Two mixed-metal carboxyl­ate–base adducts

The crystal structures of hexa-μ-propionato-1:2κ⁶O:O′;1:3κ⁶O:O′-di­quinoline-2κN,3κN-calcium(II)­dizinc(II), [Ca­Zn₂(C₃H₅O₂)₆(C₉H₇N)₂], and hexa-μ-pivalato-1:2κ⁶O:O′;1:3κ⁶O:O′-di­quinoline-2κN,3κN-calcium(II)­dicobalt(II), [Ca­Co₂(C₅H₉O₂)₆(C₉H₇N)₂], are described. Both contain a linear array of one Ca^II ion and two M^II (M = Zn, Co) ions connected by two sets of three carboxyl­ate ligands in syn–syn bridging modes. The distorted tetrahedral geometry around the M^II ion is completed by a quinoline N atom. The central Ca^II ion occupies a crystallographic inversion centre and is octahedrally coordinated by six carboxyl O atoms in each structure. The Zn^II...Ca^II and Co^II...Ca^II distances are 3.8504 (9) and 3.7929 (5) Å, respectively.

S1. Comment

For some time, a type of novel linear trinuclear assembly of general formula [M^IIM'^II₂(O₂CR)₆L₂] (M = M' = Mn, Fe, Co, Zn; M' = Zn, M = Mn, Co, Ni, Zn, Cd, Mg, Ca, Sr, Ba; L is a heterocyclic base) has been the subject of considerable attention in the literature (Catterick et al., 1974; Catterick & Hursthouse, 1976; Clegg et al., 1985, 1986, 1988, 1989). The first example characterized by single-crystal X-ray diffraction was the cobalt complex [Co₃(O₂CPh)₆(C₉H₇N)₂] reported by Catterick et al. (1974). In each case, the three divalent metals ions are arranged in a linear array within a centrosymmetric molecule. The ligands L are bound terminally to the outer metal ions, and the carboxylates form bridges between the central and outer metal ions. Several Schiff base derivatives, such as [Mn^II₃(O₂CCH₃)₄(L¹)₂(CH₃OH)₂] and [M^II₃(O₂CCH₃)(L²)₂(DMF)₂] [M = Fe, Co; L¹ = 1,3-dihydroxy-2-methyl-2-(5-chlorosalicylideamino)propane, L² = N,N'-bis(salicylidene)-2,2'-dimethylpropylenediamine], have also been synthesized and characterized (Li et al., 1988; Gerli et al., 1991; Tangoulis et al., 1996). These complexes not only provide a wealth of data about steric interactions and spectroscopic and magnetic properties, but also can serve as structural models for biological systems and solid materials.

The title complexes, (I) and (II) (Figs. 1 and 2, respectively), each consists of a centrosymmetric linear trinuclear molecule, with the central Ca^II ion on a crystallographic inversion center. Two M^II (M = Zn, Co) ions are each coordinated by three carboxyl O atoms and a quinoline molecule to form a distorted tetrahedron, whose most distorted angles are O22—Zn—N at 95.84 (13)° and O12—Co—N1 at 94.42 (12)°. Each terminal M^II ion is connected to the central Ca^II ion by three propionate bridges in a syn–syn mode. The Ca^II ion occupies a slightly distorted octahedron of O atoms, with Ca—O bond lengths in the range 2.287 (3)–2.323 (3) Å for (I) and 2.261 (3)–2.279 (3) Å for (II), and from all O—Ca—O angles within 4.5° of ideal octahedral values for both (I) and (II). The two structures are therefore similar to those observed for [MZn₂(O₂CCH═CHCH₃)₆(C₁₀H₉N)₂] (M = Ca, Sr) and [BaZn₂(O₂CCMe₃)₆(C₉H₇N)₂] (Clegg et al., 1988, 1989), but are different from that of [MgZn₂(O₂CCH═CHCH₃)₆(C₉H₇N)₂] (Clegg et al., 1988), where the central Mg^II is linked to each Zn^II ion and by three crotonate bridges: two of these are syn–syn bidentate and the third is monodentate and bridging through only one O atom. The Zn—O [1.924 (3)–1.951 (3) Å], Zn—N [2.086 (2) Å] and Zn···Ca [3.8504 (9) Å] distances in (I) are in good agreement with the corresponding values in [CaZn₂(O₂CCH═CHCH₃)₆(C₁₀H₉N)₂] (Clegg et al., 1988) and slightly longer than the Co—O [1.904 (3)–1.914 (3) Å], Co—N [2.065 (3) Å and Co—Ca [3.7929 (5) Å] distances in (II) as a consequence of the smaller radius of cobalt. The present Zn···Ca and Co···Ca distances are considerably longer than the Zn···Mg distance of 3.518 (3) Å found in MgZn₂ crotonate (Clegg et al., 1988), but significantly shorter than the related separations in SrZn₂ crotonate [4.050 (5) Å; Clegg et al., 1988] and BaZn₂ pivalate [4.18 (1) Å; Clegg et al., 1989].

S2. Experimental

For the preparation of (I), a mixture of Zn(NO₃)₂·6H₂O, Ca(NO₃)₂·6H₂O, propionic acid and quinoline (molar ratio 2:1:6:2) in EtOH was refluxed for 10 h. The resulting solution was allowed to stand in air and colourless crystals were deposited after one week. For the preparation of (II), a mixture of Co(NO₃)₂·6H₂O, Ca(NO₃)₂·6H₂O, pivalic acid and quinoline (molar ratio 2:1:6:2) in ethanol was refluxed for 12 h. The resulting solution was allowed to stand in air and purple prismatic crystals were deposited after three days.

S3. Refinement

In (I), the C21 ethyl group is wholly split into two parts, each having a site-occupancy factor of 1/2, as is the C33 methyl group. H atoms belonging to the disordered C atoms were not included in the refinement model.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989) for (I); SMART (Siemens, 1996) for (II). Cell refinement: CAD-4 Software for (I); SMART and SAINT (Siemens, 1994) for (II). Data reduction: MolEN (Fair, 1990) for (I); XPREP (1994) for (II). Program(s) used to solve structure: SHELXS86 (Sheldrick, 1990) for (I); SHELXTL (Siemens, 1994) for (II). Program(s) used to refine structure: SHELXL93 (Sheldrick, 1993) for (I); SHELXTL for (II). Molecular graphics: SHELXTL (Siemens, 1994) for (I); SHELXTL for (II). For both compounds, software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of the molecular structure of (I) showing the atom-numbering scheme and 30% probability displacement ellipsoids. Only one component of the disordered C atoms of the propionate groups is shown for clarity. [Symmetry code: (A) −1 − x, 1 − y, 1 − z.]
	Fig. 2. A view of the molecular structure of (I) showing the atom-numbering scheme and 30% probability displacement ellipsoids. [Symmetry code: (A) 1/2 − x, 1/2 − y, 1 − z.]

(I)

Crystal data

[CaZn2(C3H5O2)6(C9H7N)2]	F(000) = 900
Mr = 867.55	Dx = 1.392 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.614 (2) Å	Cell parameters from 25 reflections
b = 19.363 (4) Å	θ = 2.0–25.0°
c = 12.473 (3) Å	µ = 1.34 mm^−1
β = 95.59 (3)°	T = 293 K
V = 2070.4 (7) Å^3	Triangular prism, colorless
Z = 2	0.15 × 0.10 × 0.10 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	3007 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 25.0°, θmin = 2.0°
w scans	h = 0→10
Absorption correction: empirical (using intensity measurements) ϕ scans (Fair, 1990)	k = 0→23
Tmin = 0.735, Tmax = 0.875	l = −14→14
3633 measured reflections	3 standard reflections every 120 min
3633 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.155	H-atom parameters constrained
S = 1.15	w = 1/[σ^2(Fo^2) + (0.104P)^2 + 0.576P] where P = (Fo^2 + 2Fc^2)/3
3633 reflections	(Δ/σ)max = 0.001
238 parameters	Δρmax = 0.64 e Å^−3
3 restraints	Δρmin = −0.33 e Å^−3

Special details

Experimental. none

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn	−0.38984 (5)	0.38958 (2)	0.75272 (3)	0.0461 (2)
Ca	−0.5000	0.5000	0.5000	0.0421 (3)
O11	−0.3384 (4)	0.54016 (17)	0.6467 (2)	0.0713 (9)
O12	−0.2845 (4)	0.47508 (15)	0.7904 (2)	0.0637 (8)
O21	−0.3621 (5)	0.39771 (17)	0.4998 (3)	0.0767 (10)
O22	−0.3158 (5)	0.33211 (18)	0.6426 (2)	0.0832 (11)
O31	−0.6418 (4)	0.4493 (2)	0.6244 (3)	0.0800 (10)
O32	−0.6130 (4)	0.38731 (18)	0.7680 (3)	0.0694 (9)
N	−0.3063 (4)	0.32705 (16)	0.8818 (2)	0.0502 (8)
C11	−0.2756 (5)	0.5307 (2)	0.7375 (3)	0.0544 (10)
C12	−0.1815 (8)	0.5877 (3)	0.7923 (5)	0.097 (2)
H12A	−0.2487	0.6276	0.7965	0.117*
H12B	−0.1002	0.6003	0.7473	0.117*
C13	−0.1063 (10)	0.5727 (4)	0.9032 (6)	0.131 (3)
H13A	−0.0482	0.6124	0.9302	0.197*
H13B	−0.0371	0.5340	0.9005	0.197*
H13C	−0.1853	0.5621	0.9499	0.197*
C21	−0.3087 (7)	0.3469 (3)	0.5444 (3)	0.0760 (16)
C22	−0.2821 (14)	0.2835 (6)	0.4709 (9)	0.078 (3)*	0.50
C23	−0.127 (2)	0.2523 (13)	0.4947 (19)	0.171 (9)*	0.50
C22A	−0.1881 (13)	0.3042 (5)	0.4809 (9)	0.070 (2)*	0.50
C23A	−0.203 (2)	0.2299 (7)	0.5095 (13)	0.109 (5)*	0.50
C31	−0.6963 (5)	0.4200 (2)	0.6981 (4)	0.0565 (10)
C32	−0.8689 (7)	0.4237 (5)	0.7058 (6)	0.107 (2)
C33	−0.952 (2)	0.4576 (9)	0.6095 (14)	0.127 (5)*	0.50
C33A	−0.935 (2)	0.3804 (9)	0.7896 (14)	0.140 (6)*	0.50
C41	−0.2489 (6)	0.2659 (2)	0.8581 (4)	0.0678 (13)
H41A	−0.2472	0.2542	0.7859	0.081*
C42	−0.1912 (8)	0.2182 (3)	0.9359 (4)	0.0886 (18)
H42A	−0.1515	0.1760	0.9158	0.106*
C43	−0.1939 (8)	0.2344 (3)	1.0408 (4)	0.0866 (18)
H43A	−0.1564	0.2030	1.0935	0.104*
C44	−0.2529 (6)	0.2983 (2)	1.0708 (3)	0.0603 (11)
C45	−0.2600 (7)	0.3176 (3)	1.1790 (4)	0.0820 (16)
H45A	−0.2209	0.2881	1.2340	0.098*
C46	−0.3235 (8)	0.3789 (3)	1.2035 (4)	0.0889 (18)
H46A	−0.3301	0.3908	1.2752	0.107*
C47	−0.3792 (7)	0.4244 (3)	1.1217 (4)	0.0803 (16)
H47A	−0.4213	0.4667	1.1393	0.096*
C48	−0.3725 (6)	0.4073 (2)	1.0168 (3)	0.0610 (11)
H48A	−0.4098	0.4382	0.9632	0.073*
C49	−0.3106 (5)	0.3444 (2)	0.9881 (3)	0.0481 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn	0.0684 (3)	0.0363 (3)	0.0331 (3)	0.00394 (19)	0.0020 (2)	0.00242 (16)
Ca	0.0562 (6)	0.0370 (5)	0.0319 (5)	0.0036 (4)	−0.0022 (4)	0.0060 (4)
O11	0.097 (2)	0.0605 (19)	0.0512 (18)	−0.0162 (17)	−0.0215 (16)	0.0100 (15)
O12	0.091 (2)	0.0450 (16)	0.0518 (17)	−0.0092 (15)	−0.0097 (14)	0.0068 (13)
O21	0.111 (3)	0.063 (2)	0.0559 (19)	0.0370 (19)	0.0087 (18)	0.0084 (15)
O22	0.143 (3)	0.071 (2)	0.0371 (16)	0.044 (2)	0.0173 (18)	0.0032 (15)
O31	0.077 (2)	0.095 (3)	0.070 (2)	−0.0065 (19)	0.0180 (17)	0.0270 (19)
O32	0.075 (2)	0.075 (2)	0.0580 (19)	0.0005 (16)	0.0060 (16)	0.0168 (16)
N	0.076 (2)	0.0386 (17)	0.0350 (15)	0.0095 (15)	0.0018 (14)	0.0041 (13)
C11	0.070 (3)	0.044 (2)	0.047 (2)	−0.0069 (19)	−0.0065 (18)	0.0047 (18)
C12	0.128 (5)	0.067 (3)	0.088 (4)	−0.038 (3)	−0.036 (4)	0.011 (3)
C13	0.164 (7)	0.111 (6)	0.103 (5)	−0.037 (5)	−0.065 (5)	−0.011 (4)
C21	0.126 (4)	0.065 (3)	0.038 (2)	0.044 (3)	0.012 (2)	0.004 (2)
C31	0.062 (3)	0.053 (2)	0.055 (2)	−0.008 (2)	0.011 (2)	−0.009 (2)
C32	0.061 (3)	0.146 (7)	0.117 (5)	−0.013 (4)	0.025 (3)	0.016 (5)
C41	0.114 (4)	0.042 (2)	0.046 (2)	0.021 (2)	0.000 (2)	−0.0029 (18)
C42	0.154 (5)	0.048 (3)	0.061 (3)	0.036 (3)	−0.002 (3)	0.003 (2)
C43	0.149 (5)	0.051 (3)	0.057 (3)	0.032 (3)	−0.005 (3)	0.018 (2)
C44	0.085 (3)	0.053 (2)	0.041 (2)	0.008 (2)	−0.001 (2)	0.0094 (18)
C45	0.125 (5)	0.081 (4)	0.037 (2)	0.023 (3)	−0.002 (2)	0.016 (2)
C46	0.140 (5)	0.088 (4)	0.039 (3)	0.016 (4)	0.013 (3)	−0.002 (2)
C47	0.125 (5)	0.068 (3)	0.047 (3)	0.027 (3)	0.006 (3)	−0.007 (2)
C48	0.091 (3)	0.051 (2)	0.041 (2)	0.016 (2)	0.005 (2)	0.0049 (19)
C49	0.067 (2)	0.042 (2)	0.0351 (19)	0.0024 (17)	0.0035 (16)	0.0037 (15)

Geometric parameters (Å, º)

Zn—O12	1.924 (3)	C11—C12	1.494 (6)
Zn—O22	1.924 (3)	C12—C13	1.497 (8)
Zn—O32	1.951 (3)	C21—C22	1.563 (12)
Zn—N	2.086 (3)	C21—C22A	1.597 (11)
Ca—O11	2.323 (3)	C22—C23	1.472 (16)
Ca—O21	2.310 (3)	C22A—C23A	1.492 (14)
Ca—O31	2.287 (3)	C31—C32	1.501 (7)
Ca—O11^i	2.323 (3)	C32—C33	1.490 (19)
Ca—O21^i	2.310 (3)	C32—C33A	1.498 (15)
Ca—O31^i	2.287 (3)	C41—C42	1.396 (6)
O11—C11	1.220 (5)	C42—C43	1.347 (7)
O12—C11	1.270 (5)	C43—C44	1.403 (7)
O21—C21	1.199 (5)	C44—C45	1.408 (6)
O22—C21	1.265 (5)	C44—C49	1.417 (5)
O31—C31	1.213 (5)	C45—C46	1.355 (8)
O32—C31	1.246 (5)	C46—C47	1.397 (7)
N—C41	1.327 (5)	C47—C48	1.357 (6)
N—C49	1.372 (5)
O12—Zn—O22	119.41 (17)	O21—C21—O22	125.6 (4)
O12—Zn—O32	116.19 (15)	O21—C21—C22	116.3 (5)
O22—Zn—O32	117.04 (17)	O22—C21—C22	114.4 (6)
O12—Zn—N	101.05 (13)	O21—C21—C22A	115.7 (5)
O22—Zn—N	95.84 (13)	O22—C21—C22A	117.2 (5)
O32—Zn—N	100.44 (14)	C22—C21—C22A	33.1 (5)
O11—Ca—O21	91.10 (13)	C23—C22—C21	112.7 (13)
O11—Ca—O31	85.87 (13)	C23A—C22A—C21	107.7 (9)
O21—Ca—O31	86.64 (14)	O31—C31—O32	122.0 (4)
O31—Ca—O21^i	93.36 (14)	O31—C31—C32	119.0 (5)
O31^i—Ca—O11	94.13 (13)	O32—C31—C32	119.1 (5)
O31^i—Ca—O21	93.36 (14)	C33—C32—C33A	128.4 (12)
O21^i—Ca—O11	88.90 (13)	C33—C32—C31	111.9 (8)
O31—Ca—O11^i	94.13 (13)	C33A—C32—C31	117.8 (10)
O21—Ca—O11^i	88.90 (13)	N—C41—C42	123.4 (4)
C11—O11—Ca	149.1 (3)	C43—C42—C41	118.9 (4)
C11—O12—Zn	130.8 (3)	C42—C43—C44	120.3 (4)
C21—O21—Ca	151.2 (3)	C43—C44—C45	122.7 (4)
C21—O22—Zn	127.6 (3)	C43—C44—C49	118.2 (4)
C31—O31—Ca	170.5 (3)	C45—C44—C49	119.1 (4)
C31—O32—Zn	115.2 (3)	C46—C45—C44	120.3 (4)
C41—N—C49	118.7 (3)	C45—C46—C47	120.4 (5)
C41—N—Zn	117.0 (3)	C48—C47—C46	120.5 (5)
C49—N—Zn	124.3 (2)	C47—C48—C49	121.0 (4)
O11—C11—O12	124.5 (4)	N—C49—C48	120.7 (3)
O11—C11—C12	119.1 (4)	N—C49—C44	120.6 (4)
O12—C11—C12	116.4 (4)	C48—C49—C44	118.7 (4)
C11—C12—C13	116.5 (5)

Symmetry code: (i) −x−1, −y+1, −z+1.

(II)

Crystal data

[CaZn2(C5H9O2)6(C9H7N)2]	F(000) = 2160
Mr = 1022.98	Dx = 1.293 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.5710 (5) Å	Cell parameters from 5832 reflections
b = 13.9851 (3) Å	θ = 1.8–25.5°
c = 18.8102 (4) Å	µ = 0.79 mm^−1
β = 103.814 (7)°	T = 293 K
V = 5254.9 (2) Å^3	Triangular prism, purple
Z = 4	0.15 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4742 independent reflections
Radiation source: fine-focus sealed tube	3269 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
w scans	θmax = 25.5°, θmin = 1.8°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −24→24
Tmin = 0.879, Tmax = 0.932	k = −16→16
12636 measured reflections	l = −10→22

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.135	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.048P)^2 + 5.7771P] where P = (Fo^2 + 2Fc^2)/3
4742 reflections	(Δ/σ)max = 0.001
295 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co	0.32872 (3)	0.48044 (4)	0.45486 (3)	0.0600 (2)
Ca	0.2500	0.2500	0.5000	0.0470 (3)
O11	0.34820 (14)	0.2620 (2)	0.46565 (17)	0.0767 (8)
O12	0.37598 (14)	0.38746 (19)	0.41188 (16)	0.0736 (8)
O21	0.28780 (16)	0.3734 (2)	0.57811 (15)	0.0832 (9)
O22	0.34900 (16)	0.4911 (2)	0.55919 (17)	0.0788 (8)
O31	0.20921 (15)	0.3645 (2)	0.41631 (16)	0.0840 (9)
O32	0.23989 (14)	0.5084 (2)	0.40137 (19)	0.0848 (9)
N1	0.38516 (15)	0.5943 (2)	0.43371 (17)	0.0591 (8)
C11	0.37284 (19)	0.2989 (3)	0.4199 (2)	0.0607 (10)
C12	0.4014 (3)	0.2389 (3)	0.3698 (3)	0.0856 (14)
C13	0.4670 (3)	0.2805 (5)	0.3608 (4)	0.134 (2)
H13A	0.4847	0.2409	0.3283	0.201*
H13B	0.4983	0.2832	0.4076	0.201*
H13C	0.4595	0.3438	0.3408	0.201*
C14	0.3491 (4)	0.2416 (4)	0.2974 (3)	0.149 (3)
H14A	0.3643	0.2039	0.2618	0.224*
H14B	0.3425	0.3065	0.2806	0.224*
H14C	0.3077	0.2160	0.3041	0.224*
C15	0.4112 (4)	0.1371 (3)	0.3968 (3)	0.136 (3)
H15A	0.4297	0.0999	0.3635	0.204*
H15B	0.3688	0.1106	0.3997	0.204*
H15C	0.4413	0.1360	0.4445	0.204*
C21	0.32851 (19)	0.4355 (3)	0.6005 (2)	0.0609 (10)
C22	0.3536 (2)	0.4482 (4)	0.6817 (2)	0.0824 (14)
C23	0.3823 (4)	0.3564 (6)	0.7140 (3)	0.184 (4)
H23A	0.4184	0.3381	0.6926	0.275*
H23B	0.3483	0.3079	0.7043	0.275*
H23C	0.3988	0.3638	0.7659	0.275*
C24	0.4083 (3)	0.5211 (6)	0.6978 (4)	0.174 (4)
H24A	0.4449	0.5000	0.6783	0.261*
H24B	0.4235	0.5292	0.7498	0.261*
H24C	0.3916	0.5809	0.6758	0.261*
C25	0.2978 (3)	0.4809 (5)	0.7118 (3)	0.141 (3)
H25A	0.2809	0.5404	0.6893	0.211*
H25B	0.3132	0.4898	0.7637	0.211*
H25C	0.2628	0.4339	0.7021	0.211*
C31	0.1969 (2)	0.4448 (3)	0.3931 (2)	0.0629 (10)
C32	0.1281 (2)	0.4686 (4)	0.3494 (3)	0.0837 (14)
C33	0.1152 (3)	0.5755 (5)	0.3528 (4)	0.155 (3)
H33A	0.1486	0.6101	0.3354	0.233*
H33B	0.1171	0.5936	0.4025	0.233*
H33C	0.0717	0.5902	0.3227	0.233*
C34	0.0787 (3)	0.4141 (7)	0.3752 (5)	0.211 (5)
H34A	0.0811	0.4301	0.4254	0.317*
H34B	0.0873	0.3471	0.3715	0.317*
H34C	0.0349	0.4289	0.3460	0.317*
C35	0.1274 (3)	0.4476 (6)	0.2718 (3)	0.160 (3)
H35A	0.1609	0.4853	0.2571	0.240*
H35B	0.0842	0.4628	0.2413	0.240*
H35C	0.1366	0.3809	0.2667	0.240*
C41	0.44621 (19)	0.5731 (3)	0.4320 (2)	0.0638 (10)
H41A	0.4579	0.5089	0.4327	0.077*
C42	0.4946 (2)	0.6399 (4)	0.4293 (3)	0.0833 (14)
H42A	0.5377	0.6212	0.4282	0.100*
C43	0.4783 (3)	0.7313 (4)	0.4282 (3)	0.0926 (16)
H43A	0.5107	0.7774	0.4275	0.111*
C44	0.4139 (2)	0.7594 (3)	0.4279 (2)	0.0724 (12)
C45	0.3933 (3)	0.8543 (4)	0.4269 (3)	0.1037 (18)
H45A	0.4242	0.9027	0.4262	0.124*
C46	0.3312 (3)	0.8772 (4)	0.4269 (4)	0.1119 (19)
H46A	0.3185	0.9411	0.4262	0.134*
C47	0.2854 (3)	0.8066 (4)	0.4280 (4)	0.118 (2)
H47A	0.2414	0.8231	0.4274	0.141*
C48	0.3028 (2)	0.7138 (3)	0.4300 (3)	0.0944 (16)
H48A	0.2710	0.6668	0.4308	0.113*
C49	0.3679 (2)	0.6878 (3)	0.4309 (2)	0.0611 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0539 (3)	0.0463 (3)	0.0828 (4)	−0.0057 (2)	0.0224 (3)	0.0012 (3)
Ca	0.0485 (6)	0.0465 (6)	0.0431 (6)	−0.0106 (5)	0.0048 (4)	0.0054 (5)
O11	0.0685 (18)	0.076 (2)	0.094 (2)	−0.0032 (15)	0.0342 (16)	0.0084 (17)
O12	0.083 (2)	0.0489 (16)	0.098 (2)	−0.0037 (14)	0.0390 (17)	−0.0041 (15)
O21	0.097 (2)	0.082 (2)	0.0667 (19)	−0.0390 (18)	0.0123 (16)	−0.0183 (16)
O22	0.090 (2)	0.0723 (19)	0.079 (2)	−0.0187 (16)	0.0302 (17)	−0.0038 (16)
O31	0.078 (2)	0.076 (2)	0.085 (2)	−0.0039 (16)	−0.0060 (16)	0.0343 (17)
O32	0.0542 (17)	0.0658 (19)	0.131 (3)	−0.0090 (15)	0.0149 (17)	0.0104 (18)
N1	0.0510 (19)	0.056 (2)	0.071 (2)	−0.0068 (15)	0.0157 (16)	0.0033 (16)
C11	0.056 (2)	0.060 (3)	0.068 (3)	−0.0062 (19)	0.017 (2)	−0.001 (2)
C12	0.128 (4)	0.058 (3)	0.081 (3)	0.013 (3)	0.044 (3)	−0.001 (2)
C13	0.153 (6)	0.128 (5)	0.160 (6)	0.039 (4)	0.114 (5)	0.025 (4)
C14	0.244 (9)	0.109 (5)	0.085 (4)	0.011 (5)	0.018 (5)	−0.031 (4)
C15	0.235 (8)	0.058 (3)	0.133 (5)	0.033 (4)	0.079 (5)	−0.003 (3)
C21	0.056 (2)	0.067 (3)	0.057 (3)	−0.009 (2)	0.010 (2)	−0.015 (2)
C22	0.072 (3)	0.107 (4)	0.062 (3)	−0.005 (3)	0.003 (2)	−0.031 (3)
C23	0.266 (10)	0.181 (8)	0.074 (4)	0.087 (8)	−0.018 (5)	0.010 (5)
C24	0.123 (5)	0.248 (10)	0.139 (6)	−0.075 (6)	0.008 (4)	−0.097 (6)
C25	0.108 (4)	0.231 (8)	0.084 (4)	0.010 (5)	0.027 (3)	−0.053 (5)
C31	0.055 (2)	0.066 (3)	0.065 (3)	−0.001 (2)	0.009 (2)	0.017 (2)
C32	0.056 (3)	0.105 (4)	0.085 (3)	0.001 (3)	0.007 (2)	0.046 (3)
C33	0.118 (5)	0.146 (6)	0.200 (8)	0.053 (5)	0.034 (5)	0.072 (6)
C34	0.053 (3)	0.308 (11)	0.259 (9)	−0.029 (5)	0.008 (4)	0.188 (9)
C35	0.101 (5)	0.256 (9)	0.101 (5)	0.007 (5)	−0.021 (4)	0.043 (6)
C41	0.052 (2)	0.069 (3)	0.071 (3)	−0.007 (2)	0.015 (2)	0.003 (2)
C42	0.053 (3)	0.097 (4)	0.103 (4)	−0.016 (3)	0.025 (2)	0.003 (3)
C43	0.077 (3)	0.089 (4)	0.114 (4)	−0.036 (3)	0.027 (3)	0.008 (3)
C44	0.077 (3)	0.066 (3)	0.075 (3)	−0.020 (2)	0.020 (2)	0.011 (2)
C45	0.117 (5)	0.059 (3)	0.132 (5)	−0.028 (3)	0.025 (4)	0.011 (3)
C46	0.129 (5)	0.054 (3)	0.151 (5)	−0.001 (3)	0.029 (4)	0.007 (3)
C47	0.097 (4)	0.073 (4)	0.190 (7)	0.012 (3)	0.047 (4)	0.012 (4)
C48	0.080 (3)	0.057 (3)	0.155 (5)	−0.002 (2)	0.043 (3)	0.005 (3)
C49	0.063 (3)	0.052 (2)	0.069 (3)	−0.0088 (19)	0.018 (2)	0.004 (2)

Geometric parameters (Å, º)

Co—O12	1.914 (3)	C12—C15	1.509 (6)
Co—O22	1.912 (3)	C12—C13	1.515 (7)
Co—O32	1.904 (3)	C12—C14	1.521 (8)
Co—N1	2.065 (3)	C21—C22	1.501 (6)
Co—Ca	3.7929 (5)	C22—C25	1.469 (7)
Ca—O11^i	2.269 (3)	C22—C23	1.480 (8)
Ca—O11	2.269 (3)	C22—C24	1.495 (8)
Ca—O21	2.279 (3)	C31—C32	1.495 (6)
Ca—O21^i	2.279 (3)	C32—C34	1.445 (6)
Ca—O31	2.261 (3)	C32—C35	1.486 (8)
Ca—O31^i	2.261 (3)	C32—C33	1.522 (8)
O11—C11	1.213 (4)	C41—C42	1.374 (6)
O12—C11	1.252 (5)	C42—C43	1.320 (6)
O21—C21	1.210 (4)	C43—C44	1.380 (6)
O22—C21	1.242 (5)	C44—C49	1.389 (5)
O31—C31	1.210 (5)	C44—C45	1.392 (7)
O32—C31	1.237 (5)	C45—C46	1.318 (7)
N1—C41	1.298 (4)	C46—C47	1.369 (7)
N1—C49	1.353 (5)	C47—C48	1.345 (7)
C11—C12	1.484 (6)	C48—C49	1.383 (6)
O12—Co—O22	118.55 (13)	C15—C12—C13	110.5 (5)
O12—Co—O32	115.87 (14)	C11—C12—C14	104.6 (4)
O22—Co—O32	118.22 (14)	C15—C12—C14	109.5 (5)
O12—Co—N1	94.42 (12)	C13—C12—C14	110.4 (5)
O22—Co—N1	98.22 (13)	O21—C21—O22	122.8 (4)
O32—Co—N1	104.63 (13)	O21—C21—C22	118.7 (4)
O31—Ca—O31^i	180.00 (12)	O22—C21—C22	118.5 (4)
O31—Ca—O11^i	92.46 (11)	C25—C22—C23	112.6 (6)
O31^i—Ca—O11^i	87.54 (11)	C25—C22—C24	109.2 (5)
O11—Ca—O31	87.54 (11)	C23—C22—C24	107.5 (6)
O31^i—Ca—O11	92.46 (11)	C25—C22—C21	108.6 (4)
O11^i—Ca—O11	180.0	C23—C22—C21	108.7 (4)
O11—Ca—O21	86.43 (11)	C24—C22—C21	110.3 (5)
O21—Ca—O31	85.74 (11)	O31—C31—O32	122.8 (4)
O31^i—Ca—O21	94.26 (11)	O31—C31—C32	119.6 (4)
O11^i—Ca—O21	93.57 (11)	O32—C31—C32	117.5 (4)
O31—Ca—O21^i	94.26 (11)	C34—C32—C35	112.5 (6)
O31^i—Ca—O21^i	85.74 (11)	C34—C32—C31	110.3 (4)
O11^i—Ca—O21^i	86.43 (11)	C35—C32—C31	106.4 (4)
O11—Ca—O21^i	93.57 (11)	C34—C32—C33	111.1 (6)
O21—Ca—O21^i	180.00 (10)	C35—C32—C33	106.0 (5)
C11—O11—Ca	141.7 (3)	C31—C32—C33	110.4 (5)
C11—O12—Co	125.1 (3)	N1—C41—C42	124.0 (4)
C21—O21—Ca	150.3 (3)	C43—C42—C41	118.4 (4)
C21—O22—Co	124.8 (3)	C42—C43—C44	121.0 (4)
C31—O31—Ca	156.8 (3)	C43—C44—C49	117.3 (4)
C31—O32—Co	119.0 (3)	C43—C44—C45	124.1 (5)
C41—N1—C49	117.8 (3)	C49—C44—C45	118.6 (5)
C41—N1—Co	114.8 (3)	C46—C45—C44	121.6 (5)
C49—N1—Co	126.8 (3)	C45—C46—C47	119.8 (5)
O11—C11—O12	123.3 (4)	C48—C47—C46	121.1 (5)
O11—C11—C12	120.4 (4)	C47—C48—C49	120.3 (5)
O12—C11—C12	116.3 (4)	N1—C49—C48	119.9 (4)
C11—C12—C15	111.1 (4)	N1—C49—C44	121.5 (4)
C11—C12—C13	110.6 (4)	C48—C49—C44	118.6 (4)

Symmetry code: (i) −x+1/2, −y+1/2, −z+1.