Bis(2,2′-bipyridine)-1κ2N,N′;3κ2N,N′-hexa-μ-methacrylato-1:2κ6O:O′;2:3κ6O:O′-(nitrato-2κ2O,O′)-1,3-dicobalt(II)-2-terbium(III)

Wu, B.; Zhao, C.-X.

doi:10.1107/S1600536810031053

Bis(2,2′-bipyridine)-1κ²N,N′;3κ²N,N′-hexa-μ-methacrylato-1:2κ⁶O:O′;2:3κ⁶O:O′-(nitrato-2κ²O,O′)-1,3-dicobalt(II)-2-terbium(III)

In the title trinuclear cobalt–terbium complex, [Co₂Tb(C₄H₅O₂)₆(NO₃)(C₁₀H₈N₂)₂], the central Tb^III and each of the Co^II ions are bridged by three carboxylate groups of the methacrylate anions. The Tb^III cation is coordinated by six O atoms from six methacrylate anions and two O atoms from a chelating nitrate anion in a distorted square-antiprismatic geometry. Each Co^II ion is coordinated by three O atoms from three methylacrylate anions and two N atoms of a 2,2′-bypiridine ligand in a distorted square-pyramidal geometry. In the crystal structure, π–π stacking between the pyridine rings [centroid–centroid distances = 3.682 (8) and 3.760 (8) Å] is observed and weak intermolecular C—H

O hydrogen bonding is also present.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810031053/xu5010sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810031053/xu5010Isup2.hkl Contains datablock I

CCDC reference: 258163

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.005 Å
R factor = 0.025
wR factor = 0.060
Data-to-parameter ratio = 13.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Tb     --  O7      ..       5.84 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O4
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.597        252

Alert level G
PLAT960_ALERT_3_G Number of Intensities with I .LT. - 2*sig(I) ..           1
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C17
PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C21

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The study of heterometallic complexes containing d-transition metal and lanthanide(III) cations connected by bridging ligands is being actively pursued because of their relevance in solid-state technology and as models for magnetic studies. As a contribution to a structural study of heterometallic complexes containing d-transition metal and rare-earth(III) cations (Wu & Guo, 2004; Zhu et al., 2005; Wu, 2008), herewith we report the synthesis and crystal structure of the title compound, (I).

The crystal structure of the title Co—Tb—Co trinuclear complex is similar to the known crystal structures of the Zn—Ce—Zn, Zn—Nd—Zn, Co—Gd—Co and Co—Ce—Co complexes (Wu & Guo, 2004; Zhu et al., 2005; Wu, 2008; Wu & Hou, 2010). The Tb^III center is coordinated by six O atoms from six methacrylato ligands and two O atoms from nitrate anion in a distorted square-antiprismatic geometry. Each Co^II ion is coordinated by three O atoms from three methacrylato ligands and two N atoms from 2,2'-bypiridine ligand in a distorted pyramidal geometry. The Tb^III and each of two Co^II ions are bridged by three bidentate methacrylato ligands. Two Tb···Co separations are almost equal. The separations of Tb···Co1 and Tb···Co2 are 3.937 (1) and 3.822 (1) Å, respectively.

In the crystal structure, π-π interactions between the aromatic rings [centroid-centroid distances of 3.682 (8) and 3.760 (8) Å, respectively] link molecules into chains propagated in direction [01–1]. The aromatic stacking interactions are responsible for the supramolecular assemblies. Weak intermolecular C—H···O hydrogen bonds stabilize further the crystal packing (Table 1).

Related literature top

For the crystal structures of analogous complexes, see: Wu & Guo (2004); Zhu et al. (2005); Wu (2008); Wu & Hou (2010). For details of the preparation of TbL₃.H₂O (HL = CH₂C(CH₃)COOH), see: Lu et al. (1995).

Experimental top

TbL₃.H₂O (864 mg, 2.0 mmol; HL = CH₂C(CH₃)COOH) and Co(NO₃)₂.6H₂O (435 mg, 1.5 mmol) were dissolved in 15 ml water, and the pH adjusted to 4.0 using HL. An ethanol solution (3 ml) of 2,2'-bipyridine (234 mg, 1.5 mmol) was added into the above solution with stirring. After filtration, the filtrate was allowed to stand at room temperature and single crystals suitable for X-ray work were obtained after two weeks.

Structure description top

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. View of the molecule showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. All H atoms have been omitted for clarity.

Bis(2,2'-bipyridine)-1κ²N,N';3κ²N,N'-hexa- µ-methacrylato-1:2κ⁶O:O';2:3κ⁶O:O'- (nitrato-2κ²O,O')-1,3-dicobalt(II)-2-terbium(III) top

Crystal data top

[Co₂Tb(C₄H₅O₂)₆(NO₃)(C₁₀H₈N₂)₂]	Z = 2
M_r = 1161.64	F(000) = 1168
Triclinic, P1	D_x = 1.656 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 11.3717 (6) Å	Cell parameters from 10681 reflections
b = 13.4396 (5) Å	θ = 2.0–27.5°
c = 16.3572 (8) Å	µ = 2.28 mm⁻¹
α = 103.912 (2)°	T = 293 K
β = 99.950 (2)°	Block, brown
γ = 99.845 (3)°	0.32 × 0.31 × 0.15 mm
V = 2330.26 (19) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	8051 independent reflections
Radiation source: fine-focus sealed tube	7272 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 10.00 pixels mm^-1	θ_max = 25.1°, θ_min = 1.3°
ω scans	h = −13→13
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −16→16
T_min = 0.495, T_max = 0.709	l = −19→19
13172 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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.060	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0316P)² + 2.6217P] where P = (F_o² + 2F_c²)/3
8051 reflections	(Δ/σ)_max = 0.001
610 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.87 e Å⁻³

Crystal data top

[Co₂Tb(C₄H₅O₂)₆(NO₃)(C₁₀H₈N₂)₂]	γ = 99.845 (3)°
M_r = 1161.64	V = 2330.26 (19) Å³
Triclinic, P1	Z = 2
a = 11.3717 (6) Å	Mo Kα radiation
b = 13.4396 (5) Å	µ = 2.28 mm⁻¹
c = 16.3572 (8) Å	T = 293 K
α = 103.912 (2)°	0.32 × 0.31 × 0.15 mm
β = 99.950 (2)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	8051 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	7272 reflections with I > 2σ(I)
T_min = 0.495, T_max = 0.709	R_int = 0.031
13172 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.060	H-atom parameters constrained
S = 1.03	Δρ_max = 0.45 e Å⁻³
8051 reflections	Δρ_min = −0.87 e Å⁻³
610 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	U_iso*/U_eq
Tb	0.349851 (12)	0.235738 (10)	0.240894 (8)	0.01582 (5)
Co1	0.28569 (3)	0.09556 (3)	0.41926 (2)	0.01591 (9)
Co2	0.28401 (3)	0.42261 (3)	0.10445 (2)	0.01763 (9)
O1	0.45584 (18)	0.17936 (16)	0.47967 (13)	0.0221 (4)
O2	0.47217 (19)	0.26143 (17)	0.37769 (13)	0.0268 (5)
O3	0.19771 (19)	0.21432 (16)	0.45824 (14)	0.0253 (5)
O4	0.2203 (2)	0.2614 (3)	0.33945 (16)	0.0486 (7)
O5	0.33886 (19)	−0.01681 (16)	0.33430 (13)	0.0237 (5)
O6	0.2821 (2)	0.06055 (17)	0.23263 (16)	0.0308 (5)
O7	0.5251 (2)	0.14495 (17)	0.22325 (14)	0.0272 (5)
O8	0.56465 (19)	0.31214 (17)	0.23419 (14)	0.0253 (5)
O9	0.7096 (2)	0.2241 (2)	0.22484 (17)	0.0405 (6)
O10	0.15112 (19)	0.22751 (18)	0.16450 (14)	0.0270 (5)
O11	0.13244 (19)	0.30122 (16)	0.05503 (14)	0.0243 (5)
O12	0.35412 (19)	0.19272 (17)	0.09420 (13)	0.0255 (5)
O13	0.38403 (19)	0.33206 (16)	0.04124 (13)	0.0235 (4)
O14	0.36667 (18)	0.41464 (16)	0.24671 (13)	0.0229 (4)
O15	0.43760 (19)	0.53596 (16)	0.18666 (13)	0.0253 (5)
N1	0.1041 (2)	−0.00293 (19)	0.36608 (15)	0.0189 (5)
N2	0.2646 (2)	0.01087 (18)	0.50865 (15)	0.0173 (5)
N3	0.6023 (2)	0.2265 (2)	0.22695 (17)	0.0263 (6)
N4	0.1622 (2)	0.5164 (2)	0.14918 (16)	0.0225 (5)
N5	0.2614 (2)	0.50765 (19)	0.01371 (16)	0.0208 (5)
C1	0.0287 (3)	−0.0066 (2)	0.29172 (19)	0.0235 (6)
H1	0.0560	0.0359	0.2585	0.028*
C2	−0.0880 (3)	−0.0713 (3)	0.2625 (2)	0.0263 (7)
H2	−0.1375	−0.0727	0.2104	0.032*
C3	−0.1289 (3)	−0.1337 (2)	0.31281 (19)	0.0234 (6)
H3	−0.2066	−0.1778	0.2950	0.028*
C4	−0.0520 (3)	−0.1294 (2)	0.39046 (19)	0.0215 (6)
H4	−0.0783	−0.1698	0.4255	0.026*
C5	0.0650 (3)	−0.0639 (2)	0.41511 (18)	0.0183 (6)
C6	0.1558 (3)	−0.0565 (2)	0.49490 (18)	0.0180 (6)
C7	0.1328 (3)	−0.1151 (2)	0.55283 (19)	0.0221 (6)
H7	0.0568	−0.1598	0.5438	0.027*
C8	0.2248 (3)	−0.1057 (2)	0.6238 (2)	0.0262 (7)
H8	0.2109	−0.1443	0.6627	0.031*
C9	0.3378 (3)	−0.0386 (2)	0.6366 (2)	0.0248 (7)
H9	0.4009	−0.0320	0.6834	0.030*
C10	0.3538 (3)	0.0187 (2)	0.57728 (19)	0.0226 (6)
H10	0.4291	0.0640	0.5853	0.027*
C11	0.5147 (3)	0.2422 (2)	0.44716 (18)	0.0184 (6)
C12	0.6439 (3)	0.2969 (2)	0.4958 (2)	0.0235 (6)
C13	0.6891 (3)	0.2726 (3)	0.5778 (2)	0.0353 (8)
H13A	0.7746	0.3050	0.5992	0.053*
H13B	0.6776	0.1978	0.5676	0.053*
H13C	0.6443	0.2992	0.6196	0.053*
C14	0.7116 (3)	0.3622 (3)	0.4627 (3)	0.0372 (8)
H14A	0.7919	0.3953	0.4915	0.045*
H14B	0.6783	0.3745	0.4109	0.045*
C15	0.1775 (3)	0.2680 (2)	0.40533 (18)	0.0217 (6)
C16	0.0906 (3)	0.3387 (2)	0.4226 (2)	0.0232 (6)
C17	0.0866 (3)	0.3841 (2)	0.5151 (2)	0.0293 (7)
H17A	0.0281	0.4279	0.5176	0.044*
H17B	0.1661	0.4254	0.5467	0.044*
H17C	0.0631	0.3282	0.5401	0.044*
C18	0.0152 (4)	0.3511 (3)	0.3553 (3)	0.0415 (9)
H18A	0.0174	0.3163	0.2993	0.050*
H18B	−0.0394	0.3946	0.3644	0.050*
C19	0.3180 (2)	−0.0150 (2)	0.2567 (2)	0.0206 (6)
C20	0.3335 (3)	−0.1085 (2)	0.19035 (19)	0.0209 (6)
C21	0.3480 (3)	−0.2036 (2)	0.2209 (2)	0.0299 (7)
H21A	0.3576	−0.2581	0.1740	0.045*
H21B	0.2767	−0.2282	0.2406	0.045*
H21C	0.4190	−0.1853	0.2674	0.045*
C22	0.3347 (3)	−0.1025 (3)	0.1107 (2)	0.0348 (8)
H22A	0.3449	−0.1595	0.0695	0.042*
H22B	0.3252	−0.0411	0.0960	0.042*
C23	0.0991 (3)	0.2310 (2)	0.09099 (19)	0.0219 (6)
C24	−0.0130 (3)	0.1450 (2)	0.0413 (2)	0.0246 (7)
C25	−0.0923 (3)	0.1017 (3)	0.0924 (3)	0.0394 (9)
H25A	−0.1544	0.0431	0.0550	0.059*
H25B	−0.1304	0.1549	0.1200	0.059*
H25C	−0.0440	0.0788	0.1355	0.059*
C26	−0.0316 (3)	0.1097 (3)	−0.0457 (2)	0.0336 (8)
H26A	−0.0978	0.0549	−0.0767	0.040*
H26B	0.0217	0.1402	−0.0745	0.040*
C27	0.3746 (3)	0.2350 (2)	0.03536 (19)	0.0215 (6)
C28	0.3872 (3)	0.1660 (2)	−0.04942 (19)	0.0227 (6)
C29	0.3929 (3)	0.0663 (3)	−0.0578 (2)	0.0327 (8)
H29A	0.4009	0.0247	−0.1100	0.039*
H29B	0.3888	0.0381	−0.0115	0.039*
C30	0.3930 (3)	0.2180 (3)	−0.1208 (2)	0.0328 (8)
H30A	0.3975	0.1674	−0.1721	0.049*
H30B	0.4643	0.2745	−0.1038	0.049*
H30C	0.3210	0.2452	−0.1321	0.049*
C31	0.4425 (3)	0.5002 (2)	0.25101 (19)	0.0206 (6)
C32	0.5337 (3)	0.5618 (2)	0.33372 (19)	0.0216 (6)
C33	0.5287 (3)	0.5358 (3)	0.4066 (2)	0.0303 (7)
H33A	0.5833	0.5756	0.4579	0.036*
H33B	0.4707	0.4778	0.4064	0.036*
C34	0.6245 (3)	0.6542 (3)	0.3283 (2)	0.0351 (8)
H34A	0.6748	0.6901	0.3847	0.053*
H34B	0.5814	0.7014	0.3067	0.053*
H34C	0.6751	0.6299	0.2899	0.053*
C35	0.1151 (3)	0.5158 (3)	0.2190 (2)	0.0286 (7)
H35	0.1427	0.4767	0.2551	0.034*
C36	0.0271 (3)	0.5709 (3)	0.2390 (2)	0.0364 (8)
H36	−0.0031	0.5698	0.2882	0.044*
C37	−0.0150 (3)	0.6276 (3)	0.1847 (2)	0.0353 (8)
H37	−0.0749	0.6647	0.1967	0.042*
C38	0.0321 (3)	0.6291 (2)	0.1125 (2)	0.0282 (7)
H38	0.0045	0.6670	0.0753	0.034*
C39	0.1215 (3)	0.5727 (2)	0.09632 (19)	0.0221 (6)
C40	0.1818 (3)	0.5716 (2)	0.02266 (19)	0.0215 (6)
C41	0.1620 (3)	0.6338 (3)	−0.0332 (2)	0.0308 (7)
H41	0.1064	0.6769	−0.0268	0.037*
C42	0.2259 (3)	0.6308 (3)	−0.0981 (2)	0.0362 (8)
H42	0.2129	0.6711	−0.1363	0.043*
C43	0.3096 (3)	0.5670 (3)	−0.1056 (2)	0.0328 (8)
H43	0.3549	0.5651	−0.1479	0.039*
C44	0.3244 (3)	0.5060 (3)	−0.0484 (2)	0.0267 (7)
H44	0.3799	0.4627	−0.0535	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tb	0.01728 (8)	0.01693 (8)	0.01758 (8)	0.00519 (5)	0.00563 (5)	0.01065 (5)
Co1	0.01583 (19)	0.01565 (19)	0.01852 (19)	0.00300 (15)	0.00508 (15)	0.00846 (15)
Co2	0.0185 (2)	0.0171 (2)	0.01853 (19)	0.00386 (15)	0.00212 (16)	0.00884 (15)
O1	0.0193 (10)	0.0230 (11)	0.0249 (11)	0.0003 (9)	0.0041 (9)	0.0119 (9)
O2	0.0259 (11)	0.0333 (13)	0.0215 (11)	0.0032 (10)	0.0023 (9)	0.0127 (9)
O3	0.0244 (11)	0.0215 (11)	0.0310 (12)	0.0075 (9)	0.0049 (9)	0.0082 (9)
O4	0.0281 (13)	0.088 (2)	0.0312 (14)	0.0155 (14)	0.0114 (11)	0.0144 (14)
O5	0.0238 (11)	0.0247 (11)	0.0223 (11)	0.0069 (9)	0.0054 (9)	0.0050 (9)
O6	0.0237 (11)	0.0229 (12)	0.0546 (15)	0.0070 (9)	0.0135 (11)	0.0227 (11)
O7	0.0278 (12)	0.0296 (12)	0.0331 (12)	0.0115 (10)	0.0109 (10)	0.0187 (10)
O8	0.0252 (11)	0.0279 (12)	0.0307 (12)	0.0072 (9)	0.0108 (9)	0.0186 (9)
O9	0.0241 (12)	0.0699 (19)	0.0515 (15)	0.0244 (12)	0.0213 (12)	0.0427 (14)
O10	0.0198 (11)	0.0374 (13)	0.0260 (11)	0.0060 (9)	0.0033 (9)	0.0144 (10)
O11	0.0226 (11)	0.0178 (11)	0.0316 (11)	0.0018 (9)	0.0011 (9)	0.0108 (9)
O12	0.0299 (12)	0.0320 (12)	0.0210 (11)	0.0125 (10)	0.0091 (9)	0.0128 (9)
O13	0.0245 (11)	0.0234 (11)	0.0260 (11)	0.0081 (9)	0.0072 (9)	0.0099 (9)
O14	0.0210 (10)	0.0177 (11)	0.0317 (11)	0.0051 (9)	0.0063 (9)	0.0093 (9)
O15	0.0273 (11)	0.0231 (11)	0.0255 (11)	0.0027 (9)	0.0005 (9)	0.0128 (9)
N1	0.0193 (12)	0.0189 (13)	0.0202 (12)	0.0039 (10)	0.0057 (10)	0.0079 (10)
N2	0.0173 (12)	0.0188 (12)	0.0186 (12)	0.0048 (10)	0.0057 (10)	0.0091 (10)
N3	0.0224 (14)	0.0377 (16)	0.0293 (14)	0.0118 (12)	0.0092 (11)	0.0227 (12)
N4	0.0224 (13)	0.0229 (13)	0.0218 (13)	0.0050 (11)	0.0020 (11)	0.0077 (10)
N5	0.0189 (12)	0.0223 (13)	0.0228 (13)	0.0031 (10)	0.0029 (10)	0.0116 (10)
C1	0.0220 (15)	0.0286 (17)	0.0229 (15)	0.0039 (13)	0.0067 (13)	0.0127 (13)
C2	0.0219 (16)	0.0348 (18)	0.0227 (15)	0.0051 (13)	0.0025 (13)	0.0113 (13)
C3	0.0195 (15)	0.0198 (15)	0.0269 (16)	0.0002 (12)	0.0048 (13)	0.0021 (12)
C4	0.0238 (15)	0.0168 (15)	0.0265 (16)	0.0045 (12)	0.0088 (13)	0.0085 (12)
C5	0.0220 (15)	0.0133 (14)	0.0214 (14)	0.0054 (11)	0.0075 (12)	0.0050 (11)
C6	0.0200 (15)	0.0163 (14)	0.0220 (14)	0.0085 (12)	0.0092 (12)	0.0071 (11)
C7	0.0249 (16)	0.0177 (15)	0.0281 (16)	0.0038 (12)	0.0101 (13)	0.0121 (12)
C8	0.0337 (18)	0.0255 (17)	0.0280 (16)	0.0108 (14)	0.0094 (14)	0.0184 (13)
C9	0.0275 (16)	0.0280 (17)	0.0232 (15)	0.0124 (13)	0.0040 (13)	0.0123 (13)
C10	0.0197 (15)	0.0238 (16)	0.0274 (16)	0.0062 (12)	0.0047 (13)	0.0124 (13)
C11	0.0195 (14)	0.0166 (14)	0.0191 (14)	0.0061 (11)	0.0055 (12)	0.0026 (11)
C12	0.0187 (15)	0.0205 (15)	0.0276 (16)	0.0026 (12)	0.0027 (13)	0.0029 (12)
C13	0.0255 (17)	0.047 (2)	0.0315 (18)	0.0077 (15)	−0.0025 (15)	0.0140 (16)
C14	0.0226 (17)	0.036 (2)	0.053 (2)	−0.0016 (15)	0.0057 (16)	0.0198 (17)
C15	0.0170 (14)	0.0263 (16)	0.0187 (15)	0.0002 (12)	0.0057 (12)	0.0028 (12)
C16	0.0232 (15)	0.0193 (15)	0.0312 (16)	0.0041 (12)	0.0099 (13)	0.0125 (13)
C17	0.0368 (18)	0.0188 (16)	0.0389 (18)	0.0107 (14)	0.0166 (15)	0.0113 (14)
C18	0.047 (2)	0.041 (2)	0.045 (2)	0.0197 (18)	0.0093 (18)	0.0233 (18)
C19	0.0125 (13)	0.0190 (15)	0.0313 (17)	−0.0016 (11)	0.0078 (12)	0.0105 (12)
C20	0.0158 (14)	0.0231 (16)	0.0223 (15)	0.0007 (12)	0.0048 (12)	0.0058 (12)
C21	0.0326 (18)	0.0189 (16)	0.0344 (18)	0.0053 (13)	0.0050 (15)	0.0028 (13)
C22	0.0280 (18)	0.047 (2)	0.0315 (18)	0.0074 (16)	0.0087 (15)	0.0140 (16)
C23	0.0184 (15)	0.0221 (16)	0.0283 (16)	0.0085 (12)	0.0061 (13)	0.0093 (13)
C24	0.0200 (15)	0.0199 (16)	0.0340 (17)	0.0054 (12)	0.0006 (13)	0.0111 (13)
C25	0.0281 (18)	0.040 (2)	0.050 (2)	0.0012 (16)	0.0056 (17)	0.0205 (18)
C26	0.0332 (18)	0.0247 (17)	0.0382 (19)	0.0045 (14)	−0.0039 (15)	0.0096 (14)
C27	0.0143 (14)	0.0299 (17)	0.0223 (15)	0.0062 (12)	0.0021 (12)	0.0115 (13)
C28	0.0182 (15)	0.0315 (17)	0.0195 (15)	0.0042 (13)	0.0064 (12)	0.0087 (13)
C29	0.0376 (19)	0.0330 (19)	0.0327 (18)	0.0079 (15)	0.0194 (16)	0.0105 (15)
C30	0.0382 (19)	0.040 (2)	0.0220 (16)	0.0088 (16)	0.0088 (15)	0.0095 (14)
C31	0.0179 (14)	0.0176 (15)	0.0280 (16)	0.0079 (12)	0.0040 (12)	0.0077 (12)
C32	0.0224 (15)	0.0210 (15)	0.0230 (15)	0.0082 (12)	0.0038 (12)	0.0073 (12)
C33	0.042 (2)	0.0243 (17)	0.0219 (16)	0.0064 (14)	0.0029 (14)	0.0044 (13)
C34	0.0314 (18)	0.034 (2)	0.0337 (18)	−0.0055 (15)	−0.0004 (15)	0.0124 (15)
C35	0.0292 (17)	0.0303 (18)	0.0254 (16)	0.0033 (14)	0.0048 (14)	0.0094 (13)
C36	0.0314 (19)	0.045 (2)	0.0309 (18)	0.0080 (16)	0.0091 (15)	0.0054 (16)
C37	0.0272 (18)	0.0343 (19)	0.040 (2)	0.0126 (15)	0.0056 (15)	−0.0004 (15)
C38	0.0268 (17)	0.0203 (16)	0.0325 (17)	0.0050 (13)	−0.0004 (14)	0.0032 (13)
C39	0.0179 (15)	0.0167 (15)	0.0259 (15)	0.0006 (12)	−0.0041 (12)	0.0037 (12)
C40	0.0225 (15)	0.0148 (14)	0.0251 (15)	0.0008 (12)	−0.0002 (12)	0.0079 (12)
C41	0.0335 (18)	0.0233 (17)	0.0366 (18)	0.0075 (14)	−0.0008 (15)	0.0156 (14)
C42	0.046 (2)	0.0308 (19)	0.0366 (19)	0.0034 (16)	0.0041 (16)	0.0246 (16)
C43	0.0317 (18)	0.038 (2)	0.0320 (18)	0.0003 (15)	0.0083 (15)	0.0210 (15)
C44	0.0255 (16)	0.0283 (17)	0.0282 (16)	0.0046 (13)	0.0057 (14)	0.0126 (13)

Geometric parameters (Å, º) top

Tb—O6	2.312 (2)	C13—H13A	0.9600
Tb—O2	2.334 (2)	C13—H13B	0.9600
Tb—O12	2.340 (2)	C13—H13C	0.9600
Tb—O10	2.356 (2)	C14—H14A	0.9300
Tb—O14	2.357 (2)	C14—H14B	0.9300
Tb—O4	2.369 (2)	C15—C16	1.499 (4)
Tb—O8	2.514 (2)	C16—C18	1.337 (5)
Tb—O7	2.530 (2)	C16—C17	1.501 (4)
Co1—O1	2.012 (2)	C17—H17A	0.9600
Co1—O5	2.042 (2)	C17—H17B	0.9600
Co1—O3	2.057 (2)	C17—H17C	0.9600
Co1—N2	2.078 (2)	C18—H18A	0.9300
Co1—N1	2.160 (2)	C18—H18B	0.9300
Co2—O13	2.029 (2)	C19—C20	1.509 (4)
Co2—O11	2.051 (2)	C20—C22	1.327 (4)
Co2—N5	2.088 (2)	C20—C21	1.503 (4)
Co2—O15	2.115 (2)	C21—H21A	0.9600
Co2—N4	2.133 (3)	C21—H21B	0.9600
Co2—O14	2.389 (2)	C21—H21C	0.9600
O1—C11	1.260 (3)	C22—H22A	0.9300
O2—C11	1.260 (3)	C22—H22B	0.9300
O3—C15	1.269 (4)	C23—C24	1.518 (4)
O4—C15	1.248 (4)	C24—C26	1.354 (5)
O5—C19	1.257 (4)	C24—C25	1.473 (5)
O6—C19	1.277 (4)	C25—H25A	0.9600
O7—N3	1.263 (3)	C25—H25B	0.9600
O8—N3	1.282 (3)	C25—H25C	0.9600
O9—N3	1.232 (3)	C26—H26A	0.9300
O10—C23	1.260 (4)	C26—H26B	0.9300
O11—C23	1.266 (4)	C27—C28	1.516 (4)
O12—C27	1.265 (4)	C28—C29	1.328 (5)
O13—C27	1.269 (4)	C28—C30	1.503 (4)
O14—C31	1.293 (4)	C29—H29A	0.9300
O15—C31	1.254 (4)	C29—H29B	0.9300
N1—C1	1.346 (4)	C30—H30A	0.9600
N1—C5	1.352 (4)	C30—H30B	0.9600
N2—C10	1.347 (4)	C30—H30C	0.9600
N2—C6	1.350 (4)	C31—C32	1.508 (4)
N4—C35	1.343 (4)	C32—C33	1.328 (4)
N4—C39	1.352 (4)	C32—C34	1.503 (4)
N5—C44	1.338 (4)	C33—H33A	0.9300
N5—C40	1.353 (4)	C33—H33B	0.9300
C1—C2	1.390 (4)	C34—H34A	0.9600
C1—H1	0.9300	C34—H34B	0.9600
C2—C3	1.389 (4)	C34—H34C	0.9600
C2—H2	0.9300	C35—C36	1.381 (5)
C3—C4	1.395 (4)	C35—H35	0.9300
C3—H3	0.9300	C36—C37	1.379 (5)
C4—C5	1.396 (4)	C36—H36	0.9300
C4—H4	0.9300	C37—C38	1.382 (5)
C5—C6	1.489 (4)	C37—H37	0.9300
C6—C7	1.401 (4)	C38—C39	1.393 (4)
C7—C8	1.386 (4)	C38—H38	0.9300
C7—H7	0.9300	C39—C40	1.484 (4)
C8—C9	1.389 (5)	C40—C41	1.394 (4)
C8—H8	0.9300	C41—C42	1.383 (5)
C9—C10	1.392 (4)	C41—H41	0.9300
C9—H9	0.9300	C42—C43	1.387 (5)
C10—H10	0.9300	C42—H42	0.9300
C11—C12	1.509 (4)	C43—C44	1.391 (4)
C12—C14	1.341 (5)	C43—H43	0.9300
C12—C13	1.483 (4)	C44—H44	0.9300

O6—Tb—O2	89.72 (8)	C14—C12—C13	123.8 (3)
O6—Tb—O12	91.10 (8)	C14—C12—C11	119.2 (3)
O2—Tb—O12	141.89 (7)	C13—C12—C11	116.9 (3)
O6—Tb—O10	86.68 (8)	C12—C13—H13A	109.5
O2—Tb—O10	144.54 (7)	C12—C13—H13B	109.5
O12—Tb—O10	73.50 (7)	H13A—C13—H13B	109.5
O6—Tb—O14	165.64 (7)	C12—C13—H13C	109.5
O2—Tb—O14	97.02 (7)	H13A—C13—H13C	109.5
O12—Tb—O14	91.36 (7)	H13B—C13—H13C	109.5
O10—Tb—O14	80.47 (7)	C12—C14—H14A	120.0
O6—Tb—O4	83.07 (10)	C12—C14—H14B	120.0
O2—Tb—O4	73.78 (8)	H14A—C14—H14B	120.0
O12—Tb—O4	144.05 (8)	O4—C15—O3	124.3 (3)
O10—Tb—O4	70.76 (8)	O4—C15—C16	119.4 (3)
O14—Tb—O4	86.65 (9)	O3—C15—C16	116.2 (3)
O6—Tb—O8	122.83 (7)	C18—C16—C15	118.5 (3)
O2—Tb—O8	73.60 (7)	C18—C16—C17	123.8 (3)
O12—Tb—O8	74.10 (7)	C15—C16—C17	117.5 (3)
O10—Tb—O8	136.02 (7)	C16—C17—H17A	109.5
O14—Tb—O8	71.39 (7)	C16—C17—H17B	109.5
O4—Tb—O8	137.65 (9)	H17A—C17—H17B	109.5
O6—Tb—O7	71.84 (7)	C16—C17—H17C	109.5
O2—Tb—O7	71.68 (7)	H17A—C17—H17C	109.5
O12—Tb—O7	72.45 (7)	H17B—C17—H17C	109.5
O10—Tb—O7	138.97 (7)	C16—C18—H18A	120.0
O14—Tb—O7	122.32 (7)	C16—C18—H18B	120.0
O4—Tb—O7	136.89 (8)	H18A—C18—H18B	120.0
O8—Tb—O7	51.00 (7)	O5—C19—O6	122.9 (3)
O1—Co1—O5	95.93 (8)	O5—C19—C20	117.3 (3)
O1—Co1—O3	96.07 (8)	O6—C19—C20	119.8 (3)
O5—Co1—O3	156.98 (8)	C22—C20—C21	124.4 (3)
O1—Co1—N2	96.20 (9)	C22—C20—C19	119.4 (3)
O5—Co1—N2	96.25 (9)	C21—C20—C19	116.2 (2)
O3—Co1—N2	101.89 (9)	C20—C21—H21A	109.5
O1—Co1—N1	173.49 (8)	C20—C21—H21B	109.5
O5—Co1—N1	84.80 (9)	H21A—C21—H21B	109.5
O3—Co1—N1	85.48 (9)	C20—C21—H21C	109.5
N2—Co1—N1	77.30 (9)	H21A—C21—H21C	109.5
O13—Co2—O11	89.61 (9)	H21B—C21—H21C	109.5
O13—Co2—N5	94.45 (9)	C20—C22—H22A	120.0
O11—Co2—N5	100.68 (9)	C20—C22—H22B	120.0
O13—Co2—O15	94.95 (9)	H22A—C22—H22B	120.0
O11—Co2—O15	164.39 (8)	O10—C23—O11	125.1 (3)
N5—Co2—O15	93.85 (9)	O10—C23—C24	118.0 (3)
O13—Co2—N4	170.11 (9)	O11—C23—C24	116.9 (3)
O11—Co2—N4	86.32 (9)	C26—C24—C25	123.9 (3)
N5—Co2—N4	77.49 (10)	C26—C24—C23	119.1 (3)
O15—Co2—N4	91.34 (9)	C25—C24—C23	117.0 (3)
O13—Co2—O14	97.41 (8)	C24—C25—H25A	109.5
O11—Co2—O14	106.35 (8)	C24—C25—H25B	109.5
N5—Co2—O14	150.45 (9)	H25A—C25—H25B	109.5
O15—Co2—O14	58.29 (7)	C24—C25—H25C	109.5
N4—Co2—O14	92.38 (8)	H25A—C25—H25C	109.5
C11—O1—Co1	121.33 (18)	H25B—C25—H25C	109.5
C11—O2—Tb	158.9 (2)	C24—C26—H26A	120.0
C15—O3—Co1	115.23 (19)	C24—C26—H26B	120.0
C15—O4—Tb	162.7 (2)	H26A—C26—H26B	120.0
C19—O5—Co1	116.41 (19)	O12—C27—O13	124.7 (3)
C19—O6—Tb	141.31 (19)	O12—C27—C28	118.6 (3)
N3—O7—Tb	95.80 (17)	O13—C27—C28	116.6 (3)
N3—O8—Tb	96.05 (16)	C29—C28—C30	123.5 (3)
C23—O10—Tb	138.55 (19)	C29—C28—C27	120.7 (3)
C23—O11—Co2	125.38 (19)	C30—C28—C27	115.8 (3)
C27—O12—Tb	141.3 (2)	C28—C29—H29A	120.0
C27—O13—Co2	124.09 (18)	C28—C29—H29B	120.0
C31—O14—Tb	143.88 (18)	H29A—C29—H29B	120.0
C31—O14—Co2	84.09 (17)	C28—C30—H30A	109.5
Tb—O14—Co2	107.30 (8)	C28—C30—H30B	109.5
C31—O15—Co2	97.56 (18)	H30A—C30—H30B	109.5
C1—N1—C5	119.0 (2)	C28—C30—H30C	109.5
C1—N1—Co1	126.30 (19)	H30A—C30—H30C	109.5
C5—N1—Co1	114.68 (19)	H30B—C30—H30C	109.5
C10—N2—C6	119.5 (2)	O15—C31—O14	120.0 (3)
C10—N2—Co1	123.40 (19)	O15—C31—C32	118.6 (3)
C6—N2—Co1	117.13 (18)	O14—C31—C32	121.3 (3)
O9—N3—O7	121.5 (3)	C33—C32—C34	123.5 (3)
O9—N3—O8	121.4 (3)	C33—C32—C31	120.3 (3)
O7—N3—O8	117.1 (2)	C34—C32—C31	116.2 (3)
C35—N4—C39	118.8 (3)	C32—C33—H33A	120.0
C35—N4—Co2	125.8 (2)	C32—C33—H33B	120.0
C39—N4—Co2	115.0 (2)	H33A—C33—H33B	120.0
C44—N5—C40	119.4 (3)	C32—C34—H34A	109.5
C44—N5—Co2	124.1 (2)	C32—C34—H34B	109.5
C40—N5—Co2	116.35 (19)	H34A—C34—H34B	109.5
N1—C1—C2	122.8 (3)	C32—C34—H34C	109.5
N1—C1—H1	118.6	H34A—C34—H34C	109.5
C2—C1—H1	118.6	H34B—C34—H34C	109.5
C3—C2—C1	118.4 (3)	N4—C35—C36	122.4 (3)
C3—C2—H2	120.8	N4—C35—H35	118.8
C1—C2—H2	120.8	C36—C35—H35	118.8
C2—C3—C4	119.1 (3)	C37—C36—C35	118.7 (3)
C2—C3—H3	120.4	C37—C36—H36	120.6
C4—C3—H3	120.4	C35—C36—H36	120.6
C3—C4—C5	119.3 (3)	C36—C37—C38	119.7 (3)
C3—C4—H4	120.3	C36—C37—H37	120.1
C5—C4—H4	120.3	C38—C37—H37	120.1
N1—C5—C4	121.3 (3)	C37—C38—C39	118.8 (3)
N1—C5—C6	115.1 (2)	C37—C38—H38	120.6
C4—C5—C6	123.7 (3)	C39—C38—H38	120.6
N2—C6—C7	120.9 (3)	N4—C39—C38	121.5 (3)
N2—C6—C5	115.7 (2)	N4—C39—C40	115.0 (3)
C7—C6—C5	123.3 (3)	C38—C39—C40	123.5 (3)
C8—C7—C6	119.1 (3)	N5—C40—C41	121.1 (3)
C8—C7—H7	120.4	N5—C40—C39	115.6 (2)
C6—C7—H7	120.4	C41—C40—C39	123.3 (3)
C7—C8—C9	119.9 (3)	C42—C41—C40	119.4 (3)
C7—C8—H8	120.1	C42—C41—H41	120.3
C9—C8—H8	120.1	C40—C41—H41	120.3
C10—C9—C8	118.0 (3)	C43—C42—C41	119.3 (3)
C10—C9—H9	121.0	C43—C42—H42	120.4
C8—C9—H9	121.0	C41—C42—H42	120.4
N2—C10—C9	122.5 (3)	C42—C43—C44	118.6 (3)
N2—C10—H10	118.7	C42—C43—H43	120.7
C9—C10—H10	118.7	C44—C43—H43	120.7
O2—C11—O1	124.1 (3)	N5—C44—C43	122.2 (3)
O2—C11—C12	119.0 (3)	N5—C44—H44	118.9
O1—C11—C12	116.9 (3)	C43—C44—H44	118.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O9ⁱ	0.93	2.46	3.299 (4)	150
C9—H9···O7ⁱ	0.93	2.54	3.291 (4)	138
C38—H38···O11ⁱⁱ	0.93	2.58	3.457 (4)	157
C42—H42···O9ⁱⁱⁱ	0.93	2.42	3.259 (5)	150
C43—H43···O8ⁱⁱⁱ	0.93	2.57	3.316 (4)	138

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z; (iii) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Co₂Tb(C₄H₅O₂)₆(NO₃)(C₁₀H₈N₂)₂]
M_r	1161.64
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	11.3717 (6), 13.4396 (5), 16.3572 (8)
α, β, γ (°)	103.912 (2), 99.950 (2), 99.845 (3)
V (Å³)	2330.26 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.28
Crystal size (mm)	0.32 × 0.31 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.495, 0.709
No. of measured, independent and observed [I > 2σ(I)] reflections	13172, 8051, 7272
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.060, 1.03
No. of reflections	8051
No. of parameters	610
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.87

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O9ⁱ	0.93	2.46	3.299 (4)	150
C9—H9···O7ⁱ	0.93	2.54	3.291 (4)	138
C38—H38···O11ⁱⁱ	0.93	2.58	3.457 (4)	157
C42—H42···O9ⁱⁱⁱ	0.93	2.42	3.259 (5)	150
C43—H43···O8ⁱⁱⁱ	0.93	2.57	3.316 (4)	138

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z; (iii) −x+1, −y+1, −z.

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