0302 (10) | |
N4 | 0.7653 (3) | 0.7216 (3) | 0.19734 (17) | 0.0300 (10) | |
N5 | 0.9282 (3) | 0.7985 (3) | 0.27426 (18) | 0.0317 (10) | |
N6 | 0.9633 (3) | 0.7439 (3) | 0.17877 (17) | 0.0289 (10) | |
O1 | 0.1022 (4) | 0.4288 (3) | −0.0236 (2) | 0.0778 (16) | |
O2 | 0.0607 (4) | 0.3355 (3) | 0.03997 (19) | 0.0691 (14) | |
H2 | 0.0685 | 0.3330 | 0.0749 | 0.104* | |
O3 | 0.1306 (4) | 0.3003 (3) | 0.13913 (19) | 0.0637 (13) | |
O4 | 0.2504 (4) | 0.3572 (3) | 0.20825 (19) | 0.0571 (12) | |
O5 | 0.3743 (3) | 0.7088 (3) | 0.21193 (17) | 0.0509 (11) | |
O6 | 0.2149 (3) | 0.7459 (3) | 0.20569 (15) | 0.0418 (10) | |
H6 | 0.2389 | 0.7862 | 0.2302 | 0.063* | |
O7 | 0.2831 (3) | 0.7999 (2) | 0.09331 (15) | 0.0417 (10) | |
O8 | 0.2010 (2) | 0.7494 (2) | 0.00846 (15) | 0.0340 (8) | |
O9 | 0.1418 (3) | 1.1331 (3) | 0.04668 (16) | 0.0450 (10) | |
H9 | 0.0854 | 1.1088 | 0.0396 | 0.068* | |
O10 | 0.1505 (3) | 1.0687 (3) | −0.03662 (16) | 0.0408 (9) | |
O11 | 0.2891 (3) | 0.9612 (2) | 0.04911 (16) | 0.0395 (9) | |
H11 | 0.2935 | 0.9048 | 0.0606 | 0.059* | |
O12 | 0.4554 (3) | 0.9543 (3) | 0.07071 (18) | 0.0460 (10) | |
O13 | 0.6496 (3) | 1.2180 (3) | 0.03636 (17) | 0.0463 (10) | |
H13 | 0.7032 | 1.2433 | 0.0340 | 0.069* | |
O14 | 0.5871 (3) | 1.3554 (3) | −0.00258 (19) | 0.0535 (12) | |
O15 | 0.4067 (3) | 1.4551 (3) | 0.03123 (17) | 0.0500 (11) | |
H15 | 0.4069 | 1.5117 | 0.0204 | 0.075* | |
O16 | 0.3747 (3) | 1.4231 (3) | −0.06068 (18) | 0.0591 (12) | |
C1 | 0.1054 (5) | 0.4115 (4) | 0.0261 (3) | 0.0492 (16) | |
C2 | 0.1912 (5) | 0.3649 (4) | 0.1610 (3) | 0.0454 (15) | |
C3 | 0.2868 (4) | 0.7002 (4) | 0.1894 (2) | 0.0334 (13) | |
C4 | 0.2343 (4) | 0.7381 (4) | 0.0607 (2) | 0.0338 (13) | |
C5 | 0.1598 (4) | 0.4775 (4) | 0.0719 (2) | 0.0340 (13) | |
C6 | 0.1945 (4) | 0.4591 (3) | 0.1300 (2) | 0.0335 (13) | |
C7 | 0.2367 (4) | 0.5343 (3) | 0.1652 (2) | 0.0334 (13) | |
H7A | 0.2591 | 0.5223 | 0.2041 | 0.040* | |
C8 | 0.2469 (4) | 0.6261 (3) | 0.1450 (2) | 0.0276 (11) | |
C9 | 0.2197 (4) | 0.6428 (3) | 0.0870 (2) | 0.0285 (12) | |
C10 | 0.1751 (4) | 0.5683 (4) | 0.0523 (2) | 0.0349 (13) | |
H10A | 0.1542 | 0.5804 | 0.0132 | 0.042* | |
C11 | 0.1877 (4) | 1.1121 (4) | 0.0056 (2) | 0.0317 (12) | |
C12 | 0.3780 (4) | 0.9963 (4) | 0.0527 (2) | 0.0303 (12) | |
C13 | 0.5767 (4) | 1.2775 (4) | 0.0173 (2) | 0.0333 (12) | |
C14 | 0.3908 (4) | 1.3976 (4) | −0.0129 (3) | 0.0375 (13) | |
C15 | 0.2904 (4) | 1.1536 (3) | 0.0153 (2) | 0.0270 (11) | |
C16 | 0.3766 (4) | 1.0996 (3) | 0.0325 (2) | 0.0279 (11) | |
C17 | 0.4685 (4) | 1.1420 (3) | 0.0340 (2) | 0.0285 (11) | |
H17A | 0.5267 | 1.1050 | 0.0449 | 0.034* | |
C18 | 0.4761 (4) | 1.2383 (4) | 0.0197 (2) | 0.0305 (12) | |
C19 | 0.3898 (4) | 1.2933 (3) | 0.0046 (2) | 0.0305 (12) | |
C20 | 0.2983 (4) | 1.2505 (4) | 0.0022 (2) | 0.0339 (12) | |
H20A | 0.2401 | 1.2877 | −0.0084 | 0.041* | |
C21 | 1.1038 (4) | 0.6620 (5) | 0.3061 (2) | 0.0468 (15) | |
H21A | 1.0984 | 0.7277 | 0.3141 | 0.056* | |
C22 | 1.1904 (4) | 0.6128 (5) | 0.3320 (3) | 0.0553 (18) | |
H22A | 1.2436 | 0.6451 | 0.3557 | 0.066* | |
C23 | 1.1956 (5) | 0.5164 (5) | 0.3220 (3) | 0.0564 (18) | |
H23A | 1.2516 | 0.4812 | 0.3405 | 0.068* | |
C24 | 1.1197 (5) | 0.4707 (5) | 0.2852 (3) | 0.0526 (17) | |
H24A | 1.1227 | 0.4044 | 0.2784 | 0.063* | |
C25 | 1.0390 (4) | 0.5246 (4) | 0.2584 (2) | 0.0391 (14) | |
C26 | 0.9578 (4) | 0.4868 (4) | 0.2131 (3) | 0.0436 (14) | |
C27 | 0.9556 (5) | 0.3933 (4) | 0.1918 (3) | 0.0579 (18) | |
H27A | 1.0034 | 0.3476 | 0.2085 | 0.069* | |
C28 | 0.8810 (5) | 0.3702 (5) | 0.1456 (3) | 0.063 (2) | |
H28A | 0.8791 | 0.3088 | 0.1293 | 0.076* | |
C29 | 0.8106 (5) | 0.4362 (4) | 0.1237 (3) | 0.0581 (18) | |
H29A | 0.7597 | 0.4210 | 0.0922 | 0.070* | |
C30 | 0.8148 (4) | 0.5263 (4) | 0.1485 (3) | 0.0463 (15) | |
H30A | 0.7645 | 0.5708 | 0.1336 | 0.056* | |
C31 | 0.8664 (4) | 0.5707 (4) | 0.3345 (2) | 0.0388 (14) | |
H31A | 0.9351 | 0.5575 | 0.3431 | 0.047* | |
C32 | 0.8099 (5) | 0.5372 (4) | 0.3706 (2) | 0.0456 (15) | |
H32A | 0.8395 | 0.5027 | 0.4034 | 0.055* | |
C33 | 0.7097 (5) | 0.5550 (4) | 0.3581 (3) | 0.0481 (16) | |
H33A | 0.6696 | 0.5322 | 0.3821 | 0.058* | |
C34 | 0.6679 (4) | 0.6059 (4) | 0.3103 (3) | 0.0485 (16) | |
H34A | 0.5991 | 0.6186 | 0.3010 | 0.058* | |
C35 | 0.7297 (4) | 0.6384 (4) | 0.2759 (2) | 0.0341 (13) | |
C36 | 0.6932 (4) | 0.6951 (4) | 0.2245 (2) | 0.0336 (13) | |
C37 | 0.5943 (4) | 0.7203 (4) | 0.2045 (3) | 0.0455 (15) | |
H37A | 0.5458 | 0.7011 | 0.2242 | 0.055* | |
C38 | 0.5677 (4) | 0.7732 (4) | 0.1559 (3) | 0.0450 (15) | |
H38A | 0.5008 | 0.7899 | 0.1417 | 0.054* | |
C39 | 0.6393 (4) | 0.8016 (4) | 0.1284 (2) | 0.0421 (14) | |
H39A | 0.6224 | 0.8386 | 0.0951 | 0.050* | |
C40 | 0.7375 (4) | 0.7750 (4) | 0.1500 (2) | 0.0367 (13) | |
H40A | 0.7865 | 0.7951 | 0.1309 | 0.044* | |
C41 | 0.9079 (4) | 0.8224 (4) | 0.3237 (2) | 0.0444 (14) | |
H41A | 0.8725 | 0.7783 | 0.3412 | 0.053* | |
C42 | 0.9363 (5) | 0.9093 (4) | 0.3507 (3) | 0.0498 (16) | |
H42A | 0.9203 | 0.9230 | 0.3857 | 0.060* | |
C43 | 0.9875 (5) | 0.9742 (4) | 0.3263 (3) | 0.0514 (16) | |
H43A | 1.0092 | 1.0325 | 0.3447 | 0.062* | |
C44 | 1.0071 (4) | 0.9529 (4) | 0.2738 (2) | 0.0440 (15) | |
H44A | 1.0407 | 0.9975 | 0.2555 | 0.053* | |
C45 | 0.9767 (4) | 0.8652 (4) | 0.2485 (2) | 0.0362 (13) | |
C46 | 0.9941 (3) | 0.8351 (4) | 0.1929 (2) | 0.0305 (12) | |
C47 | 1.0360 (4) | 0.8936 (4) | 0.1586 (2) | 0.0364 (13) | |
H47A | 1.0570 | 0.9561 | 0.1702 | 0.044* | |
C48 | 1.0464 (4) | 0.8588 (4) | 0.1072 (2) | 0.0407 (14) | |
H48A | 1.0746 | 0.8975 | 0.0829 | 0.049* | |
C49 | 1.0156 (4) | 0.7676 (4) | 0.0915 (2) | 0.0351 (13) | |
H49A | 1.0216 | 0.7433 | 0.0562 | 0.042* | |
C50 | 0.9753 (4) | 0.7110 (4) | 0.1280 (2) | 0.0375 (13) | |
H50A | 0.9557 | 0.6478 | 0.1171 | 0.045* | |
O1W | −0.0520 (3) | 1.1110 (3) | 0.03642 (17) | 0.0473 (10) | |
H1WA | −0.0960 | 1.1531 | 0.0182 | 0.071* | |
H1WB | −0.0807 | 1.0602 | 0.0331 | 0.071* | |
O2W | 0.0498 (4) | 0.1267 (3) | 0.1672 (2) | 0.0772 (15) | |
H2WA | 0.0718 | 0.1326 | 0.2013 | 0.116* | |
H2WB | 0.0610 | 0.1753 | 0.1504 | 0.116* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Fe1 | 0.0280 (4) | 0.0268 (4) | 0.0302 (4) | 0.0008 (3) | 0.0036 (3) | 0.0003 (3) |
N1 | 0.030 (2) | 0.035 (3) | 0.032 (3) | 0.000 (2) | 0.006 (2) | 0.004 (2) |
N2 | 0.035 (2) | 0.029 (2) | 0.035 (3) | 0.001 (2) | 0.006 (2) | 0.000 (2) |
N3 | 0.033 (2) | 0.026 (2) | 0.030 (2) | 0.0028 (19) | 0.004 (2) | 0.0004 (19) |
N4 | 0.028 (2) | 0.028 (2) | 0.033 (3) | 0.0035 (19) | 0.006 (2) | 0.000 (2) |
N5 | 0.026 (2) | 0.031 (2) | 0.038 (3) | −0.0017 (19) | 0.006 (2) | −0.001 (2) |
N6 | 0.026 (2) | 0.030 (2) | 0.030 (2) | 0.0001 (19) | 0.005 (2) | −0.0012 (19) |
O1 | 0.130 (5) | 0.054 (3) | 0.046 (3) | −0.023 (3) | 0.012 (3) | −0.010 (2) |
O2 | 0.095 (4) | 0.041 (3) | 0.063 (3) | −0.026 (3) | 0.001 (3) | −0.004 (2) |
O3 | 0.093 (4) | 0.030 (2) | 0.069 (3) | −0.017 (2) | 0.020 (3) | 0.008 (2) |
O4 | 0.088 (3) | 0.034 (2) | 0.051 (3) | 0.002 (2) | 0.019 (3) | 0.018 (2) |
O5 | 0.033 (2) | 0.060 (3) | 0.055 (3) | −0.005 (2) | 0.001 (2) | −0.014 (2) |
O6 | 0.039 (2) | 0.043 (2) | 0.042 (2) | 0.0023 (19) | 0.0065 (19) | −0.0144 (19) |
O7 | 0.058 (3) | 0.027 (2) | 0.039 (2) | −0.0161 (18) | 0.008 (2) | 0.0037 (17) |
O8 | 0.035 (2) | 0.034 (2) | 0.033 (2) | −0.0023 (17) | 0.0047 (17) | 0.0109 (17) |
O9 | 0.034 (2) | 0.056 (3) | 0.045 (2) | −0.0101 (19) | 0.0087 (19) | −0.008 (2) |
O10 | 0.042 (2) | 0.041 (2) | 0.038 (2) | −0.0055 (19) | 0.0039 (19) | −0.0068 (19) |
O11 | 0.036 (2) | 0.0256 (19) | 0.056 (3) | −0.0045 (17) | 0.0078 (19) | 0.0089 (18) |
O12 | 0.034 (2) | 0.031 (2) | 0.071 (3) | 0.0041 (18) | 0.008 (2) | 0.014 (2) |
O13 | 0.030 (2) | 0.047 (2) | 0.061 (3) | −0.0036 (18) | 0.008 (2) | 0.023 (2) |
O14 | 0.047 (2) | 0.028 (2) | 0.092 (3) | −0.0021 (19) | 0.028 (2) | 0.014 (2) |
O15 | 0.073 (3) | 0.025 (2) | 0.054 (3) | 0.002 (2) | 0.018 (2) | 0.0042 (19) |
O16 | 0.086 (3) | 0.040 (2) | 0.043 (3) | −0.012 (2) | −0.004 (2) | 0.013 (2) |
C1 | 0.065 (4) | 0.030 (3) | 0.050 (4) | −0.006 (3) | 0.008 (3) | −0.005 (3) |
C2 | 0.062 (4) | 0.026 (3) | 0.053 (4) | 0.007 (3) | 0.023 (4) | 0.005 (3) |
C3 | 0.036 (3) | 0.025 (3) | 0.039 (3) | −0.002 (2) | 0.009 (3) | 0.003 (2) |
C4 | 0.033 (3) | 0.026 (3) | 0.044 (4) | 0.002 (2) | 0.014 (3) | 0.004 (3) |
C5 | 0.040 (3) | 0.027 (3) | 0.034 (3) | 0.004 (2) | 0.005 (3) | −0.001 (2) |
C6 | 0.036 (3) | 0.022 (3) | 0.046 (4) | 0.001 (2) | 0.016 (3) | 0.002 (2) |
C7 | 0.044 (3) | 0.026 (3) | 0.030 (3) | 0.005 (2) | 0.007 (3) | 0.008 (2) |
C8 | 0.027 (3) | 0.023 (3) | 0.035 (3) | 0.002 (2) | 0.011 (2) | 0.001 (2) |
C9 | 0.029 (3) | 0.026 (3) | 0.031 (3) | −0.001 (2) | 0.010 (2) | 0.007 (2) |
C10 | 0.043 (3) | 0.030 (3) | 0.030 (3) | −0.004 (3) | 0.005 (3) | 0.003 (2) |
C11 | 0.030 (3) | 0.027 (3) | 0.036 (3) | 0.003 (2) | 0.003 (3) | 0.008 (3) |
C12 | 0.036 (3) | 0.026 (3) | 0.031 (3) | −0.005 (2) | 0.012 (3) | 0.001 (2) |
C13 | 0.037 (3) | 0.031 (3) | 0.031 (3) | −0.002 (3) | 0.006 (3) | −0.001 (2) |
C14 | 0.042 (3) | 0.032 (3) | 0.037 (4) | −0.004 (3) | 0.005 (3) | 0.002 (3) |
C15 | 0.031 (3) | 0.026 (3) | 0.026 (3) | −0.002 (2) | 0.008 (2) | −0.003 (2) |
C16 | 0.034 (3) | 0.023 (3) | 0.028 (3) | 0.001 (2) | 0.009 (2) | 0.004 (2) |
C17 | 0.030 (3) | 0.026 (3) | 0.030 (3) | 0.000 (2) | 0.008 (2) | 0.004 (2) |
C18 | 0.033 (3) | 0.029 (3) | 0.029 (3) | −0.003 (2) | 0.008 (2) | 0.003 (2) |
C19 | 0.037 (3) | 0.021 (3) | 0.032 (3) | −0.001 (2) | 0.005 (2) | −0.001 (2) |
C20 | 0.033 (3) | 0.026 (3) | 0.042 (3) | 0.003 (2) | 0.005 (3) | 0.004 (2) |
C21 | 0.044 (3) | 0.055 (4) | 0.040 (4) | −0.002 (3) | 0.005 (3) | 0.015 (3) |
C22 | 0.037 (3) | 0.091 (6) | 0.036 (4) | 0.001 (4) | 0.006 (3) | 0.019 (4) |
C23 | 0.042 (4) | 0.074 (5) | 0.056 (4) | 0.021 (4) | 0.018 (3) | 0.020 (4) |
C24 | 0.048 (4) | 0.058 (4) | 0.056 (4) | 0.015 (3) | 0.019 (3) | 0.015 (3) |
C25 | 0.040 (3) | 0.040 (3) | 0.042 (4) | 0.010 (3) | 0.019 (3) | 0.009 (3) |
C26 | 0.051 (4) | 0.035 (3) | 0.048 (4) | 0.001 (3) | 0.017 (3) | 0.003 (3) |
C27 | 0.069 (5) | 0.041 (4) | 0.067 (5) | 0.008 (3) | 0.022 (4) | 0.002 (3) |
C28 | 0.070 (5) | 0.040 (4) | 0.084 (6) | −0.003 (4) | 0.022 (4) | −0.016 (4) |
C29 | 0.063 (4) | 0.046 (4) | 0.063 (5) | −0.004 (3) | 0.009 (4) | −0.019 (3) |
C30 | 0.045 (4) | 0.036 (3) | 0.058 (4) | −0.003 (3) | 0.011 (3) | −0.004 (3) |
C31 | 0.045 (3) | 0.031 (3) | 0.039 (3) | 0.003 (3) | 0.005 (3) | 0.002 (3) |
C32 | 0.063 (4) | 0.038 (3) | 0.034 (3) | −0.005 (3) | 0.006 (3) | 0.003 (3) |
C33 | 0.054 (4) | 0.052 (4) | 0.042 (4) | −0.014 (3) | 0.018 (3) | 0.004 (3) |
C34 | 0.041 (3) | 0.059 (4) | 0.049 (4) | −0.007 (3) | 0.016 (3) | 0.000 (3) |
C35 | 0.028 (3) | 0.038 (3) | 0.035 (3) | −0.003 (2) | 0.004 (2) | −0.006 (3) |
C36 | 0.022 (3) | 0.033 (3) | 0.044 (3) | 0.001 (2) | 0.004 (2) | −0.001 (3) |
C37 | 0.034 (3) | 0.046 (4) | 0.058 (4) | −0.003 (3) | 0.011 (3) | 0.000 (3) |
C38 | 0.031 (3) | 0.045 (4) | 0.054 (4) | 0.004 (3) | −0.001 (3) | −0.004 (3) |
C39 | 0.047 (4) | 0.030 (3) | 0.042 (4) | 0.004 (3) | −0.005 (3) | −0.001 (3) |
C40 | 0.042 (3) | 0.029 (3) | 0.038 (3) | 0.000 (3) | 0.005 (3) | 0.005 (3) |
C41 | 0.048 (4) | 0.052 (4) | 0.035 (3) | −0.008 (3) | 0.014 (3) | −0.008 (3) |
C42 | 0.060 (4) | 0.050 (4) | 0.042 (4) | −0.005 (3) | 0.017 (3) | −0.018 (3) |
C43 | 0.060 (4) | 0.042 (4) | 0.050 (4) | 0.000 (3) | 0.007 (3) | −0.017 (3) |
C44 | 0.053 (4) | 0.040 (3) | 0.038 (4) | 0.001 (3) | 0.006 (3) | −0.002 (3) |
C45 | 0.032 (3) | 0.039 (3) | 0.036 (3) | 0.005 (3) | 0.002 (3) | −0.002 (3) |
C46 | 0.021 (2) | 0.032 (3) | 0.037 (3) | 0.001 (2) | 0.003 (2) | 0.006 (2) |
C47 | 0.034 (3) | 0.034 (3) | 0.040 (3) | −0.001 (2) | 0.006 (3) | 0.005 (3) |
C48 | 0.035 (3) | 0.050 (4) | 0.037 (3) | 0.000 (3) | 0.008 (3) | 0.011 (3) |
C49 | 0.031 (3) | 0.051 (4) | 0.024 (3) | 0.007 (3) | 0.007 (2) | 0.003 (3) |
C50 | 0.034 (3) | 0.037 (3) | 0.039 (3) | 0.005 (3) | 0.002 (3) | −0.007 (3) |
O1W | 0.034 (2) | 0.047 (2) | 0.060 (3) | −0.0034 (18) | 0.006 (2) | 0.006 (2) |
O2W | 0.086 (4) | 0.050 (3) | 0.112 (4) | −0.013 (3) | 0.054 (3) | 0.010 (3) |
Geometric parameters (Å, º) top
Fe1—N1 | 1.961 (4) | C17—H17A | 0.9400 |
Fe1—N2 | 1.966 (4) | C18—C19 | 1.393 (7) |
Fe1—N3 | 1.967 (4) | C19—C20 | 1.384 (7) |
Fe1—N4 | 1.971 (4) | C20—H20A | 0.9400 |
Fe1—N5 | 1.964 (4) | C21—C22 | 1.398 (8) |
Fe1—N6 | 1.961 (4) | C21—H21A | 0.9400 |
N1—C21 | 1.343 (7) | C22—C23 | 1.367 (9) |
N1—C25 | 1.360 (7) | C22—H22A | 0.9400 |
N2—C30 | 1.328 (7) | C23—C24 | 1.371 (9) |
N2—C26 | 1.367 (7) | C23—H23A | 0.9400 |
N3—C31 | 1.341 (6) | C24—C25 | 1.379 (8) |
N3—C35 | 1.352 (6) | C24—H24A | 0.9400 |
N4—C40 | 1.349 (6) | C25—C26 | 1.480 (8) |
N4—C36 | 1.357 (6) | C26—C27 | 1.396 (8) |
N5—C41 | 1.328 (6) | C27—C28 | 1.380 (9) |
N5—C45 | 1.371 (7) | C27—H27A | 0.9400 |
N6—C50 | 1.356 (6) | C28—C29 | 1.355 (9) |
N6—C46 | 1.357 (6) | C28—H28A | 0.9400 |
O1—C1 | 1.217 (7) | C29—C30 | 1.386 (8) |
O2—C1 | 1.305 (7) | C29—H29A | 0.9400 |
O2—H2 | 0.8300 | C30—H30A | 0.9400 |
O3—C2 | 1.261 (7) | C31—C32 | 1.374 (8) |
O4—C2 | 1.255 (7) | C31—H31A | 0.9400 |
O5—C3 | 1.214 (6) | C32—C33 | 1.369 (8) |
O6—C3 | 1.308 (6) | C32—H32A | 0.9400 |
O6—H6 | 0.8300 | C33—C34 | 1.371 (8) |
O7—C4 | 1.257 (6) | C33—H33A | 0.9400 |
O8—C4 | 1.257 (6) | C34—C35 | 1.390 (7) |
O9—C11 | 1.322 (6) | C34—H34A | 0.9400 |
O9—H9 | 0.8300 | C35—C36 | 1.466 (7) |
O10—C11 | 1.201 (6) | C36—C37 | 1.386 (7) |
O11—C12 | 1.302 (6) | C37—C38 | 1.367 (8) |
O11—H11 | 0.8300 | C37—H37A | 0.9400 |
O12—C12 | 1.210 (6) | C38—C39 | 1.364 (8) |
O13—C13 | 1.305 (6) | C38—H38A | 0.9400 |
O13—H13 | 0.8300 | C39—C40 | 1.388 (7) |
O14—C13 | 1.206 (6) | C39—H39A | 0.9400 |
O15—C14 | 1.313 (6) | C40—H40A | 0.9400 |
O15—H15 | 0.8300 | C41—C42 | 1.390 (8) |
O16—C14 | 1.184 (6) | C41—H41A | 0.9400 |
C1—C5 | 1.506 (8) | C42—C43 | 1.358 (8) |
C2—C6 | 1.516 (7) | C42—H42A | 0.9400 |
C3—C8 | 1.503 (7) | C43—C44 | 1.389 (8) |
C4—C9 | 1.503 (7) | C43—H43A | 0.9400 |
C5—C10 | 1.382 (7) | C44—C45 | 1.388 (7) |
C5—C6 | 1.406 (7) | C44—H44A | 0.9400 |
C6—C7 | 1.393 (7) | C45—C46 | 1.479 (7) |
C7—C8 | 1.385 (6) | C46—C47 | 1.376 (7) |
C7—H7A | 0.9400 | C47—C48 | 1.372 (7) |
C8—C9 | 1.391 (7) | C47—H47A | 0.9400 |
C9—C10 | 1.389 (7) | C48—C49 | 1.365 (8) |
C10—H10A | 0.9400 | C48—H48A | 0.9400 |
C11—C15 | 1.497 (7) | C49—C50 | 1.386 (7) |
C12—C16 | 1.516 (7) | C49—H49A | 0.9400 |
C13—C18 | 1.501 (7) | C50—H50A | 0.9400 |
C14—C19 | 1.512 (7) | O1W—H1WA | 0.8872 |
C15—C16 | 1.389 (7) | O1W—H1WB | 0.8050 |
C15—C20 | 1.395 (7) | O2W—H2WA | 0.8201 |
C16—C17 | 1.389 (7) | O2W—H2WB | 0.8202 |
C17—C18 | 1.394 (7) | | |
| | | |
N1—Fe1—N2 | 81.71 (18) | C19—C20—C15 | 121.4 (5) |
N3—Fe1—N4 | 81.64 (17) | C19—C20—H20A | 119.3 |
N5—Fe1—N6 | 82.06 (17) | C15—C20—H20A | 119.3 |
N1—Fe1—N6 | 90.98 (17) | N1—C21—C22 | 122.5 (6) |
N1—Fe1—N5 | 93.62 (18) | N1—C21—H21A | 118.7 |
N6—Fe1—N2 | 95.27 (17) | C22—C21—H21A | 118.7 |
N5—Fe1—N2 | 174.60 (17) | C23—C22—C21 | 118.3 (6) |
N1—Fe1—N3 | 93.70 (17) | C23—C22—H22A | 120.9 |
N6—Fe1—N3 | 173.95 (17) | C21—C22—H22A | 120.9 |
N5—Fe1—N3 | 93.79 (17) | C22—C23—C24 | 120.5 (6) |
N2—Fe1—N3 | 89.22 (17) | C22—C23—H23A | 119.7 |
N1—Fe1—N4 | 174.02 (18) | C24—C23—H23A | 119.7 |
N6—Fe1—N4 | 93.94 (17) | C23—C24—C25 | 118.3 (6) |
N5—Fe1—N4 | 90.44 (17) | C23—C24—H24A | 120.9 |
N2—Fe1—N4 | 94.43 (18) | C25—C24—H24A | 120.9 |
C21—N1—C25 | 117.3 (5) | N1—C25—C24 | 122.9 (6) |
C21—N1—Fe1 | 127.4 (4) | N1—C25—C26 | 113.4 (5) |
C25—N1—Fe1 | 115.3 (4) | C24—C25—C26 | 123.7 (6) |
C30—N2—C26 | 116.9 (5) | N2—C26—C27 | 122.5 (6) |
C30—N2—Fe1 | 128.3 (4) | N2—C26—C25 | 113.6 (5) |
C26—N2—Fe1 | 114.8 (4) | C27—C26—C25 | 123.8 (6) |
C31—N3—C35 | 116.9 (5) | C28—C27—C26 | 117.9 (6) |
C31—N3—Fe1 | 128.1 (4) | C28—C27—H27A | 121.0 |
C35—N3—Fe1 | 115.1 (3) | C26—C27—H27A | 121.0 |
C40—N4—C36 | 117.3 (4) | C29—C28—C27 | 120.0 (6) |
C40—N4—Fe1 | 127.7 (4) | C29—C28—H28A | 120.0 |
C36—N4—Fe1 | 115.0 (3) | C27—C28—H28A | 120.0 |
C41—N5—C45 | 117.4 (5) | C28—C29—C30 | 119.0 (6) |
C41—N5—Fe1 | 128.2 (4) | C28—C29—H29A | 120.5 |
C45—N5—Fe1 | 114.4 (3) | C30—C29—H29A | 120.5 |
C50—N6—C46 | 116.7 (4) | N2—C30—C29 | 123.6 (6) |
C50—N6—Fe1 | 127.2 (4) | N2—C30—H30A | 118.2 |
C46—N6—Fe1 | 116.0 (3) | C29—C30—H30A | 118.2 |
C1—O2—H2 | 109.5 | N3—C31—C32 | 123.4 (5) |
C3—O6—H6 | 109.5 | N3—C31—H31A | 118.3 |
C11—O9—H9 | 109.5 | C32—C31—H31A | 118.3 |
C12—O11—H11 | 109.5 | C33—C32—C31 | 118.8 (6) |
C13—O13—H13 | 109.5 | C33—C32—H32A | 120.6 |
C14—O15—H15 | 109.5 | C31—C32—H32A | 120.6 |
O1—C1—O2 | 119.8 (6) | C32—C33—C34 | 119.8 (6) |
O1—C1—C5 | 120.7 (6) | C32—C33—H33A | 120.1 |
O2—C1—C5 | 119.4 (6) | C34—C33—H33A | 120.1 |
O4—C2—O3 | 124.0 (5) | C33—C34—C35 | 118.3 (6) |
O4—C2—C6 | 116.2 (5) | C33—C34—H34A | 120.8 |
O3—C2—C6 | 119.8 (6) | C35—C34—H34A | 120.8 |
O5—C3—O6 | 124.0 (5) | N3—C35—C34 | 122.8 (5) |
O5—C3—C8 | 124.0 (5) | N3—C35—C36 | 114.3 (4) |
O6—C3—C8 | 111.5 (4) | C34—C35—C36 | 122.9 (5) |
O7—C4—O8 | 124.9 (5) | N4—C36—C37 | 121.9 (5) |
O7—C4—C9 | 116.2 (5) | N4—C36—C35 | 114.0 (4) |
O8—C4—C9 | 118.9 (5) | C37—C36—C35 | 124.1 (5) |
C10—C5—C6 | 117.8 (5) | C38—C37—C36 | 119.6 (6) |
C10—C5—C1 | 113.2 (5) | C38—C37—H37A | 120.2 |
C6—C5—C1 | 129.1 (5) | C36—C37—H37A | 120.2 |
C7—C6—C5 | 118.7 (5) | C39—C38—C37 | 119.4 (5) |
C7—C6—C2 | 113.6 (5) | C39—C38—H38A | 120.3 |
C5—C6—C2 | 127.7 (5) | C37—C38—H38A | 120.3 |
C8—C7—C6 | 122.5 (5) | C38—C39—C40 | 119.1 (5) |
C8—C7—H7A | 118.7 | C38—C39—H39A | 120.5 |
C6—C7—H7A | 118.7 | C40—C39—H39A | 120.5 |
C7—C8—C9 | 118.9 (5) | N4—C40—C39 | 122.6 (5) |
C7—C8—C3 | 115.4 (5) | N4—C40—H40A | 118.7 |
C9—C8—C3 | 125.7 (4) | C39—C40—H40A | 118.7 |
C10—C9—C8 | 118.2 (5) | N5—C41—C42 | 123.3 (6) |
C10—C9—C4 | 118.9 (5) | N5—C41—H41A | 118.4 |
C8—C9—C4 | 122.9 (5) | C42—C41—H41A | 118.4 |
C5—C10—C9 | 123.6 (5) | C43—C42—C41 | 119.5 (6) |
C5—C10—H10A | 118.2 | C43—C42—H42A | 120.2 |
C9—C10—H10A | 118.2 | C41—C42—H42A | 120.2 |
O10—C11—O9 | 124.5 (5) | C42—C43—C44 | 118.7 (6) |
O10—C11—C15 | 122.6 (5) | C42—C43—H43A | 120.7 |
O9—C11—C15 | 112.8 (5) | C44—C43—H43A | 120.7 |
O12—C12—O11 | 125.7 (5) | C45—C44—C43 | 119.4 (6) |
O12—C12—C16 | 121.4 (5) | C45—C44—H44A | 120.3 |
O11—C12—C16 | 112.9 (4) | C43—C44—H44A | 120.3 |
O14—C13—O13 | 124.1 (5) | N5—C45—C44 | 121.6 (5) |
O14—C13—C18 | 122.2 (5) | N5—C45—C46 | 114.5 (5) |
O13—C13—C18 | 113.6 (4) | C44—C45—C46 | 123.9 (5) |
O16—C14—O15 | 125.1 (5) | N6—C46—C47 | 123.4 (5) |
O16—C14—C19 | 123.3 (5) | N6—C46—C45 | 113.0 (4) |
O15—C14—C19 | 111.6 (5) | C47—C46—C45 | 123.6 (5) |
C16—C15—C20 | 119.1 (5) | C48—C47—C46 | 118.7 (5) |
C16—C15—C11 | 123.6 (4) | C48—C47—H47A | 120.7 |
C20—C15—C11 | 117.1 (4) | C46—C47—H47A | 120.7 |
C17—C16—C15 | 119.5 (4) | C49—C48—C47 | 119.4 (5) |
C17—C16—C12 | 116.5 (4) | C49—C48—H48A | 120.3 |
C15—C16—C12 | 123.9 (4) | C47—C48—H48A | 120.3 |
C16—C17—C18 | 121.3 (5) | C48—C49—C50 | 119.7 (5) |
C16—C17—H17A | 119.4 | C48—C49—H49A | 120.1 |
C18—C17—H17A | 119.4 | C50—C49—H49A | 120.1 |
C19—C18—C17 | 119.2 (5) | N6—C50—C49 | 122.1 (5) |
C19—C18—C13 | 122.1 (4) | N6—C50—H50A | 119.0 |
C17—C18—C13 | 118.6 (5) | C49—C50—H50A | 119.0 |
C20—C19—C18 | 119.4 (4) | H1WA—O1W—H1WB | 105.3 |
C20—C19—C14 | 117.7 (5) | H2WA—O2W—H2WB | 110.3 |
C18—C19—C14 | 122.7 (5) | | |
| | | |
N6—Fe1—N1—C21 | 76.7 (5) | C16—C17—C18—C13 | −174.8 (5) |
N5—Fe1—N1—C21 | −5.4 (5) | O14—C13—C18—C19 | −6.9 (8) |
N2—Fe1—N1—C21 | 171.8 (5) | O13—C13—C18—C19 | 175.8 (5) |
N3—Fe1—N1—C21 | −99.5 (5) | O14—C13—C18—C17 | 169.0 (5) |
N6—Fe1—N1—C25 | −104.8 (4) | O13—C13—C18—C17 | −8.3 (7) |
N5—Fe1—N1—C25 | 173.1 (4) | C17—C18—C19—C20 | −2.3 (8) |
N2—Fe1—N1—C25 | −9.6 (4) | C13—C18—C19—C20 | 173.6 (5) |
N3—Fe1—N1—C25 | 79.0 (4) | C17—C18—C19—C14 | −178.6 (5) |
N1—Fe1—N2—C30 | −173.1 (5) | C13—C18—C19—C14 | −2.7 (8) |
N6—Fe1—N2—C30 | −82.9 (5) | O16—C14—C19—C20 | −79.0 (7) |
N3—Fe1—N2—C30 | 93.0 (5) | O15—C14—C19—C20 | 97.8 (6) |
N4—Fe1—N2—C30 | 11.5 (5) | O16—C14—C19—C18 | 97.4 (7) |
N1—Fe1—N2—C26 | 8.9 (4) | O15—C14—C19—C18 | −85.8 (6) |
N6—Fe1—N2—C26 | 99.1 (4) | C18—C19—C20—C15 | 0.7 (8) |
N3—Fe1—N2—C26 | −84.9 (4) | C14—C19—C20—C15 | 177.3 (5) |
N4—Fe1—N2—C26 | −166.5 (4) | C16—C15—C20—C19 | 1.9 (8) |
N1—Fe1—N3—C31 | 5.0 (4) | C11—C15—C20—C19 | −173.8 (5) |
N5—Fe1—N3—C31 | −88.9 (4) | C25—N1—C21—C22 | −1.3 (8) |
N2—Fe1—N3—C31 | 86.6 (4) | Fe1—N1—C21—C22 | 177.2 (4) |
N4—Fe1—N3—C31 | −178.8 (5) | N1—C21—C22—C23 | −2.9 (9) |
N1—Fe1—N3—C35 | −176.1 (4) | C21—C22—C23—C24 | 3.2 (9) |
N5—Fe1—N3—C35 | 90.0 (4) | C22—C23—C24—C25 | 0.5 (9) |
N2—Fe1—N3—C35 | −94.5 (4) | C21—N1—C25—C24 | 5.3 (8) |
N4—Fe1—N3—C35 | 0.1 (4) | Fe1—N1—C25—C24 | −173.4 (4) |
N6—Fe1—N4—C40 | 3.5 (4) | C21—N1—C25—C26 | −172.8 (5) |
N5—Fe1—N4—C40 | 85.6 (4) | Fe1—N1—C25—C26 | 8.5 (6) |
N2—Fe1—N4—C40 | −92.1 (4) | C23—C24—C25—N1 | −5.0 (9) |
N3—Fe1—N4—C40 | 179.3 (4) | C23—C24—C25—C26 | 172.9 (5) |
N6—Fe1—N4—C36 | −176.3 (4) | C30—N2—C26—C27 | −2.5 (8) |
N5—Fe1—N4—C36 | −94.2 (4) | Fe1—N2—C26—C27 | 175.7 (5) |
N2—Fe1—N4—C36 | 88.1 (4) | C30—N2—C26—C25 | 175.0 (5) |
N3—Fe1—N4—C36 | −0.5 (4) | Fe1—N2—C26—C25 | −6.8 (6) |
N1—Fe1—N5—C41 | −89.7 (5) | N1—C25—C26—N2 | −1.1 (7) |
N6—Fe1—N5—C41 | 179.8 (5) | C24—C25—C26—N2 | −179.2 (5) |
N3—Fe1—N5—C41 | 4.3 (5) | N1—C25—C26—C27 | 176.4 (5) |
N4—Fe1—N5—C41 | 85.9 (5) | C24—C25—C26—C27 | −1.7 (9) |
N1—Fe1—N5—C45 | 88.8 (4) | N2—C26—C27—C28 | 4.1 (9) |
N6—Fe1—N5—C45 | −1.7 (3) | C25—C26—C27—C28 | −173.2 (6) |
N3—Fe1—N5—C45 | −177.3 (4) | C26—C27—C28—C29 | −2.7 (10) |
N4—Fe1—N5—C45 | −95.6 (4) | C27—C28—C29—C30 | −0.1 (10) |
N1—Fe1—N6—C50 | 89.4 (4) | C26—N2—C30—C29 | −0.4 (8) |
N5—Fe1—N6—C50 | −177.0 (4) | Fe1—N2—C30—C29 | −178.3 (5) |
N2—Fe1—N6—C50 | 7.7 (4) | C28—C29—C30—N2 | 1.7 (10) |
N4—Fe1—N6—C50 | −87.1 (4) | C35—N3—C31—C32 | −0.6 (8) |
N1—Fe1—N6—C46 | −93.8 (4) | Fe1—N3—C31—C32 | 178.3 (4) |
N5—Fe1—N6—C46 | −0.2 (3) | N3—C31—C32—C33 | 0.8 (9) |
N2—Fe1—N6—C46 | −175.5 (3) | C31—C32—C33—C34 | −0.4 (9) |
N4—Fe1—N6—C46 | 89.7 (4) | C32—C33—C34—C35 | −0.2 (9) |
O1—C1—C5—C10 | 19.5 (9) | C31—N3—C35—C34 | −0.1 (8) |
O2—C1—C5—C10 | −160.1 (5) | Fe1—N3—C35—C34 | −179.1 (4) |
O1—C1—C5—C6 | −161.3 (6) | C31—N3—C35—C36 | 179.2 (4) |
O2—C1—C5—C6 | 19.1 (9) | Fe1—N3—C35—C36 | 0.2 (6) |
C10—C5—C6—C7 | 3.9 (8) | C33—C34—C35—N3 | 0.4 (9) |
C1—C5—C6—C7 | −175.3 (5) | C33—C34—C35—C36 | −178.8 (5) |
C10—C5—C6—C2 | −176.9 (5) | C40—N4—C36—C37 | 0.8 (7) |
C1—C5—C6—C2 | 4.0 (9) | Fe1—N4—C36—C37 | −179.3 (4) |
O4—C2—C6—C7 | −20.6 (7) | C40—N4—C36—C35 | −179.1 (4) |
O3—C2—C6—C7 | 158.9 (5) | Fe1—N4—C36—C35 | 0.7 (6) |
O4—C2—C6—C5 | 160.1 (5) | N3—C35—C36—N4 | −0.6 (7) |
O3—C2—C6—C5 | −20.4 (9) | C34—C35—C36—N4 | 178.7 (5) |
C5—C6—C7—C8 | −0.9 (8) | N3—C35—C36—C37 | 179.5 (5) |
C2—C6—C7—C8 | 179.8 (5) | C34—C35—C36—C37 | −1.2 (9) |
C6—C7—C8—C9 | −4.0 (8) | N4—C36—C37—C38 | 0.2 (8) |
C6—C7—C8—C3 | 175.5 (5) | C35—C36—C37—C38 | −179.9 (5) |
O5—C3—C8—C7 | 79.2 (7) | C36—C37—C38—C39 | −1.0 (9) |
O6—C3—C8—C7 | −92.9 (5) | C37—C38—C39—C40 | 0.7 (8) |
O5—C3—C8—C9 | −101.3 (7) | C36—N4—C40—C39 | −1.1 (7) |
O6—C3—C8—C9 | 86.6 (6) | Fe1—N4—C40—C39 | 179.1 (4) |
C7—C8—C9—C10 | 5.6 (7) | C38—C39—C40—N4 | 0.3 (8) |
C3—C8—C9—C10 | −173.9 (5) | C45—N5—C41—C42 | −2.3 (8) |
C7—C8—C9—C4 | −175.8 (5) | Fe1—N5—C41—C42 | 176.1 (4) |
C3—C8—C9—C4 | 4.7 (8) | N5—C41—C42—C43 | 0.0 (10) |
O7—C4—C9—C10 | −173.7 (5) | C41—C42—C43—C44 | 2.1 (10) |
O8—C4—C9—C10 | 3.8 (7) | C42—C43—C44—C45 | −1.9 (9) |
O7—C4—C9—C8 | 7.7 (7) | C41—N5—C45—C44 | 2.5 (8) |
O8—C4—C9—C8 | −174.8 (5) | Fe1—N5—C45—C44 | −176.1 (4) |
C6—C5—C10—C9 | −2.2 (8) | C41—N5—C45—C46 | −178.2 (5) |
C1—C5—C10—C9 | 177.0 (5) | Fe1—N5—C45—C46 | 3.2 (5) |
C8—C9—C10—C5 | −2.6 (8) | C43—C44—C45—N5 | −0.5 (8) |
C4—C9—C10—C5 | 178.8 (5) | C43—C44—C45—C46 | −179.7 (5) |
O10—C11—C15—C16 | −78.8 (7) | C50—N6—C46—C47 | −0.2 (7) |
O9—C11—C15—C16 | 104.8 (6) | Fe1—N6—C46—C47 | −177.3 (4) |
O10—C11—C15—C20 | 96.7 (6) | C50—N6—C46—C45 | 179.1 (4) |
O9—C11—C15—C20 | −79.6 (6) | Fe1—N6—C46—C45 | 2.0 (5) |
C20—C15—C16—C17 | −2.9 (7) | N5—C45—C46—N6 | −3.4 (6) |
C11—C15—C16—C17 | 172.5 (5) | C44—C45—C46—N6 | 175.9 (5) |
C20—C15—C16—C12 | 174.4 (5) | N5—C45—C46—C47 | 175.9 (5) |
C11—C15—C16—C12 | −10.2 (8) | C44—C45—C46—C47 | −4.8 (8) |
O12—C12—C16—C17 | 2.1 (7) | N6—C46—C47—C48 | 0.8 (8) |
O11—C12—C16—C17 | −178.8 (4) | C45—C46—C47—C48 | −178.4 (5) |
O12—C12—C16—C15 | −175.3 (5) | C46—C47—C48—C49 | −0.3 (8) |
O11—C12—C16—C15 | 3.8 (7) | C47—C48—C49—C50 | −0.8 (8) |
C15—C16—C17—C18 | 1.4 (7) | C46—N6—C50—C49 | −0.9 (7) |
C12—C16—C17—C18 | −176.1 (5) | Fe1—N6—C50—C49 | 175.8 (4) |
C16—C17—C18—C19 | 1.2 (8) | C48—C49—C50—N6 | 1.4 (8) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3 | 0.83 | 1.66 | 2.431 (6) | 153 |
O6—H6···O4i | 0.83 | 1.77 | 2.555 (5) | 158 |
O9—H9···O1W | 0.83 | 1.88 | 2.643 (5) | 153 |
O11—H11···O7 | 0.83 | 1.68 | 2.495 (5) | 166 |
O13—H13···O8ii | 0.83 | 1.84 | 2.567 (5) | 145 |
O15—H15···O14iii | 0.83 | 1.90 | 2.732 (5) | 175 |
O1W—H1WA···O8iv | 0.89 | 1.98 | 2.861 (5) | 169 |
O1W—H1WB···O10iv | 0.81 | 2.04 | 2.844 (5) | 172 |
O2W—H2WA···O5v | 0.82 | 2.32 | 3.101 (7) | 159 |
O2W—H2WB···O3 | 0.82 | 2.03 | 2.803 (6) | 157 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1, −y+2, −z; (iii) −x+1, −y+3, −z; (iv) −x, −y+2, −z; (v) −x+1/2, y−1/2, −z+1/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Fe(C12H8N2)3](C10H5O8)2·H2O | [Fe(C10H8N2)3](C10H4O8)·C10H6O8·2H2O |
Mr | 1120.76 | 1066.71 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, P21/n |
Temperature (K) | 223 | 223 |
a, b, c (Å) | 24.151 (5), 14.088 (3), 15.651 (3) | 13.767 (3), 13.911 (3), 24.202 (5) |
β (°) | 116.54 (3) | 102.68 (3) |
V (Å3) | 4764 (2) | 4521.7 (16) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.41 | 0.42 |
Crystal size (mm) | 0.46 × 0.22 × 0.20 | 0.40 × 0.35 × 0.10 |
|
Data collection |
Diffractometer | Rigaku Mercury CCD area-detector diffractometer | Rigaku Mercury CCD area-detector diffractometer |
Absorption correction | Multi-scan (REQAB; Jacobson, 1998) | Multi-scan (REQAB; Jacobson, 1998) |
Tmin, Tmax | 0.836, 0.923 | 0.849, 0.959 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11666, 4190, 3613 | 22163, 7925, 6272 |
Rint | 0.041 | 0.074 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.111, 1.11 | 0.093, 0.160, 1.23 |
No. of reflections | 4190 | 7925 |
No. of parameters | 366 | 676 |
No. of restraints | 1 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.37 | 0.43, −0.33 |
Selected geometric parameters (Å, º) for (I) topFe1—N1 | 1.972 (2) | Fe1—N3 | 1.984 (2) |
Fe1—N2 | 1.968 (2) | | |
| | | |
N2—Fe1—N2i | 175.22 (12) | N2—Fe1—N3i | 90.51 (9) |
N2—Fe1—N1i | 93.83 (9) | N3i—Fe1—N3 | 82.24 (12) |
N2—Fe1—N1 | 82.91 (9) | | |
Symmetry code: (i) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O8ii | 0.82 | 1.82 | 2.628 (3) | 169.5 |
O6—H6···O7iii | 0.82 | 1.85 | 2.667 (3) | 174.4 |
O1—H1···O8 | 0.82 | 1.62 | 2.443 (3) | 176.3 |
O1W—H1W···O3iv | 0.84 (3) | 2.05 (3) | 2.882 (3) | 171 (5) |
Symmetry codes: (ii) −x+1/2, −y+1/2, −z; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x+1, y, −z+1/2. |
Selected geometric parameters (Å, º) for (II) topFe1—N1 | 1.961 (4) | Fe1—N4 | 1.971 (4) |
Fe1—N2 | 1.966 (4) | Fe1—N5 | 1.964 (4) |
Fe1—N3 | 1.967 (4) | Fe1—N6 | 1.961 (4) |
| | | |
N1—Fe1—N2 | 81.71 (18) | N5—Fe1—N6 | 82.06 (17) |
N3—Fe1—N4 | 81.64 (17) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3 | 0.83 | 1.66 | 2.431 (6) | 152.7 |
O6—H6···O4i | 0.83 | 1.77 | 2.555 (5) | 157.8 |
O9—H9···O1W | 0.83 | 1.88 | 2.643 (5) | 153.0 |
O11—H11···O7 | 0.83 | 1.68 | 2.495 (5) | 166.0 |
O13—H13···O8ii | 0.83 | 1.84 | 2.567 (5) | 144.7 |
O15—H15···O14iii | 0.83 | 1.90 | 2.732 (5) | 174.8 |
O1W—H1WA···O8iv | 0.89 | 1.98 | 2.861 (5) | 169.2 |
O1W—H1WB···O10iv | 0.81 | 2.04 | 2.844 (5) | 172.1 |
O2W—H2WA···O5v | 0.82 | 2.32 | 3.101 (7) | 158.6 |
O2W—H2WB···O3 | 0.82 | 2.03 | 2.803 (6) | 156.6 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1, −y+2, −z; (iii) −x+1, −y+3, −z; (iv) −x, −y+2, −z; (v) −x+1/2, y−1/2, −z+1/2. |
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In the past few years, the design and synthesis of new coordination polymers, especially those constructed by hydrogen bonding and π–π stacking interactions, have attracted great attention, owing to their interesting structural topologies and potential application as functional materials (Batten & Robson, 1998; Wang et al., 2006; Yan & Huang, 2010; Robin & Fromm, 2006). Benzene-1,2,4,5-tetracarboxylic acid has been widely used in constructing coordination polymers, because it can act not only as a hydrogen-bond acceptor but also as hydrogen-bond donor, depending upon the number of deprotonated carboxy groups (Cheng et al., 2000; Li et al., 2003; Chen et al., 2010; Cui et al., 2010). Many transition metal complexes with benzene-1,2,4,5-tetracarboxylate have been synthesized and reported, e.g. with Zn (Rochon & Massarweh, 2000), Ni (Poleti et al., 1988; Murugavel et al., 2002), Mn (Hu et al., 2001), Co (Cheng et al., 2002), Cu (Cao et al., 2002), Ag (Jaber et al., 1997) and Fe (Chu et al., 2001). As far as we know, reports of 1,2,4,5-benzenetetracarboxylate acting only as a counter-anion are few, e.g bis[tetraaqua(1,10-phenanthroline-κ2N,N')cobalt(II)] benzene-1,2,4,5-tetracarboxylate (Wang et al., 2005), tris(2,2'-bipyridine)nickel(II) 2,5-dicarboxyterephthalate benzene-1,2,4,5-tetracarboxylic acid dihydrate (Sun et al., 2010) and aquabis(2,2'-bipyridine)chloronickel(II) 2,4,5-tricarboxybenzoate trihydrate (Sun et al., 2010). The title compounds, (I) and (II), were obtained unintentionally during an attempt to synthesize mixed-ligand transition metal complexes with benzene-1,2,4,5-tetracarboxylic acid and N-containing ligands via a solvothermal reaction.
Compound (I) crystallizes in the space group C2/c in which the FeII cation lies on a twofold axis which bisects the 1,10-phenanthroline (phen) ligand containing atom N3, whereas (II) crystallizes in the space group P21/n. In the asymmetric unit of (I), the metal ion is six-coordinated in a distorted octahedral manner by six N atoms from three chelating phen ligands. The N2—Fe—N2i angle is nearly linear [175.2 (1)°; symmetry code: (i) -x, y, -z + 1/2]. The planes of the adjacent chelating N2/C2 [N1/C1–C10/N2/C11/C12, (N1/C1–C10/N2/C11/C12)i and C13–C17/N3/C18/C13i–C17i/N3i/C18i?] groups are oriented at angles of 85.0 (1) and 75.3 (1)°, respectively [To what? Definitions need clarifying] (Fig. 1). In the anion, the three appended –COOH groups make dihedral angles of 4.1 (2) (C25/O1/O2), 87.3 (2) (C26/O3/O4) and 4.3 (2) (C27/O5/O6) with the least-squares plane of the benzene ring. The corresponding angle for the –COO- group (C28/O7/O8) is 16.8 (2)°. Thus, three of the appended groups are roughly coplanar with the central benzene ring while the fourth is approximately perpendicular to it.
In the crystal structure of (I), there is clearly an offset face-to-face π–π stacking interaction (centroid-to-centroid distance = 3.91 Å) between pairs of 2,4,5-tricarboxybenzoate anions. At the same time, the benzene-1,2,4,5-tetracarboxylate anions interact via O6v—H6v···O7 and O4ii—Hii···O8 hydrogen bonds [see Table 2 for symmetry codes; additionally, (v) -x + 1/2, y + 1/2, -z + 1/2] between the –COOH and –COO- groups of neighbouring anions to form two-dimensional sheets extending parallel to the bc plane, within which an R66(38) motif (Bernstein et al., 1995) can be discerned (Fig. 3). These sheets are interconnected by water–carboxylate O—H···O hydrogen bonds (O1W—H···O3), forming a three-dimensional supermolecular structure with one-dimensional rectangular channels through hydrogen-bond interactions (Fig. 4). The rectangular channels are filled by [Fe(phen)3]2+ cations along c, the arrangement of [Fe(phen)3]2+ cations forming a well known supramolecular motif described as an `aryl–aryl embrace' in the literature (Dance & Scudder, 1998), The separation between pairs of FeII centres is 9.440 (1) Å (Fig. 4).
The asymmetric unit of (II) consists of one tris(2,2'-bipyridine)iron(II) complex dication, one 2,5-dicarboxybenzene-1,4-dicarboxylate dianion, one benzene-1,2,4,5-tetracarboxylic acid molecule and two water molecules (Fig. 2). In the complex cation, the coordination is such that six N atoms from three 2,2'-bipyridine (bipy) ligands complete a distorted sixfold environment around the FeII cation. The planes of the adjacent chelating N2/C2 [N1/C21–C30/N2, N3/C31–C40/N4 and N5/C41–C49/N6 ?] groups make dihedral angles of 82.4 (3), 83.0 (2) and 88.9 (1)° [with what? Definitions need clarifying]. The Fe—N bond lengths are in good agreement with those observed in (I). The dihedral angles between the least-squares plane of the benzene ring of the 2,5-dicarboxybenzene-1,4-dicarboxylate anion and the carboxy/carboxylate groups are 19.8 (5) (C1/O1/O2), 21.1 (4) (C2/O3/O4), 84.6 (3) (C3/O5/O6) and 7.0 (5)° (C4/O7/O8) (Fig. 2). Thus, similar to (I), three of the groups are nearly coplanar with the central benzene ring while the fourth is approximately perpendicular to it. The corresponding dihedral angles in the benzene-1,2,4,5-tetracarboxylic acid molecule are 79.4 (2) (C11/O9/O10), 5.7 (5) (C12/O11/O12), 10.4 (3) (C13/O13/O14) and 82.2 (3)° (C14/O15/O16). In this arrangement, two groups are orthogonal to the benzene plane and two are approximately coplanar with it. The two benzene rings of the benzene-1,2,4,5-tetracarboxylic acid molecule and the 2,5-dicarboxybenzene-1,4-dicarboxylate anion are oriented at 69.9 (2)° to each other.
In the hydrogen-bonding pattern of (II), neighbouring benzene-1,2,4,5-tetracarboxylic acid molecules interact through a pair of carboxy–carboxylate O—H···O hydrogen bonds (O15—H15···O14iii and O15iii—H15iii···O14; see Table 4 for details and all symmetry codes), forming a ring with the graph-set notation R22(14). These hydrogen-bonded dimers interact with water molecules via carboxy–water O—H···O (O9—H9···O1W) and water–carboxy O—H···O (O1Wiv—H1WBiv···O10) hydrogen bonds to generate a supermolecular R44(12) ring. The R22(14) and R44(12) motifs extend alternately to create a supramolecular chain (Fig. 5). Neighbouring chains are linked through O13—H13···O8ii and O1Wvi—H···O8ii [symmetry code: (vi) x + 1, y, z] hydrogen bonds, thus building up an extended two-dimensional layer network parallel to the (001) plane (Fig. 6). These two-dimensional layers are interconnected by O2W—H···O3 and O2W—H2···O5v hydrogen bonds extending along the c cell direction, generating an extensive three-dimensional hydrogen-bonded framework (Fig. 7). As in (I), the nanoporous host of (II) manifests one-dimensional approximately square channels along b, into which are embedded embracing [Fe(bipy)3]2+ cations. Pairs of FeII centres are a little closer [8.228 (2) Å] than in (I) (Fig. 7).