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The title compound, [Co(C12H8N2)3](C4H2O4)0.5(C4H3O4)·1.5C4H4O4·4H2O, consists of the cobalt(II) complex cation with phenanthroline (phen), half a fumarate dianion, a fumarate monoanion, one and a half fumaric acid mol­ecule and uncoordinated water mol­ecules. The separations of 3.342 (8) and 3.493 (15) Å between the phen rings related by inversion centers indicate the existence of π–π-stacking interactions between the neighboring complex ions. These complex mol­ecules assemble as hydro­phobic layers via π–π stacking. Fumarate, fumaric acid and water are linked to each other to form hydro­philic layers by hydrogen bonding in the crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803009024/cv6185sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803009024/cv6185Isup2.hkl
Contains datablock I

CCDC reference: 214582

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.005 Å
  • Disorder in solvent or counterion
  • R factor = 0.052
  • wR factor = 0.135
  • Data-to-parameter ratio = 15.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Amber Alert Alert Level B:
PLAT_368 Alert B Short C(sp2)-C(sp2) Bond C54 - C54_a = 1.13 Ang.
Yellow Alert Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ....................... 5.00 Perc. PLAT_369 Alert C Long C(sp2)-C(sp2) Bond C53 - C54 = 1.54 Ang.
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

The crystals were occasionally obtained during the preparing the CoII complex bridged by fumarate. The CoII complex displays an octahedron geometry (Fig. 1), formed by three chelating phenanthroline (phen) molecules. Together with the CoII complex, the fumarate dianion, fumarate monoanion and fumaric acid occur in the crystal. They were recognized by comparing the differences in C—O bonds in the same carboxyl group. The smaller differences of 0.013 (6) Å in the C41-carboxyl group and 0.041 (8) Å in the C61-carboxyl group (Table 1) indicate that both C41- and C61-carboxyl are deprotonated groups, while the larger differences of 0.055 (6) Å in the C44-carboxyl, 0.089 (8) Å in the C51-carboxyl and 0.119 (6) Å in the C53- and C55-carboxyl groups showed that these carboxyl groups are neutral. The fumarate monoanion is located in the crystallographic general position, while fumarate dianion and neutral fumaric acid molecule are located in individual inversion centers. The CoII complex displays an octahedron coordination geometry, formed by three chelating phen molecules with normal bond distances and angles.

An extensive hydrogen-bonding network occurs between carboxyl/carboxylate groups and lattice water, as shown in Fig. 1 and Table 2. The separations of 3.342 (8) and 3.493 (15) Å indicate the existence of the ππ-stacking interaction between neighboring phen molecules related by the inversion center, as shown in Fig. 2. An approximately parallel arrangement of the C53-fumaric acid with the N5-phen ring is observed (Fig. 3). The shorter distances to the N5-phen plane of 3.341 (4) Å (C53) and 3.419 (5) Å (C54) may suggest the existence of the ππ interaction between the fumaric acid and phen ring.

The carbon skeleton of the C51-fumaric acid and C61-fumarate dianion show the disordered arrangement, like those found in manganese complex (Liu et al., 2003).

Experimental top

A dimethylformamide solution (20 ml) containing CoCl2·6H2O (0.12 g, 0.5 mmol), 1,10-phenanthroline (0.18 g, 1 mmol) and fumaric acid (0.058 g, 0.5 mmol) was refluxed under the atmosphere for 2 h. Pale pink single crystals of the title compound were obtained from the filtrate after 2 weeks.

Refinement top

The H atoms on C atoms, except those on disordered C atoms, were placed in calculated positions with C—H = 0.93 Å and included in the final cycles of refinement in riding model, with Uiso(H) = 1.2Ueq of the carrier atom. Other H atoms were located with combination of difference Fourier maps and theoretical calculation (Nardelli, 1993), and were included in the final cycles of refinement with fixed coordinates and isotropic displacement parameters of 0.08 Å2. An unreasonably short distance C54 C54(1 − x,1 − y,-z) of 1.135 (7) Å and a longer C53—C54 distance of 1.539 (6) Å were observed in the structure. It may be due to the disorder of the structure. The larger thermal parameters implied the possible disorder of the C54 atom, but it was not successfully resolved.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids. Dashed lines indicate hydrogen bonding. H atoms bonded to the C atoms and disordered C atoms have been omitted for clarity. [Symmetry codes: (i) −x, 1 − y, 1 − z; (ii) 1 − x, 1 − y, −z; (iii) 1 − x, 1 − y, 1 − z; (iv) 1 − x, −y, −z.]
[Figure 2] Fig. 2. The molecular packing diagram, H atoms have been omitted for clarity.
[Figure 3] Fig. 3. A diagram showing the ππ stacking between the fumaric acid and phen ring.
(I) top
Crystal data top
[Co(C12H8N2)3](C3H2O4)(C3H3O4)·C3H4O4·4H2OZ = 2
Mr = 1017.81F(000) = 1054
Triclinic, P1Dx = 1.506 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71069 Å
a = 12.167 (2) ÅCell parameters from 13658 reflections
b = 12.487 (2) Åθ = 1.5–27.0°
c = 17.040 (2) ŵ = 0.47 mm1
α = 102.85 (2)°T = 298 K
β = 90.28 (1)°Plate, pink
γ = 116.39 (2)°0.42 × 0.22 × 0.08 mm
V = 2245.0 (8) Å3
Data collection top
Bruker SMART CCD
diffractometer
9991 independent reflections
Radiation source: fine-focus sealed tube5138 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
ω and ϕ scansθmax = 27.6°, θmin = 1.2°
Absorption correction: empirical (using intensity measurements)
(SADABS; Bruker, 1999)
h = 1515
Tmin = 0.82, Tmax = 0.96k = 1016
14499 measured reflectionsl = 2221
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)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135H-atom parameters constrained
S = 0.86 w = 1/[σ2(Fo2) + (0.0578P)2]
where P = (Fo2 + 2Fc2)/3
9991 reflections(Δ/σ)max = 0.002
658 parametersΔρmax = 0.76 e Å3
0 restraintsΔρmin = 0.46 e Å3
Crystal data top
[Co(C12H8N2)3](C3H2O4)(C3H3O4)·C3H4O4·4H2Oγ = 116.39 (2)°
Mr = 1017.81V = 2245.0 (8) Å3
Triclinic, P1Z = 2
a = 12.167 (2) ÅMo Kα radiation
b = 12.487 (2) ŵ = 0.47 mm1
c = 17.040 (2) ÅT = 298 K
α = 102.85 (2)°0.42 × 0.22 × 0.08 mm
β = 90.28 (1)°
Data collection top
Bruker SMART CCD
diffractometer
9991 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Bruker, 1999)
5138 reflections with I > 2σ(I)
Tmin = 0.82, Tmax = 0.96Rint = 0.035
14499 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.135H-atom parameters constrained
S = 0.86Δρmax = 0.76 e Å3
9991 reflectionsΔρmin = 0.46 e Å3
658 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
xyzUiso*/UeqOcc. (<1)
Co0.81131 (3)0.82696 (4)0.23014 (2)0.03139 (13)
O10.2464 (2)0.6364 (2)0.34103 (15)0.0691 (7)
O20.1733 (2)0.7260 (3)0.2717 (2)0.0880 (9)
O30.5641 (3)1.1219 (3)0.30102 (16)0.0793 (9)
O40.5679 (2)1.0971 (2)0.42327 (16)0.0731 (8)
O110.2290 (4)0.6913 (3)0.52769 (18)0.1089 (12)
O120.1134 (3)0.7149 (3)0.6200 (2)0.0974 (11)
O130.4375 (3)0.2793 (3)0.04708 (18)0.0944 (10)
O140.6300 (3)0.4168 (3)0.06735 (18)0.0845 (9)
O150.4259 (2)0.6419 (2)0.41561 (17)0.0729 (8)
O160.2972 (2)0.4533 (3)0.42391 (19)0.0884 (10)
O170.4874 (4)0.1627 (3)0.1343 (2)0.1278 (15)
O180.5003 (3)0.0056 (3)0.15825 (19)0.0904 (10)
O210.1804 (3)0.7787 (3)0.11029 (18)0.1017 (10)
O220.8471 (3)0.3844 (3)0.04302 (19)0.0962 (10)
O230.0330 (3)0.4775 (3)0.1748 (2)0.1140 (12)
O240.0906 (3)0.3486 (4)0.2746 (2)0.1347 (15)
N10.9967 (2)0.9438 (2)0.27818 (14)0.0371 (6)
N20.7906 (2)0.9022 (2)0.34961 (14)0.0371 (6)
N30.8500 (2)0.7741 (2)0.11298 (14)0.0361 (6)
N40.8138 (2)0.9688 (2)0.18236 (15)0.0404 (6)
N50.6211 (2)0.7225 (2)0.20174 (14)0.0400 (6)
N60.7870 (2)0.6646 (2)0.25900 (14)0.0393 (6)
C11.0978 (3)0.9647 (3)0.24169 (19)0.0441 (8)
H11.09180.91000.19290.053*
C21.2133 (3)1.0656 (3)0.2732 (2)0.0525 (9)
H21.28181.07820.24530.063*
C31.2230 (3)1.1441 (3)0.3449 (2)0.0559 (10)
H31.29881.21180.36650.067*
C41.1197 (3)1.1241 (3)0.3870 (2)0.0465 (8)
C51.1235 (3)1.2009 (3)0.4649 (2)0.0563 (10)
H51.19691.27020.48870.068*
C61.0214 (3)1.1731 (3)0.5036 (2)0.0560 (10)
H61.02621.22230.55460.067*
C70.9057 (3)1.0690 (3)0.46748 (19)0.0442 (8)
C80.7961 (3)1.0351 (4)0.5047 (2)0.0574 (10)
H80.79711.08020.55630.069*
C90.6902 (3)0.9380 (3)0.4663 (2)0.0535 (9)
H90.61850.91390.49150.064*
C100.6901 (3)0.8741 (3)0.38799 (19)0.0466 (8)
H100.61600.80850.36120.056*
C110.8988 (3)0.9986 (3)0.39041 (17)0.0351 (7)
C121.0081 (3)1.0233 (3)0.35111 (17)0.0353 (7)
C130.8712 (3)0.6794 (3)0.07891 (19)0.0430 (8)
H130.87500.62960.11110.052*
C140.8881 (3)0.6511 (3)0.0019 (2)0.0483 (9)
H140.90380.58450.02270.058*
C150.8815 (3)0.7210 (3)0.0506 (2)0.0501 (9)
H150.89250.70240.10500.060*
C160.8581 (3)0.8206 (3)0.01889 (18)0.0414 (8)
C170.8512 (3)0.9005 (3)0.0649 (2)0.0554 (10)
H170.85820.88430.12010.067*
C180.8341 (3)1.0011 (4)0.0286 (2)0.0568 (10)
H180.83101.05280.05930.068*
C190.8214 (3)1.0262 (3)0.0540 (2)0.0435 (8)
C200.8089 (3)1.1317 (3)0.0956 (2)0.0578 (10)
H200.80761.18730.06770.069*
C210.7988 (3)1.1505 (3)0.1760 (2)0.0550 (9)
H210.79091.21950.20360.066*
C220.8002 (3)1.0668 (3)0.2176 (2)0.0481 (8)
H220.79111.08060.27250.058*
C230.8249 (3)0.9486 (3)0.10042 (18)0.0381 (7)
C240.8450 (3)0.8460 (3)0.06486 (17)0.0361 (7)
C250.5398 (3)0.7516 (3)0.1726 (2)0.0507 (9)
H250.56830.82640.15840.061*
C260.4119 (3)0.6734 (4)0.1622 (2)0.0603 (10)
H260.35750.69570.14010.072*
C270.3681 (3)0.5656 (4)0.1845 (2)0.0611 (11)
H270.28340.51480.17930.073*
C280.4507 (3)0.5307 (3)0.2156 (2)0.0499 (9)
C290.4146 (4)0.4185 (4)0.2399 (2)0.0664 (11)
H290.33100.36440.23660.080*
C300.4990 (4)0.3897 (3)0.2673 (2)0.0657 (11)
H300.47260.31530.28190.079*
C310.6284 (3)0.4701 (3)0.2746 (2)0.0517 (9)
C320.7199 (4)0.4443 (4)0.3023 (2)0.0658 (11)
H320.69820.37130.31800.079*
C330.8400 (4)0.5254 (4)0.3063 (2)0.0583 (10)
H330.90160.50800.32350.070*
C340.8709 (3)0.6355 (3)0.28446 (19)0.0484 (9)
H340.95400.69090.28790.058*
C350.6668 (3)0.5831 (3)0.25405 (18)0.0412 (8)
C360.5772 (3)0.6128 (3)0.22259 (18)0.0415 (8)
C410.2517 (3)0.7281 (4)0.3211 (2)0.0570 (10)
C420.3634 (3)0.8509 (4)0.3580 (2)0.0606 (10)
H420.40040.86430.40950.073*
C430.4081 (3)0.9364 (4)0.3207 (2)0.0587 (10)
H430.36810.92230.27010.070*
C440.5217 (3)1.0590 (4)0.3529 (3)0.0568 (10)
C510.1276 (5)0.6567 (4)0.5592 (3)0.0837 (16)
C52A0.002 (2)0.5374 (14)0.5287 (6)0.058 (2)0.50
C52B0.0584 (9)0.5334 (14)0.4955 (10)0.059 (3)0.50
C530.5266 (4)0.3846 (4)0.0435 (2)0.0593 (10)
C540.4705 (5)0.4527 (4)0.0054 (3)0.0842 (15)
H540.38560.41520.00920.101*
C550.3967 (4)0.5398 (4)0.4379 (2)0.0599 (10)
C560.5029 (3)0.5442 (3)0.4845 (2)0.0651 (11)
H560.57840.61470.49180.078*
C610.4901 (4)0.0653 (5)0.1113 (3)0.0753 (13)
C62A0.4823 (12)0.0240 (17)0.0290 (12)0.078 (5)0.50
C62B0.4870 (11)0.0451 (17)0.0215 (9)0.069 (3)0.50
H030.56791.10330.24990.080*
H0110.28850.75310.56270.080*
H0130.47400.26060.08720.080*
H0150.36580.66150.42370.080*
H2110.17960.74140.15660.080*
H2120.19930.73120.06600.080*
H2210.77440.39580.06010.080*
H2220.89840.43490.09520.080*
H2310.03880.46080.22550.080*
H2320.05780.55870.19220.080*
H2410.02200.32060.30290.080*
H2420.14770.38850.31360.050*
H52A0.07740.51090.54600.080*0.50
H52B0.08440.49740.45430.080*0.50
H62A0.44730.10160.01760.080*0.50
H62B0.46820.08250.00720.080*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0300 (2)0.0293 (2)0.0313 (2)0.01135 (19)0.00179 (16)0.00572 (17)
O10.0683 (18)0.0529 (18)0.0671 (18)0.0122 (15)0.0003 (13)0.0130 (15)
O20.0585 (18)0.077 (2)0.127 (3)0.0256 (16)0.0089 (17)0.0330 (19)
O30.091 (2)0.0663 (19)0.0633 (18)0.0158 (17)0.0080 (15)0.0263 (15)
O40.088 (2)0.0647 (19)0.0486 (16)0.0209 (16)0.0012 (14)0.0117 (14)
O110.128 (3)0.075 (2)0.064 (2)0.014 (2)0.004 (2)0.0244 (17)
O120.064 (2)0.090 (3)0.106 (3)0.0067 (19)0.0007 (19)0.025 (2)
O130.070 (2)0.108 (3)0.095 (2)0.024 (2)0.0140 (17)0.044 (2)
O140.0628 (19)0.084 (2)0.096 (2)0.0246 (17)0.0001 (16)0.0224 (18)
O150.0594 (17)0.0576 (18)0.099 (2)0.0195 (15)0.0122 (15)0.0294 (16)
O160.0520 (17)0.0544 (19)0.135 (3)0.0007 (15)0.0101 (17)0.0303 (19)
O170.229 (5)0.085 (3)0.059 (2)0.065 (3)0.015 (2)0.0155 (19)
O180.106 (3)0.086 (2)0.073 (2)0.047 (2)0.0059 (18)0.0023 (18)
O210.138 (3)0.098 (2)0.088 (2)0.069 (2)0.0017 (19)0.0244 (19)
O220.111 (2)0.085 (2)0.118 (3)0.067 (2)0.018 (2)0.0250 (19)
O230.095 (2)0.098 (3)0.112 (3)0.032 (2)0.021 (2)0.015 (2)
O240.069 (2)0.161 (4)0.099 (3)0.008 (2)0.0045 (18)0.011 (2)
N10.0343 (14)0.0358 (15)0.0390 (14)0.0138 (13)0.0035 (11)0.0105 (12)
N20.0355 (14)0.0369 (16)0.0362 (14)0.0148 (13)0.0026 (11)0.0079 (12)
N30.0360 (14)0.0299 (15)0.0367 (14)0.0123 (12)0.0002 (11)0.0036 (12)
N40.0378 (15)0.0369 (16)0.0455 (16)0.0168 (13)0.0051 (12)0.0091 (13)
N50.0369 (15)0.0403 (17)0.0380 (15)0.0173 (13)0.0018 (11)0.0015 (13)
N60.0408 (15)0.0376 (16)0.0349 (14)0.0155 (14)0.0030 (11)0.0055 (12)
C10.0417 (19)0.047 (2)0.0404 (18)0.0181 (17)0.0054 (15)0.0098 (16)
C20.0364 (19)0.060 (3)0.055 (2)0.0137 (19)0.0090 (16)0.021 (2)
C30.0354 (19)0.053 (2)0.066 (2)0.0049 (18)0.0020 (17)0.022 (2)
C40.046 (2)0.040 (2)0.049 (2)0.0125 (17)0.0032 (16)0.0187 (17)
C50.058 (2)0.036 (2)0.047 (2)0.0052 (18)0.0151 (18)0.0046 (17)
C60.066 (2)0.043 (2)0.0378 (19)0.015 (2)0.0065 (18)0.0081 (17)
C70.052 (2)0.040 (2)0.0419 (19)0.0217 (18)0.0056 (16)0.0110 (16)
C80.071 (3)0.071 (3)0.043 (2)0.043 (2)0.0165 (19)0.0130 (19)
C90.046 (2)0.059 (3)0.049 (2)0.021 (2)0.0118 (17)0.0056 (19)
C100.0380 (19)0.051 (2)0.047 (2)0.0180 (17)0.0082 (15)0.0111 (17)
C110.0391 (18)0.0293 (17)0.0325 (16)0.0136 (15)0.0005 (13)0.0042 (14)
C120.0361 (17)0.0294 (17)0.0331 (16)0.0091 (15)0.0009 (13)0.0070 (14)
C130.0426 (19)0.039 (2)0.0461 (19)0.0185 (17)0.0047 (15)0.0084 (16)
C140.048 (2)0.043 (2)0.047 (2)0.0205 (18)0.0076 (16)0.0013 (17)
C150.046 (2)0.051 (2)0.0385 (19)0.0136 (18)0.0067 (15)0.0020 (17)
C160.0366 (18)0.037 (2)0.0369 (17)0.0068 (16)0.0004 (14)0.0057 (15)
C170.058 (2)0.058 (3)0.039 (2)0.014 (2)0.0004 (16)0.0169 (19)
C180.058 (2)0.056 (2)0.056 (2)0.018 (2)0.0050 (18)0.032 (2)
C190.0405 (19)0.036 (2)0.047 (2)0.0100 (16)0.0005 (15)0.0135 (16)
C200.052 (2)0.045 (2)0.075 (3)0.0150 (19)0.0001 (19)0.028 (2)
C210.059 (2)0.036 (2)0.069 (3)0.0231 (19)0.0034 (19)0.0079 (19)
C220.053 (2)0.038 (2)0.052 (2)0.0228 (18)0.0046 (16)0.0034 (17)
C230.0354 (17)0.0324 (18)0.0379 (17)0.0094 (15)0.0018 (13)0.0060 (15)
C240.0325 (17)0.0349 (18)0.0349 (17)0.0104 (15)0.0002 (13)0.0079 (15)
C250.047 (2)0.055 (2)0.053 (2)0.0294 (19)0.0022 (16)0.0056 (18)
C260.044 (2)0.073 (3)0.055 (2)0.030 (2)0.0060 (17)0.009 (2)
C270.035 (2)0.063 (3)0.058 (2)0.015 (2)0.0020 (17)0.018 (2)
C280.0375 (19)0.045 (2)0.045 (2)0.0072 (17)0.0067 (15)0.0047 (17)
C290.051 (2)0.046 (3)0.068 (3)0.001 (2)0.014 (2)0.001 (2)
C300.072 (3)0.035 (2)0.064 (3)0.003 (2)0.020 (2)0.0091 (19)
C310.061 (2)0.042 (2)0.047 (2)0.017 (2)0.0168 (17)0.0157 (17)
C320.090 (3)0.051 (3)0.065 (3)0.032 (2)0.018 (2)0.030 (2)
C330.075 (3)0.059 (3)0.055 (2)0.040 (2)0.0068 (19)0.020 (2)
C340.049 (2)0.055 (2)0.046 (2)0.0261 (19)0.0064 (16)0.0164 (18)
C350.0418 (19)0.036 (2)0.0370 (17)0.0121 (16)0.0081 (14)0.0056 (15)
C360.0384 (19)0.040 (2)0.0383 (18)0.0135 (16)0.0078 (14)0.0051 (15)
C410.045 (2)0.048 (3)0.063 (2)0.017 (2)0.0011 (18)0.005 (2)
C420.063 (3)0.059 (3)0.065 (2)0.033 (2)0.017 (2)0.015 (2)
C430.057 (2)0.055 (3)0.068 (3)0.029 (2)0.0096 (19)0.016 (2)
C440.053 (2)0.053 (3)0.073 (3)0.028 (2)0.021 (2)0.024 (2)
C510.097 (4)0.046 (3)0.072 (3)0.003 (3)0.036 (3)0.012 (3)
C52A0.061 (7)0.050 (8)0.048 (5)0.015 (8)0.010 (7)0.009 (6)
C52B0.052 (6)0.041 (7)0.050 (6)0.001 (6)0.001 (7)0.013 (5)
C530.078 (3)0.058 (3)0.048 (2)0.040 (3)0.002 (2)0.007 (2)
C540.097 (4)0.065 (4)0.056 (3)0.015 (3)0.016 (2)0.000 (3)
C550.049 (2)0.050 (3)0.068 (3)0.014 (2)0.008 (2)0.011 (2)
C560.045 (2)0.051 (3)0.085 (3)0.009 (2)0.006 (2)0.019 (2)
C610.065 (3)0.086 (4)0.047 (3)0.020 (3)0.003 (2)0.005 (3)
C62A0.068 (7)0.088 (10)0.097 (16)0.044 (7)0.001 (7)0.041 (9)
C62B0.066 (6)0.120 (12)0.032 (5)0.053 (7)0.011 (4)0.020 (7)
Geometric parameters (Å, º) top
Co—N52.078 (2)C13—H130.930
Co—N32.084 (2)C14—C151.358 (4)
Co—N62.086 (3)C14—H140.930
Co—N42.097 (3)C15—C161.391 (4)
Co—N12.101 (2)C15—H150.930
Co—N22.111 (2)C16—C241.417 (4)
O1—C411.242 (4)C16—C171.429 (5)
O2—C411.255 (4)C17—C181.375 (5)
O3—C441.272 (4)C17—H170.930
O3—H030.858C18—C191.399 (4)
O4—C441.217 (4)C18—H180.930
O11—C511.277 (6)C19—C231.394 (4)
O11—H0110.877C19—C201.422 (5)
O12—C511.188 (6)C20—C211.355 (5)
O13—C531.295 (5)C20—H200.930
O13—H0130.937C21—C221.392 (4)
O14—C531.176 (4)C21—H210.930
O15—C551.307 (4)C22—H220.930
O15—H0150.872C23—C241.414 (4)
O16—C551.188 (4)C25—C261.405 (4)
O17—C611.207 (6)C25—H250.930
O18—C611.248 (5)C26—C271.353 (5)
O21—H2111.000C26—H260.930
O21—H2120.948C27—C281.403 (5)
O22—H2210.991C27—H270.930
O22—H2220.987C28—C361.406 (4)
O23—H2310.942C28—C291.428 (5)
O23—H2320.895C29—C301.343 (5)
O24—H2410.933C29—H290.930
O24—H2420.844C30—C311.428 (5)
N1—C11.328 (4)C30—H300.930
N1—C121.370 (4)C31—C321.396 (5)
N2—C101.332 (4)C31—C351.403 (4)
N2—C111.370 (4)C32—C331.348 (5)
N3—C131.330 (4)C32—H320.930
N3—C241.364 (4)C33—C341.392 (5)
N4—C221.319 (4)C33—H330.930
N4—C231.381 (4)C34—H340.930
N5—C251.324 (4)C35—C361.434 (4)
N5—C361.362 (4)C41—C421.518 (5)
N6—C341.326 (4)C42—C431.276 (5)
N6—C351.349 (4)C42—H420.930
C1—C21.402 (4)C43—C441.514 (5)
C1—H10.930C43—H430.930
C2—C31.354 (5)C51—C52B1.534 (18)
C2—H20.930C51—C52A1.59 (2)
C3—C41.402 (4)C52A—C52Ai1.21 (2)
C3—H30.930C52A—H52A0.90
C4—C121.389 (4)C52B—C52Bi1.32 (2)
C4—C51.442 (5)C52B—H52B0.88
C5—C61.351 (5)C53—C541.539 (6)
C5—H50.930C54—C54ii1.135 (7)
C6—C71.436 (4)C54—H540.930
C6—H60.930C55—C561.486 (5)
C7—C111.387 (4)C56—C56iii1.302 (7)
C7—C81.409 (4)C56—H560.930
C8—C91.345 (5)C61—C62B1.492 (16)
C8—H80.930C61—C62A1.56 (3)
C9—C101.394 (4)C62A—C62Aiv1.25 (3)
C9—H90.930C62A—H62A0.841
C10—H100.930C62B—C62Biv1.36 (3)
C11—C121.432 (4)C62B—H62B0.839
C13—C141.383 (4)
N5—Co—N394.50 (9)C21—C20—C19119.5 (3)
N5—Co—N679.85 (10)C21—C20—H20120.2
N3—Co—N693.64 (10)C19—C20—H20120.2
N5—Co—N492.65 (10)C20—C21—C22120.1 (3)
N3—Co—N479.77 (10)C20—C21—H21120.0
N6—Co—N4169.66 (10)C22—C21—H21120.0
N5—Co—N1170.34 (9)N4—C22—C21122.9 (3)
N3—Co—N195.12 (9)N4—C22—H22118.6
N6—Co—N1100.40 (10)C21—C22—H22118.6
N4—Co—N188.20 (9)N4—C23—C19122.9 (3)
N5—Co—N291.21 (9)N4—C23—C24116.7 (3)
N3—Co—N2172.92 (9)C19—C23—C24120.4 (3)
N6—Co—N291.49 (10)N3—C24—C23118.2 (3)
N4—Co—N295.80 (10)N3—C24—C16122.2 (3)
N1—Co—N279.13 (9)C23—C24—C16119.6 (3)
C44—O3—H03134.1N5—C25—C26122.3 (3)
C51—O11—H011109.7N5—C25—H25118.8
C53—O13—H013100.5C26—C25—H25118.8
C55—O15—H015108.2C27—C26—C25119.9 (4)
H211—O21—H212105.4C27—C26—H26120.1
H221—O22—H22293.6C25—C26—H26120.1
H231—O23—H23298.2C26—C27—C28119.8 (3)
H241—O24—H242100.3C26—C27—H27120.1
C1—N1—C12117.6 (3)C28—C27—H27120.1
C1—N1—Co128.7 (2)C27—C28—C36116.8 (3)
C12—N1—Co112.36 (19)C27—C28—C29124.4 (3)
C10—N2—C11117.4 (3)C36—C28—C29118.7 (3)
C10—N2—Co130.3 (2)C30—C29—C28121.2 (4)
C11—N2—Co112.30 (18)C30—C29—H29119.4
C13—N3—C24117.5 (3)C28—C29—H29119.4
C13—N3—Co129.9 (2)C29—C30—C31121.8 (4)
C24—N3—Co112.5 (2)C29—C30—H30119.1
C22—N4—C23117.8 (3)C31—C30—H30119.1
C22—N4—Co129.9 (2)C32—C31—C35117.5 (3)
C23—N4—Co112.2 (2)C32—C31—C30124.1 (4)
C25—N5—C36117.9 (3)C35—C31—C30118.5 (4)
C25—N5—Co129.3 (2)C33—C32—C31119.8 (3)
C36—N5—Co112.6 (2)C33—C32—H32120.1
C34—N6—C35117.9 (3)C31—C32—H32120.1
C34—N6—Co129.4 (2)C32—C33—C34119.4 (4)
C35—N6—Co112.6 (2)C32—C33—H33120.3
N1—C1—C2123.1 (3)C34—C33—H33120.3
N1—C1—H1118.4N6—C34—C33122.9 (3)
C2—C1—H1118.4N6—C34—H34118.6
C3—C2—C1118.6 (3)C33—C34—H34118.6
C3—C2—H2120.7N6—C35—C31122.5 (3)
C1—C2—H2120.7N6—C35—C36117.4 (3)
C2—C3—C4120.4 (3)C31—C35—C36120.0 (3)
C2—C3—H3119.8N5—C36—C28123.2 (3)
C4—C3—H3119.8N5—C36—C35116.9 (3)
C12—C4—C3117.4 (3)C28—C36—C35119.8 (3)
C12—C4—C5118.8 (3)O1—C41—O2124.9 (4)
C3—C4—C5123.7 (3)O1—C41—C42116.9 (4)
C6—C5—C4120.6 (3)O2—C41—C42118.2 (4)
C6—C5—H5119.7C43—C42—C41122.1 (4)
C4—C5—H5119.7C43—C42—H42118.9
C5—C6—C7121.2 (3)C41—C42—H42118.9
C5—C6—H6119.4C42—C43—C44124.7 (4)
C7—C6—H6119.4C42—C43—H43117.7
C11—C7—C8117.2 (3)C44—C43—H43117.7
C11—C7—C6118.9 (3)O4—C44—O3121.9 (4)
C8—C7—C6123.9 (3)O4—C44—C43123.4 (3)
C9—C8—C7120.6 (3)O3—C44—C43114.7 (4)
C9—C8—H8119.7O12—C51—O11123.7 (4)
C7—C8—H8119.7O12—C51—C52B140.7 (8)
C8—C9—C10118.7 (3)O11—C51—C52B95.6 (7)
C8—C9—H9120.6O12—C51—C52A105.9 (7)
C10—C9—H9120.6O11—C51—C52A130.4 (7)
N2—C10—C9123.4 (3)C52Ai—C52A—C51113 (3)
N2—C10—H10118.3C52Ai—C52A—H52A112
C9—C10—H10118.3C51—C52A—H52A134.4
N2—C11—C7122.7 (3)C52Bi—C52B—C51116 (2)
N2—C11—C12117.2 (3)C52Bi—C52B—H52B114
C7—C11—C12120.1 (3)C51—C52B—H52B130.7
N1—C12—C4122.7 (3)O14—C53—O13122.8 (4)
N1—C12—C11117.1 (3)O14—C53—C54129.3 (4)
C4—C12—C11120.2 (3)O13—C53—C54107.9 (4)
N3—C13—C14123.4 (3)C54ii—C54—C53122.2 (7)
N3—C13—H13118.3C54ii—C54—H54118.9
C14—C13—H13118.3C53—C54—H54118.9
C15—C14—C13119.6 (3)O16—C55—O15124.7 (4)
C15—C14—H14120.2O16—C55—C56123.1 (4)
C13—C14—H14120.2O15—C55—C56112.1 (3)
C14—C15—C16119.8 (3)C56iii—C56—C55124.2 (5)
C14—C15—H15120.1C56iii—C56—H56117.9
C16—C15—H15120.1C55—C56—H56117.9
C15—C16—C24117.5 (3)O17—C61—O18123.3 (4)
C15—C16—C17124.0 (3)O17—C61—C62B104.5 (9)
C24—C16—C17118.5 (3)O18—C61—C62B132.1 (9)
C18—C17—C16120.9 (3)O17—C61—C62A137.6 (7)
C18—C17—H17119.6O18—C61—C62A99.0 (7)
C16—C17—H17119.6C62Aiv—C62A—C61116 (2)
C17—C18—C19120.6 (3)C62Aiv—C62A—H62A116
C17—C18—H18119.7C61—C62A—H62A127.0
C19—C18—H18119.7C62Biv—C62B—C61119 (2)
C23—C19—C18120.1 (3)C62Biv—C62B—H62B114
C23—C19—C20116.8 (3)C61—C62B—H62B126.8
C18—C19—C20123.1 (3)
N3—Co—N1—C13.1 (3)Co—N3—C13—C14175.7 (2)
N6—Co—N1—C191.6 (3)N3—C13—C14—C150.9 (5)
N4—Co—N1—C182.7 (3)C13—C14—C15—C160.1 (5)
N2—Co—N1—C1178.9 (3)C14—C15—C16—C241.4 (5)
N3—Co—N1—C12163.4 (2)C14—C15—C16—C17179.1 (3)
N6—Co—N1—C12102.0 (2)C15—C16—C17—C18176.6 (3)
N4—Co—N1—C1283.8 (2)C24—C16—C17—C181.1 (5)
N2—Co—N1—C1212.44 (19)C16—C17—C18—C190.9 (5)
N5—Co—N2—C107.2 (3)C17—C18—C19—C230.5 (5)
N6—Co—N2—C1072.7 (3)C17—C18—C19—C20177.2 (3)
N4—Co—N2—C10100.0 (3)C23—C19—C20—C211.2 (5)
N1—Co—N2—C10173.0 (3)C18—C19—C20—C21179.0 (3)
N5—Co—N2—C11169.4 (2)C19—C20—C21—C220.3 (5)
N6—Co—N2—C11110.7 (2)C23—N4—C22—C211.1 (5)
N4—Co—N2—C1176.6 (2)Co—N4—C22—C21177.1 (2)
N1—Co—N2—C1110.41 (19)C20—C21—C22—N41.5 (5)
N5—Co—N3—C1390.1 (3)C22—N4—C23—C190.5 (4)
N6—Co—N3—C1310.0 (3)Co—N4—C23—C19176.1 (2)
N4—Co—N3—C13178.0 (3)C22—N4—C23—C24177.2 (3)
N1—Co—N3—C1390.8 (3)Co—N4—C23—C246.1 (3)
N5—Co—N3—C2485.8 (2)C18—C19—C23—N4179.6 (3)
N6—Co—N3—C24165.9 (2)C20—C19—C23—N41.7 (4)
N4—Co—N3—C246.04 (19)C18—C19—C23—C241.9 (5)
N1—Co—N3—C2493.3 (2)C20—C19—C23—C24176.0 (3)
N5—Co—N4—C2288.6 (3)C13—N3—C24—C23178.8 (2)
N3—Co—N4—C22177.3 (3)Co—N3—C24—C234.8 (3)
N6—Co—N4—C22131.7 (5)C13—N3—C24—C161.7 (4)
N1—Co—N4—C2281.8 (3)Co—N3—C24—C16174.7 (2)
N2—Co—N4—C222.9 (3)N4—C23—C24—N30.9 (4)
N5—Co—N4—C2387.6 (2)C19—C23—C24—N3178.8 (3)
N3—Co—N4—C236.52 (18)N4—C23—C24—C16179.5 (2)
N6—Co—N4—C2344.4 (6)C19—C23—C24—C161.7 (4)
N1—Co—N4—C23102.1 (2)C15—C16—C24—N32.4 (4)
N2—Co—N4—C23179.07 (19)C17—C16—C24—N3179.7 (3)
N3—Co—N5—C2586.3 (3)C15—C16—C24—C23178.1 (3)
N6—Co—N5—C25179.2 (3)C17—C16—C24—C230.3 (4)
N4—Co—N5—C256.4 (3)C36—N5—C25—C260.4 (5)
N2—Co—N5—C2589.5 (3)Co—N5—C25—C26175.0 (2)
N3—Co—N5—C3698.9 (2)N5—C25—C26—C271.8 (5)
N6—Co—N5—C366.0 (2)C25—C26—C27—C281.9 (5)
N4—Co—N5—C36178.8 (2)C26—C27—C28—C360.6 (5)
N2—Co—N5—C3685.3 (2)C26—C27—C28—C29179.1 (3)
N5—Co—N6—C34177.1 (3)C27—C28—C29—C30178.3 (4)
N3—Co—N6—C3483.2 (3)C36—C28—C29—C301.4 (5)
N4—Co—N6—C34133.2 (5)C28—C29—C30—C310.9 (6)
N1—Co—N6—C3412.7 (3)C29—C30—C31—C32179.6 (4)
N2—Co—N6—C3491.9 (3)C29—C30—C31—C351.3 (5)
N5—Co—N6—C356.62 (19)C35—C31—C32—C331.7 (5)
N3—Co—N6—C35100.5 (2)C30—C31—C32—C33179.3 (3)
N4—Co—N6—C3550.6 (6)C31—C32—C33—C341.5 (5)
N1—Co—N6—C35163.57 (19)C35—N6—C34—C330.2 (5)
N2—Co—N6—C3584.3 (2)Co—N6—C34—C33175.9 (2)
C12—N1—C1—C21.9 (5)C32—C33—C34—N60.5 (5)
Co—N1—C1—C2164.0 (2)C34—N6—C35—C310.1 (4)
N1—C1—C2—C31.3 (5)Co—N6—C35—C31176.8 (2)
C1—C2—C3—C40.5 (5)C34—N6—C35—C36176.9 (3)
C2—C3—C4—C121.6 (5)Co—N6—C35—C366.3 (3)
C2—C3—C4—C5177.7 (3)C32—C31—C35—N61.0 (5)
C12—C4—C5—C62.1 (5)C30—C31—C35—N6179.9 (3)
C3—C4—C5—C6177.1 (3)C32—C31—C35—C36177.8 (3)
C4—C5—C6—C71.9 (6)C30—C31—C35—C363.1 (5)
C5—C6—C7—C112.0 (5)C25—N5—C36—C280.9 (4)
C5—C6—C7—C8179.9 (3)Co—N5—C36—C28174.6 (2)
C11—C7—C8—C90.2 (5)C25—N5—C36—C35180.0 (3)
C6—C7—C8—C9178.4 (3)Co—N5—C36—C354.5 (3)
C7—C8—C9—C102.1 (5)C27—C28—C36—N50.8 (5)
C11—N2—C10—C90.4 (5)C29—C28—C36—N5179.5 (3)
Co—N2—C10—C9176.0 (2)C27—C28—C36—C35179.9 (3)
C8—C9—C10—N21.8 (5)C29—C28—C36—C350.4 (5)
C10—N2—C11—C72.4 (4)N6—C35—C36—N51.3 (4)
Co—N2—C11—C7174.7 (2)C31—C35—C36—N5178.2 (3)
C10—N2—C11—C12176.0 (3)N6—C35—C36—C28179.6 (3)
Co—N2—C11—C127.0 (3)C31—C35—C36—C282.6 (5)
C8—C7—C11—N22.1 (5)O1—C41—C42—C43149.4 (4)
C6—C7—C11—N2176.1 (3)O2—C41—C42—C4329.2 (5)
C8—C7—C11—C12176.2 (3)C41—C42—C43—C44177.8 (3)
C6—C7—C11—C125.6 (5)C42—C43—C44—O414.0 (6)
C1—N1—C12—C40.7 (4)C42—C43—C44—O3167.8 (4)
Co—N1—C12—C4167.4 (2)O12—C51—C52A—C52Ai172.8 (10)
C1—N1—C12—C11179.1 (3)O11—C51—C52A—C52Ai8.9 (14)
Co—N1—C12—C1112.8 (3)O12—C51—C52B—C52Bi4.6 (18)
C3—C4—C12—N11.0 (5)O11—C51—C52B—C52Bi177.6 (11)
C5—C4—C12—N1178.4 (3)O14—C53—C54—C54ii1.7 (9)
C3—C4—C12—C11179.2 (3)O13—C53—C54—C54ii179.2 (6)
C5—C4—C12—C111.5 (5)O16—C55—C56—C56iii1.4 (8)
N2—C11—C12—N13.9 (4)O15—C55—C56—C56iii177.9 (5)
C7—C11—C12—N1174.5 (3)O17—C61—C62A—C62Aiv27 (2)
N2—C11—C12—C4176.2 (3)O18—C61—C62A—C62Aiv153.7 (16)
C7—C11—C12—C45.4 (5)O17—C61—C62B—C62Biv167.4 (16)
C24—N3—C13—C140.1 (4)O18—C61—C62B—C62Biv9 (2)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y+1, z; (iii) x+1, y+1, z+1; (iv) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H03···O18v0.861.692.457 (4)147
O13—H013···O170.941.672.537 (5)152
O15—H015···O10.871.892.488 (4)124
O11—H011···O4vi0.881.872.642 (5)146
O21—H211···O21.002.012.962 (5)158
O21—H212···O22ii0.951.982.847 (5)151
O22—H221···O140.991.892.863 (6)167
O22—H222···O23vii0.991.922.822 (5)151
O23—H231···O240.942.092.860 (5)138
O23—H232···O20.902.072.874 (5)149
O24—H241···O12i0.932.072.990 (5)171
O24—H242···O160.842.343.168 (5)167
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y+1, z; (v) x, y+1, z; (vi) x+1, y+2, z+1; (vii) x+1, y, z.

Experimental details

Crystal data
Chemical formula[Co(C12H8N2)3](C3H2O4)(C3H3O4)·C3H4O4·4H2O
Mr1017.81
Crystal system, space groupTriclinic, P1
Temperature (K)298
a, b, c (Å)12.167 (2), 12.487 (2), 17.040 (2)
α, β, γ (°)102.85 (2), 90.28 (1), 116.39 (2)
V3)2245.0 (8)
Z2
Radiation typeMo Kα
µ (mm1)0.47
Crystal size (mm)0.42 × 0.22 × 0.08
Data collection
DiffractometerBruker SMART CCD
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Bruker, 1999)
Tmin, Tmax0.82, 0.96
No. of measured, independent and
observed [I > 2σ(I)] reflections
14499, 9991, 5138
Rint0.035
(sin θ/λ)max1)0.652
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.135, 0.86
No. of reflections9991
No. of parameters658
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.76, 0.46

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top
Co—N52.078 (2)O4—C441.217 (4)
Co—N32.084 (2)O11—C511.277 (6)
Co—N62.086 (3)O12—C511.188 (6)
Co—N42.097 (3)O13—C531.295 (5)
Co—N12.101 (2)O14—C531.176 (4)
Co—N22.111 (2)O15—C551.307 (4)
O1—C411.242 (4)O16—C551.188 (4)
O2—C411.255 (4)O17—C611.207 (6)
O3—C441.272 (4)O18—C611.248 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H03···O18i0.861.692.457 (4)147
O13—H013···O170.941.672.537 (5)152
O15—H015···O10.871.892.488 (4)124
O11—H011···O4ii0.881.872.642 (5)146
O21—H211···O21.002.012.962 (5)158
O21—H212···O22iii0.951.982.847 (5)151
O22—H221···O140.991.892.863 (6)167
O22—H222···O23iv0.991.922.822 (5)151
O23—H231···O240.942.092.860 (5)138
O23—H232···O20.902.072.874 (5)149
O24—H241···O12v0.932.072.990 (5)171
O24—H242···O160.842.343.168 (5)167
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+2, z+1; (iii) x+1, y+1, z; (iv) x+1, y, z; (v) x, y+1, z+1.
 

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